CN114539523B - Soluble and fusible copolyimide superfine powder and preparation method thereof - Google Patents
Soluble and fusible copolyimide superfine powder and preparation method thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a soluble and fusible copolyimide ultrafine powder and a preparation method thereof, wherein the soluble and fusible copolyimide ultrafine powder is prepared from diamine monomers APABI and m-PDA as well as dianhydride monomers BPADA and PMDA, and the preparation method comprises the following steps: (1) reacting diamine monomer and dianhydride monomer in polar solvent at room temperature to obtain polyamic acid solution; (2) adding a poor solvent into the polyamic acid solution obtained in the step (1) and heating to reflux, then evaporating the poor solvent and cooling, then adding a precipitating agent and heating again, and finally cooling until powder is not precipitated and filtered; (3) washing the filter cake obtained in the step (2) twice by adopting a washing solvent, and filtering; (4) and (3) sequentially carrying out vacuum drying and high-temperature blast drying on the filter cake obtained in the step (3) to obtain the soluble and fusible copolyimide ultrafine powder. The grain diameter of the polyimide superfine powder D50 is less than or equal to 20 mu m, and the grain diameter of the D90 is less than or equal to 40 mu m; but also has better thermal property and mechanical property.
Description
Technical Field
The invention belongs to the technical field of polyimide, and in particular relates to soluble and fusible copolymerized polyimide ultrafine powder and a preparation method thereof.
Background
Thermoplastic polyimide is a high-temperature resistant high-molecular material with excellent comprehensive performance, and has excellent heat resistance, mechanical property, dielectric property, flame retardance and the like. In the early stage, most thermoplastic polyimide has the characteristic of indissolvable and infusible property, influences the processing performance of the thermoplastic polyimide and limits the further wide application of the thermoplastic polyimide.
The soluble thermoplastic polyimide has good solubility and toughness, and has good application prospect in the field of modification of high-performance resin and composite materials thereof, however, the existing soluble thermoplastic polyimide has the following problems:
(1) To obtain better solubility properties, it is often necessary to introduce large side groups or non-coplanar structures, which can destroy the regularity of the molecular chains and thus lead to poor mechanical properties.
(2) Polyimide structures with better solvent properties have more flexible groups, resulting in undesirable thermal properties, including lower glass transition temperatures and higher coefficients of linear thermal expansion.
(3) The particle size is larger, and because of the better solubility, special technology is needed to prepare the ultrafine powder with smaller particle size.
Chinese patent document CN112795011a discloses a soluble thermoplastic polyimide ultrafine powder and a preparation method thereof, which is prepared from equimolar bisphenol a type diether dianhydride (BPADA) and special diamine monomer 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindan (PIDA) by adopting special polyamic acid particles. D50 particles of polyimide superfine powderThe diameter is 10-20 mu m, and the D90 particle size is 30-40 mu m; the impact strength without gaps can reach 200kJ/m 2 The material has better mechanical properties; however, the glass transition temperature is only about 250℃and the thermal properties are poor.
Chinese patent document CN113265048A discloses a polyimide superfine powder for mould pressing and a preparation method thereof, which is prepared from a conventional dianhydride monomer and a special diamine monomer 1H,1' H- (2, 2' -bisbenzimidazole) -5,5' -diamine [ BBIDA ] by adopting a special stirring process. The D50 grain diameter of the polyimide superfine powder is 10-20 mu m, and the D90 grain diameter is 30-40 mu m; the glass transition temperature can reach more than 400 ℃, the linear thermal expansion Coefficient (CTE) can reach less than 10ppm/K, and the thermal property is better; however, the unnotched impact strength is only 100 to 150kJ/m 2 The mechanical properties are poor.
Chinese patent document CN108047445a discloses a high temperature resistant thermoplastic polyimide ultra-fine powder and a preparation method thereof, which is prepared from equimolar bisphenol a type diether dianhydride [ BPADA ] and 2- (3-aminophenyl) -5-aminobenzimidazole [ APABI ] by a special gel precipitation method. The D50 grain diameter of the polyimide superfine powder is 10-20 mu m, and the D90 grain diameter is 30-70 mu m; the notched impact strength was 240kJ/m 2 About, have better mechanical properties; the glass transition temperature is 295-320 ℃, and the thermal property is good. However, the gel precipitation method adopted in the document has higher process requirements, is complicated to operate and is difficult to control; on the other hand, the gel precipitation method has higher requirements on the monomer structure, and polyimide superfine powder can not be prepared by adopting the method in any structure.
From the above documents, it is known that: polyimide superfine powder with good thermal property and mechanical property is prepared by combining matched technology on the basis of the existing conventional dianhydride and conventional diamine, and is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to solve the problems and provide the soluble and fusible copolyimide ultrafine powder which has better thermal property and mechanical property, has lower process requirements, is simple and convenient to operate and easy to control, is environment-friendly and is suitable for industrial mass production, and the preparation method thereof.
The technical scheme for realizing the aim of the invention is as follows: a soluble and fusible copolyimide superfine powder is prepared from diamine monomer and dianhydride monomer; wherein: diamine monomers are 2- (4-aminophenyl) -5-aminobenzimidazole [ hereinafter abbreviated as APABI ] and m-phenylenediamine [ hereinafter abbreviated as m-PDA ], and dianhydride monomers are bisphenol A type diether dianhydride [ hereinafter abbreviated as BPADA ] and pyromellitic anhydride [ hereinafter abbreviated as PMDA ]; the particle size satisfies the following: the particle diameter of D50 is 10-20 mu m, and the particle diameter of D90 is 30-40 mu m.
In the diamine monomer, the molar ratio of APABI is more than 85%, preferably 85% -95%.
In the dianhydride monomer, the molar ratio of BPADA is more than 85%, preferably 85% -95%.
The molar ratio of the diamine monomer to the dianhydride monomer is 1:0.95-1:1.05.
The preparation method of the soluble and fusible copolymerized polyimide ultrafine powder comprises the following steps:
(1) reacting diamine monomer and dianhydride monomer in polar solvent at room temperature to obtain polyamic acid solution;
(2) adding a poor solvent into the polyamic acid solution obtained in the step (1), heating to reflux reaction, heating to evaporate the poor solvent after the viscosity of a reaction system is obviously increased, slowly cooling to a certain temperature, quickly adding a precipitation agent under the temperature and stirring state, slowly heating until the reaction system is clear, stopping heating, naturally cooling until powder is not precipitated, and filtering; the certain temperature is 5-10 ℃ below the boiling point temperature of the precipitating agent;
(3) washing the filter cake obtained in the step (2) twice by adopting a washing solvent, and filtering (namely, washing, filtering, washing and filtering);
(4) and (3) sequentially carrying out vacuum drying and high-temperature blast drying on the filter cake obtained in the step (3) to obtain the soluble and fusible copolyimide ultrafine powder.
The polar solvent in the step (1) is one or more (including two) of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO).
The polar solvent in the step (1) is used in an amount of 2 to 6 times the total weight of the diamine monomer and the dianhydride monomer.
The poor solvent in the step (2) is toluene or xylene.
The weight ratio of the poor solvent in the step (2) to the polar solvent in the step (1) is 1:2-1:6.
The precipitating agent in the step (2) is one or more (including two) of methanol, ethanol, acetone and butanone, preferably ethanol or acetone.
The weight ratio of the precipitating agent in the above step (2) to the polar solvent in the above step (1) is 0.7:1 to 1.2:1, preferably 0.8:1 to 0.85:1.
The washing solvent in the step (3) is the same as the precipitant in the step S2.
The dosage of the washing solvent in the step (3) is 2.5-5 times of the total weight of the diamine monomer and the dianhydride monomer.
The temperature of the vacuum drying in the step (4) is 80-120 ℃ and the time is 3-6 h.
In the step (4), the high-temperature blast drying adopts temperature programming: 160 ℃/1h, 230 ℃/1h, 250 ℃/2h.
The invention has the positive effects that:
(1) The polyimide superfine powder has better thermal property and mechanical property, the glass transition temperature is more than or equal to 330 ℃, the linear thermal expansion coefficient is less than or equal to 30ppm/k, and the unnotched impact strength is more than or equal to 200kJ/m 2 。
(2) The preparation method of polyimide superfine powder adopts a method of adding a saturated amount of precipitant to naturally cool the powder at a certain temperature in the powder forming stage, thereby achieving the effect of separating out powder.
(3) The method can effectively separate and recycle various solvents, is environment-friendly, reduces the production cost and is suitable for industrial metaplasia.
Detailed Description
Example 1
The preparation method of the polyimide superfine powder of the embodiment comprises the following steps:
(1) 20.18g (0.09 mol) of APABI, 1.08g (0.01 mol) of m-PDA and 275.11g of NMP are added to a reactor equipped with a stirrer and a nitrogen protection device at room temperature, and after stirring until the diamine monomer is completely dissolved, 44.24g (0.085 mol) of BPADA and 3.27g (0.015 mol) of PMDA are added, and the stirring reaction is continued for 1 to 2 hours to obtain a polyamic acid solution.
(2) Adding 68.77g of toluene into the polyamic acid solution obtained in the step (1), heating to reflux reaction, heating to evaporate the toluene after the viscosity of a reaction system is obviously increased, slowly cooling to 70+/-2 ℃, rapidly adding 228.34g of ethanol, slowly heating until the reaction system is clear after the addition, stopping heating, naturally cooling, continuously precipitating powder, continuously stirring until the powder is not precipitated, and filtering for the first time.
(3) Adding the filter cake obtained in the step (2) in 260.71g of ethanol, stirring for 4h, performing secondary filtration, adding the filter cake obtained in the secondary filtration in 260.71g of ethanol, stirring for 4h, and performing tertiary filtration.
(4) And (3) vacuum drying the filter cake obtained in the third filtering step at 100 ℃ for 4 hours, and then carrying out high-temperature blast drying according to the following procedures: 160 ℃/1h, 230 ℃/1h, 250 ℃/2h, and obtaining polyimide ultrafine powder.
Example 2 to example 4
The preparation method of the polyimide micropowder of each example was substantially the same as in example 1, except for table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Diamine monomer Body | APABI 【0.090mol】+m- PDA【0.010mol】 | APABI 【0.085mol】+m- PDA【0.015mol】 | APABI 【0.090mol】+m- PDA【0.010mol】 | APABI 【0.085mol】+m- PDA【0.015mol】 |
| Dianhydride monomer Body | BPADA 【0.085mol】+ PMDA【0.015mol】 | BPADA 【0.090mol】+ PMDA【0.010mol】 | BPADA 【0.090mol】+ PMDA【0.010mol】 | BPADA 【0.085mol】+ PMDA【0.015mol】 |
| Step (1) Middle polarity Solvent(s) | 275.11g of NMP | 278.83g of DMAC | 281.16g of NMP | 272.79g of NMP |
| Step (2) Poor (in) Solvent(s) | 68.77g of toluene | 69.70g of xylene | 70.28g of toluene | 68.19g toluene |
| Step (2) Middle precipitation Agent | 228.34g of ethanol | 228.64g of ethanol | 236.17g of acetone | 220.96g of ethanol |
| Step (3) Middle washing Solvent(s) | 260.71g+ 260.71g of ethanol | 264.44g+ 264.44g of ethanol | 266.76g+ 266.76g of acetone | 258.39g+ 258.39g of ethanol |
Comparative example 1
The preparation method of the polyimide powder of the comparative example is as follows:
(1) 22.43g (0.1 mol) of APABI and 297.90g of NMP are added into a reactor equipped with a stirrer and a nitrogen protection device at room temperature, stirred until the APABI is completely dissolved, 52.05g (0.1 mol) of BPADA is added, and the stirring reaction is continued for 1-2 hours, to obtain a polyamic acid solution.
(2) And (2) adding 74.48g of toluene into the polyamic acid solution obtained in the step (1), heating to reflux reaction, heating to evaporate the toluene after the viscosity of a reaction system is obviously increased, slowly cooling to room temperature, pouring into a high-speed triturator containing 566.99g of deionized water, precipitating and triturating, and then performing first filtration.
(3) Adding the filter cake obtained in the step (2) in 283.50g of deionized water, stirring for 4h, performing secondary filtration, adding the filter cake obtained in the secondary filtration in 283.50g of deionized water, stirring for 4h, and performing tertiary filtration.
(4) And (3) vacuum drying the filter cake obtained in the third filtering step at 100 ℃ for 4 hours, and then carrying out high-temperature blast drying according to the following procedures: 160 ℃/1h, 230 ℃/1h, 250 ℃/2h, and obtaining the polyimide powder.
Comparative example 2
The preparation method of the polyimide powder of the comparative example is as follows:
(1) 10.81g (0.1 mol) of m-PDA and 130.50g of DMAc were charged into a reactor equipped with a stirrer and a nitrogen protection device at room temperature, stirred until the m-PDA was completely dissolved, 21.81g (0.1 mol) of PMDA was added, and the reaction was continued with stirring for 1 to 2 hours to obtain a polyamic acid solution.
(2) Adding 32.62g of dimethylbenzene into the polyamic acid solution obtained in the step (1), heating to reflux reaction, continuously precipitating powder from a reaction system in the reflux reaction process, heating to evaporate toluene after the powder is not precipitated, cooling to room temperature, and performing first filtration.
(3) Adding the filter cake obtained in the step (2) in 116.10g of ethanol, stirring for 4h, performing secondary filtration, adding the filter cake obtained in the secondary filtration in 116.10g of ethanol, stirring for 4h, and performing tertiary filtration.
(4) And (3) vacuum drying the filter cake obtained in the third filtering step at 100 ℃ for 4 hours, and then carrying out high-temperature blast drying according to the following procedures: 160 ℃/1h, 230 ℃/1h, 250 ℃/2h, and obtaining the polyimide powder.
Test example 1
The D50 particle diameter and the D90 particle diameter of the polyimide powders prepared in each example and each comparative example were measured by a laser particle size analysis method, and the results are shown in table 2.
Test example 2
The polyimide powders prepared in each example and each comparative example were hot-pressed at a pressure of 8MPa and a temperature of 360 ℃ for 4 hours, respectively, to prepare polyimide small-sized plates.
The polyimide panels were tested for their properties and the results are shown in Table 2. Wherein:
the glass transition temperature test method comprises the following steps: a dynamic thermo-mechanical analysis (DMA) instrument of the American TA company Q800 is adopted, the temperature range is 100-600 ℃, the temperature rising rate is 5 ℃/min, and the nitrogen atmosphere is adopted.
The test method of the linear thermal expansion coefficient comprises the following steps: a thermo-mechanical analysis (TMA) apparatus, Q400, from TA company, was used, the temperature was 100-600deg.C, the heating rate was 5deg.C/min, and the nitrogen atmosphere.
The method for testing the unnotched impact strength comprises the following steps: determination of impact Property of Plastic simply-supported Beam according to national Standard GB/T1043.1-2008 part 1: non-instrumented impact testing.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| D50 particle diameter (μm) | 18.4 | 19.2 | 17.9 | 17.8 | 33.5 | 34.2 |
| D90 particle diameter (μm) | 39.6 | 38.3 | 38.7 | 36.9 | 70.1 | 67.9 |
| Glass transition temperature (. Degree. C.) | 333 | 335 | 330 | 338 | 310 | 358 |
| Coefficient of linear thermal expansion (ppm/K) | 28.5 | 27.2 | 29.1 | 26.4 | 47.3 | 18.7 |
| Notched impact strength (kJ/m) 2 ） | 221 | 217 | 224 | 206 | 183 | 18 |
As can be seen from table 2:
(1) The polyimide powder of comparative example 1 had good mechanical properties, but had poor thermal properties; the polyimide powder of comparative example 2 had good thermal properties, but poor mechanical properties; and the particle diameters of the two polyimide powders are relatively large.
(2) The soluble and fusible copolymerized polyimide superfine powder has better mechanical property and thermal property, and can be applied to occasions with higher temperature resistance level requirements.
Claims (7)
1. A soluble and fusible copolyimide superfine powder is prepared from diamine monomer and dianhydride monomer; the method is characterized in that: the diamine monomer is 2- (4-aminophenyl) -5-aminobenzimidazole and m-phenylenediamine, and the dianhydride monomer is bisphenol A type diether dianhydride and pyromellitic anhydride; the particle size satisfies the following: the particle diameter of D50 is 10-20 mu m, and the particle diameter of D90 is 30-40 mu m;
the molar ratio of the diamine monomer to the dianhydride monomer is 1:0.95-1:1.05; in the diamine monomer, the molar ratio of the 2- (4-aminophenyl) -5-aminobenzimidazole is 85% -95%; in the dianhydride monomer, the mole ratio of bisphenol A type diether dianhydride is 85% -95%;
the preparation method of the soluble and fusible copolymerized polyimide ultrafine powder comprises the following steps:
(1) reacting diamine monomer and dianhydride monomer in polar solvent at room temperature to obtain polyamic acid solution;
(2) adding a poor solvent into the polyamic acid solution obtained in the step (1), heating to reflux reaction, heating to evaporate the poor solvent after the viscosity of a reaction system is obviously increased, slowly cooling to a certain temperature, quickly adding a precipitation agent under the temperature and stirring state, slowly heating until the reaction system is clear, stopping heating, naturally cooling until powder is not precipitated, and filtering; the certain temperature is 5-10 ℃ below the boiling point temperature of the precipitating agent;
(3) washing the filter cake obtained in the step (2) by adopting a washing solvent, filtering, washing and filtering;
(4) sequentially carrying out vacuum drying and high-temperature blast drying on the filter cake obtained in the step (3) to obtain soluble and fusible copolyimide ultrafine powder;
in the step (2), the precipitating agent is one or more of methanol, ethanol, acetone and butanone; the weight ratio of the precipitating agent to the polar solvent in the step (1) is 0.7:1-1.2:1.
2. A method for preparing the soluble and fusible copolyimide ultra-fine powder as claimed in claim 1, comprising the steps of:
(1) reacting diamine monomer and dianhydride monomer in polar solvent at room temperature to obtain polyamic acid solution;
(2) adding a poor solvent into the polyamic acid solution obtained in the step (1), heating to reflux reaction, heating to evaporate the poor solvent after the viscosity of a reaction system is obviously increased, slowly cooling to a certain temperature, quickly adding a precipitation agent under the temperature and stirring state, slowly heating until the reaction system is clear, stopping heating, naturally cooling until powder is not precipitated, and filtering; the certain temperature is 5-10 ℃ below the boiling point temperature of the precipitating agent;
(3) washing the filter cake obtained in the step (2) by adopting a washing solvent, filtering, washing and filtering;
(4) sequentially carrying out vacuum drying and high-temperature blast drying on the filter cake obtained in the step (3) to obtain soluble and fusible copolyimide ultrafine powder;
in the step (2), the precipitating agent is one or more of methanol, ethanol, acetone and butanone; the weight ratio of the precipitating agent to the polar solvent in the step (1) is 0.7:1-1.2:1.
3. The method for preparing the soluble and fusible copolyimide ultrafine powder according to claim 2, characterized in that: in the step (1), the polar solvent is one or more than two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the dosage of the polar solvent is 2-6 times of the total weight of the diamine monomer and the dianhydride monomer.
4. The method for preparing the soluble and fusible copolyimide ultrafine powder according to claim 2, characterized in that: in the step (2), the poor solvent is toluene or xylene; the weight ratio of the poor solvent to the polar solvent in the step (1) is 1:2-1:6.
5. The method for preparing the soluble and fusible copolyimide ultrafine powder according to claim 2, characterized in that: in the step (2), the precipitating agent is ethanol or acetone; the weight ratio of the precipitating agent to the polar solvent in the step (1) is 0.8:1-0.85:1.
6. The method for preparing the soluble and fusible copolyimide ultrafine powder according to claim 2, characterized in that: in the step (3), the washing solvent is the same as the precipitating agent in the step (2); the dosage of the washing solvent is 2.5-5 times of the total weight of the monomers.
7. The method for preparing the soluble and fusible copolyimide ultrafine powder according to claim 2, characterized in that: in the step (4), the temperature of the vacuum drying is 80-120 ℃ and the time is 3-6 h; the high-temperature blast drying adopts temperature programming: 160 ℃/1h, 230 ℃/1h, 250 ℃/2h.
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| KR102246218B1 (en) * | 2019-09-27 | 2021-04-29 | 피아이첨단소재 주식회사 | Polyamic acid composition, method for preparing the same and polyimide film comprising the same |
| CN110922754A (en) * | 2019-11-08 | 2020-03-27 | 南京湘珀新材料科技有限公司 | Preparation method and application of polyimide film |
| CN111533907A (en) * | 2020-06-28 | 2020-08-14 | 合肥工业大学 | Preparation method of heat-resistant polyimide molding powder containing benzimidazole structure |
| CN113265048B (en) * | 2021-04-11 | 2023-03-10 | 常州市尚科新材料有限公司 | Polyimide superfine powder for mould pressing and preparation method thereof |
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