CN113416127A - Cross-linkable semi-crystalline polyether-ether-ketone, preparation method and application thereof, polyether-ether-ketone polymer alloy material and preparation method thereof - Google Patents
Cross-linkable semi-crystalline polyether-ether-ketone, preparation method and application thereof, polyether-ether-ketone polymer alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to crosslinkable semicrystalline polyether-ether-ketone and a preparation method and application thereof, and a polyether-ether-ketone high polymer alloy material and a preparation method thereof. The crosslinkable semi-crystalline polyether-ether-ketone provided by the invention is a semi-crystalline polymer, and can still keep a certain crystallization property after crosslinking, and the crystal form is unchanged, so that the crosslinkable semi-crystalline polyether-ether-ketone has excellent high temperature resistance, mechanical property and solvent resistance. The cross-linkable semi-crystalline polyether-ether-ketone provided by the invention can be mixed with pure polyether-ether-ketone to prepare an alloy material, so that the high-temperature mechanical property of the alloy material at 148 ℃ is improved, and the tensile strength of the alloy material is enhanced while the toughness is kept.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to crosslinkable semicrystalline polyether-ether-ketone and a preparation method and application thereof, and a polyether-ether-ketone high polymer alloy material and a preparation method thereof.
Background
With the rapid development of the fields of aerospace, national defense science and technology, civil construction and the like, the requirement on high-temperature resistant materials is higher and higher. Polyetheretherketone is a typical wholly aromatic semi-crystalline polymer material, and has excellent heat resistance, solvent resistance and mechanical properties, so the polyetheretherketone becomes a special engineering plastic in the fields of aerospace, national defense science and technology, energy and chemical engineering, transportation and the like. However, the glass transition temperature of polyetheretherketone is around 143 ℃ and its mechanical properties are greatly attenuated at high temperatures, which makes it impossible to apply polyetheretherketone at higher temperatures.
Crosslinking is an effective way to increase the use temperature of the polymer, such as phenylethynyl terminated crosslinking. Chinese patent publication No. CN111004507A introduces phenyl alkynyl as a crosslinkable functional group, so that a polyetherimide matrix with good heat resistance undergoes a crosslinking reaction to form a network structure, thereby preparing a crosslinked polyetherimide dielectric composite film with good thermal stability and dielectric properties; chinese patent publication No. CN108102097A introduces phenyl alkynyl as a crosslinkable functional group, designs and synthesizes a series of polyimide copolymers containing phenyl alkynyl, and performs functionalization on phenyl alkynyl polyimide through thermal crosslinking and Diels Alder reaction (Diels-Alder), thereby preparing a thermal crosslinking polyimide film and a polyimide chemical modification film having high heat resistance. For the amorphous polymer, the heat resistance can be greatly improved by crosslinking, but the crystallization performance of the amorphous polymer can be damaged to a certain extent, so that the amorphous polymer still has the phenomena of brittleness and greatly reduced mechanical performance and solvent resistance after the temperature is higher than the glass transition temperature, and the amorphous polymer is not beneficial to practical application. Therefore, how to improve the high temperature resistance of the polyetheretherketone and simultaneously make the polyetheretherketone have high mechanical properties at high temperature (148 ℃) is a problem to be solved urgently.
Disclosure of Invention
In view of the above, the present invention aims to provide a crosslinkable semi-crystalline polyetheretherketone having high mechanical properties at high temperature (148 ℃) while having excellent high temperature resistance.
The invention provides a crosslinkable semi-crystalline polyether-ether-ketone which has a structure shown in a formula I:
wherein n is 1 to 3,
r1 is
And R2 is
Or R1 is
And R2 is
The invention also provides a preparation method of the cross-linkable semi-crystalline polyether-ether-ketone in the technical scheme, which comprises the following steps:
carrying out azeotropic reflux on first mixed 4,4' -difluorobenzophenone, hydroquinone, a water-carrying agent, a metal salt catalyst and an organic solvent to obtain a mixed solution;
secondly, mixing the mixed solution and an end-capping reagent for polymerization reaction to obtain the crosslinkable semi-crystalline polyether-ether-ketone with the structure shown in the formula I;
the end-capping reagent is 4- (2-phenylethynyl) phenol or 4-fluoro-4' - (phenylethynyl) benzophenone.
Preferably, the molar ratio of the 4,4' -difluorobenzophenone, the hydroquinone and the end-capping agent is 3.15:3 (0.05-0.3).
Preferably, the metal salt catalyst comprises one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride; the molar ratio of the metal salt catalyst to the hydroquinone is (0.9-2) to (0.1-0.5).
Preferably, the water-carrying agent comprises one or more of benzene, toluene, xylene and cyclohexane; the organic solvent comprises sulfolane and/or diphenyl sulfone; the dosage ratio of the water-carrying agent to the organic solvent is (10-50) mL:100 g.
Preferably, the solid content of the mixed solution obtained by mixing the 4,4' -difluorobenzophenone, the hydroquinone, the water-carrying agent, the metal salt catalyst and the organic solvent is 15-25% by mass percentage.
Preferably, the temperature of the polymerization reaction is 200-260 ℃, and the time of the polymerization reaction is 4-8 h.
The invention also provides the application of the crosslinkable semi-crystalline polyether-ether-ketone in the technical scheme or the crosslinkable semi-crystalline polyether-ether-ketone obtained by the preparation method in the technical scheme in the thermoplastic polymer material.
The invention also provides a polyether-ether-ketone polymer alloy material, which comprises polyether-ether-ketone and crosslinkable semi-crystalline polyether-ether-ketone, wherein the crosslinkable semi-crystalline polyether-ether-ketone is the crosslinkable semi-crystalline polyether-ether-ketone according to claim 1; the mass ratio of the cross-linkable semi-crystalline polyether-ether-ketone to the polyether-ether-ketone is (5-30): 100.
The invention also provides a preparation method of the polyether-ether-ketone polymer alloy material in the technical scheme, which comprises the following steps:
mixing crosslinkable semi-crystalline polyether-ether-ketone and polyether-ether-ketone, and then sequentially carrying out melt extrusion, granulation and drying to obtain crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles;
sequentially carrying out injection molding and heat treatment on the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles to obtain a polyether-ether-ketone polymer alloy material;
the temperature of the melt extrusion is 380-390 ℃; the injection molding temperature is 380-390 ℃; the temperature of the heat treatment is 350-410 ℃, and the time is 10-30 min.
The invention provides a crosslinkable semi-crystalline polyether-ether-ketone. The crosslinkable semi-crystalline polyether-ether-ketone provided by the invention belongs to a semi-crystalline polymer, can still keep a certain crystallization property after crosslinking, has a crystal form which is not changed, and has phenylalkynyl, the phenylalkynyl can be subjected to chain extension and crosslinking at 350 ℃, and polymer chain segments are more tightly stacked after chain extension and crosslinking, so that the high-temperature resistance of the crosslinkable semi-crystalline polyether-ether-ketone is improved, and the crosslinkable semi-crystalline polyether-ether-ketone has high mechanical property at high temperature (148 ℃).
In addition, the crosslinkable semi-crystalline polyether-ether-ketone provided by the invention has excellent solvent resistance, and the crosslinking temperature of the phenyl alkynyl can avoid the processing window of the polyether-ether-ketone, so that the thermosetting after processing and molding is favorably realized.
In addition, the crosslinkable semi-crystalline polyether-ether-ketone provided by the invention can be mixed with pure polyether-ether-ketone to prepare a polyether-ether-ketone polymer alloy material, and the introduction of the crosslinkable semi-crystalline polyether-ether-ketone improves the high-temperature mechanical property of the polyether-ether-ketone polymer alloy material at 148 ℃, so that the crosslinkable semi-crystalline polyether-ether-ketone polymer alloy material has certain toughness and simultaneously improves the tensile strength.
Drawings
FIG. 1 is a chart of the infrared spectra of the crosslinkable semicrystalline polyether ether ketone prepared in example 2 before and after sulfonation;
FIG. 2 is a DSC of the cross-linkable semi-crystalline polyetheretherketone prepared in example 2;
FIG. 3 is a TGA profile of a cross-linkable semi-crystalline polyetheretherketone prepared in example 2;
FIG. 4 is a DSC of the cross-linkable semi-crystalline polyetheretherketone prepared in example 2 after heat treatment;
FIG. 5 is a TGA graph of a crosslinkable semicrystalline polyether ether ketone prepared in example 2 after and after heat treatment;
FIG. 6 is XRD patterns of the crosslinkable semicrystalline polyether ether ketone prepared in example 2 before and after heat treatment;
FIG. 7 is a chart showing the infrared spectra of the crosslinkable semicrystalline polyether ether ketone prepared in example 8 before and after heat treatment;
FIG. 8 is a DSC of the cross-linkable semi-crystalline polyetheretherketone prepared in example 8;
FIG. 9 is a TGA profile of a cross-linkable semi-crystalline polyetheretherketone prepared in example 8;
FIG. 10 is a DSC of the cross-linkable semi-crystalline polyetheretherketone prepared in example 8 after heat treatment;
FIG. 11 is a TGA profile of a cross-linkable semi-crystalline polyetheretherketone prepared in example 8 after heat treatment;
FIG. 12 is an XRD pattern of the crosslinkable semicrystalline polyether ether ketone prepared in example 8 before and after heat treatment.
Detailed Description
The invention provides a crosslinkable semi-crystalline polyether-ether-ketone which has a structure shown in a formula I:
wherein n is 1 to 3,
r1 is
And R2 is
Or R1 is
And R2 is
The invention also provides a preparation method of the cross-linkable semi-crystalline polyether-ether-ketone in the technical scheme, which comprises the following steps:
carrying out azeotropic reflux on first mixed 4,4' -difluorobenzophenone, hydroquinone, a water-carrying agent, a metal salt catalyst and an organic solvent to obtain a mixed solution;
secondly, mixing the mixed solution and an end-capping reagent for polymerization reaction to obtain the crosslinkable semi-crystalline polyether-ether-ketone with the structure shown in the formula I;
the end-capping reagent is 4- (2-phenylethynyl) phenol or 4-fluoro-4' - (phenylethynyl) benzophenone.
Unless otherwise specified, the present invention does not require any particular source of the starting materials for the preparation, and any commercially available product known in the art may be used.
The method comprises the steps of mixing 4,4' -difluorobenzophenone, hydroquinone, a water-carrying agent, a metal salt catalyst and an organic solvent for the first time, and carrying out azeotropic reflux to obtain a mixed solution.
In the invention, the water-carrying agent preferably comprises one or more of benzene, toluene, xylene and cyclohexane, and more preferably xylene; when the water-carrying agents are preferably selected from the above-mentioned water-carrying agents, the proportion of different water-carrying agents is not particularly limited, and any proportion can be adopted.
In the present invention, the metal salt catalyst preferably includes one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride, and potassium fluoride, more preferably sodium carbonate and potassium carbonate; when the metal salt catalyst is preferably selected from the above-mentioned metal salt catalysts, the ratio of the metal salt catalysts of different kinds is not particularly limited, and any ratio may be used. In the invention, the molar ratio of the metal salt catalyst to the hydroquinone is (0.9-2): (0.1-0.5), and more preferably (0.9-1.5): (0.2-0.5).
In the present invention, the organic solvent preferably comprises sulfolane and/or diphenylsulfone, more preferably sulfolane; when the organic solvent is preferably selected from the above-mentioned organic solvents, the ratio of the organic solvents of different types is not particularly limited, and any ratio may be used. In the present invention, the amount ratio of the water-carrying agent to the organic solvent is preferably (10-50) mL:100g, and more preferably (15-50) mL:100 g.
In the present invention, the first mixing mode is preferably stirring, the stirring mode is preferably stirring by using an iron paddle stirring head, and the stirring speed is preferably 200 r/min.
In the invention, the temperature of the azeotropic reflux is preferably 160-180 ℃, and more preferably 170-180 ℃; the time of the azeotropic reflux is preferably 0.5 to 1.5 hours, and more preferably 1 to 1.5 hours. In the present invention, the azeotropic reflux method is not particularly limited, and any azeotropic reflux method known to those skilled in the art may be used. According to the invention, one-step salification reaction of phenolic hydroxyl is carried out through azeotropic reflux, and the phenolic hydroxyl, sodium carbonate and potassium carbonate respectively form potassium salt and sodium salt for the subsequent grafting process.
In the invention, the solid content of the mixed solution obtained by mixing 4,4' -difluorobenzophenone, hydroquinone, a water-carrying agent, a metal salt catalyst and an organic solvent is preferably 15-25% by mass percent, and more preferably 20-25% by mass percent; the solid content is preferably the mass to volume ratio of 4,4' -difluorobenzophenone and hydroquinone to the organic solvent. The invention controls the growth speed and the reaction time of the polymer chain segment by controlling the solid content in the mixed solution within the range, and prepares the crosslinkable semi-crystalline polyether-ether-ketone which has excellent high temperature resistance and can still keep high mechanical property and solvent resistance at high temperature.
After the mixed solution is obtained, the mixed solution and the end-capping reagent are mixed for a second polymerization reaction.
In the invention, the end-capping agent is 4- (2-phenylethynyl) phenol or 4-fluoro-4' - (phenylethynyl) benzophenone; the mol ratio of the 4,4' -difluorobenzophenone, the hydroquinone and the end-capping agent is preferably 3.15:3 (0.05-0.3), and more preferably 3.15:3 (0.09-0.3). In embodiments of the invention, the molar ratio of 4,4' -difluorobenzophenone, hydroquinone, and end-capping agent is specifically 3.15:3:0.09, 3.15:3:0.15, or 3.15:3: 0.3.
In the invention, the structural formula of the 4- (2-phenylethynyl) phenol is shown as a formula II, and the structural formula of the 4-fluoro-4' - (phenylethynyl) benzophenone is shown as a formula III.
The phenylalkynyl of the end-capping agent has reactivity, and the end-capping agent is easy to generate branching or even crosslinking by one-step feeding, so that the polymer chain segment is too short, the molecular weight is too low or the polymerization fails, and the linear structure of the crosslinkable semi-crystalline polyether-ether-ketone is influenced.
The stirring is preferably carried out throughout the polymerization process. In the present invention, the second mixing mode is preferably stirring, and the stirring mode is preferably stirring by using an iron paddle stirring head; the stirring rate is preferably 300 r/min.
In the invention, the temperature of the polymerization reaction is preferably 200-260 ℃, and more preferably 240-260 ℃; the time of the polymerization reaction is 4-8 h, and more preferably 4-6 h. In the examples of the present invention, the temperature of the polymerization reaction is specifically 240 ℃ or 260 ℃. The invention avoids the depolymerization of the polymer molecular chain segment by controlling the temperature and time of the polymerization reaction within the range, and prepares the crosslinkable semi-crystalline polyether-ether-ketone with complete end capping and proper molecular weight.
In the present invention, when the blocking agent is 4- (2-phenylethynyl) phenol, the crosslinkable semicrystalline polyether ether ketone can be synthesized as shown in the following formula:
when the end-capping agent is 4-fluoro-4' - (phenylethynyl) benzophenone, the crosslinkable semi-crystalline polyetheretherketone can be synthesized as shown in the following formula:
after the polymerization reaction is finished, the product solution is preferably precipitated in deionized water, and then sequentially crushed, washed and dried to obtain the crosslinkable semi-crystalline polyether-ether-ketone. The precipitation process is not particularly limited in the present invention, and the product may be completely precipitated by a precipitation process known in the art. In the present invention, the crushing apparatus is preferably a crusher. The process of the present invention for the pulverization, washing and drying is not particularly limited, and may be carried out by a process well known in the art. In the embodiment of the invention, the washing process is specifically washing with water and ethanol for 5 times, and the drying process is specifically drying in a vacuum oven at 120 ℃ for 48 hours. The invention removes water and ethanol in the product solution by drying.
The invention also provides the application of the crosslinkable semi-crystalline polyether-ether-ketone in the technical scheme or the crosslinkable semi-crystalline polyether-ether-ketone prepared by the preparation method in the technical scheme as a thermoplastic high polymer material.
The invention also provides a polyether-ether-ketone polymer alloy material which comprises polyether-ether-ketone and the crosslinkable semi-crystalline polyether-ether-ketone; the cross-linkable semi-crystalline polyether-ether-ketone is the cross-linkable semi-crystalline polyether-ether-ketone in the technical scheme. In the invention, the polyether-ether-ketone and the cross-linkable semi-crystalline polyether-ether-ketone exist in a physical mixing mode; the mass ratio of the cross-linkable semi-crystalline polyether-ether-ketone to the polyether-ether-ketone is preferably (5-30): 100, and more preferably (5-25): 100. The invention adjusts the mechanical property of the polyetheretherketone polymer alloy material by controlling the mass ratio of the polyetheretherketone to the crosslinkable semi-crystalline polyetheretherketone, and within the mass range of the invention, when the ratio of the crosslinkable semi-crystalline polyetheretherketone is increased, the mechanical property of the polyetheretherketone polymer alloy material is enhanced.
The invention also provides a preparation method of the polyether-ether-ketone polymer alloy material in the technical scheme, which comprises the following steps:
mixing crosslinkable semi-crystalline polyether-ether-ketone and polyether-ether-ketone, and then sequentially carrying out melt extrusion, granulation and drying to obtain crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles;
and sequentially carrying out injection molding and heat treatment on the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles to obtain the polyether-ether-ketone polymer alloy material.
The preparation method comprises the steps of mixing crosslinkable semi-crystalline polyether-ether-ketone and polyether-ether-ketone, and then sequentially carrying out melt extrusion, granulation and drying to obtain the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles. In the present invention, the polyetheretherketone is preferably a polyetheretherketone having a melt index of 45g/10min after drying at 140 ℃ for 4h in vacuo; the polyetheretherketone is preferably commercially available. In the invention, the test instrument of the melt index is preferably a melt flow rate instrument with the model of mu PXRZ-400A, and the test condition is preferably that the polyetheretherketone is kept for 5min at 400 ℃ under the condition of 5Kg load.
The mixing process is not particularly limited in the present invention, and a mixing process well known in the art may be used.
In the invention, the melt extrusion temperature is preferably 380-390 ℃, and more preferably 380-385 ℃; the rotating speed of the melt extrusion is preferably 40-60 r/min, and more preferably 5 r/min; the time for melt extrusion is preferably 10 to 30min, and more preferably 10 to 20 min.
In the present invention, the melt extrusion apparatus is preferably a melt extruder, and the granulating apparatus is preferably a granulator.
The drying process is not particularly limited in the present invention, and a drying process well known in the art may be used.
After the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles are obtained, the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles are subjected to injection molding and heat treatment in sequence to obtain the polyether-ether-ketone polymer alloy material. In the invention, the injection molding temperature is preferably 380-390 ℃, and more preferably 380-385 ℃; the injection molding time is preferably 5-10 min, and more preferably 5-8 min; the temperature of the heat treatment is preferably 350-410 ℃, more preferably 380-410 ℃, and the time of the heat treatment is preferably 10-30 min. In embodiments of the present invention, the time of the heat treatment is specifically 10min, 20min or 30 min. In the present invention, the heat treatment is preferably performed under vacuum conditions. At the temperature selected by the melt extrusion and the injection molding, the blend of the crosslinkable semi-crystalline polyether-ether-ketone and the polyether-ether-ketone has good fluidity, and the crosslinkable semi-crystalline polyether-ether-ketone can not be crosslinked in the injection molding and the extrusion processes.
In the present invention, the injection molding equipment is preferably an injection molding machine; the heat treatment apparatus of the present invention is not particularly limited, and a heat treatment apparatus well known in the art may be used.
The drying process is not particularly limited in the present invention, and a drying process known to those skilled in the art may be used.
According to the invention, the polyether-ether-ketone high-molecular alloy material with high tensile strength is prepared by controlling the heat treatment temperature within the range, in the heat treatment temperature range of the invention, the cross-linking degree of cross-linkable semi-crystalline polyether-ether-ketone in the polyether-ether-ketone high-molecular alloy material is higher, the polymer chain segments are tangled to cause higher tensile strength, and the phenomenon that the alloy material is subjected to brittle fracture and the elongation at break is reduced due to too high cross-linking degree caused by too high temperature is avoided.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Mixing 0.315mol of 4,4' -difluorobenzophenone, 0.3mol of hydroquinone, 80mL of xylene, 1.2mol of sodium carbonate, 0.01mol of potassium carbonate and 407g of diphenyl sulfone (stirring speed is 200r/min), and then carrying out azeotropic reflux for 1.5h at 180 ℃ to obtain a mixed solution (the solid content in the mixed solution is 19.2%);
and (2) carrying out second mixing on the mixed solution and 0.009mol of 4- (2-phenylethynyl) phenol (PEP), carrying out polymerization reaction at 240 ℃, wherein the reaction time is 6h, stirring the whole reaction process (the speed is 300r/min), pouring the obtained product into deionized water for precipitation, cooling the product, crushing the product into powder by a crusher, washing the powder for 5 times by the deionized water and ethanol, and drying the powder in an oven at 120 ℃ for 48h to obtain the crosslinkable semi-crystalline polyether ether ketone.
Examples 2-12 the same as example 1 except for the preparation conditions in Table 1.
TABLE 1 tabulated preparation conditions for crosslinkable semicrystalline polyether ether ketones in examples 1-12
Note: 3%, 5% and 10% of PEEK-PEP-3%, PEEK-PEP-5% and PEEK-PEP-10% refer to the molar percentage of the capping agent to hydroquinone.
Performance and testing
1) The crosslinkable semi-crystalline polyetheretherketone prepared in example 2 was treated in 99% concentrated sulfuric acid at room temperature for 8 hours, and infrared spectroscopy was performed on the crosslinkable semi-crystalline polyetheretherketone before and after sulfonation, the results are shown in fig. 1; as can be seen from FIG. 1, the crosslinkable semicrystalline polyether ether ketone prepared in example 2 can be 2320cm before sulfonation-1A phenylalkynyl absorption peak was observed which was 2320cm after sulfonation (8 h in 99% concentrated sulfuric acid at room temperature)-1The absorption peak of the benzene alkynyl disappears, which shows that the crosslinkable semi-crystalline polyether-ether-ketone prepared by the invention is really grafted with the benzene alkynyl, and the benzene alkynyl reacts with sulfuric acid after sulfonation, so that the disappearance of the benzene alkynyl is observed;
2) DSC test of the crosslinkable semicrystalline polyetheretherketone prepared in example 2 was carried out, the results are shown in FIG. 2; as can be seen from FIG. 2, the glass transition temperature (T) of the crosslinkable semicrystalline polyether ether ketone prepared in example 2g) At 132 ℃ melting point (T)m) At 344 ℃ and a crosslinking temperature (T)p) Enthalpy value of melting point of 413 DEG CThe crystallinity is determined according to the size of the crystallinity, so that the crystallization property of the crosslinkable semi-crystalline polyether ether ketone can be indicated by the melting point of the crosslinkable semi-crystalline polyether ether ketone;
3) TGA tests were performed on the crosslinkable semi-crystalline polyetheretherketone prepared in example 2 and the results are shown in FIG. 3; as can be seen from FIG. 3, the crosslinkable semicrystalline polyether ether ketone prepared in example 2 has a thermal decomposition temperature (T) of 5%5％) 539 ℃ and 10% thermal decomposition temperature (T)10％) 563 ℃ C;
4) the crosslinkable semicrystalline polyether ether ketone prepared in example 2 was treated at 410 ℃ for 30min and subjected to DSC test before and after the heat treatment, the results of which are shown in fig. 4; as can be seen from FIG. 4, the glass transition temperature (T) of the crosslinkable semi-crystalline polyetheretherketone prepared in example 2 was determined by heat treatment (at 410 ℃ C. for 30min)g) Increasing the melting point (T) to 138 ℃m) Is 340 ℃; the increase of the glass transition temperature shows that the crosslinkable semi-crystalline polyether-ether-ketone prepared by the invention has excellent high temperature resistance after heat treatment;
5) the crosslinkable semicrystalline polyether ether ketone prepared in example 2 was treated at 410 ℃ for 30min and subjected to TGA test before and after the heat treatment, the results of which are shown in fig. 5; as can be seen from FIG. 5, the crosslinkable semicrystalline polyether ether ketone prepared in example 2 was heat-treated (at 410 ℃ C. for 30min) to find its 5% thermal decomposition temperature (T)5％) The temperature is raised to 561 ℃ and the thermal decomposition temperature (T) is 10 percent10％) Lifting to 570 ℃; the cross-linkable semi-crystalline polyether-ether-ketone prepared by the invention is subjected to heat treatment, the phenyl alkynyl is cross-linked, and the polymer chain segments are stacked more tightly after cross-linking, so that the cross-linkable semi-crystalline polyether-ether-ketone has more excellent high-temperature resistance;
6) the crosslinkable semi-crystalline polyetheretherketone prepared in example 2 was treated at 410 ℃ for 30min and XRD measurements were carried out on the crosslinkable semi-crystalline polyetheretherketone before and after the heat treatment, the results are shown in figure 6; as can be seen from fig. 6, the XRD pattern after heat treatment (at 410 ℃ for 30min) of the crosslinkable semicrystalline polyether ether ketone prepared in example 2 shows that the diffraction peak positions of the crosslinkable semicrystalline polyether ether ketone before and after heat treatment are not transformed, and there is still a peak and the peak position is not changed after heat treatment, and it can be found from the calculation of the diffraction peak in the XRD pattern that the crystallinity of the crosslinkable semicrystalline polyether ether ketone before heat treatment is 49.8% and the crystallinity after heat treatment is 36.1%, which indicates that it still maintains a certain crystallinity and the crystal form is not changed after heat treatment, so the crosslinkable semicrystalline polyether ether ketone prepared in the present invention has high mechanical properties and solvent resistance at high temperature;
7) the crosslinkable semicrystalline polyether ether ketone prepared in example 8 was treated at 410 ℃ for 30min and infrared spectroscopy was performed on the crosslinkable semicrystalline polyether ether ketone before and after the heat treatment, and the results are shown in fig. 1; as can be seen from FIG. 7, the crosslinkable semicrystalline polyether ether ketone prepared in comparative example 8 and the IR spectrum thereof after heat treatment show that the phenyl alkynyl absorption peak disappears after the crosslinkable semicrystalline polyether ether ketone is crosslinked;
8) DSC measurements of the crosslinkable semicrystalline polyetheretherketone prepared in example 8 are shown in FIG. 8; as can be seen from FIG. 8, the glass transition temperature (T) of the crosslinkable semicrystalline polyether ether ketone prepared in example 8g) At 143 ℃ melting point (T)m) Is 343 ℃;
9) TGA tests were performed on the crosslinkable semi-crystalline polyetheretherketone prepared in example 8 and the results are shown in FIG. 9; as can be seen from FIG. 9, the crosslinkable semicrystalline polyether ether ketone prepared in example 8 has a 5% thermal decomposition temperature (T)5％) 521 ℃ and 10% thermal decomposition temperature (T)10％) 557 ℃;
10) the crosslinkable semicrystalline polyether ether ketone prepared in example 8 was heat-treated at 410 ℃ for 30min, and DSC test was performed on the crosslinkable semicrystalline polyether ether ketone prepared in example 8 before and after the heat treatment, and the results are shown in fig. 10; as can be seen from FIG. 10, the glass transition temperature (T) of the crosslinkable semicrystalline polyether ether ketone prepared in example 8 after heat treatmentg) Increasing the melting point (T) to 146 DEG Cm) At 332 ℃;
11) the crosslinkable semicrystalline polyether ether ketone prepared in example 8 was heat-treated at 410 ℃ for 30min andTGA measurements were made of the crosslinkable semi-crystalline polyetheretherketone prepared in example 8 before and after heat treatment, and the results are shown in FIG. 10; as can be seen from FIG. 11, the crosslinkable semicrystalline polyether ether ketone prepared in example 8 was heat-treated (at 410 ℃ C. for 30min) to find its 5% thermal decomposition temperature (T)5％) To raise the temperature to 541 ℃ and 10% thermal decomposition temperature (T)10％) Lifting to 562 ℃;
12) the crosslinkable semicrystalline polyether ether ketone prepared in example 8 was heat-treated at 410 ℃ for 30min, and XRD test was performed on the crosslinkable semicrystalline polyether ether ketone before and after the heat treatment, and the results are shown in fig. 12; as can be seen from fig. 12, from XRD patterns before and after heat treatment (heat treatment at 410 ℃ for 30min) of the crosslinkable semicrystalline polyether ether ketone prepared in comparative example 8, it is found that there is no transformation in diffraction peak positions before and after heat treatment, there is still a peak and the peak position is unchanged after heat treatment, and it is found from calculation of diffraction peaks in XRD patterns that the crystallinity of the crosslinkable semicrystalline polyether ether ketone before heat treatment is 41.2% and the crystallinity after heat treatment is 31.5%, which indicates that it still maintains certain crystallinity and the crystal form is unchanged after heat treatment, so the crosslinkable semicrystalline polyether ether ketone prepared in the present invention has high mechanical properties and solvent resistance at high temperature.
13) The crosslinkable semi-crystalline polyetheretherketone prepared in examples 2 and 8 was tested for solubility at room temperature by adding the crosslinkable semi-crystalline polyetheretherketone prepared in examples 2 and 8 to the respective solvents listed in table 2 at room temperature and stirring until its state no longer changed, the results are shown in table 2:
TABLE 2 solubility of the crosslinkable semicrystalline polyether ether ketones prepared in examples and 8 in different solvents
Note: "-" represents insoluble; "+" represents dissolution.
As can be seen from Table 2, the crosslinkable semi-crystalline polyetheretherketone prepared according to the present invention still has high solvent resistance compared to polyetheretherketone.
Application example 1
Mixing 10g of the crosslinkable semicrystalline polyether ether ketone (PEEK-PEP-3%) prepared in example 1 with 190g of polyether ether ketone, performing melt extrusion for 20min at 380 ℃ by using a melt extruder to prepare a wire material, and then granulating and drying the wire material by using a granulator to obtain crosslinkable semicrystalline polyether ether ketone/polyether ether ketone composite particles;
placing the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles into an injection molding machine, molding for 8min at 380 ℃ to prepare a tensile sample strip, and carrying out heat treatment on the obtained tensile sample strip for 10min at 410 ℃ under a vacuum condition to obtain the polyether-ether-ketone polymer alloy material.
Application examples 2 to 54 the same as application example 1 except for the preparation conditions shown in Table 3.
Table 3 list of preparation conditions of PEEK polymer alloy materials in application examples 1-54
According to the GB/T1042.5-2008 standard, the polyetheretherketone polymer alloy material prepared in application examples 12, 15, 18 and 24 is injection molded into dumbbell-shaped tensile test sample strips with the length of 75mm, the thickness of 2mm and the widths of 10mm and 5mm respectively, and mechanical property tests are carried out on the dumbbell-shaped tensile test sample strips, and the result shows that the polyetheretherketone polymer alloy material prepared in application example 12 has the tensile strength of 121 MPa; the tensile strength of the polyether-ether-ketone polymer alloy material prepared in application example 15 is 132 MPa; the tensile strength of the polyether-ether-ketone polymer alloy material prepared in application example 18 is 137 MPa; the tensile strength of the polyether-ether-ketone polymer alloy material prepared in application example 24 reaches 117 MPa; the polyether-ether-ketone polymer alloy material prepared by mixing the crosslinkable semi-crystalline polyether-ether-ketone into the polyether-ether-ketone has higher tensile strength.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A crosslinkable semicrystalline polyether ether ketone having a structure represented by formula I:
wherein n is 1 to 3,
r1 is
And R2 is
Or R1 is
And R2 is
2. A process for the preparation of a crosslinkable semicrystalline polyether ether ketone according to claim 1, comprising the steps of:
firstly mixing 4,4' -difluorobenzophenone, hydroquinone, a water-carrying agent, a metal salt catalyst and an organic solvent, and then carrying out azeotropic reflux to obtain a mixed solution;
secondly, mixing the mixed solution and an end-capping reagent, and then carrying out polymerization reaction to obtain the cross-linkable semi-crystalline polyether-ether-ketone with the structure shown in the formula I;
the end-capping reagent is 4- (2-phenylethynyl) phenol or 4-fluoro-4' - (phenylethynyl) benzophenone.
3. The method according to claim 2, wherein the molar ratio of the 4,4' -difluorobenzophenone, the hydroquinone and the end-capping agent is 3.15:3 (0.05-0.3).
4. The preparation method according to claim 2, wherein the metal salt catalyst comprises one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride; the molar ratio of the metal salt catalyst to the hydroquinone is (0.9-2) to (0.1-0.5).
5. The preparation method according to claim 2, wherein the water-carrying agent comprises one or more of benzene, toluene, xylene and cyclohexane; the organic solvent comprises sulfolane and/or diphenyl sulfone; the dosage ratio of the water-carrying agent to the organic solvent is (10-50) mL:100 g.
6. The preparation method according to claim 2, wherein the mixed solution obtained by mixing the 4,4' -difluorobenzophenone, the hydroquinone, the water-carrying agent, the metal salt catalyst and the organic solvent has a solid content of 15-25% by mass.
7. The method according to claim 2, wherein the polymerization temperature is 200 to 260 ℃ and the polymerization time is 4 to 8 hours.
8. Use of the crosslinkable semi-crystalline polyetheretherketone according to claim 1 or the crosslinkable semi-crystalline polyetheretherketone obtained by the method according to any one of claims 2 to 7 in a thermoplastic polymer material.
9. A polyetheretherketone polymer alloy material, wherein the polyetheretherketone polymer alloy material comprises polyetheretherketone and crosslinkable semi-crystalline polyetheretherketone, and the crosslinkable semi-crystalline polyetheretherketone is the crosslinkable semi-crystalline polyetheretherketone according to claim 1; the mass ratio of the cross-linkable semi-crystalline polyether-ether-ketone to the polyether-ether-ketone is (5-30): 100.
10. The method for preparing the polyetheretherketone polymer alloy material of claim 9, comprising the following steps:
mixing crosslinkable semi-crystalline polyether-ether-ketone and polyether-ether-ketone, and then sequentially carrying out melt extrusion, granulation and drying to obtain crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles;
sequentially carrying out injection molding and heat treatment on the crosslinkable semi-crystalline polyether-ether-ketone/polyether-ether-ketone composite particles to obtain a polyether-ether-ketone polymer alloy material;
the temperature of the melt extrusion is 380-390 ℃; the injection molding temperature is 380-390 ℃; the temperature of the heat treatment is 350-410 ℃, and the time is 10-30 min.
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