Polymer microsphere with high heat resistance and solvent resistance and preparation method thereof

Abstract

The invention discloses a polymer microsphere with high heat resistance and solvent resistance and a preparation method thereof. Cyanate ester resin, epoxy resin and bismaleimide resin are used as solvents and modifiers, allyl-terminated polyphenyl ether is dispersed in the system, after reaction, solvent treatment is adopted to obtain polymer microspheres, and the surfaces of the polymer microspheres contain groups with high reaction activity. Compared with existing similar polymer microspheres, the polymer microspheres have high heat resistance and solvent resistance, and can be used for catalysis of chemical reactions and selective adsorption and separation of molecules.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymer microspheres, and particularly relates to a high-heat-resistance and solvent-resistance polymer microsphere and a preparation method thereof. BACKGROUND

[0002] Polymer microspheres are small spherical particles composed of polymers. Based on size effect, surface functionalization characteristics and controllable release capacity, polymer microspheres have wide applications in the fields of biomedicine, oil exploitation, electronic information, chemical energy storage and chromatographic separation, such as in the fields of drug delivery, coatings, catalyst carriers and the like. However, since they belong to high polymer materials, they are usually prone to decomposition at high temperatures, which will limit their applications in high-temperature environments. In addition, polymers will swell or dissolve in organic solvents, leading to collapse of the microsphere structure and affecting the application effect. Therefore, improving the heat resistance and solvent resistance of polymer microspheres has positive significance for expanding their applications in harsh environments. SUMMARY

[0003] In view of the shortcomings of poor heat resistance and solvent resistance of the current polymer microspheres, the present application proposes to use cyanate ester resin, bismaleimide and epoxy resin and heat-resistant polyphenyl ether (PPE) oligomer as raw materials based on a high-heat-resistance thermosetting resin system, use the thermosetting resin system as a solvent and a modifier respectively, and prepare high-heat-resistance and solvent-resistance thermosetting / thermoplastic polymer microspheres based on the reaction of thermosetting and thermoplastic components.

[0004] To achieve the above-mentioned purposes, the technical solution adopted by the present application is as follows: A preparation method of high-heat-resistance and solvent-resistance polymer microspheres comprises the following steps: adding a polyphenyl ether solution into a mixed solution of cyanate ester resin, epoxy resin and bismaleimide resin, and obtaining high-heat-resistance and solvent-resistance polymer microspheres after reaction.

[0005] In the present application, the mass ratio of cyanate ester resin, epoxy resin, bismaleimide resin and polyphenyl ether is 4:1:(1-3):(0.5-2).

[0006] In the present application, the cyanate ester resin, epoxy resin and bismaleimide resin are heated to a transparent liquid at 140-160°C to obtain a mixed solution of cyanate ester resin, epoxy resin and bismaleimide resin.

[0007] In the present application, the mass concentration of the polyphenyl ether solution is 10-20%, and the solvent includes benzene solvents.

[0008] In the present application, the reaction temperature is 130-200°C, and the reaction time is 2-6h. After the reaction is completed, the obtained polymer microspheres not only have excellent heat resistance and mechanical properties, but also have excellent solvent resistance.

[0009] In the present application, the cyanate ester resin is one or mixture of bisphenol A type cyanate ester and phenolic type cyanate ester; the epoxy resin includes one or several of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin and linear aliphatic epoxy compound; the bismaleimide resin is N,N'-(4,4'-methylene diphenyl) bismaleimide and its derivatives; and the polyphenyl ether is allyl-terminated low molecular weight polyphenyl ether.

[0010] The application discloses application of the high-heat-resistance and solvent-resistance polymer microspheres in preparation of microsphere materials.

[0011] The application discloses application of the high-heat-resistance and solvent-resistance polymer microspheres in preparation of functional polymer materials.

[0012] The application discloses a high-heat-resistance and solvent-resistance material, which comprises the high-heat-resistance and solvent-resistance polymer microspheres.

[0013] The cyanate ester resin, the epoxy resin and the bismaleimide resin are heated to a transparent liquid at 140-160 DEG C in the present application; the polyphenyl ether (PPE) with terminal allyl groups is dissolved in a toluene solution (the mass concentration of the PPE is 10-20%); then the polyphenyl ether toluene solution is added into the mixed liquid under conventional stirring conditions, and the reaction is carried out at 130 DEG C-200 DEG C for 2-6 h; then the product is washed, and the polymer microspheres can be obtained. The prepared polymer microspheres have excellent heat performance and solvent resistance. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 The DSC curve of the cyanate ester resin, the epoxy resin, the bismaleimide resin and the PPE component mixture.

[0015] Figure 2 The optical microscope graph of the sample of example 1 and the samples of comparative examples 1-1 to 1-4.

[0016] Figure 3 The infrared (FTIR) spectrum of the sample of example 1 and the sample (PPE) of comparative example 1-1.

[0017] Figure 4 The appearance graph of the sample 1 of the solvent treatment example and the samples 1 to 1-4 of the comparative examples after 24 h and the solution picture (the upper right corner) after 24 h of solvent immersion. DETAILED DESCRIPTION

[0018] The application discloses a high-heat-resistance and solvent-resistance polymer microsphere and a preparation method thereof. (1) adding cyanate ester resin, epoxy resin and bismaleimide resin into a reaction container, and heating to a transparent liquid at 140-160 DEG C; (2) Dissolve the end-allyl polyphenyl ether (PPE) in toluene solution (PPE mass concentration of 10-20%) at 80°C; (3) Under stirring, add the product of step (2) into the product of step (1) and react at 130-200°C for 2-6h, then cool to 100°C, and wash the product with toluene / ethanol / acetone to obtain the polymer microspheres; The mass ratio of the cyanate ester resin (CE), the epoxy resin (EP) and the bismaleimide resin (BMI) to PPE is 4:1: (1-3): (0.5-2).

[0019] The cyanate ester resin is one or a mixture of bisphenol A type cyanate ester and phenolic type cyanate ester. The epoxy resin includes one or several of glycidyl ether type epoxy resin (such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenolic type epoxy resin), glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin and linear aliphatic epoxy compound. The bismaleimide resin is N,N'-(4,4'-methylene diphenyl) bismaleimide and its derivatives. The PPE is low molecular weight polyphenyl ether (number average molecular weight of 1600-2800) with different allyl end groups.

[0020] The polymer microspheres prepared by the method have excellent thermal performance and solvent resistance.

[0021] The technical progress of the present application is illustrated by specific experiments below. The raw materials used are existing products, the specific preparation operation and performance test are conventional techniques; the polyphenyl ether is end-allyl polyphenyl ether (PPE, number average molecular weight of 2300).

[0022] Example 1 (1) Add bisphenol A cyanate ester resin (BADCy, molecular weight of 278.31), bisphenol A type epoxy resin (trade name: E51) and N,N'-(4,4'-methylene diphenyl) bismaleimide resin into a reaction container, heat at 150°C for 20 minutes to obtain a transparent liquid; (2) Dissolve the end-allyl polyphenyl ether (PPE, number average molecular weight of 2300) in toluene solution (PPE mass concentration of 10%) at 80°C; (3) Under stirring, add the product of step (2) into the product of step (1) and react at 130°C for 6h, then naturally cool to 100°C, then wash the product with toluene once, ethanol three times and acetone three times to obtain the polymer microspheres.

[0023] The mass ratio of cyanate ester resin (CE): epoxy resin (EP): bismaleimide resin (BMI): PPE is 4:1:1:0.5.

[0024] Comparative Example 1-1 At 80°C, allyl-terminated polyphenylene ether (PPE, number average molecular weight 2300) was dissolved in toluene, and then an ethanol solution was added to precipitate PPE. The product was washed three times with ethanol and three times with acetone to obtain PPE particles.

[0025] Figure 1 These are the DSC curves of the cyanate ester resin (CE), epoxy resin (EP), bismaleimide resin (BMI), and PPE and their mixtures in this embodiment. Figure 1 It can be seen that CE can self-polymerize at approximately 312°C, BMI at approximately 249°C, and EP is unlikely to self-polymerize before 350°C. The BMI / PPE mixture can react at 211°C, prior to the self-polymerization of BMI, followed by the polymerization reactions of CE / BMI and CE / PPE. The presence of EP favors the polymerization reactions of CE and BMI. These phenomena indicate that BMI and CE can react sequentially under controlled temperature conditions. The reaction temperatures of CE / BMI / EP and CE / BMI / EP / PPE are both lower than those of CE / BMI and CE / PPE. Due to the mutual reactions among CE, BMI, EP, and PPE, the resulting polymer microspheres are multi-component copolymers.

[0026] Figure 2 This is an optical microscope image of the sample from Example 1. From... Figure 2 It can be seen that the particle size of the sample in Example 1 is approximately 10 μm. Compared to Comparative Example 1-1, the sample in Example 1 exhibits good dispersibility. Figure 3 These are the Fourier Transform Infrared (FTIR) spectra of the sample from Example 1 and the sample from Comparative Example 1-1 (i.e., the PPE sample). From... Figure 3 It can be seen that, compared with Comparative Examples 1-1, the sample of Example 1 clearly showed -OH (3400-3900 cm⁻¹). -1 -OC≡N(2240cm) -1 C=O (1716cm) -1 ), C=N bond within the triazine ring (1560cm) -1 The characteristic absorption peaks indicate that PPE was grafted with BMI, CE, and CE / BMI, CE / EP, and CE / EP / BMI components, and the synthesized microspheres have a rich functional group structure.

[0027] Comparative Examples 1-2 (1) In a reaction vessel, add bisphenol A cyanate ester resin (BADCy, molecular weight 278.31) and bisphenol A type epoxy resin (grade: E51), heat at 150°C for 20 minutes to obtain a transparent liquid; (2) At 80°C, dissolve the end-allyl polyphenyl ether (PPE, number average molecular weight 2300) in a toluene solution (PPE mass concentration 10%); (3) Under stirring conditions, add the product of step (2) to the product of step (1), react at 130°C for 6h, then naturally cool to 100°C, then sequentially wash the product once with toluene, 3 times with ethanol, and 3 times with acetone to obtain the polymer microspheres.

[0028] The mass ratio of cyanate ester resin (CE): epoxy resin (EP): PPE is 4:1:0.5.

[0029] Comparative Examples 1-3 (1) In a reaction vessel, add bisphenol A cyanate ester resin (BADCy, molecular weight 278.31) and N,N'-(4,4'-methylene diphenyl) bismaleimide resin, heat at 150°C for 30 minutes to obtain a transparent liquid; (2) At 80°C, dissolve the end-allyl polyphenyl ether (PPE, number average molecular weight 2300) in a toluene solution (PPE mass concentration 10%); (3) Under stirring conditions, add the product of step (2) to the product of step (1), react at 130°C for 6h, then naturally cool to 100°C, then sequentially wash the product once with toluene, 3 times with ethanol, and 3 times with acetone to obtain the polymer microspheres.

[0030] The mass ratio of cyanate ester resin (CE): bismaleimide resin (BMI): PPE is 4:1:0.5.

[0031] Comparative Examples 1-4 (1) In a reaction vessel, add bisphenol A type epoxy resin (grade: E51) and N,N'-(4,4'-methylene diphenyl) bismaleimide resin, heat at 150°C for 40 minutes; (2) At 80°C, dissolve the end-allyl polyphenyl ether (PPE, number average molecular weight 2300) in a toluene solution (PPE mass concentration 10%); (3) Under stirring conditions, add the product of step (2) to the product of step (1), react at 130°C for 6h, then naturally cool to 100°C, then sequentially wash the product once with toluene, 3 times with ethanol, and 3 times with acetone to obtain the polymer microspheres.

[0032] Epoxy resin (EP): Bis-maleimide resin (BMI): PPE mass ratio is 1:1:0.5.

[0033] Table 1 is the performance data of the sample of Example 1 and the samples of Comparative Examples 1-1 to 1-4. Figure 4 is the morphology of the PPE sample after 24 hours of solvent treatment and the picture of the solution after 24 hours of solvent immersion (upper right corner) of the sample 1 of the solvent treatment example and the sample of Comparative Example 1-1. The average particle size of the sample of Example 1 is 15 μm, the initial thermal decomposition temperature T di (thermal decomposition temperature of 5 wt% weight loss) is 385°C, which is obviously 57°C higher than PPE, showing excellent heat resistance. The sample of Example 1 does not dissolve in ethanol, acetone, N,N-dimethylacetamide DMF, water and toluene solvents after 24 hours of immersion, and the mass change rate is not more than ±0.5%; the sample of Comparative Example 1-1 PPE can be completely dissolved in toluene, and the samples of Comparative Examples 1-2 to 1-4 have different degrees of dissolution in organic solvents; unexpectedly, the sample of Example 1 has more excellent solvent resistance.

[0034] Table 1 is the performance data of the sample of Example 1 and the sample PPE of Comparative Example 1

[0035] The average particle size analysis of the sample is based on the microscopic image software analysis and processing.

[0036] The mass change of the microspheres in the solvent (%) = [(mass of the sample after solvent treatment - initial mass of the sample) / initial mass of the sample] x 100%. The mass of the sample after solvent treatment is obtained by weighing the sample after the solvent on the surface of the microspheres is absorbed by filter paper.

[0037] The initial thermal decomposition temperature T di is obtained by TGA analysis, the heating rate is 10°C / min, and the nitrogen flow rate is 40 ml / min.

[0038] Example 2 (1) Bisphenol A cyanate resin (BADCy, molecular weight 278.31), bisphenol A type epoxy resin (trade name: E51) and N,N'-(4,4'-methylene diphenyl) bis-maleimide resin were added to a reaction vessel, heated at 140°C for 20 minutes to obtain a transparent liquid; (2) At 80°C, the end-allyl polyphenyl ether (PPE, number average molecular weight 2300) was dissolved in toluene solution (PPE mass concentration was 10%); (3) Under stirring, the product of step (2) was added into the product of step (1), and reacted at 150°C for 4h, and then naturally cooled to 100°C. The product was washed once with toluene, 3 times with ethanol, and 3 times with acetone, to obtain the polymer microspheres.

[0039] The mass ratio of cyanate ester resin (CE) : epoxy resin (EP) : bismaleimide resin (BMI) : PPE was 4:1:1:1.

[0040] Table 2 is the performance data of the sample of Example 2. The average particle size of the sample of Example 2 was 18 μm, the initial thermal decomposition temperature Tdi (thermal decomposition temperature at 5 wt% weight loss) was 389°C, showing excellent heat resistance. The PPE can be completely dissolved in toluene, and the mass change rate of the sample of Example 2 immersed in ethanol, acetone, DMF, water and toluene solvents for 24h was not more than ±0.4%, which means that the sample of Example 2 has excellent solvent resistance.

[0041] Table 2 is the performance data of the sample of Example 2. The average particle size of the sample of Example 2 was 18 μm, the initial thermal decomposition temperature Tdi (thermal decomposition temperature at 5 wt% weight loss) was 389°C, showing excellent heat resistance. The PPE can be completely dissolved in toluene, and the mass change rate of the sample of Example 2 immersed in ethanol, acetone, DMF, water and toluene solvents for 24h was not more than ±0.4%, which means that the sample of Example 2 has excellent solvent resistance.

[0042] Example 3 (1) Bisphenol A cyanate ester resin (BADCy, molecular weight 278.31), bisphenol A type epoxy resin (trade name: E51) and N,N'-(4,4'-methylene diphenyl) bismaleimide resin were added into a reaction vessel, heated at 160°C for 15 minutes to obtain a transparent liquid; (2) At 80°C, the end-allyl polyphenyl ether (PPE, number average molecular weight 2300) was dissolved in toluene solution (PPE mass concentration 15%); (3) Under stirring, the product of step (2) was added into the product of step (1), and reacted at 160°C for 4h, and then naturally cooled to 100°C. The product was washed once with toluene, 3 times with ethanol, and 3 times with acetone, to obtain the polymer microspheres.

[0043] The mass ratio of cyanate ester resin (CE) : epoxy resin (EP) : bismaleimide resin (BMI) : PPE was 4:1:1:2.

[0044] Table 3 is the performance data of the sample of Example 3. The average particle size of the sample of Example 3 was 18 μm, the initial thermal decomposition temperature T di (thermal decomposition temperature at 5 wt% weight loss) was 392°C, showing excellent heat resistance. The PPE can be completely dissolved in toluene, and the mass change rate of the sample of Example 3 immersed in ethanol, acetone, DMF, water and toluene solvents for 24h was not more than ±0.5%, which means that the sample of Example 3 has excellent solvent resistance.

[0045] Table 3 Performance data of the sample of Example 3 and the sample of Comparative Example 1-1 PPE

[0046] Example 4 (1) Bisphenol A cyanate ester resin (BADCy, molecular weight 278.31), bisphenol A type epoxy resin (trade name: E51) and N,N'-(4,4'-methylene diphenyl) bismaleimide resin were added into a reaction vessel and heated at 150°C for 15 minutes to obtain a transparent liquid; (2) At 80°C, end-allyl polyphenyl ether (PPE, number average molecular weight 2300) was dissolved in toluene solution (PPE mass concentration 20%); (3) The product of step (2) was added to the product of step (1) under stirring, and reacted at 200°C for 2h, then naturally cooled to 100°C. The product was washed once with toluene, 3 times with ethanol and 3 times with acetone to obtain the polymer microspheres.

[0047] The mass ratio of cyanate ester resin (CE): epoxy resin (EP): bismaleimide resin (BMI): PPE was 4:1:3:2.

[0048] Table 4 is the performance data of the sample of Example 4. The average particle size of the sample of Example 4 is 5 μm, the initial thermal decomposition temperature T di (the thermal decomposition temperature at which 5wt% weight loss occurs) is 395°C, showing excellent heat resistance. The PPE can be completely dissolved in toluene, and the mass change rate of the sample of Example 4 immersed in ethanol, acetone, DMF, water and toluene solvents for 24h is not more than ±0.3%, which means that the sample of Example 3 has excellent solvent resistance.

[0049] Table 4 Performance data of the sample of Example 4 and the sample of Comparative Example 1-1 PPE

Claims

1. A method for preparing a high heat and solvent resistant polymeric microsphere, characterized in that, The process includes the following steps: adding a polyphenylene ether solution to a mixture of cyanate ester resin, epoxy resin, and bismaleimide resin; after reaction, highly heat- and solvent-resistant polymer microspheres are obtained.

2. The method for preparing high heat- and solvent-resistant polymer microspheres according to claim 1, characterized in that, The mass ratio of cyanate ester resin, epoxy resin, bismaleimide resin, and polyphenylene ether is 4:1:(1~3):(0.5~2).

3. The method for preparing high heat- and solvent-resistant polymer microspheres according to claim 1, characterized in that, Cyanate ester resin, epoxy resin and bismaleimide resin are heated to 140-160°C to liquid state to obtain a mixture of cyanate ester resin, epoxy resin and bismaleimide resin.

4. The method for preparing high heat- and solvent-resistant polymer microspheres according to claim 1, characterized in that, The mass concentration of the polyphenylene ether solution is 10-20%.

5. The method for preparing high heat- and solvent-resistant polymer microspheres according to claim 1, characterized in that, The reaction temperature is 130℃-200℃, and the reaction time is 2-6 hours.

6. The method for preparing high heat- and solvent-resistant polymer microspheres according to claim 1, characterized in that, The cyanate ester resin is one or a mixture of bisphenol A type cyanate ester and phenolic type cyanate ester; the epoxy resin includes one or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, and linear aliphatic epoxy compound; the bismaleimide resin is N,N'-(4,4'-methylenediphenyl)bismaleimide and its derivatives; the polyphenylene ether is allyl-terminated low molecular weight polyphenylene ether.

7. The high heat-resistant and solvent-resistant polymer microspheres prepared by the method described in claim 1.

8. The application of the high heat- and solvent-resistant polymer microspheres according to claim 7 in the preparation of microsphere materials.

9. The application of the high heat- and solvent-resistant polymer microspheres of claim 7 in the preparation of functional polymer materials.

10. A high heat and solvent resistant material, characterized in that, Including the high heat- and solvent-resistant polymer microspheres as described in claim 7.

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