Isosorbide polymerizable chiral agent and preparation method thereof
By preparing isosorbide-based polymerizable chiral agents, the problems of difficult catalyst separation and high cost in chiral catalytic synthesis were solved, realizing efficient and low-cost liquid crystal copolymerization and preparing chiral compounds with excellent optical properties.
Patent Information
- Application Number
- CN202310339851.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-03-31
- Publication Date
- 2026-02-06
AI Technical Summary
Existing chiral catalytic synthesis technologies suffer from problems such as difficulty in catalyst separation, difficulty in product purification, high cost, and difficulty in recycling and reuse. Furthermore, the addition of chiral compounds to liquid crystals can lead to a decrease in optical properties or complicated and costly manufacturing processes.
A method for preparing isosorbide-based polymerizable chiral agents was adopted, which combined microwave irradiation, ultraviolet irradiation, and laser irradiation to prepare isosorbide-based polymerizable chiral agents with excellent solubility and low melting point. These agents were then used for copolymerization with liquid crystal compounds, utilizing isosorbide-based polymerizable chiral agents as constituent materials of both chiral and liquid crystal compounds.
This method achieves efficient polymerization of chiral compounds, improves product purity and solubility, reduces preparation costs, and features a simple preparation process, fast reaction rate, high conversion rate, and products with excellent optical properties and low melting point.
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Figure CN121471231A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional materials technology, and relates to polymerizable chiral agents, specifically to an isosorbide-based polymerizable chiral agent and its preparation method. Background Technology
[0002] Chiral catalytic synthesis has made significant progress over the past few decades, but successes have largely been achieved in the laboratory, with only a few achieving mature industrial applications. A key reason for this is the difficulty in separating catalysts and products in homogeneous catalytic systems, the challenge of product purification, and the difficulty in recovering and recycling expensive catalysts. Currently, polymerizable chiral agents are expensive and have complex synthesis processes, primarily consisting of small organic chiral molecules with limited polymer systems. However, polymeric fillers offer undeniable advantages such as high molecular weight, good stability, and easily tunable chirality. Therefore, developing a polymerizable chiral agent with chiral properties is an essential direction for future research.
[0003] Adding chiral compounds to nematic liquid crystals to improve their optical properties is a common practice. However, adding large amounts of chiral compounds can lead to a decrease in optical properties such as liquid crystallinity, solubility, and polymer transmittance, and can also result in a high cost-benefit ratio, making it unprofitable. Some optically active compounds can solve the cost problem, but they suffer from high melting points and poor solubility. While compounds with asymmetrical structures can improve solubility, their fabrication processes are complex, costly, and difficult to purify. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the present invention aims to provide an isosorbide-based polymerizable chiral agent and its preparation method, thereby producing a chiral agent that can be used as a chiral compound and polymerized, while also exhibiting excellent solubility with other liquid crystal compounds. The product has high purity, and the preparation method is simple and cost-effective.
[0005] To achieve the above objectives, the present invention employs the following technical solution:
[0006] An isosorbide-based polymerizable chiral agent has the following general structural formula:
[0007]
[0008] Where R1 is any of the following structural formulas:
[0009]
[0010]
[0011] Where n = 1 - 25.
[0012] This invention also protects a method for preparing the isosorbide-based polymerizable chiral agent as described above, comprising the following steps:
[0013] Step 1: Prepare a type I benzoyl chloride derivative with any of the following structural formulas:
[0014]
[0015] Where n = 1 - 25;
[0016] Step 2: Take 10-20 parts by weight of isosorbide, 10-50 parts of type I benzoyl chloride derivative, 1-25 parts of 3-phenylpyridine, 50-150 parts of anhydrous ethanol, 0.1-10 parts of potassium hydroxide, and 5-20 parts of lipase catalyst, mix and stir until homogeneous.
[0017] Step 3: Under anaerobic conditions, initiate the reaction using microwave irradiation, then simultaneously apply ultraviolet and laser irradiation. The microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, the ultraviolet wavelength is 190-380nm, and the light intensity is 5mW / cm²-5W / cm². 2 The temperature is 20-100℃, and the irradiation time is 0.5-12 hours.
[0018] Preferably, the enzyme catalyst comprises any one or a mixture of several of Novozyme lipase, RMIM lipase, Purine lipase, and TCL lipase in any proportion.
[0019] Preferably, the preparation method of the first type of benzoyl chloride derivative includes:
[0020] Take 10-20 parts by mass of a type II benzoyl chloride derivative, 20-50 parts by mass of an acrylate compound, and mix 10-50 parts by mass of N,N-dimethylformamide and 10-20 parts by mass of tetrahydrofuran, and 5-20 parts by mass of an antimony-titanium bimetallic catalyst.
[0021] Irradiate for 0.5-6 hours at room temperature under ultraviolet light wavelengths of 200-350 nm and light intensity of 10 mW / cm2-10 W / cm2.
[0022] Preferably, the structural formula of the second type of benzoyl chloride derivative is any one of the following structural formulas:
[0023]
[0024] Preferably, the antimony-titanium bimetallic catalyst comprises, by weight, 0-10 parts of dipropyl titanate, 0-10 parts of antimony glycolate and 0-10 parts of antimony acrylate, and the content of the three components is 0 when they are different.
[0025] Compared with the prior art, the present invention has the following technical effects:
[0026] The material of this invention can be used as both a chiral compound and a polymer, has a strong HTP value and a low melting point, exhibits excellent solubility with other liquid crystal compounds, can be used as a constituent material of polymerizable liquid crystal polymers, and has high torsional strength, enabling the fabrication of optical anisotropy bodies with excellent optical properties.
[0027] The preparation process of this invention innovatively uses microwave irradiation, ultraviolet and solid-state pulsed laser technology simultaneously, flexibly adjusts the energy supply, improves the reaction rate, shortens the reaction time, and also increases the conversion rate;
[0028] The preparation method of this invention is simple, the raw materials are inexpensive and readily available, and the cost is low. Attached Figure Description
[0029] Figure 1 The molecular formula structure of the isosorbide-based polymerizable chiral agent prepared in Example 4 is shown below.
[0030] Figure 2 The 1H NMR (DMSO-D6, 400MHz) spectrum of the isosorbide polymerizable chiral agent prepared in Example 4;
[0031] Figure 3 The DSC diagram of the isosorbide-based polymerizable chiral agent prepared in Example 4;
[0032] Figure 4 The photoelectric curves are of the isosorbide-based polymerizable chiral agents prepared in Examples 1-6. Detailed Implementation
[0033] The specific content of the present invention will be further explained in detail below with reference to the embodiments.
[0034] Example 1
[0035] This embodiment provides a method for preparing isosorbide-based polymerizable chiral agents, including the following steps:
[0036] Step 1
[0037]
[0038] Take 10 parts by mass of a second type of benzoyl chloride derivative, 20 parts of an acrylate compound, 10 parts of N,N-dimethylformamide and 10 parts of tetrahydrofuran as solvents, and 2 parts of dipropyl titanate, 2 parts of antimony glycolate and 1 part of antimony acrylate as catalysts, and mix them evenly.
[0039] At room temperature, the ultraviolet light wavelength is 200 nm and the light intensity is 10 mW / cm².2 Irradiation for 0.5 h yielded the first type of benzoyl chloride derivative;
[0040] Step 2: Take 10 parts isosorbide and 10 parts of a type I benzoyl chloride derivative by weight, 1 part 3-phenylpyridine, 50 parts anhydrous ethanol, 0.1 part potassium hydroxide, 2 parts Novozyme lipase, 2 parts RMIM lipase, and 1 part Purine lipase and mix them thoroughly.
[0041] Under anaerobic conditions, the microwave frequency was 2350MHz, the microwave power was 400W, the ultraviolet wavelength was 190nm, and the light intensity was 5mW / cm². 2 At a temperature of 20℃, an isosorbide-based polymerizable chiral agent was obtained by irradiation for 0.5 h.
[0042] Example 2
[0043] This embodiment provides a method for preparing isosorbide-based polymerizable chiral agents, including the following steps:
[0044] Step 1
[0045]
[0046] Take 20 parts by mass of a second type of benzoyl chloride derivative, 50 parts of an acrylate compound, 50 parts of N,N-dimethylformamide and 20 parts of tetrahydrofuran as solvent, and 10 parts of dipropyl titanate, 5 parts of antimony glycol and 5 parts of antimony acrylate as catalyst, and mix them evenly.
[0047] At room temperature, the ultraviolet light wavelength is 350nm and the light intensity is 10W / cm². 2 Irradiation for 6 hours yielded the first type of benzoyl chloride derivative;
[0048] Step 2: Take 20 parts by weight of isosorbide and 50 parts by weight of a type I benzoyl chloride derivative, 25 parts by weight of 3-phenylpyridine, 150 parts by weight of anhydrous ethanol, 10 parts by weight of potassium hydroxide, 10 parts by weight of Novozyme lipase, 5 parts by weight of RMIM lipase, and 5 parts by weight of Purine lipase and mix them thoroughly.
[0049] Under anaerobic conditions, the microwave frequency was 2500MHz, the microwave power was 1500W, the ultraviolet wavelength was 380nm, and the light intensity was 5W / cm². 2 At a temperature of 100℃, irradiation for 12 hours yielded isosorbide-based polymerizable chiral agents.
[0050] Example 3
[0051] This embodiment provides a method for preparing isosorbide-based polymerizable chiral agents, including the following steps:
[0052] Step 1
[0053]
[0054] Take 15 parts by mass of a second type of benzoyl chloride derivative, 15 parts of an acrylate compound, 20 parts of N,N-dimethylformamide and 12 parts of tetrahydrofuran as solvent, and 5 parts of dipropyl titanate, 3 parts of antimony glycol and 3 parts of antimony acrylate as catalyst, and mix them evenly.
[0055] At room temperature, the ultraviolet light wavelength is 300 nm and the light intensity is 5 W / cm². 2 Irradiation for 4 hours yielded the first type of benzoyl chloride derivative;
[0056] Step 2: Take 15 parts isosorbide, 40 parts of type I benzoyl chloride derivative, 20 parts 3-phenylpyridine, 70 parts anhydrous ethanol, 5 parts potassium hydroxide, 5 parts Novozyme lipase, 2 parts RMIM lipase, and 3 parts Purine lipase by weight and mix them evenly.
[0057] Under anaerobic conditions, the microwave frequency was 2400MHz, the microwave power was 800W, the ultraviolet wavelength was 300nm, and the light intensity was 2W / cm². 2 At a temperature of 30℃, irradiation for 4 hours yielded isosorbide-based polymerizable chiral agents.
[0058] Example 4
[0059] This embodiment provides a method for preparing isosorbide-based polymerizable chiral agents, including the following steps:
[0060] Step 1
[0061]
[0062] Take 10 parts by mass of a type II benzoyl chloride derivative, 30 parts of an acrylate compound, 30 parts of N,N-dimethylformamide and 15 parts of tetrahydrofuran as solvent, 10 parts of dipropyl titanate, 3 parts of antimony glycol and 5 parts of antimony acrylate as catalyst, and mix them evenly.
[0063] At room temperature, the ultraviolet light wavelength is 320 nm and the light intensity is 10 mW / cm². 2 Irradiation for 3 hours yielded the first type of benzoyl chloride derivative;
[0064] Step 2: Take 20 parts isosorbide, 35 parts of type I benzoyl chloride derivative, 15 parts 3-phenylpyridine, 120 parts anhydrous ethanol, 5 parts potassium hydroxide, 10 parts Novozyme lipase, 2 parts RMIM lipase, and 5 parts Purine lipase by weight and mix them evenly.
[0065] Under anaerobic conditions, the microwave frequency was 2450MHz, the microwave power was 1200W, the ultraviolet wavelength was 350nm, and the light intensity was 4W / cm². 2 At a temperature of 60℃, irradiation for 10 hours yielded isosorbide-based polymerizable chiral agents.
[0066] Figure 1 The molecular formula diagram of the isosorbide-based polymerizable chiral agent prepared in Example 4 is shown; where n = 10.
[0067] Figure 2 The image shows the 1H NMR (DMSO-D6, 400MHz) spectrum of the isosorbide-based polymerizable chiral agent prepared in Example 4. Figure 2 It is clearly visible that the chemical shifts of each hydrogen atom match up, and the proportion of hydrogen atoms also matches the molecular formula.
[0068] Figure 3 The DSC chart of the isosorbide-based polymerizable chiral agent prepared in Example 4 is shown. The test temperature range was set to -20°C to 100°C. As can be seen from the chart, the sample melted at 25°C, indicating that the sample has a low melting point.
[0069] Example 5
[0070] This embodiment provides a method for preparing isosorbide-based polymerizable chiral agents, including the following steps:
[0071] Step 1
[0072]
[0073] Take 15 parts by mass of a type II benzoyl chloride derivative, 32 parts by mass of an acrylate compound, 35 parts by mass of N,N-dimethylformamide and 15 parts by mass of tetrahydrofuran, and 1 part by mass of dipropyl titanate, 3 parts by mass of antimony glycol and 1 part by mass of antimony acrylate, and mix them evenly.
[0074] At room temperature, the ultraviolet light wavelength is 310 nm and the light intensity is 5 W / cm². 2 Irradiation for 4 hours yielded the first type of benzoyl chloride derivative;
[0075] Step 2: Take 20 parts isosorbide, 35 parts of type I benzoyl chloride derivative, 15 parts 3-phenylpyridine, 120 parts anhydrous ethanol, 5 parts potassium hydroxide, 10 parts Novozyme lipase, 2 parts RMIM lipase, and 5 parts Purine lipase by weight and mix them evenly.
[0076] Under anaerobic conditions, the microwave frequency was 2450MHz, the microwave power was 1200W, the ultraviolet wavelength was 350nm, and the light intensity was 4W / cm². 2At a temperature of 60℃, irradiation for 10 hours yielded isosorbide-based polymerizable chiral agents.
[0077] Example 6
[0078] This embodiment provides a method for preparing isosorbide-based polymerizable chiral agents, including the following steps:
[0079] Step 1
[0080]
[0081] Take 15 parts by mass of a type II benzoyl chloride derivative, 32 parts by mass of an acrylate compound, 35 parts by mass of N,N-dimethylformamide and 15 parts by mass of tetrahydrofuran, and 1 part by mass of dipropyl titanate, 3 parts by mass of antimony glycol and 1 part by mass of antimony acrylate, and mix them evenly.
[0082] At room temperature, the ultraviolet light wavelength is 310 nm and the light intensity is 5 W / cm². 2 Irradiation for 4 hours yielded the first type of benzoyl chloride derivative;
[0083] Step 2: Take 15 parts isosorbide, 40 parts of type I benzoyl chloride derivative, 20 parts 3-phenylpyridine, 70 parts anhydrous ethanol, 5 parts potassium hydroxide, 5 parts Novozyme lipase, 2 parts RMIM lipase, and 3 parts Purine lipase by weight and mix them evenly.
[0084] Under anaerobic conditions, the microwave frequency was 2450MHz, the microwave power was 1200W, the ultraviolet wavelength was 350nm, and the light intensity was 4W / cm². 2 At a temperature of 60℃, irradiation for 10 hours yielded isosorbide-based polymerizable chiral agents.
[0085] Table 1 Performance test results of isosorbide-based polymerizable chiral agents prepared in Examples 1-6
[0086] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 <![CDATA[HTP value (μm -1 )]]> 101 108 115 112 128 120 Light transmittance (mm) 0.03 0.03 0.03 0.03 0.03 0.03 Yield 89.3％ 91.2％ 92.6％ 92.8％ 93.5％ 94.0％ Solubility (mol / L) 2.2 2.1 2.5 2.4 2.8 2.7 Melting point (°C) 21.1 20.3 24.8 23.7 24.8 26.9
[0087] Table 1 shows the performance test results of the isosorbide-based polymerizable chiral agents prepared in Examples 1-6. The table shows that the HTP value of this product reached 100 μm. -1 In summary, the product has excellent optical properties that fully meet the usage requirements; moreover, the product has a high yield, the catalyst used is excellent and can effectively avoid waste, its high solubility makes it suitable for use with general liquid crystals, and its low melting point also helps to achieve extremely fast and uniform mixing.
[0088] Figure 4 The image shows the photoelectric curves of the isosorbide-based polymerizable chiral agents prepared in Examples 1-6. Figure 4It can be seen that the driving voltage of this product is relatively low. At around 25V, the transmittance of the sample can reach more than 90%, and the starting driving voltage does not exceed 10V. This shows that the product has low energy consumption and the dielectric anisotropy of its liquid crystal can meet the usage standards.
[0089] It should be noted that although some embodiments of the present invention have been shown and described, various changes, modifications, substitutions and variations made by those skilled in the art without departing from the principles and spirit of the present invention are all within the scope of protection of the present invention.
Claims
1. An isosorbide-based polymerizable chiral agent, characterized in that, The general structural formula is as follows: Where R1 is any of the following structural formulas: Where n = 1 - 25.
2. A method for preparing an isosorbide-based polymerizable chiral agent as described in claim 1, characterized in that, Includes the following steps: Step 1: Prepare a type I benzoyl chloride derivative with any of the following structural formulas: Where n = 1 - 25; Step 2: Take 10-20 parts by weight of isosorbide, 10-50 parts of type I benzoyl chloride derivative, 1-25 parts of 3-phenylpyridine, 50-150 parts of anhydrous ethanol, 0.1-10 parts of potassium hydroxide, and 5-20 parts of lipase catalyst, mix and stir until homogeneous. Step 3: Under anaerobic conditions, initiate the reaction using microwave irradiation, then simultaneously apply ultraviolet and laser irradiation. The microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, the ultraviolet wavelength is 190-380nm, and the light intensity is 5mW / cm²-5W / cm². 2 The temperature is 20-100℃, and the irradiation time is 0.5-12 hours.
3. The method for preparing isosorbide-based polymerizable chiral agents as described in claim 2, characterized in that, The enzyme catalyst includes any one or a mixture of several of the following in any proportion: Novozyme lipase, RMIM lipase, Purine lipase, and TCL lipase.
4. The method for preparing isosorbide-based polymerizable chiral agents as described in claim 2, characterized in that, The preparation method of the first type of benzoyl chloride derivative includes: Take 10-20 parts by mass of a type II benzoyl chloride derivative, 20-50 parts by mass of an acrylate compound, and mix 10-50 parts by mass of N,N-dimethylformamide and 10-20 parts by mass of tetrahydrofuran, and 5-20 parts by mass of an antimony-titanium bimetallic catalyst. At room temperature, with ultraviolet light wavelengths of 200-350 nm and an irradiance of 10 mW / cm², 2 -10 W / cm 2 Under the conditions, irradiate for 0.5-6h.
5. The method for preparing isosorbide-based polymerizable chiral agents as described in claim 4, characterized in that, The structural formula of the second type of benzoyl chloride derivative is any one of the following structural formulas:
6. The method for preparing isosorbide-based polymerizable chiral agents as described in claim 4, characterized in that, The components of the antimony-titanium bimetallic catalyst, by weight, include 0-10 parts of dipropyl titanate, 0-10 parts of antimony glycolate, and 0-10 parts of antimony acrylate, and the content of the three components is 0 when they are different.