CN113292816A - Cross-linked polyetherimide/polyether-ether-ketone blending material and preparation method and application thereof - Google Patents
Cross-linked polyetherimide/polyether-ether-ketone blending material and preparation method and application thereof Download PDFInfo
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Abstract
本发明提供一种交联型聚醚酰亚胺/聚醚醚酮共混材料及其制备方法和应用，所述共混材料含有聚醚酰亚胺聚合物和聚醚醚酮聚合物。本发明的交联型聚醚酰亚胺/聚醚醚酮共混材料的玻璃化转变温度较聚醚醚酮聚合物基体的基础上提高了20℃以上，最大拉伸模量可以达到108MPa左右，同时，其结晶度仍保持在28％以上。实验证明，本发明的交联型聚醚酰亚胺/聚醚醚酮共混材料同时兼有较高的玻璃化转变温度、较高的机械性能，是一种有希望在航空航天、军事国防、新能源等领域得到应用的新型材料。
The invention provides a cross-linked polyetherimide/polyetheretherketone blend material, a preparation method and application thereof, wherein the blended material contains a polyetherimide polymer and a polyetheretherketone polymer. The glass transition temperature of the cross-linked polyetherimide/polyetheretherketone blend material of the present invention is higher than that of the polyetheretherketone polymer matrix by more than 20°C, and the maximum tensile modulus can reach about 108MPa , and at the same time, its crystallinity remains above 28%. Experiments have proved that the cross-linked polyetherimide/polyetheretherketone blend material of the present invention has both higher glass transition temperature and higher mechanical properties, and is a promising material in aerospace, military and national defense. , new energy and other fields of new materials have been applied.
Description
Technical Field
The invention belongs to the technical field of special engineering plastic materials, and particularly relates to a cross-linked polyetherimide/polyetheretherketone polymer blend material, and a preparation method and application thereof.
Background
Since the 20 th century, the aerospace technology has been rapidly developed under the influence of military competition, so that the demand of heat-resistant, light-weight and high-strength materials has been increased rapidly, and a great deal of effort has been put into developing novel materials with excellent performance in various countries around the world. The special engineering plastic is a third-generation plastic developed after a first-generation general plastic and a second-generation engineering plastic, and mainly refers to a class of plastic with a long-term use temperature higher than 150 ℃, such as Polyimide (PI), polyphenylene sulfide (PPS), Polysulfone (PSU), polyether sulfone (PES) and polyether ether ketone (PEEK). The special engineering plastic has the added values of light specific gravity, high specific strength and the like, and can be made into coatings, fibers, films, structural materials and the like according to requirements, so the special engineering plastic has wide application markets in the high and new technical fields of aerospace, electronic devices, light weight and new energy automobiles, petroleum and natural gas development, biological bone materials, biological dental materials, hemodialysis and the like. However, with the development of science and technology, the existing special engineering plastics still have some defects, mainly have higher requirements on the temperature resistance, and need to keep stable performance at higher temperature.
Among them, polyether ether ketone (PEEK) is a wholly aromatic polymer containing only benzene rings, carbonyl groups and ether bonds in the repeating units of the molecular chain. The high-temperature-resistant and high-temperature-resistant polypropylene composite material is a semi-crystalline polymer, the common crystallinity is 20-30%, the glass transition temperature Tg is about 143 ℃, the melting point Tm is as high as 343 ℃, the processing performance of the high-temperature-resistant and high-temperature-resistant polypropylene composite material is excellent, the high-temperature-resistant and high-temperature-resistant polypropylene composite material can be processed into various forms such as corresponding sheets, plates, pipes and the like by adopting various methods such as extrusion molding, injection molding, compression molding, melt spinning and the like, and the high-temperature-resistant and high-temperature-resistant polypropylene composite material is one of plastic varieties with the best comprehensive performance and the best heat-resistant grade in the existing special engineering plastics. But the relatively low Tg limits the further development of the special engineering plastic and cannot meet the requirement of the special engineering plastic on temperature resistance.
Polyetherimide (PEI) refers to a class of aromatic polymers containing imide rings on a main chain, and is one of the most abundant structural types and the most diverse forms in special engineering plastics. The high-temperature-resistant high-strength heat-resistant plastic has excellent thermal stability and mechanical properties, is resistant to temperature and radiation, and is a special engineering plastic with excellent performance. But the solvent resistance and hydrolysis resistance are poor, the viscosity in a molten state is high, and the processability is poor, which bring some limitations to the application of the polyetherimide.
Disclosure of Invention
In order to solve the problems that the performance of the existing special engineering plastic, particularly PEEK is unstable at the working temperature of more than 125 ℃ due to the low Tg of the PEEK, and the like, the invention provides a cross-linking type polyetherimide/polyetheretherketone blending material, a preparation method and application thereof, wherein the blending material has the advantages of high temperature resistance, high mechanical property and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a cross-linking type polyetherimide/polyether-ether-ketone blending material, which is prepared from raw materials containing a polyetherimide polymer and a polyether-ether-ketone polymer.
According to an embodiment of the present invention, the content of the cross-linked polyetherimide polymer in the blend material is 5 to 30% by mass, preferably 10 to 20% by mass, for example 10%, 12%, 15%, 17%, 20%.
According to an embodiment of the present invention, the content of the polyetheretherketone polymer in the blend material is 70 to 95% by mass, preferably 80 to 90% by mass, for example 80%, 83%, 85%, 88%, 90%.
According to an embodiment of the invention, the glass transition temperature Tg of the blended material is raised by at least 20 ℃ above the Tg temperature of the polyetheretherketone polymer; for example, the glass transition temperature Tg of the blended material is 160-175 ℃, and preferably 160-167.7 ℃.
According to an embodiment of the invention, the maximum tensile modulus of the blended material is from 80 to 110MPa, for example from 90 to 106 MPa.
According to an embodiment of the invention, the crystallinity of the blended material is above 28%, for example 28.5-32%.
According to an embodiment of the present invention, the blended material has a morphology substantially as shown in any one of (2) - (5) of fig. 3.
According to an embodiment of the invention, the cross-linked polyetherimide polymer and the polyether-ether-ketone polymer in the blended material are completely mutually soluble and have no phase separation.
According to an embodiment of the invention, the polyetherimide polymer is end-capped with activated functional groups. End-capping in the present invention means that at least one end of the polyetherimide polymer is end-capped with an activated functional group; preferably, both ends of the polyetherimide polymer are terminated with activated functional groups.
Preferably, the activating functional group is a phenylalkynyl group.
According to an embodiment of the invention, the activating functional group is derived from a capping agent, preferably 4-phenylethynylphthalic anhydride (PEPA).
According to an embodiment of the invention, the polyetherimide polymer is prepared after end-capping by the end-capping agent.
According to an exemplary embodiment of the invention, the polyetherimide polymer is derived from the reaction of 4, 4' -diaminodiphenyl ether (ODA), bisphenol a type diether dianhydride (BPADA), and the end-capping agent.
According to the embodiment of the invention, the molar ratio of 4, 4' -diaminodiphenyl ether (ODA), bisphenol A type diether dianhydride (BPADA) and the end-capping agent is (1.0-1.3) to 1 (0-0.6); preferably, (1.1-1.2): 1, (0.2-0.4), preferably 1.1:1:0.2 or 1.2:1: 0.4.
According to an embodiment of the invention, the crosslinked polyetherimide is derived from polyetherimide polymers having activated functional groups that crosslink with each other.
According to an exemplary aspect of the present invention, the cross-linked polyetherimide/polyetheretherketone blend material may be any one of 10 wt% (10 mol% ODA-PEI)/PEEK, 20 wt% (10 mol% ODA-PEI)/PEEK, 10 wt% (20 mol% ODA-PEI)/PEEK, or 20 wt% (20 mol% ODA-PEI)/PEEK.
The invention also provides a preparation method of the crosslinking polyetherimide/polyetheretherketone blending material, which comprises the following steps: and blending the polyetherimide polymer and the polyether-ether-ketone, and performing melt extrusion to obtain the cross-linked polyetherimide/polyether-ether-ketone blended material.
Preferably, the polyetherimide polymer, polyetheretherketone, and cross-linked polyetherimide each have the definitions as described above.
According to an embodiment of the present invention, the preparation method comprises the steps of:
(1) reacting 4, 4' -diaminodiphenyl ether (ODA), bisphenol A type diether dianhydride (BPADA) and the end-capping reagent to prepare a polyetherimide polymer;
(2) preparing or preparing polyether-ether-ketone as a matrix of the blending material;
(3) and (3) blending the polyetherimide polymer prepared in the step (1) and the polyether-ether-ketone prepared in the step (2), and performing melt extrusion to prepare the crosslinking type polyetherimide/polyether-ether-ketone blended material.
According to the embodiment of the invention, the mass ratio of the polyetherimide polymer to the polyether-ether-ketone in blending is (1-2) to (9-8), and preferably 2: 8. The polyether ether ketone used for preparing the blend material is not particularly limited in the present invention, and can be obtained by commercially available methods or methods known in the art.
According to an embodiment of the present invention, the blending may be performed by means of blending known in the art, preferably mechanical blending. Preferably, the blending time is 30s of high speed stirring.
According to an embodiment of the present invention, the blending may further include drying the blend under vacuum. The drying conditions are not particularly limited in the present invention, and a drying method commonly used in the art, for example, 90 ℃ treatment under vacuum for 12 hours, can be adopted.
According to an embodiment of the present invention, in the step (1), the mixture ratio of 4, 4' -diaminodiphenyl ether (ODA), bisphenol a type diether dianhydride (BPADA), and the end-capping agent has the mixture ratio as described above.
Preferably, the capping agent is selected as described above.
According to an embodiment of the invention, the reaction of step (1) takes place in the presence of a solvent. Preferably, the solvent is N, N-dimethylacetamide (DMAc).
According to an embodiment of the present invention, the reaction of step (1) includes copolymerization, capping and a ring-buckle reaction.
According to an embodiment of the invention, the loop reaction is carried out in the presence of triethylamine and acetic anhydride.
Preferably, the molar ratio of triethylamine to 4, 4' -diaminodiphenyl ether (ODA) is (1.5-5) to 1, preferably 3: 1; preferably, the molar ratio of triethylamine to acetic anhydride is (0.5-1.5):1, preferably 1: 1.
According to an embodiment of the invention, the polyetherimide polymer is end-capped with activated functional groups. Preferably, the activating functional group and the end-capping have the meanings as indicated above.
According to an exemplary embodiment of the present invention, the method for preparing the polyetherimide polymer of step (1) specifically comprises the steps of: dissolving ODA and BPADA in the solvent according to the proportion for polymerization; adding PEPA according to the proportion to carry out end-capping reaction; and adding triethylamine and acetic anhydride according to the proportion, and carrying out a retaining ring reaction to obtain the polyetherimide polymer.
According to the embodiment of the invention, the reaction in the step (1) is carried out at normal temperature, preferably 10-40 ℃, and more preferably 20-30 ℃.
According to an embodiment of the invention, the polymerization is carried out in an inert environment, illustratively provided by a nitrogen atmosphere;
for example, the polymerization time is 8 to 14 hours, preferably 12 hours;
for example, the end-capping time is 4-8 h, preferably 6 h;
according to the embodiment of the invention, the time of the buckle ring reaction is 2-6 h, and preferably 3 h.
According to an embodiment of the present invention, the preparation method in step (1) further comprises discharging after the buckle reaction is completed. For example, the discharge is carried out in ethanol.
The invention also provides application of the cross-linked polyetherimide/polyetheretherketone blended material in the fields of aerospace, military and national defense or new energy and the like.
The invention has the beneficial effects that:
the invention utilizes the characteristics of the PEEK and the PEI as polymers which are mutually completely compatible, combines the performances of the PEEK and the PEI simply, conveniently and effectively in a polymer blending mode, and performs advantage complementation to finally obtain a novel blending material with comprehensive performance more meeting the application requirements.
Specifically, the invention uses Polyetherimide (PEI) with good thermal and mechanical properties and containing activated functional groups (such as phenyl alkynyl end capping) to prepare the cross-linked polyetherimide/polyetheretherketone blending material with good heat resistance, flexibility and high mechanical properties by using the PEI as the blending modification material of the polyetheretherketone. The prepared cross-linked polyetherimide/polyetheretherketone blended material has higher glass transition temperature, wider temperature application range and obviously improved tensile modulus, thereby obtaining more excellent mechanical properties. The glass transition temperature of the cross-linking type polyetherimide/polyetheretherketone blending material is improved by more than 20 ℃ compared with that of a polyetheretherketone polymer matrix, and the crystallization behavior of the polyetheretherketone can not be obviously influenced due to the small addition amount of the polyetherimide. By adjusting the components and the content of the crosslinking polyetherimide, the maximum tensile modulus of the blended material can reach about 108MPa, and simultaneously, the crystallinity of the blended material is still kept above 28 percent. Experiments prove that the cross-linked polyetherimide/polyetheretherketone blended material has higher glass transition temperature and higher mechanical property, and is a novel material which is hopefully applied in the fields of aerospace, military and national defense, new energy and the like.
Compared with the development of a new variety of polymers, the polymer blending material has the advantages of shorter research period, lower research cost and more diversified products. Meanwhile, the crosslinking group (such as an activated functional group blocked by a phenyl alkynyl) is introduced, so that a more obvious effect can be achieved under the condition of doping less PEI, the material performance is ensured, the stability of the material is improved, the cost is reduced to a certain degree, and the industrialization of the material is facilitated.
Drawings
FIG. 1 is a schematic diagram of the preparation of samples of preparation examples 1 and 2.
FIG. 2 is an infrared spectrum of samples of preparation examples 1 to 2, examples 1 to 4 and comparative example 1.
FIG. 3 is a scanning electron micrograph of samples of examples 1 to 4 and comparative example 1.
FIG. 4 is a DSC curve of samples of examples 1 to 4 and comparative example 1.
FIG. 5 is a tensile stress strain curve of the samples of examples 1-4 and comparative example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Preparation example 1
Preparation of a 10% (molar content) phenylalkynyl terminated polyetherimide polymer:
adding 4.4051g (0.022mol) of ODA and 10.4097g (0.02mol) of BPADA into a reaction container, wherein the molar ratio of the ODA and the BPADA is 1.1:1, adding 100mL of DMAc solvent into the container, and stirring and reacting for 12 hours at room temperature of 20-30 ℃ in a nitrogen atmosphere; then adding 0.9930g (0.004mol) of PEPA and 10mL of DMAc, and stirring at room temperature for reaction for 6 h; adding 9.17mL (0.066mol) of triethylamine, adding 6.24mL (0.066mol) of acetic anhydride, stirring at room temperature for reaction for 3h, separating out in ethanol at room temperature, filtering to obtain a filter cake, boiling with ethanol, refluxing and washing for 6 times, filtering, and drying in a vacuum oven at 90 ℃ for 12 h; a polyetherimide polymer containing 10% of a phenyl alkynyl end cap was prepared and designated 10% ODA-PEI.
FIG. 1 is a schematic diagram of the preparation of polyetherimide (ODA-PEI).
Preparation example 2
Preparation of a polyetherimide polymer containing 20% (molar content) of a phenyl alkynyl end-capped:
the other steps are the same as the preparation example 1, and only differ:
the mol ratio of the raw materials ODA, BPADA and PEPA is 1.2:1: 0.4.
A polyetherimide polymer containing 20% phenyl alkynyl end-caps was prepared and designated 20% ODA-PEI.
Example 1
(1) Polyether-ether-ketone (manufacturer: Changchun Jida Teplastic engineering research Co., Ltd.; model: melt index 46g/10min) was purchased and used as a polymer matrix;
(2) preparing a cross-linking polyetherimide/polyether-ether-ketone polymer blending material:
the 10% ODA-PEI prepared in the preparation example 1 and the polyether-ether-ketone are taken according to the mass ratio of 1:9, mechanically blended and stirred at a high speed for 30s, and then melt extruded at 380 ℃ to prepare the cross-linked polyetherimide/polyether-ether-ketone blended material, wherein the content of 10% ODA-PEI in the blended material is 10 wt%, and the blended material is named as 10 wt% (10% ODA-PEI)/PEEK.
Example 2
The other steps are the same as example 1, except that: the mass ratio of 10% ODA-PEI to polyether ether ketone is 2: 8.
In the prepared cross-linked polyetherimide/polyetheretherketone blend material, the content of 10% ODA-PEI is 20 wt%, and the blend material is named as 20 wt% (10% ODA-PEI)/PEEK.
Example 3
The other steps are the same as example 1, except that:
the mass ratio of 20% of ODA-PEI prepared in preparation example 2 to 20% of ODA-PEI to polyether ether ketone is 1: 9.
In the prepared cross-linked polyetherimide/polyetheretherketone blend material, the content of 20% ODA-PEI is 10 wt%, and the blend material is named as 10 wt% (20% ODA-PEI)/PEEK.
Example 4
The other steps are the same as example 3, and only differ:
the mass ratio of 20% ODA-PEI to polyetheretherketone is 2: 8.
The cross-linking polyetherimide/polyetheretherketone polymer blend material is prepared, wherein the content of 20 percent ODA-PEI is 20 percent by weight, and the material is named as 20 percent by weight (20 percent ODA-PEI)/PEEK.
Comparative example 1
Polyetheretherketone (manufacturer: Changchun Jida engineering research Co., Ltd.; model: melt index 46g/10min) was used as comparative example 1.
Test example
10% ODA-PEI and 20% ODA-PEI obtained in the above preparation examples 1-2, 10 wt% (10% ODA-PEI)/PEEK, 20 wt% (10% ODA-PEI)/PEEK, 10 wt% (20% ODA-PEI)/PEEK, 20 wt% (20% ODA-PEI)/PEEK and PEEK of comparative example 1 were taken as samples and tested to obtain the following test results:
FIG. 2 is an infrared spectrum of samples of preparation examples 1-2, examples 1-4 and comparative example 1, which proves that the product is successfully prepared. The model of the testing instrument is a Nicolct Impact 410 Fourier transform infrared spectrometer. The specific test method comprises the following steps: i. for the membrane sample, air is directly used as a reference, and the membrane sample is measured at room temperature to be 400-4000 cm-1Infrared transmission curve in the range. And ii, completely drying the powder sample in a vacuum oven, and measuring the thickness of the powder sample at the room temperature of 400-4000 cm by using a tabletting method by taking potassium bromide as a reference-1Infrared transmission curve in the range. Wherein 1776cm-1And 1720cm-1The absorption peaks are respectively the absorption peaks of the symmetric stretching vibration and the asymmetric stretching vibration of the carbonyl in the polyimide, and the absorption peak is 1375cm-1The position is a tensile vibration absorption peak of an imide bond, which proves that the polyetherimide is successfully introduced into the composite material; 2210cm in the IR spectrum of 10% ODA @ PEI and 20% ODA @ PEI-1Is the absorption vibration peak of alkynyl, but the absorption peak is not existed in the infrared spectrum of the composite material, which proves that the alkynyl is crosslinked during the processing of the composite materialAnd (4) completing.
FIG. 3 is a scanning electron micrograph of samples of examples 1 to 4 and comparative example 1. The model of the testing instrument is a FEI Nova nano 450 type field emission scanning electron microscope. The specific sample preparation method comprises the following steps: the extruded and granulated sample is quenched in liquid nitrogen, adhered to a sample table by a conductive adhesive, subjected to metal spraying treatment, and tested under a vacuum condition. Wherein, (1) represents PEEK; (2) represents 10 wt% (10% ODA-PEI)/PEEK; (3) represents 20 wt% (10% ODA-PEI)/PEEK; (4) represents 10 wt% (20% ODA-PEI)/PEEK; (5) representing 20 wt% (20% ODA-PEI)/PEEK. It can thus be seen that: the blend did not phase separate and the PEEK and PEI were completely compatible.
FIG. 4 is a DSC curve of samples of examples 1 to 4 and comparative example 1, and the test apparatus model is TA Q2000 type differential scanning calorimetry analyzer. The specific test method comprises the following steps: fully drying a sample, weighing 6-7 mg of the sample, preparing the sample in a Mettler crucible, taking an empty crucible as a reference, testing in a nitrogen environment (the nitrogen flow rate is 50mL/min), and obtaining a DSC curve, wherein the temperature rise rate is 20 ℃/min and the temperature range is 30-400 ℃. As can be seen from the test results in FIG. 4, Tg (PEEK) was 144.99 deg.C, Tg (10 wt% (10% ODA-PEI)/PEEK) was 160.71 deg.C, Tg (20 wt% (10% ODA-PEI)/PEEK) was 161.62 deg.C, Tg (10 wt% (20% ODA-PEI)/PEEK) was 162.15 deg.C, and Tg (20 wt% (20% ODA-PEI)/PEEK) was 167.71 deg.C. The glass transition temperature Tg of the blending material is obviously improved compared with that of PEEK, and the glass transition temperature Tg of the blending material can be adjusted along with the adjustment of the dosage of the polyetherimide.
FIG. 5 is a tensile stress-strain curve of samples of examples 1 to 4 and comparative example 1, with a test apparatus model AG-I20KN universal tester. The specific test method comprises the following steps: the sample is hot-pressed into a film, then cut into a tensile sample with the length of 4cm and the width of 0.5cm, and the tensile property is measured at room temperature, wherein the tensile speed is 5mm/min until the sample is broken. As can be seen from FIG. 5, as the excess ODA ratio increases and the PEI content increases, the mechanical strength of the blend increases, the elongation at break decreases, i.e., the stiffness of the material increases and the toughness decreases, indicating that the mechanical properties of the blended material can be adjusted as the amount of polyetherimide is adjusted.
TABLE 1 Properties of examples 1-4 and comparative example 1 samples
| Sample (I) | Glass transition temperature/. degree.C | Degree of crystallization/%) | Maximum tensile stress/MPa |
| Comparative example 1 | 144.99 | 30.55 | 80.5 |
| Example 1 | 160.71 | 29.79 | 84.8 |
| Example 2 | 161.62 | 27.79 | 90.7 |
| Example 3 | 162.15 | 30.05 | 99.3 |
| Example 4 | 167.71 | 28.72 | 105.4 |
The invention synthesizes and adopts Polyetherimide (PEI) with good thermal and mechanical properties and containing activated functional groups (such as phenyl alkynyl end capping) as a blending modified material of polyether-ether-ketone to prepare the crosslinking type polyetherimide/polyether-ether-ketone high polymer blending material with good heat resistance, flexibility and high mechanical properties. As can be seen from Table 1, the prepared cross-linked polyetherimide/polyetheretherketone polymer blend material has a high glass transition temperature and a wide temperature application range, and the tensile modulus of the cross-linked polyetherimide/polyetheretherketone polymer blend material is also obviously improved, so that excellent mechanical properties are obtained.
The glass transition temperature of the cross-linking type polyetherimide/polyetheretherketone polymer blend material is improved by more than 20 ℃ compared with that of a polyetheretherketone polymer matrix, and the DSC curve shows that the crystallization behavior of the polyetheretherketone is not obviously influenced due to the small addition amount of the polyetherimide. The maximum tensile modulus of the prepared cross-linking polyetherimide/polyether-ether-ketone polymer blend material can reach about 108MPa by adjusting the components and the content of the cross-linking polyetherimide, and simultaneously, the crystallinity of the cross-linking polyetherimide/polyether-ether-ketone polymer blend material is still kept above 28 percent. Experiments prove that the cross-linked polyetherimide/polyetheretherketone polymer blend material has higher glass transition temperature and higher mechanical property, and is a novel material which is hopefully applied in the fields of aerospace, military and national defense, new energy and the like.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A cross-linked polyetherimide/polyetheretherketone blend material, wherein the blend material comprises a polyetherimide polymer and a polyetheretherketone polymer.
2. The blend material according to claim 1, wherein the mass percentage of the cross-linked polyetherimide polymer in the blend material is 5-30%;
preferably, the mass percentage of the polyether-ether-ketone polymer in the blending material is 70-95%.
3. The blend material according to claim 1 or 2, characterized in that the glass transition temperature Tg of the blend material is raised by at least 20 ℃ above the Tg temperature of the polyetheretherketone polymer;
preferably, the maximum tensile modulus of the blended material is 80-110 MPa;
preferably, the crystallinity of the blend material is above 28%, for example 28.5-32%.
4. The blend material of any of claims 1-3, wherein the polyetherimide polymer is end-capped with an activated functional group;
preferably, the activating functional group is a phenylalkynyl group;
preferably, the crosslinked polyetherimide is derived from polyetherimide polymers in which activated functional groups are crosslinked to each other;
preferably, the activating functional group is derived from an end-capping agent, preferably 4-phenylethynylphthalic anhydride (PEPA);
preferably, the polyetherimide polymer is prepared after the end capping agent is used for end capping;
preferably, the polyetherimide polymer is obtained by reacting 4, 4' -diaminodiphenyl ether (ODA), bisphenol a type diether dianhydride (BPADA) and the end-capping agent;
preferably, the molar ratio of the 4, 4' -diaminodiphenyl ether (ODA), the bisphenol A type diether dianhydride (BPADA) and the end-capping agent is (1.0-1.3): 1 (0-0.6).
5. The method of preparing the crosslinked polyetherimide/polyetheretherketone blend material of any one of claims 1 to 4, wherein the method of preparation comprises the steps of: and blending the polyetherimide polymer and the polyether-ether-ketone, and performing melt extrusion to obtain the cross-linked polyetherimide/polyether-ether-ketone blended material.
6. The method of claim 5, comprising the steps of:
(1) reacting 4, 4' -diaminodiphenyl ether (ODA), bisphenol A type diether dianhydride (BPADA) and the end-capping agent to prepare a polyetherimide polymer;
(2) preparing or preparing polyether-ether-ketone as a matrix of the blending material;
(3) and (3) blending the polyetherimide polymer prepared in the step (1) and the polyether-ether-ketone prepared in the step (2), and performing melt extrusion to prepare the crosslinking type polyetherimide/polyether-ether-ketone blended material.
7. The preparation method according to claim 5 or 6, wherein the mass ratio of the polyetherimide polymer to the polyether-ether-ketone in blending is (1-2) to (9-8);
preferably, the blending can also comprise drying the blend under vacuum condition;
preferably, the reaction of step (1) occurs in the presence of a solvent; preferably, the solvent is N, N-dimethylacetamide (DMAc).
8. The production method according to any one of claims 5 to 7, wherein the reaction in step (1) comprises copolymerization, end-capping, and retaining ring reaction;
preferably, the ring-opening reaction is carried out in the presence of triethylamine and acetic anhydride;
preferably, the molar ratio of triethylamine to 4, 4' -diaminodiphenyl ether (ODA) is (1.5-5): 1;
preferably, the molar ratio of triethylamine to acetic anhydride is (0.5-1.5): 1;
preferably, the polyetherimide polymer is end-capped with an activating functional group.
9. The method of any of claims 5-8, wherein the method of preparing the polyetherimide polymer of step (1) specifically comprises the steps of: dissolving ODA and BPADA in the solvent according to the proportion for polymerization; adding PEPA in proportion to carry out end capping reaction; adding triethylamine and acetic anhydride, and performing a retaining ring reaction to obtain the polyetherimide polymer;
preferably, the reaction of step (1) is carried out at normal temperature;
preferably, the polymerization is carried out in an inert environment;
preferably, the polymerization time is 8-14 h;
preferably, the end-capping time is 4-8 h;
preferably, the time of the buckle ring reaction is 2-6 h;
preferably, the preparation method in step (1) further comprises discharging after the buckle reaction is completed.
10. Use of the cross-linked polyetherimide/polyetheretherketone blend material of any one of claims 1 to 4 in the fields of aerospace, military defense or new energy.
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