Low-temperature synthesis of polyaryletherketone resin onto nano/micron-scale inorganic seedbed

Abstract

Disclosed is a low-temperature preparation method for a polyaryletherketone inorganic composite material, in particular a method for the low-temperature synthesis of a polyaryletherketone resin on a nano/micron-scale inorganic seedbed. The method comprises: adding nano/micron-scale inorganic material particles (mono-element or multi-element of aluminium oxide, silicon oxide, hydroxyapatite and the like) to a reaction system of a polyaryletherketone high-molecular polymer, and realizing the blending of inorganics in a high proportion (>50%) and organics while completing the one-step polymerization reaction, so that the common thermal degradation problem of the organic materials induced during the melting, blending and thermal processing is avoided. The composite material can be used in the technical fields of aerospace, industry, medicine and the like.

Claims

1. A method, comprising: synthesizing polyaryletherketone molecules onto nano/micron-scale inorganic particles by mixing the nano/micron-scale inorganic particles with monomers corresponding to the polyaryletherketone, including: mixing the nano/micron-scale inorganic particles, AlCl.sub.3, and dichloroethane in a reactor, dropping reaction reagents one by one in an order by firstly N-methyl pyrrolidone, then dichloroethane, and then diphenyl ether and one or more of paraphthaloyl chloride, terephthaloyl chloride, into the reactor, and adding diphenyl ether to the reactor for further reaction, wherein the monomers corresponding to the polyaryletherketone molecules onto each individual inorganic particle to wrap around each individual inorganic particle by a low temperature polymerization, wherein each individual inorganic particle acts as a seedbed for the low temperature polymerization, and a combination of each individual inorganic particle and the polyaryletherketone molecules wrapping around each individual inorganic particle forms a composite unit; and collecting all the composite units to provide nano/micron-scale inorganic polyaryletherketone composites.

2. The method according to claim 1, wherein the nano/micron-scale inorganic particles have a diameter of less than 50 m.

3. The method according to claim 1, wherein the nano/micron-scale inorganic particles are inorganic materials including at the least ceramics, or calcium phosphates and glasses.

4. The method according to claim 1, wherein the polyaryletherketone comprises at least one of the following: polyetherketone, polyetheretherketone, polyetherketoneketone, polyetheretherketoneketone, and polyetherketoneetherketoneketone.

5. The method according to claim 3, wherein the ceramics comprise at least one of the following compositions: Al.sub.2O.sub.3, BeO, ZrO.sub.2, MgO, TiO.sub.2, BC, SiC and WC.

6. The method according to claim 3, wherein the glasses comprise at least one of the following compositions: SiO.sub.2, Na.sub.2O, K.sub.2O, CaO, MgO, BaO, PdO, ZnO, B.sub.2O.sub.3 and P.sub.2O.sub.5.

7. The method according to claim 3, wherein the calcium phosphates comprise at least one of the following compositions: Ca(H.sub.2PO.sub.4).sub.2, Ca.sub.3(PO.sub.4).sub.2, Ca.sub.3(PO.sub.4).sub.2, Ca.sub.5(PO.sub.4).sub.3(OH), Ca.sub.5(PO.sub.4).sub.3(OH), Ca.sub.10(PO.sub.4).sub.6(OH, F, Cl or Br).sub.2, Ca.sub.8H.sub.2(PO.sub.4).sub.6.5H.sub.2O.

8. The method according to claim 1, wherein the nano/micron-scale inorganic polyaryletherketone composites has a content of an inorganic material above 50 wt % of the total weight of the nano/micron-scale inorganic polyaryletherketone composites.

9. The method according to claim 1, wherein the low temperature polymerization is controlled at a low temperature ranging from 20 C. to 26 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a is an electronic microscope photograph of an Al.sub.2O.sub.3 particle as a polymer carrier; and

(2) FIG. 1b is an electronic microscope photograph of the Al.sub.2O.sub.3 particle where PEKK has formed onto each of Al.sub.2O.sub.3 particles.

DETAILED DESCRIPTION

(3) Embodiment 1

(4) Firstly add 5 gram of Al.sub.2O.sub.3 of 300 nm diameter, 4 to 5 gram AlCl.sub.3 and 10 ml dichloroethane into a 500 mL three-necked flask reactor equipped with a mechanical stirrer, a thermometer and a nitrogen delivery tube to introduce high-purity nitrogen in the reactor for 1 to 2 hours. It follows by cooling the reactor to a low temperature between 10 C. to 15 C. and then starting stirring, and making sure all dissolvable solids are completely dissolved at this temperature. After that, gently dropping three reaction reagents one by one in the order firstly a mixed solution of 1.25 mL of N-methyl pyrrolidone and 5 mL of dichloroethane; then dichloroethane, and the last 1.6 mL of diphenyl ether and 2.03 g of paraphthaloyl chloride (and/or terephthaloyl chloride) into the three-necked flask reactor. Keep reaction at low temperature between 5 C. and 15 C. for 1 to 2 hours, then raise the temperature of the reaction system to a temperature between 15 C. and 26 C. and keep the reaction for 10 to 15 hours. After that add 400 L of diphenyl ether to the three-necked flask reactor to further reaction for 3 hours. Finally, add 100 mL of methanol to the three-necked flask reactor to precipitate a white solid; and wash the white solid by using distilled water, methanol and distilled water in turn, and drying the final product at 80 C. to 120 C. for 10 to 20 hours. The end product is the composite of PEKK that has been naturally coated onto each inorganic particles during polynmerization.

(5) Embodiment 2

(6) Firstly add 5 gram of Al.sub.2O.sub.3 of 20 m diameter, 4 to 5 gram AlCl.sub.3 and 10 ml dichloroethane into a 500 mL three-necked flask reactor equipped with a mechanical stirrer, a thermometer and a nitrogen delivery tube to introduce high-purity nitrogen in the reactor for 1 to 2 hours. It follows by cooling the reactor to a low temperature between 10 C. to 15 C. and then starting stirring, and making sure all dissolvable solids are completely dissolved at this temperature. After that, gently dropping three reaction reagents one by one in the order firstly a mixed solution of 1.25 mL of N-methyl pyrrolidone and 5 mL of dichloroethane; then the 1.6 mL of diphenyl ether and 2.03 g of paraphthaloyl chloride (and/or terephthaloyl chloride) into the three-necked flask reactor. Keep reaction at low temperature between 5 C. and 15 C. for 1 to 2 hours, then raise the temperature of the reaction system to a temperature between 15 C. and 26 C. and keep the reaction for 10 to 15 hours. After that, add 400 L, of diphenyl ether to the three-necked flask reactor to further reaction for 3 hours. Finally, add 100 mL of methanol to the three-necked flask reactor to precipitate a white solid; and wash the white solid by using distilled water, methanol and distilled water in turn, and drying the final product at 80 C. to 120 C. for 10 to 20 hours. The end product is the composite of PEKK that has been naturally coated onto each inorganic particles during polynmerization.

(7) Embodiment 3

(8) Firstly add 7 gram of SiO.sub.2 of 50 nm diameter, 4 to 5 gram AlCl.sub.3 and 10 ml dichloroethane into a 500 mL three-necked flask reactor equipped with a mechanical stirrer, a thermometer and a nitrogen delivery tube to introduce high-purity nitrogen in the reactor for 1 to 2 hours. It follows by cooling the reactor to a low temperature between 10 C. to 15 C. and then starting stirring, and making sure all dissolvable solids are completely dissolved at this temperature. After that, gently dropping three reaction reagents one by one in the order firstly a mixed solution of 1.25 mL of N-methyl pyrrolidone and 5 mL of dichloroethane; then the 1.6 mL of diphenyl ether and 2.03 g of paraphthaloyl chloride (and/or terephthaloyl chloride) into the three-necked flask reactor. Keep reaction at low temperature between 5 C. and 15 C. for 1 to 2 hours, then raise the temperature of the reaction system to a temperature between 15 C. and 26 C. and keep the reaction for 10 to 15 hours. After that, add 4004, of diphenyl ether to the three-necked flask reactor to further reaction for 3 hours. Finally, add 100 mL of methanol to the three-necked flask reactor to precipitate a white solid; and wash the white solid by using distilled water, methanol and distilled water in turn, and drying the final product at 80 C. to 120 C. for 10 to 20 hours.

(9) Embodiment 4

(10) Firstly add 7 gram of SiO.sub.2 of 20 m diameter, 4 to 5 gram AlCl.sub.3 and 10 ml dichloroethane into a 500 mL three-necked flask reactor equipped with a mechanical stirrer, a thermometer and a nitrogen delivery tube to introduce high-purity nitrogen in the reactor for 1 to 2 hours. It follows by cooling the reactor to a low temperature between 10 C. to 15 C. and then starting stirring, and making sure all dissolvable solids are completely dissolved at this temperature. After that, gently dropping three reaction reagents one by one in the order firstly a mixed solution of 1.25 mL of N-methyl pyrrolidone and 5 mL of dichloroethane; then the 1.6 mL of diphenyl ether and 2.03 g of paraphthaloyl chloride (and/or terephthaloyl chloride) into the three-necked flask reactor. Keep reaction at low temperature between 5 C. and 15 C. for 1 to 2 hours, then raise the temperature of the reaction system to a temperature between 15 C. and 26 C. and keep the reaction for 10 to 15 hours. After that, add 4004, of diphenyl ether to the three-necked flask reactor to further reaction for 3 hours. Finally, add 100 mL of methanol to the three-necked flask reactor to precipitate a white solid; and wash the white solid by using distilled water, methanol and distilled water in turn, and drying the final product at 80 C. to 120 C. for 10 to 20 hours.

(11) Embodiment 5

(12) Firstly add 7 gram of HAP of 20 nm diameter, 4 to 5 gram AlCl.sub.3 and 10 ml dichloroethane into a 500 mL three-necked flask reactor equipped with a mechanical stirrer, a thermometer and a nitrogen delivery tube to introduce high-purity nitrogen in the reactor for 1 to 2 hours. It follows by cooling the reactor to a low temperature between 10 C. to 15 C. and then starting stirring, and making sure all dissolvable solids are completely dissolved at this temperature. After that, gently dropping three reaction reagents one by one in the order firstly a mixed solution of 1.25 mL of N-methyl pyrrolidone and 5mL of dichloroethane; then the 1.6 mL of diphenyl ether and 2.03 g of paraphthaloyl chloride (and/or terephthaloyl chloride) into the three-necked flask reactor. Keep reaction at low temperature between 5 C. and 15 C. for 1 to 2 hours, then raise the temperature of the reaction system to a temperature between 15 C. and 26 C. and keep the reaction for 10 to 15 hours. After that, add 400 L of diphenyl ether to the three-necked flask reactor to further reaction for 3 hours. Finally, add 100 mL of methanol to the three-necked flask reactor to precipitate a white solid; and wash the white solid by using distilled water, methanol and distilled water in turn, and drying the final product at 80 C. to 120 C. for 10 to 20 hours.

(13) Embodiment 6

(14) Firstly add 7 gram of HAP of 20 m diameter, 4 to 5 gram AlCl.sub.3 and 10 ml dichloroethane into a 500 mL three-necked flask reactor equipped with a mechanical stirrer, a thermometer and a nitrogen delivery tube to introduce high-purity nitrogen in the reactor for 1 to 2 hours. It follows by cooling the reactor to a low temperature between 10 C. to 15 C. and then starting stirring, and making sure all dissolvable solids are completely dissolved at this temperature. After that, gently dropping three reaction reagents one by one in the order firstly a mixed solution of 1.25 mL of N-methyl pyrrolidone and 5 mL of dichloroethane; then the 1.6 mL of diphenyl ether and 2.03 g of paraphthaloyl chloride (and/or terephthaloyl chloride) into the three-necked flask reactor. Keep reaction at low temperature between 5 C. and 15 C. for 1 to 2 hours, then raise the temperature of the reaction system to a temperature between 15 C. and 26 C. and keep the reaction for 10 to 15 hours. After that, add 400 L of diphenyl ether to the three-necked flask reactor to further reaction for 3 hours. Finally, add 100 mL of methanol to the three-necked flask reactor to precipitate a white solid; and wash the white solid by using distilled water, methanol and distilled water in turn, and drying the final product at 80 C. to 120 C. for 10 to 20 hours.