CN105061605A - Modified polysaccharide with fluorescent property as well as preparation method and application thereof - Google Patents
Modified polysaccharide with fluorescent property as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses modified polysaccharide with a fluorescent property as well as a preparation method and an application thereof. Fluorescence groups containing perylene structures are introduced in the acylation process through hydroxyl groups periodically distributed on a macromolecular chain of polysaccharide (starch, glucan, chitosan, chitin, alginic acid, cellulose and cellulose derivatives, so that the function of isolation of the fluorescence groups is achieved, an ACQ (aggregation-caused quenching) phenomenon of perylene type fluorescent molecules is eliminated, and accordingly, low-cost, efficient and practical modified polysaccharide with the fluorescent property is obtained. A fluorescent material prepared from the modified polysaccharide maintains the fluorescence characteristic of perylene light functional groups, has excellent properties of polysaccharide macromolecular materials, can be easily processed and formed, can be manufactured in various forms such as films, fiber, coatings, microspheres, micelle and the like, and has important practical value in fields of films, fiber, coating, ink, dye and the like.
Description
Technical field
The present invention relates to polysaccharide-based fluorescent material of a kind of Han perylene structure and preparation method thereof, belong to organic fluorescence materials preparation field.
Background technology
(Perylene) is Ji the derivative of perylene for perylene, it is aggregation inducing cancellation (ACQ) the type fluorescence molecule of a quasi-representative, its extremely low concentration solution has excellent fluorescent characteristic, and its highly concentrated solution and solid state, fluorescence quantum yield is extremely low, fluorescent effect is extremely faint even not to be had, and thus limits the widespread use of such fluorescence molecule.Eliminating the most direct mode of ACQ phenomenon is having the molecule of ACQ character mutually " isolation ", Ru being distributed to equably in the middle of macromolecule matrix by perylene fluorescence molecule, just can regain fluorescence.But simple physical blending exists some drawbacks, one is that fluorescence molecule is difficult to reach the dispersed of molecular level in polymeric matrix; Two is that fluorescent small molecule still has certain degree of freedom in the composite, and along with duration of service extends, it easily migration occurs and forms larger gathering, and cause material fluorescence property to change, fluorescent stability is poor.
Summary of the invention
The present invention utilizes periodic distribution on polysaccharide polymer, abundant reactive functional groups and semi-rigid polymer chain structure, by esterification Jiang the molecule " riveted joint " of Han perylene structure on polysaccharide polymer chain, polysaccharide polymer Lian is utilized to be kept apart by perylene functional group, fluorescence between You effect ground Xiao Chu perylene molecule assembles quenching effect, thus obtains the polysaccharide-based fluorescent material that a class has important application prospect Han perylene structure.The content of You Yu perylene is less, obtain the character that fluorescent material still remains polysaccharide polymer material, be easy to machine-shaping, the various patterns such as coating, film, fiber, colloid can be prepared into, there is important using value.
For achieving the above object, the invention provides following technical scheme:
There is a modified polysaccharide for photoluminescent property, its by polysaccharide or polysaccharide derivates Yu the acylating reagent of Han perylene is prepared by acylation reaction.
Wherein, described polysaccharide or polysaccharide derivates are selected from one or more in starch, dextran, chitosan, chitin, Lalgine, Mierocrystalline cellulose or derivatived cellulose.
According to the present invention, described starch is selected from least one in amylopectin, amylose starch.Described Mierocrystalline cellulose is selected from least one in Microcrystalline Cellulose, Cotton Pulp, wood pulps, bamboo pulp, absorbent cotton, bagasse, timber and Mierocrystalline cellulose obtained from straw.Described derivatived cellulose is selected from containing at least one in substituent ether of cellulose and cellulose ester, and wherein, described substituting group is selected from C
1-C
4at least one in alkyl.
Preferably, described cellulose ester is selected from least one in cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate, cellulose nitrate, cellulose benzoate.
More preferably, described ether of cellulose is selected from least one in methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol.
According to the present invention, the acylating reagent of described Han perylene is with carboxylic acid, acid anhydrides or acyl halide group perylene.Be preferably in the acid of Jun 3,4, 9, 10-perylenetetracarboxylic dianhydride, Jun perylene tetracarboxylic acid, perylene one or more.
Wherein, described polysaccharide or polysaccharide derivates are Yu the mass ratio of acylating reagent of Han perylene is 1:0.001-1:1; Be preferably 1:0.002-1:0.5; Be more preferably 1:0.005-1:0.2.
Wherein, the substitution value of described modified polysaccharide Zhong Han perylene group is 0.0001-1.0, is preferably 0.0005-0.1, more preferably 0.001-0.05.
The present invention also provides following technical proposals:
The above-mentioned preparation method with the modified polysaccharide of photoluminescent property, described method comprises the steps:
1) be dissolved in solvent by polysaccharide or polysaccharide derivates, then add acylating reagent and the catalyzer of Han perylene, mixing solutions is in 0-150 DEG C of reaction 0.5-72 hour;
2) be poured in precipitation agent by reaction soln, be settled out solid product, washing, drying, can obtain the described modified polysaccharide with photoluminescent property.
Wherein, described polysaccharide or polysaccharide derivates are selected from one or more in starch, dextran, chitosan, chitin, Lalgine, Mierocrystalline cellulose or derivatived cellulose.
Wherein, described starch is selected from least one in amylopectin, amylose starch.
Wherein, described Mierocrystalline cellulose is selected from least one in Microcrystalline Cellulose, Cotton Pulp, wood pulps, bamboo pulp, absorbent cotton, bagasse, timber and Mierocrystalline cellulose obtained from straw.
Wherein, described derivatived cellulose is selected from containing at least one in substituent ether of cellulose and cellulose ester; Wherein, described substituting group is selected from least one in C1-C4 alkyl.Preferably, described cellulose ester is selected from least one in cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate, cellulose nitrate, cellulose benzoate.Preferably, described ether of cellulose is selected from least one in methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol.
Wherein, the acylating reagent of described Han perylene is with carboxylic acid, acid anhydrides or acyl halide group perylene.Preferably, one or more in the acid of Wei Jun 3,4, 9, 10-perylenetetracarboxylic dianhydride, Jun perylene tetracarboxylic acid, perylene.
Step 1 of the present invention) in, described polysaccharide or polysaccharide derivates are Yu the mass ratio of acylating reagent of Han perylene is 1:0.001-1:1; Be preferably 1:0.002-1:0.5; Be more preferably 1:0.005-1:0.2.
Step 1 of the present invention) in, described solvent is selected from N, N-dimethyl sulfoxide (DMSO) (DMSO), N, at least one in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), tetrahydrofuran (THF) (THF), acetone, chloroform, pyridine, N-Methyl pyrrolidone, ionic liquid.Wherein, for polysaccharide such as Mierocrystalline cellulose, starch, chitosan and chitins, solvent preferred ion liquid; For derivatived cellulose, as cellulose acetate, at least one in the preferred DMSO of solvent, DMF, DMAc, THF, acetone, chloroform, N-Methyl pyrrolidone, pyridine.
Wherein, described ionic liquid by imidazoles or pyridine type positively charged ion and negatively charged ion formed, fusing point lower than organic melting salt of 100 DEG C, preferably can organic melting salt of the polysaccharide such as dissolving cellulos, starch, chitosan and chitin.The present invention can use ion liquid dissolving Mierocrystalline cellulose, starch, the polysaccharide such as chitosan and chitin of mixing, the ionic liquid of wherein said mixing can be all can the ionic liquid of the polysaccharide such as dissolving cellulos, starch, chitosan and chitin, also can be can the mixture of ionic liquid of the polysaccharide such as ionic liquid and not dissolving cellulos, starch, chitosan and chitin of the polysaccharide such as dissolving cellulos, starch, chitosan and chitin.
Preferably, the positively charged ion of ionic liquid be selected from following any one: 1-ethyl-3-methylimidazole positively charged ion, 1-propyl group-3-methyl imidazolium cation, 1-allyl group-3-methyl imidazolium cation, 1-butyl-3-methyl imidazolium cation, N-ethylpyridinium cations, N-butyl-pyridinium positively charged ion, N-n-hexyl pyridylium.Described positively charged ion especially preferably following any one: 1-ethyl-3-methylimidazole positively charged ion, 1-allyl group-3-methyl imidazolium cation and 1-butyl-3-methyl imidazolium cation.
Preferably, the negatively charged ion of ionic liquid be selected from following any one: chlorion, bromide anion, formate ion, acetate ion, propionate ion, butyrate ion and methyl orthophosphoric acid ion.Described negatively charged ion especially preferably following any one: chlorion, formate ion, acetate ion and methyl orthophosphoric acid ion.
According to the present invention, described solvent all can be used alone or cosolvent used in combination.
Step 1) in, described polysaccharide or polysaccharide derivates mass percentage concentration is in the solution 0.25-15%, is preferably 0.3-5%.
Step 1) in, described catalyzer is selected from least one in 4-dimethylaminopyridine (DMAP), dicyclohexylcarbodiimide (DCC), triethylamine, imidazoles, pyridine, N, N'-carbonyl dimidazoles (CDI), 124 Triazole.
Step 1) in, the consumption of described catalyzer is the 0.1-200% of acylating reagent quality of Han perylene, and preferred 0.5-100%, is more preferably 1-15%.
Step 2) in, described precipitation agent is one or both the mixture in water, alcohol, alkaline aqueous solution.Preferably, described alkaline aqueous solution is at least one in the aqueous solution of the sodium hydroxide of 0.001-0.01mol/L, potassium hydroxide, ammoniacal liquor, pyridine, triethylamine; Preferably, described alcohol is selected from least one in methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol.The mixture neutral and alkali aqueous solution of two kinds and the volume ratio of alcohol are 1:1-20:1; Preferred 1:1-10:1.
Be 0.0001-1.0 according to the substitution value with ， Han perylene group in the modified polysaccharide of photoluminescent property that described method prepares, be preferably 0.0005-0.1, more preferably 0.001-0.05.
The present invention also provides following technical scheme:
A kind of homogeneous phase solution, it is by being dissolved in the described modified polysaccharide with photoluminescent property in organic solvent, ionic liquid or cosolvent and being formed.
Wherein, described organic solvent is selected from N, N-dimethyl sulfoxide (DMSO) (DMSO), N, at least one in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), tetrahydrofuran (THF) (THF), acetone, chloroform, pyridine, N-Methyl pyrrolidone.
Wherein, the same definition of described ionic liquid.
Wherein, described cosolvent is selected from least any two kinds in described ionic liquid and described organic solvent.Such as, can be at least two kinds of the described ionic liquid cosolvent formed, the cosolvent that formed of at least two kinds of cosolvent or at least one of described ionic liquid formed of described organic solvent and at least one of described organic solvent.
Wherein, the mass percentage concentration of described homogeneous phase solution is 0.001-60%, is preferably 0.01-30%.
The present invention also provides following technical scheme:
A kind of fluorescent material, it is characterized in that, described fluorescent material comprises the modified polysaccharide with photoluminescent property of the present invention.
A kind of fluorescent material, it is prepared by above-mentioned homogeneous phase solution and obtains.
Wherein, described material has yellow-green fluorescence characteristic.Particularly, described material is film, coating, fiber, micella or microballoon.
Wherein, preparing described fluorescent material by described homogeneous phase solution, as pressed powder, film (as fexible film), coating, fiber, silk, micella or microballoon etc., is adopt customary preparation methods well known by persons skilled in the art preparation.For pressed powder, directly poured into by described homogeneous phase solution in water or alkaline aqueous solution, the precipitation freeze-drying obtained can obtain solid fluorescence powder.For fexible film, adopt and scrape embrane method, with blade applicator, described homogeneous phase solution is spread to certain thickness liquid film, at a certain temperature, after solvent evaporates is complete, uniform fexible film can be obtained.For coating, described homogeneous phase solution is directly coated on matrix, after solvent evaporates is dry, can fluoresent coating be obtained.For fiber, with above-mentioned homogeneous phase solution for raw material, adopt Electrospinning or solvent spinning technology can obtain fluorescent fiber or silk.For micella, described homogeneous phase solution is joined in poor solvent, stable fluorescence micella can be obtained under ultrasonic wave added condition.For microballoon, adopt emulsion solvent volatilization method can obtain the fluorescent microsphere with certain size.
The invention has the beneficial effects as follows:
The modified polysaccharide with photoluminescent property provided by the invention, not only there is high fluorescence intensity, and, because the content of Qi Zhong perylene is lower, material body is still based on polysaccharide polymer material, thus can while its excellent fluorescent characteristic of performance, still remain the processing characteristics of original polysaccharide polymer material excellence, conveniently be processed into the material of the various forms such as pressed powder, film, coating, fiber, silk, micella or microballoon, can be used as fluorescence dye, coating, film, fiber, ink, there is important practical value.
Accompanying drawing explanation
The comparison diagram of the FTIR containing perylene cellulose acetate ester derivative of the pure cellulose acetate of Fig. 1 and embodiment 1.
In the pure cellulose acetate of Fig. 2 and embodiment 1 containing perylene cellulose acetate ester derivative
1the comparison diagram of H-NMR.
The luminous intensity curve of the fluorescent material in Fig. 3 embodiment.
The in kind fluorescence photo of Fig. 4 various Han perylene acetyl cellulose fluorescent material goods under 365nm ultraviolet lamp, is followed successively by fluorescent powder, coating, flexible membrane, silk from left to right.
Embodiment
Substitution value described in the present invention is determined by the following method:
1) formulate typical curve, owing to having the UV, visible light charateristic avsorption band being different from polysaccharide or polysaccharide derivates, thus can be measured the substitution value of group in polysaccharide or polysaccharide derivates by ultraviolet-visible absorption spectroscopy calibration curve method.First be the standardized solution that 0-0.5 configures that a series of mass concentration is 100 μ g/mL by substitution value scope; Then its ultraviolet-visible absorption spectroscopy is tested respectively.Finally set up substitution value-maximum absorbance typical curve.
2) measure substitution value, same preparation mass concentration is the testing sample solution of 100 μ g/mL, tests its ultraviolet-visible absorption spectroscopy, obtains the substitution value of group in testing sample according to substitution value-maximum absorbance typical curve.
As previously mentioned, the modified polysaccharide with photoluminescent property disclosed by the invention is by polysaccharide or polysaccharide derivates Yu the acylation reaction of the acylating agent of Han perylene prepares; For cellulose acetate with Jun perylene tetracarboxylic acid, its reaction formula is shown below:
The present invention utilizes the oh group of periodic distribution on polysaccharide or polysaccharide derivates (as starch, dextran, chitosan, chitin, Lalgine, Mierocrystalline cellulose and derivatived cellulose etc.) macromolecular chain; the fluorophor of Han perylene structure is introduced by acylation process; thus play the effect of isolation fluorophor; Yi Xiao Chu perylene class fluorescence molecule aggregation inducing quenching phenomenon, thus obtain that a class is with low cost, the modified polysaccharide with photoluminescent property of highly effective.The fluorescent characteristic of the fluorescent material prepared by described modified polysaccharide both Bao Liu perylene light functional group, there is again polyose macromolecular material excellent properties, be easy to machine-shaping, can be made into the various patterns such as film, fiber, coating, microballoon and micella, in fields such as film, fiber, coating, ink, dyestuffs, there is important practical value.
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
Embodiment 1
0.47g cellulose acetate (CA), 0.004g perylene tetracarboxylic acid (PTCA), 0.006gDMAP, 0.25gDCC are dissolved in 250mLDMF solution, in the oil bath of 150 DEG C, and back flow reaction 1h.Reaction terminate after, revolve steam removing most of DMF after, reaction strong solution is joined in methyl alcohol, through precipitation, washing, drying can obtain substitution value be 0.0013 contain perylene cellulose acetate ester derivative (being designated as CA-g-perylene).
Embodiment 2
0.46g ethyl cellulose (MC), 0.05g perylene tetracarboxylic acid, 0.006gDMAP, 0.25gDCC are dissolved in 250mLDMF solution, in the oil bath of 150 DEG C, and back flow reaction 1h.After reaction terminates, revolve after steaming the most of DMF of removing, join in the sodium hydroxide solution of about 100mL0.001mol/L by reaction strong solution, through precipitation, washing, can to obtain substitution value be 0.032 Han perylene ethyl cellulose ester derivative (being designated as MC-g-perylene) in drying.
Embodiment 3
0.53g soluble cotton (CN), 0.05g perylene tetracarboxylic acid, 0.006gDMAP, 0.25gDCC are dissolved in 250mLDMF solution, in the oil bath of 150 DEG C, and back flow reaction 0.8h.After reaction terminates, revolve after steaming the most of DMF of removing, reaction strong solution is joined about 150mL sodium hydroxide (0.001mol/L) and methyl alcohol (v/v, in mixing solutions 4:1), through precipitation, washing, can to obtain substitution value be 0.012 Han perylene soluble cotton ester derivative (being designated as CN-g-perylene) in drying.
Embodiment 4
0.33g amylose starch, 0.055g perylene tetracarboxylic acid, 0.006gDMAP, 0.25gDCC are dissolved in 100g1-allyl group-3-Methylimidazole chlorine type ionic liquid, in the oil bath of 80 DEG C, and reaction 3h.After reaction terminates, reaction strong solution joined in the mixing solutions of about 150mL sodium hydroxide (0.001mol/L) and methyl alcohol (v/v, 4:1), through precipitating, washing, can to obtain substitution value be 0.009 Han perylene starch derivative in drying.
Embodiment 5
0.33g chitosan, 0.05g perylene tetracarboxylic acid, 0.006gDMAP, 0.25gDCC are dissolved in 100g1-butyl-3-Methylimidazole acetic acid ion liquid, in the oil bath of 80 DEG C, and reaction 4h.After reaction terminates, reaction strong solution is joined in about 150mL methanol solution, through precipitation, wash, can to obtain substitution value be 0.011 Han perylene chitosan derivatives in drying.
Embodiment 6
0.33g dextran, 0.055g perylene tetracarboxylic acid, 0.006gDMAP, 0.25gDCC are dissolved in 100gN-methyl pyrrolidone solvent, in the oil bath of 80 DEG C, and reaction 3h.After reaction terminates, reaction strong solution is joined in the about 150mL aqueous solution, through precipitation, wash, can to obtain substitution value be 0.015 Han perylene glucan derivative in drying.
The structural characterization containing perylene cellulose acetate ester derivative of embodiment 7 embodiment 1
The chemical structure containing perylene cellulose acetate ester derivative of the embodiment 1 synthesized according to described method can by FTIR and
1h-NMR is confirmed (see Fig. 1,2).
As shown in Figure 1, in FTIR collection of illustrative plates, and pure cellulose acetate (CA) contrast, 3058cm
-1phenyl ring C-H stretching vibration peak in Gui Shu Yu perylene structure; 734 and 702cm
-1belong to the out-of-plane deformation vibration peak of phenyl ring C-H, 1260cm
-1belong to C-O stretching vibration peak in remnants-COOH.
As shown in Figure 2,
1in H-NMR collection of illustrative plates; contrast with pure cellulose acetate (CA); except hydrogen (7H) in the cellulose skeleton of hydrogen (3H) and δ=2.5-5.5ppm in δ=1.5-2.0ppm formyl group, there is benzene ring hydrogen (4H in perylene structure at δ=8.13ppm and δ=7.95ppm
aand 4H
b).
The fluorescent material goods of embodiment 8 Han perylene polysaccharide or polysaccharide derivates
For the substitution value of embodiment 1 be 0.0013 containing perylene cellulose acetate ester derivative, its pressed powder fully can be dissolved in DMF solvent and form homogeneous phase solution, and be processed into various Mierocrystalline cellulose fluorescent material with this, can be specifically pressed powder, coating, fexible film or silk (see Fig. 4) etc., these materials all have excellent fluorescence property (see Fig. 3).
Protection scope of the present invention is not limited only to above-described embodiment.According to content disclosed by the invention, those skilled in the art will recognize that when the technical characteristic do not departed from given by technical solution of the present invention and scope, to the above embodiment make many changes and amendment all belong to protection scope of the present invention.
Claims (10)
1. have a modified polysaccharide for photoluminescent property, it is by polysaccharide or polysaccharide derivates and prepared by acylation reaction containing the acylating reagent of perylene.
2. modified polysaccharide according to claim 1, is characterized in that, described polysaccharide or polysaccharide derivates be selected from starch, dextran, chitosan, chitin, Lalgine, Mierocrystalline cellulose or derivatived cellulose one or more.
Preferably, described starch is selected from least one in amylopectin, amylose starch.
Preferably, described Mierocrystalline cellulose is selected from least one in Microcrystalline Cellulose, Cotton Pulp, wood pulps, bamboo pulp, absorbent cotton, bagasse, timber and Mierocrystalline cellulose obtained from straw.
Preferably, described derivatived cellulose is selected from containing at least one in substituent ether of cellulose and cellulose ester, and wherein, described substituting group is selected from least one in C1-C4 alkyl.Preferably, described cellulose ester is selected from least one in cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate, cellulose nitrate, cellulose benzoate.Preferably, described ether of cellulose is selected from least one in methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol.
Preferably, the acylating reagent of described Han perylene is with carboxylic acid, acid anhydrides or acyl halide group perylene.Be preferably in the acid of Jun 3,4, 9, 10-perylenetetracarboxylic dianhydride, Jun perylene tetracarboxylic acid, perylene one or more.
Preferably, described polysaccharide or polysaccharide derivates are Yu the mass ratio of acylating reagent of Han perylene is 1:0.001-1:1; Be preferably 1:0.002-1:0.5; Be more preferably 1:0.005-1:0.2.
3. modified polysaccharide according to claim 1 and 2, is characterized in that the substitution value of ， Han perylene group is 0.0001-1.0, is preferably 0.0005-0.1, more preferably 0.001-0.05.
4. the preparation method with the modified polysaccharide of photoluminescent property described in any one of claim 1-3, described method comprises the steps:
1) be dissolved in solvent by polysaccharide or polysaccharide derivates, then add acylating reagent and the catalyzer of Han perylene, mixing solutions is in 0-150 DEG C of reaction 0.5-72 hour;
2) be poured in precipitation agent by reaction soln, be settled out solid product, washing, drying, can obtain the described modified polysaccharide with photoluminescent property.
5. preparation method according to claim 4, is characterized in that, described polysaccharide or polysaccharide derivates be selected from starch, dextran, chitosan, chitin, Lalgine, Mierocrystalline cellulose or derivatived cellulose one or more.
Preferably, described starch is selected from least one in amylopectin, amylose starch.
Preferably, described Mierocrystalline cellulose is selected from least one in Microcrystalline Cellulose, Cotton Pulp, wood pulps, bamboo pulp, absorbent cotton, bagasse, timber and Mierocrystalline cellulose obtained from straw.
Preferably, described derivatived cellulose is selected from containing at least one in substituent ether of cellulose and cellulose ester; Wherein, described substituting group is selected from least one in C1-C4 alkyl.Preferably, described cellulose ester is selected from least one in cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate, cellulose nitrate, cellulose benzoate.Preferably, described ether of cellulose is selected from least one in methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol.
Preferably, the acylating reagent of described Han perylene is with carboxylic acid, acid anhydrides or acyl halide group perylene.Preferably, one or more in the acid of Wei Jun 3,4, 9, 10-perylenetetracarboxylic dianhydride, Jun perylene tetracarboxylic acid, perylene.
Preferably, step 1) in, described polysaccharide or polysaccharide derivates are Yu the mass ratio of acylating reagent of Han perylene is 1:0.001-1:1; Be preferably 1:0.002-1:0.5; Be more preferably 1:0.005-1:0.2.
6. preparation method according to claim 4, it is characterized in that, step 1) in, described solvent is selected from N, N-dimethyl sulfoxide (DMSO) (DMSO), N, at least one in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), tetrahydrofuran (THF) (THF), acetone, chloroform, pyridine, N-Methyl pyrrolidone, ionic liquid.Wherein, for polysaccharide such as Mierocrystalline cellulose, starch, chitosan and chitins, solvent preferred ion liquid; For derivatived cellulose, as cellulose acetate, at least one in the preferred DMSO of solvent, DMF, DMAc, THF, acetone, chloroform, N-Methyl pyrrolidone, pyridine.
Preferably, described ionic liquid by imidazoles or pyridine type positively charged ion and negatively charged ion formed, fusing point lower than organic melting salt of 100 DEG C, preferably can organic melting salt of the polysaccharide such as dissolving cellulos, starch, chitosan and chitin.The present invention can use ion liquid dissolving Mierocrystalline cellulose, starch, the polysaccharide such as chitosan and chitin of mixing, the ionic liquid of wherein said mixing can be all can the ionic liquid of the polysaccharide such as dissolving cellulos, starch, chitosan and chitin, also can be can the mixture of ionic liquid of the polysaccharide such as ionic liquid and not dissolving cellulos, starch, chitosan and chitin of the polysaccharide such as dissolving cellulos, starch, chitosan and chitin.
Preferably, the positively charged ion of ionic liquid be selected from following any one: 1-ethyl-3-methylimidazole positively charged ion, 1-propyl group-3-methyl imidazolium cation, 1-allyl group-3-methyl imidazolium cation, 1-butyl-3-methyl imidazolium cation, N-ethylpyridinium cations, N-butyl-pyridinium positively charged ion, N-n-hexyl pyridylium.Described positively charged ion especially preferably following any one: 1-ethyl-3-methylimidazole positively charged ion, 1-allyl group-3-methyl imidazolium cation and 1-butyl-3-methyl imidazolium cation.
Preferably, the negatively charged ion of ionic liquid be selected from following any one: chlorion, bromide anion, formate ion, acetate ion, propionate ion, butyrate ion and methyl orthophosphoric acid ion.Described negatively charged ion especially preferably following any one: chlorion, formate ion, acetate ion and methyl orthophosphoric acid ion.
Preferably, described solvent all can be used alone or cosolvent used in combination.
7. preparation method according to claim 4, is characterized in that, step 1) in, described polysaccharide or polysaccharide derivates mass percentage concentration is in the solution 0.25-15%, is preferably 0.3-5%.
Preferably, step 1) in, described catalyzer is selected from least one in 4-dimethylaminopyridine (DMAP), dicyclohexylcarbodiimide (DCC), triethylamine, imidazoles, pyridine, N, N'-carbonyl dimidazoles (CDI), 124 Triazole.
Preferably, step 1) in, the consumption of described catalyzer is the 0.1-200% of acylating reagent quality of Han perylene, is preferably 1-15%.
Preferably, step 2) in, described precipitation agent is one or both the mixture in water, alcohol, alkaline aqueous solution.Preferably, described alkaline aqueous solution is at least one in the aqueous solution of the sodium hydroxide of 0.001-0.01mol/L, potassium hydroxide, ammoniacal liquor, pyridine, triethylamine; Preferably, described alcohol is selected from least one in methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol.The mixture neutral and alkali aqueous solution of two kinds and the volume ratio of alcohol are 1:1-20:1; Preferred 1:1-10:1.
Preferably, be 0.0001-1.0 according to the substitution value with ， Han perylene group in the modified polysaccharide of photoluminescent property that described method prepares, be preferably 0.0005-0.1, more preferably 0.001-0.05.
8. a homogeneous phase solution, it is by being dissolved in the modified polysaccharide with photoluminescent property described in any one of claim 1-3 in organic solvent, ionic liquid or cosolvent and being formed.
Preferably, described organic solvent is selected from N, N-dimethyl sulfoxide (DMSO) (DMSO), N, at least one in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), tetrahydrofuran (THF) (THF), acetone, chloroform, pyridine, N-Methyl pyrrolidone.
Preferably, the same definition of described ionic liquid.
Preferably, described cosolvent is selected from least any two kinds in described ionic liquid and described organic solvent.
Preferably, the mass percentage concentration of described homogeneous phase solution is 0.001-60%, is preferably 0.01-30%.
9. a fluorescent material, is characterized in that, described fluorescent material comprises the modified polysaccharide with photoluminescent property described in any one of claim 1-3; Or prepared by homogeneous phase solution according to claim 8 and obtain.
10. fluorescent material according to claim 9, is characterized in that, described material has yellow-green fluorescence characteristic, and preferably, described material is pressed powder, film (as fexible film), coating, fiber, silk, micella or microballoon.
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