CN114106397A - Preparation method of low-modulus porous PMMA (polymethyl methacrylate) bionic bone cement, product and application thereof - Google Patents
Preparation method of low-modulus porous PMMA (polymethyl methacrylate) bionic bone cement, product and application thereof Download PDFInfo
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 80
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 80
- 239000002639 bone cement Substances 0.000 title claims abstract description 72
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 108010010803 Gelatin Proteins 0.000 claims abstract description 64
- 229920000159 gelatin Polymers 0.000 claims abstract description 64
- 239000008273 gelatin Substances 0.000 claims abstract description 64
- 235000019322 gelatine Nutrition 0.000 claims abstract description 64
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 35
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 33
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 16
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 16
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000003592 biomimetic effect Effects 0.000 claims description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003462 bioceramic Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 210000000988 bone and bone Anatomy 0.000 description 4
- 208000001132 Osteoporosis Diseases 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 208000001164 Osteoporotic Fractures Diseases 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 206010010214 Compression fracture Diseases 0.000 description 1
- 206010034156 Pathological fracture Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 208000016097 disease of metabolism Diseases 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000001009 osteoporotic effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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Abstract
The invention relates to a preparation method of low-modulus porous PMMA bionic bone cement, a product and application thereof.A gelatin pore-making technology is used, inorganic calcium salt particles are suspended in a gelatin solution, and glutaraldehyde is added to make the inorganic calcium salt particles cross-linked; freeze drying the cross-linking solution, crushing and sieving the product to obtain gelatin coated calcium salt particles with different particle sizes; uniformly mixing the particles and PMMA bone cement powder, and blending the mixture with a curing liquid to prepare the low-modulus porous PMMA bionic bone cement. According to the invention, inorganic calcium salt particles coated by gelatin are used as a filler and a pore-forming agent, and the particle size with a controllable range is favorable for forming a uniform micropore structure and promoting cells to grow in micropores; the gelatin and PMMA have good compatibility, the influence on the compressive strength of the bone cement is small, and the low rigidity of the gelatin reduces the elastic modulus of the PMMA bone cement, thereby meeting the requirement of clinical use.
Description
Technical Field
The invention relates to a method in the technical field of biomedical materials, and relates to a preparation method of low-modulus porous PMMA (polymethyl methacrylate) bionic bone cement, a product and application thereof, in particular to a method for preparing low-modulus porous PMMA bionic bone cement by using a gelatin pore-making technology and preparing gelatin-coated inorganic calcium salt particles with controllable particle sizes as filling materials.
Background
Osteoporosis (OP) is a common systemic bone metabolic disease characterized by low bone mass and damage to bone microarchitectural tissue, which is prone to non-traumatic fractures. Osteoporotic Vertebral Compression Fractures (OVCFs) are the most common osteoporotic fractures, accounting for about 45% of osteoporotic fractures. The Percutaneous Vertebroplasty (PVP) is the most commonly used minimally invasive technology for treating OVCFs, the conventional PVP usually uses PMMA bone cement as filling bone cement, the bone cement has high mechanical strength but large elastic modulus and does not have osteogenesis stimulating bioactivity, and research reports show that about 8% -52% of patients with OVCFs can cause adjacent vertebral body to be compressed and fractured after PVP operation (acute vertebral fracture, AVF), so that the biomechanical performance of the PMMA bone cement is improved, the elastic modulus of the PMMA bone cement is reduced to be matched with the elastic modulus of the adjacent vertebral body, and the clinical requirement for reducing the risk of AVF occurrence is met.
Adding organic or inorganic bioactive filler into PMMA bone cement is an effective means for improving biocompatibility and biomechanical properties of bone cement, but in past researches, inorganic powder is often directly mixed with PMMA powder, so that the brittleness of bone cement is improved and the compressive strength is obviously reduced while the elastic modulus is reduced, for example, CPC and PMMA powder are compounded to prepare CPC/PMMA bone cement [ baoliu, journal of osteoporosis, 2012, china); compounding natural bone powder, chitosan and PMMA powder [ Kim SB, Biomaterials, 2004], and the like.
Disclosure of Invention
The invention aims to provide a preparation method of low-modulus porous PMMA bionic bone cement.
Yet another object of the present invention is to: provides a low-modulus porous PMMA bionic bone cement product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of porous PMMA bionic bone cement with low modulus is characterized in that a gelatin pore-making technology is used, inorganic calcium salt particles are suspended in gelatin solution, and glutaraldehyde is added to make the inorganic calcium salt particles cross-linked; freeze drying the cross-linking solution, crushing and sieving the product to obtain gelatin coated calcium salt particles with different particle sizes; uniformly mixing the particles and PMMA bone cement powder, and blending the mixture with a curing liquid to prepare the low-modulus porous PMMA bionic bone cement, which comprises the following steps:
(1) preparing gelatin coated inorganic calcium salt particles:
preparing 10% (g/mL) gelatin aqueous solution, adding inorganic calcium salt powder into the gelatin aqueous solution according to the proportion of 0.1-1:1 (g/mL), stirring at high speed for 10min at 35 ℃, and then continuously adding 1wt% glutaraldehyde solution with the volume of 1% of the gelatin solution for crosslinking for half an hour. Freezing the cross-linked solution with liquid nitrogen, and freeze-drying; crushing the dried product by using a mortar or a pulverizer, and sieving to obtain gelatin particles with different particle size ranges;
(2) the porous PMMA bone cement formula comprises:
the PMMA bone cement solid phase powder consists of 54 to 89 percent of polymethyl methacrylate, 5 to 40 percent of gelatin particles, 5 percent of barium sulfate developer and 1 percent of Benzoyl Peroxide (BPO) initiator, and the mass percentage of the components is that the total sum is 100 percent. The liquid phase consists of 85 to 99.5 percent of methyl methacrylate monomer, 0.25 to 7.75 percent of polymerization promoter N, N-dimethyl-p-toluidine and 0.25 to 7.75 percent of stabilizer hydroquinone, and the mass percentage of the components is 100 percent;
(3) mixing PMMA bone cement powder and curing liquid according to the solid-to-liquid ratio of 1.5-2g/mL to obtain the low-modulus porous PMMA bionic bone cement.
The inorganic calcium salt in the step (1) comprises calcium silicate, calcium phosphate and calcium sulfate biological ceramic powder.
The sieving in the step (1) is realized by using a micron-sized sieve, and the particle size can be in any range of 50-500 mu m.
The invention provides low-modulus porous PMMA bionic bone cement prepared by any one of the methods.
The invention provides application of bone cement in preparation of a low-modulus porous PMMA bionic bone cement preparation material.
Suspending inorganic calcium salt particles in gelatin solution, adding glutaraldehyde to make them cross-linked; freeze drying the cross-linking solution, crushing and sieving the product to obtain gelatin coated calcium salt particles with different particle sizes; and uniformly mixing the particles and PMMA bone cement powder, and blending the mixture with a curing liquid to prepare the low-modulus porous PMMA bionic bone cement.
The invention comprises the following steps:
1. preparing a gelatin water solution with the concentration of 10% (g/mL), wherein the preparation method is to stir and dissolve the gelatin water solution at 50 ℃.
2. Adding inorganic calcium salt powder into gelatin water solution at a ratio of 0.1-1:1 (g/mL), stirring at high speed at 35 deg.C for 10min, and adding 1wt% glutaraldehyde solution with a volume of 1% of the gelatin solution for crosslinking for half an hour.
3. Freezing the cross-linked solution with liquid nitrogen, and freeze-drying; and crushing the dried product by using a mortar or a pulverizer, and sieving to obtain the gelatin particles with different particle size ranges.
4. The PMMA bone cement solid phase powder consists of 54 to 89 percent of polymethyl methacrylate, 5 to 40 percent of gelatin particles, 5 percent of barium sulfate developer and 1 percent of Benzoyl Peroxide (BPO) initiator, and the mass percentage of the components is that the total sum is 100 percent. The liquid phase consists of methyl methacrylate monomer 85-99.5 wt%, polymerization promoter N, N-dimethyl p-toluidine 0.25-7.75 wt% and stabilizer hydroquinone 0.25-7.75 wt%, and the total amount is 100 wt%.
5. Mixing PMMA bone cement powder and curing liquid according to the solid-to-liquid ratio of 1.5-2g/mL to obtain the low-modulus porous PMMA bionic bone cement.
The invention has the advantages that:
1. inorganic calcium salt particles coated by gelatin are used as a filler and a pore-forming agent, and the particle size with controllable range is favorable for forming a uniform micropore structure and promoting the growth of cells in micropores.
2. The gelatin has better compatibility with PMMA, has less influence on the compressive strength of the bone cement, and the lower rigidity of the gelatin reduces the elastic modulus of the PMMA bone cement.
Drawings
FIG. 1 is an SEM image of porous PMMA biomimetic bone cement;
figure 2 is a graph of the compressive strength of PMMA bone cement doped with gelatin microparticles in different proportions.
Detailed Description
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation procedures are given, but the scope of the invention is not limited to the following examples.
Example 1
A low-modulus porous PMMA bionic bone cement uses a gelatin pore-making technology, inorganic calcium salt particles are suspended in a gelatin solution, and glutaraldehyde is added to make the inorganic calcium salt particles cross-linked; freeze drying, pulverizing and sieving the crosslinking solution to obtain gelatin coated calcium salt particles with different particle sizes; uniformly mixing the gelatin-coated calcium salt particles with PMMA bone cement powder, and blending the mixture with a curing liquid to prepare the low-modulus porous PMMA bionic bone cement, wherein the preparation method comprises the following steps:
(1) preparing gelatin coated inorganic calcium salt particles:
weighing 1g of gelatin, dissolving the gelatin in 10mL of ultrapure water, heating at 50 ℃ to prepare a solution to prepare a gelatin aqueous solution with the concentration of 10% (g/mL), adding 5g of inorganic calcium salt alpha-TCP powder into the solution, stirring at a high speed of 35 ℃ for 10min, and then continuously adding 1wt% glutaraldehyde solution with the volume of 1% of the gelatin solution for crosslinking for half an hour; freezing the cross-linked solution with liquid nitrogen, and freeze-drying; crushing the dried product by a crusher, sieving by a 100-mesh sieve and a 300-mesh sieve, and collecting particles smaller than 100 meshes and larger than 300 meshes;
(2) the porous PMMA bone cement formula comprises:
the PMMA bone cement solid phase powder comprises the following components in percentage by mass: consists of 84 percent of polymethyl methacrylate, 10 percent of gelatin particles, 5 percent of barium sulfate as a developing agent and 1 percent of Benzoyl Peroxide (BPO) as an initiator;
the curing liquid consists of 95 percent of methyl methacrylate monomer, 2.5 percent of polymerization promoter N, N-dimethyl-p-toluidine and 2.5 percent of stabilizer hydroquinone by mass percentage;
(3) mixing PMMA bone cement powder with curing liquid according to the solid-to-liquid ratio of 2g/mL to obtain the low-modulus porous PMMA bionic bone cement.
Example 2
A low-modulus porous PMMA biomimetic bone cement, otherwise identical to example 1 except that the proportion of gelatin microparticles was replaced with 20%, 30%, 40%, prepared by the following steps:
(1) preparing gelatin coated inorganic calcium salt particles:
preparing a gelatin aqueous solution with the concentration of 10% (g/mL), adding inorganic calcium salt powder into the gelatin aqueous solution according to the proportion of 0.1-1:1 (g/mL), stirring at a high speed of 35 ℃ for 10min, and then continuously adding 1wt% glutaraldehyde solution with the volume of 1% of the gelatin solution for crosslinking for half an hour; freezing the cross-linked solution with liquid nitrogen, and freeze-drying; crushing the dried product by using a mortar or a pulverizer, and sieving to obtain gelatin particles with different particle size ranges;
(2) the porous PMMA bone cement formula comprises:
(A) the PMMA bone cement solid phase powder comprises the following components in percentage by mass: consists of 74 percent of polymethyl methacrylate, 20 percent of gelatin particles, 5 percent of barium sulfate as a developing agent and 1 percent of Benzoyl Peroxide (BPO) as an initiator; and
(B) the PMMA bone cement solid phase powder comprises the following components in percentage by mass: consists of 64 percent of polymethyl methacrylate, 30 percent of gelatin particles, 5 percent of barium sulfate as a developing agent and 1 percent of Benzoyl Peroxide (BPO) as an initiator; and
(C) the PMMA bone cement solid phase powder comprises the following components in percentage by mass: consists of 54 percent of polymethyl methacrylate, 40 percent of gelatin particles, 5 percent of barium sulfate as a developing agent and 1 percent of Benzoyl Peroxide (BPO) as an initiator;
the curing liquid consists of 95 percent of methyl methacrylate monomer, 2.5 percent of polymerization promoter N, N-dimethyl-p-toluidine and 2.5 percent of stabilizer hydroquinone by mass percentage;
(3) and (C) mixing the PMMA bone cement powder and the curing liquid according to the solid-liquid ratio of 2g/mL to obtain the low-modulus porous PMMA bionic bone cement.
Cylindrical test specimens with a diameter of 6 mm. times.12 mm were prepared and tested for compressive strength according to YY0459-2003, the results are shown in the following table and FIG. 2. The sample with the content of 40 percent has a cross-section SEM picture shown in figure 1 after 2 weeks of degradation weight loss treatment
Example 3
The other process was the same as example 1 except that the inorganic calcium salt powder was replaced with hydroxyapatite from α -TCP to prepare a low-modulus porous PMMA biomimetic bone cement.
Example 4
The same as example 1 except that the inorganic calcium salt powder was replaced with calcium silicate powder from α -TCP, a low-modulus porous PMMA biomimetic bone cement was prepared.
Claims (6)
1. A preparation method of porous PMMA bionic bone cement with low modulus is characterized in that a gelatin pore-making technology is used, inorganic calcium salt particles are suspended in gelatin solution, and glutaraldehyde is added to make the inorganic calcium salt particles cross-linked; freeze drying, pulverizing and sieving the crosslinking solution to obtain gelatin coated calcium salt particles with different particle sizes; the method comprises the following steps of uniformly mixing the gelatin-coated calcium salt particles with PMMA bone cement powder, and blending the mixture with a curing liquid to prepare the low-modulus porous PMMA bionic bone cement, wherein the method comprises the following steps:
(1) preparing gelatin coated inorganic calcium salt particles:
preparing a gelatin aqueous solution with the concentration of 10% (g/mL), adding inorganic calcium salt powder into the gelatin aqueous solution according to the proportion of 0.1-1:1 (g/mL), stirring at a high speed of 35 ℃ for 10min, and then continuously adding 1wt% glutaraldehyde solution with the volume of 1% of the gelatin solution for crosslinking for half an hour; freezing the cross-linked solution with liquid nitrogen, and freeze-drying; crushing the dried product by using a mortar or a pulverizer, and sieving to obtain gelatin particles with different particle size ranges;
(2) the porous PMMA bone cement formula comprises:
the PMMA bone cement solid phase powder consists of 54 to 89 percent of polymethyl methacrylate, 5 to 40 percent of gelatin particles, 5 percent of barium sulfate as a developing agent and 1 percent of Benzoyl Peroxide (BPO) as an initiator according to mass percentage;
the curing liquid consists of 85 to 99.5 mass percent of methyl methacrylate monomer, 0.25 to 7.75 mass percent of polymerization promoter N, N-dimethyl p-toluidine and 0.25 to 7.75 mass percent of stabilizer hydroquinone;
(3) mixing PMMA bone cement powder and curing liquid according to the solid-to-liquid ratio of 1.5-2g/mL to obtain the low-modulus porous PMMA bionic bone cement.
2. The method for preparing low-modulus porous PMMA bionic bone cement according to the claim 1, characterized in that in the step (1), the inorganic calcium salt at least comprises one or more of calcium silicate, calcium phosphate, calcium sulfate bioceramic powder.
3. The method for preparing low-modulus porous PMMA bionic bone cement according to claim 1, characterized in that in step (1), the sieve is sieved by a micron-sized sieve with any particle size range between 50 and 500 μm.
4. The method for preparing the low-modulus porous PMMA bionic bone cement according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) preparing gelatin coated inorganic calcium salt particles:
weighing 1g of gelatin, dissolving the gelatin in 10mL of ultrapure water, heating at 50 ℃ to prepare a solution to prepare a gelatin aqueous solution with the concentration of 10% (g/mL), adding 5g of inorganic calcium salt alpha-TCP powder into the solution, stirring at a high speed of 35 ℃ for 10min, and then continuously adding 1wt% glutaraldehyde solution with the volume of 1% of the gelatin solution for crosslinking for half an hour; freezing the cross-linked solution with liquid nitrogen, and freeze-drying; crushing the dried product by a crusher, sieving by a 100-mesh sieve and a 300-mesh sieve, and collecting particles smaller than 100 meshes and larger than 300 meshes;
(2) the porous PMMA bone cement formula comprises:
the PMMA bone cement solid phase powder comprises the following components in percentage by mass: consists of 84 percent of polymethyl methacrylate, 10 percent of gelatin particles, 5 percent of barium sulfate as a developing agent and 1 percent of Benzoyl Peroxide (BPO) as an initiator;
the curing liquid consists of 95 percent of methyl methacrylate monomer, 2.5 percent of polymerization promoter N, N-dimethyl-p-toluidine and 2.5 percent of stabilizer hydroquinone by mass percentage;
(3) mixing PMMA bone cement powder with curing liquid according to the solid-to-liquid ratio of 2g/mL to obtain the low-modulus porous PMMA bionic bone cement.
5. A low modulus porous PMMA bionic bone cement, characterized in that it is obtained by the process according to any one of claims 1 to 4.
6. Use of the bone cement according to claim 4 in the preparation of a low modulus porous PMMA biomimetic bone cement preparation material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023109377A1 (en) * | 2021-12-17 | 2023-06-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for drug-loaded mesoporous calcium silicate modified pmma bone cement, product, and use |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1255382A (en) * | 1998-11-26 | 2000-06-07 | 瑞安大药厂股份有限公司 | Bone filler and its preparing process |
| CN103893829A (en) * | 2014-03-27 | 2014-07-02 | 西安理工大学 | Preparation method of injectable porous compound bone cement |
| CN105288741A (en) * | 2015-07-24 | 2016-02-03 | 苏州大学 | Acrylic compound bone cement with partial degradation function and preparation method of acrylic compound bone cement with partial degradation function |
| CN107412852A (en) * | 2017-07-26 | 2017-12-01 | 山东冠龙医疗用品有限公司 | Bone cement compositions and its set group |
| CN107812240A (en) * | 2017-10-19 | 2018-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano zinc oxide modified preparation method of antibacterial Injectable calcium-phosphate bone cement and products thereof and application |
| CN110339395A (en) * | 2018-04-03 | 2019-10-18 | 暨南大学 | A kind of hydration bone cement of PMMA base and the preparation method and application thereof |
-
2021
- 2021-11-09 CN CN202111321093.4A patent/CN114106397A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1255382A (en) * | 1998-11-26 | 2000-06-07 | 瑞安大药厂股份有限公司 | Bone filler and its preparing process |
| CN103893829A (en) * | 2014-03-27 | 2014-07-02 | 西安理工大学 | Preparation method of injectable porous compound bone cement |
| CN105288741A (en) * | 2015-07-24 | 2016-02-03 | 苏州大学 | Acrylic compound bone cement with partial degradation function and preparation method of acrylic compound bone cement with partial degradation function |
| CN107412852A (en) * | 2017-07-26 | 2017-12-01 | 山东冠龙医疗用品有限公司 | Bone cement compositions and its set group |
| CN107812240A (en) * | 2017-10-19 | 2018-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano zinc oxide modified preparation method of antibacterial Injectable calcium-phosphate bone cement and products thereof and application |
| CN110339395A (en) * | 2018-04-03 | 2019-10-18 | 暨南大学 | A kind of hydration bone cement of PMMA base and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BLANCA VA ZQUEZ ET AL.: ""Acrylic bone cements modified with b-TCP particles encapsulated with poly(ethylene glycol)"", 《BIOMATERIALS》 * |
| SHYH MING KUO ET AL.: ""Evaluating Chitosan/ -Tricalcium Phosphate/Poly(methylmethacrylate) Cement Composites as Bone-Repairing Materials"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023109377A1 (en) * | 2021-12-17 | 2023-06-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for drug-loaded mesoporous calcium silicate modified pmma bone cement, product, and use |
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