阅读说明：本技术 一种具有聚集诱导发光性质的荧光羧酸类化合物及其制备方法和应用 (A kind of fluorescence carboxylic acid compound and its preparation method and application with aggregation-induced emission property ) 是由 张海良 袁勇杰 刘薇 周丰平 于 2019-07-31 设计创作，主要内容包括：本发明公开一种具有聚集诱导发光性质的荧光羧酸类化合物及其制备方法和应用。合成时首先利用4-羟基二苯甲酮或4,4’-二羟基二苯甲酮通过McMurry偶联反应,生成顺反异构的两种二羟基四苯乙烯或四羟基四苯乙烯,所得含羟基的四苯乙烯类化合物分别与4-氟苯甲腈在碱作用下通过SN<Sub>2</Sub>亲核反应生成带腈基的化合物,再通过水解反应得到含四苯乙烯的羧酸类化合物。该类化合物具有聚集诱导(AIE)发光性质,作为环氧树脂固化剂使用时,不仅能单独或两种以上混合使用,还可与其它各类固化剂混合使用,与环氧树脂相容性好、毒性低、固化效率高,固化后的环氧树脂具有聚集诱导发光性质,在紫外光下能够发出强烈的荧光。(The present invention discloses a kind of fluorescence carboxylic acid compound and its preparation method and application with aggregation-induced emission property.First with 4- dihydroxy benaophenonel or 4 when synthesis, 4'- dihydroxy benaophenonel passes through McMurry coupling reaction, the two kinds of dihydroxy tetraphenyl ethylenes or tetrahydroxy tetraphenyl ethylene of cis-trans isomerism are generated, the tetraphenyl ethylene class compound of gained hydroxyl passes through SN under alkali effect with 4- fluorobenzonitrile respectively 2 Necleophilic reaction generates the compound with itrile group, then obtains the carboxylic acid compound containing tetraphenyl ethylene by hydrolysis.Such compound has aggregation inducing (AIE) luminosity, when being used as epoxy curing agent, it can not only be used in mixed way alone or in any combination, it can be also used in mixed way with other all kinds of curing agent, with epoxy resin compatibility is good, toxicity is low, curing efficiency is high, epoxy resin after solidification has aggregation-induced emission property, can issue strong fluorescence under ultraviolet light.)

1. a kind of fluorescence carboxylic acid compound with aggregation-induced emission property, which is characterized in that its chemical structural formula such as formula (I), shown in (II) or (III):

2. the preparation method of the fluorescence carboxylic acid compound described in claim 1 with aggregation-induced emission property, feature It is, includes the following steps:

(1) synthesis of the tetraphenyl ethylene ethene derivatives of hydroxyl

(a) 4- dihydroxy benaophenonel generation McMurry coupling reaction under the action of titanium chloride and reducing agent is obtained along anteiso- Aqueous slkali is added dropwise while stirring until layering, collects organic phase after liquid separation, add after the reaction was completed in the dihydroxy tetraphenyl ethylene of structure Enter anhydrous magnesium sulfate dried filtrate, filters, crude product is obtained after filtrate is spin-dried for, crude product is through being recrystallized to give pure products；

Or (b) 4,4- dihydroxy benaophenonel McMurry coupling reaction occurs under the action of titanium chloride is with reducing agent obtains After the reaction was completed, aqueous slkali is added dropwise while stirring until layering, collects organic phase after liquid separation, addition is anhydrous in tetrahydroxy tetraphenyl ethylene Magnesium sulfate dried filtrate filters, crude product is obtained after filtrate is spin-dried for, crude product is through being recrystallized to give pure products；

(2) synthesis of the nitrile-based compound of the base containing tetraphenyl ethylene

The dihydroxy tetraphenyl ethylene of cis-trans isomerism obtained by step (a) and SN is occurred in the presence of alkali to fluorobenzonitrile₂Reaction, which generates, to be contained The dicyano compound of tetraphenyl ethylene；Or tetrahydroxy tetraphenyl ethylene obtained by step (b) occurs in the presence of alkali with to fluorobenzonitrile SN₂Reaction generates the four cyano compound containing tetraphenyl ethylene；Dicyano compound containing tetraphenyl ethylene and four containing tetraphenyl ethylene Cyano compound is referred to as the cyano compound containing tetraphenyl ethylene；

(3) synthesis of the carboxylic acid compound of the base containing tetraphenyl ethylene

Cyano compound containing tetraphenyl ethylene is obtained into the carboxylic acid of the base containing tetraphenyl ethylene by hydrolysis under acid or alkaline conditions Class compound.

3. the preparation method of the fluorescence carboxylic acid compound according to claim 1 with aggregation-induced emission property, It is characterized in that, in step (1), the titanium chloride is titanium trichloride or titanium tetrachloride, and the reducing agent is sodium, potassium, zinc Or one of magnesium, the alkali are potassium carbonate or sodium carbonate, reaction condition is to be heated to reflux.

4. the preparation method of the fluorescence carboxylic acid compound according to claim 1 with aggregation-induced emission property, It is characterized in that, in step (1), reaction uses solvent, and the solvent is tetrahydrofuran.

5. the preparation method of the fluorescence carboxylic acid compound according to claim 1 with aggregation-induced emission property, It is characterized in that, in step (2), the alkali is potassium carbonate or sodium carbonate, and the solvent is DMF or SMSO, and reaction condition is It is heated to reflux.

6. the preparation method of the fluorescence carboxylic acid compound according to claim 1 with aggregation-induced emission property, It is characterized in that, in step (2), reaction uses solvent, and the solvent is DMF or DMSO.

7. the preparation method of the fluorescence carboxylic acid compound according to claim 1 with aggregation-induced emission property, It is characterized in that, in step (3), alkaline condition is controlled by addition potassium hydroxide or sodium hydroxide, is used under alkaline condition molten Agent is the water-ethanol admixture that volume ratio is 1:1, and reaction condition is to be heated to reflux, in and/or acidification use hydrochloric acid or sulfuric acid；Acid Property the solvent that is used by the addition concentrated sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid or hydrogen bromide control, under acid condition of condition be methanol or Ethyl alcohol, reaction condition are to be heated to reflux.

8. the fluorescence carboxylic acid compound described in claim 1 with aggregation-induced emission property is as answering in curing agent With.

9. application according to claim 8, which is characterized in that the exclusive use or two or more of fluorescence carboxylic acid compound It is used in mixed way, or is used in mixed way with other curing agent.

Technical field

The present invention relates to the preparations of coating curing agent, and in particular to a kind of fluorescence carboxylic acid with aggregation-induced emission property Class curing agent and its preparation method and application.

Background technique

Epoxy resin is widely used in building, mechanical, electricity because of its excellent mechanical performance, thermal stability, insulating properties etc. Son and high-tech area, are most basic one of the chemicals of current macromolecule resin industry, wherein the city of bisphenol A type epoxy resin Field dosage and application prospect are the most considerable.Individual epoxy resin itself is not no application value, is only reacted with curing agent Just has excellent performance after forming cross-linked network structure, therefore curing agent plays very important effect in the epoxy. The properity of curing agent directly influences the practical application of epoxy resin.The epoxy curing agent reported at present mainly has Three categories, respectively amine curing agent, acid anhydride type curing agent and acids curing agent.Wherein amine curing agent type is more, using wide, Usually low-temperature setting；The solidification temperature of acid anhydride type curing agent generally requires to reach 120 DEG C or more, belongs to intermediate temperature curing agent；Carboxylic acid The research of class curing agent is relatively fewer, and principal item is high acid value polyester resin, is used for epoxide powder coating, usually needs high temperature solid Change.

Though the type of epoxy curing agent is more, function is all relatively simple, and the most of epoxy resin reported at present is solid Agent only plays crosslinking curing.With the diversification of people's demand, the function of epoxy resin is also more and more diversified instantly, Chinese invention CN104449219A discloses a kind of modified epoxy resin paint of heat-proof combustion-resistant, compares similar anti-flaming dope, this The curing rate of kind of coating faster, condition of cure it is lower, and be easier to operate.The functional epoxy cold coating reported at present is also There are the various functional epoxy cold coatings such as antifouling, radiation protection, light accumulation type, luminescence generated by light type.Fluorescence epoxy coating is certainly It does not shine under right light, the light of particular color can be issued under ultraviolet light, can be used for advanced anti-fake material.Fluorescence epoxy resin Peculiar property and broad application prospect cause the extensive concern of people.Fluorescence epoxy resin mainly passes through thereto at present It adds fluorescent material to prepare, such as adds luminescent rare earths or inorganic fluorescent powder lamp.Chinese invention CN105385397A is public A kind of method for preparing the epoxy resin that shines by adding fluorescent powder is opened.Although the method can obtain the excellent ring of luminescent properties Oxygen resin, but fluorescent powder or other luminescent substances are usually bad with epoxy resin compatibility, and this not only adds the complexity of technique Degree, and the addition of inorganic particulate particulate matter will affect the mechanical performance of final epoxy coating.Only has single solidification The curing agent of function can not meet demand, therefore there is an urgent need to develop new functional curing agent.

Summary of the invention

The purpose of the present invention is being directed to the present Research of current epoxy curing agent, provide that a kind of synthesis is simple, preparation It is easy, low VOC, the fluorescence carboxylic acids curing agent that various types epoxy resin is fixed and luminescent properties are excellent can be widely used in And preparation method thereof.It is coupled first with 4- dihydroxy benaophenonel or 4,4'- dihydroxy benaophenonel by McMurry when synthesis Reaction, generates the two kinds of dihydroxy tetraphenyl ethylenes or tetrahydroxy tetraphenyl ethylene of cis-trans isomerism, the tetraphenyl ethylene of obtained hydroxyl Class compound passes through SN under alkali effect with 4- fluorobenzonitrile respectively₂Necleophilic reaction generates the compound with itrile group, then passes through Hydrolysis obtains the carboxylic acid compound containing tetraphenyl ethylene.

The present invention realizes in the following way:

A kind of fluorescence carboxylic acid compound with aggregation-induced emission property, chemical structural formula such as formula (I), (II) or (III) shown in:

The preparation method of the above-mentioned fluorescence carboxylic acid compound with aggregation-induced emission property, includes the following steps:

(1) synthesis of the tetraphenyl ethylene ethene derivatives of hydroxyl

(a) 4- dihydroxy benaophenonel occur under the action of titanium chloride is with reducing agent McMurry coupling reaction obtain it is suitable Aqueous slkali is added dropwise while stirring until layering, is collected organic after liquid separation after the reaction was completed in the dihydroxy tetraphenyl ethylene of anteiso- structure Anhydrous magnesium sulfate dried filtrate is added in phase, filters, crude product is obtained after filtrate is spin-dried for, crude product is recrystallized to give pure production Object；

Or (b) under the action of titanium chloride and reducing agent McMurry coupling reaction occurs for 4,4- dihydroxy benaophenonel It obtains tetrahydroxy tetraphenyl ethylene after the reaction was completed, aqueous slkali is added dropwise while stirring until being layered, organic phase is collected after liquid separation, is added Anhydrous magnesium sulfate dried filtrate filters, crude product is obtained after filtrate is spin-dried for, crude product is through being recrystallized to give pure products；

(2) synthesis of the nitrile-based compound of the base containing tetraphenyl ethylene

The dihydroxy tetraphenyl ethylene of cis-trans isomerism obtained by step (a) and SN is occurred in the presence of alkali to fluorobenzonitrile₂Reaction Generate the dicyano compound containing tetraphenyl ethylene；Or step (b) obtained by tetrahydroxy tetraphenyl ethylene with to fluorobenzonitrile alkali effect Lower generation SN₂Reaction generates the four cyano compound containing tetraphenyl ethylene；Dicyano compound containing tetraphenyl ethylene and contain four benzene second The four cyano compound of alkene is referred to as the cyano compound containing tetraphenyl ethylene；

(3) synthesis of the carboxylic acid compound of the base containing tetraphenyl ethylene

Cyano compound containing tetraphenyl ethylene is obtained into the base containing tetraphenyl ethylene by hydrolysis under acid or alkaline conditions Carboxylic acid compound.

Further, in step (1), the titanium chloride is titanium trichloride or titanium tetrachloride, and the reducing agent is One of sodium, potassium, zinc or magnesium, the alkali are potassium carbonate or sodium carbonate, and reaction condition is to be heated to reflux.

Further, in step (1), reaction uses solvent, and the solvent is tetrahydrofuran.

Further, in step (2), the alkali is potassium carbonate or sodium carbonate, and the solvent is DMF or SMSO, instead Answering condition is to be heated to reflux.

Further, in step (2), reaction uses solvent, and the solvent is DMF or DMSO.

Further, in step (3), alkaline condition is controlled by addition potassium hydroxide or sodium hydroxide, under alkaline condition The solvent used is the water-ethanol admixture that volume ratio is 1:1, and reaction condition is to be heated to reflux, in and/or acidification use hydrochloric acid Or sulfuric acid；Acid condition is controlled by the addition concentrated sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid or hydrogen bromide, is used under acid condition molten Agent is methanol or ethyl alcohol, and reaction condition is to be heated to reflux.

The above-mentioned fluorescence carboxylic acid compound with aggregation-induced emission property is used as curing agent, can individually be made With or it is two or more be used in mixed way, or be used in mixed way with other curing agent.

The beneficial effects of the present invention are:

Gained compound of the invention has aggregation inducing (AIE) luminosity, as epoxy curing agent in use, not It is only capable of being used in mixed way alone or in any combination, can also be used in mixed way with other all kinds of curing agent, such curing agent and asphalt mixtures modified by epoxy resin Lipid phase capacitive is good, toxicity is low, curing efficiency is high, can be widely used in the solidification of each based epoxy resin, the epoxy resin tool after solidification There is aggregation-induced emission property, strong fluorescence can be issued under ultraviolet light, can be used as advanced anti-counterfeit paint, widened epoxy The application range of resin.

Detailed description of the invention

Fig. 1 is the nuclear-magnetism figure of diacid compounds in embodiment 1.

Fig. 2 is diacid compounds in embodiment 1 in different proportion H₂Fluorescence emission spectra figure in O/THF solution, wherein Solution concentration is 0.01mg/mL, excitation wavelength 360nm.With the increase of water content, the fluorescence radiation intensity of solution enhances, table Reveal aggregation-induced emission property.

Fig. 3 is diacid compounds in embodiment 1 in different proportion H₂Fluorescence radiation in O/THF solution emphasize with it is diacid The ratio of object fluorescence radiation intensity in pure tetrahydrofuran solution is closed, wherein solution concentration is 0.01mg/mL, excitation wavelength 360nm。

Specific embodiment

Combined with specific embodiments below, the present invention is furture elucidated, it is necessary to which indicated herein is that following embodiment is only used In the present invention is described further, it should not be understood as limiting the scope of the invention, person skilled in art's root Protection scope of the present invention is still fallen within according to some nonessential modifications and adaptations that the content of present invention makes the present invention.