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WO2008039002A1 - Ciments au phosphate de calcium hautement résistants - Google Patents

Ciments au phosphate de calcium hautement résistants Download PDF

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Publication number
WO2008039002A1
WO2008039002A1 PCT/KR2007/004716 KR2007004716W WO2008039002A1 WO 2008039002 A1 WO2008039002 A1 WO 2008039002A1 KR 2007004716 W KR2007004716 W KR 2007004716W WO 2008039002 A1 WO2008039002 A1 WO 2008039002A1
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WO
WIPO (PCT)
Prior art keywords
calcium phosphate
cement
acid
phosphate cement
phosphate
Prior art date
Application number
PCT/KR2007/004716
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English (en)
Inventor
Sung Soo Kim
Original Assignee
Korea Reserach Institute Of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Reserach Institute Of Chemical Technology filed Critical Korea Reserach Institute Of Chemical Technology
Publication of WO2008039002A1 publication Critical patent/WO2008039002A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • C04B28/346—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more phosphates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/02—Phosphate cements
    • C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications

Definitions

  • the present invention relates to a calcium phosphate cement, and, more particularly, to a high- strength calcium phosphate cement having a short setting time for joining bone, which is produced by mixing calcium phosphate powder, such as dicalcium phosphate anhydrous (DCPA) powder, tetracalcium phosphate (TTCP) powder, ⁇ - tricalcium phosphate ( ⁇ -TCP) powder, or the like, with biodegradable and water- insoluble polymeric acid powder.
  • DCPA dicalcium phosphate anhydrous
  • TTCP tetracalcium phosphate
  • ⁇ -TCP ⁇ - tricalcium phosphate
  • cement for joining bone has been widely used to set artificial joints, such as an artificial hip joint, an artificial knee joint, and the like, to fill missing bone portions after a brain operation, to provide a filler after a bone tumor operation, and to conduct bone fracture treatment, plastic surgery, dental treatment, and the like.
  • Acrylic cement which includes polymethylmethacrylate (PMMA) as a main component, has been chiefly used as this cement for joining bone.
  • PMMA polymethylmethacrylate
  • this acrylic cement has high mechanical strength, it is disadvantageous in that it cannot regenerate bone tissue because it is not biodegradable. Further, although this acrylic cement has been recently applied to vertebroplasty for osteoporosis patients, it has a problem in that it damages vertebral nerves because the reaction is highly exothermic, and thus patients may become paralyzed on one side.
  • Neutral or basic calcium phosphates such as tetracalcium phosphate (TTCP), ⁇ -tricalcium phosphate ( ⁇ -TCP), and the like
  • acidic calcium phosphates such as dicalcium phosphate anhydrous (DCPA), monocalcium phosphate monohydrate (MCPM), dicalcium phosphate dihydrate (DCPD), and the like
  • DCPA dicalcium phosphate anhydrous
  • MCPM monocalcium phosphate monohydrate
  • DCPD dicalcium phosphate dihydrate
  • Citric acid, maleic acid, etc., and salts thereof are used as the setting accelerator.
  • calcium phosphate particles include powder, which is a main component, and an aqueous solution containing a setting acceleration material, such as phosphate, when these calcium phosphate cements are used in a clinical usage, they are injected by appropriately mixing the powder with the aqueous solution prior to the use thereof, or are directly injected into the affected part of the body.
  • a setting acceleration material such as phosphate
  • calcium phosphate cement has low mechanical properties. That is, compact bone has a compression strength of 130 ⁇ 220 MPa and a tensile strength of 80 ⁇ 150 MPa, and acrylic cement has a compression strength of 100 ⁇ 110 MPa and a tensile strength of 32 ⁇ 34 MPa. In contrast, calcium phosphate cement at most has a compression strength of 10 ⁇ 55 MPa and a tensile strength of 2.1 MPa.
  • calcium phosphate cement has a problem in that it is limitedly used only in affected parts suffered with a low load and requiring low strength, such as the hands, arms, face, and the like, and it cannot be used in affected parts suffered with a high load and requiring high strength, such as the vertebrae, legs, and the like. Disclosure of Invention Technical Problem
  • the present invention has been made to overcome the above problems occurring in the prior art, and an object of the present invention is to provide a high- strength calcium phosphate cement having a short setting time, which is produced by mixing calcium phosphate powder with a biodegradable and water- insoluble polymeric organic compound and using a polyvalent organic acid compound as a setting accelerator.
  • the present invention provides a high- strength calcium phosphate cement having a short setting time for joining bone, which is produced by mixing calcium phosphate powder, such as dicalcium phosphate anhydrous (DCPA), monocalcium phosphate monohydrate (MCPM), tetracalcium phosphate (TTCP), ⁇ -tricalcium phosphate ( ⁇ -TCP), or the like, with biodegradable and water-insoluble polymeric acid powder, such as polyaspartic acid (PAA), polyglutamic acid (PGA), alginic acid (AA), carrageenanic acid (CA), or the like.
  • DCPA dicalcium phosphate anhydrous
  • MCPM monocalcium phosphate monohydrate
  • TTCP tetracalcium phosphate
  • ⁇ -TCP ⁇ -tricalcium phosphate
  • biodegradable and water-insoluble polymeric acid powder such as polyaspartic acid (PAA), polyglutamic acid (PGA), alginic acid (AA), carrageenanic
  • the present invention provides a high-strength and biodegradable cement, including a water-insoluble and biodegradable polymeric acid compound.
  • the calcium phosphate cement according to the present invention is advantageous in that, since it has a short setting time and high strength, the range of application thereof can be expanded.
  • FIG. 1 shows the schematic of ionic crosslinks through ionic bonds between hydroxy apatite and acidic biodegradable polymers in the calcium phosphate cement:
  • FIG. 2 shows calcium phosphate cement (CPC) and a process of injecting the calcium phosphate cement((l) ⁇ -PGA/ ⁇ -TCP;(2) 10% citric acid;(3) The mixture of (1) and (2); (4) PBS);
  • FIG. 3 is a graph showing the weight change in the CPC depending on the incubation time((a) Example 5 ;(b) Comparative example 5);
  • FIG. 4 is a graph comparing the compression strength of the CPC of the present invention with those of the commercial products. Best Mode for Carrying Out the Invention
  • the present invention provides a calcium phosphate cement composition for joining bone, which is produced by mixing a calcium phosphate compound with one or more biodegradable and water-insoluble polymeric acids selected from among polyaspartic acid (PAA), polyglutamic acid (PGA), alginic acid (AA), and carrageenanic acid (CA).
  • PAA polyaspartic acid
  • PGA polyglutamic acid
  • AA alginic acid
  • CA carrageenanic acid
  • the calcium phosphate cement of the present invention is produced by mixing the calcium phosphate cement composition, in which the powdered calcium phosphate compound and the powdered biodegradable polymeric acid compound are mixed and pulverized, with water.
  • the amount of water in the mixture of the mixed and pulverized calcium phosphate compound and biodegradable polymeric acid compound may be in the range of 25 ⁇ 40 parts by weight.
  • the amount of water is below 25 parts by weight, there is a problem in that the viscosity of the cement is excessively high, and thus the cement is difficult to handle.
  • the amount of water is above 40 parts by weight, there is a problem in that the viscosity of the cement is excessively low, and thus the cement runs.
  • the cement when the cement is applied to a human body, there is a problem in that the cement may be lost in body fluids.
  • a setting accelerator or a setting adjuster may be selectively added to the calcium phosphate cement. It has been found that the setting time of the calcium phosphate cement is decreased to about 5 - 10 minutes using the setting accelerator or setting adjuster, and that the compression strength thereof is increased to 60 MPa or more. The present invention is accomplished based on these findings. When the setting time thereof is above 10 minutes, at the time of applying the cement to the human body, the cement is not cured at one joining part, partially washes out along with body fluids, and is thus lost, so that the cement can not act for joining bones and can be harmful to the human body.
  • a biodegradable calcium phosphate cement having improved strength and a short setting time can be produced by introducing water- insoluble and biodegradable polymeric acid compounds thereinto.
  • the calcium phosphate compound may be one or more powdered calcium phosphate compounds selected from among dicalcium phosphate anhydrous (DCPA), tetracalcium phosphate (TTCP), and ⁇ -tricalcium phosphate ( ⁇ -TCP).
  • DCPA dicalcium phosphate anhydrous
  • TTCP tetracalcium phosphate
  • ⁇ -TCP ⁇ - tricalcium phosphate
  • the strength of the calcium phosphate cement is improved by adding a polymeric compound, which can increase the strength thereof by forming ionic crosslinks through ionic bonds, to the calcium phosphate cement. Since the polymeric compound has relatively high flexibility, the polymeric compound serves to improve the material properties of cement, which is weak and brittle.
  • This method of improving the strength of the calcium phosphate cement by adding the polymeric compound is similar to a method of reinforcing an earthen brick by putting straw therein or a method of reinforcing a lime-plastered wall by adding algin, extracted from brown seaweed, thereto.
  • the polymeric acid compound (R-COOH) has acidic functional groups, such as a carboxylic acid group, a sulfonic acid group, and the like. These acidic functional groups are ionized in water, and thus hydrogen ions are formed, as represented by Equation 1. These hydrogen ions accelerate the ionization of calcium phosphate, as represented by Equation 2. Further, this polymeric acid compound is reacted with calcium ions and thus ionic-bonded therewith, as represented by Equation 3. Since this polymeric acid compound has a large number of acidic functional groups in the molecule thereof, ionic crosslinks are formed through ionic bonds.
  • acidic functional groups such as a carboxylic acid group, a sulfonic acid group, and the like. These acidic functional groups are ionized in water, and thus hydrogen ions are formed, as represented by Equation 1. These hydrogen ions accelerate the ionization of calcium phosphate, as represented by Equation 2. Further, this polymeric acid compound is reacted with calcium ions and thus
  • FIG. 1 shows the formation of ionic crosslinks through ionic bonds between hydroxyapatite and acidic biodegradable polymers in the calcium phosphate cement.
  • the salts of the polymeric acid compound can also form ionic crosslinks. However, according to the experiment of the present invention, it was found that they accelerate the absorption of water into cement, thus decreasing the strength of the cement, contrary to expectations. The reason for this is determined to be that the cations and phosphate ions adhered on the salts of the polymeric acid compound are reacted with each other, thus forming water-soluble salts, and the functional groups of the salts of the organic acid, which are not bonded with calcium ions, accelerate the absorption of water.
  • the polymeric acid compound of the present invention may include compounds which can be biodegraded in the body, such as polyaspartic acid, polyglutamic acid, alginic acid, carrageenanic acid, and the like. These compounds are characterized in that, since these compounds, which are kinds of amino acid polymers or polysaccharides, are hydrolyzed or decomposed by an enzyme in the body, they cause few side effects in the human body.
  • the amount of the polymeric acid compound may be 1 ⁇ 50 parts by weight, and more preferably 5 - 30 parts by weight, based on 100 parts by weight of the calcium phosphate compound.
  • the amount of the polymeric acid compound is much more than that of the calcium phosphate compound, the number of hydrophilic functional groups, which are not bonded with calcium ions, is increased, so that the absorption of water is increased, thereby decreasing the strength of the cement.
  • the amount of the polymeric acid compound is much less than that of the calcium phosphate compound, insufficient ionic crosslinks are formed, and thus the strength of the cement is not good.
  • the setting accelerator of the present invention may include phosphate compounds, which accelerate the formation of hydroxy apatite (HA) by accelerating the precipitation reaction of calcium ions and phosphate ions, such as NaH PO , K HPO , NH
  • H PO hydroxy apatite
  • HA hydroxy apatite
  • organic acids such as citric acid, maleic acid, propionic acid, and the like, may be added to the cement, so that the ionization of calcium phosphate is accelerated, thereby accelerating the setting of the cement.
  • the setting accelerator it was found that a setting time of about 10 minutes was attained.
  • the setting adjuster of the present invention serving to control the setting rate of the cement, may be citrate, pyrophosphate, or the like.
  • the calcium phosphate cement according to the present invention is advantageous in that, when it is injected into bone fracture portions or bone defect portions, it can join bone tissue because a setting reaction takes place, and can regenerate the bone tissue because it is biodegradable and thus slowly decomposes in the body.
  • the compression strength of the calcium phosphate cement was measured using a universal testing machine (UTM 4482, manufactured by Instron Corp.) according to ASTM F451-86.
  • UTM 4482 manufactured by Instron Corp.
  • ASTM F451-86 the crosshead rate in the compression strength test was 20 mm/ min, and cylindrical samples having a diameter of 6 mm and a length of 20 mm were used.
  • the DTS of the calcium phosphate cement was measured using a universal testing machine (UTM 4482, manufactured by Instron Corp.). In this case, the crosshead rate in the DTS test was 20 mm/min, and cylindrical samples having a diameter of 6 mm and a height of 3 mm were used.
  • the cement was put into an incubator having a temperature of 37 0 C and a relative humidity of 100%. Subsequently, the cement was pressed with a Vicat needle having a diameter of 1 mm by applying a force of 400 gf to the Vicat needle. Then, the time period to the time at which any recognizable mark did not remain on the cement was defined as the setting time.
  • lOOg of ⁇ -TCP particles having an average particle size of 8 D was mixed with 1Og of ⁇ -PGA particles having a molecular weight of 2,000,000 g/mol, and then the mixture was stirred and pulverized using a ball mill at a rotational speed of 230 rpm for 24 hours to form the powder component of the cement.
  • the calcium phosphate powder component and a 10% citric acid solution as a liquid component were mixed at a ratio of 2: 1 (the ratio of the weight (g) of the calcium phosphate powder to the volume (ml) of the citric acid solution), and then the mixed solution was put into a syringe.
  • the cement was injected into a glass tube and then left in a PBS (phosphate-buffered saline) solution for 7 days.
  • PBS phosphate-buffered saline
  • FIG. 2 shows calcium phosphate cement (CPC) and a process of injecting the calcium phosphate cement.
  • ⁇ -TCP-citric acid cement was produced using the same method as in Example 1, except that PGA was not used.
  • the compression strength of the ⁇ -TCP-citric acid cement was 12.7+1.2 MPa
  • the DTS thereof was 2.4+0.8 MPa
  • the setting time thereof was about 12 minutes.
  • lOOg of TTCP particles having an average particle size of 5 D was mixed with 2Og of alginic acid particles, and then the mixture was stirred and pulverized using a ball mill at a rotational speed of 230 rpm for 24 hours to form the powder component of the cement.
  • the calcium phosphate powder componentand a 10% citric acid solution as a liquid component were mixed at a ratio of 2: 1 (the ratio of the weight (g) of the calcium phosphate powder to the volume (ml) of the citric acid solution), and then the mixed solution was put into a syringe.
  • the cement was injected into a glass tube and then left in a PBS (phosphate -buffered saline) solution for 7 days.
  • PBS phosphate -buffered saline
  • the sample was put in acetone for 1 hour, thus ceasing the dissociation-precipitation reaction in the cement, and was then dried.
  • the compression strength of the calcium phosphate cement was 61.5+10.0 MPa
  • the DTS thereof was 18.9+1.8 MPa
  • the setting time thereof was about 5 minutes.
  • TTCP-citric acid cement was produced using the same method as in Example 2, except that alginic acid was not used.
  • the compression strength of the TTCP-citric acid cement was 10.7+1.9 MPa
  • the DTS thereof was 2.1+0.5 MPa
  • the setting time thereof was about 20 minutes.
  • DCPA CaHPO 4 particles having an average particle size of 5 D, and then 1Og of polyaspartic acid particles, having a molecular weight of about 20,000 g/mol, was mixed therewith. Thereafter, the mixture was stirred and pulverized using a ball mill at a rotational speed of 230 rpm for 24 hours to form the powder component of the cement. Subsequently, the calcium phosphate powder componentand a 2.5% by weight Na HPO solution as a liquid component were mixed at a ratio of 2: 1 (the ratio of the weight (g) of the calcium phosphate powder to the volume (ml) of the Na HPO solution), and then the mixed solution was put into a syringe. Subsequently, the cement was injected into a glass tube and then left in a PBS (phosphate-buffered saline) solution for 7 days.
  • PBS phosphate-buffered saline
  • the sample was put in acetone for 1 hour, thus ceasing the dissociation-precipitation reaction in the cement, and was then dried.
  • the compression strength of the calcium phosphate cement was 52.5+6.2 MPa
  • the DTS thereof was 14.9+1.2 MPa
  • the setting time thereof was about 10 minutes.
  • Example 3 except that polyaspartic acid was not used.
  • the compression strength of the ⁇ -TCP-DCPA cement was 10.2+1.2 MPa MPa
  • the DTS thereof was 1.6+0.5 MPa
  • the setting time thereof was about 30 minutes.
  • DCPA calcium phosphate powder component and a 15% citric acid solution as a liquid component were mixed at a ratio of 2:1 (the ratio of the weight (g) of the calcium phosphate powder to the volume (ml) of the citric acid solution), and then the mixed solution was put into a syringe. Subsequently, the cement was injected into a glass tube and then left in a PBS (phosphate -buffered saline) solution for 7 days.
  • PBS phosphate -buffered saline
  • the sample was put in acetone for 1 hour, thus ceasing the dissociation-precipitation reaction in the cement, and was then dried.
  • the compression strength of the calcium phosphate cement was 55.7+5.3 MPa
  • the DTS thereof was 14.9+1.2 MPa
  • the setting time thereof was about 6 minutes.
  • TTCP-DCPA cement was produced using the same method as in
  • Example 4 except that carrageenanic acid was not used.
  • the compression strength of the TTCP-DCPA cement was 6.2+1.2 MPa
  • the DTS thereof was 1.2+0.5 MPa
  • the setting time thereof was about 25 minutes.
  • PGA-TCP cements was produced using the same method as in Example 1, except that the mixed ratio of the ⁇ -PGA-incorporated ⁇ -TCP powder (weight(g)) to the citric acid solution (volume (ml)) was 5:2.
  • TCP-citric acid cement was produced usign the same as in
  • Example 5 except that ⁇ -PGA was not used.
  • Example 5 Comparative Example 5.
  • PBS phosphate-buffered saline
  • incubation times were 0, 1, 2, and 3 months, respectively.
  • the decomposition rate of the CPC was evaluated by measuring the weight of the CPC. The results are shwon in FIG 4.
  • FIG. 3 is a graph showing the weight change in the CPC depending on the incubation time.
  • FIG. 4 is a graph comparing the compression strength of the CPC of the present invention with those of the commercial products.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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Abstract

L'invention concerne un ciment au phosphate de calcium hautement résistant, à court temps de prise pour jonction d'os, caractérisé en ce qu'il est produit par mélange d'une poudre de phosphate de calcium, tel que du phosphate dicalcique anhydre (DCPA), du phosphate tétracalcique (TTCP), du phosphate α-tricalcique (α-TCP), ou analogue, avec une poudre acide polymère biodégradable et insoluble dans l'eau, telle que l'acide polyaspartique (PAA), l'acide polyglutamique (PGA), l'acide alginique (AA), l'acide des carraghénanes (CA), ou analogue.
PCT/KR2007/004716 2006-09-28 2007-09-27 Ciments au phosphate de calcium hautement résistants WO2008039002A1 (fr)

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KR1020060094548A KR100844136B1 (ko) 2006-09-28 2006-09-28 고강도 인산칼슘 시멘트
KR10-2006-0094548 2006-09-28

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CN115417642B (zh) * 2022-09-21 2023-06-30 成都精准混凝土有限公司 一种低碳混凝土及其制备方法

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CN112546294A (zh) * 2020-12-03 2021-03-26 上海纳米技术及应用国家工程研究中心有限公司 聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法及其产品和应用

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