CN105820339A - Pegylated fluorescent aliphatic polyamide-imide and preparation method and application thereof - Google Patents
Pegylated fluorescent aliphatic polyamide-imide and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to pegylated fluorescent aliphatic polyamide-imide and a preparation method and application thereof .Pegylated fluorescent aliphatic polyamide-imide has a structure shown as the formula (III) in the description .Novel pegylated fluorescent aliphatic polyamide-imide has fluorescence in a solvent or in a solid state, and in the solvent, the fluorescence intensity of pegylated fluorescent aliphatic polyamide-imide is reduced along with increasing of the polarity of the solvent; besides, pegylated fluorescent aliphatic polyamide-imide can be well dissolved in low-polarity solvents including acetone, dichloromethane, tetrahydrofuran and dioxane, so that the application range of polyamide-imide is greatly expanded, and a foundation is laid for preparing composite materials or super-performance special materials .According to pegylated fluorescent aliphatic polyamide-imide, preparation cost is low, reaction conditions are mild, reaction time is short, reaction operation is easy and convenient, the reaction yield is high, and the application range is wide.
Description
Technical field
The invention belongs to chemical field, the fluorescent aliphatic polyamide acyl being specifically related to a kind of Pegylation is sub-
Amine and preparation method thereof and purposes.
Background technology
Polyamidoimide is the engineering material that a class is advanced, have concurrently polyamide and the excellent mechanical strength of polyimides,
Heat stability and compliance.Recently, polyamidoimide is at membrane material, gel electrolyte used for solar batteries and fluorescent polymer
Aspect receives the biggest concern.As a rule, polyamidoimide does not has fluorescence, only aromatic series or have fluorescence primitive
The semiaromatic polyamide composition acid imide modified just has fluorescence.Professor Endo proposes the most former of design hyperfluorescence polyimides
Then: alicyclic diamine and the aromatic diacid acid anhydride containing compliance unit must be used.Conversely, because the forbidden transition of amide group
Closing quenching effect, fatty polyamide does not the most absorb does not has fluorescence yet.
Chinese patent literature CN102241822A discloses a kind of fatty polyamide acid imide, and its solubility is good, is having
After machine solvent NMP, DMF, DMAc or DMSO are heated to 60 DEG C, can all dissolve, dissolubility 6g/100mL, overcome virtue
The slightly solubility of fragrant race PAI, the weak point of difficult machine-shaping.But, this fatty polyamide acid imide does not the most absorb and does not has yet
There is fluorescence.
Therefore, research dissolubility preferable fatty polyamide acid imide is significant.
Summary of the invention
To this end, the present invention proposes the fluorescent aliphatic polyamidoimide of a kind of Pegylation, and then it is provided to prepare
Method and purposes.
For solving above-mentioned technical problem, the present invention is achieved through the following technical solutions:
The present invention provides the fluorescent aliphatic polyamidoimide of a kind of Pegylation, has the knot shown in formula III
Structure,
Wherein, the number of repeat unit for corresponding repetitive that x, y represent respectively, x is selected from the integer of 0～300, and y is selected from 0
～the integer of 150, and x and y be not simultaneously selected from 0, P represent for polyethylene glycols residue, R selected from include C2～C18 alkyl,
Including C2～C18 alcyl alkyl, include the Arylalkvl of C2～C18.
Preferably, the fluorescent aliphatic polyamidoimide of the above-mentioned Pegylation of the present invention,
P is selected from
X selected from 0～250 integer, y selected from 0～125 integer, n selected from 1～1000 integer, R selected from include C2～
The alkyl of C12, include the alcyl alkyl of C2～C12, include the Arylalkvl of C2～C12.
It is further preferred that the fluorescent aliphatic polyamidoimide of the above-mentioned Pegylation of the present invention,
X selected from 0～200 integer, y selected from 0～100 integer, n selected from 1～500 integer, R selected from include C3, C5,
The alkyl of C10 or include the Arylalkvl of C8.
It is further preferred that the fluorescent aliphatic polyamidoimide of the above-mentioned Pegylation of the present invention,
X is selected from the integer of 0～100, and y is selected from the integer of 0～50, and n is selected from the integer of 1～100,
R is selected from
The present invention also provides for the intermediate of a kind of fluorescent aliphatic polyamidoimide preparing above-mentioned Pegylation, tool
There is the structure shown in formula I,
Wherein, the number of repeat unit for corresponding repetitive that x, y represent respectively, x is selected from the integer of 0～300, and y is selected from 0
～the integer of 150, and x and y be not simultaneously selected from 0, R selected from include C2～C18 alkyl, include C2～C18 alcyl alkyl,
Arylalkvl including C2～C18.
The present invention also provides for the preparation method of a kind of above-mentioned intermediate, comprises the following steps:
Wherein, the number of repeat unit for corresponding repetitive that x, y represent respectively, x is selected from the integer of 0～300, and y is selected from 0
～the integer of 150, and x and y be not simultaneously selected from 0, R selected from include C2～C18 alkyl, include C2～C18 alcyl alkyl,
Arylalkvl including C2～C18.
Preferably, the preparation method of the above-mentioned intermediate of the present invention, comprise the following steps:
Preferably, the preparation method of the above-mentioned intermediate of the present invention, comprise the following steps:
(1) preparation of the compound shown in formula (d): the compound shown in formula (a), alkali are dissolved in polar aprotic solvent
In, under ice bath and argon shield, under stirring, it is slowly added dropwise the compound shown in formula (b), stirring reaction under room temperature, prepare formula
Compound shown in (c)；Compound shown in formula (c) is dissolved in polar aprotic solvent, under argon shield, stirs lower point
Criticize and add Hydrazoic acid,sodium salt, 50～60 DEG C of stirring reactions, obtain the compound shown in formula (d)；
(2) preparation of the compound shown in formula (g): the compound shown in formula (e) and the compound shown in formula (f) are dissolved in
In glacial acetic acid, under room temperature lucifuge, stirring reaction overnight, obtains the compound shown in formula (g)；
(3) preparation of the compound shown in formula II: by molten to the compound shown in formula (g) and the compound shown in formula (d)
In the mixed solvent of polar aprotic solvent and water, stirring is lower adds copper sulfate and sodium ascorbate, and under room temperature, stirring is anti-
Should, obtain the compound shown in formula II；
(4) preparation of the compound shown in formula I: under argon shield, by the compound shown in formula II and NH2-R-
NH2In polar aprotic solvent, under room temperature, at least 12h is reacted in stirring, obtains the intermediate shown in formula I.
Preferably, the compound shown in formula II and NH2-R-NH2Mol ratio be 1:1.
The present invention also provides for the preparation method of the fluorescent aliphatic polyamidoimide of a kind of above-mentioned Pegylation, including
Following steps:
Intermediate shown in formula I is dissolved in polar aprotic solvent, with the mole of the intermediate shown in formula I
On the basis of, adding the Tributyl phosphate of 5%～10% mole of times amount, stirring reaction 1h under room temperature, then stirring is lower adds poly-second
Glycol compound, continues stirring reaction under room temperature, obtains the compound shown in formula III；Or
Compound shown in formula II and Polyethylene Glycol compounds are dissolved in polar aprotic solvent, protect at argon
Protect down, under stirring, add NH2-R-NH2, under room temperature, stirring reaction, obtains the fluorescent aliphatic of the Pegylation shown in formula III
Polyamidoimide；
Wherein, described Polyethylene Glycol compounds is selected from
N is selected from the integer of 1～1000, and R is selected from including the alkyl of C2～C18, including the alcyl alkyl of C2～C18, bag
Include the Arylalkvl of C2～C18.
Preferably, the preparation method of the fluorescent aliphatic polyamidoimide of the above-mentioned Pegylation of the present invention, formula I institute
The intermediate shown is 1:(1～2 with the mol ratio of Polyethylene Glycol compounds), the compound shown in formula II and polyethylene glycols
The mol ratio of compound is 1:(1～2).
It is further preferred that the preparation method of the fluorescent aliphatic polyamidoimide of the above-mentioned Pegylation of the present invention,
Intermediate shown in formula I is 1:1.2 with the mol ratio of Polyethylene Glycol compounds, the compound shown in formula II and poly-second two
The mol ratio of alcohol compound is 1:1.2.
It is further preferred that the preparation method of the fluorescent aliphatic polyamidoimide of the above-mentioned Pegylation of the present invention,
Add the Tributyl phosphate of 5% mole of times amount.
The present invention also provides for the fluorescent aliphatic polyamidoimide of above-mentioned Pegylation and is preparing optics, photic
Off-color material, solaode, polymer hollow fiber membrane, Polymeric fluorescent material, composite or super performance special material
In application.
The technique scheme of the present invention has the advantage that compared to existing technology
(1) present invention devises the fluorescent aliphatic polyamidoimide of a kind of novel Pegylation, not only molten
Agent neutralizes solid itself and is respectively provided with fluorescence, and in a solvent, along with the increase of solvent polarity, its fluorescence intensity weakens；And, low
Polar solvent acetone, dichloromethane, oxolane, dioxane all can dissolve well, this greatly extend polyamide-
Imido range of application, lays a good foundation for preparing composite or super performance special material；
(2) the fluorescent aliphatic polyamidoimide of the Pegylation of the present invention, preparation cost is relatively low, reaction condition relatively
Gentle, the response time is shorter, operation is easier, reaction yield is higher, the scope of application is wider.
Accompanying drawing explanation
In order to make present disclosure be more likely to be clearly understood, below according to the specific embodiment of the present invention and combine
Accompanying drawing, the present invention is further detailed explanation, wherein:
Fig. 1 (a) and Fig. 1 (b) be in the embodiment of the present invention 2 the dynamic nuclear-magnetism of fluorescent aliphatic polyamidoimide PAI1 with
The result of track；
Fig. 2 (a) and Fig. 2 (b) is that in the embodiment of the present invention 2, thiolactone-maleimide and 1,3-propane diamine polycondensation are anti-
The monomer conversion answered and molecular weight distribution width (PDI)；
Fig. 3 is the structure confirmation data of fluorescent aliphatic polyamidoimide PAI2 in the embodiment of the present invention 3；
Fig. 4 is the structure confirmation data of fluorescent aliphatic polyamidoimide PAI3 in the embodiment of the present invention 3；
Fig. 5 is the structure confirmation data of fluorescent aliphatic polyamidoimide PAI4 in the embodiment of the present invention 5；
Fig. 6 (a) and Fig. 6 (b) is the poly-second two of fluorescent aliphatic polyamidoimide PAI1 in the embodiment of the present invention 6 or 7
The structure confirmation data of esterification product；
Fig. 7 is different polyamide acid imide fluorescence, ultraviolet and optical picture under DMSO and body in experimental example of the present invention；
Fig. 8 is dissolubility, ultraviolet and the change in fluorescence in experimental example of the present invention before and after PAI1 Pegylation.
Detailed description of the invention
For a more detailed description to the present invention by embodiment below, following example are only embodiment party optimal to the present invention
The description of formula, does not have any restriction to the scope of the present invention.
1, reagent explanation
The present invention synthesizes and raw materials used is commercially available product.
2, instrument explanation
Nuclear magnetic resonance analyser Bruker Avance 400,
Fluorescence spectrophotometer PE LS55,
Ultra-violet and visible spectrophotometer UV-2601, SHIMADZU,
Chromatograph of gel permeation (Waters chromatographic column).
Embodiment 1The synthesis of intermediate thiolactone-maleimide monomer (II)
(1) synthesis of 2-bromo-2-methyl-nitrogen-(2-oxo Tetramethylene sulfide-3-base) propionic acid amide. (c)
Homocysteine thiolactone (7.10g, 46.3mmol), triethylamine (11.2g, 110.9mmol) are dissolved in 150mL
Chloroform, ice bath, logical argon.2-bromine isobutyl acylbromide (12.65g, 55.5mmol) is slowly dropped into reactant liquor, stirred overnight at room temperature.Instead
After should terminating, reactant liquor dchloromethane (150mL), filter, wash (60mL*3).Merge organic facies, anhydrous MgSO4Dry
Dry, filter after obtain pale yellowish oil liquid.After crossing column chromatography (ethyl acetate/normal hexane=1:2), obtain white crystal.Productivity:
49.7%.
Structure confirmation data is as follows:1HNMR (300MHz, CDCl3, ppm) and δ 7.04 (s, 1H), 4.45 (dt, J=13.0Hz,
J=6.5Hz, 1H), 3.47-3.20 (m, 2H), 2.89 (dt, J=12.0Hz, J=6.4Hz, 1H), 2.11-1.87 (m, 7H)
.13CNMR (75MHz, CDCl3, ppm) and δ 204.70,172.45,60.95,32.18,30.81,27.41.
The synthesis of 2-nitrine-2-methyl-nitrogen-(2-oxygen Tetramethylene sulfide-3-base) propionic acid amide. (d)
Bromine thiolactone (5.91g, 22.3mmol) is dissolved in 130mLDMF, logical argon.Excess Hydrazoic acid,sodium salt (5.80g,
89.2mmol) being dividedly in some parts reactant liquor, reactant liquor is gradually become orange by light yellow, and 55 DEG C are stirred 24 hours.After reaction terminates,
Decompression extracts DMF, and reacting coarse product is redissolved in 500mL dchloromethane.Then by reacting liquid filtering, concentration, post color is crossed
After spectrum (ethyl acetate/normal hexane=1:1), obtain pale yellow crystals.Productivity: 45.2%.
Structure confirmation data is as follows:1HNMR (300MHz, CDCl3, ppm) and δ 6.86 (s, 1H), 4.46 (dt, J=13.1Hz,
J=6.7Hz, 1H), 3.45-3.18 (m, 2H), 2.89 (dt, J=12.2Hz, J=5.9Hz, 1H), 2.08-1.84 (m, 1H),
1.55 (d, J=5.3Hz, 6H).13CNMR (75MHz, CDCl3, ppm) and δ 204.68,173.05,64.33,59.36,31.54,
27.52,24.61.
(2) synthesis of 1-propargyl-1 hydrogen pyrrole-2,5-diones (g)
Maleic anhydride (2.50g, 25.5mmol) and propargylamine (1.40g, 25.5mmol) are dissolved in 40mL glacial acetic acid, and room temperature is kept away
Light is stirred overnight.After reaction terminates, decompression extracts glacial acetic acid, and crude product is dissolved in 8mL acetic anhydride (containing sodium acetate 450mg), 65 DEG C
Stirring 2h, is then cooled to room temperature, pours 75mL frozen water into.Merge organic facies, anhydrous MgSO4It is dried, drying under reduced pressure, crosses column chromatography
After (ethyl acetate/normal hexane=1:2), obtain yellow oily liquid.Productivity: 31.5%.
Structure confirmation data is as follows:1HNMR (400MHz, CDCl3, ppm) and δ 6.76 (s, 2H), 4.29 (d, J=2.5Hz,
2H), 2.21 (t, J=2.5Hz, 1H).13CNMR (100MHz, CDCl3) δ 169.25,134.48,76.93,71.55,26.82.
(3) 2-(4-((2,5-dioxy-2,5-dihydro-1 hydrogen pyrroles's-1-base) methyl) 1 hydrogen-1,2,3-triazol-1-yl)-2-
The synthesis of methyl-nitrogen-(2-oxygen Tetramethylene sulfide-3-base) propionic acid amide. (II)
Alkynes maleimide (475.2mg, 3.52mmol) and nitrine thiolactone (882.6mg, 3.87mmol) are dissolved in
30mLTHF, is subsequently added copper sulphate pentahydrate (48.4mg, 0.194mmol) and sodium ascorbate (76.7mg, 0.387mmol)
Aqueous solution (10mL).Thin layer chromatography is followed the tracks of, and after reaction, drains reactant liquor and is redissolved in dichloromethane, filters, concentrates, crosses post
After chromatograph (ethyl acetate/normal hexane=4:3), obtain white powder.Productivity: 36.4%.
Structure confirmation data is as follows:1HNMR (400MHz, DMSO-d6, ppm) and δ 8.08 (d, J=11.0Hz, 2H), 7.52
(s, 1H), 4.70 (s, 2H), 4.57 (ddd, J=12.7Hz, J=8.3Hz, J=7.1Hz, 1H), 3.46-3.34 (m, 1H),
3.27 (ddd, J=11.0Hz, J=7.1Hz, J=1.4Hz, 1H), 2.34 (dddd, J=12.4Hz, J=6.9Hz, J=
5.4Hz, J=1.4Hz, 1H), 2.17 (qd, J=12.3Hz, J=7.1Hz, 1H), 1.79 (d, J=2.0Hz, 6H).13CNMR
(100MHz, DMSO-d6, ppm) and δ 204.83,170.98,168.30,165.10,141.64,132.81,130.62,122.26,
64.79,58.69,33.62,29.33,26.66,25.62,25.47.
Embodiment 2The synthesis of fluorescent aliphatic polyamidoimide PAI1
Polycondensation reaction: thiolactone-maleimide monomer (36.3mg, 0.1mmol) is dissolved in 1mL DMSO, logical argon,
It is subsequently adding 1,3-propane diamine (7.4mg, 0.1mmol), it is stirred at room temperature, dynamic kernel magnetic tracking.After reaction terminates, reactant liquor is third
Ketone precipitates, is vacuum dried 3 hours.
The equivalent reaction of thiolactone-maleimide and 1,3-propane diamine makees catalyst without adding alkali.1,3-the third two
Amine will carry out ring-opening reaction with thiolactone simultaneously, and maleimide carries out Michael addition reaction.We follow the tracks of with nuclear-magnetism
Shown in reaction, experimental result such as Fig. 1 (a) and Fig. 1 (b).
From Fig. 1 (a) and Fig. 1 (b), (δ=7.08ppm, h) with homotype half at the double bond proton signal peak of maleimide
(δ=7.08ppm h) gradually weakens along with the response time and translates respectively at the methine proton signal peak of cystine thiolactone
To 3.77ppm (j) and 4.3ppm (c ').Same in carbon-13 nmr spectra, change after maleimide (12,135ppm) reaction
Become butanimide (12 ' and 12 ", 56ppm and 33ppm), thiolactone (4,205ppm) be transformed to amide (4 ',
177ppm)。
Thiolactone-maleimide and the monomer conversion of 1,3-propane diamine polycondensation reaction and molecular weight distribution
Width (PDI) is as shown in Fig. 2 (a) and Fig. 2 (b).
From Fig. 2 (a) and Fig. 2 (b), the Michael addition reaction of amine and maleimide will be far faster than thiolactone
Ring-opening reaction, the former completes in 0.5h, and the conversion ratio of thiolactone is 41% (1h), 68% (3h), and convert needs about completely
12h.The equivalent of reactant is extremely important to preparing heavy polymer in step-reaction, gained fluorescent aliphatic polyamide
The molecular weight of acid imide PAI1 is 25000, and molecular weight distribution width is 1.55.
Embodiment 3The synthesis of fluorescent aliphatic polyamidoimide PAI2
Polycondensation reaction: thiolactone-maleimide monomer (36.3mg, 0.1mmol) is dissolved in 1mL DMSO, logical argon,
It is subsequently adding 2,2-dimethyl-1,3-propane diamine (0.1mmol), it is stirred at room temperature, dynamic kernel magnetic tracking.After reaction terminates, reaction
Liquid precipitates in acetone, is vacuum dried 3h.
Structure confirmation data is as shown in Figure 3.
Embodiment 4The synthesis of fluorescent aliphatic polyamidoimide PAI3
Polycondensation reaction: thiolactone-maleimide monomer (36.3mg, 0.1mmol) is dissolved in 1mL DMSO, logical argon,
It is subsequently adding three oxygen-1,13-decamethylene diamine (0.1mmol), is stirred at room temperature, dynamic kernel magnetic tracking.After reaction terminates, reactant liquor is third
Ketone precipitates, is vacuum dried 3h.
Structure confirmation data is as shown in Figure 4.
Embodiment 5The synthesis of fluorescent aliphatic polyamidoimide PAI4
Polycondensation reaction: thiolactone-maleimide monomer (36.3mg, 0.1mmol) is dissolved in 1mL DMSO, logical argon,
It is subsequently adding benzyl diamidogen (0.1mmol), is stirred at room temperature, dynamic kernel magnetic tracking.After reaction terminates, reactant liquor sinks in acetone
Form sediment, be vacuum dried 3h.
Structure confirmation data is as shown in Figure 5.
The molecular weight and molecualr weight distribution width of different fluorescent aliphatic polyamidoimides is as shown in table 1.
The molecular weight and molecualr weight distribution width of the different fluorescent aliphatic polyamidoimide of table 1
Note: e. is recorded by GPC
As shown in Table 1,2,2-dimethyl-1, when diamidogen made by 3-propane diamine, the molecule of gained polyamide-imides (PAI2)
Amount and the dispersion of distribution are 26400 and 1.64.For 4,7,10-tri-oxygen-1,13-decamethylene diamine, molecular chain conformation width is 20100
With 1.39, the relatively low longer strand of diamidogen that is because of molecular weight causes polymer to have more preferable compliance, it is easier to initial ring
Change causes.On the other hand, what nucleophilicity was more weak carries out polycondensation reaction, molecular chain conformation the most efficiently to benzyl diamidogen
Width is respectively 36500 and 1.96, and molecular weight is significantly greater than the polyamide-imides prepared by aliphatic diamine.This is because,
The polyamide-imides structure more rigidity corresponding to benzyl diamidogen, the entanglement of strand is suppressed significantly with cyclisation, more favorably with
Linear mode increases.This shows, the method scope of application is wider.
Embodiment 6The PEGylated product of fluorescent aliphatic polyamidoimide PAI1
Rear modification method: be dissolved in 1mL DMSO by fluorescent aliphatic polyamidoimide PAI1 (0.1mmol), adds
The Tributyl phosphate (TCEP) of 0.005mmol, stirs 1h, the disulfide bond of reductive coupling under room temperature；Then, add 0.12mmol'sThe spectrum monitoring reaction of nucleus magnetic hydrogen spectrum, carbon.After reaction terminates, reactant liquor acetone precipitates two
Secondary, 35 DEG C of vacuum drying 2h.
Shown in structure confirmation data such as Fig. 6 (a) and Fig. 6 (b).
Embodiment 7The PEGylated product of fluorescent aliphatic polyamidoimide PAI1
Orthogonal Method: the compound (36.3mg, 0.1mmol) shown in formula II and
(60mg, 0.12mmol) is dissolved in 1mLDMSO, logical argon 10min.Then, addition 1,3-propane diamine (7.4mg, 0.1mmol),
Being stirred at room temperature, nucleus magnetic hydrogen spectrum, carbon spectrum follows the tracks of reaction.After being polymerized, product precipitates twice in acetone, and vacuum at 35 DEG C
It is dried 3h.
Shown in structure confirmation data such as Fig. 6 (a) and Fig. 6 (b).
Experimental exampleOptical property is tested
The imido optical data of different polyamide is as shown in table 2.
Table 2 different polyamide acid imide optical data under DMSO and bulk state
DMSO tests；B. near maximum excitation peak, there is no obvious absworption peak；C. under DMSO and bulk state
Maximum red shift wavelength.
As shown in Table 2, as a example by PAI1, along with the increase of solvent polarity, fluorescence intensity weakens；The low absorption of PAI1 is with non-
Typicality fluorescent polymer is similar with the phenomenon of multicolor carbon quantum points, and the quantum yield of PAI1 is 4.3% (DMF), and 4.1%
(DMSO), < 0.05 (methanol)；The solid fluorescence of PAI1 and solution fluorescence have the biggest difference.
Different polyamide acid imide fluorescence, ultraviolet and optical picture under DMSO and body is as shown in Figure 6.
As shown in Figure 7, PAI1 presents blue-fluorescence (λ max～460nm) in DMSO, and presents orange at solid state
Color fluorescence (λ max～595nm), this is the most relevant with the change of molecular stacks.It addition, intramolecular active force can under bulk state
To cause molecule to assemble, change optical physics and the photochemical properties of molecule, thus cause the significant change of fluorogram.On the contrary,
PAI2 and PAI3 presents blue-green fluorescent (PAI2: λ max～470nm in DMSO；PAI3: λ max～472nm), solid state
Only have the least red shift (Δ λ < 15nm).The red shift less compared to PAI1, PAI2 and PAI3 is by the number of alkyl substituent
Increase and cause, cause the molecular stacks the loosest, it is suppressed that molecule is reunited, thus fluorogram change is the most obvious.PAI4
Solid fluorescence change similar to PAI1.
Dissolubility, ultraviolet and change in fluorescence before and after PAI1 Pegylation are as shown in Figure 8.
As shown in Figure 8, before Pegylation, PAI1 is the most insoluble in most organic solvents and water；After Pegylation,
The molecular weight of PAI1 increases 67000, and dissolubility significantly improves, low polar solvent acetone, dichloromethane, oxolane,
All can dissolve well in dioxane, this is very big facilitates the functionalization of polyamide-imides in liquid phase.It addition, poly-second
After diolation, the optical property of PAI1 (absorbing and fluorescence) does not change a lot, in DMSO the quantum yield of PAI1 from
4.3% is reduced to 2.9%, and this is that the space conformation making PAI1 molecule the submissiveest due to PEG long-chain promotes non-radiative
The generation of decay.This shows, the fluorescent aliphatic polyamidoimide of the Pegylation that the present invention prepares, and not only has
Absorbing and fluorescence, and dissolubility is preferable, this greatly extends the range of application of polyamide-imides, for preparing composite wood
Material or super performance special material are laid a good foundation.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. the fluorescent aliphatic polyamidoimide of a Pegylation, it is characterised in that there is the structure shown in formula III,
Wherein, the number of repeat unit for corresponding repetitive that x, y represent respectively, x selected from 0～300 integer, y selected from 0～
The integer of 150, and x and y be not simultaneously selected from 0, P represent for polyethylene glycols residue, R is selected from including the alkyl of C2～C18, bag
Include the alcyl alkyl of C2～C18, include the Arylalkvl of C2～C18.
The fluorescent aliphatic polyamidoimide of Pegylation the most according to claim 1, it is characterised in that
P is selected from
X is selected from the integer of 0～250, and y is selected from the integer of 0～125, and n is selected from the integer of 1～1000, and R is selected from including C2's～C12
Alkyl, include the alcyl alkyl of C2～C12, include the Arylalkvl of C2～C12.
The fluorescent aliphatic polyamidoimide of Pegylation the most according to claim 2, it is characterised in that
X is selected from the integer of 0～200, and y is selected from the integer of 0～100, and n is selected from the integer of 1～500, and R is selected from including C3, C5, C10
Alkyl or include the Arylalkvl of C8.
The fluorescent aliphatic polyamidoimide of Pegylation the most according to claim 3, it is characterised in that
X is selected from the integer of 0～100, and y is selected from the integer of 0～50, and n is selected from the integer of 1～100,
R is selected from
5. the centre of the fluorescent aliphatic polyamidoimide of the Pegylation prepared described in any one of claim 1-4
Body, it is characterised in that there is the structure shown in formula I,
Wherein, the number of repeat unit for corresponding repetitive that x, y represent respectively, x selected from 0～300 integer, y selected from 0～
The integer of 150, and x and y be not simultaneously selected from 0, R is selected from including the alkyl of C2～C18, including the alcyl alkyl of C2～C18, bag
Include the Arylalkvl of C2～C18.
6. the preparation method of the intermediate described in a claim 5, it is characterised in that comprise the following steps:
Wherein, the number of repeat unit for corresponding repetitive that x, y represent respectively, x selected from 0～300 integer, y selected from 0～
The integer of 150, and x and y be not simultaneously selected from 0, R is selected from including the alkyl of C2～C18, including the alcyl alkyl of C2～C18, bag
Include the Arylalkvl of C2～C18.
The preparation method of intermediate the most according to claim 6, it is characterised in that comprise the following steps:
(1) preparation of the compound shown in formula (d): the compound shown in formula (a), alkali are dissolved in polar aprotic solvent,
Under ice bath and argon shield, under stirring, it is slowly added dropwise the compound shown in formula (b), stirring reaction under room temperature, prepare formula (c) institute
The compound shown；Compound shown in formula (c) is dissolved in polar aprotic solvent, under argon shield, adds under stirring in batches
Enter Hydrazoic acid,sodium salt, 50～60 DEG C of stirring reactions, obtain the compound shown in formula (d)；
(2) preparation of the compound shown in formula (g): the compound shown in formula (e) and the compound shown in formula (f) are dissolved in ice vinegar
In acid, under room temperature lucifuge, stirring reaction overnight, obtains the compound shown in formula (g)；
(3) preparation of the compound shown in formula II: the compound shown in formula (g) and the compound shown in formula (d) are dissolved in pole
Property non-protonic solvent and water mixed solvent in, lower copper sulfate and the sodium ascorbate of adding of stirring, stirring reaction under room temperature, i.e.
Obtain the compound shown in formula II；
(4) preparation of the compound shown in formula I: under argon shield, by the compound shown in formula II and NH2-R-NH2?
In polar aprotic solvent, under room temperature, at least 12h is reacted in stirring, obtains the intermediate shown in formula I.
8. the preparation side of the fluorescent aliphatic polyamidoimide of the Pegylation described in an any one of claim 1-4
Method, it is characterised in that comprise the following steps:
Intermediate shown in formula I is dissolved in polar aprotic solvent, with the mole of the intermediate shown in formula I as base
Standard, adds the Tributyl phosphate of 5%～10% mole of times amount, and under room temperature, stirring reaction 1h, then adds Polyethylene Glycol under stirring
Compounds, continues stirring reaction under room temperature, obtains the compound shown in formula III；Or
Compound shown in formula II and Polyethylene Glycol compounds are dissolved in polar aprotic solvent, in argon shield
Under, add NH under stirring2-R-NH2, stirring reaction under room temperature, the fluorescent aliphatic obtaining the Pegylation shown in formula III gathers
Amide imide；
Wherein, described Polyethylene Glycol compounds is selected from
N selected from 1～1000 integer, R is selected from including the alkyl of C2～C18, including the alcyl alkyl of C2～C18, include C2
～the Arylalkvl of C18.
The preparation method of the fluorescent aliphatic polyamidoimide of Pegylation the most according to claim 8, its feature
Being, the intermediate shown in formula I is 1:(1～2 with the mol ratio of Polyethylene Glycol compounds), the compound shown in formula II
It is 1:(1～2 with the mol ratio of Polyethylene Glycol compounds).
10. the fluorescent aliphatic polyamidoimide of the Pegylation described in any one of claim 1-4 is preparing optics device
Part, photochromic material, solaode, polymer hollow fiber membrane, Polymeric fluorescent material, composite or super performance are special
Plant the application in material.
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| CN109792054A (en) * | 2016-10-06 | 2019-05-21 | 株式会社丰田自动织机 | The manufacturing method of high-molecular compound, intermediate constituent, negative electrode, electrical storage device and high-molecular compound |
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