CN110330683B - Preparation method of bionic polyether-ether-ketone artificial joint mortar with soft-hard composite structure - Google Patents

Preparation method of bionic polyether-ether-ketone artificial joint mortar with soft-hard composite structure Download PDF

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CN110330683B
CN110330683B CN201910501851.7A CN201910501851A CN110330683B CN 110330683 B CN110330683 B CN 110330683B CN 201910501851 A CN201910501851 A CN 201910501851A CN 110330683 B CN110330683 B CN 110330683B
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polyether
ether
ketone
artificial joint
joint mortar
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刘昀彤
赵晓铎
熊党生
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Nanjing University of Science and Technology
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Abstract

The invention discloses a preparation method of a bionic polyether-ether-ketone artificial joint mortar with a soft-hard composite structure. According to the method, a hard polyether-ether-ketone or derivative artificial joint mortar cup is used as a matrix, a hole structure is built on the surface of the artificial joint mortar cup by adopting a laser punching method, then an ultraviolet irradiation graft polymerization technology is combined, a layer of soft hydrogel layer is prepared on the surface of the polyether-ether-ketone artificial joint mortar cup with the hole structure, and finally the hydrogel-polyether-ether-ketone composite material is immersed into an iron ion solution to reinforce the hydrogel layer, so that the bionic low-friction polyether-ether-ketone artificial joint mortar cup is obtained. The surface of the polyether-ether-ketone joint mortar cup is provided with the soft hydrogel layer, so that the surface wettability and the friction coefficient of the polyether-ether-ketone joint mortar cup are obviously improved on the basis of keeping the body performance of polyether-ether-ketone or derivatives thereof, the friction coefficient and the abrasion loss are effectively reduced, the soft hydrogel layer on the surface can protect a base body, and the bionic design of a natural joint lubricating system is realized from the structural and functional aspects.

Description

Preparation method of bionic polyether-ether-ketone artificial joint mortar with soft-hard composite structure
Technical Field
The invention relates to the technical field of bionic materials, and relates to a preparation method of a bionic polyether-ether-ketone artificial joint mortar with a soft-hard composite structure.
Background
Polyetheretherketone (PEEK) is a nontoxic material with good chemical stability and biocompatibility, and is widely used in the field of artificial joint manufacturing at present. However, the PEEK surface is hydrophobic and chemically inert, and the pure PEEK material has a relatively high friction coefficient, which severely limits its clinical application.
Chinese patent application 201510797209.X uses plasma immersion ion implantation technology to perform zirconium ion implantation modification on a polyetheretherketone material, introduces a micro-nano structure on the surface of the material, and also introduces a bioactive component, namely zirconium oxide, so as to improve the mechanical properties, bioactivity and osteogenic properties of polyetheretherketone, and endow the material with a certain antibacterial property. However, this method does not improve the surface tribological properties of PEEK. In order to improve the tribological performance of the PEEK material, chinese patent 201510629322.7 uses a carbon fiber reinforced PEEK composite material as a carrier substrate to prepare a multi-scale carrier surface layer formed by compounding a nano-scale polymer brush layer with good wettability and biocompatibility and a micro-scale surface texture layer. Although this method reduces the friction coefficient of the artificial joint mortar to 0.099, the friction coefficient and wear resistance are still further improved.
In the natural joint lubrication system, a layer of soft cartilage with a spongy structure is bonded to hard subchondral bone through a calcified layer to form a layered structure with soft-hard composite. Wherein, the soft cartilage surface can play a lubricating role in absorbing and storing joint synovial fluid and reducing friction in motion; the hard subchondral bone is cancellous bone, can absorb stress, buffer shock and maintain the shape of a joint when stressed, and plays an important role in protecting cartilage.
Disclosure of Invention
The invention aims to provide a preparation method of a bionic polyether-ether-ketone artificial joint mortar with a soft-hard composite structure. The method simulates the structure and the function of the artificial joint mortar cup according to the composite structure of the articular cartilage and the subchondral bone, takes hard PEEK (or derivatives thereof) as a base material, constructs a soft hydrogel layer on the surface of the artificial joint mortar cup, realizes the construction of a soft-hard composite layered structure, obviously improves the tribological performance of the PEEK artificial joint and prolongs the service life of the PEEK artificial joint.
The technical scheme of the invention is as follows:
the preparation method of the bionic polyether-ether-ketone artificial joint mortar with the soft-hard composite structure comprises the following steps of:
step 1, constructing a porous structure in regular arrangement on the surface of polyetheretherketone or a derivative thereof by using a laser surface texturing technology;
step 2, dissolving acrylamide, acrylic acid, a crosslinking agent N, N '-methylene bisacrylamide and a photoinitiator alpha-ketoglutaric acid in water, and uniformly stirring to obtain a hydrogel prepolymerization solution, wherein the mass ratio of the acrylic acid to the acrylamide is 1: 3-1: 5, and the N, N' -methylene bisacrylamide is 0.1% -0.5% of the total mass of the acrylamide and the acrylic acid;
step 3, dripping a hydrogel prepolymerization solution on the surface of the polyether-ether-ketone or the derivative thereof obtained in the step 1, and placing the solution under an ultraviolet lamp for irradiation to obtain a hydrogel-polyether-ether-ketone composite material;
and 4, soaking the hydrogel-polyether-ether-ketone composite material into the iron ion solution to reinforce the hydrogel layer, so as to obtain the bionic polyether-ether-ketone artificial joint mortar with the soft and hard composite structure.
In the specific embodiment of the present invention, in step 1, the porous structure is a circular micro-pore array with a radius of 100 μm and a distance of 400 μm between the centers of two adjacent micro-pores.
In an embodiment of the present invention, in step 2, the concentration of acrylamide in the hydrogel pre-polymerization solution is 3 mol/L.
In a specific embodiment of the present invention, in step 2, the α -ketoglutaric acid is 0.1% of the sum of the amounts of acrylamide and acrylic acid species.
In a specific embodiment of the invention, in the step 3, the irradiation time under a 500w mercury lamp is 0.5-1 h.
Preferably, in step 4, the iron ion solution is an iron nitrate or iron chloride solution, and the concentration is 0.25 mol/L.
Preferably, in step 4, the soaking time is more than 24 hours.
Compared with the prior art, the invention has the following advantages:
(1) the surface of the polyether-ether-ketone joint mortar cup provided by the invention is provided with a layer of soft hydrogel layer, the surface soft polyacrylic acid-polyacrylamide-iron ion hydrogel layer can protect a substrate, and the polyether-ether-ketone joint mortar cup has a soft-hard composite layered structure, and realizes the bionic design of a natural joint lubricating system from the structural and functional aspects.
(2) Compared with pure polyether-ether-ketone (0.32), the friction coefficient of the bionic polyether-ether-ketone artificial joint mortar prepared by the invention is reduced by 91% to be as low as about 0.03 under the same friction test conditions. In addition, the hydrogel layer can play a role in storing and releasing the lubricant, and can effectively improve the tribological performance of the bearing interface of the artificial joint; and the hard PEEK substrate provides excellent bearing capacity, effectively protects the hydrogel layer and prolongs the service life of the bearing interface of the artificial joint.
(3) The method has the advantages of low cost, low requirement on equipment, simple, efficient and quick operation, no need of high-precision surface polishing treatment on the surface of the polyether-ether-ketone (or the derivative thereof), and suitability for industrial mass production.
Drawings
Fig. 1 is a schematic diagram of a preparation process of a bionic polyether-ether-ketone artificial joint mortar with a soft-hard composite structure.
Fig. 2 is a schematic diagram showing the comparison of the friction coefficients of pure PEEK and a bionic polyether ether ketone artificial joint mortar with a soft and hard composite structure under the load of 8N.
Fig. 3 is a surface grinding mark image of a bionic polyether-ether-ketone artificial joint mortar with a soft and hard composite structure and pure PEEK (a), (b) after being rubbed for 15min under a load of 8N, and (c) after being rubbed for 15min under a load of 8N, soaked in deionized water for 15 days, and then the bionic polyether-ether-ketone artificial joint mortar with the soft and hard composite structure is ground.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
In the following examples, the friction performance test conditions were as follows:
and testing and evaluating the friction performance of the bionic polyether-ether-ketone artificial joint mortar cup by adopting a UMT friction wear testing machine. The friction matching pair is a stainless steel ball (R is 60mm), the friction mode is a reciprocating sliding mode, the lubricating medium is deionized water, the applied load is 5N-8N, the sliding length is 2mm, the sliding speed is 2mm/s, and the friction test duration is 15 min. Compared with pure PEEK materials, the friction coefficient of the bionic polyether-ether-ketone artificial joint mortar with the soft and hard composite structure is reduced by 91%, the grinding mark is obviously shallow, and the bionic polyether-ether-ketone artificial joint mortar can be basically recovered after being soaked in deionized water for 15 days. The friction coefficient and the wear scar comparison of the bionic polyether-ether-ketone artificial joint mortar with the soft-hard composite structure and the pure PEEK material are respectively shown in fig. 2 and fig. 3.
Example 1
The artificial joint mortar cup of the polyether-ether-ketone (or the derivative thereof) is placed under a laser marking machine, and a porous structure (the porous structure is a circular micropore array with the radius of 100 mu m and the distance between the centers of two adjacent micropores of which is 400 mu m) is prepared on the surface of the mortar cup by using a laser drilling method. 2.1324g of acrylamide (3mol/L), 0.7206g of acrylic acid (the amount of the acrylic acid amide is 1:3), 0.0062g N, N' -methylene bisacrylamide (0.1 percent of the sum of the amounts of the acrylamide and the acrylic acid substances) and 0.0058g of alpha-ketoglutaric acid (0.1 percent of the sum of the amounts of the acrylamide and the acrylic acid substances) are added into 10ml of deionized water, and the mixture is stirred uniformly to obtain a hydrogel prepolymerization solution. 1ml of hydrogel prepolymerization solution is dripped on the surface of the polyetheretherketone, a glass slide is covered on the surface of the polyetheretherketone, and the polyetheretherketone is irradiated for 0.5h under an ultraviolet lamp (500w mercury lamp). Preparing 0.25mol/L ferric nitrate solution, immersing the obtained hydrogel-polyether-ether-ketone composite material into the ferric nitrate solution for 24 hours, reinforcing the hydrogel layer, immersing the hydrogel layer into deionized water for 3 days, and removing redundant iron ions to obtain the bionic low-friction polyether-ether-ketone artificial joint mortar cup. The coefficient of friction was found to be 0.07 under a load of 5N.
Example 2
The artificial joint mortar cup of the polyether-ether-ketone (or the derivative thereof) is placed under a laser marking machine, and a porous structure (the porous structure is a circular micropore array with the radius of 100 mu m and the distance between the centers of two adjacent micropores of which is 400 mu m) is prepared on the surface of the mortar cup by using a laser drilling method. 2.1324g of acrylamide (3mol/L), 0.5405g of acrylic acid (the amount of the acrylic acid to the acrylamide substance is 1:4), 0.0173g N, N' -methylenebisacrylamide (0.3% of the sum of the amounts of the acrylamide and the acrylic acid substances) and 0.0055g of alpha-ketoglutaric acid (0.1% of the sum of the amounts of the acrylamide and the acrylic acid substances) are added to 10ml of deionized water, and the mixture is stirred uniformly to obtain a hydrogel prepolymerization solution. 1ml of hydrogel prepolymerization solution is dripped on the surface of the polyetheretherketone, a glass slide is covered on the surface of the polyetheretherketone, and the polyetheretherketone is irradiated for 1h under an ultraviolet lamp (a 500w mercury lamp). Preparing 0.25mol/L ferric nitrate solution, immersing the obtained hydrogel-polyether-ether-ketone composite material into the ferric nitrate solution for 24 hours, reinforcing the hydrogel layer, immersing the hydrogel layer into deionized water for 3 days, and removing redundant iron ions to obtain the bionic low-friction polyether-ether-ketone artificial joint mortar cup. The coefficient of friction was measured to be 0.05 under a load of 8N.
Example 3
The artificial joint mortar cup of the polyether-ether-ketone (or the derivative thereof) is placed under a laser marking machine, and a porous structure (the porous structure is a circular micropore array with the radius of 100 mu m and the distance between the centers of two adjacent micropores of which is 400 mu m) is prepared on the surface of the mortar cup by using a laser drilling method. 2.1324g of acrylamide (3mol/L), 0.4324g of acrylic acid (the amount of the acrylic acid to the acrylamide substance is 1:5), 0.0278g N, N' -methylenebisacrylamide (0.5% of the sum of the amounts of the acrylamide and the acrylic acid substance), and 0.0053g of alpha-ketoglutaric acid (0.1% of the sum of the amounts of the acrylamide and the acrylic acid substance) were added to 10ml of deionized water, and stirred uniformly to obtain a hydrogel prepolymer solution. 1ml of hydrogel prepolymerization solution is dripped on the surface of the polyetheretherketone, a glass slide is covered on the surface of the polyetheretherketone, and the polyetheretherketone is irradiated for 0.5h under an ultraviolet lamp (500w mercury lamp). Preparing 0.25mol/L ferric nitrate solution, immersing the obtained hydrogel-polyether-ether-ketone composite material into the ferric nitrate solution for 24 hours, reinforcing the hydrogel layer, immersing the hydrogel layer into deionized water for 3 days, and removing redundant iron ions to obtain the bionic low-friction polyether-ether-ketone artificial joint mortar cup. The coefficient of friction was measured to be 0.03 under a load of 5N.
Comparative example 1
The artificial joint mortar cup of the polyether-ether-ketone (or the derivative thereof) is placed under a laser marking machine, and a porous structure (the porous structure is a circular micropore array with the radius of 100 mu m and the distance between the centers of two adjacent micropores of which is 400 mu m) is prepared on the surface of the mortar cup by using a laser drilling method. 2.1324g of acrylamide (3mol/L), 0.3603g of acrylic acid (the amount of the acrylic acid to the acrylamide substance is 1:6), 0.0027g N g of N' -methylenebisacrylamide (0.05% of the sum of the amounts of the acrylamide and the acrylic acid substance), and 0.0051g of alpha-ketoglutaric acid (0.1% of the sum of the amounts of the acrylamide and the acrylic acid substance) are added to 10ml of deionized water, and the mixture is stirred uniformly to obtain a hydrogel prepolymerization solution. 1ml of hydrogel prepolymerization solution is dripped on the surface of the polyetheretherketone, a glass slide is covered on the surface of the polyetheretherketone, and the polyetheretherketone is irradiated for 0.5h under an ultraviolet lamp (500w mercury lamp). Preparing 0.25mol/L ferric nitrate solution, immersing the obtained hydrogel-polyether-ether-ketone composite material into the ferric nitrate solution for 24 hours, reinforcing the hydrogel layer, immersing the hydrogel layer into deionized water for 3 days, and removing redundant iron ions to obtain the bionic low-friction polyether-ether-ketone artificial joint mortar cup. The coefficient of friction measured under a load of 2N was 0.15, and the surface gel layer was worn away after the friction, and the wear resistance was poor.
Comparative example 2
The artificial joint mortar cup of the polyether-ether-ketone (or the derivative thereof) is placed under a laser marking machine, and a porous structure (the porous structure is a circular micropore array with the radius of 100 mu m and the distance between the centers of two adjacent micropores of which is 400 mu m) is prepared on the surface of the mortar cup by using a laser drilling method. 2.1324g of acrylamide (3mol/L), 1.0809g of acrylic acid (the amount of the acrylic acid amide is 1:2), 0.0694g N, N' -methylene bisacrylamide (accounting for 1 percent of the sum of the amounts of the acrylamide and the acrylic acid substances) and 0.0066g of alpha-ketoglutaric acid (accounting for 0.1 percent of the sum of the amounts of the acrylamide and the acrylic acid substances) are added into 10ml of deionized water and stirred uniformly to obtain a hydrogel prepolymerization solution. 1ml of hydrogel prepolymerization solution is dripped on the surface of the polyetheretherketone, a glass slide is covered on the surface of the polyetheretherketone, and the polyetheretherketone is irradiated for 1h under an ultraviolet lamp (a 500w mercury lamp). Preparing 0.25mol/L ferric nitrate solution, immersing the obtained hydrogel-polyether-ether-ketone composite material into the ferric nitrate solution for 24 hours, reinforcing the hydrogel layer, immersing the hydrogel layer into deionized water for 3 days, and removing redundant iron ions to obtain the bionic low-friction polyether-ether-ketone artificial joint mortar cup. The coefficient of friction was measured to be 0.2 under a load of 10N.
Comparative example 3
The artificial joint mortar cup of the polyether-ether-ketone (or the derivative thereof) is placed under a laser marking machine, and a porous structure (the porous structure is a circular micropore array with the radius of 100 mu m and the distance between the centers of two adjacent micropores of which is 400 mu m) is prepared on the surface of the mortar cup by using a laser drilling method. 2.1324g of acrylamide (3mol/L), 1.0809g of acrylic acid (the amount of the acrylic acid amide is 1:2), 0.0347g N, N' -methylene bisacrylamide (accounting for 0.5 percent of the sum of the amounts of the acrylamide and the acrylic acid substances) and 0.0066g of alpha-ketoglutaric acid (accounting for 0.1 percent of the sum of the amounts of the acrylamide and the acrylic acid substances) are added into 10ml of deionized water and stirred uniformly to obtain a hydrogel prepolymerization solution. 1ml of hydrogel prepolymerization solution is dripped on the surface of the polyetheretherketone, a glass slide is covered on the surface of the polyetheretherketone, and the polyetheretherketone is irradiated for 1.5 hours under an ultraviolet lamp (a 500w mercury lamp). Preparing 0.25mol/L ferric nitrate solution, immersing the obtained hydrogel-polyether-ether-ketone composite material into the ferric nitrate solution for 24 hours, reinforcing the hydrogel layer, immersing the hydrogel layer into deionized water for 3 days, and removing redundant iron ions to obtain the bionic low-friction polyether-ether-ketone artificial joint mortar cup. The coefficient of friction was measured to be 0.17 under a load of 10N.

Claims (8)

1. The preparation method of the bionic polyether-ether-ketone artificial joint mortar with the soft-hard composite structure is characterized by comprising the following specific steps of:
step 1, constructing a porous structure in regular arrangement on the surface of polyetheretherketone by using a laser surface texturing technology;
step 2, dissolving acrylamide, acrylic acid, a crosslinking agent N, N '-methylene bisacrylamide and a photoinitiator alpha-ketoglutaric acid in water, and uniformly stirring to obtain a hydrogel prepolymerization solution, wherein the mass ratio of the acrylic acid to the acrylamide is 1: 3-1: 5, and the N, N' -methylene bisacrylamide is 0.1% -0.5% of the total mass of the acrylamide and the acrylic acid;
step 3, dripping a hydrogel prepolymerization solution on the surface of the polyether-ether-ketone obtained in the step 1, and placing the solution under an ultraviolet lamp for irradiation to obtain a hydrogel-polyether-ether-ketone composite material;
and 4, soaking the hydrogel-polyether-ether-ketone composite material into the iron ion solution to reinforce the hydrogel layer, so as to obtain the bionic polyether-ether-ketone artificial joint mortar with the soft and hard composite structure.
2. The method according to claim 1, wherein in step 1, the porous structure is a circular micropore array with a radius of 100 μm and a distance of 400 μm between the centers of two adjacent micropores.
3. The method according to claim 1, wherein the concentration of acrylamide in the hydrogel prepolymerization solution in the step 2 is 3 mol/L.
4. The method according to claim 1, wherein in step 2, the amount of α -ketoglutaric acid is 0.1% of the sum of the amounts of acrylamide and acrylic acid.
5. The preparation method according to claim 1, wherein in the step 3, the irradiation time is 0.5-1 h under a 500w mercury lamp.
6. The method according to claim 1, wherein in step 4, the ferric ion solution is ferric nitrate or ferric chloride solution.
7. The method according to claim 1, wherein the concentration of the iron ion solution in step 4 is 0.25 mol/L.
8. The method according to claim 1, wherein the immersion time in step 4 is 24 hours or more.
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