阅读说明：本技术 用于聚氨酯基Cu2+识别的荧光化学传感器的制备方法 (For polyurethane based Cu2+Method for producing a fluorescent chemical sensor for identification ) 是由 田赛琦 陈银燕 朱一凡 蔡姗姗 于 2020-05-20 设计创作，主要内容包括：本发明公开了一种用于聚氨酯基Cu<Sup>2+</Sup>识别的荧光化学传感器的制备方法,改性后的罗丹明荧光化合物通过化学键引入到聚氨酯结构中,荧光基团分散均匀,使用过程中不迁移析出,具有稳定持久的荧光特性。Cu<Sup>2+</Sup>能够较好的结合到罗丹明中的亚氨基上的N原子和羰基的O原子上,从而改变其荧光特性,达到识别Cu<Sup>2+</Sup>的目的。本发明的荧光化学传感器以聚氨酯泡沫为基质,拥有比表面积大、孔隙结构可调的独特性能,其多孔结构可增大Cu<Sup>2+</Sup>与分子链上荧光基团的接触,大幅提高荧光化学传感器的灵敏性,实现Cu<Sup>2+</Sup>的快速检测,且固体泡沫形式便于储存使用,合成方法简单、成本低、具有良好的推广前景。(The invention discloses a Cu for polyurethane base 2+ According to the preparation method of the identified fluorescence chemical sensor, the modified rhodamine fluorescent compound is introduced into a polyurethane structure through a chemical bond, fluorescent groups are uniformly dispersed, and the rhodamine fluorescent compound is not migrated and separated out in the use process and has a stable and lasting fluorescence characteristic. Cu 2+ Can be well combined with N atoms on imino groups and O atoms on carbonyl groups in rhodamine, thereby changing the fluorescence characteristics of the rhodamine to achieveIdentification of Cu 2+ The purpose of (1). The fluorescent chemical sensor takes polyurethane foam as a substrate, has the unique properties of large specific surface area and adjustable pore structure, and the porous structure of the fluorescent chemical sensor can increase Cu 2+ The contact with fluorescent groups on molecular chains greatly improves the sensitivity of the fluorescence chemical sensor and realizes the Cu 2+ The method has the advantages of quick detection, convenient storage and use of the solid foam form, simple synthesis method, low cost and good popularization prospect.)

1. Cu for polyurethane base²⁺A method of making an identified fluorescent chemical sensor, comprising: comprises the following steps of (a) carrying out,

step (1) modifying a rhodamine fluorescent compound, namely dissolving rhodamine 6G in ethanol, slowly dropwise adding ethylenediamine, refluxing and stirring at room temperature for a certain time in a nitrogen atmosphere, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound a; dissolving a rhodamine fluorescent compound a in ethanol, adding 4- (diethylamino) salicylaldehyde, refluxing and stirring at room temperature for a certain time under the atmosphere of nitrogen, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound b;

step (2) urethane-based Cu²⁺Preparing a fluorescence identification chemical sensor, adding polymer diol, diisocyanate, a micromolecular diol chain extender, a cross-linking agent, water, a rhodamine fluorescent compound b and a catalyst into a reaction container, stirring at a high speed, pouring into a polytetrafluoroethylene beaker, and baking in a baking oven at 60-90 ℃ to obtain polyurethane-based Cu²⁺Identifying a fluorescent chemical sensor; wherein the dosage ratio of the mixed components is as follows: 50-100 parts of polymer dihydric alcohol, 50-100 parts of diisocyanate, 2-4 parts of micromolecular dihydric alcohol chain extender, 0.25-0.5 part of cross-linking agent, 50-100 parts of water, 21-5 parts of rhodamine fluorescent compound and 0.1-0.2 part of catalyst.

2. The Cu for polyurethane base according to claim 1²⁺A method of making an identified fluorescent chemical sensor, comprising: in the step (2), the polymer diol is any one or combination of polypropylene glycol, polyethylene glycol or polytetrahydrofuran glycol with the number average molecular weight of 1000-.

3. The Cu for polyurethane base according to claim 1²⁺A method of making an identified fluorescent chemical sensor, comprising: in the step (2), the diisocyanate is any one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 1, 6-hexyl diisocyanate, diphenylmethane diisocyanate or 4,4' -dicyclohexylmethane diisocyanate.

4. The Cu for polyurethane base according to claim 1²⁺A method of making an identified fluorescent chemical sensor, comprising: in the step (2), the micromolecular dihydric alcohol chain extender isAny one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, or diethylene glycol.

5. The Cu for polyurethane base according to claim 1²⁺A method of making an identified fluorescent chemical sensor, comprising: in the step (2), the cross-linking agent is any one of trimethylolpropane and diethanolamine.

6. The Cu for polyurethane base according to claim 1²⁺A method of making an identified fluorescent chemical sensor, comprising: in the step (2), the catalyst is any one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, bis-dimethylamino ethyl ether or dimethyl cyclohexylamine.

Technical Field

The invention relates to the field of synthesis of high polymer materials, in particular to Cu for polyurethane base²⁺A method of making an identified fluorescent chemical sensor.

Background

Copper ion is one of the essential trace elements in animals and plants, and plays a very important role in life, and Cu²⁺The proper amount of Cu in vivo is beneficial to maintaining normal body work²⁺The disruption of metabolic balance may lead to a range of diseases such as Burmese's syndrome and Wilson's syndrome. Copper ions are also widely present in the environment, and although not at high concentrations, they accumulate over a long period of time and cannot be effectively degraded to cause toxic effects, and are therefore considered to be environmentally-polluting Cu²⁺. Therefore, the rapid, simple and accurate quantitative detection of the polypeptide has important research value.

Cu²⁺The detection methods include chromatography, spectrometry, ion transfer method and the like, but the methods have various problems, such as high price, inconvenient carrying, complex operation and the like, and the fluorescence detection method is simple and convenient, and has the advantages of high sensitivity, small sampling amount, simplicity, rapidness and the like. Therefore, the fluorescent substance is stable and stable against Cu²⁺The organic fluorescent probe with excellent identification capability has important significance.

Rhodamine compounds are fluorescent dyes with strong molar absorption coefficient and high fluorescence quantum yield, and are common fluorescent probes, however, the sensitivity of the traditional fluorescent micromolecules as sensors to a detected object is often low, the detection limit is high, the response time is relatively long, and in practical application, the problems of narrow solution pH adaptation range and the like exist, so that the rhodamine compounds are not beneficial to Cu²⁺Detection in the detection field.

Disclosure of Invention

To is directed atThe present invention provides a Cu material for urethane base²⁺The preparation method of the identified fluorescent chemical sensor realizes the modification of rhodamine fluorescent micromolecules and can effectively modify Cu²⁺And (6) detecting.

To achieve the above object, the present invention provides a Cu for urethane base²⁺A method for preparing an identified fluorescence chemical sensor, comprising the steps of,

step (1) modifying a rhodamine fluorescent compound, namely dissolving rhodamine 6G in ethanol, slowly dropwise adding ethylenediamine, refluxing and stirring at room temperature for a certain time in a nitrogen atmosphere, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound a; dissolving a rhodamine fluorescent compound a in ethanol, adding 4- (diethylamino) salicylaldehyde, refluxing and stirring at room temperature for a certain time under the atmosphere of nitrogen, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound b;

step (2) urethane-based Cu²⁺Preparing a fluorescence identification chemical sensor, adding polymer diol, diisocyanate, a micromolecular diol chain extender, a cross-linking agent, water, a rhodamine fluorescent compound b and a catalyst into a reaction container, stirring at a high speed, pouring into a polytetrafluoroethylene beaker, and baking in a baking oven at 60-90 ℃ to obtain polyurethane-based Cu²⁺Identifying a fluorescent chemical sensor; wherein the dosage ratio of the mixed components is as follows: 50-100 parts of polymer dihydric alcohol, 50-100 parts of diisocyanate, 2-4 parts of micromolecular dihydric alcohol chain extender, 0.25-0.5 part of cross-linking agent, 50-100 parts of water, 21-5 parts of rhodamine fluorescent compound and 0.1-0.2 part of catalyst.

As a further configuration of the present invention, in the step (2), the polymer diol is any one or a combination of polypropylene glycol, polyethylene glycol or polytetrahydrofuran glycol with a number average molecular weight of 1000-2000.

As a further configuration of the present invention, in the step (2), the diisocyanate is any one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 1, 6-hexyl diisocyanate, diphenylmethane diisocyanate, or 4,4' -dicyclohexylmethane diisocyanate.

As a further configuration of the present invention, in the step (2), the small molecule diol chain extender is any one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, or diethylene glycol.

In a further aspect of the present invention, in the step (2), the crosslinking agent is one of trimethylolpropane and diethanolamine.

As a further configuration of the present invention, in the step (2), the catalyst is any one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, bis-dimethylamino ethyl ether, or dimethylcyclohexylamine.

The method has the advantages that the modified rhodamine fluorescent compound is embedded into a polyurethane structure through a chemical bond, fluorescent groups are uniformly dispersed, and a fluorescent agent is not migrated and separated out in the use process, so that the modified rhodamine fluorescent compound has stable and lasting fluorescent characteristics; the fluorescent chemical sensor takes polyurethane foam as a substrate, has the unique properties of large specific surface area and adjustable pore structure, and the porous structure of the fluorescent chemical sensor can increase Cu²⁺The contact with fluorescent groups on molecular chains greatly improves the sensitivity of the fluorescence chemical sensor and realizes the Cu²⁺Rapid detection of (2); the further fluorescence chemical sensor is solid foam, is convenient to store and use, has a simple synthesis method and low cost, and has a good popularization prospect.

Drawings

FIG. 1 is a specific route diagram for modification of rhodamine 6G in an embodiment of the invention;

FIG. 2 is a schematic diagram of Cu2+ recognition detection coordination in an embodiment of the present invention.

Detailed Description

The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.

A first embodiment of the invention, comprises the steps of,

step (1) modifying a rhodamine fluorescent compound, namely dissolving 5G of rhodamine 6G in 150mL of ethanol, slowly dropwise adding 4.5G of ethylenediamine, refluxing and stirring at room temperature for 6 hours under the atmosphere of nitrogen, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound a; dissolving 2g of rhodamine fluorescent compound a in 160mL of ethanol, adding 0.8g of 4- (diethylamino) salicylaldehyde, refluxing and stirring at room temperature for 6 hours under the atmosphere of nitrogen, evaporating the solvent, fully washing the product with ethanol, and drying in a vacuum drying oven to obtain the modified rhodamine fluorescent compound b.

Step (2) urethane-based Cu²⁺Preparing a fluorescence identification chemical sensor, adding 50 parts of polypropylene glycol with the average molecular weight of 1000, 50 parts of isophorone diisocyanate, 2 parts of 1, 4-butanediol, 0.25 part of trimethylolpropane, 50 parts of water, 1 part of rhodamine fluorescent compound b and 0.1 part of bismuth neodecanoate catalyst into a reaction container, stirring at a high speed for 5min, pouring into a polytetrafluoroethylene beaker, and putting into a 90 ℃ oven for 2h to obtain polyurethane-based Cu²⁺A fluorescent chemical sensor is identified.

A second embodiment of the present invention, comprises the steps of,

step (1) modifying a rhodamine fluorescent compound, namely dissolving 5G of rhodamine 6G in 150mL of ethanol, slowly dropwise adding 4.5G of ethylenediamine, refluxing and stirring at room temperature for 6 hours under the atmosphere of nitrogen, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound a; dissolving 2g of rhodamine fluorescent compound a in 160mL of ethanol, adding 0.8g of 4- (diethylamino) salicylaldehyde, refluxing and stirring at room temperature for 6 hours under the atmosphere of nitrogen, evaporating the solvent, fully washing the product with ethanol, and drying in a vacuum drying oven to obtain the modified rhodamine fluorescent compound b.

Step (2) urethane-based Cu²⁺Preparing a fluorescence chemical sensor by mixing 50 parts of polytetrahydrofuran diol with the average molecular weight of 2000, 50 parts of polyethylene glycol with the average molecular weight of 2000, 100 parts of 4,4' -dicyclohexyl methane diisocyanate and 4 parts ofAdding diethylene glycol, 0.5 part of diethanolamine, 100 parts of water, 5 parts of rhodamine fluorescent compound b and 0.2 part of bismuth laurate into a reaction container, stirring at high speed for 5min, pouring into a polytetrafluoroethylene beaker, and putting into a 75 ℃ oven for 2h to obtain the polyurethane-based Cu²⁺A fluorescent chemical sensor is identified.

A third embodiment of the present invention, comprises the steps of,

step (1) modifying a rhodamine fluorescent compound, namely dissolving 5G of rhodamine 6G in 150mL of ethanol, slowly dropwise adding 4.5G of ethylenediamine, refluxing and stirring at room temperature for 6 hours under the atmosphere of nitrogen, evaporating the solvent, fully washing a product with ethanol, and drying in a vacuum drying oven to obtain a modified rhodamine fluorescent compound a; dissolving 2g of rhodamine fluorescent compound a in 160mL of ethanol, adding 0.8g of 4- (diethylamino) salicylaldehyde, refluxing and stirring at room temperature for 6 hours under the atmosphere of nitrogen, evaporating the solvent, fully washing the product with ethanol, and drying in a vacuum drying oven to obtain the modified rhodamine fluorescent compound b.

Step (2) urethane-based Cu²⁺Preparing a fluorescence identification chemical sensor, adding 80 parts of polyethylene glycol with the average molecular weight of 2000, 75 parts of diphenylmethane diisocyanate, 3 parts of 1, 3-propylene glycol, 0.3 part of trimethylolpropane, 75 parts of water, 2.5 parts of rhodamine fluorescent compound b and 0.15 part of bismuth isooctanoate into a reaction container, stirring at a high speed for 5min, pouring into a polytetrafluoroethylene beaker, and putting into a 60 ℃ oven for 2h to obtain polyurethane-based Cu²⁺A fluorescent chemical sensor is identified.

The above example is only one of the preferred embodiments of the present invention, and general changes and substitutions by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.