CN106957405B - A kind of preparation method and products thereof of ceramic toughening polymer HA-PDLLA-PUU - Google Patents
A kind of preparation method and products thereof of ceramic toughening polymer HA-PDLLA-PUU Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5048—Phosphates
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/83—Macromolecular compounds
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6922—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from hydroxy carboxylic acids
Abstract
The present invention relates to the preparation methods and products thereof of ceramic toughening polymer HA-PDLLA-PUU a kind of, specific preparation step is first to cause lactide ring-opening polymerisation by hydroxyapatite (HA) to form HA- polylactic acid macromolecular alcohol (HA-PDLLA), then aliphatic diisocyanate and chain extender is added and obtains ceramic toughening polymer HA-PDLLA-PUU through two-step method chain extension, the bridge between polymer and HA porous ceramics is served as using HA-PDLLA-PUU obtained, improve the interface compatibility of polymer and HA porous ceramics, to more effectively improve the mechanical property of composite ceramics；It is significant to the mechanical property of effective enhancing HA ceramics with better toughness and energy to failure.
Description
Technical field
The invention belongs to technical field of biological material, are related to the preparation method of ceramic toughening polymer HA-PDLLA-PUU a kind of,
Further relate to the ceramics containing ceramic toughening polymer HA-PDLLA-PUU.
Background technique
Hydroxyapatite (HA) is a kind of safe and nontoxic, the Bone Defect Repari material with good biocompatibility and osteoconductive
Material, but merely by HA process HA ceramics have the shortcomings that brittleness is big, toughness is low, cause its in load-bearing Bone Defect Repari application by
To limitation.Nature bone be by mineral facies, as hydroxyapatite (HA), calcium phosphate and organic phase for example collagen form it is porous compound
Material, collagen provides toughness as large biological molecule for nature bone, and mineral facies then provide just for nature bone as inorganic material
Degree and intensity, the two assign nature bone unique mechanical property jointly.It is inspired by this, numerous studies attempt to gather using HA with organic
It closes object Material cladding and forms inorganic-organic composite material, to improve branch while keeping HA porous support strength and stiffness
The toughness of frame.The mechanical property of interface binding power and organic polymer itself between HA and organic polymer is to influence HA/
An important factor for polymer compound rest mechanical property.To improve the interface binding power between HA and polymer, numerous studies benefit
Organic Polymer Chemistry is fixed on the surface HA with the reactive OH of HA particle surface, organic polymer is formed and is grafted HA (HA-
Polymer), such as polyethylene glycol grafting HA, polyacrylate grafting HA, polycaprolactone grafting HA, polylactic acid are grafted HA.It is this kind of
HA in HA-polymer may act as the bridge between polymer and HA particle, to improve the interface knot between polymer and HA
With joint efforts.
In above-mentioned HA-polymer, HA, which is helped, causes polylactic acid grafting HA (HA-PLA) times that lactide ring-opening polymerisation is formed
It is concerned, because PLA itself has been the bone fixation and bone renovating material in clinical use many years, while being also successfully used as operation seam
Zygonema, drug release material etc..But lack stronger noncovalent interaction, such as hydrogen bond between PLA segment and HA ceramics in HA-PLA
Effect leads to compound rest so that the interface compatibility of HA-PLA and HA ceramics is confined to the function served as bridge of HA in HA-PLA
Mechanical property improve it is limited.Therefore, the HA-polymer of hydrogen bond action can be formed for effectively increasing with HA particle by researching and developing one kind
The mechanical property of strong HA ceramics is significant.
Summary of the invention
In view of this, one of the objects of the present invention is to provide the preparations of ceramic toughening polymer HA-PDLLA-PUU a kind of
Method, the purpose of the present invention and be to provide ceramic toughening polymer HA-PDLLA-PUU prepared by the above method；This hair
The bright third purpose is to provide the HA porous ceramics enhanced by ceramic toughening polymer HA-PDLLA-PUU；The purpose of the present invention
Four be to provide the preparation method of HA porous ceramics.
In order to achieve the above objectives, the invention provides the following technical scheme:
A kind of preparation method of ceramic toughening polymer HA-PDLLA-PUU includes the following steps: first by hydroxyapatite
Cause lactide ring-opening polymerisation and form polylactic acid macromolecular alcohol, aliphatic diisocyanate and chain extender is then added through two-step method
Chain extension obtains ceramic toughening polymer HA-PDLLA-PUU.
In the present invention, the preparation step of the polylactic acid macromolecular alcohol is as follows: after hydroxyapatite is mixed with lactide,
Using stannous octoate as catalyst, reacted 8-48 hours under 130-160 DEG C, oxygen free condition.
In the present invention, the molar ratio of the hydroxyapatite and lactide is 1:5~1:200；Preferably, the hydroxyl phosphorus
The ratio between lime stone and lactide molal quantity are 1:10~1:100.It is more optimized, the molal quantity of the hydroxyapatite and lactide it
Than for 1:10~1:50.
In the present invention, in the chain extension, the molar ratio of polylactic acid macromolecular alcohol, aliphatic diisocyanate and chain extender is
1.0:1.1~1.8:0.1~0.8.
In the present invention, the aliphatic diisocyanate is hexamethylene diisocyanate or lysine diisocyanate；
The chain extender is small molecule glycol or small molecule diamines.
In the present invention, the two steps chain extension specifically: aliphatic diisocyanate is added in polylactic acid macromolecular alcohol and exists
2h~8h is reacted at 60 DEG C~90 DEG C, small molecule glycol is then added, and 2h~for 24 hours is reacted at 60 DEG C~90 DEG C；Preferably, add
Enter after small molecule glycol in 70 DEG C~85 DEG C reaction 5h~18h；More preferably, it is added after small molecule glycol at 80 DEG C~85 DEG C instead
Answer 10~15h；
Or aliphatic diisocyanate is added in polylactic acid macromolecular alcohol and reacts 2h~8h at 60 DEG C~90 DEG C, then
Small molecule diamines is added, 2h~for 24 hours is reacted at 15 DEG C~50 DEG C；Preferably, it is added after small molecule diamines at 25 DEG C~40 DEG C
5h~18h is reacted, more preferably, is added after small molecule diamines in 40 DEG C~50 DEG C 10~15h of reaction.
In the present invention, the small molecule glycol is any one of ethylene glycol, propylene glycol, butanediol or isobide, institute
Stating small molecule diamines is any one of ethylenediamine, propane diamine, butanediamine, hexamethylene diamine or piperazine.
2. the ceramic toughening polymer HA-PDLLA-PUU as made from the preparation method.
3. application of the ceramic toughening polymer HA-PDLLA-PUU in enhancing HA porous ceramics toughness.
4. using the method for ceramic toughening polymer HA-PDLLA-PUU enhancing HA porous ceramics, including walking as follows
It is rapid: the ceramic toughening polymer HA-PDLLA-PUU is dissolved in methylene chloride, is configured to the solution of 1-10wt.%, it is sufficiently molten
The HA porous ceramics of sinter molding, is then soaked in solution, shakes at 18~25 DEG C at least 12 hours by solution, dry, obtains
The HA porous ceramics of HA-PDLLA-PUU enhancing；
The HA porous ceramics is prepared by following methods: HA particle being soaked in distilled water, polypropylene is added with stirring
Amide, stir to uniform ceramic mud is formed, then form, ceramic precursor be made after freeze-drying, re-sinter HA is porous
Ceramics.
Further, the HA porous ceramics is prepared by following methods: HA being soaked in distilled water, then in mechanical stirring
Under, PAM is added, is kept stirring 1h after solution is in semi-solid, forms uniform ceramic mud, then pour into ceramic mud
Formed in 24 orifice plates, be placed in -20 DEG C of refrigerator freezings stay overnight, finally be freeze-dried 48 hours, ceramic precursor；Then it will be made
Ceramic precursor be placed in high temperature sintering furnace, be heated to 1100 DEG C under vacuum environment with the heating rate of 10 DEG C/min, keep the temperature 4h
After be down to room temperature (25 DEG C), obtain HA porous ceramics.
The beneficial effects of the present invention are: the invention discloses the preparation methods of ceramic toughening polymer HA-PDLLA-PUU
And ceramic toughening polymer HA-PDLLA-PUU obtained, urethano and urea groups abundant is utilized in HA-PDLLA-PUU can be with
HA porous ceramics forms hydrogen bond action, therefore can improve polymer and the porous boundary HA by the function served as bridge of HA-PDLLA-PUU
Face compatibility, to more effectively improve the mechanical property of composite ceramics；Compared with HA-PDLLA,
HA-PDLLA-PUU has better toughness and energy to failure, to have better toughness to enhance ability.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out
Illustrate:
Fig. 1 is HA-PDLLA-PUU's1H NMR spectra.
Fig. 2 is HA-PDLLA's1H NMR spectra.
Fig. 3 is that the SEM after PDLLA, HA-PDLLA and HA-PDLLA-PUU and sintering HA Ceramic Composite schemes.
Fig. 4 is HA-PDLLA and HA-PDLLA-PUU and is sintered the compound load-deformation curve of HA porous ceramics.
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail.
Embodiment 1
Scheme one
A kind of preparation method of ceramic toughening polymer HA-PDLLA-PUU, includes the following steps:
(1) HA-PDLLA is synthesized: by dry HA, lactide particles, 1:150 is mixed in proportion, at Sn (Oct)2Under catalysis
140 DEG C, react for 24 hours under vacuum condition, then purify twice with methylene chloride and n-hexane co-precipitation system, must after vacuum drying
To HA surface grafting PDLLA material HA-PDLLA；
(2) HA-PDLLA-PUU is synthesized: the HA-PDLLA that step (1) obtains being substantially dissolved in dry toluene, by HA-
PDLLA: six methylene diisocyanate: piperazine molar ratio is that hexamethylene diisocyanate is first added in 1.0:1.8:0.8, at 70 DEG C
Lower reaction 5h, then adds piperazine, and 10h is reacted at 50 DEG C, after completion of the reaction, solution is added dropwise to dehydrated alcohol, collects
Product, and with methylene chloride/dehydrated alcohol system purified product 2 times, obtain material HA-PDLLA-PUU after HA-PDLLA chain extension.
Scheme two
A kind of preparation method of ceramic toughening polymer HA-PDLLA-PUU, includes the following steps:
(1) HA-PDLLA is synthesized: by dry HA, lactide particles, 1:100 is mixed in proportion, at Sn (Oct)2Under catalysis
150 DEG C, react 36h under vacuum condition, then purify twice with methylene chloride and n-hexane co-precipitation system, must after vacuum drying
To HA surface grafting PDLLA material HA-PDLLA；
(2) HA-PDLLA-PUU is synthesized: the HA-PDLLA that step (1) obtains being substantially dissolved in dry toluene, by HA-
PDLLA: six methylene diisocyanate: piperazine molar ratio is that hexamethylene diisocyanate is first added in 1.0:1.5:0.5, at 60 DEG C
Lower reaction 10h, then adds piperazine, reacts at 30 DEG C for 24 hours, after completion of the reaction, solution is added dropwise to dehydrated alcohol, collects
Product, and with methylene chloride/dehydrated alcohol system purified product 2 times, obtain material HA-PDLLA-PUU after HA-PDLLA chain extension.
Scheme three
A kind of preparation method of ceramic toughening polymer HA-PDLLA-PUU, includes the following steps:
(1) HA-PDLLA is synthesized: by dry HA, lactide particles, 1:50 is mixed in proportion, at Sn (Oct)2Under catalysis
160 DEG C, react 12h under vacuum condition, then purify twice with methylene chloride and n-hexane co-precipitation system, must after vacuum drying
To HA surface grafting PDLLA material HA-PDLLA；
(2) HA-PDLLA-PUU is synthesized: the HA-PDLLA that step (1) obtains being substantially dissolved in dry toluene, by HA-
PDLLA: six methylene diisocyanate: piperazine molar ratio is that hexamethylene diisocyanate is first added in 1.0:1.2:0.2, at 90 DEG C
Lower reaction 2h, then adds piperazine, and 2h is reacted at 50 DEG C, after completion of the reaction, solution is added dropwise to dehydrated alcohol, collects and produces
Object, and with methylene chloride/dehydrated alcohol system purified product 2 times, obtain material HA-PDLLA-PUU after HA-PDLLA chain extension.
The product of acquisition is carried out1H H NMR spectroscopy map analysis, as a result as depicted in figs. 1 and 2.HA-PDLLA is in δ 4.36ppm
The lactoyl methine hydrogen C being connected at (a ' in Fig. 1) with terminal hydroxy groupHAbsorption peak, in HA-PDLLA- after HDI and PP chain extension
It disappears substantially in PUU, shows that the end OH of HA-PDLLA is reacted with HDI.Meanwhile HA-PDLLA-PUU is in δ 3.08-
3.28ppm (c), at δ 1.20-1.40ppm (d, e in Fig. 2, A) has increased two groups of absorption peaks newly in Fig. 2, A, provides from HDI
Two end methylene CH 2Proton uptake peak；δ 3.31-3.44ppm (in Fig. 2, A f) place increased newly one it is unimodal, from
Four methylene C that piperazine providesH 2Proton uptake peak.Demonstrate the successful synthesis of HA-PDLLA and HA-PDLLA-PUU.
Sn (Oct) in the present invention2Hydroxyapatite causes the condition of lactide open loop under 130-160 DEG C, oxygen free condition
Reaction 8-48 hours；The molar ratio of HA and lactide influences the molecular weight of HA-PDLLA, general hydroxyapatite and third
The molar ratio of lactide is 1:5~1:200；Preferably, the ratio between the hydroxyapatite and lactide molal quantity are 1:10~1:
100.More optimized, the ratio between molal quantity of the hydroxyapatite and lactide is 1:10~1:50.
In chain extension of the present invention, the molar ratio of polylactic acid macromolecular alcohol, aliphatic diisocyanate and chain extender is 1.0:1.1
~1.8:0.1~0.8；Aliphatic diisocyanate is hexamethylene diisocyanate or lysine diisocyanate；It can also be with
For other aliphatic diisocyanates；The chain extender is small molecule glycol or small molecule diamines；The small molecule glycol is second
Any one of glycol, propylene glycol, butanediol or isobide, the small molecule diamines be ethylenediamine, propane diamine, butanediamine,
Any one of hexamethylene diamine or piperazine.
In two step chain extensions of the invention, the first step is that aliphatic diisocyanate is added in polylactic acid macromolecular alcohol at 60 DEG C
2h~8h is reacted at~90 DEG C, preferably in 70 DEG C~85 DEG C reaction 3h~5h.More preferably, 80 DEG C~85 DEG C reaction 3h~
4h；Second step is that 2h~for 24 hours is reacted at 60 DEG C~90 DEG C when the condition that small molecule glycol is added；Preferably, 70 DEG C~85
DEG C reaction 5h~18h；More preferably, in 80 DEG C~85 DEG C 10~15h of reaction；Second step be added small molecule diamines condition be
2h~for 24 hours is reacted at 15 DEG C~50 DEG C；Preferably, in 25 DEG C~40 DEG C reaction 5h~18h, more preferably, at 40 DEG C~50 DEG C
React 10~15h.
Embodiment 2
Using the method for ceramic toughening polymer HA-PDLLA-PUU enhancing HA porous ceramics, include the following steps:
HA-PDLLA-PUU is dissolved in methylene chloride, is configured to the solution of 1-10wt.%, is placed on magnetic stirring apparatus and stirs
Mix makes it sufficiently dissolve and be uniformly dispersed overnight.Then, the HA porous ceramics of sinter molding is soaked in wherein, is placed in and shakes
Bed takes out after rocking concussion at room temperature 24 hours, the dry 48 hours HA porous ceramics to get HA-PDLLA-PUU enhancing.
Fig. 3 is that the SEM after PDLLA, HA-PDLLA and HA-PDLLA-PUU and sintering HA Ceramic Composite schemes, the results showed that,
PDLLA forms one layer of cavernous film in rack surface after PDLLA and HA porous ceramics are compound, and between HA porous ceramics
There are apparent laminations.As HA-PDLLA and HA porous ceramics compound tense, HA-PDLLA is in the not no company of being formed of ceramic surface
Continuous film, but infiltrate through in the hole of porous ceramics, so that the ceramics after compound still retain more macropore and aperture；Into
One step amplifying observation can find there is good interface cohesion between part HA-PDLLA and ceramics, but part HA-PDLLA is still
Exist between HA porous ceramics and significantly separates.After HA porous ceramics and HA-PDLLA-PUU are compound, HA-PDLLA-PUU is very
It infiltrates through well in the hole of ceramics, it is basic without changing the original macroporosity pattern of ceramics；Ceramic wall is magnified, can be sent out
Without apparent interface between existing HA-PDLLA-PUU and ceramic matrix, compound HA-PDLLA-PUU up is in the hole of ceramics
Form the aperture with micro-nano size.Above-mentioned SEM the result shows that, after PDLLA is grafted to the surface HA, the presence of HA can be mentioned
The interface compatibility of high PDLLA and HA ceramics, and being further introduced into for PUU, can further improve the boundary of polymer Yu HA ceramics
Face compatibility；HA-PDLLA-PUU has best HA porous ceramics interface compatibility.
Fig. 4 is HA-PDLLA and HA-PDLLA-PUU and the compound load-deformation curve of HA porous ceramics, the results showed that HA
The stress of porous ceramics increases with strain is presented apparent zigzag increase；After compound with HA-PDLLA, compressive strength is bright
It is aobvious to increase, and jagged frequency declines；After compound with HA-PDLLA-PUU, zigzag disappears substantially, and compressive strength is into one
Step increases, and breaking strain is about 2 times of HA porous ceramics.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (8)
1. a kind of preparation method of ceramic toughening polymer HA-PDLLA-PUU, which comprises the steps of: first by hydroxyl
Base apatite causes lactide ring-opening polymerisation and forms polylactic acid macromolecular alcohol, and aliphatic diisocyanate and chain extender is then added
Ceramic toughening polymer HA-PDLLA-PUU is obtained through two-step method chain extension；
The aliphatic diisocyanate is hexamethylene diisocyanate or lysine diisocyanate；The chain extender is small
Molecule glycol or small molecule diamines；
The two-step method chain extension specifically: aliphatic diisocyanate is added in polylactic acid macromolecular alcohol at 60 DEG C ~ 90 DEG C
2h ~ 8h is reacted, small molecule glycol is then added, 2h ~ for 24 hours is reacted at 60 DEG C ~ 90 DEG C；Or it is added in polylactic acid macromolecular alcohol
Aliphatic diisocyanate reacts 2h ~ 8h at 60 DEG C ~ 90 DEG C, and small molecule diamines is then added, reacts 2h at 15 DEG C ~ 50 DEG C
~24h。
2. the preparation method of ceramic toughening polymer HA-PDLLA-PUU according to claim 1, it is characterised in that: described poly-
The preparation step of lactic acid macromolecular alcohol is as follows: after hydroxyapatite is mixed with lactide, using stannous octoate as catalyst,
130-160 DEG C, react 8-48 hours under oxygen free condition.
3. the preparation method of ceramic toughening polymer HA-PDLLA-PUU according to claim 2, it is characterised in that: the hydroxyl
The molar ratio of base apatite and lactide is 1:5 ~ 1:200.
4. the preparation method of ceramic toughening polymer HA-PDLLA-PUU according to claim 1, it is characterised in that: the expansion
In chain, the molar ratio of polylactic acid macromolecular alcohol, aliphatic diisocyanate and chain extender is 1.0: 1.1 ~ 1.8: 0.1 ~ 0.8.
5. the preparation method of ceramic toughening polymer HA-PDLLA-PUU described in claim 1, it is characterised in that: the small molecule
Glycol is any one of ethylene glycol, propylene glycol, butanediol or isobide, the small molecule diamines be ethylenediamine, propane diamine,
Any one of butanediamine, hexamethylene diamine or piperazine.
6. the ceramic toughening polymer HA-PDLLA-PUU as made from claim 1 ~ 5 described in any item preparation methods.
7. application of the ceramic toughening polymer HA-PDLLA-PUU described in claim 6 in enhancing HA porous ceramics toughness.
8. using the method for the enhancing HA porous ceramics toughness of ceramic toughening polymer HA-PDLLA-PUU described in claim 6,
It is characterized in that, includes the following steps: the ceramic toughening polymer HA-PDLLA-PUU being dissolved in methylene chloride, be configured to 1-10
The solution of wt.%, sufficiently dissolve, then the HA porous ceramics of sinter molding is soaked in solution, shaken at 18 ~ 25 DEG C to
It is 12 hours few, it is dry, obtain the HA porous ceramics for enhancing toughness by HA-PDLLA-PUU；
The HA porous ceramics is prepared by following methods: HA particle is soaked in distilled water, polyacrylamide is added with stirring,
Then stirring forms to uniform ceramic mud is formed, ceramic precursor is made after freeze-drying, re-sinter to obtain HA porous ceramics.
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