CN107602856B - Thermosetting polyimide prepolymer with high solubility, preparation method and application thereof - Google Patents
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Abstract
The invention discloses a thermosetting polyimide prepolymer with high solubility, which is shown as a formula (I), and discloses a preparation method and application of the thermosetting polyimide prepolymer. The preparation method comprises the following steps: stirring a diamine monomer mixture and a dianhydride monomer mixture for 5-8 hours at room temperature in a polar aprotic solvent under the protection of nitrogen, adding a blocking agent 4-phenylacetylene phthalic anhydride, and continuously stirring for 6-24 hours; adding an azeotropic water-carrying agent, and heating and refluxing for 6-24 hours; and after the reaction is finished, cooling to room temperature, pouring the solution into a poor solvent, filtering after powder is separated out, taking filter residues, boiling and washing and drying to obtain thermosetting polyimide prepolymer powder. The prepolymer is suitable for preparing thermosetting polyimide resin matrix composite materials with low porosity. The composite material prepared by the invention can be widely applied to the high-tech fields of aerospace, space, precision machinery, petrochemical industry, automobiles and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a thermosetting polyimide prepolymer with high solubility in a low-boiling-point solvent at room temperature, and a preparation method and application thereof.
Background
Polyimide has excellent high temperature resistance, high strength, high modulus, high toughness, insulating property and the like, and is an important structural material and polymer film material in the fields of aerospace, microelectronics and the like. However, they have great difficulty in molding because they generally exhibit high melt viscosity and poor solubility in organic solvents.
In order to solve the problem that high melt viscosity, low solubility, and the like of high performance polymers are difficult to process, the development of thermosetting polyimide prepolymers containing reactive groups has attracted much attention. Compared with thermoplastic polyimide, thermosetting polyimide prepolymer has low molecular weight, better solubility, lower melt viscosity and higher glass transition temperature after curing and crosslinking, and is commonly used as matrix resin for preparing composite materials.
The traditional thermosetting polyimide composite material is usually prepared by pre-soaking resin solution and fiber by adopting a PMR method or a polyamic acid solution method, then removing the solvent and imidizing by pressurizing and heating to prepare the pre-soaking material, and finally adopting a hot-die pressing or autoclave process to prepare the composite material. In the process of preparing the prepreg by adopting the polyamic acid solution, the polyamic acid solution usually adopts a high-boiling point reagent such as N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide and the like as a solvent, and is difficult to volatilize, and in addition, water generated in the imidization process of the polyamic acid is added, so that the porosity of the composite material is high, and the final performance of the composite material is influenced. Although the PMR method uses alcohols as a solvent, which are easily volatilized during the preparation of the prepreg, water generated during in-situ polymerization of resin monomers during the thermosetting of the composite material still causes high porosity of the composite material, which affects the performance of the composite material. It can be seen that in the preparation of the fiber reinforced thermosetting polyimide prepreg, the volatilization of the solvent and the release of water in the imidization process are easy to cause the composite material to generate gaps, so that the performance of the composite material is reduced.
In order to solve the above problems, studies on highly soluble thermosetting polyimide prepolymers have been attracting attention in recent years. The polyimide pre-polymer which is fully imidized is mainly dissolved in an organic solvent (the solid content is more than 30 percent) and then is presoaked with fibers to prepare the prepreg, so that the imidization process does not exist in the heating process, and no water is released, so that the volatilization of the solvent becomes a main factor influencing the porosity of the composite material.
Non-patent documents Polymer Journal (2013)45,594-.
The invention patent of CN 1282687C discloses a polyimide prepolymer with high solubility and high toughness containing benzene side group and a preparation technology, which discloses a polyimide prepolymer which can only be dissolved in high boiling point solvents of N-methyl pyrrolidone and N, N-dimethyl acetamide.
It can be seen that the polyimide prepolymer in the prior art has high solubility only in high-boiling-point solvents, and has poor solubility in low-boiling-point solvents. On the basis of the prior art, the development of the thermosetting polyimide prepolymer with high solubility in a low-boiling-point solvent at normal temperature has important significance for further reducing the porosity generated in the preparation process of the composite material and improving the comprehensive performance of the composite material.
Disclosure of Invention
The present invention has an object to provide a thermosetting polyimide prepolymer having high solubility in a low boiling point solvent under room temperature conditions.
The structural general formula of the thermosetting polyimide prepolymer with high solubility provided by the invention is shown as formula I,
wherein m and n are polymerization degrees, wherein m is more than 0, and n is more than or equal to 0;
Ar1、Ar2is aromatic diamine monomer residue, and is selected from one of the following structural formulas:
wherein R is2Is one of the following structural formulas:
-O--CH2--SO2-
wherein R is3、R4、R5、R6Is one of the following structural formulas:
-CxH2x+1-CF3 
wherein x is an integer, and x is more than or equal to 0 and less than or equal to 4.
The aromatic diamine monomer residue, such as phenyl, trifluoromethyl, methyl and other side groups introduced into the main chain, can reduce the interaction force between molecular chains without changing the rigidity of the molecular chains, so as to improve the solubility of the polyimide prepolymer1、 Ar2Is selected from one of the following structural formulas:
ar' is aromatic dianhydride monomer residue and is selected from one of the following structural formulas:
wherein R is1Is one of the following structural formulas:
-O--S-
the aromatic dianhydride monomer residue Ar' introduces heterogeneous dianhydride with a nonlinear and non-coplanar structure into a molecular chain, so that the molecular chain is prevented from being closely packed, the intermolecular interaction force is reduced, and the solubility of the polyimide prepolymer is improved, wherein the structural formula is preferably one of the following structural formulas (a), (b) and (c):
the reaction principle of the preparation method of the thermosetting polyimide prepolymer with high solubility is as follows:
the invention also provides a preparation method of the thermosetting polyimide prepolymer with high solubility, which comprises the following steps:
(1) under the protection of nitrogen, dissolving diamine monomer mixtures shown in structural formulas (IV) and (V) into a polar aprotic solvent;
(2) adding a dianhydride monomer mixture shown in a structural formula (II) and a structural formula (III), wherein the feeding molar ratio of the two components is 7/3-10/0, and stirring for 5-8 hours at room temperature;
(3) adding a blocking agent 4-phenylacetylene phthalic anhydride, and stirring at room temperature for 6-24 hours;
(4) adding an azeotropic water-carrying agent, wherein the mass ratio of the water-carrying agent to the solvent is 1: 2-5, and heating and refluxing for 6-24 hours;
(5) after the system is cooled to room temperature, pouring the solution into a poor solvent, separating out powder, filtering, taking filter residue, boiling, washing and drying to obtain thermosetting polyimide prepolymer powder;
ar' is selected from one of the following structural formulas:
wherein R is1Is one of the following structural formulas:
-O-，-S-，
Ar1、Ar2one selected from the following structural formulas:
wherein R is2Is one of the following structural formulas:
-O-，-CH2-，-SO2-，
wherein R is3、R4、R5、R6Is one of the following structural formulas:
-CxH2x+1-CF3 
wherein x is an integer, and x is more than or equal to 0 and less than or equal to 4.
The polar aprotic solvent in the step (1) is one of N-methylpyrrolidone, N '-dimethylacetamide and N, N' -dimethylformamide.
The mole ratio of the dianhydride monomer mixture, the diamine monomer mixture and the end capping agent in the steps (1) to (3) is p (p +1) to 2, wherein p is more than 0. The amount of the end-capping agent is calculated from the theoretical molecular weight of the designed thermosetting polyimide prepolymer, and the molecular weight of the thermosetting polyimide prepolymer is controlled by adding the end-capping agent.
The water-carrying agent in the step (4) is toluene or xylene.
The poor solvent in the step (5) is one of methanol, ethanol or deionized water.
The number average molecular weight of the thermosetting polyimide prepolymer obtained by the preparation method is between 500g/mol and 10000g/mol, preferably between 2000g/mol and 4000g/mol, because not only the polyimide prepolymer in the molecular weight region has good solubility, but also the film obtained after the polyimide prepolymer in the molecular weight region is cured has excellent thermal property and mechanical property.
The thermosetting polyimide prepolymer prepared by the invention is a fully imidized resin, which is prepared at normal temperature in a high-boiling-point solvent such as: the solubility in solvents such as N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide and the like is more than 30% (mass fraction), and the solvents have low boiling point such as: the solubility of tetrahydrofuran, 1, 4-dioxane, chloroform, acetone and other solvents is also more than 30 percent (mass fraction).
The thermosetting polyimide prepolymer prepared by the invention has good solubility at normal temperature, and the polyimide film obtained after curing for 1 hour at 370 ℃ still has excellent thermal property and mechanical property: the glass transition temperature is more than 330 ℃, the tensile modulus is 1.9-2.2 GPa, the tensile stress is 70-90 MPa, and the elongation at break is 6-9%.
The invention also provides application of the thermosetting polyimide prepolymer with high solubility in preparation of the thermosetting polyimide resin-based composite material with low porosity.
The good solubility of the thermosetting polyimide prepolymer in a low-boiling-point solvent at normal temperature enables the thermosetting polyimide prepolymer prepared by the method to be simple in solvent molecule removal in the process of preparing the composite material, no solvent or water molecule is released in the later processing process, the porosity of the composite material can be effectively reduced, and the thermosetting polyimide prepolymer is suitable for the conditions of high porosity and performance reduction of the composite material caused by volatilization of the solvent and/or release of water in the imidization process.
The thermosetting polyimide resin-based composite material with low porosity prepared by the invention can be widely applied to the high-tech fields of aerospace, space, precision machinery, petrochemical industry, automobiles and the like.
Drawings
FIG. 1 is an infrared spectrum of a thermosetting polyimide prepolymer obtained in example 1 of the present invention.
FIG. 2 shows the cured thermosetting polyimide prepolymers obtained in examples 1 to 5 of the present invention
DSC scan of (a).
Detailed Description
Example 1
Adding 16.1mmol (5.4285g) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether and 20m L N-methylpyrrolidone into a 100m L three-neck round-bottom flask filled with nitrogen, adding 12.4mmol (2.700g) of pyromellitic dianhydride after diamine is completely dissolved, stirring for 6 hours at room temperature, adding 7.5mmol (1.8702g) of 4-phenylacetylene phthalic anhydride, controlling the solid content of the solution to be about 30%, stirring for 12 hours at room temperature, adding 9m L dimethylbenzene, mounting a water separator and a condenser on the flask, heating to 190 ℃ and refluxing for 12 hours, cooling the system to room temperature after the reaction is finished, pouring the solution into ethanol, filtering to obtain a precipitate, boiling and washing with ethanol for three times, drying a filter cake in a common oven at 100 ℃ for 2 hours, and then drying in a vacuum oven at 220 ℃ for 4 hours to obtain thermosetting polyimide prepolymer powder, wherein the theoretical calculated molecular weight is 2000 g/mol.
In this example, the polyimide prepolymer has the following structural formula:
the IR spectrum of the polyimide prepolymer is shown in FIG. 1, from which it can be seen that 1780cm-1And 1722cm-11391cm as carbonyl absorption peak-1And 735cm-1Absorption peak at 2210cm for imine ring-1Is phenylethynyl absorption peak.
The obtained polyimide prepolymer powder was added to N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, chloroform, 1, 4-dioxane, and acetone, and the solubility of the polyimide prepolymer powder in the above respective solvents was measured, and the results are shown in table 1. The solids content was 33%.
And (3) placing the obtained polyimide prepolymer powder on a flat vulcanizing machine preheated to 200 ℃ for film pressing, and curing at 370 ℃ for 1h to obtain a polyimide film with the thickness of 50 um. The glass transition temperature and mechanical properties of the films are shown in Table 2.
Example 2
Adding 17.5mmol (4.8335g) of 2- (4-aminophenoxy) -5-aminobiphenyl and 20m L N-methylpyrrolidone into a 100m L three-neck round-bottom flask filled with nitrogen, stirring at room temperature until diamine is completely dissolved, adding 12.6mmol (2.7561g) of pyromellitic dianhydride, stirring at room temperature for 6 hours, adding 9.7mmol (2.4109g) of 4-phenylacetylene phthalic anhydride, controlling the solid content of the solution to be about 30%, stirring at room temperature for 12 hours, adding 9m L dimethylbenzene, mounting a water separator and a condenser on the flask, heating to 190 ℃ and refluxing for 12 hours, cooling the system to room temperature after the reaction is finished, pouring the solution into ethanol, filtering to obtain a precipitate, boiling and washing with ethanol for three times, drying a filter cake in a common oven at 100 ℃ for 2 hours, and drying in a vacuum oven at 220 ℃ for 4 hours to obtain thermosetting polyimide prepolymer powder, wherein the theoretical calculated molecular weight is 2000 g/mol.
In this example, the polyimide prepolymer has the following structural formula:
the obtained polyimide prepolymer powder was added to N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, chloroform, 1, 4-dioxane, and acetone, and the solubility of the polyimide prepolymer powder in the above respective solvents was measured, and the results are shown in table 1. The solids content was 33%.
And (3) placing the obtained polyimide prepolymer powder on a flat vulcanizing machine preheated to 200 ℃ for film pressing, and curing at 370 ℃ for 1h to obtain a polyimide film with the thickness of 50 um. The glass transition temperature and mechanical properties of the films are shown in Table 2.
Example 3
Adding 20.6mmol (4.6554g) of 4,4 '-diamino-3, 3' -dimethyl diphenyl methane and 20m L N-methyl pyrrolidone into a 100m L three-neck round-bottom flask into which nitrogen is introduced, adding 17.5mmol (3.8134g) of pyromellitic dianhydride after diamine is completely dissolved, stirring for 6 hours at room temperature, adding 6.2mmol (1.5326g) of 4-phenylacetylene phthalic anhydride, controlling the solid content of the solution to be 30%, stirring for 12 hours at room temperature, adding 9m L xylene, installing a water separator and a condenser on the flask, heating to 190 ℃, refluxing for 12 hours, cooling the system to room temperature after the reaction is finished, pouring the solution into ethanol, filtering to obtain a precipitate, boiling and washing with ethanol for three times, drying the filter cake in a common oven at 100 ℃ for 2 hours, and drying in a vacuum oven at 220 ℃ for 4 hours to obtain thermosetting polyimide prepolymer powder, wherein the molecular weight is 3000g/mol theoretically calculated.
In this example, the polyimide prepolymer has the following structural formula:
the obtained polyimide prepolymer powder was added to N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, chloroform, 1, 4-dioxane, and acetone, and the solubility of the polyimide prepolymer powder in the above respective solvents was measured, and the results are shown in table 1. The solids content was 33%.
And (3) placing the obtained polyimide prepolymer powder on a flat vulcanizing machine preheated to 200 ℃ for film pressing, and curing at 370 ℃ for 1h to obtain a polyimide film with the thickness of 50 um. The glass transition temperature and mechanical properties of the films are shown in Table 2.
Example 4
15.3mmol (5.1522g) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether and 20m L N-methylpyrrolidone are added into a 100m L three-neck round-bottom flask into which nitrogen is introduced, 5.8mmol (1.2651g) of pyromellitic dianhydride and 5.8mmol (1.7065g) of 2,3,3',4' -biphenyltetracarboxylic dianhydride are sequentially added after diamine is completely dissolved, 7.6mmol (1.8762g) of 4-phenylacetylene phthalic anhydride is added after stirring for 6 hours at room temperature, the solid content of the solution is controlled to be 30%, stirring for 12 hours at room temperature is carried out, 9m L xylene is added, a water separator and a condenser are installed on the flask, the temperature is raised to 190 ℃ for reflux for 12 hours, the system is cooled to room temperature after the reaction is finished, the solution is poured into ethanol, precipitate is obtained by filtration, the precipitate is boiled and washed three times by ethanol, the filter cake is dried in a common oven at 100 ℃ for 2 hours, and then is dried in a vacuum oven at 220 ℃ for 4 hours to obtain thermosetting polyimide powder, and the theoretical molecular weight of the prepolymer is 3000.
In this example, the polyimide prepolymer has the following structural formula:
the obtained polyimide prepolymer powder was added to N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, chloroform, 1, 4-dioxane, and acetone, and the solubility of the polyimide prepolymer powder in the above respective solvents was measured, and the results are shown in table 1. The solids content was 33%.
And (3) placing the obtained polyimide prepolymer powder on a flat vulcanizing machine preheated to 200 ℃ for film pressing, and curing at 370 ℃ for 1h to obtain a polyimide film with the thickness of 50 um. The glass transition temperature and mechanical properties of the films are shown in Table 2.
Example 5
Adding 8.5mmol (2.8694g) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 8.5mmol (2.3593g) of 2- (4-aminophenoxy) -5-aminobiphenyl and 20m L N-methylpyrrolidone into a 100m L three-neck round-bottom flask filled with nitrogen, adding 13.3mmol (2.9058g) of trimellitic dianhydride after diamine is completely dissolved, stirring for 6 hours at room temperature, adding 7.5mmol (1.8638g) of 4-phenylacetylene phthalic anhydride, controlling the solid content of the solution to be 30%, stirring for 12 hours at room temperature, adding 9m L xylene, installing a water separator and a condenser on the flask, heating to 190 ℃ and refluxing for 12 hours, cooling the system to room temperature after the reaction is finished, pouring the solution into ethanol, filtering to obtain a precipitate, boiling and washing with ethanol for three times, drying the filter cake in a common oven at 100 ℃ for 2 hours, and then drying in a vacuum oven at 220 ℃ for 4 hours to obtain thermosetting polyimide prepolymer powder, wherein the theoretical calculated molecular weight is 2500 g/mol.
In this example, the polyimide prepolymer has the following structural formula:
the polyimide prepolymer powder was added to N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, chloroform, 1, 4-dioxane, and acetone, and the solubility of the polyimide prepolymer powder in the above respective solvents was measured, and the results are shown in table 1. The solids content was 33%.
And (3) placing the obtained polyimide prepolymer powder on a flat vulcanizing machine preheated to 200 ℃ for film pressing, and curing at 370 ℃ for 1h to obtain a polyimide film with the thickness of 50 um. The glass transition temperature and mechanical properties of the films are shown in Table 2.
TABLE 1 solubility of the prepolymers of the invention in various solvents at room temperature
Note: the solubility at room temperature is more than 30 percent
TABLE 2 glass transition temperature and mechanical Properties of films after curing of prepolymers according to the invention
Note: curing conditions, 1 hour at 370 ℃.
Claims (8)
1. A thermosetting polyimide prepolymer with high solubility is characterized in that the structural general formula of the thermosetting polyimide prepolymer is shown as formula (I):
wherein m and n are polymerization degrees, wherein m is more than 0, and n is more than or equal to 0;
Ar1、Ar2one selected from the following structural formulas:
ar' is aromatic dianhydride monomer residue and is selected from one of the following structural formulas:
wherein R is1Is one of the following structural formulas:
the solubility of the thermosetting polyimide prepolymer in low-boiling-point solvents of tetrahydrofuran, 1, 4-dioxane, chloroform and acetone is more than 30 wt%.
2. The thermosetting polyimide prepolymer having high solubility according to claim 1, wherein Ar' is selected from one of the following structural formulas (a), (b), (c):
3. the thermosetting polyimide prepolymer with high solubility according to claim 1, wherein the number average molecular weight of the thermosetting polyimide prepolymer is 500g/mol to 10000 g/mol.
4. The method for preparing the thermosetting polyimide prepolymer having high solubility according to any one of claims 1 to 3, comprising the steps of:
(1) under the protection of nitrogen, dissolving diamine monomer mixtures shown in structural formulas (IV) and (V) into a polar aprotic solvent;
(2) adding a dianhydride monomer mixture shown in a structural formula (II) and a structural formula (III), wherein the feeding molar ratio of the two components is 7/3-10/0, and stirring for 5-8 hours at room temperature;
(3) adding a blocking agent 4-phenylacetylene phthalic anhydride, and stirring at room temperature for 6-24 hours;
(4) adding an azeotropic water-carrying agent, wherein the mass ratio of the water-carrying agent to the solvent is 1: 2-5, and heating and refluxing for 6-24 hours;
(5) cooling the system to room temperature, pouring the solution into a poor solvent, precipitating powder, filtering, taking the filter residue, boiling, washing and drying to obtain thermosetting polyimide prepolymer powder,
wherein Ar' and Ar1And Ar2Of claim 1 to 3Ar' in any item1And Ar2The structural definition of (a) is consistent;
the molar ratio of the dianhydride monomer mixture, the diamine monomer mixture and the end capping agent in the steps (1) to (3) is p (p +1) to 2, wherein p is more than 0.
5. The method of claim 4, wherein the polar aprotic solvent is one of N-methylpyrrolidone, N '-dimethylacetamide and N, N' -dimethylformamide.
6. The method of claim 4, wherein the water-carrying agent is toluene or xylene.
7. The method of claim 4, wherein the poor solvent is one of methanol, ethanol and deionized water.
8. Use of the thermosetting polyimide prepolymer with high solubility according to claim 1 for the preparation of low porosity thermosetting polyimide resin based composites.
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| JP2009286868A (en) * | 2008-05-28 | 2009-12-10 | Jfe Chemical Corp | Linear polyimide precursor, linear polyimide, thermally cured product thereof, production method, adhesive and copper-clad laminate |
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