WO2017035893A1 - 一种用于sls技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法 - Google Patents

一种用于sls技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法 Download PDF

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WO2017035893A1
WO2017035893A1 PCT/CN2015/091159 CN2015091159W WO2017035893A1 WO 2017035893 A1 WO2017035893 A1 WO 2017035893A1 CN 2015091159 W CN2015091159 W CN 2015091159W WO 2017035893 A1 WO2017035893 A1 WO 2017035893A1
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reaction precursor
peek
preparation
precursor
reaction
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French (fr)
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闫春泽
史玉升
傅轶
史云松
潘腾
汪艳
魏青松
刘洁
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广东银禧科技股份有限公司
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Priority to DE112015006691.8T priority Critical patent/DE112015006691B4/de
Publication of WO2017035893A1 publication Critical patent/WO2017035893A1/zh
Priority to US15/887,486 priority patent/US10106651B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention belongs to the field of advanced manufacturing technology and material preparation, and more particularly to a polyetheretherketone/nanohydroxyapatite composite material for SLS technology and a preparation method thereof.
  • SLS Selective Laser Sintering
  • PEEK Polyetheretherketone
  • Hydroxyapatite is a major component of vertebrate bones and teeth, with a content of about 96 wt.% in human enamel and about 69 wt.% in bone.
  • hydroxyapatite has excellent osteoinductivity, which is very beneficial to the attachment and growth of bone cells on its surface, and thus is widely used in bone tissue engineering.
  • HA implanted in the body can form a closed bond with the tissue and grow new tissue to achieve implantation. The combination of matter and bone. The finer the grain size of HA, the higher the biological activity.
  • the combination of nano-hydroxyapatite and polyetheretherketone can significantly improve the biological activity of PEEK and ensure sufficient strength, which is suitable for the field of load-bearing bone replacement and bone repair.
  • the polyetheretherketone/nano-hydroxyapatite composite powder material is used in the manufacture of personalized bone prostheses by SLS, which can achieve sufficient shape, good biocompatibility and sufficient strength for bearing bones. Higher clinical use value and broad market prospects.
  • the mechanical mixing method is to mix two kinds of powders using a mechanical mixing device.
  • the method is simple, but the nano-filler cannot be uniformly dispersed in the polymer matrix at a nanometer scale;
  • Twin-screw extrusion-cryogenic pulverization method is to first melt-blend, extrude and granulate two materials using a twin-screw extruder, and then use cryogenic pulverization to prepare a powder suitable for the SLS process, although this method can The two materials are uniformly mixed, but because of the high strength and toughness of polyetheretherketone, cryogenic pulverization cannot be prepared into a small particle size (10-100 micron) powder required by the SLS process, and the powder particle shape is extremely Irregular, poor liquidity;
  • Solvent mixing method usually requires the use of some organic solvents, which are harmful to the environment and the human body, and the residual solvent may adversely affect the biocompatibility of the composite material.
  • the dispersion of nano-hydroxyapatite in an organic solvent usually requires the use of a surfactant, and the residual surfactant reduces the biocompatibility of the composite.
  • the Fuhua Group uses a N,N'-dimethylamide solvent to prepare a polyetheretherketone/nano-hydroxyapatite composite powder material for SLS.
  • Solvent precipitation method is generally applicable to the preparation of nylon composite powder materials.
  • ZL200710053668.2 uses solvent precipitation method to prepare inorganic nanofiller reinforced nylon composite materials for SLS
  • ZL200710053667.8 uses solvent precipitation method to prepare clay reinforcement for SLS Nylon composite. Since polyetheretherketone has a very strong solvent resistance, this method is not suitable for the preparation of polyetheretherketone composite powder materials.
  • the present invention provides a polyetheretherketone/nano-hydroxyapatite composite material for SLS selective laser sintering technology and a preparation method thereof, and the invention uses in situ composite in an aqueous solution.
  • the method discloses that the nano-hydroxyapatite is uniformly dispersed in the polymer matrix, thereby solving the technical problem that the current PEEK/nano-hydroxyapatite composite material for SLS has poor fluidity, uneven morphology and poor biocompatibility.
  • a method for preparing a polyetheretherketone/nanohydroxyapatite composite for SLS technology comprising the steps of:
  • reaction mixture solution is suction filtered, washed, dried and ground to finally obtain the polyetheretherketone/nano hydroxyapatite composite material;
  • the reaction precursor 1 is a calcium ion-containing precursor solution
  • the reaction precursor 2 is a phosphate ion-containing precursor solution
  • the amount of the reaction precursor 1 and the reaction precursor 2 satisfies Ca/P.
  • the molar ratio is 1.67 to 2.0.
  • the PEEK has a particle diameter of from 20 ⁇ m to 70 ⁇ m.
  • the concentration of the aqueous solution of the reaction precursor 1 is from 0.5 mol/L to 1.0 mol/L; and the concentration of the aqueous solution of the reaction precursor 2 is from 1.0 to 2.0 mol/L.
  • the reaction precursor 1 is calcium hydroxide or calcium nitrate
  • the reaction precursor 2 is phosphoric acid or diammonium hydrogen phosphate.
  • the reaction precursor 1 is calcium hydroxide (Ca(OH) 2 ); in the step (3), the reaction precursor 2 is phosphoric acid (H 3 PO 4 ) ).
  • the reaction precursor 1 is calcium nitrate, more preferably calcium nitrate tetrahydrate (Ca(NO 3 ) 2 .4H 2 O); in the step (3), the reaction precursor 2 described is diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ).
  • the invention also provides a polyetheretherketone/nanohydroxyapatite composite material which can be used in the SLS technology prepared by the above preparation method.
  • the composite material is a powder material.
  • the nano-hydroxyapatite is present in the composite in an amount from 10% by weight to 50% by weight.
  • the in-situ composite method of the present invention uniformly disperses hydroxyapatite in a polymer matrix polyetheretherketone to form a good interfacial bond, and the obtained polyetheretherketone/nanohydroxyapatite
  • the material has uniform shape, good sphericity and good fluidity, which is very suitable for SLS forming high-performance personalized bone restoration.
  • the composite material is more favorable for the powdering and forming of SLS.
  • Figure 1 (a) is a microscopic topography of pure PEEK powder.
  • Figure 1 (b) is an EDX elemental analysis of pure PEEK powder.
  • Fig. 2 (a) is a microscopic top view of a composite powder of PEEK/HA (20 wt%) in Example 1.
  • Fig. 2(b) is an EDX elemental analysis diagram of PEEK/HA (20 wt%) in Example 1.
  • Example 3 is a transmission electron micrograph of PEEK of PEEK/HA (20 wt%) in Example 1.
  • XRD 4 is an X-ray diffraction analysis (XRD) pattern of a pure PEEK powder material and PEEK/HA composite powder materials of Examples 1, 2, and 6.
  • the method for preparing a polyetheretherketone/nanohydroxyapatite composite material for SLS technology adopts a method for in-situ recombination in an aqueous solution, and specifically comprises the following steps:
  • the PEEK selected by the step (1) is added to the aqueous solution of the reaction precursor 1 and ultrasonically treated for 30 min to 60 min to be uniformly dispersed in the aqueous solution;
  • the reaction precursor 1 is a precursor solution containing calcium ions.
  • the reaction precursor 1 is calcium hydroxide (Ca(OH) 2 ) or calcium nitrate tetrahydrate (Ca(NO 3 ) 2 .4H 2 O); the concentration of the aqueous solution of the reaction precursor 1 is Is 0.5-1.0 mol / L;
  • the mixed solution obtained in the step (2) is vigorously stirred while the aqueous solution of the reaction precursor 2 is slowly dropped dropwise, and finally the pH of the mixed solution is adjusted to 10-12 with a pH adjuster;
  • the body 2 is a precursor solution containing a phosphate ion, and preferably, the reaction precursor 2 is phosphoric acid (H 3 PO 4 ) or diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ); the reaction precursor
  • the concentration of the aqueous solution 2 is 1.0-2.0 mol/L; the reaction in the mixed solution is continued in an alkaline environment for 24 to 48 hours under vigorous stirring; the amount of the reaction precursor 1 and the reaction precursor 2 satisfies Ca/P
  • the molar ratio is 1.67 to 2.0.
  • reaction mixture solution was suction filtered, washed with distilled water, vacuum dried, and ground to finally obtain the polyetheretherketone/nano hydroxyapatite composite.
  • the particle diameter of the PEEK is preferably from 20 ⁇ m to 70 ⁇ m.
  • the preferred particle size range is mainly for the purpose of facilitating SLS forming. If the particle size is too large, the SLS forming part has low precision, the surface is rough, the particle size is easy to agglomerate, and it is difficult to lay powder, resulting in defects of the SLS forming part.
  • reaction precursor 1 is selected to be Ca(OH) 2
  • reaction precursor 2 is preferably H 3 PO 4
  • amount of Ca(OH) 2 and H 3 PO 4 is such that the Ca/P molar ratio is preferably 1.67.
  • the reaction precursor 1 is selected to be Ca(NO 3 ) 2 .4H 2 O
  • the reaction precursor 2 is preferably (NH 4 ) 2 HPO 4 , Ca(NO 3 ) 2 .4H 2 O and (NH 4 ) 2 .
  • the amount of HPO 4 to be used satisfies the Ca/P molar ratio of preferably 1.67, and the reaction proceeds as follows:
  • the pH adjusting agent may be a regulator commonly used in the art, preferably 10% aqueous ammonia.
  • the rate of slowly dropping the aqueous solution of the precursor 2 into the step (3) was 1 to 20 ml/min.
  • the invention provides a polyetheretherketone/nano-hydroxyapatite composite material for SLS technology, wherein the nano-hydroxyapatite is uniformly dispersed in polyetheretherketone, the material is powdery, the particle diameter is uniform, spherical A good degree of selective laser sintering is used to create a personalized, complex bone graft restoration.
  • the content of the nano hydroxyapatite in the composite material is 10% by weight to 50% by weight.
  • the nano hydroxyapatite in the composite material of the invention has a needle-like morphology, a width of 20 nm to 30 nm, and a length of about 100 to 150 nm.
  • step (3) The mixed solution obtained in the step (2) is vigorously stirred, while 333 mL, 1.0 mol/L H 3 PO 4 aqueous solution is slowly dropped dropwise at a rate of 10 ml/min, and finally the pH of the mixed solution is 10% ammonia water. Adjusted to 10; under vigorous stirring, the reaction in the mixed solution was continued in an alkaline environment for 24 h;
  • reaction mixture solution is suction filtered, and the obtained powder aggregate is washed by distilled water, vacuum dried and ground to obtain a polyetheretherketone/nano hydroxyapatite composite powder having a nano hydroxyapatite content of 10% by weight. .
  • step (3) The mixed solution obtained in the step (2) is vigorously stirred, while 747 mL, 1.0 mol/L H 3 PO 4 aqueous solution is slowly dropped dropwise at a rate of 10 ml/min, and finally the pH of the mixed solution is 10% ammonia water. Adjusted to 10; under vigorous stirring, the reaction in the mixed solution was continued in an alkaline environment for 24 h;
  • reaction mixture solution is suction filtered, and the obtained powder aggregate is washed by distilled water, vacuum dried and ground to obtain a polyetheretherketone/nano hydroxyapatite composite powder having a nano hydroxyapatite content of 20% by weight. .
  • the mixed solution obtained in the step (2) is vigorously stirred while gradually dropping 1.5 L of a 2.0 mol/L H 3 PO 4 aqueous solution at a rate of 20 ml/min, and finally, the pH of the mixed solution is 10% ammonia water. The value is adjusted to 10; under vigorous stirring, the reaction in the mixed solution is continued in an alkaline environment for 48 h;
  • reaction mixture solution is suction filtered, and the obtained powder aggregate is washed by distilled water, vacuum dried and ground to finally obtain a polyether ether ketone/nano hydroxyapatite composite powder having a nano hydroxyapatite content of 50% by weight. .
  • reaction mixture solution is suction filtered, and the obtained powder aggregate is washed by distilled water, vacuum dried and ground to finally obtain a polyether ether ketone/nano hydroxyapatite composite powder having a nano hydroxyapatite content of 50% by weight. .
  • Step (1) screening out 500gPEEK powder is added to 2.49L, 0.5mol / L, Ca ( NO 3) 2 .4H 2 O in aqueous solution by sonication 30min, uniformly dispersed in the water;
  • step (3) The mixed solution obtained in the step (2) was vigorously stirred, and 747 mL of the aqueous solution of 1.0 mol/L (NH 4 ) 2 HPO 4 in the step (3) was slowly dropped dropwise at a rate of 10 ml/min. Finally, the pH of the mixed solution is adjusted to 10 with 10% ammonia water; under vigorous stirring, the reaction in the mixed solution is continued in an alkaline environment for 24 h;
  • reaction mixture solution is suction filtered, and the obtained powder aggregate is washed by distilled water, vacuum dried and ground to obtain a polyetheretherketone/nano hydroxyapatite composite powder having a nano hydroxyapatite content of 20% by weight. .
  • Step (1) screening out 500gPEEK powder is added to 4.28L, 0.5mol / L, Ca ( NO 3) 2 .4H 2 O in aqueous solution by sonication 30min, uniformly dispersed in the water;
  • step (3) The mixed solution obtained in the step (2) is vigorously stirred while the 1.28 L, 1.0 mol/L (NH 4 ) 2 HPO 4 aqueous solution in the step (3) is slowly dropped at a rate of 10 ml/min. Finally, the pH of the mixed solution is adjusted to 10 with 10% ammonia water; the reaction in the mixed solution is continued in an alkaline environment for 48 hours under vigorous stirring;
  • reaction mixture solution is suction filtered, and the obtained powder aggregate is washed by distilled water, vacuum dried and ground to finally obtain a polyetheretherketone/nano hydroxyapatite composite powder having a nano hydroxyapatite content of 30% by weight. .
  • the invention adopts the method of in-situ recombination in water, and uniformly disperses the nano hydroxyapatite in the polymer matrix polyetheretherketone, and the obtained powder composite material has uniform morphology, good interface bonding, good sphericity and good fluidity. , no pollution to the environment.
  • Figure 1 shows the microstructure and EDX elemental analysis of a pure PEEK powder.
  • the PEEK powder material particles have an irregular shape and a relatively smooth surface.
  • the EDX element analysis was performed on the white box area in Fig. 1(a), and the result is shown in Fig. 1(b). It can be found that the powder material consists mainly of C and O elements.
  • Figure 2 shows the microstructure and EDX elemental analysis of PEEK/HA (20wt%) composite powder. Comparing Fig. 1(a) with Fig.
  • FIG. 3 is a transmission electron micrograph of the nano-HA prepared in Example 1, and it can be seen that HA has a needle-like morphology, about 20 nm in width and about 100 nm in length. 3 shows that the nano-hydroxyapatite prepared by the invention has good grain morphology, and the needle-shaped HA has excellent biological activity and good quality.
  • the HA size structure of the invention is moderate, and is very suitable for selective laser sintering. Process.
  • HA had a needle-like morphology, and the dimensional values thereof were about 30 nm*100 nm, 30*150 nm, and 20*150 nm, respectively.
  • Figure 4 is an X-ray diffraction analysis (XRD) of pure PEEK and the PEEK/HA composite powder material prepared by the method of the present invention. It can be found that the XRD patterns of the three PEEK/HA composite materials are at 25.9°, 31.8°, 39.8°, 46.7. °, 49.5°, 53.2°, etc.
  • the HA characteristic peak indicates that the present invention synthesizes HA on the surface of PEEK powder particles by chemical precipitation, and the preparation method of the present invention well protects the performance of PEEK compared with pure PEEK.

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Abstract

本发明公开了一种用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法。所述复合材料的制备方法，包括选取10μm-100μm的PEEK和两种反应前驱体1和2水溶液，将PEEK均匀分散到反应前驱体1水溶液中，在搅拌的同时将反应前驱体2水溶液滴入反应前驱体1水溶液和PEEK的混合溶液中，将混合液的pH值调节至10-12后继续反应24-48h。本发明提供的制备方法所得到的复合材料生物相容性好，形态均匀，流动性良好，利于SLS技术的铺粉和成形过程。

Description

一种用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法 【技术领域】
本发明属于先进制造技术和材料制备领域，更具体地，涉及一种用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法。
【背景技术】
选择性激光烧结(Selective LaserSintering，SLS)技术是增材制造技术的重要分支，它是基于离散、堆积成形的思想，采用激光有选择地扫描烧结粉末材料，分层制造、逐层叠加，形成实体模型。与传统的去除成形、拼合成形及受迫成形等加工方法不同，它是利用材料累加法来加工制造高分子材料、陶瓷、金属及各种复合材料的模型和功能零件。由于SLS技术不受成形件复杂度的影响，因此广泛应用于生物医疗领域，可以最高效的制作个性化、复杂医疗产品，最大程度的满足患者需求。
聚醚醚酮(PEEK)是一种全芳香半结晶高聚物，机械性能良好，且具有优异的耐辐射性、绝缘性等特点，在许多特殊领域可替代金属、陶瓷等传统材料，减轻重量且不影响使用性能。在医疗器械领域，PEEK在脊柱手术、外伤和骨科类医疗产品的临床应用越来越广泛。与其他植入材料相比，PEEK具有较好的生物相容性以及可调的力学性能，并且在CT和MRI扫描时不可见。但PEEK缺乏生物活性，使得PEEK在医用领域的使用受到限制。羟基磷灰石(HA)是脊椎动物骨骼和牙齿的主要成分，人的牙釉质中含量约96wt.％，骨头中约69wt.％。相比不锈钢、钛合金、陶瓷等传统骨替代材料，羟基磷灰石具有优良的骨诱导性，非常利于骨细胞在其表面附着、生长，因而广泛应用于骨组织工程中。通过释放钙离子和磷酸根离子，植入体内的HA能够和组织之间形成封闭粘结，并长出新的组织，实现植入 物与骨的结合。HA的晶粒越细，其生物活性越高，将纳米羟基磷灰石与聚醚醚酮复合，可显著提高PEEK的生物活性，并保证足够的强度，适用于承重骨替代、骨修复领域。综上所述，聚醚醚酮/纳米羟基磷灰石复合粉末材料，用于SLS制造个性化骨修复体，可实现形状可控、良好生物相容性和承重骨所需的足够强度，具有较高的临床使用价值和广阔的市场前景。
目前SLS用复合粉末材料的制备方法主要有四种，即机械混合法、双螺杆挤出-深冷粉碎法、溶剂混合法以及溶剂沉积法。但是这四种制备方法在制备SLS用聚醚醚酮/纳米羟基磷灰石复合粉末时均存在明显缺点，主要表现在：
(1)机械混合法是使用机械混合设备将两种粉末混合，这种方法工艺简单，但无法将纳米填料以纳米尺度均匀地分散在高分子基体中；
(2)双螺杆挤出-深冷粉碎法是首先使用双螺杆挤出机将两种材料熔融共混、挤出造粒，然后采用深冷粉碎制备适合SLS工艺的粉末，虽然这种方法可将两种材料混合均匀，但是由于聚醚醚酮具有很高的强度和韧性，因此深冷粉碎无法将其制备成SLS工艺要求的小粒径(10-100微米)粉末，而且粉末颗粒形状极不规则，流动性差；
(3)溶剂混合法通常需要使用一些有机溶剂，对环境和人体存在危害，残存的溶剂会对复合材料的生物相容性有不利影响。此外，纳米羟基磷灰石在有机溶剂中分散，通常需要借助表面活性剂，残存的表面活性剂会降低复合材料的生物相容性。例如，付华组使用N,N’-二甲基酰胺溶剂制备SLS用聚醚醚酮/纳米羟基磷灰石复合粉末材料。
(4)溶剂沉淀法一般适用于尼龙复合粉末材料的制备，例如，ZL200710053668.2使用溶剂沉淀法制备用于SLS的无机纳米填料增强尼龙复合材料；ZL200710053667.8使用溶剂沉淀法制备用于SLS的粘土增强尼龙复合材料。由于聚醚醚酮具有非常强的耐溶剂性，因此该法不适合用于制备聚醚醚酮复合粉末材料。
【发明内容】
针对现有技术存在的缺陷，本发明提供了一种用于SLS选择性激光烧结技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法，本发明在水溶液中使用原位复合的方法将纳米羟基磷灰石以均匀地分散在高分子基体中，由此解决了目前SLS用的PEEK/纳米羟基磷灰石复合材料流动性差、形态不均匀且生物相容性差的技术问题。
为实现上述目的，按照本发明的一个方面，提供了一种用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料的制备方法，包括以下步骤：
(1)选取粒径范围为10-100μm的PEEK聚醚醚酮；
(2)将步骤(1)中的PEEK粉末加入到反应前驱体1水溶液中，使其均匀分散于水溶液中；
(3)将步骤(2)所得的混合溶液搅拌，同时滴入反应前驱体2水溶液，将pH值调节为10-12；在搅拌下反应24-48h；
(4)最后，将反应混合溶液抽滤，洗涤、干燥以及研磨，最终获得所述的聚醚醚酮/纳米羟基磷灰石复合材料；
其中，所述的反应前驱体1为含钙离子的前驱体溶液，所述的反应前驱体2为含磷酸根离子的前驱体溶液，反应前驱体1和反应前驱体2的用量满足Ca/P的摩尔比为1.67～2.0。
优选地，在步骤(1)中，所述PEEK的粒径为20μm-70μm。
优选地，所述的反应前驱体1水溶液的浓度为0.5mol/L-1.0mol/L；所述的反应前驱体2水溶液的浓度为1.0-2.0mol/L。
优选地，所述的反应前驱体1为氢氧化钙或硝酸钙，所述的反应前驱体2为磷酸或磷酸氢二铵
优选地，在步骤(2)中，所述的反应前驱体1为氢氧化钙(Ca(OH)2)；在步骤(3)中，所述的反应前驱体2为磷酸(H3PO4)。
更优选地，在步骤(2)中，所述的反应前驱体1为硝酸钙，更优选为 四水硝酸钙(Ca(NO3)2.4H2O)；在步骤(3)中，所述的反应前驱体2为磷酸氢二铵((NH4)2HPO4)。
本发明还提供了一种上述制备方法制备得到的可用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料。其中，该复合材料为粉末材料。
优选地，纳米羟基磷灰石在复合材料中的含量为10wt％-50wt％。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，取得下列有益效果：
(1)本发明采用原位复合方法，将羟基磷灰石均匀地分散在高分子基体聚醚醚酮中，形成了良好的界面粘接，制得的聚醚醚酮/纳米羟基磷灰石材料形态均匀、球形度好流动性良好，非常适合SLS成形高性能个性化骨修复体。
(2)本发明的制备方法中采用水为反应介质，不会对环境和人体造成危害；在制备方法中没有引入其他对复合材料生物相容性有损害的物质，大大降低了材料的毒性。
(3)通过对制备方法中各参数和各成分如粉末的粒径、反应前驱体的选择以及钙磷比等参数的进一步研究设计，使得到的复合材料更有利于SLS的铺粉和成形。
【附图说明】
图1(a)是纯PEEK粉末的微观形貌图。
图1(b)是纯PEEK粉末的EDX元素分析图。
图2(a)是实施例1中PEEK/HA(20wt％)的复合粉末微观形貌图。
图2(b)是实施例1中PEEK/HA(20wt％)的EDX元素分析图。
图3是实施例1中PEEK/HA(20wt％)的纳米HA的透射电子显微镜图。
图4是纯PEEK粉末材料和实施例1、2及6中PEEK/HA复合粉末材料的X衍射分析(XRD)图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明提供的用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料的制备方法，采用在水溶液中原位复合的方法，具体包括以下步骤：
(1)选取粒径范围为10-100μm的PEEK聚醚醚酮；
(2)将步骤(1)筛选出来的PEEK加入到反应前驱体1水溶液中，超声处理30min-60min，使其均匀分散于水溶液中；所述的反应前驱体1为含钙离子的前驱体溶液，优选地，所述的反应前驱体1为氢氧化钙(Ca(OH)2)或四水硝酸钙(Ca(NO3)2.4H2O)；所述的反应前驱体1水溶液的浓度为0.5-1.0mol/L；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将反应前驱体2水溶液逐滴缓慢滴入，最后用pH调节剂将混合溶液的pH值调节为10-12；所述的反应前驱体2为含磷酸根离子的前驱体溶液，优选地，所述的反应前驱体2为磷酸(H3PO4)或磷酸氢二铵((NH4)2HPO4)；所述的反应前驱体2水溶液的浓度为1.0-2.0mol/L；在剧烈搅拌下，使混合溶液中的反应在碱性环境中继续进行24-48h；反应前驱体1和反应前驱体2的用量满足Ca/P的摩尔比为1.67～2.0。
(4)最后，将反应混合溶液抽滤，蒸馏水洗涤、真空干燥以及研磨，最终获得所述的聚醚醚酮/纳米羟基磷灰石复合材料。
在步骤(1)中，所述PEEK的粒径优选为20μm-70μm。优选粒径范围主要是为了有利于SLS成形，粒度过大则SLS成形件精度低、表面粗糙，粒度过细则易团聚，不易铺粉，造成SLS成形件缺陷。
如果选用反应前驱体1为Ca(OH)2，那么反应前驱体2优选为H3PO4， Ca(OH)2和H3PO4所取用量满足Ca/P摩尔比优选为1.67，反应按下式进行：
10Ca(OH)2+6H3PO4→Ca10(PO4)6(OH)2+18H2O
如果选用反应前驱体1可为Ca(NO3)2.4H2O，那么反应前驱体2优选为(NH4)2HPO4，Ca(NO3)2.4H2O和(NH4)2HPO4所取用量满足Ca/P摩尔比优选为1.67，反应按下式进行：
6(NH4)2HPO4+10Ca(NO3)2.4H2O→Ca10(PO4)6(OH)2+20NH4NO3
在步骤(3)中，pH调节剂可以为本领域中常用的调节剂，优选为10％氨水。向步骤(3)中缓慢滴入前驱体2水溶液的速度为1-20ml/min。
本发明提供了一种用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料，其中，纳米羟基磷灰石均匀分散在聚醚醚酮中，材料呈粉末状，粒径均匀，球形度好，利用选择性激光烧结成形来制造个性化、复杂骨移植修复体。其中，纳米羟基磷灰石在复合材料中的含量为10wt％-50wt％。本发明的复合材料中纳米羟基磷灰石具有针状形貌，宽为20纳米～30纳米，长约100～150纳米。
以下为实施例：
实施例1
(1)选取粒径范围为20-70μm的PEEK粉末材料；
(2)将步骤(1)筛选出来的500gPEEK粉末加入到1.11L，0.5mol/LCa(OH)2水溶液中，通过超声处理60min，使其均匀分散于水中；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将333mL，1.0mol/L H3PO4水溶液以10ml/min的速度逐滴缓慢滴入，最后用10％氨水将混合溶液的pH值调节为10；在剧烈搅拌下，使混合溶液中的反应在碱性环境中继续进行24h；
(4)最后，将反应混合溶液抽滤，获得的粉末聚集体通过蒸馏水洗涤、真空干燥以及研磨，最终获得纳米羟基磷灰石含量为10wt％的聚醚醚酮/纳米羟基磷灰石复合粉末。
实施例2
(1)选取粒径范围为20-70μm的PEEK粉末材料；
(2)将步骤(1)筛选出来的500gPEEK粉末加入到2.49L，0.5mol/LCa(OH)2水溶液中，通过超声处理30min，使其均匀分散于水中；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将747mL，1.0mol/LH3PO4水溶液以10ml/min的速度逐滴缓慢滴入，最后用10％氨水将混合溶液的pH值调节为10；在剧烈搅拌下，使混合溶液中的反应在碱性环境中继续进行24h；
(4)最后，将反应混合溶液抽滤，获得的粉末聚集体通过蒸馏水洗涤、真空干燥以及研磨，最终获得纳米羟基磷灰石含量为20wt％的聚醚醚酮/纳米羟基磷灰石复合粉末。
实施例3
(1)选取粒径范围为20-70μm的PEEK粉末材料；
(2)将步骤(1)筛选出来的500gPEEK粉末加入到4.98L，1.0mol/LCa(OH)2水溶液中，通过超声处理60min，使其均匀分散于水中；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将1.5L，2.0mol/LH3PO4水溶液以20ml/min的速度逐滴缓慢滴入，最后用10％氨水将混合溶液的pH值调节为10；在剧烈搅拌下，使混合溶液中的反应在碱性环境中继续进行48h；
(4)最后，将反应混合溶液抽滤，获得的粉末聚集体通过蒸馏水洗涤、真空干燥以及研磨，最终获得纳米羟基磷灰石含量为50wt％的聚醚醚酮/纳米羟基磷灰石复合粉末。
实施例4
(1)选取粒径范围为20-70μm的PEEK粉末材料；
(2)将步骤(1)筛选出来的500gPEEK粉末加入到4.98L，1.0mol/LCa(NO3)2.4H2O水溶液中，通过超声处理60min，使其均匀分散于水 中；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将1.5L，2.0mol/L(NH4)2HPO4水溶液以20ml/min的速度逐滴缓慢滴入，最后用10％氨水将混合溶液的pH值调节为10；在剧烈搅拌下，使混合溶液中的反应在碱性环境中继续进行48h；
(4)最后，将反应混合溶液抽滤，获得的粉末聚集体通过蒸馏水洗涤、真空干燥以及研磨，最终获得纳米羟基磷灰石含量为50wt％的聚醚醚酮/纳米羟基磷灰石复合粉末。
实施例5
(1)选取粒径范围为20-70μm的PEEK粉末材料；
(2)将步骤(1)筛选出来的500gPEEK粉末加入到2.49L，0.5mol/L，Ca(NO3)2.4H2O水溶液中，通过超声处理30min，使其均匀分散于水中；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将步骤(3)中所配747mL，1.0mol/L(NH4)2HPO4水溶液以10ml/min的速度逐滴缓慢滴入，最后用10％氨水将混合溶液的pH值调节为10；在剧烈搅拌下，使混合溶液中的反应在碱性环境中继续进行24h；
(4)最后，将反应混合溶液抽滤，获得的粉末聚集体通过蒸馏水洗涤、真空干燥以及研磨，最终获得纳米羟基磷灰石含量为20wt％的聚醚醚酮/纳米羟基磷灰石复合粉末。
实施例6
(1)选取粒径范围为20-70μm的PEEK粉末材料；
(2)将步骤(1)筛选出来的500gPEEK粉末加入到4.28L，0.5mol/L，Ca(NO3)2.4H2O水溶液中，通过超声处理30min，使其均匀分散于水中；
(3)将步骤(2)所得的混合溶液剧烈搅拌，同时将步骤(3)中所配1.28L，1.0mol/L(NH4)2HPO4水溶液以10ml/min的速度逐滴缓慢滴入，最后用10％氨水将混合溶液的pH值调节为10；在剧烈搅拌下，使混合溶液中的 反应在碱性环境中继续进行48h；
(4)最后，将反应混合溶液抽滤，获得的粉末聚集体通过蒸馏水洗涤、真空干燥以及研磨，最终获得纳米羟基磷灰石含量为30wt％的聚醚醚酮/纳米羟基磷灰石复合粉末。
实施例7
本发明采用在水中原位复合的方法，将纳米羟基磷灰石均匀分散在高分子基体聚醚醚酮中，得到的粉末复合材料形态均匀，有良好的界面粘接，球形度好流动性良好，对环境无污染。
以实施例1中的复合材料为例，使用各种检测手段对本发明的复合材料进行表征。图1是一种纯PEEK粉末微观形貌和EDX元素分析。从图1(a)可以看出，该PEEK粉末材料颗粒具有不规则形状和较为光滑的表面。对图1(a)中白色方框区域做EDX元素分析，结果如图1(b)所示。可以发现粉末材料主要由C和O元素组成。图2是PEEK/HA(20wt％)复合粉末微观形貌和EDX元素分析。对比图1(a)和图2(a)，可以发现PEEK粉末颗粒表面附着了一层微小颗粒物质。对图2(a)中白色方框区域做EDX元素分析，结果如图2(b)所示，可以发现粉末材料由C、O、P和Ca组成。这是由于在原位复合反应过程中，纳米HA在PEEK颗粒表面生长，最终在PEEK颗粒表面形成一个HA薄层。这样就将HA均匀分散在PEEK基体中，并形成良好的界面粘接。图3是实施例1中所制备得到的纳米HA的透射电子显微镜图，可以看出HA具有针状形貌，宽约20纳米，长约100纳米。图3表明本发明制备的纳米羟基磷灰石具有良好的晶粒形貌，针状形貌的HA具有优良的生物活性，质量较好，本发明的HA尺寸结构适中，非常适合选择性激光烧结工艺。另外，实施例2-4中HA均具有针状形貌，其尺寸值分别约为30nm*100nm、30*150nm、20*150nm。图4是纯PEEK及本发明方法制备的PEEK/HA复合粉末材料的X衍射分析(XRD)，可以发现三种PEEK/HA复合材料的XRD谱图中在25.9°、31.8°、39.8°、46.7°、49.5°、53.2°等位置存在 HA特征峰，说明本发明通过化学沉淀法在PEEK粉末颗粒表面合成出HA，且与纯PEEK相比，本发明的制备方法很好的保护了PEEK的性能。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (8)

  1. 一种用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料的制备方法，其特征在于，所述的制备方法包括以下步骤：
    (1)选取粒径范围为10-100μm的PEEK聚醚醚酮；
    (2)将步骤(1)中的PEEK加入到反应前驱体1水溶液中，使其均匀分散于水溶液中；
    (3)将步骤(2)所得的混合溶液搅拌，同时滴入反应前驱体2水溶液，将pH值调节为10-12；在搅拌下反应24-48h；
    (4)最后，将反应混合溶液抽滤，洗涤、干燥以及研磨，最终获得所述的聚醚醚酮/纳米羟基磷灰石复合材料；
    其中，所述的反应前驱体1为含钙离子的前驱体溶液，所述的反应前驱体2为含磷酸根离子的前驱体溶液，反应前驱体1和反应前驱体2的用量满足Ca/P的摩尔比为1.67～2.0。
  2. 如权利要求1所述的制备方法，其特征在于，在步骤(1)中，所述PEEK的粒径为20μm-70μm。
  3. 如权利要求1所述的制备方法，其特征在于，所述的反应前驱体1水溶液的浓度为0.5mol/L-1.0mol/L；所述的反应前驱体2水溶液的浓度为1.0-2.0mol/L。
  4. 如权利要求1所述的制备方法，其特征在于，所述的反应前驱体1为氢氧化钙或硝酸钙，所述的反应前驱体2为磷酸或磷酸氢二铵。
  5. 如权利要求4所述的制备方法，其特征在于，在步骤(2)中，所述的反应前驱体1为氢氧化钙(Ca(OH)2)；在步骤(3)中，所述的反应前驱体2为磷酸(H3PO4)。
  6. 如权利要求4所述的制备方法，其特征在于，在步骤(2)中，所述的反应前驱体1为四水硝酸钙(Ca(NO3)2.4H2O)；在步骤(3)中，所述 的反应前驱体2为磷酸氢二铵((NH4)2HPO4)。
  7. 一种如权利要求1-6中任一项所述的制备方法制备得到的可用于SLS技术的聚醚醚酮/纳米羟基磷灰石复合材料。
  8. 如权利要求7所述的复合材料，其特征在于，纳米羟基磷灰石在复合材料中的含量为10wt％-50wt％。
PCT/CN2015/091159 2015-09-02 2015-09-30 一种用于sls技术的聚醚醚酮/纳米羟基磷灰石复合材料及其制备方法 WO2017035893A1 (zh)

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