CN105233335B - Biologically active porous poly(aryl ether ketone) material of one kind and the preparation method and application thereof - Google Patents
Biologically active porous poly(aryl ether ketone) material of one kind and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of biologically active porous poly(aryl ether ketone)（PAEK）Material and the preparation method and application thereof belongs to field of biomedical materials.The present invention is by PAEK powder and calcium phosphate ceramic（CPC）The mixture that spheric granules pore-foaming agent wet method obtains after evenly mixing is filled into mold, pressure excludes extra PAEK powder while promoting the pore-foaming agent of hard to be bordering on close packed array, PAEK powder melt molding under heat is made by mold heating again, PAEK/CPC green bodies are obtained, porous PAEK materials are obtained after dilute hydrochloric acid impregnates removal pore-foaming agent CPC.It is impregnated in simulated body fluid after dense sulfuric acid treatment, obtains the bioactivity, porous PAEK materials with surface bone like apatite layer.This method is simple for process, reproducible, and gained is easy to adjust with macropore of the bioactive materials with complete three-dimensional perforation and abundant surface micropore, big pore size and porosity, while can prepare the bioactivity, porous material with graded pore structure.The bioactivity, porous PAEK materials can be used for the reparation of bone defect, be particularly suitable for the Invasive lumbar fusion device of backbone reparation.
Description
Technical field
The invention belongs to biomedical materials and implanted medical device field, and in particular to a kind of biologically active more
Hole poly(aryl ether ketone) material and the preparation method and application thereof.
Technical background
Poly(aryl ether ketone) (polyetherketon eketone, PAEK）Polymer is a kind of high temperature thermoplasticity polymer, by
Fragrant benzene radicals link keto group and ether group are combined according to different order and ratio forms its backbone structure.Wherein,
Representative PAEK Type of Collective object has PEEK and PEKK materials.In recent years, PAEK Type of Collective object is due to unique chemical geometry knot
Structure assigns its good chemoresistance, radioparency, thermal stability and bone is more nearly for metal material
Mechanical performance and be more and more used as biomaterial to be applied to orthopaedics, wound and backbone are implanted into Material Field.However it compares
Combining closely between titanium implant and bone, due to the chemistry and biologically inert of PAEK polymer, implant and bone
Between produce a large amount of fibr tissue, result in and show limited mechanically link between PAEK implants and bone tissue.
Researcher has done many related works to improve the bioactivity of PAEK materials, is broadly divided into：1）Physics changes
Property, such as plasma modification（Oxygen plasma, ammonia plasma treatment, nitrogen/oxygen plasma, methane/oxygen plasma, oxygen/argon etc.
Gas ions, ammonia/argon plasma, hydrogen/argon plasma etc.）, accelerate beam of neutral atoms and electronic laser beam modifying etc.；2）Chemistry
It is modified, surface-active and micropore PAEK materials are obtained as sulfonation handles modified PAEK material surfaces, by specific reaction and is passed through
Surface functional group converts to obtain the PAEK of surface phenolic hydroxy group and carboxyl, by wet-chemical selectivity in PAEK material surfaces
Carboxyl, carbonyl, amino, glutamy amido and surface covalent bond connected valleys amino acid are introduced, is also connected by extracellular matrix protein fibre
The absorption of protein modified PAEK and covalence graft bonding；3）It is coating modified, by some materials such as hydroxyapatite, titanium, titanium dioxide
The materials such as titanium and diamond-like are by various methods such as cold spraying, rf magnetron sputtering, rotary coating, aerosol deposition, plasma
Body deposits, and the injection of plasma immersion particle, electron beam deposition, vacuum plasma spray and physical vapour deposition (PVD) etc. deposit
On the surface of PAEK materials to promote its bioactivity；4）PAEK composite materials are used as perforating agent and PAEK by sodium chloride
Aftershaping is mixed, then removes sodium chloride and obtains porous PAEK timbering materials to promote the connection between PAEK implants and bone, or
Person is by some materials such as hydroxyapatite（HA）, calcium silicates, the materials such as bio-vitric and PAEK materials pass through injection molding, hot melt, pressure
The bioactivity etc. that system and the modes such as laser sintered prepare composite material to promote PAEK.
Invention content
Following deficiency exists in the prior art by the comprehensive analysis to the prior art in inventor：The PAEK/ of preparation
Its mechanical performance of HA composite materials has limitation in the application due to being combined into physical connection between two kinds of materials；And it adopts
With the PAEK after plasma modification, modified effect can be continuously decreased with the extension of time, and long-term effectiveness needs to obtain
Improve；The PAEK materials obtained using solvent etched only have surface to have lamellate three-dimensional micropore pore structure, implant and bone group
There is no closer connection between knitting；By the PAEK materials after grafting modification, the attaching of cell is dependent on modification
Effect, and the absorption stability of cell needs very big promotion；It is obtained as perforating agent and poly(aryl ether ketone) by using sodium chloride
Remove obtained porous PAEK holders after sodium chloride after composite material, bioactivity has to be hoisted, and only has big ruler
Very little intercommunicating pore.
And research at this stage, mostly all just in PEEK materials, relative to PEEK materials, PEKK has in performance
Have many similitudes with PEEK, but PEKK have more excellent mechanical performance and thermal stability and its in diketone base
Modification advantage with bigger on key.However, the research of the raising bioactivity for PEKK materials, does not have both at home and abroad now
Achievement in research is reported.
In view of the above-mentioned problems, the present invention provides a kind of biologically active porous poly(aryl ether ketone) material and its preparation sides
Method, using calcium phosphate ceramic（calcium phosphate ceramic, CPC）Powder prepares porous polyarylether as pore-foaming agent
Ketone material obtains comparatively ideal pore structure, has good bioactivity and mechanical performance.It provides a kind of by certain proportion
PAEK powder and calcium phosphate ceramic（calcium phosphate ceramic, CPC）Spheric granules pore-foaming agent wet method is uniform
The mixture obtained after mixing is filled into special mold, and pressure promotes the pore-foaming agent of hard to be arranged while close packed array
Make its melt molding except extra PAEK powder, then by mould heat pressure, obtain PAEK/CPC mixture green bodies, dilute hydrochloric acid impregnates
Porous PAEK materials are obtained after removal pore-foaming agent, then in simulated body fluid after dense sulfuric acid treatment（simulated body fluid,
SBF）It impregnates and generates surface osteoid apatite sedimentary, the method for obtaining biologically active porous PAEK materials.
The present invention is achieved through the following technical solutions：
A kind of biologically active porous poly(aryl ether ketone) body of material, including poly(aryl ether ketone) material skeleton and it is filled in institute
State the calcium phosphate ceramic powder pore-foaming agent in poly(aryl ether ketone) material skeleton.Using calcium phosphate ceramic powder as pore-foaming agent, it is easy
It includes macropore to remove pore-foaming agent by pickling and obtain（100 microns or more）And micropore（100 microns or less）Composite pore structural is causing
The position that hole agent occupied originally leaves macropore, and pickle can be formed simultaneously abundant table again with poly(aryl ether ketone) material skeleton function
Face micropore；In addition, since using the calcium phosphate ceramic powder for itself having bioactivity, as pore-foaming agent, remaining pore-foaming agent is not
It will not only adversely affect, can also impart to the certain bioactivity of the porous poly(aryl ether ketone) material of gained.
Alternately, the calcium phosphate ceramic powder is spheric granules, and the pore-foaming agent is in poly(aryl ether ketone) material bone
Close packed array in frame.The grain size of the calcium phosphate powder be 300-1200 micron, by adjusting calcium phosphate powder grain size and
Dosage can regulate and control the aperture of the porous poly(aryl ether ketone) material of gained and voidage.
Alternately, the perforating agent is the calcium phosphate ceramic spheric granules being sintered through 1200 DEG C or more, grain size
It is 300-1200 microns.
Alternately, the calcium phosphate ceramic is hydroxyapatite（hydroxyapatite, HA）, tricalcium phosphate
（tricalcium phosphate, TCP）, at least one of HA/TCP biphase ceramics, preferably hydroxyapatite.
Alternately, the poly(aryl ether ketone) PAEK materials are polyether ketone ketone（PEKK）, polyether-ether-ketone（PEEK）, polyethers
Ketone（PEK）, polyetherketoneetherketoneketone（PEKEKK）At least one of material.
Alternately, one kind during the PAEK materials are unformed or semicrystalline.It is preferred that half crystal form PAEK,
Material has more stable physics and chemical property in this way.
The present invention also provides a kind of biologically active porous poly(aryl ether ketone) material, contain in the poly(aryl ether ketone) material
There are porous structure, the porous structure to be made as pore-foaming agent using calcium phosphate ceramic powder, i.e., it is above-mentioned any one by removing
Calcium phosphate ceramic powder pore-foaming agent in kind green body is made.
Alternately, the porous poly(aryl ether ketone) material of the bioactivity has the macropore of three-dimensional perforation and abundant
Surface micropore.Further, big pore size and porosity are easy to adjust, ranging from 300-1200 microns of macropore diameter, porosity
Ranging from 30% ~ 90%.
Alternately, the porous poly(aryl ether ketone) material of the bioactivity has bottom densification, intermediate porosity layer rate
It incrementally increases, the graded pore structure of the connection of surface layer macropore and hole wall microporous connectivity.Multistage intercommunicating pore structure is more advantageous to cell, group
It knits and blood vessel is grown into.
Alternately, hydrophilic sulfo is also contained in the porous poly(aryl ether ketone) material of the bioactivity
Layer.The hydrophily for promoting material surface not only improves the deposition of hydroxyapatite layer and is also beneficial to the attaching, migration and life of cell
It is long.Hydrophilic sulfo group is introduced in material surface by chemical modification, greatly enhances the class bone phosphorus of material surface
Lime stone deposition capability, to be deposited by the hydrophily osteoid apatite after the porous structure combination chemical modification on physical layer
Surface has been obviously improved the bioactivity of PAEK materials.
Alternately, the porous poly(aryl ether ketone) material of the bioactivity also contains osteoid apatite sedimentary.On
The bioactivity of material can further be promoted by stating osteoid apatite sedimentary, convenient for synostosis occurs with implant site, may be used also
The self-bone grafting and osteoconductive energy for promoting material, promote the proliferation of osteocyte, the regeneration of differentiation and bone tissue.
The present invention also provides a kind of methods preparing above-mentioned porous poly(aryl ether ketone) body of material, with calcium phosphate ceramic ball
Shape powder is as pore-foaming agent, and the composite material that poly(aryl ether ketone) powder and perforating agent progress wet method are obtained after evenly mixing is through hot pressing
Molding.
Further, this method is by a certain proportion of PAEK powder and calcium phosphate ceramic（calcium phosphate
ceramic, CPC）The mixture that spheric granules pore-foaming agent wet method obtains after evenly mixing is filled into mold, and pressure promotes hard
The pore-foaming agent of matter to exclude extra PAEK powder while close packed array, then by mould heat pressure make PAEK powder melts at
Type obtains PAEK/CPC mixture green bodies.
Alternately, in the preparation method of above-mentioned green body, the perforating agent is the phosphorus being sintered through 1200 DEG C or more
Sour calcium ceramic spherical particle, grain size are 300 μm or more.Further, grain size is 300-1200 microns.
Alternately, in the preparation method of above-mentioned green body, include the following steps：
1) perforating agent is added into poly(aryl ether ketone) powder, is mixed well after adding appropriate solvent, obtain composite material；
2) by above-mentioned steps 1）Described in composite material spread in mold, heating mould is to 335-400 DEG C；
3) by above-mentioned steps 2）In mold be put on press, apply pressure, heat-insulation pressure keeping 1 hour is demoulded after cooling and taken
Go out composite body sample.
Alternately, above-mentioned steps 1）Described in solvent be ethyl alcohol or isopropanol.
Alternately, above-mentioned steps 1）Described in the weight of CPC spheric granules be 0-6 times of PAEK.
Alternately, above method step 3）In pressing pressure be 20-100MPaMPa.
Alternately, in the preparation method of above-mentioned green body, include the following steps：
1) it is separately added into the perforating agent of different proportion and/or different-grain diameter in PAEK powder, is filled after appropriate solvent is added
Divide mixing, obtains a series of composite materials of different drilling agent contents and/or different perforating agent grain sizes；
2) by above-mentioned steps 1）Described in composite material it is single or combination spread in mold, heating mould is extremely
335-400℃；
3）By above-mentioned steps 2）In mold be put on press, apply pressure 20-100MPaMPa, heat-insulation pressure keeping 1 hour,
Composite body sample is taken out in demoulding after cooling.
Alternately, above method step 1）Described in pore-foaming agent quality be 0-6 times of PAEK powder qualities.
Alternately, above method step 2）In, by step 1）Described in composite material according to drilling agent content
Have from low to high or according to perforating agent grain size small to spreading in mold successively greatly.
Alternately, above method step 2）In the group of composite material be divided into arbitrary parts by weight of composition, passing through
Later after phase removal perforating agent, material can have gradient level physically, i.e. bottom is compacted zone, and upper layer is gradually
Connected porous gradient porous structure.
The present invention also provides a kind of methods preparing above-mentioned porous poly(aryl ether ketone) material, including use any one of the above
Method prepares porous poly(aryl ether ketone) body of material, then green body is impregnated through pickling and removes perforating agent.
Alternately, the pickling solvent used through pickling soaking step is one kind in hydrochloric acid or sulfuric acid,
It is preferential to select hydrochloric acid.
Alternately, described to be specially through pickling soaking step：Sample is put into cleaning solvent and is impregnated 1-5 hours
CPC spheric granules is removed afterwards, is put into after fully being cleaned using deionized water in 37-60 DEG C of baking oven 3-7 hours dry.Further
, during above-mentioned immersion removes CPC spheric granules, it can also be assisted by stirring or ultrasound.
Alternately, it in the above-mentioned method for preparing above-mentioned porous poly(aryl ether ketone) material, is impregnated in pickling and removes drilling
Further include that substrate chemical modification processing is carried out to the porous sample of gained after agent.Further, the chemical modification processing is logical
Persulfuric acid carries out chemical modification sulfuric acid concentration and preferentially selects 50-98wt%.On the one hand material enables to after sulfuric acid modified
Material surface has three-dimensional communication microcellular structure, on the other hand can introduce hydrophilic sulfo group in material surface, to
The osteoid apatite deposition being more advantageous to above material.
Alternately, the sulfuric acid modified step is specially：Sample is immersed in sulfuric acid solution 1-24 hours, is located
It is fully cleaned using deionized water after having managed, places into 37-60 DEG C of oven drying 3-7 hours.
Alternately, further include in porous polyarylether in the above-mentioned method for preparing above-mentioned porous poly(aryl ether ketone) material
Ketone material surface deposits bone like apatite layer.
Alternately, the deposition bone like apatite layer step is specially：Porous material sample is put into analogue body
Liquid（SBF）It is taken out after the deposition osteoid apatite of middle immersion 1-7 days, is slightly rinsed using deionized water and be put into 37-60 DEG C of baking oven and do
3-7 hours dry, obtaining deposition has the porous PAEK materials of deposition bone like apatite layer.
Alternately, the above-mentioned method for preparing above-mentioned porous poly(aryl ether ketone) material specifically includes following steps：
1）It is separately added into the perforating agent of different proportion and/or different-grain diameter in PAEK powder, appropriate mixed solvent is added
After mix well, obtain the composite material of different drilling agent contents；
2）By above-mentioned steps 1）Described in composite material according to drilling agent content from low to high or according to perforating agent grain size
Have it is small to it is single successively greatly or combination spread in mold, heating mould is to 335-400 DEG C；
3）By above-mentioned steps 2）In mold be put on press, apply pressure 20-100MPaMPa, heat-insulation pressure keeping 1 hour,
Composite body sample is taken out in demoulding after cooling；
4）To step 3）The composite body sample of gained carries out perforating agent removing, and sample is put into cleaning solvent and is stirred
It mixes or ultrasound removes CPC microballoons after 1-5 hour, it is small that dry 3-7 is put into 37-60 DEG C of baking oven after fully being cleaned using deionized water
When, the cleaning solvent of the removing perforating agent is hydrochloric acid or sulfuric acid；
5）By above-mentioned steps 4）The sample of middle gained carries out substrate modification, and sample is immersed in 1-24 in sulfuric acid solution
Hour, handle and fully cleaned using deionized water afterwards, has placed into 37-60 DEG C of oven drying 3-7 hours, the sulfuric acid solution
A concentration of 50-98wt%；
6）By above-mentioned steps 5）The sample of gained is put into simulated body fluid（simulated body fluid, SBF）Middle immersion
It is taken out after 1-7 days deposition osteoid apatites, is slightly rinsed using deionized water and be put into 37-60 DEG C of oven drying 3-7 hours, acquisition
Biologically active porous PAEK materials.
Alternately, the simulated body fluid in the above-mentioned methods（SBF）Group is divided into：Na+(140-150mM), K+(4-
6mM), Mg2+(1-3mM), Ca2+(2-4mM), Cl-(140-150mM), HCO3 -(3-10mM), HPO4 -(0.5-1.0mM),
SO4 2-(0.5-1.0mM), pH(7.0-7.5)。
The present invention also provides a kind of application of above-mentioned biologically active porous PAEK materials, use it for making bone
The reparation of defect or for making Invasive lumbar fusion device material.The wherein described material with gradient porous structure is particularly suitable for making
Make the Invasive lumbar fusion device material with functionally gradient.As optional, the Invasive lumbar fusion device is gradient-structure poly(aryl ether ketone) material
Composition, upper and lower surface are porous, and middle layer is densification.Further, the poly(aryl ether ketone) Invasive lumbar fusion device has good
Bioactivity.
The present invention also provides a kind of molds being used to prepare biologically active porous PAEK body of material, including packet
The pedestal containing stepped hole is included, the interior annular coordinated successively with the stepped hole from inside to outside（Form inner cavity）, middle annulus, outer toroid
（Form exocoel）, cover board is arranged in the interior annular top（For extra slurry to be excluded mold）, the outer toroid top
Higher than the exocoel that the top of middle annulus, outer toroid is formed, the outer top of chamber is provided with pressure head.The further cover board with it is interior
Annulus tip clearance coordinates, and the pressure head and the tip clearance of the outer toroid coordinate.
As optional, the interior annular is split type split structure（Convenient for stripping operation）, preferably by three pieces of arc shaped tiles
The circular ring structure pieced together.
As optional, spout hole is provided on the cover board.
In use, the mixture paste that PAEK powder and CPC spheric granules pore-foaming agent wet methods obtain after evenly mixing is filled
Skeleton pattern intracavitary is inserted, cover board is placed into, pressure excludes while promoting the HA spheric granules of hard to be bordering on close packed array
Extra PAEK powder, then PAEK powder melt molding under heat is made by mold heating, obtain porous PAEK body of material.
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
Beneficial effects of the present invention：
The present invention mixed as perforating agent with PAEK powder using CPC spheric granules, hot pressing, and perforating agent is removed by solvent
Porous PAEK samples are obtained, then introduce hydrophilic sulfo group after being handled by chemical modification to promote the bone-like apatite of material
Stone deposition capability is prepared to pass through deposition osteoid apatite after three-dimensional porous structure combination chemical modification physically
Biologically active porous PAEK materials overcome limited combination in existing method between PAEK materials and bone tissue etc. and lack
It falls into.
The preparation method simple production process, reproducible, the bioactivity, porous PAEK materials prepared have three-dimensional
The macropore of perforation and abundant surface micropore, big pore size and porosity are easy to adjust, and can prepare living with biology
Property gradient porous PAEK materials, i.e. bottom is fine and close, and intermediate porosity layer rate is placed in the middle, and surface layer porosity is high and macropore is connected to, hole wall
The gradient porous structure of microporous connectivity.Contain the undissolved CPC ingredients in part in the interior surface of material hole so that material has excellent
It remains certain mechanical strength while good biocompatibility, and is introduced in material surface by chemical modification hydrophilic
The sulfo group of property so that osteoid apatite is preferably deposited while material becomes surface hydrophilic, to pass through physical layer
On structure gradient porous combination chemical modification after deposition osteoid apatite be obviously improved the bioactivity of material.It utilizes
Bioactivity, porous PAEK materials prepared by the present invention can be used for the reparation of bone defect, can especially prepare bottom densification, surface layer
Three-dimensional connected porous functionally gradient Invasive lumbar fusion device material is applied to backbone reparation.
Description of the drawings：
Shown in Fig. 1：For a kind of structural schematic diagram of porous poly(aryl ether ketone) body of material of the present invention；
Shown in Fig. 2：The mold definition graph of biologically active porous PAEK materials is prepared for the present invention；
Shown in Fig. 3：The process flow diagram of biologically active porous PAEK materials is prepared for the present invention；
Shown in Fig. 4：It is porous after perforating agent to be removed according to the PEKK/HA composite material bad bodies of the invention prepared and hydrochloric acid
PEKK-P surface topography map scanning electron microscope（SEM）Figure；
Shown in Fig. 5：Cross-section morphology scanning electron microscope for the porous PEKK-P materials prepared according to the present invention（SEM）Figure；
Shown in Fig. 6：For the porous PEKK-P prepared according to the present invention（a）, sulfonated porous PEKK-SP（b）And bone-like apatite
The post-depositional sulfonated porous PEKK-BSP of stone（c）Surface topography scanning electron microscope（SEM）Figure；
Shown in Fig. 7：The surface after SBF is impregnated for the porous PEKK-P prepared according to the present invention and sulfonated porous PEKK-SP
Topography scan Electronic Speculum（SEM）Figure
Shown in Fig. 8：Porous PEKK-P, sulfonated porous PEKK-SP and osteoid apatite to be prepared according to the present invention are deposited
The infrared spectrum of sulfonated porous PEKK-BSP material surfaces afterwards（IR）Figure；
Shown in Fig. 9：Porous PEKK-P, sulfonated porous PEKK-SP and osteoid apatite to be prepared according to the present invention are deposited
The osteoid apatite deposition characterization X-ray diffraction of sulfonated porous PEKK-BSP material surfaces afterwards（XRD）Figure；
Shown in Figure 10：Porous PEKK-P, sulfonated porous PEKK-SP and osteoid apatite to be prepared according to the present invention are deposited
The contact angle result figure of sulfonated porous PEKK-BSP material surfaces afterwards；
Shown in Figure 11：Porous PEKK-P, sulfonated porous PEKK-SP and osteoid apatite to be prepared according to the present invention are deposited
The uniaxial compression Mechanical test results figure of sulfonated porous PEKK-BSP material surfaces afterwards.
Description of the drawings：10 be CPC spheric granules pore-foaming agents, and 20 be PAEK skeletons, and 1 is pressure head, and 2 be cover board, and 3 be inner circle
Ring is middle annulus, and 5 be outer toroid, and 6 be pedestal.
Specific implementation mode：
The present invention preparation process flow be（As shown in Fig. 3）：By a certain proportion of PAEK powder and CPC spheric granules
The mixture that pore-foaming agent wet method obtains after evenly mixing is filled into special mold, and pressure promotes the pore-foaming agent of hard with Mi Dui
Extra PAEK powder is excluded while product arrangement, then its melt molding is made by mould heat pressure, obtains PAEK/CPC mixtures
Green body, dilute hydrochloric acid obtain porous PAEK materials after impregnating removal pore-foaming agent, then impregnate and give birth in simulated body fluid after dense sulfuric acid treatment
At surface osteoid apatite sedimentary, the method for obtaining biologically active porous PAEK materials.
Used a kind of mold as described in Figure 2 in following embodiment, included the pedestal 6 containing stepped hole, from inside to outside according to
The secondary interior annular with stepped hole cooperation（Form inner cavity）3, middle annulus, outer toroid 5（Form exocoel）, the interior annular top
Cover board 2 is set（For extra slurry to be excluded mold）, the outer toroid top is higher than middle annulus, the top shape of outer toroid
At exocoel, the outer top of chamber is provided with pressure head 1, and the pressure head and the tip clearance of the outer toroid coordinate, the inner circle
Ring is split type split structure（Convenient for stripping operation）, the circular ring structure preferably pieced together by three pieces of arc shaped tiles, the cover board
On be provided with spout hole.For above-mentioned mold design, multiple heating mode can be used, such as：Heating mantle heats, hot press and radiation
Heating etc..
Several most preferred embodiments set forth below for the present invention, these embodiments are used only as being described further the present invention
And illustration, but it is never limited in protection scope of the present invention.
Embodiment 1
The specific preparation process of porous PEKK materials is as follows in the present embodiment：
1）Weigh 0.20gPEKK powder（Powder diameter is 50 mesh）It is put into mold after being mixed with ethanol in proper amount, applies pressure
Power 42Mpa compactings；
2）Weigh again 0.08gPEKK powder and 0.40gHA spheric granules be added after mixing ethanol in proper amount carry out again it is wet
Method mixes；
3）Again by step 2）In be uniformly mixed material be added mold in so that it is spread in step 1）On the material of middle compacting
Side, is heated to 380 DEG C；
4）Pressure is applied to mold again（40MPa）While carry out heat-insulation pressure keeping 1 hour, after natural cooling demoulding take out examination
Sample obtains mixing material green body；
5）It will（4）In obtained green body sample be put into hydrochloric acid to stir 3 hours and remove HA spheric granules, obtain porous
PEKK is put into deionized water and is cleaned by ultrasonic 15min, 3 hours dry after repeated washing 4 times, obtains porous PEKK samples, is denoted as
Sample 1.
To gained sample（It is denoted as porous PEKK-P）Surface topography observation is carried out, using scanning electron microscope（SEM）It is disconnected to material
Face pattern, porous structure are observed, and as a result as shown in Figure 4 and Figure 5, material has bottom densification, the big gradient pores of surface layer unicom
Porous structure.
Embodiment 2
Contrast experiment before and after chemical modification
The porous PEKK-P of chemical modification in the present embodiment（Sulfonated porous PEKK-SP）The specific preparation process of material is as follows：
The porous PEKK-P samples prepared in embodiment 1 are put into the sulfuric acid of a concentration of 60wt% and are modified processing 1 hour, processing
It is put into deionized water after complete and is ultrasonically treated 15min, obtained sulfonated porous PEKK-SP within dry 5 hours after repeated washing 4 times, remember
For sample 2.
Using scanning electron microscope（SEM）And infrared spectrum（IR）To sulfonated porous PEKK（Fig. 6 b）Sample and porous PEKK（Figure
6a）Sample carries out surface topography and physico-chemical property comparison characterization, as shown in Figure 6 and Figure 8, after chemical modification, one side energy
Enough so that material surface has three-dimensional communication microcellular structure, on the other hand hydrophilic sulfo group base can be introduced in material surface
Group.
Embodiment 3
The front and back contrast test of osteoid apatite deposition
The specific preparation process of bioactivity, porous PEKK-P materials is as follows in the present embodiment：By sulfonated porous PEKK-SP
Impregnate simulated body fluid（SBF）Deposit osteoid apatite, after 7 days taking-up slightly cleaned with deionized water, clean after dry 3 hours
Bioactivity, porous PEKK-BSP materials are obtained, sample 3 is denoted as.As a comparison, the not sulfonated processing prepared in Example 1
Porous PEKK carry out deposition osteoid apatite operation under the same conditions, products therefrom is denoted as sample 4.
In the present embodiment, the simulated body fluid（SBF）It can be commercially available simulated body fluid, it can also be by following components voluntarily
Configuration：Na+(140-150mM), K+(4-6mM), Mg2+(1-3mM), Ca2+(2-4mM), Cl-(140-150mM), HCO3 -
(3-10mM), HPO4 -(0.5-1.0mM), SO4 2-(0.5-1.0mM), pH(7.0-7.5)。
Using scanning electron microscope（SEM）And X-ray diffraction（XRD）It lives to porous PEKK-P, sulfonated porous PEKK-SP and biology
Property porous PEKK-BSP samples carry out morphology observation and characterization, as shown in Fig. 6, Fig. 7, Fig. 8 and Fig. 9, found not after impregnating SBF
The surfaces PEKK-P of sulfonated processing（Fig. 7）There is no the deposition of osteoid apatite, and the processed sample PEKK-SP's of sulfonation
Surface is found that apparent sedimentary occurs, and shows that the bioactivity of material has obtained greatly carrying after being handled by sulfonation
It rises.
Hydrophilic and hydrophobic characterization is carried out to porous PEKK, PEKK-S and PEKK-BS using contact angle tester, as a result such as Figure 10
Shown, the contact angle of the sample after sulfonation has significant decrease relative to the PEKK samples for processing, and in deposition class bone
After apatite, the contact angle reduction of PEKK-BS becomes apparent.Show after sulfonation modifying the hydrophily of material obtain
It is obviously improved, and deposits the amplitude bigger improved after osteoid apatite, therefore have in terms of cell attachment, proliferation and differentiation
Greater advantages.
Using Material Testing Machine to porous PEKK-P, sulfonated porous PEKK-SP and osteoid apatite deposited porous PEKK-
BSP carries out uniaxial compression test, and test result is as shown in figure 11, and the compressive strength of material has reached 20-40MPa, wherein PEKK-
For SP due to the appearance of micropore, the intensity of material has a part reduction, and PEKK-BSP is due to there is the appearance of osteoid apatite sedimentary,
So intensity is all improved relative to PEKK-P and PEKK-SP.
Embodiment 4
The specific preparation process of bioactivity, porous PEKK materials is as follows in the present embodiment：
1）It weighs 0.10gPEKK powder and 0.45gHA spheric granules is added ethanol in proper amount and carries out wet method again after mixing
Mixing；
2）It weighs 0.12gPEKK powder and 0.50gHA spheric granules is added ethanol in proper amount and carries out wet method again after mixing
Mixing,
3）By step 1）With step 2）In material be sequentially placed into punching block, be heated to 380 °C；
4）Pressure is applied to punching block（45MPa）While carry out heat-insulation pressure keeping 1 hour, after natural cooling demoulding take out examination
Sample；
5）By above-mentioned steps 4）In obtained sample be put into hydrochloric acid to stir 3 hours and remove HA spheric granules, obtain porous
PEKK-P, sample, which is put into deionized water, is cleaned by ultrasonic 15min, 4 hours dry after repeated washing 5 times；
6）Porous PEKK-P samples are put into the sulfuric acid of a concentration of 70wt% and are modified processing 1 hour, are put after having handled
Enter and be ultrasonically treated 15min in deionized water, obtains sulfonation PEKK-SP within dry 5 hours after repeated washing 5 times；
7）Sulfonation PEKK-SP is impregnated into simulated body fluid（SBF）Osteoid apatite is deposited, taking-up deionized water is light after 7 days
Micro- cleaning obtains the bioactivity, porous PEKK-BSP materials that porosity is 73% in dry 3 hours after having cleaned, is denoted as sample 5,
With the different structure of two layer porosities.
Embodiment 5
The specific preparation process of bioactivity, porous PEEK materials is as follows in the present embodiment：
1）Weigh 0.18gPEEK powder（Powder diameter is 55 mesh）It is put into mold after being mixed with ethanol in proper amount, applies pressure
Power 47Mpa compactings；
2）It weighs 0.12gPEEK powder and 0.55gHA spheric granules is added ethyl alcohol and carries out wet-mixing again after mixing；
3）It weighs 0.10gPEEK powder and 0.60gHA spheric granules is added ethyl alcohol and carries out wet-mixing again after mixing；
4）By step 2）With step 3）Material is put into the punching block of autonomous Design, is heated to 350 °C；
5）Pressure is applied to punching block（60MPa）While carry out heat-insulation pressure keeping 1 hour, after natural cooling demoulding take out examination
Sample；
6）By 5）In obtained sample be put into hydrochloric acid to stir 5 hours and remove HA spheric granules, obtain porous PEEK-P, put
Enter and is cleaned by ultrasonic 15min in deionized water, it is 4 hours dry after repeated washing 4 times；
7）Porous PEEK-P samples are put into the sulfuric acid of a concentration of 75wt% and are modified processing 2 hours, are put after having handled
Enter and be ultrasonically treated 15min in deionized water, obtains sulfonation PEEK-SP within dry 5 hours after repeated washing 6 times；
8）Sulfonation PEEK-SP is impregnated into simulated body fluid（SBF）Osteoid apatite is deposited, taking-up deionized water is light after 7 days
Micro- cleaning obtains the bioactivity, porous PEEK-BSP materials that porosity is 76% in dry 5 hours after having cleaned, is denoted as sample 6,
With bottom densification, intermediate porosity layer rate incrementally increases, the graded pore structure of the connection of surface layer macropore and hole wall microporous connectivity.
Embodiment 6
The specific preparation process of bioactivity, porous PEKK materials is as follows in the present embodiment：
1）It weighs 0.15gPEKK powder to be uniformly mixed with 0.60gCPC spheric granules, ethanol in proper amount is added after mixing
Wet-mixing is carried out again；
2）Uniformly mixed material is put into the punching block of autonomous Design, is heated to 385 °C；
3）Pressure is applied to punching block（100MPa）While carry out heat-insulation pressure keeping 1 hour, after natural cooling demoulding take out examination
Sample；
4）It will（3）In obtained sample be put into hydrochloric acid to stir 3 hours and remove CPC spheric granules, obtain porous PEKK-P,
It is put into deionized water and is cleaned by ultrasonic 15min, it is 4 hours dry after repeated washing 5 times；
5）Porous PEKK-P samples are put into the sulfuric acid of a concentration of 80wt% and are modified processing 1 hour, are put after having handled
Enter and be ultrasonically treated 15min in deionized water, obtains sulfonation PEKK-SP within dry 5 hours after repeated washing 6 times；
6）Sulfonation PEKK-SP is impregnated into simulated body fluid（SBF）Osteoid apatite is deposited, taking-up deionized water is light after 7 days
Micro- cleaning obtains the bioactivity, porous PEKK-BSP materials that porosity is 80% in dry 6 hours after having cleaned, is denoted as sample 7,
With uniform porous structure.
7 biological assessment of embodiment
Separately sampled product 1 ~ 7 and newborn rabbit mescenchymal stem cell（MSCs）Cell co-cultures, and carries out biological assessment, takes commercially available
The porous PAEK materials prepared using sodium chloride as pore-foaming agent as a contrast, be denoted as sample 0.
(1) it passes on 2 times after extracting MSCs in newborn rabbit bone marrow, after the cell fusion, is counted after being digested with pancreatin, used
It is 1 × 10 that α MEM cell culture mediums (GIBCO companies) containing 10% too cow's serum, which are diluted to cell concentration,5 Cell/ml's
Cell suspension.
(2) each sample is taken respectively（Each sample takes 5 Duplicate Samples）, sterilize and be placed in 24 orifice plates, 1ml is added per hole
Prepared cell suspension in step (1), in 37 DEG C, 5v%CO after bat is even2Under the conditions of co-culture 72 hours.
Using the cell proliferative conditions in mtt assay detection scanning electron microscopic observation evaluation each sample, the results showed that, sample 1 ~ 7
All there is good biocompatibility, cell can be attached in the porous structure of material, migrate and grow and can enter hole
Inside gap structure.Although and sample 0 does not show apparent cytotoxicity in control group, its proliferation rate and microscope same field of view
Under cell quantity be substantially lower than sample 1 ~ 7, and the attaching situation of cell is also poor, additionally, due to the connectivity of its pore structure
Difference hinders migration of the cell in material surface.Sample 1 is compared with sample 2, and cell is in 2 surface spreading get Geng Kai of sample, carefully
Cell quantity under born of the same parents' proliferation rate and same field of view illustrates that sulfonation processing increases the hydrophily of material surface also all due to sample 1,
The attaching for being conducive to cell is sprawled and is proliferated.Cell adherence and proliferative conditions are due to sample 2 compared with sample 2 for sample 3, and sample
Product 3 can also induce MC3T3-E1 cells to break up to osteoblast direction.The basic phase of cell proliferative conditions of sample 4 and sample 2
When, but cell sprawls situation sample 2 is not slightly poor.The various aspects testing result and sample 3 of sample 5 ~ 7 are almost the same.
Embodiment 8
Polyether-ether-ketone is respectively adopted（PEEK）Or polyetherketoneetherketoneketone（PEKEKK）Instead of the PEKK in above-described embodiment, together
Sample is successfully prepared corresponding porous PAEK materials, and pore structure and the pore structure of resulting materials in above-mentioned corresponding embodiment are basic
It is identical.Biological assessment structure is also almost the same with the structure in embodiment 7.
The foregoing is merely the preferred embodiment of the present invention, are merely illustrative for the purpose of the present invention, and not restrictive；
Those of ordinary skill in the art understand that can carry out many to it in the spirit and scope defined by the claims in the present invention changes
Become, modification or even equivalent change, but falls within protection scope of the present invention.
Claims (10)
1. a kind of biologically active porous poly(aryl ether ketone) body of material, which is characterized in that including poly(aryl ether ketone) material skeleton
It is gone by pickling in the green body with the calcium phosphate ceramic powder pore-foaming agent being filled in the poly(aryl ether ketone) material skeleton
Except pore-foaming agent can obtain the composite pore structural comprising macropore and micropore, leaves aperture in the position that pore-foaming agent occupied originally and exist
100 microns or more of macropore, pickle can be formed simultaneously abundant surface micropore, institute again with poly(aryl ether ketone) material skeleton function
Micropore size is stated at 100 microns hereinafter, the calcium phosphate ceramic powder pore-foaming agent is with close packed array, the poly(aryl ether ketone) material
In the gap that the close packed array structure is formed.
2. a kind of biologically active porous poly(aryl ether ketone) material, which is characterized in that containing more in the poly(aryl ether ketone) material
Pore structure, the porous structure is made using calcium phosphate ceramic powder as pore-foaming agent, i.e., by removing poly(aryl ether ketone) material blank
Calcium phosphate ceramic powder pore-foaming agent in body is made, and the poly(aryl ether ketone) body of material includes poly(aryl ether ketone) material skeleton and filling
Calcium phosphate ceramic powder pore-foaming agent in the poly(aryl ether ketone) material skeleton, removing pore-foaming agent by pickling can be included
The composite pore structural of macropore and micropore leaves aperture in 100 microns or more of macropore, pickling in the position that pore-foaming agent occupied originally
Liquid and poly(aryl ether ketone) material skeleton function can be formed simultaneously abundant surface micropore again, the micropore size 100 microns with
Under.
3. porous poly(aryl ether ketone) material according to claim 2, which is characterized in that the porous polyarylether of the bioactivity
Ketone material has bottom fine and close, and intermediate porosity layer rate incrementally increases, the gradient pore knot of the connection of surface layer macropore and hole wall microporous connectivity
Structure.
4. porous poly(aryl ether ketone) material according to claim 2, which is characterized in that the porous polyarylether of the bioactivity
Also contain hydrophilic sulfo layer in ketone material.
5. porous poly(aryl ether ketone) material according to claim 2, which is characterized in that the porous polyarylether of the bioactivity
Ketone material also contains osteoid apatite sedimentary.
6. a kind of preparation method of porous poly(aryl ether ketone) body of material as described in claim 1, which is characterized in that with calcium phosphate
Ceramic spherical powder carries out the composite material that wet method obtains after evenly mixing as pore-foaming agent, by poly(aryl ether ketone) powder and pore-foaming agent
Through hot press molding.
7. body preparation method according to claim 6, which is characterized in that include the following steps：
1）It is separately added into the pore-foaming agent of different proportion and/or different-grain diameter in PAEK powder, is added after appropriate solvent fully mixed
It is even, obtain a series of composite materials of different pore agent contents and/or different pore-foaming agent grain sizes；
2）By above-mentioned steps 1）Described in composite material it is single or combination spread in mold, heating mould to 335-400
℃；
3）By above-mentioned steps 2）In mold be put on press, apply pressure 20-100MPa, heat-insulation pressure keeping 1 hour takes off after cooling
Mould takes out composite body sample.
8. a kind of preparation method of porous poly(aryl ether ketone) material as claimed in claim 2, which is characterized in that with calcium phosphate ceramic
Spherical powder is as pore-foaming agent, and the composite material that poly(aryl ether ketone) powder and pore-foaming agent progress wet method are obtained after evenly mixing is through warm
Molded acquisition green body, then green body is impregnated through pickling and removes pore-foaming agent.
9. preparation method according to claim 8, which is characterized in that include the following steps：
1）The pore-foaming agent of different proportion and/or different-grain diameter is separately added into PAEK powder, the pore-foaming agent quality is PAEK
0-6 times of powder quality mixes well after appropriate solvent is added, and obtains different pore agent contents and/or different pore-foaming agent grain sizes
A series of composite materials；
2）By above-mentioned steps 1）Described in composite material according to pore agent content from low to high or according to pore-foaming agent grain size by small
To spreading in mold successively greatly, heating mould is to 335-400 DEG C；
3）By above-mentioned steps 2）In mold be put on press, apply pressure 40-50MPa, heat-insulation pressure keeping 1 hour takes off after cooling
Mould takes out composite body sample；
4）To step 3）The composite body sample of gained carries out pore-foaming agent removing, and sample is put into cleaning solvent and impregnates 1-
CPC microballoons are removed after 5 hours, and drying 3-7 hours in 37-60 DEG C of baking oven are put into after fully being cleaned using deionized water, it is described
The cleaning solvent for removing pore-foaming agent is hydrochloric acid or sulfuric acid；
5）By above-mentioned steps 4）The sample of middle gained carries out substrate modification, and it is small that sample is immersed in 1-24 in sulfuric acid solution
When, it is fully cleaned using deionized water after having handled, places into 37-60 DEG C of oven drying 3-7 hours, the sulfuric acid solution is dense
Degree is 50-98wt%；
6）By above-mentioned steps 5）The sample of gained is put into simulated body fluid to impregnate 1-7 days and be taken out after deposition osteoid apatite, uses
Deionized water slightly rinses and is put into 37-60 DEG C of oven drying 3-7 hour, the biologically active porous poly(aryl ether ketone) material of acquisition
Material.
10. a kind of application of biologically active porous poly(aryl ether ketone) material according to claim 2, feature exist
In, use it for make bone defect reparation or for making Invasive lumbar fusion device material.
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| CN113754918B (en) * | 2021-09-29 | 2022-11-08 | 复旦大学 | Surface-modified polyether-ether-ketone material and preparation method and application thereof |
| CN113817215B (en) * | 2021-09-29 | 2023-01-17 | 复旦大学 | Artificial bone material without loss of elastic modulus and preparation method and application thereof |
| CN114773854B (en) * | 2022-05-10 | 2023-04-25 | 沈阳航空航天大学 | Porous silicon rubber with uniform pore diameter and preparation method thereof |
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