WO2005011763A1 - Melange pour produire du ciment d'os bioactif et procede de production de ciment d'os bioactif au moyen de ce melange - Google Patents

Melange pour produire du ciment d'os bioactif et procede de production de ciment d'os bioactif au moyen de ce melange Download PDF

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Publication number
WO2005011763A1
WO2005011763A1 PCT/KR2003/001916 KR0301916W WO2005011763A1 WO 2005011763 A1 WO2005011763 A1 WO 2005011763A1 KR 0301916 W KR0301916 W KR 0301916W WO 2005011763 A1 WO2005011763 A1 WO 2005011763A1
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WIPO (PCT)
Prior art keywords
bone cement
cao
producing
pmma
powder
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PCT/KR2003/001916
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English (en)
Inventor
Sung-Baek Cho
Sang-Bae Kim
Keon-Joon Cho
Chikara Ohtsuki
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Korea Institute Of Geoscience And Mineral Resources
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Publication date
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Priority to AU2003264957A priority Critical patent/AU2003264957A1/en
Publication of WO2005011763A1 publication Critical patent/WO2005011763A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/0047—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L24/0052—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with an inorganic matrix
    • A61L24/0068—Inorganic materials not covered by groups A61L24/0057 or A61L24/0063
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • This invention relates to a mixture for producing a bioactive bone cement and a method for producing a bioactive bone cement using the same. More particularly this invention relates to a mixture for producing a bioactive bone cement, comprising mainly PMMA (polymethylmethacrylate) and CaO-Si0 2 which is obtained by the sol-gel method and a method for producing a bioactive bone cement, which comprises the step of adding MMA (methylmethacrylate) solution to the above mixture.
  • PMMA polymethylmethacrylate
  • CaO-Si0 2 which is obtained by the sol-gel method
  • a method for producing a bioactive bone cement which comprises the step of adding MMA (methylmethacrylate) solution to the above mixture.
  • Bones enable our body to maintain its structure and protect the important internal organs such as brain and intestines. Moreover, bones make it possible for us to exercise in various ways due to its characteristic that enables each of them to move independently. Recently, the cases of getting bones damaged have been increasing because of car accidents or osteoporosis along with growing number of senior citizens. There have been studies on materials for repairing an injured bone tissue for a long time. The materials such as Alumina(Al 2 0 3 ), metal stainless steel and metal titan(Ti), that have hydrophilic properties and produce no harmful substances in human body, have been used for this purpose. However, the above materials make no chemical bonds with bones in the body directly.
  • cement materials are preferable, the cement materials being which when its powder is mixed with liquid, the mixture has fluidity for a few minutes, and then hardened to bond with bones of the surroundings, after that, shows dynamical properties similar to bones.
  • Such materials enable bone defects from disease like osteoporosis to be repaired by injecting them into the affected parts.
  • they have developed the method of hardening MMA (methylmethacrylate) monomer by polymerization or the method of hardening various ceramics powder by mixing with water, sodium phosphate solution, organic acid or polymer solution.
  • bioactive cement important properties for a bioactive cement are appropriate time for hardening after being injected to an affected part and high strength of cement injected to the affected part after being filled.
  • Hardening time and strength of cement are very various, depending on the ratio of powder to liquid when mixing cement. If the ratio of powder to liquid is adjusted high, as a rule, the hardening time becomes short and a hardened body with high strength is produced. However, if the ratio of powder to liquid is too high, full filling may not be achieved because the injection workability of the cement to an affected part becomes low.
  • a hydrating agent such as surfactant has been used in making cement for building industry to achieve the above purpose.
  • conventional PMMA (polymethylmethacrylate) bone cement mostly used for clinical purposes has been known not to show bioactivity, which is the property of binding directly to bones. Accordingly, it is required to have bioactivity for bone cement to bond with natural bones chemically so that bone cement can be stable in a living body for a long period of time.
  • Bioactive bone cement Generally, human body tends to isolate an artificial material filled in bone defects from bones of the surroundings by wrapping the artificial material with fibrous film. However, some inorganic solid materials make strong chemical bonds with bones of the surroundings without causing fibrous film in direct contact. These kinds of ceramics are called bioactive ceramics. Until now, several kinds of glass, crystallized glass and sintered ceramics are known to bond with bones in addition to the above Na 2 0-CaO-Si0 2 -P 2 0 5 glass (Bioglass). The Bioglass is used as filler for artificial middle-ear bone and teeth because it has the property of binding to bones in a short time.
  • Crystallized hydroxyapatite (Ca 10 (PO ) 6 (OH 2 )) sintered body is used for bone filler because it has bone component only.
  • Crystallized ⁇ -3CaO-P 2 0 5 sintered body is also used as bone filler because it has the property of substitution for bones.
  • the following crystallized glass are known for showing bioactivity, the property of binding to bones directly without causing fibrous film: Na 2 0-K 2 0-MgO-CaO-Si0 2 -P 2 0 5 crystallized glass that has a ⁇ atite(Ca 10 (PO 4 ) 6 (O,F 2 )) educed, implant-Ll having apatite with a little different composition from A-W and wollastonite educed, Na 2 0-K 2 0-MgO-CaO-Al 2 0 3 -Si0 2 -P 2 ⁇ 5 -F crystallized glass (Bioverit) having apatite and ((Na,K)Mg 3 (AlSiO 10 )F 2 ) educed, crystallized natural calcite, crystallized glass having magnetite(Fe 2 0 3 ) and ⁇ - wollastonite educed.
  • the above apatite layers are formed on the surface of ceramics in the SBF (Simulated Body Fluid (mM): Na + 142.0, K “ 5.0, Mg 2+ 1.5, Ca 2+ 2.5, CI “ 147.8, HC0 3 - 4.2, HP0 4 2" 1.0, S0 4 2" 0.5 (J. Am. Ceram. Soc, 78, 1769-74, 1995)) having inorganic ion concentration without cell or protein the same as human body fluid.
  • SBF Simulated Body Fluid
  • the above apatite is similar to that of bones in the body because it contains C0 3 " ion, the Ca/P ratio of the above apatite is lower than the Ca/P ratio (1.67) of hydroxyapatite (Ca 10 (PO 4 ) 6 (OH 2 )) and it consists of fine grains.
  • osteoblast producing bones are more likely to divide and increase the number of cells than fibroblast, producing fibrous film on the surface of the apatite ⁇
  • bones come from the surroundings, can contact with the superficial apatite. And then, a chemical bond between bone apatite and superficial apatite is formed to combine artificial material and bones.
  • a prerequisite for artificial material to bond with bones in the body is formation of apatite layer having similar property to that of bones in the body on its surface when the artificial material is filled in a living body.
  • the cement used commonly to fix artificial material to bones of the surroundings or to fill bone defects with artificial material, is PMMA DDS which is made by mixing PMMA powder and MMA monomer liquid and hardening it in a living body.
  • Zirconium Oxide powder or Barium Sulfate powder has been occasionally added to the above powder to improve the opacity against X-ray.
  • the above mixture paste shows fluidity which enable it to form any structure for about 4 minutes and show compressive strength up to 90Mpa.
  • the present inventors have attempted to decrease the amount of heat generation of bone cement and to give the property of binding to bones to bone cement, and consequently, developed the present invention, which prepares bone cement by mixing PMMA powder with CaO-Si0 2 gel powder having the property of binding to bones in the body, and adding MMA solution, thereby perfecting the present invention wherein the inventive bone cement has excellent biocompatibility.
  • an object of the present invention is to provide a mixture for producing a bioactive bone cement which has the amount of heat generation decreased and has the property of direct binding ability to bones, and a method for producing a bioactive bone cement using the above mixture.
  • the present invention provides a mixture for producing a bioactive bone cement, comprising PMMA powder and CaO-Si0 2 gel.
  • the present invention provides a method for producing PMMA/CaO-Si0 2 bone cement, comprising the step of adding hardening solution to the above mixture, and a PMMA/CaO-Si0 2 bone cement produced by the above method.
  • CaO-Si0 2 gel is prepared by adding TEOS (tetraethoxysilane: Si(C 2 H 5 0 )) to a mixture solution of Ca(N0 3 )-4H 2 0 and PEG and stirring the above solution.
  • the hardening solution is preferably MMA solution.
  • CaO : Si0 2 is preferably between 2:98 and 30:70 by molar ratio in the above CaO-Si0 2 gel.
  • the content of CaO-Si0 2 is preferred to be 3 ⁇
  • bioactive ceravital crystallized glass powder or gel mainly contains CaO-Si0 2 prepared by sol-gel method instead of hydroxyapatite fiber, is used.
  • FIG. 1 shows the preparation process of PMMA/CaO-Si0 2 bone cement.
  • FIG. 2 shows schematic diagram of X ray diffraction pattern of sample, analyzed by thin film X-ray diffraction, after adding bone cement, prepared by mixing PMMA powder and 20CaO-80SiO 2 gel powder by 90:10 weight ratio to SBF (simulated body fluid).
  • FIG. 3 shows SEM (scanning electron microscopy) picture of superficial structure changes when bone cement, prepared by mixing PMMA powder and 20CaO-80SiO 2 gel powder by 90: 10 weight ratio, is added to SBF.
  • FIG. 1 shows the preparation process of PMMA/CaO-Si0 2 bone cement.
  • FIG. 2 shows schematic diagram of X ray diffraction pattern of sample, analyzed by thin film X-ray diffraction, after adding bone cement, prepared by mixing PMMA powder and 20CaO-80SiO 2 gel powder by 90:10 weight ratio to SBF (simulated body fluid).
  • FIG. 4 shows schematic diagram of X ray diffraction pattern of sample, analyzed by thin film X-ray diffraction, after adding bone cement, prepared by mixing PMMA powder and 20CaO-80 Si0 2 gel powder by 70:30 weight ratio to SBF.
  • FIG. 5 shows SEM picture of superficial structure changes when bone cement, prepared by mixing PMMA powder and 20CaO-80 Si0 2 gel powder by 70:30 weight ratio, is added to SBF.
  • Example 1 Preparation of CaO-SiO? gel
  • CaO-Si0 2 gels with various compositions are prepared by hydrolysis of TEOS (tetraethoxysilane: Si(C 2 H 5 0 4 )) in an aqueous solution and then polycondensation.
  • Nitric acid 62 wt%), as a catalyst, was added to the solution which PEG (polyethylene glycol) with MW 10,000 was dissolved in distilled water with Ca(N0 3 )-4H 2 0.
  • TEOS was added to the above solution under vigorous stirring and then there was additional 5 minutes stirring after stirring until it gets transparent, the solution was transferred into a plastic petri-dish with its lid tightly sealed, and kept at 40 °C in an air- circulating oven for preparing wet gel. After it was aged for 18 hours in 40 °C oven, the obtained wet gel was washed with nitric acid solution (1 mol/dm ) for 6 hours and aqueous PEG in the above gel was removed. The nitric acid solution was renewed every 2 hours. After the obtained wet gel washed by nitric acid solution was dried for 6 days in 40 ° C oven, it was heated in furnace using Siliconit as heating material.
  • the temperature of the above furnace was increased up to 200-1300 ° C at a heating rate of 100°C/h. After heat treatment for 2 hours at each temperature, it was cooled to room temperature. Then the obtained gel was used as a starting material being kept in desiccator.
  • Table 1 Amount of starting material for producing xCaO-(100-x)SiO 2 gel
  • Example 2 Preparation of PMMA/CaO-SiO? cement xCaO-(100-x)SiO 2 gel prepared in the Example 1 was weighed and mixed with PMMA powder using mortar for 30 minutes (FIG. 1). The mixing ratio of PMMA powder to xCaO-(100-x)SiO 2 is shown in Table 2.
  • Table 2 Composition of PMMA powder and xCaO-(100-x)SiO 2
  • 0.029g of benzoylperoxide, as hardening initiator was added to 0.971g of powder mixture as shown in Table 2 and it was mixed by using mortar for 30 minutes.
  • Hardening solution (hereinafter we call it 'MMA solution') was prepared by mixing 0.008g of N,N-dimethyl- / r>-tolune with 0.992g of liquid phase of MMA. After MMA solution was added to the above powder mixture to produce the cement, the paste was shaped into cylindrical specimen in mould and then setting time is determined by measuring the time when the hardening is completed. The powder mixture was mixed with the MMA solution at a powder to liquid ratio of 2: 1 by weight ratio when producing cement.
  • Example 3 Evaluation of bioactivity using SBF To be tested in vitro, as shown in Table 3, NaCl, NaHC0 3 , KC1, K 2 HP0 4 '3H 2 0, MgCl 2 -6H 2 0, IN HC1, CaCl 2 , Na 2 S0 4, respectively was added to distilled water in polyethylene beaker to prepare SBF with the same ion concentration as that of inorganic ion of human blood plasma inorganic ion. The above reagent was added to beaker after making sure that the former reagent was dissolved completely. Finally, pH of the above solution in beaker was adjusted to 7.25 at 36.5 "C using Tris-buffer and 1N-HC1 solution.
  • FIG. 2 shows schematic diagram of X ray diffraction pattern of the sample, analyzed by thin film X-ray diffraction, after adding bone cement, prepared by mixing PMMA powder and 20CaO-80SiO 2 gel powder by 90: 10 weight ratio to SBF (simulated body fluid).
  • SBF simulated body fluid
  • FIG. 3 shows SEM (scanning electron microscopy) picture of superficial structure changes when bone cement, prepared by adding 10wt% of 20CaO-80SiO 2 gel powder instead of PMMA powder, is added to SBF.
  • Spherical PMMA powder and 20CaO-80SiO 2 gel powder were shown on the surface of bone cement before soaked in SBF.
  • leaflike apatite was formed on the surface of bone cement after soaked in SBF for 2 weeks.
  • FIG. 4 shows schematic diagram of X ray diffraction pattern of sample analyzed by thin film X-ray diffraction after adding bone cement, prepared by mixing PMMA powder and 20CaO-80SiO 2 gel powder by 70:30 weight ratio to SBF.
  • the above bone cement showed only amorphous diffraction pattern caused by diffraction of PMMA bone cement as shown in FIG. 2.
  • a diffraction pattern caused by apatite was shown after soaked for a week. Therefore, is suggested that increasing the adding amount of 20CaO-80SiO 2 gel powder to PMMA powder raised the rate of forming apatite on the surface of the cement in SBF.
  • FIG. 5 shows SEM picture of superficial structure changes when bone cement prepared by mixing PMMA powder and 20CaO-80 Si0 2 gel powder by 70:30 weight ratio, is added to SBF. It shows that apatite covered completely the surface of bone cement as 20CaO-80SiO 2 gel powder was added by 30wt% compared to by 10wt% in FIG. 3. This result indicates that apatite forming rate is increased when 20CaO-80SiO 2 gel powder is added to PMMA powder by weight 30% instead of 10%. Therefore, the rate of binding to bones could be increased.
  • PMMA/CaO-Si0 2 bone cement according to this invention can bind to bones due to the ability of forming apatite on the surface when it was soaked in SBF. Moreover, it can be used as an adhesive which fixes metal, polymer, ceramics etc. to bones and can be used under the load because it can bind to bones firmly at a short time. Furthermore, since the inventive bone cement has fluidity as conventional PMMA bone cement, it can be used as a substitute for injectable bone for repairing bone defects caused by osteoporosis and others. Therefore, bone cement according to this invention can be used for not only fixating implant such as artificial joint in orthopedics but also repairing bones or teeth, and filling defects.

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Abstract

La présente invention concerne un mélange destiné à la production de ciment d'os bioactif. Ce mélange est fait de polyméthyl-méthacrylate (PMMA) en poudre et de gel à base de CaO-SiO2. L'invention concerne également un procédé de production d'un ciment d'os bioactif au moyen de ce mélange. L'invention concerne plus particulièrement, d'une part un procédé de production de ciment d'os à base de PMMA/CaO-SiO2 par adjonction d'une solution de méthyl-méthacrylate (MMA) à un mélange de gel de CaO-SiO2 et de PMMA en poudre, et d'autre part un ciment d'os à base de PMMA/CaO-SiO2 produit selon le procédé de l'invention. Ce ciment d'os à base de PMMA/cao-sio2, qui convient pour coller aux os les métaux, les polymères, et les céramiques notamment, convient également à une utilisation sous la charge car il peut se lier fermement aux os en un temps très court.
PCT/KR2003/001916 2003-07-31 2003-09-19 Melange pour produire du ciment d'os bioactif et procede de production de ciment d'os bioactif au moyen de ce melange WO2005011763A1 (fr)

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AU2003264957A AU2003264957A1 (en) 2003-07-31 2003-09-19 Mixture for producing a bioactive bone cement and method for producing a bioactive bone cement using the same

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KR10-2003-0053233 2003-07-31
KR1020030053233A KR100559171B1 (ko) 2003-07-31 2003-07-31 생체활성 골 시멘트 제조용 혼합물 및 이를 이용한생체활성 골 시멘트의 제조방법

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293115B (zh) * 2008-06-25 2011-05-04 山东大学 一种在聚合物中引入SiO2制备具有生物活性多孔支架的方法
CN103550823A (zh) * 2013-11-07 2014-02-05 中山大学 一种可注射复合型骨水泥及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101007182B1 (ko) * 2008-04-30 2011-01-12 한국지질자원연구원 하이브리드 나노 복합체를 이용한 생체 조성물 및 그제조방법
KR100890935B1 (ko) * 2008-04-30 2009-04-02 한국지질자원연구원 피이이케이와 산화칼슘-이산화규소를 이용한 인공골용생체활성 복합체 및 제조방법
KR101486241B1 (ko) * 2013-07-11 2015-01-27 한국지질자원연구원 칼슘용액 유래 규산칼슘계 화합물로부터 유사체액에서의 생체활성능 평가방법

Citations (4)

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Publication number Priority date Publication date Assignee Title
US5527836A (en) * 1992-02-28 1996-06-18 Nippon Electric Glass Co., Ltd. Bioactive cement
JPH11164879A (ja) * 1997-12-08 1999-06-22 Nippon Electric Glass Co Ltd 生体活性セメント組成物
JP2000005297A (ja) * 1998-06-26 2000-01-11 Nippon Electric Glass Co Ltd 生体活性セメント組成物
US20010034662A1 (en) * 2000-02-16 2001-10-25 Morris Robert A. Method and system for facilitating a sale

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5527836A (en) * 1992-02-28 1996-06-18 Nippon Electric Glass Co., Ltd. Bioactive cement
JPH11164879A (ja) * 1997-12-08 1999-06-22 Nippon Electric Glass Co Ltd 生体活性セメント組成物
JP2000005297A (ja) * 1998-06-26 2000-01-11 Nippon Electric Glass Co Ltd 生体活性セメント組成物
US20010034662A1 (en) * 2000-02-16 2001-10-25 Morris Robert A. Method and system for facilitating a sale

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293115B (zh) * 2008-06-25 2011-05-04 山东大学 一种在聚合物中引入SiO2制备具有生物活性多孔支架的方法
CN103550823A (zh) * 2013-11-07 2014-02-05 中山大学 一种可注射复合型骨水泥及其制备方法和应用

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AU2003264957A1 (en) 2005-02-15
KR20050014570A (ko) 2005-02-07

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