阅读说明：本技术 一类具有非传统荧光性能的新型α-氨基膦酸酯高分子材料 (Novel alpha-aminophosphonate polymer material with non-traditional fluorescent property ) 是由 陶磊 何贤哲 于 2020-12-07 设计创作，主要内容包括：本发明公开了一种α-氨基膦酸酯类功能聚合物及其制备方法与应用。所述聚合物的结构式如式I所示,式I中,R_1选自C1-C13的醛基；R_2和R_3均独立的选自C1-C4的烷基；n为大于20的自然数。本发明以一锅法的方式合成含有α-氨基膦酸酯类结构的功能聚合物材料。该方法制备过程简单、产率高、原料价廉易得、反应条件温和。本发明提供的高分子材料具有显著的非传统荧光发射,发射波长可实现从蓝光到红光的全波段发射,具有较好的应用价值。(The invention discloses an alpha-aminophosphonate functional polymer, a preparation method and application thereof. The structural formula of the polymer is shown as formula I, wherein R in the formula I 1 An aldehyde group selected from C1-C13; r 2 And R 3 Each independently selected from C1-C4 alkyl; n is a natural number greater than 20. The invention synthesizes the functional polymer material containing the alpha-aminophosphonate structure in a one-pot method. The method has the advantages of simple preparation process, high yield, cheap and easily available raw materials and mild reaction conditions. The high polymer material provided by the invention has remarkable non-traditional fluorescence emission, can realize full-band emission from blue light to red light at emission wavelength, and has good application value.)

1. Alpha-aminophosphonate functional polymer shown in formula I,

in the formula I, R₁An aldehyde group selected from C1-C13;

R₂and R₃Each independently selected from C1-C4 alkyl;

n is a natural number greater than 20.

2. The polymer of claim 1, wherein: in the formula I, R₁Selected from any one of the following groups: n-hexyl, 2-hexenal, 2, 4-hexenal, phenyl, cocaldehyde, cinnamaldehyde, cuminurn aldehyde, perillaldehyde, myrtenal aldehyde, cresyl aldehyde and citronellal;

the R is₂,R₃Are all independentThe substituent is selected from any one of the following groups: methyl, ethyl, n-butyl and isobutyl.

n is a natural number of 20 to 50.

3. The method for preparing the alpha-aminophosphonate functional polymer as shown in claim 1 or 2, which comprises the following steps:

under the condition of no oxygen and in the presence of a free radical initiator and an acid-binding agent, an amino-containing monomer compound, an aldehyde compound and a phosphite ester compound synchronously carry out Kabachnik-Fields reaction and free radical polymerization reaction to obtain the alpha-aminophosphonate functional polymer shown in the formula I.

4. The production method according to claim 3, characterized in that:

the monomer compound containing amino is N- (3-aminopropyl) methacrylic acid hydrochloride;

the molecular formula of the aldehyde compound is R₁CHO，R₁Is as defined in said formula I, said aldehyde compound is preferably a compound represented by formula II;

the structural formula of the phosphite ester compound is shown as the formula III:

in the formula III, R₂And R₃Is as defined in said formula I.

5. The production method according to claim 3 or 4, characterized in that:

the acid-binding agent is triethylamine;

the free radical initiator can be an azo initiator and/or a peroxide initiator;

the azo initiator is specifically selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile;

the peroxide initiator is selected in particular from dibenzoyl peroxide.

6. The production method according to any one of claims 3 to 5, characterized in that: the monomer compound containing amino, the acid-binding agent, the aldehyde compound and the phosphite ester compound are sequentially fed in a molar ratio of 1: 1-1.3: 1-1.5: 1-2;

the feeding molar ratio of the free radical initiator to the monomer compound containing the amino group is 0.01-0.05: 1.

7. the production method according to any one of claims 3 to 6, characterized in that: the temperature of the Kabachnik-Fields reaction and the free radical polymerization reaction is 55-100 ℃, and the time is 4-20 h.

8. The method according to any one of claims 3-7, wherein: the oxygen-free condition is formed by the following modes 1) or 2):

1) introducing inert gas for bubbling;

the flow rate of the inert gas is 10-100 mL/min, and the bubbling time is 5-60 min;

2) performing liquid nitrogen freezing-vacuumizing-unfreezing cycle operation for multiple times;

the Kabachnik-Fields reaction and the radical polymerization reaction are carried out in an anhydrous organic solvent;

the organic solvent is at least one selected from ethanol, acetonitrile, methanol and dichloromethane.

9. The use of the α -aminophosphonate functional polymer of formula I as defined in claim 1 or 2 in the preparation of fluorescent or organic light-emitting materials.

10. A fluorescent or organic light-emitting product, whose light-emitting component is the α -aminophosphonate functional polymer represented by formula I as described in claim 1 or 2.

Technical Field

The invention belongs to the field of new chemical materials, and particularly relates to a novel alpha-aminophosphonate polymer material with non-traditional fluorescent property.

Background

Fluorescent materials have wide application in the fields of photoelectricity, sensing, biology and the like. Compared with small-molecule fluorescent materials, the fluorescent polymer has better processability, film-forming property, biocompatibility and synergistic amplification effect. Meanwhile, the fluorescent polymer is also beneficial to solving the defects of the small molecular fluorescent material in functional compounding, so that the development of a novel fluorescent polymer has very important significance. At present, fluorescent polymers are developed mainly by introducing fluorescent groups with conjugated structures into main chains and side chains, so that the polymers obtain fluorescent properties. Recent studies have found that some polymers having no conjugated structure of aromatic ring, such as poly (amidoamine), polythioamide, cellulose, etc., exhibit a specific fluorescence emission phenomenon. This unconventional fluorescence emission phenomenon is mainly attributed to the aggregation of heteroatoms in the molecular structure, which provides a new design concept for the development of novel fluorescent polymers. However, fluorescent polymers prepared based on this approach have been rarely reported. How to select a suitable organic reaction to introduce different heteroatoms into the structure of the polymer simultaneously is a key and important challenge in developing this new class of fluorescent polymers.

Disclosure of Invention

The invention aims to provide a non-traditional fluorescent polymer containing an alpha-aminophosphonate structure and a preparation method thereof. The invention can prepare a series of functional polymers containing alpha-aminophosphonate group rapidly, efficiently and massively; the method has the advantages of simple preparation process, high yield, cheap and easily obtained raw materials and mild reaction conditions. We find for the first time that the obtained polymer material has a remarkable non-traditional fluorescence emission phenomenon, and the adjustment of fluorescence wavelength is realized by using different substrates. The non-traditional fluorescent polymer has potential application value in the fields of photoelectricity, biology, medicine and the like.

The structural formula of the alpha-aminophosphonate functional polymer provided by the invention is shown as the formula I:

in the formula I, R₁An aldehyde group selected from C1-C13;

R₂and R₃Each independently selected from C1-C4 alkyl;

n is a natural number greater than 20.

In the formula I, R₁Selected from any one of the following groups: n-hexyl, 2-hexenal, 2, 4-hexadienal, phenyl, cocaldehyde, cinnamaldehyde, cuminurn aldehyde, perilla aldehyde, myrtenal aldehyde, cresyl aldehyde, citronellal;

the R is₂,R₃Are independently selected from any one of the following groups: methyl, ethyl, n-butyl, isobutyl.

n is a natural number of 20 to 50.

According to one embodiment of the invention, in the formula I, R₁Is n-hexyl, R₂,R₃Are all ethyl;

according to one embodiment of the invention, in the formula I, R₁Is 2-hexenoyl, R₂,R₃Are all ethyl;

according to one embodiment of the invention, in the formula I, R₁Is 2, 4-adienal, R₂,R₃Are all ethyl groups.

The invention also provides a preparation method of the alpha-aminophosphonate functional polymer shown in the formula I, which comprises the following steps:

under the condition of no oxygen and in the presence of a free radical initiator and an acid-binding agent, an amino-containing monomer compound, an aldehyde compound and a phosphite ester compound synchronously carry out Kabachnik-Fields reaction and free radical polymerization reaction to obtain an alpha-aminophosphonate functional polymer shown in a formula I;

the molecular formula of the aldehyde compound is R₁CHO，R₁Is as defined for formula I, preferably a compound of formula II;

the structural formula of the phosphite ester compound is shown as the formula III:

in the formula III, R₂And R₃Is as defined in formula I.

In the above-mentioned preparation method, the first step,

the acid-binding agent can be triethylamine;

the monomer compound containing an amino group may be N- (3-aminopropyl) methacrylic acid hydrochloride;

the free radical initiator can be an azo initiator and/or a peroxide initiator;

the azo initiator is specifically selected from at least one of Azobisisobutyronitrile (AIBN) and Azobisisoheptonitrile (ABVN); the peroxide initiator is specifically selected from dibenzoyl peroxide (BPO for short);

in the above preparation method, the monomer compound containing amino group, the acid-binding agent, and the feeding molar ratio of the aldehyde compound to the phosphite ester compound may be, in order, 1: 1-1.3: 1-1.5: 1-2; specifically, the ratio may be 1:1:1.2: 1.4.

The feeding molar ratio of the free radical initiator to the monomer compound containing the amino group is 0.01-0.05: 1.

in the above preparation method, before the Kabachnik-Fields reaction and the radical polymerization reaction are started, the method further comprises a step of mixing the raw materials within 10-20 min.

In the above preparation method, the Kabachnik-Fields reaction and the radical polymerization reaction are carried out at a temperature of 55 to 100 ℃ (specifically 65 ℃) for 4 to 20 hours (specifically 12 hours), and can be carried out under the condition of oil bath.

In the above preparation method, the oxygen-free condition is formed by:

1) introducing inert gas for bubbling;

the flow rate of the inert gas is 10-100 mL/min, and the bubbling time is 5-60 min;

the inert gas is nitrogen or argon;

2) performing liquid nitrogen freezing-vacuumizing-unfreezing cycle operation for multiple times;

the Kabachnik-Fields reaction and the radical polymerization reaction are carried out in an organic solvent;

the organic solvent is a mixed solvent of ethanol and acetonitrile, and the volume ratio of the ethanol to the acetonitrile is 1:1.

The method further comprises the following steps: after the Kabachnik-Fields reaction and the radical polymerization reaction, the reaction system was subjected to the following steps of isolation and purification:

and (3) placing the reaction bottle in ice water for cooling, dialyzing and purifying the reaction solution in an organic solvent, performing rotary evaporation, and freeze-drying.

Specifically, in the dialysis step, the cut-off molecular weight of a dialysis membrane is 1000-10000, and the dialysis time is 24-72 h;

the organic reagent is at least one of ethanol, methanol, acetonitrile and dichloromethane;

the temperature of the rotary evaporation is 30-60 ℃, and the rotating speed is 0.5-10 r/s;

the temperature of the freeze drying is-20 to-50 ℃, and the vacuum degree is 0.1 to 30 Pa; the time is 12-72h, specifically 24 h.

In addition, the invention also provides the application of the alpha-aminophosphonate functional polymer shown in the formula I in the preparation of fluorescent or organic luminescent materials, and the application also belongs to the protection scope of the invention.

The application of the fluorescence emission is that under the excitation of exciting light with a certain wavelength, the alpha-aminophosphonate functional polymer shown in the formula I can show fluorescence emission with a certain wavelength range in a solution state and a solid state;

specifically, the wavelength of the exciting light is 250-700 nm, and the fluorescence emission wavelength is 300-750 nm.

The invention also protects a fluorescent or organic light-emitting product.

The luminescent component of the fluorescent or organic luminescent product is the alpha-aminophosphonate functional polymer shown in the formula I in claim 1 or 2.

Compared with the prior art, the invention has the following beneficial effects:

the invention synthesizes the functional polymer material containing the alpha-aminophosphonate structure in a one-pot method. The invention can prepare the high molecular fluorescent material containing alpha-aminophosphonate group in a large amount, simply and efficiently; the method has the advantages of simple preparation process, high yield, cheap and easily obtained raw materials and mild reaction conditions. The high polymer material provided by the invention has remarkable non-traditional fluorescence emission, can realize full-band emission from blue light to red light at emission wavelength, and has good application value.

Drawings

FIG. 1 is a schematic of the synthesis scheme for alpha-aminophosphonate polymers of the present invention;

FIG. 2 shows the hydrogen nuclear magnetic spectrum of the alpha-aminophosphonate polymer synthesized in example 1: (¹H-NMR)；

FIG. 3 is a Gel Permeation Chromatography (GPC) of the synthesized alpha-aminophosphonate polymer of example 1 of the present invention;

FIG. 4 shows the hydrogen nuclear magnetic spectrum of the alpha-aminophosphonate polymer synthesized in example 2: (¹H-NMR)；

FIG. 5 is a Gel Permeation Chromatography (GPC) of the synthesized alpha-aminophosphonate polymer of example 2 of the present invention;

FIG. 6 shows the hydrogen nuclear magnetic spectrum of the alpha-aminophosphonate polymer synthesized in example 3: (¹H-NMR)；

FIG. 7 is a Gel Permeation Chromatography (GPC) of the synthesized alpha-aminophosphonate polymer of example 3 of the present invention;

FIG. 8 is a fluorescent photograph of an alpha-aminophosphonate polymer of examples 1, 2, 3 of the present invention;

FIG. 9 is a graph showing fluorescence excitation and emission spectra of alpha-aminophosphonate polymers of examples 1, 2 and 3 of the present invention.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.

Example 1 preparation of an alpha-aminophosphonate Polymer from n-hexanal, diethyl phosphite

The reaction equation is shown in FIG. 1.

1) A25 mL polymerization tube was charged with (540mg, 3mmol) N- (3-aminopropyl) methacrylic acid hydrochloride, (334mg, 3.3mmol) triethylamine, (360mg,3.6mmol) N-hexanal, (580mg, 4.2mmol) diethyl phosphite (where the molar ratio of N- (3-aminopropyl) methacrylic acid hydrochloride, triethylamine, N-hexanal, diethyl phosphite was 1:1.1:1.2:1.4), (7.5mg,0.03mmol) Azobisisoheptonitrile (ABVN), 2mL acetonitrile and 2mL ethanol as solvents. The solution was deoxygenated with nitrogen and placed in a 65 ℃ oil bath for reaction.

2) Cooling the reaction liquid reacted for 12 hours in the step 1) in ice water, and dialyzing and purifying the reaction liquid in a methanol solution for 48 hours by using a dialysis bag with the molecular weight cutoff of 3500. The alpha-aminophosphonate polymer was collected by rotary evaporation, freeze drying. Subjecting the polymer to¹H-NMR characterization, wherein the structure is shown as formula I-1, R₁Is n-hexyl, R₂、R₃Are all ethyl groups.

As is clear from FIG. 2, in the nuclear magnetic hydrogen spectrum of the polymer, the chemical shift of the methylene group (adjacent to the amide bond) of the α -aminophosphonate group was 3.37ppm, the chemical shift of the methylene group of the phosphonate ester was 3.97ppm, and the chemical shift of the methyl group at the terminus of hexanal was 0.82 ppm. This demonstrates that the α -aminophosphonate ester structure is formed by the reaction of N-hexanal, diethyl phosphite and N- (3-aminopropyl) methacrylic acid hydrochloride.

As can be seen from fig. 3, the molecular weight distribution of the synthesized polymer is typically normal, and the GPC test result is: number average molecular weight M_n＝23700gmol^-1(M_nIs Number-average Molecular Weight, M_nSpecific abbreviation for number average molecular weight), the molecular weight distribution coefficient was 1.71.

EXAMPLE 2 preparation of alpha-aminophosphonate Polymer from 2-hexenal diethyl phosphite

The reaction equation is shown in FIG. 1.

1) A25 mL polymerization tube was charged with (540mg, 3mmol) N- (3-aminopropyl) methacrylic acid hydrochloride, (334mg, 3.3mmol) triethylamine, (353mg,3.6mmol) 2-hexenal, (580mg, 4.2mmol) diethyl phosphite (wherein the molar ratio of N- (3-aminopropyl) methacrylic acid hydrochloride, triethylamine, 2-hexenal, diethyl phosphite was 1:1.1:1.2:1.4), (7.5mg,0.03mmol) Azobisisoheptonitrile (ABVN), 2mL acetonitrile and 2mL ethanol as solvents. The solution was deoxygenated with nitrogen and placed in a 65 ℃ oil bath for reaction.

2) Cooling the reaction liquid reacted for 12 hours in the step 1) in ice water, and dialyzing and purifying the reaction liquid in a methanol solution for 48 hours by using a dialysis bag with the molecular weight cutoff of 3500. The alpha-aminophosphonate polymer was collected by rotary evaporation, freeze drying. Subjecting the polymer to¹H-NMR characterization, wherein the structure is shown as formula I-2, R₁Is 2-hexenoyl, R₂、R₃Are all ethyl groups.

As can be seen from FIG. 4, in the nuclear magnetic hydrogen spectrum of the polymer, the chemical shift of the peak of the double bond of the hexenal in the α -aminophosphonate group was 5.2 to 5.7ppm, the chemical shift of the methylene group of the phosphonate was 3.98ppm, the chemical shift of the methyl group of the phosphonate was 1.19ppm, and the chemical shift of the methyl group at the end of hexenal was 0.83 ppm. This demonstrates that the α -aminophosphonate ester structure is formed by the reaction of 2-hexenal, diethyl phosphite and N- (3-aminopropyl) methacrylic acid hydrochloride.

As can be seen from fig. 5, the molecular weight distribution of the synthesized polymer is typically normal, and the GPC test result is: number average molecular weight M_n＝15600gmol^-1(M_nIs Number-average Molecular Weight, M_nIs a specific abbreviation for number average molecular weight), the molecular weight distribution coefficient was 1.43.

Example 3 preparation of an alpha-aminophosphonate Polymer from 2, 4-hexadienal and diethyl phosphite

The reaction equation is shown in FIG. 1.

1) A25 mL polymerization tube was charged with (540mg, 3mmol) N- (3-aminopropyl) methacrylic acid hydrochloride, (334mg, 3.3mmol) triethylamine, (346mg,3.6mmol)2, 4-hexadienal, (580mg, 4.2mmol) diethyl phosphite (wherein the molar ratio of N- (3-aminopropyl) methacrylic acid hydrochloride, triethylamine, 2, 4-hexadienal, diethyl phosphite was 1:1.1:1.2:1.4), (7.5mg,0.03mmol) Azobisisoheptonitrile (ABVN), 2mL acetonitrile and 2mL ethanol as solvents. The solution was deoxygenated with nitrogen and placed in a 65 ℃ oil bath for reaction.

2) Cooling the reaction liquid reacted for 12 hours in the step 1) in ice water, and dialyzing and purifying the reaction liquid in a methanol solution for 48 hours by using a dialysis bag with the molecular weight cutoff of 3500. The alpha-aminophosphonate polymer was collected by rotary evaporation, freeze drying. Subjecting the polymer to¹H-NMR characterization, wherein the structure is shown as formula I-3, wherein R₁Is 2, 4-adienal, R₂、R₃Are all ethyl groups.

As can be seen from FIG. 6, in the nuclear magnetic hydrogen spectrum of the polymer, the chemical shift of the peak of the double bond of 2, 4-hexadienal in the α -aminophosphonate group was 5.2 to 5.7ppm, the chemical shift of the methylene group of the phosphonate was 3.98ppm, and the chemical shift of the methyl group of the phosphonate was 1.19ppm, thus demonstrating that the α -aminophosphonate structure was produced by the reaction of 2, 4-hexadienal, diethyl phosphite and N- (3-aminopropyl) methacrylic acid hydrochloride.

As can be seen from fig. 7, the molecular weight distribution of the synthesized polymer is typically normal, and the GPC test result is: number average molecular weight M_n＝12100gmol^-1(M_nIs Number-average Molecular Weight, M_nIs a specific abbreviation for number average molecular weight), the molecular weight distribution coefficient was 1.50.

Example 4 fluorescence emission experiment of Polymer containing alpha-aminophosphonate Structure

1. 100mg of the α -aminophosphonate polymers prepared in examples 1, 2 and 3 were dissolved in 5mL of methanol to prepare 20mg/mL polymer solutions.

2. As can be seen from fig. 8, a solution prepared from the polymer of example 1 above was excited by ultraviolet light (365nm) and significant blue fluorescence emission was observed. Upon excitation with yellow light (570nm) of a solution prepared from the polymer of example 2 above, a significant orange fluorescence emission was observed. Upon excitation with yellow light (570nm) of the solution prepared from the polymer of example 3 above, a significant red fluorescence emission was observed.

3. The fluorescence excitation spectrum and fluorescence emission spectrum of the polymers of examples 1, 2 and 3 were measured by a fluorescence spectrophotometer. As can be seen from FIG. 9, the maximum fluorescence excitation wavelength of the polymer solution of example 1 was 377nm and the maximum fluorescence emission wavelength was 463 nm; the maximum fluorescence excitation wavelength of the polymer solution in the above example 2 is 555nm, and the maximum fluorescence emission wavelength is 601 nm; the maximum fluorescence excitation wavelength of the polymer solution of example 3 above was 673nm, and the maximum fluorescence emission wavelength was 698 nm.