阅读说明：本技术 3d打印级聚醚醚酮树脂专用料及制备和应用、3d打印层间增强聚醚醚酮合金材料及制备 (Special material for 3D printing-grade polyether-ether-ketone resin, preparation and application thereof, 3D printing interlayer reinforced polyether-ether-ketone alloy material and preparation thereo) 是由 张海博 徐勤飞 商赢双 李雪峰 杨洋 尹鑫 周晨义 刘新 于畅 于 2021-09-28 设计创作，主要内容包括：本发明提供了3D打印级聚醚醚酮树脂专用料及制备和应用、3D打印层间增强聚醚醚酮合金材料及制备,属于3D打印材料技术领域。本发明采用耐温等级更高的4-氟基二苯砜作为封端基团,使得聚醚醚酮树脂具有非常稳定的含氟端基,能够使聚醚醚酮在更高温度的加工条件下保持良好的流动性和稳定性,以满足3D打印高温加工的需求。另外,将该专用料与层间增强改性剂共混,制备的3D打印层间增强聚醚醚酮合金材料在保持聚醚醚酮优良机械性能的同时还大幅提高了层间粘结强度。(The invention provides a special material for 3D printing-grade polyether-ether-ketone resin, preparation and application thereof, a 3D printing interlayer reinforced polyether-ether-ketone alloy material and preparation thereof, and belongs to the technical field of 3D printing materials. According to the invention, 4-fluoro diphenyl sulfone with higher temperature resistance grade is used as an end capping group, so that the polyether-ether-ketone resin has a very stable fluorine-containing end group, and the polyether-ether-ketone can keep good fluidity and stability under a processing condition of higher temperature so as to meet the requirement of high-temperature processing of 3D printing. In addition, the special material is blended with an interlayer reinforcing modifier, and the prepared 3D printing interlayer reinforcing polyether-ether-ketone alloy material maintains the excellent mechanical property of polyether-ether-ketone and greatly improves the interlayer bonding strength.)

1. A special material for 3D printing grade polyether-ether-ketone resin has a structure shown in formula I:

in formula I, n is the degree of polymerization and n is an integer: the melt index of the special material for the 3D printing grade polyether-ether-ketone resin is 20-40 g/10 min.

2. The preparation method of the special material for the 3D printing grade polyetheretherketone resin, which is disclosed by claim 1, comprises the following steps:

mixing 4, 4' -difluorobenzophenone, hydroquinone, an alkali catalyst, melted diphenyl sulfone and a water-carrying agent, carrying out water-carrying and polymerization reaction in sequence, adding 4-fluoro diphenyl sulfone into the obtained product, and carrying out end capping to obtain the special material for the 3D printing-grade polyether-ether-ketone resin.

3. The preparation method of claim 2, wherein the molar ratio of the 4, 4' -difluorobenzophenone to the hydroquinone is (1.005-1.05): 1, and the base catalyst comprises sodium carbonate and potassium carbonate; the molar ratio of the sodium carbonate to the potassium carbonate to the hydroquinone is (1-1.2): 0.01-0.08): 1.

4. The method according to claim 2, wherein the temperature of the water is 140-170 ℃ and the time is 1-3 h.

5. The method of claim 2, wherein the polymerization reaction comprises: in the first stage, reaction is carried out for 1-3 h at 200-220 ℃; in the second stage, reacting for 2-3 h at 230-250 ℃; in the third stage, the reaction is carried out for 0.5 to 1 hour at the temperature of 300 to 310 ℃; the molar ratio of the 4-fluoro diphenyl sulfone to the hydroquinone is (0.01-0.03): 1; the temperature of the end capping is 310 ℃, and the reaction time of the end capping is 0.5-2 h.

6. The 3D printing grade special material for polyether-ether-ketone resin according to claim 1 or the 3D printing grade special material for polyether-ether-ketone resin prepared by the preparation method according to any one of claims 2 to 5 is applied to preparation of a 3D printing interlayer reinforced polyether-ether-ketone alloy material.

7. A preparation method of a 3D printing interlayer reinforced polyether-ether-ketone alloy material is characterized by comprising the following steps:

premixing a special material for 3D printing grade polyether-ether-ketone resin and an interlayer reinforcing modifier to obtain blended powder; the special material for the 3D printing grade polyether-ether-ketone resin is the special material for the 3D printing grade polyether-ether-ketone resin in claim 1 or the special material for the 3D printing grade polyether-ether-ketone resin prepared by the preparation method in any one of claims 2 to 5;

sequentially extruding, cooling and rolling the blended powder to obtain a 3D printing interlayer reinforced polyether-ether-ketone alloy wire;

and 3D printing is carried out on the 3D printing interlayer reinforced polyether-ether-ketone alloy wire to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy material.

8. The method of claim 7, wherein the interlayer reinforcing modifier is a polyaryletherketone having a structure represented by formula II:

in formula II, n is the degree of polymerization and n is an integer; r is

The specific viscosity eta of the polyaryletherketone is 0.4-0.6 dL/g.

9. The preparation method of claim 7, wherein in the blended powder, the mass percentage of the special material for the 3D printing-grade polyetheretherketone resin is 70-98 wt%, and the mass percentage of the interlayer reinforcing modifier is 2-30 wt%; the extrusion speed of the extrusion is 10-30 r/min, the winding speed of the winding is 5-10 m/min, and the diameter of the 3D printing interlayer reinforced polyether-ether-ketone alloy wire is 1.75 +/-0.05 mm; the conditions of the 3D printing include: the temperature of the spray head is 380-450 ℃, the height of a printing layer is 0.1-0.2 mm, and the printing speed is 30-60 mm/s.

10. The 3D printing interlayer reinforced polyether-ether-ketone alloy material prepared by the preparation method of any one of claims 7 to 9.

Technical Field

The invention relates to the technical field of 3D printing materials, in particular to a special material for 3D printing grade polyether-ether-ketone resin, preparation and application thereof, and a 3D printing interlayer reinforced polyether-ether-ketone alloy material and preparation thereof.

Background

Polyether ether ketone (PEEK) has excellent heat resistance and mechanical properties, good chemical corrosion resistance, self-lubricity and biocompatibility, is widely applied in the fields of aerospace, automobile industry and medical treatment, and is known as a variety of pyramid tips of plastic product systems. In recent years, 3D printing technology is rapidly developed, the polyetheretherketone resin material is widely applied to 3D printing due to excellent comprehensive performance, but the processing of the polyetheretherketone is difficult during printing due to high viscosity of a commercialized polyetheretherketone melt; on the other hand, the existing commercialized polyetheretherketone is of an injection molding grade, the crystallization rate is very high, and the phenomena of warping and interlayer delamination are easy to occur due to uneven heating in the printing process, so that the application of polyetheretherketone in the field of 3D printing is further limited.

Disclosure of Invention

The invention aims to provide a special material for 3D printing grade polyether-ether-ketone resin, preparation and application thereof, a 3D printing interlayer reinforced polyether-ether-ketone alloy material and preparation thereof. The special material for the 3D printing grade polyether-ether-ketone resin has high temperature resistance and processing stability, so that good fluidity is maintained, 3D printing is facilitated, and the problem of poor material decomposition and interlayer adhesion in the printing process is solved through the alloy material prepared by blending the special material with the interlayer reinforcing modifier.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a special material for 3D printing grade polyether-ether-ketone resin, which has a structure shown in a formula I:

in formula I, n is the degree of polymerization and n is an integer: the melt index of the special material for the 3D printing grade polyether-ether-ketone resin is 20-40 g/10 min.

The invention provides a preparation method of the special material for the 3D printing grade polyetheretherketone resin, which comprises the following steps:

mixing 4, 4' -difluorobenzophenone, hydroquinone, an alkali catalyst, melted diphenyl sulfone and a water-carrying agent, carrying out water-carrying and polymerization reaction in sequence, adding 4-fluoro diphenyl sulfone into the obtained product, and carrying out end capping to obtain the special material for the 3D printing-grade polyether-ether-ketone resin.

Preferably, the molar ratio of the 4, 4' -difluorobenzophenone to the hydroquinone is (1.005-1.05): 1, the base catalyst comprises sodium carbonate and potassium carbonate, and the molar ratio of the sodium carbonate, the potassium carbonate and the hydroquinone is (1-1.2): 0.01-0.08): 1.

Preferably, the temperature of the water is 140-170 ℃ and the time is 1-3 h.

Preferably, the polymerization process comprises: in the first stage, reaction is carried out for 1-3 h at 200-220 ℃; in the second stage, reacting for 2-3 h at 230-250 ℃; in the third stage, the reaction is carried out for 0.5 to 1 hour at the temperature of 300 to 310 ℃; the molar ratio of the 4-fluoro diphenyl sulfone to the hydroquinone is (0.01-0.03): 1; the temperature of the end capping is 310 ℃, and the reaction time of the end capping is 0.5-2 h.

The invention provides an application of the special material for the 3D printing grade polyether-ether-ketone resin in the technical scheme or the special material for the 3D printing grade polyether-ether-ketone resin prepared by the preparation method in the technical scheme in preparation of a 3D printing interlayer reinforced polyether-ether-ketone alloy material.

The invention provides a preparation method of a 3D printing interlayer reinforced polyether-ether-ketone alloy material, which comprises the following steps:

premixing a special material for 3D printing grade polyether-ether-ketone resin and an interlayer reinforcing modifier to obtain blended powder; the special material for the 3D printing grade polyether-ether-ketone resin is the special material for the 3D printing grade polyether-ether-ketone resin in the technical scheme or the special material for the 3D printing grade polyether-ether-ketone resin prepared by the preparation method in the technical scheme;

sequentially extruding, cooling and rolling the blended powder to obtain a 3D printing interlayer reinforced polyether-ether-ketone alloy wire;

and 3D printing is carried out on the 3D printing interlayer reinforced polyether-ether-ketone alloy wire to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy material.

Preferably, the interlayer reinforcing modifier is polyaryletherketone, and the polyaryletherketone has a structure shown in a formula II:

in formula II, n is the degree of polymerization and n is an integer; r is

The specific viscosity eta of the polyaryletherketone is 0.4-0.6 dL/g.

Preferably, in the blended powder, the mass percentage of the special material for the 3D printing-grade polyether-ether-ketone resin is 70-98 wt%, and the mass percentage of the interlayer reinforcing modifier is 2-30 wt%; the extrusion speed of the extrusion is 10-30 r/min, the winding speed of the winding is 5-10 m/min, and the diameter of the 3D printing interlayer reinforced polyether-ether-ketone alloy wire is 1.75 +/-0.05 mm; the conditions of the 3D printing include: the temperature of the spray head is 380-450 ℃, the height of a printing layer is 0.1-0.2 mm, and the printing speed is 30-60 mm/s.

The invention provides the 3D printing interlayer reinforced polyether-ether-ketone alloy material prepared by the preparation method in the technical scheme.

The invention provides a special material for 3D printing grade polyether-ether-ketone resin, which adopts 4-fluoro diphenyl sulfone with higher temperature resistance grade as an end capping group, so that the polyether-ether-ketone resin has very stable fluorine-containing end groups, and the polyether-ether-ketone can keep good fluidity and stability under the processing condition of higher temperature so as to meet the requirement of 3D printing high-temperature processing. Therefore, the special material for the 3D printing grade polyether-ether-ketone resin provided by the invention has high temperature resistance and stability, ensures good processing stability during 3D processing, and can be used as the special material for the 3D printing polyether-ether-ketone resin with processing requirements under a higher temperature condition.

According to the invention, the 3D printing interlayer reinforced polyether-ether-ketone alloy material is prepared by blending the special material for the 3D printing grade polyether-ether-ketone resin and the interlayer reinforced modifier, so that the interlayer bonding strength of the 3D printing interlayer reinforced polyether-ether-ketone alloy material is greatly improved while good compatibility with the 3D printing polyether-ether-ketone resin is ensured and excellent mechanical properties of polyether-ether-ketone are maintained, and the problems of decomposition and poor interlayer bonding of the conventional polyether-ether-ketone alloy material in the 3D printing process are solved.

Drawings

FIG. 1 is a graph of melt index stability of a 3D printing grade PEEK resin special material prepared in example 1;

FIG. 2 is an infrared spectrum of the special material for 3D printing grade polyetheretherketone resin prepared in example 1;

FIG. 3 is a TGA graph of a 3D print grade PEEK resin specialty and a commercially available PEEK prepared from example 1;

FIG. 4 is a graph showing the tensile properties of the injection molded sample piece and the 3D-printed sample strip of the special material for 3D-printed grade polyetheretherketone resin prepared in example 2;

FIG. 5 is a DSC of 3D printed interlayer reinforced PEEK alloy material prepared in application example 1 and application example 3 and commercial PEEK;

fig. 6 is a graph of tensile properties of the 3D printed interlayer reinforced polyetheretherketone alloy material prepared in application example 1 and application example 3 and commercially available polyetheretherketone.

Detailed Description

The invention provides a special material for 3D printing grade polyether-ether-ketone resin, which has a structure shown in a formula I:

in formula I, n is the degree of polymerization and n is an integer: the melt index of the special material for the 3D printing grade polyether-ether-ketone resin is 20-40 g/10min, and more preferably 21-30 g/10 min.

The invention provides a preparation method of the special material for the 3D printing grade polyetheretherketone resin, which comprises the following steps:

mixing 4, 4' -difluorobenzophenone, hydroquinone, an alkali catalyst, melted diphenyl sulfone and a water-carrying agent, carrying out water-carrying and polymerization reaction in sequence, adding 4-fluoro diphenyl sulfone into the obtained product, and carrying out end capping to obtain the special material for the 3D printing-grade polyether-ether-ketone resin.

In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.

In the present invention, the molar ratio of 4, 4' -difluorobenzophenone to hydroquinone is preferably (1.005 to 1.05):1, more preferably 1.02 to 1.05:1, and still more preferably 1.03: 1.

In the present invention, the base catalyst preferably comprises sodium carbonate, preferably anhydrous sodium carbonate, and potassium carbonate, preferably anhydrous potassium carbonate; the molar ratio of the sodium carbonate to the potassium carbonate to the hydroquinone is preferably (1-1.2): 0.01-0.08): 1, and more preferably 1.2:0.01: 1.

In the invention, the heating temperature of the melted diphenyl sulfone is preferably 120-140 ℃, and more preferably 130 ℃; the diphenyl sulfone acts as a reaction solvent.

In the present invention, the water-carrying agent preferably includes xylene; the process of mixing 4,4 '-difluorobenzophenone, hydroquinone, a base catalyst, molten diphenyl sulfone and a water-carrying agent is preferably to add 4, 4' -difluorobenzophenone, anhydrous sodium carbonate, anhydrous potassium carbonate, hydroquinone and a water-carrying agent to molten diphenyl sulfone under the condition of mechanical stirring. The stirring process is not particularly limited in the present invention, and the materials are fully mixed according to the process known in the art. In the invention, the volume of the water-carrying agent is preferably 30-50% of the volume of the melted diphenyl sulfone.

In the invention, the solid content of the reaction system obtained by mixing the 4, 4' -difluorobenzophenone, the hydroquinone, the base catalyst and the melted diphenyl sulfone is preferably 10-30 wt%, and more preferably 25 wt%.

After the mixing is finished, the temperature is preferably raised to the water carrying temperature for carrying out water carrying; the temperature of the water is preferably 140-170 ℃, and more preferably 150-160 ℃; the time is preferably 1-3 h, and more preferably 2 h; the rate of temperature rise to the water-carrying temperature is not particularly limited in the present invention, and the temperature rise may be carried out at a rate well known in the art. In the water-carrying process, hydroquinone is subjected to a salt formation process with sodium carbonate and potassium carbonate to generate phenolate.

After the water is brought, the temperature is preferably raised to the temperature of the polymerization reaction for the polymerization reaction; the process of the polymerization reaction preferably comprises: in the first stage, reaction is carried out for 1-3 h at 200-220 ℃; in the second stage, reacting for 2-3 h at 230-250 ℃; in the third stage, the reaction is carried out at 300-310 ℃ for 0.5-1 h. In the present invention, the temperature rising rate of the polymerization reaction and the temperature rising rate during the polymerization reaction are not particularly limited, and the temperature may be raised according to a process known in the art. During the polymerization reaction, the fluoro group of 4, 4' -difluorobenzophenone reacts with a phenoxide salt and gradually undergoes a condensation reaction to form a polymerization product.

When the temperature of the polymerization reaction reaches 310 ℃, the invention adds the end-capping reagent 4-fluoro diphenyl sulfone into the obtained reaction system to perform end capping. In the invention, the molar ratio of the 4-fluoro diphenyl sulfone to the hydroquinone is preferably (0.01-0.03): 1, more preferably (0.01): 1; the blocking temperature is preferably 310 ℃, and the blocking reaction time is preferably 0.5-2 h, and more preferably 1 h.

After the end capping is finished, preferably discharging the obtained product system into deionized water, crushing the obtained strip-shaped product in a high-speed crusher, and washing the obtained crushed material for 5 times by using acetone and deionized water respectively to obtain the special material for the 3D printing-grade polyether-ether-ketone resin. The process of discharging, pulverizing and washing is not particularly limited in the present invention and may be performed according to a process well known in the art. The particle size of the crushed material is not specially limited, and the particle size can be adjusted according to actual requirements.

The invention provides an application of the special material for the 3D printing grade polyether-ether-ketone resin in the technical scheme or the special material for the 3D printing grade polyether-ether-ketone resin prepared by the preparation method in the technical scheme in preparation of a 3D printing interlayer reinforced polyether-ether-ketone alloy material.

The invention provides a preparation method of a 3D printing interlayer reinforced polyether-ether-ketone alloy material, which comprises the following steps:

premixing a special material for 3D printing grade polyether-ether-ketone resin and an interlayer reinforcing modifier to obtain blended powder; the special material for the 3D printing grade polyether-ether-ketone resin is the special material for the 3D printing grade polyether-ether-ketone resin in the technical scheme or the special material for the 3D printing grade polyether-ether-ketone resin prepared by the preparation method in the technical scheme;

sequentially extruding, cooling and rolling the blended powder to obtain a 3D printing interlayer reinforced polyether-ether-ketone alloy wire;

and 3D printing is carried out on the 3D printing interlayer reinforced polyether-ether-ketone alloy wire to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy material.

The invention mixes the special material for 3D printing grade polyether-ether-ketone resin and the interlayer reinforcing modifier to obtain the blending powder. In the invention, the interlayer reinforcing modifier is preferably polyaryletherketone, and the polyaryletherketone has a structure shown in a formula II:

in formula II, n is the degree of polymerization and n is an integer; r is

The specific viscosity eta of the polyaryletherketone is 0.4-0.6 dL/g.

In the invention, the structural formula of the polyaryletherketone is preferably

The reduced viscosity eta was 0.5 dL/g.

In the present invention, the polyaryletherketone is preferably prepared according to the method described in the prior art (the business win-multiple-wall carbon nanotube/graphite/polyetheretherketone composite material and the research on the friction performance thereof [ D ] Jilin university).

In the invention, in the blended powder, the mass percentage of the special material for the 3D printing grade polyetheretherketone resin is preferably 70-98 wt%, more preferably 70-95 wt%, and the mass percentage of the interlayer reinforcing modifier is preferably 2-30 wt%, more preferably 5-30 wt%.

In the present invention, the premixing is preferably performed in a high-speed mixer, and the specific process of the premixing is not particularly limited in the present invention, and may be performed according to a process well known in the art. After the premixing is finished, the obtained material is preferably dried for 3-5 hours at the temperature of 120-140 ℃ to obtain the blended powder.

After the blended powder is obtained, the blended powder is sequentially extruded, cooled and rolled to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy wire.

In the present invention, the extrusion is preferably carried out in a twin-screw extruder; the type of the twin-screw extruder is not particularly limited in the present invention, and the corresponding apparatus well known in the art may be used. In the invention, the extrusion speed of the extrusion is preferably 10-30 r/min, more preferably 25r/min, the temperature of each section of the twin-screw extruder is preferably 320-340 ℃, 360-380 ℃ and 350-370 ℃ in sequence, and the temperature of the die head is preferably 360-370 ℃, more preferably 365 ℃.

After the extrusion is finished, the obtained extruded material is cooled, preferably, the cooling comprises three sections of cooling devices in sequence, wherein the first section adopts an air cooling device with the temperature of 20-30 ℃ for preliminary cooling, the second section adopts a water cooling device with the temperature of 50-70 ℃ for cooling, and the third section adopts a water cooling device with the temperature of 10-20 ℃ for cooling. The cooling device is not particularly limited in the present invention, and any corresponding cooling device known in the art can achieve the above temperature range.

After the cooling is finished, the obtained material is rolled; the rolling is preferably carried out in a traction wire rolling machine; the winding speed of the winding is preferably 5-10 m/min, and more preferably 8 m/min.

In the invention, the diameter of the 3D printing interlayer reinforced polyether-ether-ketone alloy wire is preferably 1.75 +/-0.05 mm.

After the 3D printing interlayer reinforced polyether-ether-ketone alloy wire is obtained, 3D printing is carried out on the 3D printing interlayer reinforced polyether-ether-ketone alloy wire, and the 3D printing interlayer reinforced polyether-ether-ketone alloy material is obtained. In the present invention, the conditions for 3D printing preferably include: the temperature of the spray head is 380-450 ℃, and more preferably 410 ℃; the printing layer height is 0.1-0.2 mm, the printing speed is 30-60 mm/s, and the cavity temperature is 230 ℃. The 3D printer used for 3D printing is not particularly limited in the present invention, and may be a corresponding device well known in the art.

The invention provides the 3D printing interlayer reinforced polyether-ether-ketone alloy material prepared by the preparation method in the technical scheme.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Adding 997.992g of diphenyl sulfone into a three-neck flask with an argon port, heating to 140 ℃ until the diphenyl sulfone is melted into liquid, sequentially adding 222.564g (1.02mol) of 4, 4' -difluorobenzophenone, 127.2g (1.2mol) of anhydrous sodium carbonate, 1.38g (1.01mol) of anhydrous potassium carbonate and 110.1g (1mol) of hydroquinone, wherein the solid content of the obtained reaction system is 25 wt%, finally adding 300mL of xylene, gradually heating to 170 ℃ to carry water for 2h, continuously heating to 210 ℃ for reaction for 1h, heating to 250 ℃ for reaction for 2h, and finally heating to 310 ℃ for reaction for 1 h; adding 4-fluoro diphenyl sulfone monomer (2.36g) (0.01mol) into the obtained product, continuing to react for 1h, discharging into deionized water, crushing the obtained strip product by a high-speed crusher, and respectively washing the crushed strip product for 5 times by acetone and deionized water to obtain the special material for the 3D printing-grade polyether-ether-ketone resin, wherein the structural formula is shown as formula I, and the melt index is 21g/10 min.

Example 2

Adding 1004.538g of diphenyl sulfone into a three-neck flask with an argon port, heating to 140 ℃ until the diphenyl sulfone is melted into liquid, sequentially adding 224.746g (1.03mol) of 4, 4' -difluorobenzophenone, 127.2g (1.2mol) of anhydrous sodium carbonate, 1.38g (0.01mol) of anhydrous potassium carbonate and 110.1g (1mol) of hydroquinone respectively, wherein the solid content of the obtained reaction system is 25 wt%, finally adding 300mL of xylene, gradually heating to 170 ℃, carrying out water for 2h, continuously heating to 210 ℃ for reaction for 1h, gradually heating to 250 ℃ for reaction for 2h, and finally heating to 310 ℃ for reaction for 1 h; adding 4-fluoro diphenyl sulfone monomer (2.36g) (0.01mol) into the obtained product, continuously reacting for 1h, discharging into deionized water, crushing the obtained strip product by a high-speed crusher, and respectively cleaning with acetone and deionized water for 5 times to obtain the special material for the 3D printing-grade polyether-ether-ketone resin, wherein the structural formula is shown as formula I, and the melt index is 30g/10 min.

Example 3

Adding 1017.63g of diphenyl sulfone into a three-neck flask with an argon port, heating to 140 ℃ until the diphenyl sulfone is melted into liquid, sequentially adding 229.11g (1.05mol) of 4, 4' -difluorobenzophenone, 127.2g (1.2mol) of anhydrous sodium carbonate, 1.38g (0.01mol) of anhydrous potassium carbonate and 110.1g (1mol) of hydroquinone respectively, wherein the solid content of the obtained reaction system is 25 wt%, finally adding 300mL of xylene, gradually heating to 170 ℃, carrying out water for 2h, continuously heating to 210 ℃ for reaction for 1h, gradually heating to 250 ℃ for reaction for 2h, and finally heating to 310 ℃ for reaction for 1 h; adding 4-fluoro diphenyl sulfone monomer (2.36g) (0.01mol) into the obtained product, continuing to react for 1h, discharging into deionized water, crushing the obtained strip product by a high-speed crusher, and respectively cleaning the crushed strip product for 5 times by using acetone and deionized water to obtain the special material for the 3D printing-grade polyether-ether-ketone resin, wherein the structural formula is shown as formula I, and the melt index is 40g/10 min.

In the following application examples 1 to 3, the interlayer reinforcing modifier is bisphenol A type polyether ether ketone and has the following structure:

the reduced viscosity eta is 0.5 dL/g;

the preparation method of the bisphenol A type polyether-ether-ketone comprises the following steps: 65.46g of 4, 4' -difluorobenzophenone (0.3mol) and 68.487g of bisphenol A (0.3mol) are put into a three-neck flask with mechanical stirring, a nitrogen port and a water carrier, 49.76g of anhydrous potassium carbonate is used as a catalyst, 535.84g of sulfolane is used as a solvent, 100ml of toluene is used as a water carrier, under the protection of nitrogen, after water is carried at 140 ℃ for 1h, the temperature is gradually increased to 180 ℃ for reaction for 2h, the mixture is discharged into deionized water, after being crushed, the deionized water is respectively washed with ethanol and distilled water for 5 times, and then the mixture is placed into a vacuum oven for drying, so that the bisphenol A type polyether ether ketone interlayer reinforcing modifier is obtained.

Application example 1

The alloy material comprises the components of a polyether-ether-ketone/interlayer reinforcing modifier alloy material, wherein according to 100 wt%, 98 wt% of the special material for 3D printing grade polyether-ether-ketone resin with the melt index of 30g/10min prepared in example 2 and 2 wt% of interlayer reinforcing modifier are premixed in a high-speed mixer, dried for 3h at the high temperature of 120 ℃, added into a double-screw extruder, the rotating speed of a double-screw host is 25r/min, the temperature of each processing section of a screw rod of the double-screw extruder is 330 ℃, 360 ℃, 370 ℃, and the temperature of a die head is 365 ℃, then the obtained extruded materials are respectively wound through a 25 ℃ air cooling device, a 60 ℃ water cooling device and a 20 ℃ water cooling device and a traction wire winding machine with the winding speed of 8m/min to obtain a 3D printing interlayer reinforcing polyether-ether-ketone alloy wire rod, the diameter of the wire rod is 1.75mm, the wire rod is wound at the nozzle temperature of 410 ℃, and 3D printing is carried out in a 3D printer with the printing layer height of 0.2mm, the printing speed of 30mm/s and the cavity temperature of 230 ℃ to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy material.

Application example 2

The alloy material comprises the components of a polyether-ether-ketone/interlayer reinforcing modifier alloy material, according to 100 wt%, 95 wt% of the special material for 3D printing grade polyether-ether-ketone resin with the melt index of 30g/10min prepared in example 2 and 5 wt% of interlayer reinforcing modifier are premixed in a high-speed mixer, dried at 120 ℃ for 3h, added into a double-screw extruder, the rotating speed of a double-screw host is 25r/min, the temperature of each processing section of a screw of the double-screw extruder is 330 ℃, 360 ℃, 370 ℃, and the temperature of a die head is 365 ℃, then the obtained extruded materials are respectively wound through a 25 ℃ air cooling device, a 60 ℃ water cooling device and a 20 ℃ water cooling device and a traction wire winding machine with the winding speed of 8m/min to obtain a 3D printing interlayer reinforcing polyether-ether-ketone alloy wire rod, the diameter of the wire rod is 1.75mm, the wire rod is wound at the nozzle temperature of 410 ℃, and 3D printing is carried out in a 3D printer with the printing layer height of 0.2mm, the printing speed of 30mm/s and the cavity temperature of 230 ℃ to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy material.

Application example 3

The alloy material comprises the components of a polyetheretherketone/interlayer reinforcing modifier alloy material, wherein 93 wt% of the special material for printing grade polyetheretherketone resin with the melt index of 30g/10min3D prepared in example 2 and 7 wt% of the interlayer reinforcing modifier are premixed in a high-speed mixer, dried at 120 ℃ for 3h, added into a double-screw extruder with the rotating speed of a double-screw host of 25r/min, the processing temperature of each section of a screw of the double-screw extruder of 330 ℃, 360 ℃, 370 ℃ and the die head temperature of 365 ℃, and then the obtained extruded material is respectively wound by a 25 ℃ air cooling device, a 60 ℃ water cooling device and a 20 ℃ water cooling device through a wire winding machine with the winding speed of 8m/min to obtain a 3D printing interlayer reinforcing polyetheretherketone alloy wire rod with the wire rod diameter of 1.75mm, the wire rod is wound at the nozzle temperature of 410 ℃ and the printing layer height of 0.2mm, and 3D printing is carried out in a 3D printer with the printing speed of 30mm/s and the cavity temperature of 230 ℃ to obtain the 3D printing interlayer reinforced polyether-ether-ketone alloy material.

Performance testing

1) The melt index stability test is carried out on the special material for the 3D printing grade polyether-ether-ketone resin prepared in the embodiment 1, the method is that the special material for the 3D printing grade polyether-ether-ketone resin is respectively kept in a melt index instrument at 400 ℃ for 5min, 15min, 30min, 45min and 60min, then the melt index is tested, and the obtained result is shown in figure 1; as can be seen from FIG. 1, after aging at high temperature for different periods of time, the polyetheretherketone resin still has good fluidity, which confirms that the polyetheretherketone prepared has good high temperature resistance.

2) The polyether ether ketone resin prepared in example 1 was subjected to infrared testing, and the results are shown in fig. 2; as can be seen from FIG. 2, it was found that the thickness was 1657cm^-1The vibrational band of the polyether-ether-ketone carbonyl group is generated at 1600cm^-1And 1489cm^-1The peak absorption is a better assignment for the planar vibration band of the phenylene ether, confirming the successful preparation of the PEEK resin.

3) TGA test was performed on the 3D printing grade PEEK resin speciality prepared in example 1 and compared with a commercial PEEK (Geigold plastic PEEK-022G), and the results are shown in FIG. 3; as can be seen from fig. 3, the special material for 3D printing grade peek resin prepared in example 1 has higher grade of heat resistance than ordinary peek.

4) Tensile tests of injection molding and sample strip printing are respectively carried out on the special material for the 3D printing resin polyetheretherketone prepared in the example 2 by adopting GB/T1042.5-2008 test standards, and the obtained results are shown in a figure 4; as can be seen from FIG. 4, the tensile strength of the injection molded sample is 100MPa and the elongation at break is 36%, while the tensile strength of the 3D printed sample is 95MPa and the elongation at break is 31%, and the tensile properties of the resin special for printing are very close to the injection molding level.

5) DSC test is carried out on the 3D printing interlayer reinforced polyetheretherketone alloy material prepared in the corresponding example 1 and the application example 3, and the DSC test is compared with the commercially available polyetheretherketone (PEEK-021G, Geigar superplastic), and the obtained result is shown in figure 5; as can be seen from FIG. 5, the interlayer reinforcing modifier and the special material for 3D printing polyetheretherketone resin have only one Tg, which indicates that the two materials have good compatibility.

6) The tensile property test is carried out on the 3D printing interlayer reinforced polyether-ether-ketone alloy material prepared in the corresponding example 1 and the application example 3 by adopting a GB/T1042.5-2008 test standard, the tensile property test is compared with the commercially available polyether-ether-ketone, and the obtained result is shown in figure 6: as can be seen from fig. 6, the interlayer bonding strength (tensile strength) of the 3D printed interlayer reinforced polyetheretherketone alloy material prepared in application example 3 is as high as 32MPa, which is nearly 3 times the strength of interlayer unmodified resin (commercially available polyetheretherketone PEEK-021G).

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.