CN101130110B - Method of preparing compound osseous tissue renovating material interconsistency agent of polylactic acid/hydroxyapatite - Google Patents
Method of preparing compound osseous tissue renovating material interconsistency agent of polylactic acid/hydroxyapatite Download PDFInfo
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- CN101130110B CN101130110B CN2007100302247A CN200710030224A CN101130110B CN 101130110 B CN101130110 B CN 101130110B CN 2007100302247 A CN2007100302247 A CN 2007100302247A CN 200710030224 A CN200710030224 A CN 200710030224A CN 101130110 B CN101130110 B CN 101130110B
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Abstract
The invention relates to a method for preparing an inclusive agent of a polylactic acid or hydroxyapatite composite bone tissue restoring material, which comprises the following steps: getting processed hydroxyapatite by refluxing hydroxyapatite in the alcohol solution with surface modifier as the coupler for 12-48 hours; dissolving polylactic acid macromole monomer with terminal ethenyl and the processed hydroxyapatite in the organic solvent with initiating agent; protecting with nitrogen; extracting after extracting and drying the reactor; separating and purifying no-grafted polylactic acid macromole monomer; extracting the remainder; drying; getting the inclusive agent. The inclusive agent has the wide application, the low cost, the simple method, the mild synthesis condition, the strong utility and the easy industry production, which provides the boundary interaction of the organic or inorganic phase in polylactic acid or hydroxyapatite composite bone tissue restoring material, and improves the ergology property of bone tissue restoring material.
Description
Technical field
The present invention relates to a kind of preparation method that is used for the compatilizer of polylactic acid/hydroxy apatite compound osseous tissue renovating material.
Background technology
Bone wound is the common disease of surgical clinical, in China, is caused by a variety of causes and bone injury, spinal fusion, bone cyst patient every year up to surplus 10,000,000, wherein need use 500,000 examples that account for of bone renovating material.Serious day by day along with aging, traffic and the manufacturing development of population structure, environmental pollution, this numeral is also constantly soaring.The pathological changes of osseous tissue and damage directly influence people's quality of life, so the reparation of osseous tissue damage is the medical research problem that people pay special attention to always.Adopt artificial material to implant to repair or alternative pathological changes and damaged bone tissue are main clinically Therapeutic Method.
Early treatment's fracture and the damaged implants of bone are metal object basically, need to take out once more after knitting but its major defect is a metal object; Burden on increase patient's economy, psychology and the health; Increase the postoperative infection rate; The metal inner matter can cause osteoporosis and osteanabrosis, the mechanical performance of influence healing bone etc.; Metal object is become flexible and is deteriorated and causes inflammatory reaction, and surrounding soft tissue and osseous tissue are produced chronic stimulation, causes molten bone, causes clinical symptoms.From the later stage sixties, many scientists explored exploitation biological activity and degradable one after another and absorb the orthopaedics implants, and were applied to clinically in 1984, and the material of mainly selecting for use comprises from nature bone materials such as body bone, corpse bone, animal bone; Inorganic material and highly purified poly-lactic acid materials such as hydroxyapatite (HA), tricalcium phosphate (TCP), bio-vitric, but all there is certain defective in these materials, mainly be that the nature bone material source is limited, there is the problem on communicate illness and the immunology, and when clinical practice, the open damage location that need undergo surgery, the patient will bear the painful and burden economically on the health, and recovers slowly; Though hydroxyl apatite bioceramic has biological activity preferably, degradability and mechanical property are all undesirable; Tricalcium phosphate has good degradability, but biological activity is undesirable; Though bioactivity glass has had the history in more than 30 year, because aspects such as its physicochemical property and preparation technology have only granular product to be used for the osseous tissue injury repairing at present; It is acid that the polylactic acid catabolite is, and late period, the foreign body inflammatory reaction was higher, and mechanical property is lower, and decay is too fast, can not satisfy cortical bone or the fixed needs of bone that bear a heavy burden fully, and range of application is little.
The composite bioactivity osseous tissue renovating material is the research focus at present.Because organism is a very complicated system, biological tissue is actually a very complicated composite, therefore all there is such or such defective in the biomaterial of any one-component, and may prepare the biomaterial that has near biological properties by being compounded with, the bone tissue restoration target of realizing ideal.But the compatibility of natural macromolecular material and hydroxyapatite is poor, and the mechanical property of composite is not high.Thereby, hydroxyapatite/macromolecular material interface bond mechanism and Study on Compatibility are just become the emphasis that this type of composite bio-active material is studied.
Summary of the invention
The objective of the invention is provides a kind of preparation method that is applied to the compatilizer of polylactic acid/hydroxy apatite composite bone repairing material in order to overcome above-mentioned defective.
For achieving the above object, the present invention by the following technical solutions.The preparation method of compatilizer is carried out as follows:
(1) is surface modifier with coupling agent, makes hydroxyapatite backflow in 12～48 hours in containing the alcoholic solution of coupling agent; Wherein, the mass ratio of coupling agent and hydroxyapatite is 1～10: 100, and the volume ratio of ethanol and alcoholic solution is 10～80: 100, and alcoholic solution is 100ml: 1～10g with the volume mass ratio of coupling agent;
(2) will contain the hydroxyapatite that obtains in the polylactic acid macromonomer of end-vinyl and the step (1) is dissolved in the organic solvent that contains initiator, logical nitrogen protection, 50～70 ℃ were reacted 12～36 hours, wherein, the mass ratio that contains polylactic acid macromonomer, hydroxyapatite and the initiator of end-vinyl is: 40～98: 1.4～59.9: 0.1～0.6; The organic solvent of 100ml is 100ml: 1～10g with the volume mass ratio of polylactic acid macromonomer; Initiator is under 40～95 ℃ of conditions, has 105～150kJ/mol dissociation energy and can produce free radical to cause the polymeric material of olefinic monomer; Perhaps
With the aqueous hydrogen peroxide solution is initiator, to contain the hydroxyapatite ultraviolet light cross-linking that obtains in the polylactic acid macromonomer of end-vinyl and the step (1), wherein, contain the polylactic acid macromonomer of end-vinyl, the mass ratio of hydroxyapatite is: 40～98: 2～60, crosslinking time is 7～60min;
(3) with the product in the step (2) after extracting drying, use the cable type extractor according extracting, with not grafted polylactic acid macromonomer purifies and separates, the extracting residue promptly gets the compatilizer that is used for the polylactic acid/hydroxy apatite compound osseous tissue renovating material after drying.
Described coupling agent in the silane type that contains a carbon carbon unsaturated double-bond at least, aluminic acid ester type, borate-type, the titanate esters type coupling agent any one or multiple.
Described silane type coupling agent is one of vinyltrimethoxy silane, VTES, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane.
Described hydroxyapatite is micron order or nanoscale.
Described initiator comprises one of potassium peroxydisulfate, Ammonium persulfate., azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, hydrogen peroxide.
Described organic solvent is one or more in dioxane, oxolane, the dimethyl formamide.
The present invention compared with prior art has following advantage: compatilizer of the present invention, and can make polylactic acid and hydroxyapatite two-phase interface fuzzy, hot strength improves 20%, and bending strength improves 80%.Compatilizer of the present invention is used face width, cost is low, method is easy, synthesis condition gentleness, practical, be easy to suitability for industrialized production, can improve the interfacial interaction of organic/inorganic phase in the polylactic acid/hydroxy apatite composite bone repairing material, improve the mechanical mechanics property of bone renovating material, the use of this compatilizer can be widened the range of application of polylactic acid/hydroxy apatite compound osseous tissue renovating material.
Description of drawings
Fig. 1 is the infrared spectrum of the hydroxyapatite crossed through the vinyltrimethoxy silane coupling agent treatment.
Fig. 2 is an initiator for azodiisobutyronitrile, and dioxane is a reaction dissolvent, contains the polylactic acid macromonomer of end-vinyl and the infrared spectrum of the hydroxyapatite solution polymerization thing handled through silane coupler.
Fig. 3 is for aqueous hydrogen peroxide solution is an initiator, contain the polylactic acid macromonomer of end-vinyl and the hydroxyapatite handled through silane coupler through the infrared spectrum of ultraviolet light cross-linking reactant.
The specific embodiment
Embodiment 1: do the coupling agent treatment hydroxyapatite with vinyltrimethoxy silane.
10g micron order hydroxyapatite was refluxed in the 10ml of 0.1g vinyltrimethoxy silane 80% alcoholic solution in 40 hours, detects the hydroxyapatite surface of handling with Fourier transform infrared spectroscopy, Fourier transform infrared spectroscopy as shown in Figure 1,3000cm
-1About the stretching vibration peak of C-H appears, confirm to have introduced the vinyltrimethoxy silane that contains ethylene double bond of free redical reaction in hydroxyapatite surface by Fourier transform infrared spectroscopy.
Embodiment 2: do the coupling agent treatment hydroxyapatite with γ-methacryloxypropyl triethoxysilane and vinyltrimethoxy silane.
With the backflow in 12 hours in the 10ml of 0.5g γ-methacryloxypropyl triethoxysilane, 0.5g vinyltrimethoxy silane 50% alcoholic solution of 10g micron order hydroxyapatite, detect the hydroxyapatite surface of handling with Fourier transform infrared spectroscopy, Fourier transform infrared spectroscopy as shown in Figure 1,3000cm
-1About the stretching vibration peak of C-H appears, confirm to have introduced the γ that the contains ethylene double bond-methacryloxypropyl triethoxysilane of free redical reaction in hydroxyapatite surface by Fourier transform infrared spectroscopy.
Embodiment 3: handle hydroxyapatite with two (oleic acid two diethyl acetal ester groups) aluminic acid isopropyl ester.
With the backflow in 24 hours in the 10ml10% alcoholic solution of 0.3g two (oleic acid two diethyl acetal ester groups) aluminic acid isopropyl ester of 10g nano-grade hydroxy apatite, detect the hydroxyapatite surface of handling with Fourier transform infrared spectroscopy, Fourier transform infrared spectroscopy and Fig. 1 are similar, at 3000cm
-1Occurred hydrocarbon stretching vibration peak about wave number, confirmed to have introduced two (oleic acid two diethyl acetal ester groups) aluminic acid isopropyl ester that contains ethylene double bond of free redical reaction by Fourier transform infrared spectroscopy in hydroxyapatite surface.
Embodiment 4: handle hydroxyapatite with boric acid neopentyl glycol methacrylic acid 2-hydroxyl ethyl ester, isopropyl stearoyl two acryloyl titanate esters, two (oleic acid two diethyl acetal ester groups) aluminic acid isopropyl ester.
With the backflow in 48 hours in 10ml 20% alcoholic solution of 0.2g boric acid neopentyl glycol methacrylic acid 2-hydroxyl ethyl ester, 0.1g isopropyl stearoyl two acryloyl titanate esters and 0.1g two (oleic acid two diethyl acetal ester groups) aluminic acid isopropyl ester of 10g nano-grade hydroxy apatite, detect the hydroxyapatite surface of handling with Fourier transform infrared spectroscopy, Fourier transform infrared spectroscopy and Fig. 1 are similar, at 3000cm
-1Occurred hydrocarbon stretching vibration peak about wave number, confirmed to have introduced the boric acid neopentyl glycol methacrylic acid 2-hydroxyl ethyl ester Organic substance that contains ethylene double bond of free redical reaction by Fourier transform infrared spectroscopy in hydroxyapatite surface.
Embodiment 5: handle hydroxyapatite with isopropyl stearoyl two acryloyl titanate esters.
With the backflow in 48 hours in 10ml 20% alcoholic solution of the isopropyl stearoyl two acryloyl titanate esters of 0.1 g of 10g nano-grade hydroxy apatite, detect the hydroxyapatite surface of handling with Fourier transform infrared spectroscopy, Fourier transform infrared spectroscopy and Fig. 1 are similar, at 3000cm
-1Occurred hydrocarbon stretching vibration peak about wave number, confirmed to have introduced the isopropyl stearoyl that the contains ethylene double bond two acryloyl titanate esters of free redical reaction by Fourier transform infrared spectroscopy in hydroxyapatite surface.
Embodiment 6: select for use azodiisobutyronitrile as initiator, dioxane prepares the compatilizer of polylactic acid/hydroxy apatite compound osseous tissue renovating material as reaction dissolvent.
Select for use azodiisobutyronitrile 1mg as initiator; the 10ml dioxane is as reaction dissolvent; add 0.4g and contain the polylactic acid macromonomer of end-vinyl and the hydroxyapatite that 0.599g handled through silane coupler; logical 50 ℃ of protective reactions of nitrogen 12 hours; product is filtered extracting; the extracting residue detects with Fourier transform infrared spectroscopy, Fourier transform infrared spectroscopy as shown in Figure 2,1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Embodiment 7: select for use Ammonium persulfate. as initiator, oxolane, dimethyl formamide, dioxane prepare the compatilizer of polylactic acid/hydroxy apatite compound osseous tissue renovating material as reaction dissolvent.
Select for use Ammonium persulfate. 6mg as initiator; 0.8ml oxolane, 5ml dimethyl formamide, 4ml dioxane are as reaction dissolvent; add 0.98g and contain the polylactic acid macromonomer of end-vinyl and the hydroxyapatite that 0.014g handled through silane coupler; logical 60 ℃ of protective reactions of nitrogen 24 hours; product is filtered extracting; the extracting residue detects with Fourier transform infrared spectroscopy, and Fourier transform infrared spectroscopy and Fig. 2 are similar, 1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Embodiment 8: select for use hydrogen peroxide as initiator, dimethyl formamide prepares the compatilizer of polylactic acid/hydroxy apatite compound osseous tissue renovating material as reaction dissolvent.
Select for use hydrogen peroxide 5mg as initiator; the 50ml dimethyl formamide is as reaction dissolvent; add 0.5g and contain the polylactic acid macromonomer of end-vinyl and the hydroxyapatite that 0.495g handled through silane coupler; logical 70 ℃ of protective reactions of nitrogen 36 hours; product is filtered extracting; the extracting residue detects with Fourier transform infrared spectroscopy, and Fourier transform infrared spectroscopy and Fig. 2 are similar, 1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Embodiment 9: select for use dibenzoyl peroxide as initiator, dimethyl formamide, dioxane prepare the compatilizer of polylactic acid/hydroxy apatite compound osseous tissue renovating material as reaction dissolvent.
Select for use hydrogen peroxide 5mg as initiator; 5ml dimethyl formamide, 5ml dioxane are as reaction dissolvent; add 0.5g and contain the polylactic acid macromonomer of end-vinyl and the hydroxyapatite that 0.495g handled through silane coupler; logical 70 ℃ of protective reactions of nitrogen 24 hours; product is filtered extracting; the extracting residue detects with Fourier transform infrared spectroscopy, and Fourier transform infrared spectroscopy and Fig. 2 are similar, 1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Embodiment 10: a kind of reaction condition of the compatilizer of preparation polylactic acid/hydroxy apatite compound osseous tissue renovating material.
Select for use aqueous hydrogen peroxide solution 10ml as initiator, 0.4g is contained the polylactic acid macromonomer of end-vinyl and hydroxyapatite that 0.6g handled through silane coupler reacts 42min through ultraviolet light cross-linking, reactant becomes white solid by original liquid, product is filtered extracting, the extracting residue detects with Fourier transform infrared spectroscopy, its spectrum as shown in Figure 3,1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Embodiment 11: a kind of reaction condition of the compatilizer of preparation polylactic acid/hydroxy apatite compound osseous tissue renovating material.
Select for use aqueous hydrogen peroxide solution 10ml as initiator, 9.8g is contained the polylactic acid macromonomer of end-vinyl and hydroxyapatite that 0.2g handled through silane coupler reacts 7min through ultraviolet light cross-linking, product is filtered extracting, the extracting residue detects with Fourier transform infrared spectroscopy, its spectrum and Fig. 3 are similar, 1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Embodiment 12: a kind of reaction condition of the compatilizer of preparation polylactic acid/hydroxy apatite compound osseous tissue renovating material.
Select for use aqueous hydrogen peroxide solution 10ml as initiator, 0.9g is contained the polylactic acid macromonomer of end-vinyl and hydroxyapatite that 0.1g handled through silane coupler reacts 60min through ultraviolet light cross-linking, product is filtered extracting, the extracting residue detects with Fourier transform infrared spectroscopy, its spectrum and Fig. 3 are similar, 1637cm
-1Near the stretching vibration peak of institute's carbon-carbon double bonds disappearance on the polylactic acid macromonomer wave number, confirm that through Fourier transform infrared spectroscopy two keys have participated in reaction, illustrate that the polylactic acid macromonomer that contains end-vinyl has been grafted on the hydroxyapatite that silane coupler was handled.
Claims (4)
1. the preparation method of a polylactic acid/hydroxy apatite compound osseous tissue renovating material compatilizer is characterized in that may further comprise the steps:
(1) be surface modifier with coupling agent, the hydroxyapatite that makes hydroxyapatite in containing the alcoholic solution of coupling agent, reflux and obtain handling in 12～48 hours; Wherein, the mass ratio of coupling agent and hydroxyapatite is 1～10: 100, and the volume ratio of ethanol and alcoholic solution is 1～8: 10, and alcoholic solution is 100ml: 1～10g with the volume mass ratio of coupling agent;
(2) hydroxyapatite that will contain the processing that obtains in the polylactic acid macromonomer of end-vinyl and the step (1) is dissolved in the organic solvent that contains initiator, logical nitrogen protection, 50～70 ℃ were reacted 12-36 hour, wherein, the mass ratio that contains polylactic acid macromonomer, hydroxyapatite and the initiator of end-vinyl is 40～98: 1.4～59.9: 0.1～0.6; Organic solvent is 100ml: 1～10g with the volume mass ratio of polylactic acid macromonomer; Initiator is potassium peroxydisulfate, Ammonium persulfate., azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide or hydrogen peroxide; Perhaps
Aqueous solution with hydrogen peroxide is an initiator, the hydroxyapatite ultraviolet light cross-linking that will contain the processing that obtains in the polylactic acid macromonomer of end-vinyl and the step (1), wherein, contain the polylactic acid macromonomer of end-vinyl, the mass ratio of hydroxyapatite is: 40～98: 2～60, crosslinking time is 7～60min;
(3) with the product in the step (2) after extracting drying, use the cable type extractor according extracting, with not grafted polylactic acid macromonomer purifies and separates, the extracting residue promptly gets the compatilizer that is used for the polylactic acid/hydroxy apatite compound osseous tissue renovating material after drying;
Described coupling agent is one or more in the silane type that contains at least one carbon carbon unsaturated double-bond, aluminic acid ester type, borate-type, the titanate esters type coupling agent.
2. the preparation method of compatilizer according to claim 1 is characterized in that described silane type coupling agent is vinyltrimethoxy silane, VTES, γ-methacryloxypropyl trimethoxy silane or γ-methacryloxypropyl triethoxysilane.
3. the preparation method of compatilizer according to claim 1 is characterized in that described hydroxyapatite is micron order or nanoscale.
4. the preparation method of compatilizer according to claim 1 is characterized in that described organic solvent is one or more in dioxane, oxolane, the dimethyl formamide.
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| FI122326B (en) * | 2006-12-15 | 2011-11-30 | Jvs Polymers Oy | Biopolymer composition in heterophase |
| CN101401965B (en) * | 2008-11-17 | 2013-09-11 | 昆明理工大学 | Synthesis of composite bone restoration bioactive material |
| CN104927319B (en) * | 2015-06-29 | 2016-07-27 | 河南工程学院 | A kind of preparation method of hydroxyapatite grafted polylactic acid |
| CN105133022B (en) * | 2015-09-22 | 2018-01-23 | 西北大学 | A kind of hydrophilically modified method of Hydroxyapatite mono-crystal nano-rod |
| CN109568675B (en) * | 2018-12-13 | 2021-06-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of polyester/periodic mesoporous bone filling composite material with fluorescence-labeled degradation rate, product and application |
| CN109939909B (en) * | 2019-03-29 | 2021-10-22 | 西安理工大学 | Preparation method of biological piezoelectric composite gradient coating on titanium or titanium alloy surface |
| CN110279901B (en) * | 2019-07-02 | 2021-06-18 | 成都美益达医疗科技有限公司 | Preparation method of absorbable bone internal fixation material |
| CN111388752B (en) * | 2020-05-20 | 2022-05-27 | 中鼎凯瑞科技成都有限公司 | PVA fiber/polyamino acid/hydroxyapatite bone supporting material and preparation thereof |
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