Highly hydrophilic polystyrene and its preparation method

Abstract

The present invention provides a highly hydrophilic polystyrene and a preparation method thereof, belonging to the field of highly hydrophilic materials. The highly hydrophilic polystyrene comprises polystyrene and a hyperbranched hydrophilic compound grafted onto the polystyrene. The hyperbranched hydrophilic compound is a hydrophilic compound of hyperbranched glycidyl with amino groups. The preparation method of the highly hydrophilic polystyrene is as follows: first, under acidic conditions, the benzene ring of polystyrene is halogenoacetylated or halomethylated by Friedel-Crafts reaction to obtain substance A, and then under alkaline conditions, the hyperbranched hydrophilic compound is reacted with substance A to obtain the highly hydrophilic polystyrene. The highly hydrophilic polystyrene of the present invention has more hydroxyl groups, which can improve the hydrophilicity of polystyrene, thereby reducing the non-specific adsorption with proteins, and further reducing the analysis error.

Description

Technical Field

[0001] The present invention belongs to the field of highly hydrophilic materials, and particularly relates to a highly hydrophilic polystyrene. In addition, the present invention also relates to a preparation method of the highly hydrophilic polystyrene. Background Art

[0002] Polystyrene (PS) materials have excellent water resistance, light weight, high hardness, high impact resistance, corrosion resistance, good heat insulation performance and other characteristics, and can be used to prepare various containers. However, in analytical experiments, non-specific adsorption of biological macromolecules such as proteins will produce misleading results. For example, the adsorption of antibodies and antigens on a 96-well plate will lead to a decrease in detection accuracy, and the non-specific adsorption of proteins on a chromatographic medium will lead to sample inactivation and loss.

[0003] Hydrophobic interaction is the main factor for the non-specific adsorption of proteins by PS materials. Therefore, increasing the hydrophilicity of the material will greatly reduce the protein adsorption amount, thereby reducing the error caused by non-specific adsorption of proteins and the like.

[0004] Currently, commonly used hydrophilic modification methods include physical adsorption hydrophilic modification and chemical coupling hydrophilic modification. Physical adsorption usually adsorbs a layer of hydrophilic / hydrophobic amphiphilic polymer on the material surface and then crosslinks it. Although the hydrophilicity of the material surface is effectively improved after physical adsorption plating, the plating is prone to fall off, especially when in a protein solution, which will limit the number of times the material can be reused.

[0005] Compared with physical adsorption, there are fewer reports on grafting hydrophilic polymers by chemical coupling method. In the existing literature, polyethylene glycol is mostly coupled on the surface of polystyrene microspheres. Specifically, active groups are first introduced onto the benzene ring of polystyrene through Friedel-Crafts reaction, and then the active groups are further modified. However, since the grafted PEG chain contains only one hydroxyl group, that is, the amount of hydroxyl groups grafted on the microsphere surface is greatly reduced, resulting in the hydrophilicity of the material not meeting the requirements. Summary of the Invention

[0006] Based on the above background problems, the present invention aims to provide a highly hydrophilic polystyrene, which includes polystyrene and a hyperbranched hydrophilic compound grafted on the polystyrene. The hyperbranched hydrophilic compound is a hydrophilic compound of hyperbranched glycidyl with amino groups, which has more hydroxyl groups, can improve the hydrophilicity of polystyrene, thereby reducing the non-specific adsorption with proteins, and further reducing the analysis error.

[0007] Another object of the present invention is to provide a preparation method of the highly hydrophilic polystyrene.

[0008] To achieve the above object, on the one hand, the technical solution provided by the embodiment of the present invention is:

[0009] Highly hydrophilic polystyrene, comprising polystyrene and a hyperbranched hydrophilic compound grafted onto the polystyrene, the chemical structural formula of the hyperbranched hydrophilic compound being shown in Formula I:

[0010]

[0011] On the other hand, an embodiment of the present invention provides a method for preparing highly hydrophilic polystyrene, comprising the following steps:

[0012] S1. Under acidic conditions, the benzene ring of polystyrene is halogenoacetylated or halomethylated by a Friedel-Crafts reaction to obtain a substance A shown in Formula II:

[0013]

[0014] S2. Under basic conditions, the hyperbranched hydrophilic compound shown in Formula I is reacted with the substance A shown in Formula II to obtain highly hydrophilic polystyrene.

[0015] In one embodiment, the pH in step S1 is 2 - 3, the reaction temperature is 30 - 40 °C, and the reaction time is 3 - 8 h.

[0016] In one embodiment, the mass ratio of the hyperbranched hydrophilic compound to polystyrene in step S2 is 1 - 3:1, the reaction temperature is 50 - 70 °C, and the reaction time is 10 - 24 h.

[0017] In one embodiment, the preparation of the hyperbranched hydrophilic compound comprises the following steps:

[0018] A1. 4-Aminobutanol and di-tert-butyl dicarbonate are added to a solvent and reacted at 25 - 40 °C for 5 - 8 h to obtain compound I;

[0019] A2. Epichlorohydrin, a base, and the compound I are added to a solvent and reacted at 25 - 40 °C for 16 - 20 h to obtain compound II;

[0020] A3. Trimethylolpropane and a base are added to a solvent and reacted at 25 - 40 °C for 30 - 60 min to obtain compound III;

[0021] A4. The compound II, the compound III, and glycidol are added to a solvent and reacted at 100 - 150 °C for 24 - 26 h to obtain compound IV;

[0022] A5. The compound IV and an acid are added to a solvent and reacted at 25 - 40 °C for 1 - 3 h to obtain the hyperbranched hydrophilic compound.

[0023] In one embodiment, a basic auxiliary agent is further added in step A1.

[0024] Further, the basic auxiliary agent is triethylamine.

[0025] In one embodiment, the solvents in steps A1 and A5 are both dichloromethane; the solvents in steps A2 and A3 are one or more of tert-butanol, methanol, ethanol, isopropanol, and n-butanol; the solvent in step A4 is one or more of diethyl ether, tetrahydrofuran, dichloromethane, chloroform, and ethylene glycol dimethyl ether.

[0026] In one embodiment, the bases in steps A2 and A3 are one or more of potassium tert-butoxide, potassium methoxide, sodium methoxide, and sodium ethoxide.

[0027] In one embodiment, the acids in step A5 are one or more of trifluoroacetic acid, acetic acid, and hydrochloric acid.

[0028] Compared with the prior art, the embodiments of the present invention have at least the following effects:

[0029] The present invention provides a highly hydrophilic polystyrene, which includes polystyrene and a hyperbranched hydrophilic compound grafted on the polystyrene. The hyperbranched hydrophilic compound has a relatively large number of hydroxyl groups, which can improve the hydrophilicity of the polystyrene, thereby reducing the non-specific adsorption with proteins and further reducing the analysis error; in addition, a large number of hydroxyl groups on the hyperbranched hydrophilic compound can also be derivatized into various functional groups. Description of the Drawings

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments.

[0031] Figure 1 It is the infrared spectrum analysis diagram of substance A in Embodiment 1 of the present invention;

[0032] Figure 2 It is the infrared spectrum analysis diagram of the highly hydrophilic polystyrene in Embodiment 1 of the present invention. Detailed Embodiments

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0034] To solve the problem that the hydrophilicity of existing polystyrene modification still cannot meet the requirements, the embodiment of the present invention provides a highly hydrophilic polystyrene, which includes polystyrene and a hyperbranched hydrophilic compound grafted on the polystyrene. The hyperbranched hydrophilic compound has a large number of hydroxyl groups, which can improve the hydrophilicity of polystyrene, thereby reducing the non-specific adsorption with proteins and further reducing the analysis error.

[0035] Next, the technical solution of the present invention will be described through specific embodiments.

[0036] Example 1

[0037] The highly hydrophilic polystyrene is prepared by the following steps:

[0038] (1) Chlorination acetylation of polystyrene: Add 1.2 g of polystyrene board and 1.2 g of anhydrous aluminum trichloride to 30 mL of dichloromethane. After stirring evenly (the solution turns yellow), add 1 mL of chloroacetyl chloride dropwise, and then react in a water bath at 30 °C for 6 h. The reaction equation is as follows;

[0039]

[0040] After the reaction is completed, filter the reaction solution under anhydrous conditions, pour the separated solid into ice hydrochloric acid and stir, and then centrifuge and wash with deionized water until neutral; finally, replace with ethanol and vacuum dry to obtain substance A.

[0041] The chlorine content of substance A was measured to be 21.43% by the sodium hydroxide melting method. The infrared spectrum analysis of substance A is as Figure 1 shown. From Figure 1 it can be seen that substance A shows a strong carbonyl stretching vibration absorption peak connected to the benzene ring at 1683 cm -1 and a very strong chlorine atom (-Cl) stretching vibration peak at 645 cm -1 , indicating that substance A is chloroacetylated polystyrene.

[0042] (2) Preparation of hyperbranched hydrophilic compound:

[0043] 2.1 Add 9.984 g (112 mmol) of 4-amino-1-butanol, 30.554 g (140 mmol) of di-tert-butyl dicarbonate, and 11.333 g (112 mmol) of triethylamine to 120 mL of dichloromethane, and react at 30 °C for 6 h. The addition of triethylamine provides an alkaline environment, which can improve the reaction rate; the reaction equation is as follows:

[0044]

[0045] After the reaction, extraction was carried out with deionized water, the organic phase was collected, dried over anhydrous sodium sulfate, and a colorless transparent oily compound I was obtained after vacuum distillation;

[0046] 2.2 Compound I (76.6 mmol), 8.595 g (76.6 mmol) of potassium tert-butoxide, and 42.468 g (459 mmol) of epichlorohydrin were added to 100 mL of tert-butanol, and the reaction was carried out at 30 °C for 18 h. The reaction equation is as follows:

[0047]

[0048] After the reaction, extraction was carried out with deionized water and dichloromethane, the organic phase was collected, dried over anhydrous sodium sulfate, and a pale yellow oily substance was obtained after vacuum distillation. Chromatographic column separation was carried out using dichloromethane:n-hexane = 1:100 to obtain a colorless oily compound II. The NMR data and mass spectrometry data of compound II are as follows:

[0049] 1H NMR (600 MHz, DMSO-d6): δ ppm 3.61 (dd, 1H, J = 11.6 and 2.8 Hz,), 3.34 - 3.40 (m, 2H,), 3.18 (dd, 1H, J = 11.5 and 6.3 Hz,), 3.03 - 3.05 (m, 1H,), 2.88 (q, 2H, J = 6.7 Hz,), 2.68 (dd, 1H, J = 4.3 and 5.1 Hz,), 2.49 (dd, 1H, J = 5.1 and 2.6 Hz,), 1.42 - 1.47 (m, 2H,), 1.36 - 1.39 (m, 2H,), 1.34 (s, 9H,);

[0050] MS (m / z + Na+, ESI+) The calculated molecular formula of compound II is C 12 H 23 NO2, and the relative molecular mass is 268.3.

[0051] 2.3 0.063 g (0.47 mmol) of trimethylolpropane and 0.0075 g (0.14 mmol) of sodium methoxide were added to 60 mL of methanol, and the reaction was carried out at 30 °C for 30 min. The reaction equation is as follows:

[0052]

[0053] After the reaction, compound III was obtained by vacuum distillation.

[0054] 2.4 Add 0.322 g (1.2 mmol) of Compound II and 0.062 g (0.4 mmol) of Compound III to 50 mL of ethylene glycol diethyl ether. Dissolve 1.726 g (23.3 mmol) of glycidol in 20 mL of ethylene glycol diethyl ether, and slowly add the glycidol solution to the solution of Compound II and Compound III using a dropping funnel. React at 120 °C for 25 h. The reaction equation is as follows:

[0055]

[0056] After the reaction is completed, add 10 mL of methanol, cool to room temperature, place in the refrigerator and cool overnight. Then perform suction filtration, wash the filter residue with ether, and dry to obtain a white solid powder Compound IV. The mass spectrometry data of Compound IV is as follows:

[0057] MS (m / z + H⁺, ESI⁺) The calculated molecular formula of Compound IV is C 66 H 131 N₃O 31 , with a relative molecular mass of 1461.88.

[0058] 2.5 Add 3.362 g (2.3 mmol) of Compound IV and 0.285 g (2.5 mmol) of trifluoroacetic acid to 60 mL of dichloromethane, and react at 30 °C for 2 h under stirring. The reaction equation is as follows:

[0059]

[0060] After the reaction is completed, perform distillation under reduced pressure, add 2 mL of methanol, precipitate with ether, then filter, wash the filter residue with ether, and dry to obtain a white solid powder, which is the hyperbranched hydrophilic compound. The NMR data and mass spectrometry data of the hyperbranched hydrophilic compound are as follows:

[0061] ¹H NMR (500 MHz, Chloroform-d) δ 4.14 (hd, J = 6.2, 4.4 Hz, 2H), 3.96 - 3.18 (m, 74H), 3.16 - 3.10 (m, 3H), 2.84 - 2.57 (m, 6H), 1.90 (t, J = 6.1 Hz, 2H), 1.85 (t, J = 6.1 Hz, 2H), 1.80 - 1.40 (m, 16H), 0.84 (t, J = 7.2 Hz, 3H).

[0062] MS The calculated molecular formula of the hyperbranched hydrophilic compound is C 51 H 107 N₃O 25 , with a relative molecular mass of 1162.72665.

[0063] (3) Coupling reaction: Add 1 g of the chloroacetylated polystyrene in step (1) and 3 g of the hyperbranched hydrophilic compound in step (2) into 50 mL of deionized water, add 1.5 g of sodium hydroxide, and stir and react at 60 °C in a water bath for 12 h. The reaction equation is as follows:

[0064]

[0065] After the reaction is completed, centrifuge and wash with deionized water until neutral, and then dry to obtain highly hydrophilic polystyrene microspheres.

[0066] Perform infrared spectroscopy analysis on the product. As Figure 2 shown, it can be seen that a very strong hydroxyl absorption peak appears at 3433 cm -1 -1, and the very strong C-Cl stretching vibration peak at 645 cm -1 -1 in the infrared spectrum of chloroacetylated polystyrene has disappeared. This indicates that the hyperbranched hydrophilic compound has been successfully coupled to the polystyrene microspheres. The calculated hydroxyl content is 5.21 mmol / L.

[0067] Example 2

[0068] Highly hydrophilic polystyrene is prepared by the following method:

[0069] (1) Bromoacetylation of polystyrene: Add 1.2 g of polystyrene plate and 1.2 g of anhydrous stannic chloride into 30 mL of dichloromethane. After stirring evenly (the solution turns yellow), add 1 mL of bromoacetyl bromide dropwise, and then react in a water bath at 30 °C for 6 h;

[0070] After the reaction is completed, filter the reaction solution under anhydrous conditions, pour the separated solid into ice hydrochloric acid and stir, and then centrifuge and wash with deionized water until neutral; finally, displace with ethanol and vacuum dry to obtain bromoacetylated polystyrene microspheres. The bromine content in the microspheres is 24.5%.

[0071] (2) Coupling reaction: Add 1 g of the hyperbranched hydrophilic compound prepared in Example 1 and 1 g of the bromoacetylated polystyrene in step (1) into 50 mL of deionized water, add 1.5 g of sodium hydroxide, and stir and react at 60 °C in a water bath for 12 h;

[0072] After the reaction is completed, centrifuge and wash with deionized water until neutral to obtain microspheres with a hydroxyl content of 4.87 mmol / g.

[0073] Example 3

[0074] Highly hydrophilic polystyrene is prepared by the following method:

[0075] (1) Bromoacetylation of polystyrene: Add 1.2 g of polystyrene plate and 1.2 g of anhydrous tin tetrachloride to 30 mL of dichloromethane. After stirring evenly (the solution turns yellow), add 0.5 mL of bromoacetyl bromide dropwise, and then react in a water bath at 30 °C for 6 h;

[0076] After the reaction is completed, filter the reaction solution under anhydrous conditions. Pour the separated solid into ice hydrochloric acid and stir, then wash it by centrifugation with deionized water until neutral. Finally, replace it with ethanol and dry it under vacuum to obtain bromoacetylated polystyrene microspheres. The bromine content in the microspheres is 16.3%.

[0077] (2) Coupling reaction: Add 2 g of the hyperbranched hydrophilic compound prepared in Example 1 and 1 g of the bromoacetylated polystyrene in step (1) to 50 mL of deionized water, add 1.5 g of sodium hydroxide, and take 1.5 g of the hyperbranched hydrophilic compound and stir and react in a water bath at 60 °C for 12 h;

[0078] After the reaction is completed, wash it by centrifugation with deionized water until neutral to obtain microspheres with a hydroxyl content of 5.16 mmol / L.

[0079] Example 4

[0080] Highly hydrophilic polystyrene is prepared by the following method:

[0081] (1) Bromoacetylation of polystyrene: Add 1.2 g of polystyrene plate and 1.2 g of anhydrous tin tetrachloride to 30 mL of dichloromethane. After stirring evenly (the solution turns yellow), add 0.5 mL of bromoacetyl bromide dropwise, and then react in a water bath at 30 °C for 8 h;

[0082] After the reaction is completed, filter the reaction solution under anhydrous conditions. Pour the separated solid into ice hydrochloric acid and stir, then wash it by centrifugation with deionized water until neutral. Finally, replace it with ethanol and dry it under vacuum to obtain bromoacetylated polystyrene microspheres.

[0083] (2) Coupling reaction: Add 2 g of the hyperbranched hydrophilic compound prepared in Example 1 and 1 g of the bromoacetylated polystyrene in step (1) to 50 mL of deionized water, add 1.5 g of sodium hydroxide, and take 1.5 g of the hyperbranched hydrophilic compound and stir and react in a water bath at 50 °C for 24 h. After the reaction is completed, wash it by centrifugation with deionized water until neutral to obtain highly hydrophilic polystyrene.

[0084] Example 5

[0085] Highly hydrophilic polystyrene is prepared by the following method:

[0086] (1) Bromoacetylation of polystyrene: Add 1.2 g of polystyrene plate and 1.2 g of anhydrous tin tetrachloride to 30 mL of dichloromethane. After stirring evenly (the solution turns yellow), add 0.5 mL of bromoacetyl bromide, and then react in a water bath at 40 °C for 3 h;

[0087] After the reaction is completed, filter the reaction solution under anhydrous conditions, pour the separated solid into ice hydrochloric acid and stir, then wash it by centrifugation with deionized water until neutral; finally, replace it with ethanol and dry it under vacuum to obtain bromoacetylated polystyrene microspheres.

[0088] (2) Coupling reaction: Add 2 g of the hyperbranched hydrophilic compound prepared in Example 1 and 1 g of the bromoacetylated polystyrene in step (1) to 50 mL of deionized water, add 1.5 g of sodium hydroxide, and take 1.5 g of the hyperbranched hydrophilic compound and stir and react in a water bath at 70 °C for 10 h; after the reaction is completed, wash it by centrifugation with deionized water until neutral to obtain highly hydrophilic polystyrene.

[0089] Example 6

[0090] Highly hydrophilic polystyrene is prepared by the following method:

[0091] (1) Chloromethylation of polystyrene: Add 5 g of polystyrene spheres and 50 mL of chloromethyl ether to a 250 mL reaction flask, then add 5 g of anhydrous tin chloride, and react at 30 °C for 6 h;

[0092] After the reaction is completed, filter the reaction solution under anhydrous conditions, pour the separated solid into ice hydrochloric acid and stir, then wash it by centrifugation with deionized water until neutral; finally, replace it with ethanol and dry it under vacuum to obtain chloromethylated polystyrene microspheres, and the chlorine content in the microspheres is 20.5%.

[0093] (2) Coupling reaction: Add 1 g of the hyperbranched hydrophilic compound prepared in Example 1 and 1 g of the chloromethylated polystyrene in step (1) to 50 mL of deionized water, add 1.5 g of sodium hydroxide, and stir and react in a water bath at 60 °C for 12 h;

[0094] After the reaction is completed, wash it by centrifugation with deionized water until neutral, and the hydroxyl content of the obtained microspheres is 4.96 mmol / g.

[0095] It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all belong to the protection scope of the present invention.

Claims

1. High hydrophilic polystyrene, characterized in that, It includes polystyrene and a hyperbranched hydrophilic compound grafted on the polystyrene. The chemical structural formula of the hyperbranched hydrophilic compound is shown in Formula I: Formula I; The preparation method of the highly hydrophilic polystyrene includes the following steps: S1. Under acidic conditions, the benzene ring of polystyrene is halogenoacetylated or halomethylated by Friedel-Crafts reaction to obtain Substance A; S2. Under basic conditions, the hyperbranched hydrophilic compound shown in Formula I is reacted with Substance A to obtain highly hydrophilic polystyrene; In Step S2, the mass ratio of the hyperbranched hydrophilic compound to Substance A is 1-3:1, the reaction temperature is 50-70 °C, and the reaction time is 10-24 h.

2. The highly hydrophilic polystyrene according to claim 1, characterized in that, In Step S1, the pH is 2-3, the reaction temperature is 30-40 °C, and the reaction time is 3-8 h.

3. The highly hydrophilic polystyrene according to claim 1, characterized in that, The preparation of the hyperbranched hydrophilic compound includes the following steps: A1. 4-Aminobutanol and di-tert-butyl dicarbonate are added to a solvent and reacted at 25-40 °C for 5-8 h to obtain Compound I; A2. Epichlorohydrin, a base, and Compound I are added to a solvent and reacted at 25-40 °C for 16-20 h to obtain Compound II; A3. Trimethylolpropane and a base are added to a solvent and reacted at 25-40 °C for 30-60 min to obtain Compound III; A4. Compound II, Compound III, and glycidol are added to a solvent and reacted at 100-150 °C for 24-26 h to obtain Compound IV; A5. Compound IV and an acid are added to a solvent and reacted at 25-40 °C for 1-3 h to obtain the hyperbranched hydrophilic compound.

4. The highly hydrophilic polystyrene according to claim 3, wherein A basic auxiliary agent is also added in Step A1.

5. The highly hydrophilic polystyrene according to claim 4, wherein The basic auxiliary agent is triethylamine.

6. The highly hydrophilic polystyrene according to claim 3, wherein The solvents in Steps A1 and A5 are both dichloromethane; the solvents in Steps A2 and A3 are one or more of tert-butanol, methanol, ethanol, isopropanol, and n-butanol; the solvent in Step A4 is one or more of diethyl ether, tetrahydrofuran, dichloromethane, chloroform, and ethylene glycol dimethyl ether.

7. The highly hydrophilic polystyrene according to claim 3, wherein The bases in Steps A2 and A3 are one or more of potassium tert-butoxide, potassium methoxide, sodium methoxide, and sodium ethoxide.

8. The highly hydrophilic polystyrene according to claim 3, wherein The acids in Step A5 are one or more of trifluoroacetic acid, acetic acid, and hydrochloric acid.

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