Method for upgrading and recycling acrylate polymer and preparing multicolor fluorescent polymer material
Through an upgrade recovery method of acrylate polymer, a dihalogenated compound reacts with acrylic polymers to generate multi-color fluorescent polymer materials with different fluorescent colors, solving the recovery of acrylate polymers in the prior art and the shortcomings of fluorescent molecules have achieved efficient preparation and application of fluorescent materials.
Patent Information
- Application Number
- CN202411651831.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-19
- Publication Date
- 2025-02-18
AI Technical Summary
It is difficult to effectively upgrade and recover acrylate polymers in the prior art, and traditional fluorescent molecule preparation methods have problems such as complex synthesis process, low fluorescence luminescence efficiency, and difficult to regulate fluorescence color.
Through an upgrade recovery method of acrylate polymer, a dihalogenated compound reacts with acrylic polymers to generate a multi-color fluorescent polymer material with different fluorescent colors. The method includes reacting with metal magnesium in a polymerization tube under anhydrous tetrahydrofuran environment, followed by introducing a dihaloaryl compound to adjust the fluorescence emission wavelength by adjusting the reactant feed ratio and performing Grignard reaction.
The efficient upgrade and recovery of acrylate polymers has been achieved, and a multi-color fluorescent polymer material with high quantum yield and controllable can be prepared, which can be used in white LED lamps and provide excellent fluorescence effect and thermal stability.
Smart Images
Figure CN119463291A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of plastics upgrading and recycling and fluorescent material preparation, and specifically relates to an upgrading and recycling method of acrylic ester polymers and the preparation of a fluorescent agent of an adjustable multicolor fluorescent polymer material with high quantum yield and its application in white light LED lamps. Background Art
[0002] Acrylic polymers are polymer materials obtained by polymerization of acrylic monomers. Common acrylic polymers include polymethyl methacrylate (PMMA), polymethyl acrylate (PMA), polybutyl acrylate (PBA), etc. This type of polymer has the characteristics of high transparency, chemical corrosion resistance, good heat resistance, etc., and is widely used in daily life. For example, PMMA, also known as organic glass, has the characteristics of good mechanical properties and good transparency, and is usually used as a transparent display board; PMA has good elasticity and is usually used as an acrylic rubber substrate; PBA has a soft texture and good solubility, and is often used to produce pharmaceutical intermediates. Since acrylic polymers are widely used in people's daily lives, the upgrading and recycling of waste polyester materials produced is in urgent need of being solved. Traditional recycling methods usually use melt regeneration, thermal cracking, incineration, etc. The present invention prepares waste polymer materials into fluorescent luminescent materials through simple synthesis, providing a more efficient method for upgrading and recycling acrylic polymers.
[0003] Fluorescent materials play an indispensable role in people's daily lives and are usually used for lighting, biological imaging, sensors, textile fibers, etc. Polyester materials are a type of engineering plastics with excellent performance and wide applications. They are usually used to make fibers, films, and plastic products, and have good processing properties. Polyester materials usually do not have fluorescence or have weak blue fluorescence. Polyester materials are modified with polymer fluorescent additives with good processing properties, so that the polyester materials can produce bright fluorescent effects after modification, which has application value in clothing decoration and lighting imaging.
[0004] At present, there are many existing methods for preparing fluorescent molecules, which mainly introduce fluorescent groups into reactants to generate fluorescent small molecules or macromolecules. Although these methods can obtain fluorescent substances, they have shortcomings such as complex synthesis process, low fluorescence luminescence efficiency and difficulty in controlling fluorescence color. At the same time, traditional fluorescent molecules also have the phenomenon of aggregation-induced quenching in the solid state, which makes it difficult to use solid fluorescent substances in the processing of polyester plastics.
[0005] The present invention provides a high quantum yield controllable multicolor fluorescent acrylic polymer material, which has good photoluminescence and good thermal stability, and can well make up for the application of traditional fluorescent polymer materials in processing engineering plastics. At the same time, the fluorescent color of the material can be controlled by simple operation, which greatly enriches the fluorescent color library and has excellent market application prospects in the preparation of photoluminescent fluorescent engineering plastics. Summary of the invention
[0006] The purpose of the present invention is to provide a method for recycling acrylic acid ester polymers and preparing multicolor fluorescent polymer materials. The polymer material prepared by the method has photoluminescence characteristics and a high quantum yield, which enables it to give polyester an excellent fluorescent effect at a relatively low addition amount, and is a method for recycling acrylic acid polymers. At the same time, the fluorescent polymer material obtained by the present invention has aggregation-induced emission characteristics and good thermal stability, and can be used in the preparation of white light LED lamps.
[0007] The object of the present invention is achieved by providing an upgraded recycling method for acrylic polymers, characterized in that a one-pot reaction is used, by adjusting the feed ratio of reactants, utilizing dihalogenated compounds to react with acrylic polymers, and the resulting polymers can produce different fluorescent colors at the optimal excitation wavelength and have a high quantum yield, and can be used as fluorescent dyes.
[0008] Furthermore, the polymer is reacted with polymethyl methacrylate as the main body, and the dihalogenated aromatic compound is introduced into the polymethyl methacrylate polymer chain through the Grignard reaction. By adjusting the ratio of the dihalogenated aromatic compound to polymethyl methacrylate, the generated polymer has different optimal fluorescence emission wavelengths and produces different fluorescence colors; the optimal fluorescence emission wavelength of the polymer is adjusted in the range of 400nm-600nm.
[0009] Furthermore, the generated polymer is a multicolor fluorescent polymer material with adjustable quantum yield, and has high luminous efficiency, with a quantum yield of up to 80%.
[0010] Furthermore, the generated polymer is a quantum yield-adjustable multicolor fluorescent polymer material having an aggregation-induced emission effect.
[0011] Furthermore, the generated polymer is a controllable multicolor fluorescent polymer material, which can be used as a fluorescent dye additive. Only a small amount of the multicolor fluorescent polymer material can be added to achieve a good fluorescent effect.
[0012] Furthermore, the method for upgrading and recycling acrylic acid ester polymers is characterized by comprising the following steps:
[0013] (1) using a dihalogenated compound and a methyl acrylate polymer as starting materials, reacting with magnesium metal in a polymerization tube in an anhydrous tetrahydrofuran environment for 24 hours, wherein the dihalogenated compound is dibromobenzene, dichlorodiphenylmethane or 4,4-dibromobiphenyl, and the methyl acrylate polymer is polymethyl acrylate, polymethyl methacrylate or polybutyl acrylate;
[0014] (2) After the reaction in step (1) is completed, the reaction is quenched with saturated ammonium chloride, extracted with water and dichloromethane, and then the product is precipitated with petroleum ether to obtain the final product.
[0015] Furthermore, the method for upgrading and recycling acrylic acid ester polymers is characterized by comprising the following specific steps:
[0016] (1) Using dichlorodiphenylmethane, 1,4-dibromobiphenyl, and polymethyl methacrylate as starting materials, wherein the equivalent ratio of dichlorodiphenylmethane:1,4-dibromobiphenyl:polymethyl methacrylate is from 0.1:0.1:1 to 0.5:0.5:1, dichlorodiphenylmethane, 1,4-dibromobiphenyl, polymethyl methacrylate, and magnesium are sequentially added into a polymerization tube, and reacted for 24 hours under magnetic stirring;
[0017] (2) After step (1) reacts for 24 hours, the reaction is quenched with saturated ammonium chloride to terminate the reaction process; the quenched reaction is extracted with water and dichloromethane, the organic phase is dehydrated with anhydrous magnesium sulfate, the filtrate is filtered and concentrated by rotary evaporation, and then precipitated with petroleum ether to finally obtain a reaction product.
[0018] Furthermore, the method for upgrading and recycling acrylic acid ester polymers is characterized in that the chemical reaction formula is:
[0019]
[0020] The application of the polymer fluorescent material with high quantum yield and multicolor fluorescence prepared by the above method of the present invention is characterized in that the polymer fluorescent material has a high quantum yield, and the fluorescence of the polymer fluorescent material can be regulated by changing the ratio of reactants. When the polymer fluorescent material with a content of 5wt% is mixed with polymethyl methacrylate, a good fluorescence effect can be achieved, and it can be used as a fluorescent dye and can be used in white light LED lamps as a wick material for white light LED lamps.
[0021] Specifically, the purpose of the present invention is achieved through the following solutions:
[0022] In one aspect, the present invention provides a method for upgrading and recycling acrylic acid ester polymers and preparing multicolor fluorescent polymer materials, wherein the reaction equation is:
[0023]
[0024] On the other hand, the present invention also provides a method for preparing the above-mentioned adjustable multicolor fluorescent polymer material with high quantum yield, comprising the following preparation process:
[0025] Step 1: using dichlorodiphenylmethane, 1,4-dibromobiphenyl and polymethyl methacrylate as starting materials and tetrahydrofuran as reaction solvent, wherein the equivalent ratio of dichlorodiphenylmethane:1,4-dibromobiphenyl:polymethyl methacrylate is 0.1:0.1:1, adding metal magnesium, dichlorodiphenylmethane, 1,4-dibromobiphenyl and polymethyl methacrylate into a polymerization tube in sequence, and reacting for 24 hours under magnetic stirring;
[0026] Step 2: After reacting for 24 hours, the reaction was quenched with saturated ammonium chloride to terminate the reaction process. The quenched reaction was extracted with water and dichloromethane, the organic phase was dehydrated with anhydrous magnesium sulfate, the filtrate was concentrated by rotary evaporation after filtration, and then precipitated with petroleum ether to finally obtain the reaction product.
[0027] On the other hand, the adjustable multicolor fluorescent polymer material with high quantum yield has high luminescence efficiency, with a quantum yield of up to 80%, and has an aggregation-induced emission effect, and the fluorescent color of the polymer can be changed by simply changing the reaction ratio of the reactants.
[0028] Furthermore, the adjustable multicolor fluorescent polymer material is characterized in that as a polymer fluorescent agent, it has good thermal stability, and a good fluorescent effect can be achieved by adding 5% fluorescent polymer material by mass of polyester.
[0029] Furthermore, the adjustable multicolor fluorescent polymer material is characterized in that it can be used as a wick material for making white light LED lamps.
[0030] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0031] The present invention relates to a method for upgrading and recycling acrylic ester polymers and preparing multicolor fluorescent polymer materials. The method has a novel chemical structure, high luminous efficiency, multiple fluorescent color types, good thermal stability, and is easy to be used in polyester material processing. When used as a fluorescent agent, only a small amount of the method can be added to the polyester material to achieve a good fluorescent effect. The method can be used to make white light LED lamp wick materials, and is an excellent polyester processing material. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Figure 1 The NMR ( 1H NMR) spectrum, in which: the signal peak at 0.77-1.09ppm is attributed to -CH3 in the polymethyl methacrylate repeating unit, the signal peak at 1.73-2.10ppm is the H in -CH2- in the polymethyl methacrylate fragment, the peak at 3.60ppm is the proton peak signal of -OCH3, and the characteristic signal of phenyl proton at 7.80-6.90ppm;
[0033] Figure 2 This is the Fourier transform infrared (FTIR) image of the polymer chain PMMA-M1-0.1 finally obtained in step (2) of Example 1, where 1740 cm -1 The C=O bond is at 1240cm. As the reaction proceeds, the carbonyl group in PMMA participates in the reaction and the signal gradually weakens. -1 The C-O-C bond is located at 1630 cm. As the proportion of reactants increases, the ester group participates in the reaction and falls off, and the signal gradually weakens. -1 The C=C bond of the benzene ring is located at the center. As the proportion of the reactants increases, the signal of the C=C bond of the benzene ring gradually increases.
[0034] Figure 3 is the gel permeation chromatogram (GPC) of the polymer chain PMMA-M1-0.1 finally obtained in step (2) of Example 1, wherein the M n =451800,M w / M n =1.43.
[0035] Figure 4 This is the thermogravimetric analysis (TGA) of the polymer chain PMMA-M1-0.1 finally obtained in step (2) of Example 1, wherein the thermal decomposition temperature of PMMA-M1-0.1 is 294°C.
[0036] Figure 5 This is a fluorescence intensity diagram of the water / tetrahydrofuran solution of the polymer chain PMMA-M1-0.1 finally obtained in step (2) of Example 1. As the water content increases from 0% to 90%, the solution gradually becomes turbid and the fluorescence intensity gradually increases.
[0037] Figure 6 The excitation and emission fluorescence spectra of the polymer chain PMMA-M1-0.1 finally obtained in step (2) of Example 1, wherein it does not emit in solution but exhibits yellow fluorescence in the solid state, with an optimal emission wavelength of 565 nm and an optimal excitation wavelength of 449 nm;
[0038] Figure 7 The excitation and emission fluorescence spectra of the polymer chain PMMA-M1-0.3 finally obtained in Example 6, the optimal emission wavelength is 563nm, and the optimal excitation wavelength is 407nm;
[0039] Figure 8 The excitation and emission fluorescence spectra of the polymer chain PMMA-M1-0.6 finally obtained in Example 7, the optimal emission wavelength is 455nm, and the optimal excitation wavelength is 350nm;
[0040] Fig. 9 This is the excitation and emission fluorescence spectrum of the polymer chain PMMA-M1-1 finally obtained in Example 8. The optimal emission wavelength is 590 nm, and the optimal excitation wavelength is 473 nm.
[0041] Fig.10 This is a schematic diagram of a model for making fluorescent dyes using the fluorescent polymer of the present invention.
[0042] Fig.11 This is a schematic diagram of using the fluorescent polymer of the present invention as a white light LED lamp material. DETAILED DESCRIPTION
[0043] The specific implementation modes of the present invention are further described in detail below with reference to the accompanying drawings.
[0044] Example 1
[0045] Step 1: Take 23 mg (1.2 eq) of fresh magnesium metal chips and put them into the polymerization tube, blow the polymerization tube under vacuum conditions, pass nitrogen after cooling, and repeat the above operation 3 times. Using dichlorodiphenylmethane, 1,4-dibromobiphenyl, and polymethyl methacrylate as starting materials, the mass ratio of dichlorodiphenylmethane: 1,4-dibromobiphenyl: polymethyl methacrylate is 0.1:0.1:1, dichlorodiphenylmethane (6.2 mg), 4,4-dibromobiphenyl (5.7 mg), and polymethyl methacrylate (200 mg) are added to the polymerization tube in sequence under nitrogen atmosphere, and then 5 mL of anhydrous tetrahydrofuran is injected, and the reaction is stirred magnetically at 80°C for 24 hours;
[0046] Step 2: After 24 hours of reaction, the reaction was quenched with 3 mL of saturated ammonium chloride to terminate the reaction process. The quenched reaction solution was extracted with water and dichloromethane, and the lower organic phase was taken. Anhydrous magnesium sulfate was added to the organic phase, and the filtrate was concentrated by rotary evaporation after filtration, and then precipitated with petroleum ether to finally obtain the reaction product (the detection data of which is shown in Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 6 ). Figure 1 The NMR ( 1H NMR) spectrum, in which: the signal peak at 0.77-1.09ppm is attributed to -CH3 in the polymethyl methacrylate repeating unit, the signal peak at 1.73-2.10ppm is the H in -CH2- in the polymethyl methacrylate fragment, the peak at 3.60ppm is the proton peak signal of -OCH3, and the characteristic signal of phenyl proton at 7.80-6.90ppm; Figure 2 This is the Fourier infrared image (FT IR) of the polymer chain PMMA-M1-0.1 finally obtained in step 2 of Example 1, where 1740 cm -1 The C=O bond is at 1240cm. As the reaction proceeds, the carbonyl group in PMMA participates in the reaction and the signal gradually weakens. -1 The C-O-C bond is located at 1630 cm. As the proportion of reactants increases, the ester group participates in the reaction and falls off, and the signal gradually weakens. -1 The C=C bond of the benzene ring is located at the center. As the proportion of the reactants increases, the signal of the C=C bond of the benzene ring gradually increases. Figure 3 The gel permeation chromatogram (GPC) of the polymer chain PMMA-M1-0.1 finally obtained in step 2 of Example 1, wherein the M n =451800,M w / M n =1.43. Figure 4 This is the thermogravimetric analysis (TGA) of the polymer chain PMMA-M1-0.1 finally obtained in step 2 of Example 1, wherein the thermal decomposition temperature of PMMA-M1-0.1 is 294°C. Figure 6 This is the excitation and emission fluorescence spectrum of the polymer chain PMMA-M1-0.1 finally obtained in step 2 of Example 1, wherein it does not emit in solution but exhibits yellow fluorescence in the solid state, with the optimal emission wavelength being 565 nm and the optimal excitation wavelength being 449 nm.
[0047] Example 2
[0048] The reaction product described in Example 1 was subjected to a fluorescence test, and the test showed that the reaction product had yellow fluorescence, wherein the quantum yield could reach 80%.
[0049] Example 3
[0050] 50 mg of the reaction product described in Example 1 was mixed with polymethyl methacrylate (1 g) powder, dissolved in tetrahydrofuran, stirred with a magnetic stirrer for 1-2 hours, and poured into a mold after the tetrahydrofuran was volatilized to prepare a model with bright yellow fluorescence under a 365 nm ultraviolet lamp. Fig.10 shown.
[0051] Example 4
[0052] The reaction product described in Example 1 was prepared into a 0.2 mg / mL water / tetrahydrofuran mixed solution. When the water content was 0%, the solution had no obvious fluorescence intensity. When the water content was 90%, the solution changed from a clear liquid to turbid, and there was obvious yellow fluorescence under ultraviolet light observation, as shown in FIG. Figure 5 This phenomenon indicates that the reaction product has the effect of aggregation-induced emission.
[0053] Example 5
[0054] The reaction product described in Example 1 was dissolved in tetrahydrofuran, and the solution was evenly applied to the lens of a 460nm blue LED chip. After the tetrahydrofuran evaporated, a thin film was formed on the lens surface of the commercial blue LED chip. With a 6V power supply, the commercial blue LED chip can be successfully converted into a white LED. Fig.11 shown.
[0055] Example 6
[0056] According to the steps of Example 1, the mass ratio of dichlorodiphenylmethane:1,4-dibromobiphenyl:polymethyl methacrylate was changed to 0.3:0.3:1, and the rest of the preparation method was the same as Example 1.
[0057] Example 7
[0058] According to the steps of Example 1, the mass ratio of dichlorodiphenylmethane:1,4-dibromobiphenyl:polymethyl methacrylate was changed to 0.6:0.6:1, and the rest of the preparation method was the same as Example 1.
[0059] Example 8
[0060] According to the steps of Example 1, the mass ratio of dichlorodiphenylmethane:1,4-dibromobiphenyl:polymethyl methacrylate was changed to 1:1:1, and the rest of the preparation method was the same as Example 1.
[0061] Conclusion: It can be seen from the above figures and examples that the compounds of the present invention have bright fluorescence after modification. By changing the ratio of reactants, the compounds can produce different fluorescent colors. By utilizing the fluorescent properties of the modified compounds, the compounds can be used as fluorescent dyes. At the same time, by using "blue light technology" in combination with fluorescent materials, it can be used to prepare white light LDE wicks.
Claims
1. A method for upgrading and recycling acrylic acid ester polymers, characterized in that: By using a one-pot reaction and adjusting the feed ratio of reactants, a dihalogenated compound is reacted with an acrylic polymer. The resulting polymer can produce different fluorescent colors at the optimal excitation wavelength and has a high quantum yield, and can be used as a fluorescent dye.
2. The method for upgrading and recycling acrylic acid ester polymers according to claim 1, characterized in that: The polymer is reacted with polymethyl methacrylate as the main body, and a dihalogenated aromatic compound is introduced into the polymethyl methacrylate polymer chain through a Grignard reaction. By adjusting the ratio of the dihalogenated aromatic compound to polymethyl methacrylate, the generated polymer has different optimal fluorescence emission wavelengths and produces different fluorescence colors; the optimal fluorescence emission wavelength of the polymer is adjusted in the range of 400 nm-600 nm.
3. The method for upgrading and recycling acrylic acid ester polymers according to claim 1 or 2, characterized in that: The generated polymer is a multicolor fluorescent polymer material with adjustable quantum yield, and has high luminous efficiency, with a quantum yield of up to 80%.
4. The method for upgrading and recycling acrylic acid ester polymers according to claim 1 or 2, characterized in that: The generated polymer is a quantum yield-adjustable multicolor fluorescent polymer material, which has an aggregation-induced emission effect.
5. A method for upgrading and recycling acrylic acid ester polymers according to any one of claims 1 to 4, characterized in that: The generated polymer is a controllable multicolor fluorescent polymer material, and can be used as a fluorescent dye additive. Only a small amount of the multicolor fluorescent polymer material is added to achieve a good fluorescent effect.
6. A method for upgrading and recycling acrylic acid ester polymers according to any one of claims 1 to 4, characterized in that: The specific steps include: (1) Using a dihalogenated compound and a methyl acrylate polymer as starting materials, reacting with magnesium metal in a polymerization tube in an anhydrous tetrahydrofuran environment for 24 hours, wherein the dihalogenated compound is dibromobenzene, dichlorodiphenylmethane or 4,4-dibromobiphenyl, and the methyl acrylate polymer is polymethyl acrylate, polymethyl methacrylate or polybutyl acrylate; (2) After the reaction in step (1) is completed, the reaction is quenched with saturated ammonium chloride, extracted with water and dichloromethane, and then the product is precipitated with petroleum ether to obtain the final product.
7. The method for upgrading and recycling acrylic acid ester polymers according to claim 6, characterized in that: The specific steps are: (1) Using dichlorodiphenylmethane, 1,4-dibromobiphenyl and polymethyl methacrylate as starting materials, wherein the equivalent ratio of dichlorodiphenylmethane:1,4-dibromobiphenyl:polymethyl methacrylate is from 0.1:0.1:1 to 0.5:0.5:1, dichlorodiphenylmethane, 1,4-dibromobiphenyl, polymethyl methacrylate and magnesium are added into a polymerization tube in sequence, and reacted for 24 hours under magnetic stirring; (2) After step (1) reacts for 24 hours, the reaction is quenched with saturated ammonium chloride to terminate the reaction process; the quenched reaction is extracted with water and dichloromethane, the organic phase is dehydrated with anhydrous magnesium sulfate, the filtrate is filtered and concentrated by rotary evaporation, and then precipitated with petroleum ether to finally obtain a reaction product.
8. The method for upgrading and recycling acrylic acid ester polymers according to claim 6, characterized in that: The chemical reaction formula is: 。 9. Use of a polymer fluorescent material having high quantum yield and multicolor fluorescence prepared by the method according to any one of claims 1 to 8, characterized in that: The polymer fluorescent material has a high quantum yield, and the fluorescence of the polymer fluorescent material can be regulated by changing the ratio of reactants. When the polymer fluorescent material with a content of 5wt% is mixed with polymethyl methacrylate, a good fluorescence effect can be achieved, and the polymer fluorescent material can be used as a fluorescent dye and can be used in white light LED lamps as a wick material for white light LED lamps.