TW202417579A - Reactive dye, method for producing the same, and contact lens - Google Patents

Abstract

A reactive dye, a method for producing the same, and a contact lens are provided, respectively. The method includes mixing a hydrophilic molecule and water according to a weight ratio of 10:1 to 1:3 to form a co-solvent; and adjusting the co-solvent to a predetermined pH value with a weak base; and adding a dye to the co-solvent to perform a synthesis reaction between the dye and the hydrophilic molecule to form a reaction product including a reactive dye. The hydrophilic molecule is an acrylic ester with a hydroxyl group. The chemical structure of the dye has a reactive functional group to react with the hydroxyl group of the hydrophilic molecule in the synthesis reaction. The reactive functional group of the dye is at least one of a vinyl-sulfonate functional group, a sodium mono-sulfonate functional group, and a mono-sulfonate functional group.

Description

Reactive dye, method for producing the same, and contact lens

The present invention relates to a method for producing a dye, in particular to a reactive dye suitable for contact lenses and a method for producing the same, and also to contact lenses.

With the increasing popularity of 3C products such as computers and smartphones, people now spend more and more time using these 3C products every day. However, computers or smartphones release blue light through the screen, which can affect the user's eye health and sleep quality. Therefore, many related products with anti-blue light functions are currently available on the market, such as contact lenses with anti-blue light functions, which can reduce the degree of blue light absorption by the eyes while users are wearing contact lenses.

In the prior art, the method of preparing contact lenses with anti-blue light function can be, for example, adding a dye with a blue light absorbing function to the contact lenses. However, the dye has a poor compatibility with the raw material composition for preparing the contact lenses. The formula liquid after the dye and the raw material composition are configured will appear stratified after being placed for a period of time. Or, in a hydrogel system, the dye may be washed out during the hydration process of the process, resulting in the final contact lens failing to meet the anti-blue light standard. The reason may be that the dye has poor compatibility with the raw material composition of the contact lens, resulting in uneven dispersion of the dye and incomplete bridging.

The inventor of this application plans to synthesize a dye with a hydrophilic molecule (such as HEMA), thereby expecting to obtain a reactive dye in which the dye and the hydrophilic molecule are combined. The reactive dye has good compatibility with the hydrophilic component (such as HEMA) in the contact lens raw material composition and is suitable for application in various formulation systems.

In the prior art, some related patents are known to propose hydrophilic molecules grafted with reactive dyes for introduction into the formulation of contact lenses, such as US Patent Publication No. US 8865929 B2 (applicant - Cooper Optics) and US Patent Publication No. US7216975 B2 (applicant - Visionox).

U.S. Patent Publication No. US8865929B2 discloses a reactive dye for contact lenses. The specification of the patent discloses a specific preparation method of the reactive dye. A round-bottom flask is pre-dried at 110°C. Hydrophilic molecule hydroxyethyl methacrylate (HEMA) is pre-dried at 170°C using 3A molecular sieve, and dye RB19, 4-methoxyphenol (MEHQ), dried HEMA (anhydrous conditions), and anhydrous sodium hydroxide or potassium carbonate are added under nitrogen. The reaction mixture is stirred at 40°C under nitrogen.

The inventor of the present application actually tried to synthesize Y15-HEMA under anhydrous conditions according to the method disclosed in US8865929B2, and used dye RY15 or dye Y15 as the starting material. After the experiment, the reaction product was subjected to HPLC detection, and it was found that the desired reactive dye (Y15-HEMA) was not present in the reaction product, and it was found that the reaction product only contained the above-mentioned starting material and the undesired by-product (Y15-OH).

U.S. Patent Publication No. US7216975B2 discloses a method for preparing a reactive dye compound and a colored contact lens. The patent discloses that the synthesis reaction of Y15-HEMA is mainly carried out in water. The preparation method comprises: using RY15 as a starting material, and pouring RY15, sodium carbonate, and distilled water into a round-bottomed flask and stirring them for 10 minutes to form a reaction liquid; then, heating the reaction liquid to 40°C and reacting for 1 hour; finally, adding about 1.5 equivalents of a hydrophilic molecule (HEMA) and hydroquinone into the round-bottomed flask and stirring to carry out the synthesis reaction of Y15-HEMA, which is reacted at a temperature of 30°C for 24 hours.

The inventor of the present application also tried to synthesize Y15-HEMA in pure water using the method disclosed in US7216975B2, and used dye RY15 or dye Y15 as the starting material. After the experiment, the reaction product was subjected to HPLC detection, and it was found that the desired reactive dye (Y15-HEMA) was not present in the reaction product, and it was found that the reaction product only contained the above starting material and the undesired by-product (Y15-OH).

The above two experiments show that no matter whether dye RY15 or dye Y15 is used as the starting material, the desired reactive dye (Y15-HEMA) cannot be obtained.

The inventor of the present application speculates that the reason why Y15-HEMA cannot be obtained under anhydrous conditions is that dried hydroxyethyl methacrylate (HEMA) will hydrolyze into methacrylic acid (MAA) and ethylene glycol (EG) under strong alkali. Since part of the hydrophilic molecule HEMA will hydrolyze into ethylene glycol in the HEMA solvent environment (anhydrous conditions), the synthetic reaction cannot obtain Y15-HEMA, but only Y15-OH.

The inventor of the present application speculates that the reason why Y15-HEMA cannot be obtained under pure water conditions is that, under alkaline conditions of HEMA:pure water at 1:40 (i.e., 2.5% HEMA aqueous solution) and sodium hydroxide, HEMA has been hydrolyzed at 30°C for 24 hours. Therefore, the reaction products will only produce Y15 and Y15-OH, but not Y15-HEMA.

The above speculation can be supported by the content mentioned in the paper "concentration effects in the base-catalyzed hydrolysis of oligo (ethylene glycol)-and amine-containing methacrylic monomers" in the journal "Designed Monomers and Polymers": The rate of alkali-catalyzed hydrolysis of esters is proportional to the concentration of esters and hydroxide ions. It has been confirmed that water-soluble hydroxyethyl methacrylate is rapidly hydrolyzed in aqueous solution in a strong alkaline environment and at room temperature. The hydrolysis mechanism can refer to the following reaction mechanism. In addition, the above paper also pointed out that the hydrolysis rate increases significantly when the concentration of hydrophilic molecules is less than 20%. Compared with high concentrations, the degree of hydrolysis decreases with decreasing pH.

[Hydrolysis mechanism]: HEMA + H ₂ O → MAA + EG.

The inventors of the present application also tested, based on the above-mentioned paper, that HEMA and alkali can be stirred at room temperature or heated to obtain hydrolyzed compounds.

In summary, the synthesis reactions according to US8865929B2 (Cooper Optics) and US7216975B2 (Oxygen) will cause the hydrophilic molecule HEMA to undergo a hydrolysis reaction. The synthetic reaction pathways of Cooper and Oxygen are that RB19 and RY15 undergo an elimination reaction to obtain an intermediate dye. Under Cooper's synthetic conditions (anhydrous and strong alkaline), HEMA is presumed to be hydrolyzed into MAA and EG.

In the presence of HEMA and EG, the hydroxyl groups of the two compounds compete with each other to graft with the vinylsulfonate functional group of the dye. However, since the hydroxyl group of HEMA is surrounded by weak electron-withdrawing groups, its synthesis efficiency is slower than that of EG. Cooper's method uses a strong base for the reaction. However, a strong base will accelerate the hydrolysis efficiency. Based on this, the final synthesis result will be Y15 and part of Y15-OH.

Under the pure water reaction conditions of Shimao, 1.6% HEMA aqueous solution is hydrolyzed into ethylene glycol by most of the water and alkali. The above paper points out that the aqueous solution of hydrophilic molecules below 20% will be quickly hydrolyzed into ethylene glycol. Then, ethylene glycol undergoes oxa-Michael reaction (OMR), thus obtaining more Y15-OH.

That is to say, whether the reaction is carried out under the anhydrous conditions of Cooper Optics or under the pure water conditions of Opto-Scan, the problem of the hydrophilic molecule HEMA being hydrolyzed into EG in large quantities cannot be solved. Therefore, the synthetic reaction using the methods of the above two prior patents obviously cannot obtain the desired reactive dye (Y15-HEMA), but can only obtain the starting material Y15 or the undesirable byproduct (Y15-OH).

For the purification of the reaction product, the purification method of US8865929B2 (Cooper Optics) is to use column chromatography, which takes a lot of time and produces a lot of solid waste. The purification method of US7216975B2 (Violet) is to use 95% ethanol extraction three times, which greatly reduces the yield. This purification method can only obtain a 30% yield.

Since the desired reactive dye (Y15-HEMA) cannot be obtained in either anhydrous or pure water conditions, the reactive dye has both hydrophilic and lipophilic properties in its structure, making it more compatible with the special contact lens formulation system than the hydrophilic structure of the dye (Y15) itself.

Therefore, the inventor of the present application felt that the above defects could be improved, and therefore conducted intensive research and applied scientific principles, and finally proposed the present invention which is rationally designed and effectively improves the above defects. In this way, the problem that the desired reactive dye cannot be obtained regardless of the reaction under anhydrous conditions or pure water conditions is solved, and the reaction product has a high yield of the target product.

The technical problem to be solved by the present invention is to provide a method for producing a reactive dye suitable for contact lenses, which has a high yield of the target product (reactive dye) in view of the shortcomings of the prior art.

In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a method for preparing a reactive dye, comprising: performing a configuration step, which comprises: mixing a hydrophilic molecule and water according to a weight ratio of 10:1 to 1:3 to form a co-solvent; and adjusting the co-solvent to a pH range with a weak base, wherein the hydrophilic molecule is an acrylic ester with a hydroxyl group; and performing a synthesis step, which comprises: A dye is added to the co-solvent, and the dye is subjected to a synthesis reaction with the hydrophilic molecule to form a reaction product containing a reactive dye; wherein the chemical structure of the dye has a reactive functional group to react with the hydroxyl group of the hydrophilic molecule in the synthesis reaction; wherein the reactive functional group of the dye is at least one of a vinyl sulfonate functional group, a sodium sulfonate functional group, and a sulfonate functional group.

The beneficial effect of the present invention is that the manufacturing method of the reactive dye provided by the present invention can be achieved by "implementing a configuration step, comprising: mixing a hydrophilic molecule and water according to a weight ratio of 10:1 to 1:3 to form a co-solvent; and adjusting the co-solvent to a pH range with a weak base; wherein the hydrophilic molecule is an acrylic ester with a hydroxyl group" and "implementing a synthesis step, comprising: adding a dye to the co-solvent, so that the dye and the hydrophilic molecule react with each other. The invention discloses a technical scheme of "performing a synthesis reaction to form a reaction product including a reactive dye" and "the chemical structure of the dye has a reactive functional group to react with the hydroxyl group of the hydrophilic molecule in the synthesis reaction; wherein the reactive functional group of the dye is at least one of a vinyl sulfonate functional group, a sodium sulfonate functional group, and a sulfonate functional group" to effectively improve the yield of the target product (reactive dye) and effectively reduce the generation of undesirable by-products.

To further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only used for reference and description and are not used to limit the present invention.

The following is a specific embodiment to illustrate the implementation method disclosed by the present invention. The technical personnel in this field can understand the advantages and effects of the present invention from the content disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments. The details in this specification can also be modified and changed based on different viewpoints and applications without deviating from the concept of the present invention. In addition, the drawings of the present invention are only for simple schematic illustration and are not depicted according to the actual size. Please note in advance.

The following implementations will further illustrate the relevant technical contents of the present invention, but the disclosed contents are not intended to limit the protection scope of the present invention.

In this document, in order to describe a specific numerical range, the term "a certain value to another numerical value" is used herein, which should be interpreted as covering any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical range were explicitly stated in the specification.

In addition, for the sake of simplicity, the structures of various polymers or groups in this article are sometimes expressed as skeletal formulas, thereby omitting the carbon atoms, hydrogen atoms, and carbon-hydrogen bonds in the actual structure. However, when specific atoms or atomic groups are clearly drawn in the structural formula, the structural formula is based on the drawn atoms or atomic groups.

[Method for producing reactive dye]

The purpose of the present invention is to allow hydrophilic molecules and dyes to undergo a synthesis reaction in the presence of a co-solvent to form a reactive dye (monomer-dye compound). The manufacturing method provided by the present invention can effectively improve the yield of the target product (reactive dye) and can effectively reduce the generation of undesirable by-products. Some unreacted dye raw materials can also participate in the reaction at the application end (such as contact lens production). In addition, the purification method provided by the present invention uses the polarity difference of the organic solvent to precipitate the product, thereby effectively improving the purification efficiency and the recovery rate of the target product.

As shown in FIG1 , in order to achieve the above-mentioned purpose, the present invention provides a method for preparing a reactive dye, which comprises: step S110, step S120, and step S130. It must be noted that the order of each step and the actual operation method in the embodiment of the present invention can be adjusted according to the needs and are not limited to the embodiment.

The step S110 is to implement a configuration step, including: mixing a hydrophilic molecule and water according to a weight ratio to form a co-solvent; and adjusting the co-solvent to a pH range with a weak base.

Wherein, the hydrophilic molecule is an acrylic ester with a hydroxyl group. In various embodiments of the present invention, the hydrophilic molecule is selected from at least one of the group consisting of the following materials: hydroxyethyl methacrylate (HEMA), 4-hydroxybutyl acrylate (HBA), glycidyl methacrylate (GMA), hydroxypropyl methacrylate (HPMA), 2-hydroxyisopropyl methacrylate (HIPMA), and hydroxybutyl methacrylate (HBMA). In a preferred embodiment of the present invention, the hydrophilic molecule is hydroxyethyl methacrylate.

The water in the co-solvent may be, for example, pure water, filtered water, distilled water, or electrolyzed water, and is preferably pure water, but the present invention is not limited thereto.

In the co-solvent, the weight ratio of the hydrophilic molecules to water may be, for example, hydrophilic molecules: water = 10:1 to 1:3, preferably 9:1 to 1:3, and particularly preferably 9:1 to 1:1. In other words, the hydrophilic molecules account for approximately 25% to 91% of the co-solvent, and preferably 50% to 90%.

For example, the co-solvent may be prepared by mixing 10 parts by weight of hydrophilic molecules with 1 part by weight of water (the hydrophilic molecules account for about 91%). Alternatively, the co-solvent may be prepared by mixing 1 part by weight of hydrophilic molecules with 3 parts by weight of water (the hydrophilic molecules account for about 25%), but the present invention is not limited thereto.

Wherein, the weak base can be, for example, a sodium salt or an ammonium salt. In various embodiments of the present invention, the sodium salt is at least one selected from the group consisting of the following materials: sodium carbonate, sodium bicarbonate, sodium oxalate, sodium acetate, and sodium benzoate. In addition, the ammonium salt can be, for example, ammonium carbonate. In a preferred embodiment of the present invention, the weak base is sodium carbonate or sodium bicarbonate, but the present invention is not limited thereto.

The pH value of the co-solvent adjusted by weak alkali is preferably between 8.0 and 10.5, more preferably between 8.5 and 10.5, and particularly preferably between 9.0 and 10.2. The above pH value ranges make the co-solvent weakly alkaline.

The step S120 is a synthesis step, which includes: adding a dye to the co-solvent, and allowing the dye to undergo a synthesis reaction with a hydrophilic molecule to form a reaction product including a reactive dye.

The chemical structure of the dye has a chromophore group and a reactive functional group located at at least one end of the chromophore group. In one embodiment of the present invention, the reactive functional group is a vinyl sulfonate functional group (CH ₂ ═CHSO ₂ -). In another embodiment of the present invention, the reactive functional group is a sodium sulfonate functional group (sodium sulfonate, -SO ₃ Na) or a sulfonic acid functional group (sulfonic acid group, -SO ₃ ^- or -SO ₃ H).

Furthermore, the chromophore has a plurality of benzene ring structures. The chromophore can have an absorption peak for light in a specific wavelength range, for example, the chromophore of the following chemical formula (I) can have an absorption peak for blue light with a wavelength between 380 nm and 460 nm, but the present invention is not limited thereto.

In various embodiments of the present invention, the chemical structure of the dye may be, for example, at least one of the following chemical formulas (I) to (VI). These chemical formulas all have the functional group characteristics described above. However, it should be noted that the dyes listed below are only exemplary, and the dyes of the present invention are not limited to the compounds listed below. As long as the selected dyes meet the chemical functional group characteristics described above, they meet the protection spirit of the present invention and belong to the protection scope of the present invention.

[Chemical structures of related dyes] Chemical formula (I) Chemical formula (II) Chemical formula (III) Chemical formula (IV) Chemical formula (V) Chemical formula (VI)

As described above, the hydrophilic molecule is an acrylic ester having a hydroxyl group (-OH), and the dye has a reactive functional group.

In the synthesis reaction, the hydroxyl group of the hydrophilic molecule is covalently bonded to the reactive functional group of the dye (such as vinylsulfonate functional group or sulfonate functional group) during the reaction, thereby forming the reactive dye. Further, after the hydroxyl group of the hydrophilic molecule is covalently bonded to the reactive functional group of the dye, an ether group (R-O-R') bonded between the hydrophilic molecule and the dye is formed. For example, in a specific embodiment of the present invention, the hydrophilic molecule is hydroxyethyl methacrylate (HEMA), and the chemical structure of the dye is as shown in the above chemical formula (I). The synthesis reaction is as follows.

Synthesis reaction (I).

In another specific embodiment of the present invention, the hydrophilic molecule is hydroxyethyl methacrylate (HEMA), and the chemical structure of the dye is as shown in the above chemical formula (IV). The synthesis reaction is as follows.

Synthesis reaction (II).

The reactive dye (Y15-HEMA) formed by the above-mentioned synthesis reaction can simultaneously have a hydrophilic end (such as sodium sulfonate functional group -SO ₃ Na) and a lipophilic end (such as the residue of HEMA), so it has better compatibility in a special contact lens formulation system than the hydrophilic structure of the dye itself.

According to the above configuration, the co-solvent configures the hydrophilic molecules and water according to the above weight ratio, the co-solvent is adjusted to the above pH value range by weak alkali, and the dye has a specific material selection. Accordingly, the manufacturing method provided by the present invention can effectively help improve the yield of the target product (reactive dye) and effectively reduce the generation of undesirable by-products compared to the anhydrous conditions or pure water conditions of the prior art. The undesirable by-product (Y15-OH) has the following chemical structure.

Below is the chemical structure of Y15-OH.

In general, in the synthesis reaction system, the initial weight ratio of each component is as follows: [dye: hydrophilic molecule: pure water: weak base] weight ratio = 1: 2~20: 2~20: 0.1~0.6.

In other words, based on 1 part by weight of the dye, the amount of the hydrophilic molecule added is 2 to 20 parts by weight, the amount of pure water added is 2 to 20 parts by weight, and the amount of the weak base added is 0.1 to 0.6 parts by weight, but the present invention is not limited thereto.

In order to improve the efficiency of the above-mentioned synthesis reaction, in some embodiments of the present invention, the weight ratio of hydrophilic molecules to pure water is further limited, that is, the weight ratio of [hydrophilic molecules: pure water] = 10:1 to 1:3, preferably 9:1 to 1:3, and particularly preferably 9:1 to 1:1.

Furthermore, in terms of the reaction conditions of the polymerization reaction, a reaction temperature of the polymerization reaction is preferably between 50° C. and 70° C., more preferably between 50° C. and 65° C., and particularly preferably between 55° C. and 65° C. In addition, a reaction time of the polymerization reaction is preferably between 12 hours and 72 hours, more preferably between 16 hours and 52 hours, and particularly preferably between 18 hours and 48 hours.

In addition, after completing the synthesis step, a reaction product containing the reactive dye can be obtained. In some embodiments of the present invention, the reaction product is analyzed using a high performance liquid chromatography (HPLC) and a wavelength of 254 nanometers, and a content of the reactive dye in the reaction product can be obtained to be greater than or equal to 30 weight %, preferably between 30 weight % and 70 weight %, and particularly preferably between 30 weight % and 65 weight %. In order to improve the purity of the reactive dye in the reaction product, the present invention further provides the following purification step (step S130).

The step S130 is a purification step, which includes: using an alcohol solvent and a hydrocarbon solvent to perform a precipitation operation on the reaction product produced by the above synthesis step (step S120), so as to utilize a polarity difference between the alcohol solvent and the hydrocarbon solvent to precipitate the reactive dye in the reaction product to form a precipitation product.

In terms of material types, the alcohol solvent may be, for example, an alcohol having a carbon number between C1 and C5, and preferably an alcohol having a carbon number between C1 and C4.

In various embodiments of the present invention, the alcohol solvent is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, and n-butanol.

In terms of material type, the hydrocarbon solvent may be, for example, a hydrocarbon having a carbon number between C4 and C8, and preferably a hydrocarbon having a carbon number between C5 and C7.

In various embodiments of the present invention, the hydrocarbon solvent is at least one selected from the group consisting of pentane, hexane, and heptane.

In terms of dosage, the weight ratio of the alcohol solvent to the hydrocarbon solvent is approximately between 5:1 and 1:5. In other words, the weight of the alcohol solvent is between 5 times and 1/5 times the weight of the hydrocarbon solvent.

In the purification step, the weight ratio of the dye to the solvent (alcohol solvent and hydrocarbon solvent) is approximately between 1:20 and 100 to improve the precipitation efficiency of the target product.

In some embodiments of the present invention, the purification step (step S130) may further include: performing a water removal operation on the reaction product; and performing a filtration operation on the reaction product to filter solid impurities in the reaction product; and then performing the precipitation operation. It should be noted that the water removal operation and the filtration operation are not limited to the order stated above, and the order of the two operations may also be interchanged according to production requirements. The water removal operation may, for example, be to dehydrate the reaction product using a dehydrating agent, or may, for example, be to dehydrate the reaction product using other physical methods.

In various embodiments of the present invention, the dehydrating agent may be at least one of molecular sieve, sodium sulfate, calcium, and diatomaceous earth, but the present invention is not limited thereto.

In some embodiments of the present invention, the purification step (step S130) may further include: washing the precipitated product with an ether solvent after the reaction product is precipitated with an alcohol solvent and a hydrocarbon solvent; then, filtering and concentrating the precipitated product in sequence (e.g., vacuum concentration) to obtain a solid product with high purity. The purity of the target product (reactive dye) after purification can be increased to more than 85% by weight.

The production method provided by the present invention can effectively improve the yield of the target product (reactive dye) and precipitate the product by the polarity difference of the organic solvent, thereby effectively improving the purification efficiency.

Furthermore, the present invention also provides a reactive dye, which is prepared by the above-mentioned reactive dye preparation method.

Furthermore, an embodiment of the present invention provides a contact lens comprising the above-mentioned reactive dye.

[Experimental data and test results]

The content of the present invention is described in detail below with reference to Examples 1 to 5 and Comparative Examples 1 to 3. However, the following examples are only used to help understand the present invention, and the scope of the present invention is not limited to these examples. Examples 1 to 5 are to verify that the dye can obtain a high yield of reactive dye under the conditions of co-solvent and specific acid-base value.

Example 1: The configuration step comprises configuring 18 parts by weight of a hydrophilic molecule and 2 parts by weight of pure water (hydrophilic molecule: pure water = 9:1) to form a co-solvent, and the co-solvent is adjusted to a pH value of 9.03 with a weak base. Among them, the hydrophilic molecule is hydroxyethyl methacrylate (HEMA), and the weak base is sodium carbonate. The synthesis step comprises adding 1 part by weight of a dye to the above-mentioned co-solvent, and allowing the dye and the hydrophilic molecule to undergo a synthesis reaction to form a reaction product containing a reactive dye. Among them, the dye (Y15) with the chemical formula (I) listed above is selected as a starting material. The reaction temperature of the synthesis reaction is controlled at 55~65°C, and the reaction time of the synthesis reaction is controlled at 18 hours. The reaction product obtained after the reaction was completed was analyzed by HPLC using a wavelength of 254 nm, and the content of the reactive dye (Y15-HEMA) in the reaction product was 50.5 wt %, the content of the starting dye (Y15) in the reaction product was 25 wt %, and the content of the by-product (Y15-OH) in the reaction product was 24.5 wt %. The purification step includes removing water from the reaction product with a dehydrating agent (molecular sieve); filtering the reaction product after the water removal; then configuring an alcohol solvent and a hydrocarbon solvent with the reaction product to precipitate a precipitate product, which contains a high-purity reactive dye; then freezing the precipitate product; then, washing with an ether solvent, such as methoxymethane, ethyl methyl ether or ether, and sequentially filtering and concentrating the precipitate product (such as vacuum concentration) to obtain a high-purity solid product. The purity of the purified target product (reactive dye) can be increased to more than 85% by weight.

The preparation methods of the reactive dyes of Examples 2 to 5 are substantially the same as those of Example 1, except that the weight ratio of the hydrophilic molecule (HEMA) to pure water in the co-solvent, the type of weak base used, and the pH value of the co-solvent are adjusted. The reaction conditions and reaction results of Examples 2 to 5 are listed in Table 1 below. The experimental results show that the content of the reactive dye (Y15-HEMA) in the reaction product is greater than 30% by weight, specifically, between 34.2% and 60.1% by weight, and preferably between 50.2% and 60.1% by weight.

Comparative Example 1 is a synthetic reaction under anhydrous conditions (20 parts by weight of hydrophilic molecules and 0 parts by weight of water). Comparative Examples 2-3 are synthetic reactions under pure water conditions (0 parts by weight of hydrophilic molecules and 20 parts by weight of water). The dyes of the comparative examples are selected from the dyes (RY15) having the chemical formula (IV) listed above as starting materials.

The reaction product of Comparative Example 1 (anhydrous conditions) contains 55.7 wt% of the starting dye (RY15) and 44.3 wt% of the byproduct (RY15-OH). The reaction product of Comparative Example 1 does not contain the reactive dye (RY15-HEMA) to be synthesized. The reason is that the hydrophilic molecule HEMA is hydrolyzed into EG.

Comparative Example 2 (pure water condition) uses a dye (RY15) having the chemical formula (IV). The hydrophilic molecule is added during the synthesis reaction. HPLC analysis revealed that the reaction product of Comparative Example 2 contained 73.9 wt % of the dye (Y15), which was mainly formed by the conversion of RY15, and contained 3 wt % of a byproduct (RY15-OH). The reaction product of Comparative Example 2 contained almost no reactive dye to be synthesized.

Comparative Example 3 (pure water condition) uses a dye (RY15) having the chemical formula (IV). The hydrophilic molecule is added during the synthesis reaction. HPLC analysis revealed that the reaction product of Comparative Example 3 contained 85.7% by weight of a byproduct (RY15-OH), which was mainly formed by the reaction of RY15 with EG generated by the hydrolysis of HEMA. The reaction product of Comparative Example 3 did not contain the reactive dye to be synthesized.

The experimental results of the above comparative examples 1 to 3 all show that the inventors of the present application have expected the synthesis of reactive dyes (RY15-HEMA) under anhydrous conditions and pure water conditions in the prior art.

The reaction product was analyzed using a high performance liquid chromatography (HPLC) at a wavelength of 254 nanometers to obtain the content of each component (Y15, Y15-HEMA, Y15-OH). The HPLC-related analysis conditions are shown in Table 2 below.

[Table 1 Reaction conditions and reaction results] Item Reaction conditions Reaction results Co-solvent - Hydrophilic molecule: pure water Add weak alkali Co-solvent pH Response time Starting material - dye (weight %) Product - Reactive dye (weight %) By-products (weight %) Embodiment 1 18:2 Sodium carbonate 9.03 18hr 25.0 50.5 24.5 Embodiment 2 15:6 Sodium carbonate 10.2 48hr 10.1 60.1 29.8 Embodiment 3 15:6 Sodium bicarbonate 9.17 48hr 34.8 52.4 12.9 Embodiment 4 10:10 Sodium carbonate 9.03 42hr 23.7 50.2 26.1 Embodiment 5 5:15 Sodium carbonate 10.0 42hr 36.5 34.2 29.3 Comparison Example 1 20:0(no water) Sodium carbonate 6.8 48hr 55.7 0 44.3 Comparison Example 2 0:20 (pure water) Sodium carbonate 9.65 24hr 95.2 0.1 4.7 Comparison Example 3 0:20 (pure water) Sodium carbonate 10.2 42hr 14.2 0 85.8

[Table 2 HPLC analysis conditions] HPLC equipment: HPLC (Agilent 1260 infinity) HPLC Column: ZORBAX Eclipse XDB-C8 4.6*150mm 5um Detection wavelength: 254nm or 410nm Mobile Phase A: MeOH, B: 10mM ammonium acetate Flow 1 mL/min Stoptime 15 min Oven Temp. 40℃ Wavelength 254 nm Inj. Volume 10 µL Sample preparation Prepare 100ppm of the test substance (MeOH: pure water is 1:1)

The above experimental results confirm that the method for preparing the reactive dye provided by the present invention can effectively solve the problem mentioned in the prior art that the desired reactive dye cannot be obtained regardless of whether the reaction is carried out under anhydrous conditions or pure water conditions.

The inventors of the present application have discovered that a co-solvent is a hydrophilic molecule and water in an appropriate ratio that can dissolve alkaline salts (weak bases) and increase reactivity. Synthetic reactive dyes can be synthesized from synthetically available dyes. The synthesis reaction can be carried out in the environment of a co-solvent. Adding a weak base and adjusting the pH value to carry out the synthesis reaction can reduce the problem of by-product generation. The above technical solution solves the problem that hydrophilic molecules may be hydrolyzed in an anhydrous environment or a pure water environment. In terms of purification, the present invention proposes to configure a solvent for precipitating products under conditions calculated by the Hansen solubility parameters, which can purify and increase the yield of the target product by more than 85% by weight.

The final synthesized reactive dye has a hydrophilic end and a lipophilic end, which has good compatibility with the raw material composition of contact lenses and is suitable for various formulation system applications. After the product of the synthetic reaction is dehydrated and filtered, the product can be directly introduced into the composition for making contact lenses. The reason is that the product contains reactive dyes and reactive dyes that can be used directly.

In terms of the analysis results of the reaction product, FIG. 2 is a result diagram of the reaction product of an embodiment of the present invention analyzed by LC-PDA, and FIG. 3 is a result diagram of the reaction product of an embodiment of the present invention analyzed by LC-MS. As shown in FIG. 2, the signal position 8.411 is the signal of the reactive dye (Y15-HEMA). The signal position 7.578 is the signal of the dye (Y15). The signal position 5.928 is the signal of the byproduct (Y15-OH). Furthermore, FIG. 3 confirms that the reactive dye (Y15-HEMA) with a molecular weight of approximately 622+1 does appear successfully in the reaction product and has the maximum signal intensity.

It should be noted that in the above Examples 1 to 5, although only one or two types of hydrophilic molecules, dyes, and weakly alkaline materials are used as examples for illustration, the above Examples 1 to 5 are mainly to prove that the hydrophilic molecules and dyes are synthesized in the presence of a co-solvent, and that the yield of the target product (reactive dye) can be effectively increased within a specific pH range, and the generation of undesirable by-products can be effectively reduced. Accordingly, the types of materials for the above components of the present invention should not be limited to Examples 1 to 5.

[Beneficial Effects of the Embodiments]

The beneficial effect of the present invention is that the manufacturing method of the reactive dye of the present invention can be achieved by "implementing a configuration step, comprising: mixing a hydrophilic molecule and water according to a weight ratio of 10:1 to 1:3 to form a co-solvent; and adjusting the co-solvent to a pH range with a weak base; wherein the hydrophilic molecule is an acrylic ester with a hydroxyl group" and "implementing a synthesis step, comprising: adding a dye to the co-solvent, allowing the dye to react with the hydrophilic molecule. A technical solution of "a synthesis reaction to form a reaction product containing a reactive dye" and "the chemical structure of the dye has a reactive functional group to react with the hydroxyl group of the hydrophilic molecule in the synthesis reaction; wherein the reactive functional group of the dye is at least one of a vinyl sulfonate functional group, a sodium sulfonate functional group, and a sulfonate functional group" is provided to effectively improve the yield of the target product (reactive dye) and effectively reduce the generation of undesirable by-products.

The contents disclosed above are only preferred feasible embodiments of the present invention and are not intended to limit the scope of the patent application of the present invention. Therefore, all equivalent technical changes made using the contents of the specification and drawings of the present invention are included in the scope of the patent application of the present invention.

FIG1 is a flow chart of a method for producing a reactive dye according to an embodiment of the present invention.

FIG. 2 is a graph showing the results of LC-PDA analysis of the reaction product of one embodiment of the present invention.

FIG3 is a graph showing the results of LC-MS analysis of the reaction product of one embodiment of the present invention.

Claims (16)

A method for manufacturing a reactive dye comprises: Implementing a configuration step, which comprises: mixing a hydrophilic molecule and water according to a weight ratio of 10:1 to 1:3 to form a co-solvent; and adjusting the co-solvent to a pH range; wherein the hydrophilic molecule is an acrylic ester with a hydroxyl group; and Implementing a synthesis step, which comprises: adding a dye to the co-solvent, allowing the dye and the hydrophilic molecule to undergo a synthesis reaction to form a reaction product containing the reactive dye; wherein the chemical structure of the dye has a reactive functional group to react with the hydroxyl group of the hydrophilic molecule in the synthesis reaction; wherein the reactive functional group of the dye is at least one of a vinyl sulfonate functional group, a sodium sulfonate functional group, and a sulfonate functional group. The method for producing a reactive dye as described in claim 1, wherein the weight ratio of hydrophilic molecules to water in the co-solvent is between 9:1 and 1:3. The method for producing a reactive dye as described in claim 1, wherein the pH range is a pH value between 8.0 and 10.5. A method for producing a reactive dye as described in claim 1, wherein the hydrophilic molecule is at least one selected from the group consisting of: hydroxyethyl methacrylate (HEMA), 4-hydroxybutyl acrylate (HBA), glycidyl methacrylate (GMA), hydroxypropyl methacrylate (HPMA), 2-hydroxyisopropyl acrylate (HIPMA), and hydroxybutyl methacrylate (HBMA). The method for producing a reactive dye as described in claim 1, wherein the weak base is at least one of a sodium salt and an ammonium salt. A method for producing a reactive dye as described in claim 5, wherein the sodium salt is at least one selected from the group consisting of the following materials: sodium carbonate, sodium bicarbonate, sodium oxalate, sodium acetate, and sodium benzoate; and the ammonium salt is selected from ammonium carbonate. The method for producing a reactive dye as described in claim 1, wherein the hydroxyl group of the hydrophilic molecule is covalently bonded to the reactive functional group of the dye in the synthesis reaction to form the reactive dye; wherein, after the hydroxyl group of the hydrophilic molecule is covalently bonded to the reactive functional group of the dye, an ether group bonded between the hydrophilic molecule and the dye is formed. The method for producing a reactive dye as described in claim 1, wherein the reactive dye has a hydrophilic end and a lipophilic end. A method for producing a reactive dye as described in claim 1, wherein a reaction temperature of the polymerization reaction is between 50°C and 70°C, and a reaction time of the polymerization reaction is between 12 hours and 72 hours. A method for producing a reactive dye as described in any one of claims 1 to 9, wherein the reaction product is analyzed using a high performance liquid chromatography (HPLC) to obtain a content of the reactive dye in the reaction product that is greater than or equal to 30 wt%. The method for producing a reactive dye as described in claim 1 further comprises: implementing a purification step, which includes: using an alcohol solvent and a hydrocarbon solvent to perform a precipitation operation on the reaction product formed by the synthesis reaction to precipitate the reactive dye and form a precipitation product. The method for producing a reactive dye as described in claim 11, wherein the alcohol solvent is an alcohol having a carbon number between C1 and C5, and the hydrocarbon solvent is a hydrocarbon having a carbon number between C4 and C8. The method for producing a reactive dye as described in claim 12, wherein a content of the reactive dye in the precipitated product is greater than or equal to 85 wt%. The method for producing a reactive dye as described in claim 1, wherein the chemical structure of the dye added in the synthesis step is at least one of the following formulas (I) to (VI): Formula (I); Formula (II); Formula (III); Formula (IV); Formula (V); Formula (VI). A reactive dye is prepared by the method for producing a reactive dye as described in claim 1 to claim 14. A contact lens comprising the reactive dye as described in claim 15.

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