Carboxylic acid modifier containing multiple functionalities as well as preparation method and application of carboxylic acid modifier

Abstract

The invention discloses a carboxylic acid modifier containing multiple degrees of functionality and a preparation method and application thereof, the carboxylic acid modifier has the following structure: H2C = CX-A-B-(MZ) n-N-Y-C = O-OH, in the formula, X is a hydrogen atom, alkyl or alkoxy; a is an alkylene group, an amide group, an acyloxy group or an oxygen atom; b, M, N and Y are one or more of carboxyl, acylamino, alkylene and derivatives thereof, alkyleneoxy and derivatives thereof, alkyleneamine and derivatives thereof or arylene and derivatives thereof; z is a vinyl group, an acrylamide group, an acryloyloxy group and a derivative thereof; n is a natural integer. The carboxylic acid modifier can meet the application requirements of optical film materials and is applied to surface modification of nano oxide, and the modified nano oxide can be dispersed in different acrylic resin monomers to form nano composite resin with high refractive index, high light transmittance and low haze.

Description

Technical Field

[0001] This invention relates to the field of optical materials, specifically to a carboxylic acid modifier with multiple functionalities, its preparation method, and its application. Background Technology

[0002] With the rapid development of information technology, optical film materials for display devices with high refractive index and high transmittance are increasingly widely used. However, the highest refractive index of pure organic acrylic resins currently on the market is no more than 1.62, which cannot meet the high refractive index requirements. While inorganic nanomaterials (such as nano-zirconia and nano-titanium oxide) have high refractive indices, they are solid materials and cannot be directly applied to optical film materials. Currently, nanocomposite resins are the preferred choice for preparing high-refractive-index optical film materials, which are doped with inorganic nanomaterials with high refractive indices and other organic resin monomers. However, pure inorganic nanomaterials are incompatible with organic matter, which can lead to phase separation when the two are mixed, resulting in opaque optical films. According to the principle of "like dissolves like," substances with similar polarity can dissolve together. Therefore, in order to disperse inorganic nanomaterials in organic matter, it is necessary to graft some organic matter onto the surface of inorganic nanomaterials through chemical bonds or hydrogen bonds, thereby encapsulating the inorganic nanomaterials. Inorganic nanomaterials encapsulated by organic matter acquire oleophilicity, thus enabling them to disperse within the organic matter. This process of altering the properties of inorganic nanomaterials is called modification, and the organic matter that imparts oleophilicity to inorganic nanomaterials is called a modifier. Currently, most reported modifiers are simple alkyl derivatives. For example, US patents No. 6,376,590 (Kolb et al.), No. 7,241,437, and No. 7,429,422 (both granted to Davidson et al.) utilize short-chain carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, or combinations thereof as modifiers to modify nano-zirconia. Currently, most commercially available carboxylic acids do not contain acrylate bonds or each modifier molecule contains only one acrylate bond, resulting in linear crosslinking during photocuring, low crosslinking density, and unstable structure after curing, limiting their application range. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a carboxylic acid modifier with multiple functionalities, its preparation method, and its application.

[0004] The technical solution of the present invention is as follows:

[0005] A carboxylic acid modifier containing multiple functionalities has the following structure:

[0006] H2C = CX - AB - (MZ) n -NYC=O-OH

[0007] Wherein, X is a hydrogen atom, alkyl or alkoxy group; A is an alkylene group, amide group, acyloxy group or oxygen atom; B, M, N, Y are one or more of carboxyl, amide, alkylene and its derivatives, alkoxy and its derivatives, alkylamine and its derivatives or aryl and its derivatives; Z is vinyl, acrylamide, acryloxy and its derivatives; n is a natural integer.

[0008] Optionally, A is an alkylene group having the following structure:

[0009] -(CH2) m1 -(CHR1) m2 -(CH2) m3 -

[0010] Wherein, R1 is selected from 1 to 10 alkyl chains, and m1, m2, and m3 each take natural integer values.

[0011] Optionally, B is an alkylene group having the following structure:

[0012] -(CH2) m1 -(CHR1) m2 -(CH2) m3 -

[0013] Wherein, R1 is selected from 1 to 10 alkyl chains, and m1, m2, and m3 each take natural integer values.

[0014] Optionally, B is an alkylene derivative having the following structure:

[0015] -(CHR2) m1 -(CHR1) m2 -(CHR3) m3 -

[0016] Wherein, R1 is selected from 1 to 10 alkyl chains or alkoxy chains, R2 and R3 are each selected from hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and m1, m2 and m3 are each natural integers.

[0017] A method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities involves sequentially adding sodium 3-((2-hydroxyethyl)amino)propionate, dichloromethane, and triethylamine to a flask, controlling the temperature at -10°C. Acryloyl chloride is then added to a constant-pressure dropping funnel, and after replacing the air with nitrogen, the mixture is continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition is complete, the reaction continues. After the reaction is complete, the solid is removed by vacuum filtration, acidified with hydrochloric acid, and filtered again. The reaction solution is then extracted three times with 20 wt% deionized water, and the reaction solution is desolventized. After decolorization and impurity removal by column chromatography, the carboxylic acid modifier with multiple functionalities is obtained.

[0018] A method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities involves sequentially adding sodium 3-((2-((2-hydroxyethyl)amino)ethyl)amino)propionate, dichloromethane, and triethylamine to a flask, controlling the temperature at -10°C. Acryloyl chloride is added to a constant-pressure dropping funnel, and after replacing the air with nitrogen, the mixture is continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition is complete, the reaction continues. After the reaction is complete, the solid is removed by vacuum filtration, acidified with hydrochloric acid, filtered again, and extracted three times with 20 wt% deionized water. The reaction solution is then desolventized, decolorized and purified by column chromatography, and the solvent is removed to obtain the carboxylic acid modifier with multiple functionalities.

[0019] A method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities involves sequentially adding 4,6-dihydroxyhexanoic acid, dichloromethane, and triethylamine to a flask, controlling the temperature at -10°C, adding acryloyl chloride to a constant-pressure dropping funnel, replacing the air with nitrogen, and continuously adding and stirring to keep the reaction temperature below 10°C. After the addition is complete, the reaction continues. After the reaction is complete, the solid is removed by suction filtration, acidified with hydrochloric acid, filtered again, and extracted three times with 20wt% deionized water. The reaction solution is then desolventized, decolorized and purified by column chromatography, and the solvent is removed to obtain the carboxylic acid modifier with multiple functionalities.

[0020] A method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities involves sequentially adding sodium 3-((2-((2-(methylamino)ethyl)amino)ethyl)amino)propionate, dichloromethane, and triethylamine to a flask, controlling the temperature at -10°C. Acryloyl chloride is added to a constant-pressure dropping funnel, and after replacing the air with nitrogen, the mixture is continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition is complete, the reaction continues. After the reaction is complete, the solid is removed by vacuum filtration, acidified with hydrochloric acid, filtered again, and extracted three times with 20wt% deionized water. The reaction solution is then desolventized, decolorized and purified by column chromatography, and the solvent is removed to obtain the carboxylic acid modifier with multiple functionalities.

[0021] A method based on the application of the above-mentioned carboxylic acid modifier containing multiple functions involves applying the carboxylic acid modifier containing multiple functions to the surface modification of nano-oxides, and then dispersing the modified nano-oxides in different acrylic resin monomers to form a nanocomposite resin.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention prepares a carboxylic acid modifier containing multiple highly polar groups such as acryloyloxy or acrylamide, secondary or tertiary amine, alkoxy or alkeneoxy, alkyl or alkylene, siloxane, aryl and their derivatives, which can meet the application requirements of optical film materials. When applied to the surface modification of nano-oxides, the modified nano-oxides can be dispersed in different acrylic resin monomers to form a nanocomposite resin with high refractive index, high transmittance and low haze. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 A preferred structural diagram of a carboxylic acid modifier containing multiple functionalities provided by the present invention. Figure 1 ;

[0025] Figure 2 A preferred structural diagram of a carboxylic acid modifier containing multiple functionalities provided by the present invention. Figure 2 ;

[0026] Figure 3 A preferred structural diagram of a carboxylic acid modifier containing multiple functionalities provided by the present invention. Figure 3 ;

[0027] Figure 4 This is a schematic diagram illustrating the synthesis of a carboxylic acid modifier containing multiple functionalities, as provided in Example 1 of the present invention.

[0028] Figure 5 This is a schematic diagram illustrating the synthesis of a carboxylic acid modifier containing multiple functionalities, as provided in Example 2 of the present invention.

[0029] Figure 6 This is a schematic diagram illustrating the synthesis of a carboxylic acid modifier containing multiple functionalities, as provided in Example 3 of the present invention.

[0030] Figure 7 This is a schematic diagram illustrating the synthesis of a carboxylic acid modifier containing multiple functionalities, as provided in Example 4 of the present invention. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0032] This invention provides a carboxylic acid modifier containing multiple functionalities, having the following structure:

[0033] H2C = CX - AB - (MZ) n -NYC=O-OH

[0034] Wherein, X is a hydrogen atom, alkyl or alkoxy group; A is an alkylene group, amide group, acyloxy group or oxygen atom; B, M, N, Y are one or more of carboxyl, amide, alkylene and its derivatives, alkoxy and its derivatives, alkylamine and its derivatives or aryl and its derivatives; Z is vinyl, acrylamide, acryloxy and its derivatives; n is a natural integer.

[0035] Optionally, A is an alkylene group having the following structure:

[0036] -(CH2) m1 -(CHR1) m2 -(CH2) m3 -

[0037] Wherein, R1 is selected from 1 to 10 alkyl chains, and m1, m2, and m3 each take natural integer values.

[0038] Optionally, B is an alkylene group having the following structure:

[0039] -(CH2) m1 -(CHR1) m2 -(CH2) m3 -

[0040] Wherein, R1 is selected from 1 to 10 alkyl chains, and m1, m2, and m3 each take natural integer values.

[0041] Optionally, B is an alkylene derivative having the following structure:

[0042] -(CHR2) m1 -(CHR1) m2 -(CHR3) m3 -

[0043] Wherein, R1 is selected from 1 to 10 alkyl chains or alkoxy chains, R2 and R3 are each selected from hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and m1, m2 and m3 are each natural integers.

[0044] Better, combination Figures 1-3 The diagram shows a preferred structure of the carboxylic acid modifier containing multiple functionalities according to the present invention.

[0045] To illustrate the technical solution described in this invention, specific embodiments are described below.

[0046] Example 1

[0047] This embodiment provides a method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities. In a 300 mL round-bottom flask, 15.51 g of sodium 3-((2-hydroxyethyl)amino)propionate, 150 g of dichloromethane, and 20 g of triethylamine are added sequentially. The temperature is controlled at -10 °C. 18.1 g of acryloyl chloride (0.2 mol) is added to a 250 mL constant-pressure dropping funnel. After replacing the air with nitrogen, the mixture is continuously added dropwise with stirring, maintaining the reaction temperature below 10 °C. After the addition is complete, the reaction continues for 2 hours. After the reaction is complete, the solid is removed by filtration, and a small amount of hydrochloric acid is added for acidification. The mixture is then filtered again, and the reaction solution is extracted three times with 20 wt% deionized water. The reaction solution is then desolventized, decolorized by column chromatography, and the solvent is removed to obtain 16.09 g of the carboxylic acid modifier with multiple functionalities, with a yield of 66.7%, a refractive index of 1.458 (25 °C), and a viscosity of 250 cp (25 °C).

[0048] 1H NMR (500MHz, Chloroform-d) δ6.56,6.14,6.12,6.10,6.09,5.96,5.94,5.87,5.84,4.26,3.53,3.32,2.58.

[0049] 13C NMR (125MHz, Common NMR Solvents) δ176.97, 170.12, 168.89, 130.60, 130.42, 129.76, 127.87, 64.49, 50.41, 42.77, 36.21.

[0050] Example 2

[0051] This embodiment provides a method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities. In a 300 mL round-bottom flask, 19.81 g (0.1 mol) of sodium 3-((2-((2-hydroxyethyl)amino)ethyl)amino)propionate, 150 g of dichloromethane, and 30 g of triethylamine are added sequentially. The temperature is controlled at -10 °C. Then, 27.15 g of acryloyl chloride (0.3 mol) is added to a 250 mL constant-pressure dropping funnel. After purging the air with nitrogen, the solution is continuously dripped... Stirring was added to keep the reaction temperature below 10℃. After the addition was complete, the reaction continued for 2 hours. After the reaction was complete, the solid was removed by filtration, a small amount of hydrochloric acid was added for acidification, and the mixture was filtered again. The reaction solution was extracted three times with 20wt% deionized water. The reaction solution was desolventized, decolorized and purified by column chromatography, and the solvent was removed to obtain 21.11g of a carboxylic acid modifier with multiple functionalities, with a yield of 62.4%, a refractive index of 1.468 (25℃), and a viscosity of 278cp (25℃).

[0052] 1H NMR (500MHz, Chloroform-d) δ6.56,6.56,6.14,6.12,6.12,6.10,6.09,5.96,5.94,5.87,5.84,4.26,3.53,3.53,3.46,3.25,2.58.

[0053] 13C NMR (125MHz, Common NMR Solvents) δ176.97,170.18,170.12,169.92,130.71,130.60,130.42,129.76,127.98,127.87,64.49,49.93,44.39,43.90,36.19.

[0054] Example 3

[0055] This embodiment provides a method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities. In a 500 mL round-bottom flask, 29.62 g of 4,6-dihydroxyhexanoic acid (0.2 mol), 300 g of dichloromethane, and 40 g of triethylamine were added sequentially. The temperature was controlled at -10°C. 36.2 g of acryloyl chloride (0.4 mol) was added to a constant-pressure dropping funnel. After replacing the air with nitrogen, the mixture was continuously added dropwise with stirring, maintaining the reaction temperature below 10°C. After the addition was complete, the reaction continued for 2 hours. After the reaction was complete, the solid was removed by filtration, and a small amount of hydrochloric acid was added for acidification. The mixture was filtered again, and the reaction solution was extracted three times with 20 wt% deionized water. The reaction solution was then desolventized, decolorized by column chromatography, and the solvent was removed to obtain 34.9 g of the carboxylic acid modifier with multiple functionalities, with a yield of 68.1%, a refractive index of 1.459 (25°C), and a viscosity of 194 cp (25°C).

[0056] 1H NMR(500MHz,Chloroform-d)δ6.14,6.12,6.07,6.06,6.05,6.01,5.96,5.94,5.91,5.88,4.75, 4.33,4.30,4.20,4.18,2.48,2.46,2.40,2.38,2.29,2.26,2.12,2.10,2.04,2.02,1.94,1.91.

[0057] 13C NMR (125MHz, Common NMR Solvents) δ177.24, 170.05, 169.30, 130.95, 130.57, 129.70, 129.57, 81.44, 64.93, 34.57, 31.75, 30.48.

[0058] Example 4

[0059] This embodiment provides a method for preparing the above-mentioned carboxylic acid modifier with multiple functionalities, wherein 63.33g of [amount missing] is added sequentially to a 300mL round-bottom flask. Sodium 3-((2-((2-(methylamino)ethyl)amino)ethyl)amino)propionate, 150g dichloromethane, and 90g triethylamine were added to a 250mL constant pressure dropping funnel at a controlled temperature of -10℃. After replacing the air with nitrogen, the mixture was continuously added dropwise with stirring to keep the reaction temperature below 10℃. After the addition was complete, the reaction continued for 2 hours. After the reaction was complete, the solid was removed by suction filtration, and a small amount of hydrochloric acid was added for acidification. The mixture was filtered again, and the reaction solution was extracted three times with 20wt% deionized water. The reaction solution was then desolventized, decolorized and purified by column chromatography, and the solvent was removed to obtain 70.41g of a carboxylic acid modifier with multiple functionalities, with a yield of 66.84%, a refractive index of 1.471 (25℃), and a viscosity of 267cp (25℃).

[0060] 1H NMR (500MHz, Chloroform-d) δ6.56,6.36,6.12,6.10,6.09,6.06,5.87,5.85,5.84,5.83,3.53,3.52,3.52,3.51,3.25,2.98,2.58.

[0061] 13C NMR (125MHz, Common NMR Solvents) δ176.97,170.50,170.18,169.98,130.71,130.52,129.27,127.98,127.83,47.58,44.35,44.33,43.90,36.19,35.69.

[0062] A carboxylic acid modifier with multiple functionalities prepared in Examples 1 to 4 was applied to the surface modification of nano-oxides. The modified nano-oxides could be dispersed in different acrylic resin monomers to form nanocomposite resins with high refractive index, high transmittance, and low haze. The measurement results are shown in the table below:

[0063]

[0064] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A carboxylic acid modifier containing multiple functionalities, characterized in that, It has the following structure: H2C=CX-A-B-(MZ) n -N-Y-C=O-OH Wherein, X is a hydrogen atom, alkyl or alkoxy group; A is an alkylene group, amide group, acyloxy group or oxygen atom; B, M, N, Y are one or more of carboxyl, amide, alkylene and its derivatives, alkoxy and its derivatives, alkylamine and its derivatives or aryl and its derivatives; Z is vinyl, acrylamide, acryloxy and its derivatives; n is a natural integer.

2. The carboxylic acid modifier containing multiple functionalities according to claim 1, characterized in that, A is an alkylene group, which has the following structure: -(CH2) m1 -(CHR1) m2 -(CH2) m3 - Wherein, R1 is selected from 1 to 10 alkyl chains, and m1, m2, and m3 each take natural integer values.

3. A carboxylic acid modifier containing multiple functionalities according to claim 1, characterized in that: The B is an alkylene group, which has the following structure: -(CH2) m1 -(CHR1) m2 -(CH2) m3 - Wherein, R1 is selected from 1 to 10 alkyl chains, and m1, m2, and m3 each take natural integer values.

4. A carboxylic acid modifier containing multiple functionalities according to claim 1, characterized in that, B is an alkylene derivative having the following structure: -(CHR2) m1 -(CHR1) m2 -(CHR3) m3 - Wherein, R1 is selected from 1 to 10 alkyl chains or alkoxy chains, R2 and R3 are each selected from hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and m1, m2 and m3 are each natural integers.

5. A method for preparing a carboxylic acid modifier containing multiple functionalities as described in any one of claims 1 to 4, characterized in that, Sodium 3-((2-hydroxyethyl)amino)propionate, dichloromethane, and triethylamine were added sequentially to a flask, and the temperature was controlled at -10°C. Acryloyl chloride was added to a constant-pressure dropping funnel, and after replacing the air with nitrogen, it was continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition was complete, the reaction continued. After the reaction was complete, the solid was removed by vacuum filtration, acidified with hydrochloric acid, and filtered again. The reaction solution was extracted three times with 20wt% deionized water, and the reaction solution was desolventized. After decolorization and impurity removal by column chromatography, the solvent was removed to obtain a carboxylic acid modifier with multiple functionalities.

6. A method for preparing a carboxylic acid modifier containing multiple functionalities as described in any one of claims 1 to 4, characterized in that, Sodium 3-((2-((2-hydroxyethyl)amino)ethyl)amino)propionate, dichloromethane, and triethylamine were added sequentially to a flask. The temperature was controlled at -10°C. Acryloyl chloride was added to a constant-pressure dropping funnel. After replacing the air with nitrogen, the mixture was continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition was complete, the reaction continued. After the reaction was complete, the solid was removed by vacuum filtration, acidified with hydrochloric acid, and filtered again. The reaction solution was extracted three times with 20 wt% deionized water. The reaction solution was then desolventized, decolorized and purified by column chromatography, and the solvent was removed to obtain a carboxylic acid modifier with multiple functionalities.

7. A method for preparing a carboxylic acid modifier containing multiple functionalities as described in any one of claims 1 to 4, characterized in that, 4,6-Dihydroxyhexanoic acid, dichloromethane, and triethylamine were added sequentially to a flask, and the temperature was controlled at -10°C. Acryloyl chloride was added to a constant-pressure dropping funnel, and after replacing the air with nitrogen, the mixture was continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition was complete, the reaction continued. After the reaction was complete, the solid was removed by vacuum filtration, acidified with hydrochloric acid, and filtered again. The reaction solution was extracted three times with 20wt% deionized water, and the solvent was removed from the reaction solution. The solution was then decolorized and purified by column chromatography, and the solvent was removed to obtain a carboxylic acid modifier with multiple functionalities.

8. A method for preparing a carboxylic acid modifier containing multiple functionalities as described in any one of claims 1 to 4, characterized in that, Sodium 3-((2-((2-(methylamino)ethyl)amino)ethyl)amino)propionate, dichloromethane, and triethylamine were added sequentially to a flask. The temperature was controlled at -10°C. Acryloyl chloride was added to a constant-pressure dropping funnel. After replacing the air with nitrogen, the mixture was continuously added dropwise with stirring to keep the reaction temperature below 10°C. After the addition was complete, the reaction continued. After the reaction was complete, the solid was removed by vacuum filtration, acidified with hydrochloric acid, and filtered again. The reaction solution was extracted three times with 20wt% deionized water. The reaction solution was then desolventized, decolorized and purified by column chromatography, and the solvent was removed to obtain a carboxylic acid modifier with multiple functionalities.

9. The application of a carboxylic acid modifier containing multiple functionalities according to any one of claims 1 to 4, characterized in that, Carboxylic acid modifiers with multiple functionalities are applied to the surface modification of nano-oxides, and then the modified nano-oxides are dispersed in different acrylic resin monomers to form nanocomposite resins.

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