阅读说明：本技术 一种用于制备类玻璃体高分子的组合物、类玻璃体高分子及其制备方法和应用 (Composition for preparing glass-like polymer, glass-like polymer and preparation method and application thereof ) 是由 王粉粉 孙平川 于 2020-07-23 设计创作，主要内容包括：本发明涉及一种用于制备类玻璃体高分子的组合物、类玻璃体高分子及其制备方法和应用,所述组合物包括如下组分：酸酐或含有至少两个羧基的有机酸、荧光固化剂和催化剂；所述荧光固化剂包括含有环氧基团的四苯乙烯衍生物和/或含有环氧基团的三苯乙烯衍生物。通过本发明的组合物制备得到的类玻璃体高分子具有荧光功能,荧光分子不会溶出迁移,同时材料可再加工,且具有良好的力学性能,另外可实现通过变温荧光来测定材料的玻璃化转变温度和拓扑冻结转变温度。(The invention relates to a composition for preparing a vitreous body-like polymer, the vitreous body-like polymer, a preparation method and an application thereof, wherein the composition comprises the following components: anhydride or organic acid containing at least two carboxyl groups, fluorescent curing agent and catalyst; the fluorescent curing agent comprises tetraphenylethylene derivatives containing epoxy groups and/or triphenylethylene derivatives containing epoxy groups. The glass-like polymer prepared by the composition has a fluorescence function, fluorescent molecules cannot be dissolved out and migrated, the material can be reprocessed, the material has good mechanical property, and the glass transition temperature and the topological freezing transition temperature of the material can be measured by temperature-variable fluorescence.)

1. A composition for preparing a vitreous macromolecule, wherein the composition comprises the following components: anhydride or organic acid containing at least two carboxyl groups, fluorescent curing agent and catalyst;

the fluorescent curing agent comprises tetraphenylethylene derivatives containing epoxy groups and/or triphenylethylene derivatives containing epoxy groups.

2. The composition of claim 1, wherein the tetraphenylethylene derivative containing epoxy groups has the structure of formula I;

in the formula I, R is₁、R₂And R₃Each independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy or

m is an integer of 1-3, preferably 1;

preferably, said R is₁、R₂And R₃Each independently selected from any of hydrogen, methyl, methoxy or glycidoxyThe method is as follows;

preferably, the tetraphenylethylene derivative containing an epoxy group has a structure represented by formula I-1;

in the formula I-1, R is₁、R₂And R₃All have the same limitations as in formula I;

preferably, the tetraphenylethylene derivatives containing epoxy groups include 1- [ (4 '-glycidoxy) phenyl ] -1,2, 2-triphenylethylene, 1- [ (4' -glycidoxy) phenyl ] -1,2, 2-tris (4 '-tolyl) ethylene, 1- [ (4' -glycidoxy) phenyl ] -2, 2-diphenylethylene, 1,1,2- [ (4 '-epoxypropoxy) phenyl ] -2-phenylethene, tetra [ (4' -epoxypropoxy) phenyl ] ethene or 1,1- [ (4 '-epoxypropoxy) phenyl ] -2,2- [ (4' -methoxy) phenyl ] ethene, or a combination of at least two thereof.

3. The composition of claim 1, wherein the triphenylethylene derivative containing an epoxy group has a structure represented by formula II;

in the formula II, R is₄And R₅Each independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy or

n is an integer of 1-3, preferably 1;

preferably, said R is₄And R₅Each is independently selected from any one of hydrogen, methyl, methoxy or epoxy propoxy;

preferably, the triphenylethylene derivative containing the epoxy group has a structure shown in formula II-1;

in the formula II-1, the R₄And R₅All having the same limitations as in formula II;

preferably, the triphenylethylene derivative containing an epoxy group includes any one or at least two combinations of 1- [ (4' -epoxypropoxy) phenyl ] -2, 2-diphenylethylene, 1- [ (4' -epoxypropoxy) phenyl ] -2-phenylethene, 1- [ (4' -epoxypropoxy) phenyl ] -2- (4' -methoxy) phenylethene or 1,1,2- [ (4' -epoxypropoxy) phenyl ] ethylene.

4. The composition according to any one of claims 1 to 3, wherein the organic acid having at least two carboxyl groups comprises a fatty acid having at least two carboxyl groups and/or an aromatic acid having at least two carboxyl groups;

preferably, the fatty acid containing at least two carboxyl groups comprises a fatty dibasic acid, preferably any one or a combination of at least two of platinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dodecanedioic acid;

preferably, the aromatic acid containing at least two carboxyl groups comprises any one or at least two combinations of aromatic dibasic acid, aromatic tribasic acid, aromatic tetrabasic acid or aromatic hexabasic acid, preferably any one or at least two combinations of phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid or mellitic acid;

preferably, the acid anhydride comprises a cyclic acid anhydride, preferably any one or a combination of at least two of succinic anhydride, maleic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, trimellitic anhydride, dodecenyl succinic anhydride, pyromellitic dianhydride, cyclopentanetetracarboxylic dianhydride, or polyazelaic dianhydride;

preferably, the catalyst comprises any one or at least two combinations of pyridine catalyst, guanidine catalyst, phosphazene salt or organometallic complex, preferably any one or at least two combinations of triphenylphosphine, 4-pyrrolidinopyridine, dimethylaminopyridine, triazabicyldecene, diazabicycloundecene, di-o-tolylguanidine, tetrakis (tris (dimethylamino) n-phosphoimino) phosphine oxide, tetrakis (dimethylamino) n-phosphoimino) acetate, zinc acetylacetonate, titanium propoxide or cobalt bis (diacetone) cobalt.

5. The composition according to any one of claims 1 to 4, wherein the composition further comprises an epoxy resin comprising at least two epoxy groups, preferably any one or a combination of at least two of bisphenol A epoxy resin and derivatives thereof, bisphenol F epoxy resin or novolac epoxy resin;

preferably, the bisphenol a epoxy resin and derivatives thereof comprise bisphenol a diglycidyl ether.

6. A composition according to any of claims 1 to 5, wherein the ratio of the total molar amount of carboxyl groups to the total molar amount of epoxide groups in the composition is 1 (0.8 to 1.6), preferably 1 (1.0 to 1.5), further preferably 1 (1.1 to 1.2), more preferably 1: 1;

preferably, the molar amount of the catalyst in the composition is 1.0 to 10.0%, preferably 2.5 to 8.0%, and more preferably 5.0 to 6.5% of the total molar amount of the epoxy groups;

preferably, the molar amount of epoxy groups on the fluorescent curing agent in the composition is 0.1-100.0%, preferably 0.2-50%, more preferably 0.3-30%, and even more preferably 0.5-2.0% of the total molar amount of epoxy groups in the composition.

7. The composition according to any one of claims 1 to 6, wherein the composition further comprises a solvent;

preferably, the solvent includes any one or a combination of at least two of dimethylformamide, dimethylacetamide, tetrahydrofuran, chloroform, toluene, or acetone.

8. A vitreous polymer, which is prepared from a raw material comprising the composition according to any one of claims 1 to 7.

9. A method for preparing the vitreous macromolecule of claim 8, wherein the method comprises the steps of:

(1) mixing anhydride or organic acid containing at least two carboxyl groups, a fluorescent curing agent, a catalyst and a solvent to obtain a mixed solution;

(2) heating, preserving heat and cooling the mixed solution to obtain the glass-like polymer;

preferably, step (1) comprises: mixing anhydride or organic acid containing at least two carboxyl groups, a fluorescent curing agent, a catalyst, epoxy resin containing at least two epoxy groups and a solvent to obtain a mixed solution;

preferably, in step (1), the mixing comprises: adding acid anhydride or organic acid containing at least two carboxyl groups, epoxy resin containing at least two epoxy groups and a fluorescent curing agent into a solvent in sequence, stirring, and adding a catalyst;

preferably, in the step (1), the solid content of the mixed solution is 5-50%;

preferably, step (1') is performed after step (1): distilling the mixed solution under reduced pressure until the solid content is more than 95 percent;

preferably, the temperature of the reduced pressure distillation is 10-150 ℃;

preferably, in the step (2), the heating temperature is 130-180 ℃;

preferably, in the step (2), the heat preservation time is 6-24 h;

preferably, step (2) is carried out in a polytetrafluoroethylene container;

preferably, the preparation method specifically comprises the following steps:

(1) adding anhydride or organic acid containing at least two carboxyl groups, epoxy resin containing at least two epoxy groups and a fluorescent curing agent into a solvent in sequence, stirring, and adding a catalyst to obtain a mixed solution with the solid content of 5-50%;

(1') distilling the mixed solution obtained in the step (1) at 10-150 ℃ under reduced pressure until the solid content of the mixed solution is more than 95%, and then transferring the mixed solution to a polytetrafluoroethylene container;

(2) and heating the polytetrafluoroethylene container filled with the mixed solution to 130-180 ℃, preserving the heat for 6-24h, and cooling to room temperature to obtain the glass-like polymer.

10. Use of the vitreous polymer according to claim 8, wherein the vitreous polymer is used in an organic light emitting device, a chemical sensor, a biosensor, an organic solar cell, a coating, an adhesive or an insulating member.

Technical Field

The invention relates to the technical field of thermosetting resin, in particular to a composition for preparing a glass-like polymer, the glass-like polymer, a preparation method and application thereof.

Background

Thermosetting resins are generally crosslinked polymers and are widely used in the fields of aerospace, electronic and electrical products, petrochemical industry, civil engineering and construction, automobile machinery and the like because of their excellent mechanical properties, high heat resistance and high corrosion resistance. However, most thermosetting resins cannot be processed again once they are molded, and are difficult to recycle, which is not in accordance with the sustainable development concept. In 2011, professor of French Ludwik Leibler invented a polymer material containing exchangeable dynamic covalent bonds, named vitrimer resin (Science,2011,334,965 and 968.), and professor of Zhang xi of Qinghua university named as a glass-like polymer. The material has a characteristic temperature-topological network solidification transition temperature (Tv), when the temperature is lower than the Tv, dynamic covalent bond exchange is slow, and the vitrimer resin shows excellent physical properties of the thermosetting resin; above Tv, the dynamic covalent bond exchange is fast, the crosslinked network is in a "fluid" state, and the vitrimer resin can be arbitrarily shaped, exhibiting processability and recyclability.

In recent years, thermosetting polymers based on vitrier resins have become a research focus in the field of high molecular materials, and a group of new materials with practical value has been developed. Patent application CN106459377A specifies that the introduction of polyol during the manufacturing process of epoxy resin expands the temperature range in which the vitrier transesterification effect occurs, which is beneficial to improve the hot workability of epoxy resin. In order to promote the rate of the transesterification of the vitrimer, m.capelot et al propose to use Triazabicyldecene (TBD) as a catalyst in the reaction process of the epoxy resin and the acid curing agent (ACS macro.letters,2012,1,789-792.), patent CN103314030A selects zinc acetylacetonate as the catalyst, and patent application CN106661196A discloses that the organometallic titanium complex is used as the catalyst, so that the processability of the vitrimer resin is improved, and the application of the vitrimer resin in thermosetting polymers is promoted.

However, in the prior art, much attention is paid to the improvement of the mechanical properties of the material, and the attention on additional functions such as photoelectricity is less, so that the research on the vitrimer resin with the photoelectric properties is urgently needed in the field.

Disclosure of Invention

In view of the defects of the prior art, one of the purposes of the invention is to provide a composition for preparing a glass-like polymer, wherein the glass-like polymer prepared by the composition has a fluorescent function, and simultaneously, the mechanical property of the material and the reworkability of the thermosetting resin are ensured.

In order to achieve the purpose, the invention adopts the following technical scheme:

one of the objects of the present invention is to provide a composition for preparing a vitreous polymer, the composition comprising the following components: anhydrides or organic acids containing at least two (e.g., 2, three, 4, 5, or 6, etc.) carboxyl groups, fluorescent curing agents, and catalysts;

the fluorescent curing agent comprises tetraphenylethylene derivatives containing epoxy groups and/or triphenylethylene derivatives containing epoxy groups.

In the present invention, the glass-like polymer is a generic name of a thermosetting resin having reworkability, and may also be referred to as vitrine resin.

The invention provides a novel composition for preparing a glass-like polymer, wherein a tetraphenylethylene derivative containing an epoxy group and/or a triphenylethylene derivative containing an epoxy group are introduced into a formula, and the two fluorescent curing agents contain a polymerization induced emission (AIE) group and an epoxy group, wherein on one hand, the AIE group endows the resin with a fluorescent function, and on the other hand, the epoxy group in the fluorescent curing agent molecule participates in the formation of a thermosetting resin cross-linked network, so that the migration and exudation of the AIE group are avoided. Meanwhile, the epoxy group and the carboxyl group react rapidly under the action of the catalyst to generate a dynamic ester exchange structure, so that the thermosetting resin has the capacity of reprocessing while the mechanical property of the material is ensured.

In addition, the prior art has limitations on the testing of the glass transition temperature and the topological freezing transition temperature of the material, such as dynamic mechanical analysis, external force is required to be applied to the material during the testing process, and the obtained result is not the static property of the material. The intensity of fluorescence emitted by the glass-like polymer prepared from the composition changes along with the change of temperature, the temperature-rising fluorescence is reduced, particularly the temperature is near the transition temperature, the chain segment motion is intensified, and the fluorescence is greatly reduced, so that the glass transition temperature and the topology freezing transition temperature of the material can be tested by measuring a fluorescence spectrum, a new idea for testing the glass transition temperature and the topology freezing transition temperature of the material is provided, and the limitation of the prior art is overcome.

The term "thermosetting" resin as used herein refers to monomers, oligomers and any macromolecule capable of chemical crosslinking. For the purposes of the present invention, a crosslinked resin is considered to be thermosetting when, after exposure to a solvent, the resin has a residual weight of greater than 75% of the weight of the resin prior to exposure to the solvent. Further, when those skilled in the art verify that the resin is thermosetting according to the conventional method, the resin is considered to be the thermosetting resin according to the present invention.

Preferably, the tetraphenylethylene derivative containing epoxy groups has a structure shown in formula I;

in the formula I, R is₁、R₂And R₃Each independently selected from hydrogen, halogen, C1-C10 (e.g. C1, C2, C3, C3, C5, C6, C7, C8 or C9) alkyl, C1-C10 (e.g. C1, C2, C3, C3, C5, C6, C7, C8 or C9) alkoxy or C9Any one of the above; the bond at the wavy line mark represents a group;

m is an integer of 1 to 3, for example 2, preferably 1.

Preferably, said R is₁、R₂And R₃Each independently selected from any one of hydrogen, methyl, methoxy or epoxy propoxy.

In the present invention, the C1-C10 alkyl group may be illustratively selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and the like.

In the present invention, the C1-C10 alkoxy group may be illustratively selected from methoxy, ethoxy, propoxy, or the like.

Preferably, the tetraphenylethylene derivative containing an epoxy group has a structure represented by formula I-1;

in the formula I-1, R is₁、R₂And R₃All having the same selection ranges as in formula I.

When R is₁、R₂And R₃When three are H, methyl or methoxyl, the fluorescent curing agent contains an epoxy group; when R is₁、R₂And R₃When two of the epoxy group and the epoxy group are H, methyl or methoxyl and one is epoxy propoxy, the fluorescent curing agent contains two epoxy groups; when R is₁、R₂And R₃One is H, methyl or methoxyl, and when two are epoxy propoxy, the fluorescent curing agent contains three epoxy groups; when R is₁、R₂And R₃When the three epoxy propoxy groups are all epoxy propoxy groups, the fluorescent curing agent contains four epoxy groups.

In particular, when R₁、R₂And R₃When both are H, the tetraphenylethylene derivative containing an epoxy group is 1- [ (4' -glycidoxy) phenyl]-1,2, 2-triphenylethylene; when R is₁、R₂And R₃When both are methyl, the tetraphenylethylene derivative containing an epoxy group is 1- [ (4' -glycidoxy) phenyl]1,2, 2-tris (4' -tolyl) ethylene.

Preferably, the tetraphenylethylene derivatives containing epoxy groups include 1- [ (4 '-glycidoxy) phenyl ] -1,2, 2-triphenylethylene, 1- [ (4' -glycidoxy) phenyl ] -1,2, 2-tris (4 '-tolyl) ethylene, 1- (4' -glycidoxy) phenyl ] -2, 2-phenylethene, 1,1,2- [ (4 '-epoxypropoxy) phenyl ] -2-phenylethene, tetra [ (4' -epoxypropoxy) phenyl ] ethene or 1,1- [ (4 '-epoxypropoxy) phenyl ] -2,2- [ (4' -methoxy) phenyl ] ethene, or a combination of at least two thereof.

In the present invention, the tetraphenylethylene derivative containing an epoxy group is commercially available, and can also be prepared by nucleophilic substitution reaction of hydroxy tetraphenylethylene with epichlorohydrin, which is a well-established reaction in the art, and therefore, the present invention provides only an exemplary synthetic route as follows:

wherein THF represents tetrahydrofuran;

those skilled in the art can substitute the kind of the reaction raw materials based on the above reaction to obtain tetraphenylethylene derivatives containing epoxy groups with different structures, and may also choose other preparation methods to prepare, which is not specifically limited in the present invention.

Preferably, the triphenylethylene derivative containing the epoxy group has a structure shown in formula II;

in the formula II, R is₄And R₅Each independently selected from hydrogen, C1-C10 (e.g., C1, C2, C3, C3, C5, C6, C7, C8, C9, etc.) alkyl, C1-C10 (e.g., C1, C2, C3, C3, C5, C6, C7, C8, C9, etc.) alkoxy, orAny one of the above; the bond at the wavy line mark represents a group;

the n is an integer of 1 to 3, such as 2, preferably 1.

Preferably, said R is₄And R₅Each independently selected from any one of hydrogen, methyl, methoxy or epoxy propoxy.

Preferably, the triphenylethylene derivative containing the epoxy group has a structure shown in formula II-1;

in the formula II-1, the R₄And R₅All having the same selection range as in formula II.

When R is₄And R₅When the two are H, methyl or methoxyl, the fluorescent curing agent contains an epoxy group; when R is₄And R₅One is H, methyl or methoxyl, and when the other is glycidoxy, the fluorescent curing agent contains two epoxy groups; when R is₄And R₅When two are epoxy propoxy groups, the fluorescent curing agent contains three epoxy groups.

In particular, when R₄And R₅When both are H, the triphenylethylene derivative containing an epoxy group is 1- [ (4' -epoxypropoxy) phenyl]-2, 2-diphenylethylene; when R is₄Is methyl, R₅In the case of glycidoxy group, the triphenylethylene derivative containing an epoxy group is 1,1- [ (4' -glycidoxy) phenyl group]-2-tolylethylene.

Preferably, the triphenylethylene derivative containing an epoxy group includes any one or at least two combinations of 1- [ (4' -epoxypropoxy) phenyl ] -2, 2-diphenylethylene, 1- [ (4' -epoxypropoxy) phenyl ] -2-phenylethene, 1- [ (4' -epoxypropoxy) phenyl ] -2- (4' -methoxy) phenylethene or 1,1,2- [ (4' -epoxypropoxy) phenyl ] ethylene.

Epoxy-containing triphenylethylene derivatives are commercially available or can be prepared by nucleophilic substitution of a hydroxytriphenylethylene with an epoxy halide, illustratively providing the following synthetic route:

those skilled in the art can substitute the kind of the reaction raw material on the basis of the above reaction to obtain triphenylethylene derivatives containing epoxy groups with different structures, and may also select other preparation methods to prepare, which is not specifically limited in the present invention.

Preferably, the organic acid containing at least two carboxyl groups comprises a fatty acid containing at least two (e.g., 2, three, 4, 5, or 6, etc.) carboxyl groups and/or an aromatic acid containing at least two (e.g., 2, three, 4, 5, or 6, etc.) carboxyl groups.

Preferably, the fatty acid containing at least two carboxyl groups comprises a fatty dibasic acid, preferably any one or a combination of at least two of platinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or dodecanedioic acid.

Preferably, the aromatic acid containing at least two carboxyl groups comprises any one or at least two combinations of aromatic dibasic acid, aromatic tribasic acid, aromatic tetrabasic acid or aromatic hexahydric acid, preferably any one or at least two combinations of phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid or mellitic acid.

Preferably, the acid anhydride comprises a cyclic acid anhydride, preferably any one or a combination of at least two of succinic anhydride, maleic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, trimellitic anhydride, dodecenyl succinic anhydride, pyromellitic dianhydride, cyclopentanetetracarboxylic dianhydride, or polyazelaic dianhydride.

When the fluorescent curing agent contains an epoxy group and reacts with a cyclic acid anhydride or an organic acid containing two carboxyl groups, a linear polymer chain containing beta-hydroxy ester is firstly generated, and then the beta-hydroxy ester among the molecular chains can generate ester exchange reaction, so that a dynamic cross-linked network is formed, and the thermosetting resin is formed.

When the fluorescent curing agent contains one epoxy group and reacts with organic acid containing three or more carboxyl groups, firstly a star-shaped polymer chain containing beta-hydroxy ester is generated, and then the beta-hydroxy ester among the molecular chains can generate ester exchange reaction, thereby forming a dynamic cross-linked network and forming the thermosetting resin.

When the fluorescent curing agent contains two or more epoxy groups and reacts with the carboxyl groups in the acid anhydride or the organic acid containing at least two carboxyl groups, a network-like cross-linked structure is directly generated to form the thermosetting resin.

According to a preferred embodiment of the present invention, when the fluorescent curing agent is glycidoxy tetraphenyl ethylene and reacted with adipic acid, the esterification and transesterification processes are as follows:

wherein TBD represents 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and DMF represents dimethylformamide.

Preferably, the catalyst comprises any one or at least two combinations of a pyridine catalyst, a guanidine catalyst, a phosphazene salt, or an organometallic complex, preferably any one or at least two combinations of triphenylphosphine, 4-pyrrolidinopyridine, dimethylaminopyridine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 8-diazabicyclo (5.4.0) undec-7-ene, di-o-tolylguanidine, tetrakis (tris (dimethylamino) n-phosphoimino) phosphine oxide, tetrakis (tris (dimethylamino) n-phosphoimino) acetate, zinc acetylacetonate, titanium propoxide, or cobalt bis (diacetone).

Preferably, the composition further comprises an epoxy resin containing at least two epoxy groups, preferably any one or a combination of at least two of bisphenol a epoxy resin and derivatives thereof, bisphenol F epoxy resin or novolac epoxy resin.

Preferably, the bisphenol a epoxy resin and derivatives thereof comprise bisphenol a diglycidyl ether (DGEBA). The fluorescent vitrimer resin prepared based on DGEBA has excellent impact resistance, good heat resistance, better metal adhesion performance and excellent electrical insulation performance.

The novolac epoxy resin can be prepared by a two-step process: firstly, phenol reacts with formaldehyde to generate phenolic resin under the action of acid catalysis, and secondly, the phenolic resin reacts with epichlorohydrin to generate novolac epoxy resin under the action of sodium hydroxide. The novolac epoxy resins typically contain more than three epoxy groups thereon, which can react with the polyacid to produce a high density thermoset resin. Therefore, the fluorescent vitrimer resin prepared from the composition containing the novolac epoxy resin has excellent heat resistance, strong mechanical properties and excellent molding capacity, and can be used for manufacturing insulating parts of electric appliances.

Preferably, the ratio of the total molar amount of carboxyl groups to the total molar amount of epoxy groups in the composition is 1 (0.8-1.6), such as 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc., preferably 1 (1.0-1.5), more preferably 1 (1.1-1.2), and still more preferably 1:1. The "total molar amount of carboxyl groups" refers to the total molar amount of carboxyl groups in the organic acid having at least two carboxyl groups and carboxyl groups obtained by hydrolysis of the acid anhydride in the composition, and the "total molar amount of epoxy groups" refers to the total molar amount of epoxy groups in the fluorescent curing agent and epoxy groups in the epoxy resin having at least two epoxy groups.

According to the invention, the ratio of the total molar amount of carboxyl to the total molar amount of epoxy is preferably selected, so that the mechanical property of the glass-like polymer can be further improved, and the too high or too low content of epoxy can reduce the crosslinking degree of the system, which can cause the reduction of the mechanical property of the material.

Preferably, the molar amount of catalyst in the composition is 1.0-10.0%, preferably 2.5-8.0%, such as 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, etc., more preferably 5.0-6.5% of the total molar amount of epoxy groups.

Preferably, the molar amount of epoxy groups on the fluorescent curing agent in the composition is 0.1-100.0% of the total molar amount of epoxy groups in the composition, such as 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, etc., preferably 0.2-50%, more preferably 0.3-30%, and even more preferably 0.5-2.0%.

According to the invention, the specific molar ratio of the epoxy groups on the fluorescent curing agent is optimized, so that the glass-like polymer has good fluorescent property and processability, the fluorescent curing agent has a small ratio, which can cause weak emitted fluorescence, and the epoxy groups on the fluorescent curing agent has a large ratio, which can cause high processing temperature of thermosetting resin, and increase process difficulty.

Preferably, the composition further comprises a solvent.

Preferably, the solvent includes any one or a combination of at least two of dimethylformamide, dimethylacetamide, tetrahydrofuran, chloroform, toluene, or acetone.

The other object of the present invention is to provide a vitreous polymer, particularly a vitreous polymer having a fluorescent property, which is prepared from a raw material comprising the composition according to the first object.

The glassy polymers provided herein include coatings, films, sheets, blocks, rods, tubes, ribbons, powders, granules, or other forms known to those skilled in the art.

The glassy polymers of the present invention can be formed by injection molding, extrusion, calendering, spin coating, blow molding, spray coating, or any other method known to those skilled in the art. Preferably, the powder or particle form of the vitreous polymer of the present invention can be prepared by mechanical grinding; the film, sheet form may be coated by roller or brush; the tube or strip form may be formed by an extruder.

The glass-like polymer provided by the invention has the temperature higher than T_vDuring the process, the article can be deformed by a method of externally adding mechanical stress, so that the object can be reprocessed, assembled, welded, repaired and recycled. Any other method of deforming the vitreous like polymer known to those skilled in the art is suitable for use with the vitreous like polymers of the present invention.

The third object of the present invention is to provide a method for producing the above-mentioned glass-like polymer, the method comprising the steps of:

(1) mixing anhydride or organic acid containing at least two carboxyl groups, a fluorescent curing agent, a catalyst and a solvent to obtain a mixed solution;

(2) and heating, preserving heat and cooling the mixed solution to obtain the glass-like polymer.

Preferably, step (1) comprises: mixing anhydride or organic acid containing at least two carboxyl groups, a fluorescent curing agent, a catalyst, epoxy resin containing at least two epoxy groups and a solvent to obtain a mixed solution.

Preferably, in step (1), the mixing comprises: adding acid anhydride or organic acid containing at least two carboxyl groups, epoxy resin containing at least two epoxy groups and a fluorescent curing agent into a solvent in sequence, stirring, and adding a catalyst.

Preferably, in step (1), the solid content of the mixed solution is 5 to 50%, for example, 10%, 15%, 20%, 25%, 0%, 35%, 40%, 45%, etc., preferably 10 to 45%, and more preferably 30 to 40%. In the present invention, "solid content" means the percentage of the total mass of other substances (acid anhydride or organic acid containing at least two carboxyl groups, fluorescent curing agent, catalyst, and epoxy resin containing at least two epoxy groups) in the solution excluding the solvent to the total mass of the solution.

Preferably, step (1') is performed after step (1): the mixed solution is distilled under reduced pressure until the solid content is > 95%, for example 96%, 97%, 98%, etc., further > 97%, still further preferably > 99.5%.

Preferably, the reduced pressure distillation temperature is 10-150 degrees C, such as 20 degrees C, 30 degrees C, 40 degrees C, 50 degrees C, 60 degrees C, 70 degrees C, 80 degrees C, 90 degrees C, 100 degrees C, 110 degrees C, 120 degrees C, 130 degrees C, 140 degrees C, preferably 30-90 degrees C, more preferably 50-70 degrees C.

Preferably, in the step (2), the heating temperature is 130-.

Preferably, in step (2), the heating is performed in a vacuum oven.

Preferably, in step (2), the incubation time is 6-24h, such as 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, etc., preferably 15-20h, and more preferably 8-12 h.

Preferably, step (2) is carried out in a polytetrafluoroethylene vessel.

Preferably, the preparation method specifically comprises the following steps:

(1) adding anhydride or organic acid containing at least two carboxyl groups, epoxy resin containing at least two epoxy groups and a fluorescent curing agent into a solvent in sequence, stirring, and adding a catalyst to obtain a mixed solution with the solid content of 5-50%;

(1') distilling the mixed solution obtained in the step (1) at 10-150 ℃ under reduced pressure until the solid content of the mixed solution is more than 95%, and then transferring the mixed solution to a polytetrafluoroethylene container;

(2) and heating the polytetrafluoroethylene container filled with the mixed solution to 130-180 ℃, preserving the heat for 6-24h, and cooling to room temperature to obtain the glass-like polymer.

The fourth object of the present invention is to provide an application of the glass-like polymer according to the second object, which is applied to an organic light emitting device, a chemical sensor, a biosensor, an organic solar cell, a coating, an adhesive, or an insulating member.

The application field of the glass-like polymer provided by the invention covers the industries of mechanical automobiles, aerospace, ships and marine transportation, civil construction, electronic and electric appliances, electrical insulation, wind power generation and packaging and printing. The composition and the glass-like polymer of the present invention may be used alone or as an additive. For example, as a light emitting material as a core component of an organic light emitting device; probes for use as chemical or biological sensors; an energy conversion element for an organic solar cell; together with antioxidants, flame retardants or pigments, as surface coatings for floors, pipes, containers; the adhesive is used as an adhesive for plastic, metal and inorganic materials; the composite material is used as a packaging device of a circuit board, and is used as an insulating layer and a protective layer of a shell of an electric appliance or a conductive core of a cable.

The fluorescent glass polymer of the present invention may be used alone or in combination with at least one of conventional epoxy resins, polyurethane resins and acrylic resins. In addition, in addition to the above-mentioned resins, the resin may be used in combination with a filler, a pigment, an anti-ultraviolet agent, an antioxidant, a flame retardant, a foaming agent, a mildewproofing agent, and the like as needed, and those skilled in the art may select the resin according to actual circumstances.

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

(1) the invention provides a novel composition for preparing a glass-like polymer, wherein a tetraphenylethylene derivative containing an epoxy group and/or a triphenylethylene derivative containing an epoxy group are introduced into a formula, and the two fluorescent curing agents contain a polymerization induced emission (AIE) group and an epoxy group, wherein on one hand, the AIE group endows the resin with a fluorescent function, and on the other hand, the epoxy group in the fluorescent curing agent molecule participates in the formation of a cross-linked network of the thermosetting resin, so that the migration and exudation of the AIE group are avoided. Meanwhile, the epoxy group and the carboxyl group react rapidly under the action of the catalyst to generate a dynamic ester exchange structure, so that the thermosetting resin has the capacity of reprocessing while the mechanical property of the material is ensured.

(2) The glass-like polymer provided by the invention can emit fluorescence with the wavelength of 462-488 nm, does not have the situation that fluorescent micromolecules are dissolved out and migrated, and has good mechanical properties, wherein the breaking strength is 23-56 MPa, and the breaking elongation is 5-16%.

(3) According to the invention, the AIE group is introduced into the polymer chain of the glass-like body, so that the glass transition temperature and the topological freezing transition temperature of the material can be measured by temperature-variable fluorescence, and the limitation of the existing test method is overcome.

Drawings

FIG. 1 is a schematic representation of the reprocessing of the fluorescent vitrimer resin of example 3.

FIG. 2 is a stress-strain curve of the fluorescent vitrimer resin of example 1.

FIG. 3 is a fluorescence emission spectrum of the fluorescent vitrimer resin of example 1.

FIG. 4 is a plot of temperature swing fluorescence spectra of the fluorescent vitrimer resin of example 1.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The bisphenol A glycidyl ether used in the following examples and comparative examples was purchased from Sigma-aldrich and sold under the trade designation 1675-54-3.