CN113402709A - High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof - Google Patents
High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses high-temperature resistant polyimide soluble in o-diallyl bisphenol A and a preparation method thereof, belonging to the technical field of high polymer materials. The polyimide provided by the invention is soluble in the ortho-diallyl bisphenol A, can be introduced into the ortho-diallyl bisphenol A-bismaleimide resin prepolymer, and solves the problem of mixing compatibility of the ortho-diallyl bisphenol A-bismaleimide resin prepolymer and the high temperature resistant polyimide toughening component.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to high-temperature-resistant polyimide soluble in o-diallyl bisphenol A and a preparation method thereof.
Background
The pure bismaleimide resin has brittle cured physical property and poor impact resistance, and needs toughening modification. Allyl compounds (mainly o-diallyl bisphenol A) have been the most effective way for toughening and modifying bismaleimide resin cured products by pre-polymerization of o-diallyl bisphenol A and bismaleimide resin (to form o-diallyl bisphenol A-bismaleimide resin pre-polymer) because they can improve the toughness of bismaleimide resin cured products without reducing the heat resistance (the heat resistance of the polymer is usually measured by the glass transition temperature, the higher the heat resistance is, the better the glass transition temperature is, the glass transition temperature is abbreviated as Tg, and the same is used below). However, in order to further improve the toughness of the ortho-diallylbisphenol a-bismaleimide resin copolymer without lowering the heat resistance thereof, it is necessary to introduce a high temperature resistant type polyimide toughening component. At present, polyimide with Tg of more than 290 ℃ and capable of being dissolved in an o-diallyl bisphenol A-bismaleimide resin prepolymer has not been disclosed. The main reason for this is that polyimides having a Tg of 290 ℃ or higher (e.g., P84) are difficult to dissolve in ortho-diallylbisphenol A and are difficult to dissolve in ortho-diallylbisphenol A-bismaleimide resin prepolymers.
Therefore, it is highly desirable to provide a high temperature resistant polyimide soluble in ortho-diallyl bisphenol a to meet the need for improved toughening of ortho-diallyl bisphenol a-bismaleimide resin copolymers.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide high-temperature resistant polyimide soluble in ortho-diallyl bisphenol A.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme:
a high temperature resistant polyimide soluble in ortho-diallyl bisphenol A has a structural formula shown in formula (I):
wherein the structure of Rx is one of (a) or (b);
in the formula (I), Ry has one or more structures of (c), (d), (e) and (f);
in the formula (I), k and m are natural numbers, and n is zero or a natural number; and the following relationships exist among k, m and n:
(1) k/(k + m + n) is more than or equal to 0.30 and less than or equal to 0.70, (2) m + n)/(k + m + n) is more than or equal to 0.30 and less than or equal to 0.70, and (3) when n is not zero, m/n is more than or equal to 4.
The polyimide disclosed by the invention is based on a unique molecular chain structure, can be dissolved in the o-diallyl bisphenol A, can also have Tg (glass transition temperature) higher than 290 ℃, and has the basis of meeting the requirements of toughening and heat resistance improvement of the o-diallyl bisphenol A-bismaleimide resin copolymer. In addition to the present invention, there is no disclosure of a polyimide having a Tg of 290 ℃ or higher and being soluble in ortho-diallylbisphenol A (and further used for toughening an ortho-diallylbisphenol A-bismaleimide resin copolymer).
The preparation method of the high-temperature resistant polyimide soluble in the o-diallyl bisphenol A comprises the following steps:
(1) solution polymerization of A: controlling the temperature of the reaction kettle to be 10-30 ℃ (controlling the temperature by water bath circulation), preferably 20 ℃, and firstly adding A diamine, wherein the A diamine is one or a mixture of two of 2, 2-bis (4-aminophenyl) propane and alpha, alpha' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, and preferably 2, 2-bis (4-aminophenyl) propane; adding a solvent, wherein the solvent is N, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone, and stirring until the solvent is dissolved; adding dianhydride, stirring and polymerizing for 1-20 h to prepare solution A;
(2) b, solution polymerization: controlling the temperature of the reaction kettle to be 10-30 ℃ (controlling the temperature by water bath circulation), preferably 20 ℃, firstly adding diamine B, wherein the diamine B is one or a mixture of more of 2, 6-diaminotoluene, 4 '-diaminodiphenylmethane, (2,4) -/(2,6) - (mixed) diaminotoluene and 2, 4-diaminotoluene, preferably 4,4' -diaminodiphenylmethane and 2, 4-diaminotoluene, then adding a solvent, wherein the solvent is N, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone, preferably N, N-dimethylacetamide, and stirring until the N, N-dimethylacetamide is completely dissolved; adding dianhydride, stirring and polymerizing for 1-20 h to prepare a solution B;
(3) preparation of polyamic acid solution: firstly transferring the solution B into the solution A, then washing a solution B reactor by using a solvent, wherein the solvent is N, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone, preferably N, N-dimethylacetamide, and the washing liquid is also completely transferred into the solution A; controlling the temperature of the reactor to be 10-30 ℃ (controlling the temperature in a water bath circulation manner), adding dianhydride, and stirring and polymerizing to obtain a polyamic acid solution;
(4) chemical imidization: adding acetic anhydride into the polyamic acid solution obtained in the step (3), controlling the temperature to be 10-30 ℃, and stirring and dispersing; and adding an N, N-dimethylacetamide solution of triethylene diamine, wherein the mass concentration of the triethylene diamine in the N, N-dimethylacetamide solution of the triethylene diamine is 50%, stirring and dispersing, then heating to 20-70 ℃, and keeping stirring for 0.5-5 hours to prepare the high-temperature resistant polyimide solution.
Further, the dianhydride is one or a mixture of two of 3,3',4,4' -benzophenone tetracarboxylic dianhydride and 4, 4-hexafluoroisopropyl phthalic anhydride.
Further, the solvent is N, N-dimethylacetamide.
In the step (1), the molar ratio of the A diamine to the dianhydride is 0.975-1.025; the total mass of the A diamine and the dianhydride is 5-45% of the mass of the solvent in the step (1).
In the step (2), the molar ratio of the diamine B to the dianhydride is 1.005-2.225; the total mass of the diamine and the dianhydride is 5-45% of the mass of the solvent in the step (2).
In the step (3), the mass of the solvent for cleaning the solution B reactor is 0.4-1.0 times of that of the solvent in the step (2).
In the step (4), the molar amount of the acetic anhydride is not less than 6 times of the total molar amount of the A diamine in the step (1) and the B diamine in the step (2); the molar amount of the triethylenediamine is not less than 4 times the total molar amount of the A diamine in step (1) and the B diamine in step (2).
In the step (4), the high-temperature resistant polyimide solution is prepared into high-temperature resistant polyimide powder by the following method:
(S1) wet powder forming: cooling the polyimide solution to 20 ℃, and circularly controlling the temperature of the water bath to 20 ℃; adding methanol under high-speed shearing and stirring to prepare polyimide turbid liquid; and (3) centrifugally separating the turbid solution to obtain wet polyimide powder, soaking the wet polyimide powder again by using methanol and centrifuging the soaked wet polyimide powder for three times, wherein the addition amount of the methanol is not less than 0.8 time of the total mass of the solvent in the steps (1), (2) and (3) of claim 2, the methanol is used for soaking each time, and the soaking time is not less than 8 hours, so that the wet polyimide powder is prepared.
(S2) drying the wet powder: the polyimide wet powder prepared in (S1) was dried in a vacuum oven, the drying procedure was as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a 100-mesh stainless steel sieve to obtain the high-temperature resistant polyimide powder.
Has the advantages that:
the polyimide provided by the invention can be introduced into an o-diallyl bisphenol A-bismaleimide resin prepolymer based on the solubility of the polyimide in the o-diallyl bisphenol A, can solve the problem of mixing and compatibility of the o-diallyl bisphenol A-bismaleimide resin prepolymer and a high-temperature resistant polyimide toughening component, and has the basis of meeting the toughening and heat resistance improvement of an o-diallyl bisphenol A-bismaleimide resin copolymer.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
1. Preparation of polyamic acid solution:
1) solution polymerization of A: in a 10L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 79.212 g of 2, 2-bis (4-aminophenyl) propane is added, 875 g of N, N-dimethylacetamide is added, and the mixture is stirred until the mixture is completely dissolved; 112.777 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and stirred and polymerized for 4 hours to prepare a solution A.
2) B, solution polymerization: in a 5L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 63.529 g of 2, 4-diaminotoluene and 25.774 g of 4,4' -diaminodiphenylmethane are added, 1000 g of N, N-dimethylacetamide is added, and the mixture is stirred until the N, N-dimethylacetamide is completely dissolved; 133.272 g of 4, 4-hexafluoroisopropyl phthalic anhydride was added thereto, and polymerization was carried out for 14 hours with stirring to prepare a solution B.
3) Preparation of polyamic acid solution: firstly transferring the solution B into the solution A, then cleaning a solution B reactor by 528 g of N, N-dimethylacetamide, and transferring all cleaning solution into the solution A; the water bath circulation temperature is controlled at 20 ℃, 112.777 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added, and stirring polymerization is carried out for 4 hours to prepare the polyamic acid solution.
2. Preparation of polyimide powder:
4) chemical imidization: controlling the temperature of the water bath to be 20 ℃ circularly, adding 816.720 g of acetic anhydride into the polyamic acid solution prepared in the step 3), and stirring and dispersing for 0.5 hour; 1121.800 g of an N, N-dimethylacetamide solution of triethylenediamine (50 mass concentration) was added thereto, and the mixture was dispersed with stirring for 0.5 hour, and then heated to 45 ℃ and kept stirring for 2 hours to prepare a polyimide solution.
5) Wet powder forming: cooling the polyimide solution prepared in the step 4) to 20 ℃, and controlling the temperature of the water bath to be 20 ℃ in a circulating manner; 2400 g of methanol is added under high-speed shearing and stirring to prepare polyimide turbid liquid; and centrifuging the turbid solution to obtain wet polyimide powder, soaking the wet polyimide powder in methanol again and centrifuging the soaked polyimide powder for three times, wherein 2400 g of methanol is used for soaking each time, and the soaking time is not less than 8 hours each time. Preparing the polyimide wet powder.
6) Drying wet powder: drying the polyimide wet powder prepared in the step 5) in a vacuum drying oven, wherein the drying procedure is as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a 100-mesh stainless steel sieve, and the fine powder obtained by sieving is polyimide powder, and is subjected to Tg test and dissolution test.
3. Tg test of polyimide powder:
the heat resistance of the polyimide in the present invention is measured by its own Tg, and a higher Tg means a higher heat resistance. The Tg of the polyimide powder was measured using DSC double scan, as follows: heating from room temperature to 350 ℃, wherein the heating rate is 10 ℃/min; naturally cooling to room temperature; and then heating from room temperature to 420 ℃, wherein the heating rate is 10 ℃/min, and the inflection point temperature of the baseline moving towards the heat absorption direction on the atlas is the Tg of the sample. The same applies below.
The Tg of the polyimide powder prepared in this example was measured by DSC double scan and was 332 ℃.
4. Dissolution test of polyimide powder:
the solubility test of the polyimide powder was carried out according to the following procedure: adding polyimide powder into ortho-diallyl bisphenol A at room temperature, wherein the mass ratio of the polyimide powder to the ortho-diallyl bisphenol A is 30: 70; vacuumizing to below 0.09MPa, starting high-speed shearing and stirring, uniformly dispersing the polyimide powder in the diallyl bisphenol A, gradually heating to 160 ℃, and carrying out high-speed shearing and stirring at 160 ℃ for 2 hours, wherein if the solution is transparent and not turbid, the polyimide powder is good in solubility in the diallyl bisphenol A, and if the solution is turbid and not transparent, the polyimide powder is not good in solubility in the o-diallyl bisphenol A. The same applies below.
The polyimide powder prepared in the example forms an orange transparent solution in the o-diallyl bisphenol A, and has no turbidity and the dissolution rate of 100%.
Example 2
1. Preparation of polyamic acid solution:
1) solution polymerization of A: in a 10L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 223.919 g of alpha, alpha '-bis (4-aminophenyl) -1, 4-diisopropylbenzene and 1974 g of N, N-dimethylformamide are added and stirred until the alpha, alpha' -bis (4-aminophenyl) -1, 4-diisopropylbenzene is completely dissolved; 209.443 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and stirred and polymerized for 4 hours to prepare a solution A.
2) B, solution polymerization: in a 5L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; 42.760 g of 2, 4-diaminotoluene is added, 408 g of N, N-dimethylformamide is added, and the mixture is stirred until the mixture is completely dissolved; 96.666 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and stirred and polymerized for 4 hours to prepare a solution B.
3) Preparation of polyamic acid solution: firstly transferring the solution B into the solution A, then cleaning a solution B reactor by 300 g of N, N-dimethylformamide, and transferring all cleaning solution into the solution A; the water bath circulation temperature is controlled at 20 ℃, 16.111 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added, and stirring polymerization is carried out for 4 hours to prepare the polyamic acid solution.
2. Preparation of polyimide powder:
4) chemical imidization: controlling the temperature of the water bath to be 20 ℃ circularly, adding 816.720 g of acetic anhydride into the polyamic acid solution prepared in the step 3), and stirring and dispersing for 0.5 hour; 1121.800 g of a triethylenediamine N, N-dimethylformamide solution (50% by mass) was added thereto, and the mixture was dispersed with stirring for 0.5 hour, and then heated to 45 ℃ and kept stirring for 2 hours to prepare a polyimide solution.
5) Wet powder forming: cooling the polyimide solution prepared in the step 4) to 20 ℃, and controlling the temperature of the water bath to be 20 ℃ in a circulating manner; 2680 g of methanol is added under high-speed shearing and stirring to prepare polyimide turbid liquid; and centrifuging the turbid solution to obtain wet polyimide powder, soaking the wet polyimide powder in methanol again and centrifuging the soaked polyimide powder for three times, wherein 2680 g of methanol is used for soaking each time, and the soaking time is not less than 8 hours each time. Preparing the polyimide wet powder.
6) Drying wet powder: drying the polyimide wet powder prepared in the step 5) in a vacuum drying oven, wherein the drying procedure is as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a 100-mesh stainless steel sieve, and the fine powder obtained by sieving is polyimide powder, and is subjected to Tg test and dissolution test.
3. Tg test of polyimide powder:
the Tg of the polyimide powder prepared in this example was determined by DSC double scan and was 337 ℃.
4. Dissolution test of polyimide powder:
the polyimide powder prepared in the example forms an orange transparent solution in the o-diallyl bisphenol A, and has no turbidity and the dissolution rate of 100%.
Example 3
1. Preparation of polyamic acid solution:
1) solution polymerization of A: in a 10L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 120.572 g of alpha, alpha '-bis (4-aminophenyl) -1, 4-diisopropylbenzene and 1063 g of N-methylpyrrolidone are added and stirred until the alpha, alpha' -bis (4-aminophenyl) -1, 4-diisopropylbenzene is completely dissolved; 112.777 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and stirred and polymerized for 4 hours to prepare a solution A.
2) B, solution polymerization: in a 5L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 63.528 g of (2,4) -/(2,6) - (mixed) diaminotoluene and 25.774 g of 4,4' -diaminodiphenylmethane are added, 861 g of N-methyl pyrrolidone is added, and the mixture is stirred until the N-methyl pyrrolidone is completely dissolved; 167.554 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and stirred and polymerized for 4 hours to prepare a solution B.
3) Preparation of polyamic acid solution: firstly transferring the solution B into the solution A, then cleaning a reactor of the solution B by using 500 g of N-methylpyrrolidone, and transferring all cleaning liquid into the solution A; the water bath circulation temperature is controlled at 20 ℃, 41.889 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added, and stirring polymerization is carried out for 4 hours to prepare the polyamic acid solution.
2. Preparation of polyimide powder:
4) chemical imidization: controlling the temperature of the water bath to be 20 ℃ circularly, adding 816.720 g of acetic anhydride into the polyamic acid solution prepared in the step 3), and stirring and dispersing for 0.5 hour; 1121.800 g of a triethylenediamine N-methylpyrrolidone solution (50% by mass) was added thereto, and the mixture was dispersed with stirring for 0.5 hour, and then heated to 45 ℃ and kept stirring for 2 hours to prepare a polyimide solution.
5) Wet powder forming: cooling the polyimide solution prepared in the step 4) to 20 ℃, and controlling the temperature of the water bath to be 20 ℃ in a circulating manner; 2424 g of methanol is added under the high-speed shearing and stirring to prepare polyimide turbid liquid; centrifuging the turbid solution to obtain wet polyimide powder, soaking the wet polyimide powder in methanol again and centrifuging the soaked polyimide powder for three times, wherein 2424 g of methanol is used for soaking each time, and the soaking time is not less than 8 hours. Preparing the polyimide wet powder.
6) Drying wet powder: drying the polyimide wet powder prepared in the step 5) in a vacuum drying oven, wherein the drying procedure is as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a 100-mesh stainless steel sieve, and the fine powder obtained by sieving is polyimide powder, and is subjected to Tg test and dissolution test.
3. Tg test of polyimide powder:
the Tg of the polyimide powder prepared in this example was measured by DSC double scan and was 330 ℃.
4. Dissolution test of polyimide powder:
the polyimide powder prepared in the example forms an orange transparent solution in the o-diallyl bisphenol A, and has no turbidity and the dissolution rate of 100%.
Example 4
1. Preparation of polyamic acid solution:
1) solution polymerization of A: in a 10L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 101.844 g of 2, 2-bis (4-aminophenyl) propane is added, 1124 g of N, N-dimethylacetamide is added, and the mixture is stirred until the mixture is completely dissolved; 144.999 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and stirred and polymerized for 4 hours to prepare a solution A.
2) B, solution polymerization: in a 5L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 67.194 g of 2, 4-diaminotoluene and 769 g of N, N-dimethylacetamide are added and stirred until the materials are completely dissolved; 44.424 g of 4, 4-hexafluoroisopropyl phthalic anhydride and 128.888 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride were added and polymerized with stirring for 14 hours to prepare a solution B.
3) Preparation of polyamic acid solution: firstly transferring the solution B into the solution A, then cleaning a solution B reactor by 400 g of N, N-dimethylacetamide, and transferring all cleaning solution into the solution A; the water bath circulation temperature is controlled at 20 ℃, 16.111 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added, and stirring polymerization is carried out for 4 hours to prepare the polyamic acid solution.
2. Preparation of polyimide powder:
4) chemical imidization: controlling the temperature of the water bath to be 20 ℃ circularly, adding 816.720 g of acetic anhydride into the polyamic acid solution prepared in the step 3), and stirring and dispersing for 0.5 hour; 1121.800 g of an N, N-dimethylacetamide solution of triethylenediamine (50 mass concentration) was added thereto, and the mixture was dispersed with stirring for 0.5 hour, and then heated to 45 ℃ and kept stirring for 2 hours to prepare a polyimide solution.
5) Wet powder forming: cooling the polyimide solution prepared in the step 4) to 20 ℃, and controlling the temperature of the water bath to be 20 ℃ in a circulating manner; adding 2300 g of methanol under high-speed shearing and stirring to prepare polyimide turbid liquid; and centrifuging the turbid solution to obtain wet polyimide powder, soaking the wet polyimide powder with methanol for three times, wherein 2300 g of methanol is used for soaking each time, and the soaking time is not less than 8 hours. Preparing the polyimide wet powder.
6) Drying wet powder: drying the polyimide wet powder prepared in the step 5) in a vacuum drying oven, wherein the drying procedure is as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a stainless steel sieve of 100 meshes, and the fine powder screened out is polyimide powder and is used for Tg test and dissolution test.
3. Tg test of polyimide powder:
the Tg of the polyimide powder prepared in this example was measured by DSC double scan and was 330 ℃.
4. Dissolution test of polyimide powder:
the polyimide powder prepared in the example forms an orange transparent solution in the o-diallyl bisphenol A, and has no turbidity and the dissolution rate of 100%.
Comparative example 1
1. Preparation of P84 Polyamic acid solution
1) In a 10L double-layer glass polymerization kettle, the water bath circulation temperature is controlled at 20 ℃; firstly, 97.736 g of (2,4) -/(2,6) - (mixed) diaminotoluene and 39.652 g of 4,4' -diaminodiphenylmethane are added, and 2094 g of N, N-dimethylacetamide is added and stirred until the N, N-dimethylacetamide is completely dissolved; 322.220 g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride was added thereto, and the mixture was stirred and polymerized for 4 hours to prepare a P84 polyamic acid solution.
Preparation of P84 polyimide powder:
2) chemical imidization: controlling the temperature of the water bath to be 20 ℃ circularly, adding 816.720 g of acetic anhydride into the polyamic acid solution prepared in the step 1), and stirring and dispersing for 0.5 hour; 1121.800 g of an N, N-dimethylacetamide solution of triethylenediamine (50 mass concentration) was added thereto, and the mixture was dispersed with stirring for 0.5 hour, and then heated to 45 ℃ and kept stirring for 2 hours to prepare a polyimide solution.
3) Wet powder forming: cooling the polyimide solution prepared in the step 2) to 20 ℃, and controlling the temperature of the water bath to be 20 ℃ in a circulating manner; adding 2100 g of methanol under high-speed shearing and stirring to prepare polyimide turbid liquid; and centrifuging the turbid solution to obtain wet polyimide powder, soaking the wet polyimide powder in methanol again and centrifuging the soaked wet polyimide powder for three times, wherein 2100 g of methanol is used for soaking each time, and the soaking time is not less than 8 hours each time. Preparing the polyimide wet powder.
4) Drying wet powder: drying the polyimide wet powder prepared in the step 3) in a vacuum drying oven, wherein the drying procedure is as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a 100-mesh stainless steel sieve, and the fine powder obtained by sieving is polyimide powder, and is subjected to Tg test and dissolution test.
Tg test of P84 polyimide powder:
the Tg of the polyimide powder P84 prepared in this comparative example was measured by DSC two-shot scanning and was 325
Dissolution test of P84 polyimide powder:
the polyimide powder P84 prepared in this comparative example formed a cloudy orange solution in ortho-diallyl bisphenol A and was not soluble well.
In conclusion, the invention provides the high-temperature resistant polyimide soluble in the o-diallyl bisphenol A, and is expected to meet the requirement of toughening and improving the o-diallyl bisphenol A-bismaleimide resin copolymer.
Claims (10)
1. A high temperature resistant polyimide soluble in ortho-diallyl bisphenol A has a structural formula shown in formula (I):
wherein the structure of Rx is one of (a) or (b);
in the formula (I), Ry has one or more structures of (c), (d), (e) and (f);
in the formula (I), k and m are natural numbers, and n is zero or a natural number; and the following relationships exist among k, m and n:
(1) k/(k + m + n) is more than or equal to 0.30 and less than or equal to 0.70, (2) m + n)/(k + m + n) is more than or equal to 0.30 and less than or equal to 0.70, and (3) when n is not zero, m/n is more than or equal to 4.
2. The method for preparing a high temperature resistant polyimide soluble in ortho-diallyl bisphenol a as recited in claim 1, comprising the steps of:
(1) solution polymerization of A: controlling the temperature of a reaction kettle to be 10-30 ℃, and adding A diamine which is one or a mixture of two of 2, 2-bis (4-aminophenyl) propane and alpha, alpha' -bis (4-aminophenyl) -1, 4-diisopropylbenzene; adding a solvent, and stirring until the solvent is dissolved; adding dianhydride, stirring and polymerizing to prepare solution A;
(2) b, solution polymerization: controlling the temperature of the reaction kettle to be 10-30 ℃, firstly adding diamine B, wherein the diamine B is one or a mixture of more of 2, 6-diaminotoluene, 4' -diaminodiphenylmethane, (2,4) -/(2,6) - (mixed) diaminotoluene and 2, 4-diaminotoluene, then adding a solvent, and stirring until the mixture is completely dissolved; then adding dianhydride, stirring and polymerizing to prepare solution B;
(3) preparation of polyamic acid solution: firstly transferring the solution B into the solution A, then cleaning the solution B reactor by using a solvent, and transferring all cleaning liquid into the solution A; controlling the temperature of the reactor to be 10-30 ℃, adding dianhydride, stirring and polymerizing to obtain a polyamide acid solution;
(4) chemical imidization: adding acetic anhydride into the polyamic acid solution obtained in the step (3), controlling the temperature to be 10-30 ℃, and stirring and dispersing; and adding an N, N-dimethylacetamide solution of triethylene diamine, wherein the mass concentration of the triethylene diamine in the N, N-dimethylacetamide solution of the triethylene diamine is 50%, stirring and dispersing, then heating to 20-70 ℃, and keeping stirring for 0.5-5 hours to prepare the high-temperature resistant polyimide solution.
3. The method for preparing the high temperature resistant polyimide soluble in ortho-diallyl bisphenol A as claimed in claim 2, wherein the dianhydride is one or a mixture of 3,3',4,4' -benzophenone tetracarboxylic dianhydride and 4, 4-hexafluoroisopropyl phthalic anhydride.
4. The method for preparing the high temperature resistant polyimide soluble in ortho-diallyl bisphenol A as claimed in claim 2, wherein the solvent is N, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
5. The method for preparing the high temperature resistant polyimide soluble in ortho-diallyl bisphenol A according to the claim 2, wherein in the step (1), the molar ratio of the A diamine to the dianhydride is 0.975-1.025; the total mass of the A diamine and the dianhydride is 5-45% of the mass of the solvent in the step (1).
6. The method for preparing the high temperature resistant polyimide soluble in ortho-diallyl bisphenol A as claimed in claim 2, wherein in the step (2), the molar ratio of diamine B to dianhydride is 1.005-2.225; the total mass of the diamine and the dianhydride is 5-45% of the mass of the solvent in the step (2).
7. The method for preparing o-diallyl bisphenol A soluble high temperature resistant polyimide according to claim 2, wherein the solvent used for cleaning the B solution reactor in the step (3) is 0.4 to 1.0 times the mass of the solvent in the step (2).
8. The method for preparing an ortho-diallyl bisphenol a soluble high temperature resistant polyimide according to claim 2, wherein in step (4), the molar amount of acetic anhydride is not less than 6 times the total molar amount of the a diamine in step (1) and the B diamine in step (2) in claim 2;
the molar amount of the triethylenediamine is not less than 4 times the total molar amount of the A diamine in step (1) and the B diamine in (2) of claim 2.
9. The method for preparing the high temperature resistant polyimide soluble in ortho-diallyl bisphenol A as claimed in claim 2, wherein in the step (4), the high temperature resistant polyimide solution is prepared into the high temperature resistant polyimide powder by the following method:
(S1) wet powder forming: cooling the polyimide solution to 20 ℃, and controlling the temperature to be 20 ℃; adding methanol under high-speed shearing and stirring to prepare polyimide turbid liquid; centrifuging the turbid solution to obtain polyimide wet powder, soaking the polyimide wet powder in methanol again and centrifuging the soaked polyimide wet powder for three times, wherein the methanol is used for soaking each time, and the soaking time is not less than 8 hours, so that the polyimide wet powder is prepared;
(S2) drying the wet powder: the polyimide wet powder prepared in (S1) was dried in a vacuum oven, the drying procedure was as follows: 60 ℃/2hr → 120 ℃/2hr → 160 ℃/2hr → 190 ℃/4hr, the vacuum degree is kept within 0.09MPa in the drying process; the prepared dry powder is crushed by a fluted disc crusher and then passes through a 100-mesh stainless steel sieve to obtain the high-temperature resistant polyimide powder.
10. The method for producing an ortho-diallyl bisphenol a-soluble high temperature resistant polyimide according to claim 9, wherein the amount of methanol added is not less than 0.8 times the total mass of the solvent in steps (1), (2) and (3) of claim 2.
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