阅读说明：本技术 含巯基的萘并吡喃类光致变色化合物及其制备方法与应用 (Mercapto-containing naphthopyran photochromic compound and preparation method and application thereof ) 是由 甘家安 宋熊荣 于 2019-11-04 设计创作，主要内容包括：本发明公开了一种含巯基的萘并吡喃类光致变色化合物,结构如式I或II所示：<Image he="316" wi="700" file="DDA0002259118440000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>各取代基定义详见说明书。本发明还公开了一种由上述含巯基的萘并吡喃类光致变色化合物制备的水溶性光致变色组合物,是由以下重量份的组分制成：光致变色单元1～20份、水溶性聚合物40～500份、溶剂10～500份,所述光致变色单元为所述含巯基的萘并吡喃类光致变色化合物。本发明还提供了一种所述水溶性光致变色组合物在制备水性光变色指甲油中的应用。本发明制备的水溶性光致变色组合物可应用于水性光变色指甲油、防伪油墨、化妆品、服装、工艺品、室外装饰材料和光学镜片中。(The invention discloses a naphthopyran photochromic compound containing sulfydryl, which has a structure shown as a formula I or II: the definition of each substituent is shown in the specification. The invention also discloses a compound containing the sulfydrylThe water-soluble photochromic composition prepared from the naphthopyran photochromic compound is prepared from the following components in parts by weight: 1-20 parts of a photochromic unit, 40-500 parts of a water-soluble polymer and 10-500 parts of a solvent, wherein the photochromic unit is the naphthopyran photochromic compound containing sulfydryl. The invention also provides an application of the water-soluble photochromic composition in preparing water-based photochromic nail polish. The water-soluble photochromic composition prepared by the invention can be applied to water-based photochromic nail polish, anti-counterfeiting ink, cosmetics, clothes, artware, outdoor decorative materials and optical lenses.)

1. A naphthopyran photochromic compound containing sulfydryl is characterized in that the structure is shown as formula I or II:

in formula I: r₁Selected from hydrogen、C₁～C₁₂An alkyl group, a carboxyl group,

R₂、Rˊ₂、R₃、Rˊ₃、R₄、R₅、R₆、R₇each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, aromatic ring radical, aromatic heterocyclic radical, halogen, C₁～C₅Aminoalkyl, arylamino, diarylamino, nitrogen-containing heterocyclic groups of 4-8 carbons;

n is an integer of 1 to 3;

in formula II: r₁、Rˊ₁、R₂、Rˊ₂、R₃、R₄、R₅Each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, aromatic ring radical, aromatic heterocyclic radical, halogen, C₁～C₄Aminoalkyl, arylamino, diarylamino, nitrogen-containing heterocyclic groups of 4-8 carbons;

n is an integer of 1 to 3.

2. The mercapto-containing naphthopyran-based photochromic compound according to claim 1, wherein in said mercapto-containing naphthopyran-based photochromic compound,

in formula I: r₁Selected from hydrogen, C₁～C₁₂An alkyl group, a carboxyl group,

R₂、Rˊ₂、R₃、Rˊ₃、R₄、R₅、R₆、R₇each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, piperidinyl;

n is an integer of 1 to 3;

in formula II: r₁、Rˊ₁、R₂、Rˊ₂、R₃、R₄、R₅Each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂An alkoxy group;

n is an integer of 1 to 3.

3. The mercapto-containing naphthopyran-based photochromic compound according to claim 2, wherein said mercapto-containing naphthopyran-based photochromic compound has a structure selected from one of the following structures:

4. a method for preparing the mercapto group-containing naphthopyran-based photochromic compound according to any one of claims 1 to 3, comprising the steps of:

dissolving a hydroxy-containing naphthopyran photochromic compound in a solvent at room temperature, adding mercaptoethanol to react for 1-72 hours, wherein the molar ratio of mercaptoethanol to the hydroxy-containing naphthopyran photochromic compound is (1.5-2.5): 1, dropwise adding excessive concentrated sulfuric acid, dividing water for 1-12 hours at the temperature of 110-120 ℃ after dropwise adding, cooling to room temperature, and carrying out column chromatography to obtain the mercapto-containing naphthopyran photochromic compound.

5. The method for preparing a mercapto-containing naphthopyran-based photochromic compound according to claim 4, wherein said hydroxy-containing naphthopyran-based photochromic compound has the following structure:

the molar ratio of the mercaptoethanol to the hydroxyl-containing naphthopyran photochromic compound is 2: 1;

the solvent is one of toluene, xylene, tetrahydrofuran, ethyl acetate, dichloromethane and N, N-dimethylformamide.

6. The water-soluble photochromic composition is characterized by being prepared from the following components in parts by weight:

1-20 parts of photochromic unit,

40-500 parts of a water-soluble polymer,

10-500 parts of a solvent;

the photochromic unit is the thiol-group-containing naphthopyran-based photochromic compound of any one of claims 1 to 3.

7. The water-soluble photochromic composition of claim 6 wherein the water-soluble photochromic composition is prepared from the following components in parts by weight:

15 parts of a photochromic unit, namely a photochromic material,

50 parts of water-soluble polymer, namely,

20 parts of a solvent.

8. The water-soluble photochromic composition of claim 6 or 7 wherein the water-soluble polymer is at least one of an aqueous urethane acrylate, an acrylated acrylate, an aqueous epoxy acrylate, or an aqueous polyester acrylate;

the solvent is at least one selected from water, nitrogen-containing solvent and polyhydric alcohol.

9. A process for preparing a water-soluble photochromic composition according to any one of claims 6 to 8, comprising the following steps: reacting the photochromic unit and the water-soluble polymer for 1-72 hours at the temperature of 25-100 ℃ under the protection of argon according to the proportion, cooling to room temperature, and adding a solvent for reaction for 1-24 hours to obtain the water-soluble photochromic composition; the photochromic unit is a naphthopyran photochromic compound containing sulfydryl.

10. Use of a water-soluble photochromic composition according to any one of claims 6 to 8 in the preparation of an aqueous photochromic nail varnish.

Technical Field

The invention belongs to the technical field of polymer chemistry, and particularly relates to a naphthopyran photochromic compound containing sulfydryl as well as a preparation method and application thereof.

Background

Photochromism is a light-induced reversible color-changing reaction based on the principle of chemical reactions. Light energy is a clean renewable energy source, so the development and application of the material have very wide prospects. At present, the most commercially widespread application fields are variable color glasses, high-end cosmetics, color-changing clothes and the like, and potential application fields are intelligent window film coatings, organic photoelectric information storage units, color-changing anti-counterfeiting inks and the like.

Photochromic materials can be classified into T-type and P-type photochromic materials according to the driving force of the reverse reaction. The T-shaped material is unstable thermally, namely, the T-shaped material can perform reverse reaction under thermodynamic action to return to an original state after the light source is removed; the P-type material is a material which can perform reversible reaction under the irradiation of another light source and can not spontaneously return to the original state. Currently, the type of material mainly used in commercialization is T-type photochromic material, which can be mainly classified into three types: spiropyrans, spirooxazines and naphthopyrans photochromic materials.

In recent years, a great deal of research has been conducted on the commercial application and the expansion of the application field of photochromic materials. Synthetic and commercial values of naphthopyran-based photochromic materials were reported by the full-line companies in the United states in the beginning of the 90 s (U.S. Pat. No. 005238981A; U.S. Pat. No. 005274132A). Furthermore, osmund mede laboratory european ltd discloses siloxane-based photochromic polymers with enhanced depth and speed of discoloration (CN 102112528B).

The application of the current commercial photochromic compound is mainly limited in an organic combination system such as a lens, a water-soluble system cannot be involved, and the large-amount use of an organic solvent is not beneficial to environmental protection and long-term development. The application fields of the aqueous photochromic material can be greatly widened, such as the cosmetic industry, the clothing industry and the like, so that the aqueous photochromic material is an environment-friendly photochromic material with great potential.

In order to prepare the water-soluble photochromic composition, the current solution is mainly to prepare photochromic water-soluble microspheres, and patent CN 102382232A discloses a photochromic anti-counterfeiting microsphere obtained by physically mixing a photochromic material and a polymer, but the preparation method has the defects of complex process, difficult commercialization and the like.

Click Chemistry (Click Chemistry), colloquially, is a green chemical reaction that has simple reaction conditions, readily available raw materials, extremely high chemical yield, stereoselectivity, and produces only harmless byproducts, such as Huisgen cycloaddition reaction, Diels-Alder reaction, and Thiol-ene reaction (angle. The Thiol-ene click Reaction (Thiol-ene Reaction) is initiated by light or heat to generate a sulfhydryl radical, and then the sulfhydryl radical and ethylenic carbon undergo reverse Markov Nikov addition, and the generated hydrogen radical can further initiate a chain Reaction until the Reaction is terminated. Thiol-ene reaction is convenient from the chemical synthesis, and the chain transfer and chain extension (homopolymerization) processes of the reaction can efficiently form the dendrimer of the homogeneous polymer.

In addition, the application of photo-or thermal-initiated polymerization reactions is very wide, including the fields of nanotechnology, biomaterials, material science and the like, but the common photo-or thermal-initiated reactions are prone to premature termination due to the presence of oxygen. While Thiol-ene reaction combines the above advantages of both photo-initiated polymerization and click chemistry, so that the click reaction can be rapidly and quantitatively performed in the presence of water and oxygen.

Disclosure of Invention

The first object of the present invention is to provide a mercapto group-containing naphthopyran-based photochromic compound.

The second object of the present invention is to provide a water-soluble photochromic composition prepared from the mercapto group-containing naphthopyran-based photochromic compound.

The third object of the present invention is to provide a method for preparing the water-soluble photochromic composition.

The fourth purpose of the invention is to provide the application of the water-soluble photochromic composition in preparing the water-based photochromic nail polish.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a naphthopyran photochromic compound containing a sulfhydryl group, which has a structure shown in a formula I or II:

in formula I: r₁Selected from hydrogen, C₁～C₁₂An alkyl group, a carboxyl group,

R₂、Rˊ₂、R₃、Rˊ₃、R₄、R₅、R₆、R₇each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, aromatic ring radical, aromatic heterocyclic radical, halogen, C₁～C₅Aminoalkyl, arylamino, diarylamino, nitrogen-containing heterocyclic groups of 4-8 carbons;

n is an integer of 1 to 3;

in formula II: r₁、Rˊ₁、R₂、Rˊ₂、R₃、R₄、R₅Each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, aromatic ring radical, aromatic heterocyclic radical, halogen, C₁～C₄Aminoalkyl, arylamino, diarylamino, nitrogen-containing heterocyclic groups of 4-8 carbons;

n is an integer of 1 to 3.

In the naphthopyran photochromic compound containing sulfydryl,

in formula I: r₁Selected from hydrogen, C₁～C₁₂An alkyl group, a carboxyl group,

R₂、Rˊ₂、R₃、Rˊ₃、R₄、R₅、R₆、R₇each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, piperidinyl;

n is an integer of 1 to 3;

in formula II: r₁、Rˊ₁、R₂、Rˊ₂、R₃、R₄、R₅Each independently selected from hydrogen and C₁～C₁₂Alkyl radical, C₁～C₁₂An alkoxy group;

n is an integer of 1 to 3.

The structure of the naphthopyran photochromic compound containing the sulfydryl is selected from one of the following structures:

the second aspect of the invention provides a preparation method of the thiol-containing naphthopyran photochromic compound, which comprises the following steps:

dissolving a hydroxy-containing naphthopyran photochromic compound in a solvent at room temperature, adding mercaptoethanol to react for 1-72 hours, wherein the molar ratio of mercaptoethanol to the hydroxy-containing naphthopyran photochromic compound is (1.5-2.5): 1, dropwise adding excessive concentrated sulfuric acid, dividing water for 1-12 hours at the temperature of 110-120 ℃ after dropwise adding, cooling to room temperature, and carrying out column chromatography to obtain the mercapto-containing naphthopyran photochromic compound.

The structure of the naphthopyran photochromic compound containing hydroxyl is as follows:

the molar ratio of the mercaptoethanol to the hydroxyl-containing naphthopyran photochromic compound is 2: 1.

The solvent is one of toluene, xylene, tetrahydrofuran, ethyl acetate, dichloromethane and N, N-dimethylformamide.

The third aspect of the invention provides a water-soluble photochromic composition, which is prepared from the following components in parts by weight:

1-20 parts of photochromic unit,

40-500 parts of a water-soluble polymer,

10-500 parts of a solvent.

The photochromic unit is a naphthopyran photochromic compound containing sulfydryl.

Preferably, the water-soluble photochromic composition is prepared from the following components in parts by weight:

15 parts of a photochromic unit, namely a photochromic material,

50 parts of water-soluble polymer, namely,

20 parts of a solvent.

The water-soluble polymer is at least one of water-based polyurethane acrylate, acrylic acid esterified acrylate, water-based epoxy acrylate or water-based polyester acrylate.

The solvent is at least one selected from water, nitrogen-containing solvent and polyhydric alcohol.

The polyhydric alcohol is at least one of diethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, glycerol, butanediol, sorbitol, ethylene glycol and ethanol.

The nitrogen-containing solvent is N-methylpyrrolidone, formamide, N-dimethylformamide, N-diethylformamide, 2-pyrrolidone, ethylenediamine, propylenediamine and acetonitrile.

The composition can also be added with a surfactant, such as TWEEN series, polyoxyethylene ester series and polyoxyethylene alcohol ether series, and added according to the same mass parts of photochromic units.

The fourth aspect of the present invention provides a method for preparing the water-soluble photochromic composition, comprising the steps of:

reacting the photochromic unit and the water-soluble polymer for 1-72 hours at the temperature of 25-100 ℃ under the protection of argon according to the proportion, cooling to room temperature, and adding a solvent for reaction for 1-24 hours to obtain the water-soluble photochromic composition;

the photochromic unit is a naphthopyran photochromic compound containing sulfydryl.

The fifth aspect of the invention provides application of the water-soluble photochromic composition in preparing water-based photochromic nail polish.

According to the application, the traditional color-changing material is connected with a mercapto functional group through etherification, and then click reaction and water-soluble resin are partially combined, so that the function that the traditional color-changing material cannot be dissolved in water-soluble or alcohol-soluble resin is realized, and the water-based optically-variable color-changing nail polish is prepared from the traditional color-changing material.

The aqueous photochromic nail polish is prepared from the following components:

40-55 parts of waterborne polyurethane, 20-25 parts of waterborne acrylic emulsion, 1-4 parts of water-soluble photochromic composition, 0-1 part of flatting agent or defoaming agent, 4-8 parts of thickening agent, 4-8 parts of film-forming assistant and 0-20 parts of deionized water.

Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:

the preparation method of the water-soluble photochromic composition creatively utilizes the click reaction principle to synthesize the high-molecular photochromic composition which is water-soluble or soluble in a large polar solvent, widens the original application field of the photochromic material, has simple and efficient synthesis method, does not need to add extra catalyst, and has no residual influence. The preparation method comprises the steps of creatively introducing a mercaptoethanol functional group into the traditional color-changing material, and combining a mercapto group with a water-based resin monomer by utilizing high-efficiency click reaction to obtain a water-soluble high-molecular functional compound different from the traditional color-changing material. Through experiments, the material can be well used in the field of water-based nail polish, and finally the water-based photochromic nail polish which is environment-friendly and beautiful is obtained.

The water-soluble photochromic composition prepared by the invention can be applied to water-based photochromic nail polish, anti-counterfeiting ink, cosmetics, clothes, artware, outdoor decorative materials and optical lenses.

Drawings

FIG. 1 is a schematic view of an ultraviolet absorption curve of the water-soluble photochromic composition IV-1 prepared in example 1.

FIG. 2 is a schematic view of a water-soluble photochromic composition IV-1 prepared in example 1 at a concentration of 2% before color change.

FIG. 3 is a schematic view of the water-soluble photochromic composition IV-1 prepared in example 1 at a concentration of 2% after color change.

FIG. 4 is a schematic view of an ultraviolet absorption curve of the water-soluble photochromic composition IV-2 prepared in example 2.

FIG. 5 is a schematic view of the ultraviolet absorption curve of the water-soluble photochromic composition IV-3 prepared in example 3.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

In the following examples, the room temperature is (20 ℃ C. -30 ℃ C.). The reagents used in the examples of the invention were all purchased from alatin.