CN103849350A - Biological bone binder and preparation method thereof - Google Patents
Biological bone binder and preparation method thereof Download PDFInfo
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- CN103849350A CN103849350A CN201210499975.4A CN201210499975A CN103849350A CN 103849350 A CN103849350 A CN 103849350A CN 201210499975 A CN201210499975 A CN 201210499975A CN 103849350 A CN103849350 A CN 103849350A
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- tamanori
- biological bone
- prepolymer
- calcium carbonate
- hydroxyapatite
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Abstract
The invention discloses a preparation method of a biological bone binder. The preparation method comprises that dibenzylmethane-4,4'-diisocyanate (MDI) and polyol undergo a reaction to produce a prepolymer, and the prepolymer, polyol as a curing agent and hydroxyapatite and calcium carbonate as fillers are mixed according to a certain ratio and then undergo a reaction at a room temperature for 1-30min to produce the biological bone binder having controllable curing time. The biological bone binder comprises, by weight, 20-50% of MDI, 35-55% of polytetrahydrofuran glycol, 0-2% of 1,4-butylene glycol, 0-10% of polyglycidol, 0-6% of hydroxyapatite and 10-30% of calcium carbonate. The preparation method has the characteristics of mild reaction conditions, high bonding strength after curing, low heat released by a curing reaction, adjustable curing time and adjustable curing strength.
Description
Technical field
The present invention relates to field of medical materials, relate in particular to a kind of biological bone tamanori and preparation method thereof.
Background technology
For unstable fracture, the particularly treatment of serious comminuted fracture, is difficult to fix with gypsum, technique for fixing in conventionally needing.In addition, in Spinal Trauma, fracture of the sternum treatment, conventional screw, draw point, steel wire, silk thread etc. are fixed fracture site, but this method can be brought larger misery to patient, also may cause the sequela such as limbs disturbance.
Adopting medical bio bone tamanori to carry out bonding reset to bone fragment is more promising a kind of methods for the treatment of at present.Conventionally adopt the methods such as cyanoacrylate biological bone tamanori, polymethylmethacrylate biological bone tamanori, series of calcium phosphate bone cement, sodium alginate biological bone tamanori to realize bone at present bonding.But all there is larger defect in aforesaid method, thereby can not get widespread use in different application performance.The most general problem is: solidified surface needs to process, and Waterproofing/oilproofing performance is poor; There is to some extent the foreign body reaction to biological tissue, hinder organization healing; Curing polymkeric substance is emitted toxic substance in reaction process; Polymkeric substance water repelling property is poor, facile hydrolysis, and hydrolysate has toxicity; The heat that solidification process produces, heat easily makes bonding plane tissue sustain damage etc.It is significant that research and development have the biological bone tamanori that can realize quick-binding under good biocompatibility, degradable, normal temperature and not affect union of fracture characteristic etc.
Summary of the invention
Biological bone tamanori provided by the invention, be with one taking MDI, polytetrahydrofuran diol, BDO, poly-R-GLYCIDOL, hydroxyapatite, calcium carbonate as raw material, the biological bone tamanori that a kind of set time of preparation is adjustable.
Biological bone tamanori provided by the invention and preparation method are as follows:
The feature of biological bone tamanori of the present invention is that component and weight percent content are: MDI 20-50%, polytetrahydrofuran diol 35-55%, BDO 0-2%, poly-R-GLYCIDOL 0-10%, hydroxyapatite 0-6%, calcium carbonate 10-30%.
The preparation method of prepolymer: take a certain amount of MDI melting at 38 DEG C, progressively add while stirring quantitative polytetrahydrofuran diol, be warmed up to 70 DEG C～90 DEG C reactions 4 hours; Cool to subsequently 50 DEG C, slowly add BDO, poly-R-GLYCIDOL, react and within 5-8 hour, obtain performed polymer.
The preparation method of weighting agent: by hydroxyapatite and calcium carbonate according to: hydroxyapatite 0-38%, the ratio of calcium carbonate 62-100% is mixed, and obtains weighting agent.
According to requirement set time, prepolymer and polyvalent alcohol, weighting agent are mixed in proportion, at room temperature reacting just can be bonding for bone after 0.2-2 hour.Tackiness agent solidified after 24 hours, and its maximum compressive strength can reach 40Mpa left and right; Tensile bond strength is greater than 2MPa.
Compared with prior art, the present invention adopts MDI and polytetrahydrofuran diol, BDO, gathers the polyol reactions such as R-GLYCIDOL, forms polymer network structure; Hydroxyapatite, calcium carbonate are filled in polymer network as weighting agent, and the organic and inorganic structure forming has good biocompatibility, and has higher mechanical strength.In addition, the present invention has solved conventional biological bone tamanori heat release problem in adhesion process by the method for performed polymer and polyol reaction; By adjusting the ratio of prepolymer pre-polymerization degree, prepolymer and polyvalent alcohol and inorganics, make the biological bone tamanori degraded gradually in 3-6 month after solidifying.
Brief description of the drawings
Embodiment
Embodiment 1
Take 80gMDI, melting at 38 DEG C, slowly adds 100g polytetrahydrofuran diol, 90 DEG C of reactions 4 hours, obtains performed polymer; By 15g hydroxyapatite, 120g calcium carbonate mixes, and obtains weighting agent; 75g polytetrahydrofuran diol is mixed with 135g weighting agent, add subsequently 240g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 1.5-2 hour set time, maximum compressive strength 37Mpa after 24 hours; Tensile bond strength 2.1Mpa.
Embodiment 2
Take 90gMDI, melting at 38 DEG C, slowly adds 80g polytetrahydrofuran diol, 70 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 5g1, and 4-butyleneglycol, the poly-R-GLYCIDOL of 10g, react and within 5 hours, obtain performed polymer.By 2.5g hydroxyapatite, 22.5g calcium carbonate mixes, and obtains weighting agent; 40g polytetrahydrofuran diol is mixed with 25g weighting agent, add subsequently 185g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 1-1.5 hour set time, maximum compressive strength 41Mpa after 24 hours; Tensile bond strength 2.8Mpa.
Embodiment 3
Take 90gMDI, melting at 38 DEG C, slowly adds 80g polytetrahydrofuran diol, 80 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 10g to gather R-GLYCIDOL, reacts and within 6 hours, obtains performed polymer; 40g polytetrahydrofuran diol is mixed with 50g calcium carbonate, add subsequently 185g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 1-1.5 hour set time, maximum compressive strength 43Mpa after 24 hours; Tensile bond strength 2.2Mpa.
Embodiment 4
Take 90gMDI, melting at 38 DEG C, slowly adds 35g polytetrahydrofuran diol, 80 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 20g to gather R-GLYCIDOL, reacts and within 8 hours, obtains performed polymer.By 5g hydroxyapatite, 20g calcium carbonate mixes, and obtains weighting agent; 45g polytetrahydrofuran diol is mixed with 25g weighting agent, add subsequently 150g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 1-1.5 hour set time, maximum compressive strength 39Mpa after 24 hours; Tensile bond strength 2.6Mpa.
Embodiment 5
Take 85gMDI, melting at 38 DEG C, slowly adds 40g polytetrahydrofuran diol, 80 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 2g BDO, reacts and within 5 hours, obtains performed polymer.By 2.5g hydroxyapatite, 17.5g calcium carbonate mixes, and obtains weighting agent; 20g polytetrahydrofuran diol is mixed with 20g weighting agent, add subsequently 132g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 0.2-0.5 hour set time, maximum compressive strength 31Mpa after 24 hours; Tensile bond strength 2.1Mpa.
Embodiment 6
Take 90gMDI, melting at 38 DEG C, slowly adds 40g polytetrahydrofuran diol, 80 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 5g to gather R-GLYCIDOL, reacts and within 8 hours, obtains performed polymer.By 15g hydroxyapatite, 25g calcium carbonate mixes, and obtains weighting agent; 60g polytetrahydrofuran diol is mixed with 40g weighting agent, add subsequently 135g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 0.5-1 hour set time, maximum compressive strength 47Mpa after 24 hours; Tensile bond strength 2.8Mpa.
Embodiment 7
Take 90gMDI, melting at 38 DEG C, slowly adds 140g polytetrahydrofuran diol, 80 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 5g to gather R-GLYCIDOL, reacts and within 8 hours, obtains performed polymer.40g polytetrahydrofuran diol is mixed with 60g calcium carbonate, add subsequently 215g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 1-2 hour set time, maximum compressive strength 42Mpa after 24 hours; Tensile bond strength 2.3Mpa.
Embodiment 8
Take 90gMDI, melting at 38 DEG C, slowly adds 100g polytetrahydrofuran diol, 80 DEG C of reactions 4 hours, cools to subsequently 50 DEG C, slowly adds 15g to gather R-GLYCIDOL, reacts and within 8 hours, obtains performed polymer.By 15g hydroxyapatite, 25g calcium carbonate mixes, and obtains weighting agent; 80g polytetrahydrofuran diol is mixed with 80g weighting agent, add subsequently 200g performed polymer, fully mix, obtain biological bone tamanori.
This biological bone tamanori 0.5-1 hour set time, maximum compressive strength 32Mpa after 24 hours; Tensile bond strength 2.0Mpa.
Claims (7)
1. a biological bone tamanori, it is characterized in that: component and weight percent content are: MDI (molecular weight 1000) 20-50%, polytetrahydrofuran diol 35-55%, 1,4-butyleneglycol 0-2%, poly-R-GLYCIDOL (molecular weight 1000) 0-10%, hydroxyapatite 0-6%, calcium carbonate 10-30%.
2. biological bone tamanori as claimed in claim 1, is characterized in that: form prepolymer by MDI and polyvalent alcohol.
3. biological bone tamanori as claimed in claim 1, is characterized in that: form weighting material by hydroxyapatite and calcium carbonate.
4. prepolymer as claimed in claim 2, it is characterized in that: component and weight percent content are: MDI quality accounts for the 38-67% of prepolymer total mass, polytetrahydrofuran diol quality accounts for the 25-60% of prepolymer total mass, 1,4-butyleneglycol quality accounts for the 0-3% of prepolymer total mass, and poly-R-GLYCIDOL quality accounts for the 0-14% of prepolymer total mass.
5. biological bone tamanori weighting agent as claimed in claim 3, is characterized in that: component and weight percent content are: hydroxyapatite quality accounts for the 0-38% of weighting agent total mass, and calcium carbonate quality accounts for the 62-100% of weighting agent total mass.
6. biological bone tamanori as claimed in claim 1, is characterized in that: the preparation method of prepolymer is as follows:
After MDI is mixed with polytetrahydrofuran diol, under anhydrous and oxygen-free condition, 70 DEG C～90 DEG C reactions 4 hours, cool to subsequently 50 DEG C, slowly add BDO and poly-R-GLYCIDOL, react and within 5-8 hour, obtain performed polymer.
7. biological bone tamanori as claimed in claim 1, is characterized in that: prepolymer is mixed with polytetrahydrofuran diol, weighting agent, just can obtain biological bone tamanori after 0.2-2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210499975.4A CN103849350A (en) | 2012-11-30 | 2012-11-30 | Biological bone binder and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210499975.4A CN103849350A (en) | 2012-11-30 | 2012-11-30 | Biological bone binder and preparation method thereof |
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| CN103849350A true CN103849350A (en) | 2014-06-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109260505A (en) * | 2018-11-12 | 2019-01-25 | 上海交通大学 | A kind of multi-component bone jointing material and application method |
| CN111744053A (en) * | 2020-05-19 | 2020-10-09 | 湖北大学 | Dual-network surgical adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266608A (en) * | 1990-06-29 | 1993-11-30 | Technion Research & Dev't Foundation, Ltd. | Biomedical adhesive compositions |
| CN1942497A (en) * | 2004-03-03 | 2007-04-04 | 联邦科学和工业研究组织 | Biocompatible polymer compositions for dual or multistaged curing |
| CN101391113B (en) * | 2008-11-07 | 2012-09-19 | 四川大学 | Polyurethane medical compound film and preparation method thereof |
-
2012
- 2012-11-30 CN CN201210499975.4A patent/CN103849350A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266608A (en) * | 1990-06-29 | 1993-11-30 | Technion Research & Dev't Foundation, Ltd. | Biomedical adhesive compositions |
| CN1942497A (en) * | 2004-03-03 | 2007-04-04 | 联邦科学和工业研究组织 | Biocompatible polymer compositions for dual or multistaged curing |
| CN101391113B (en) * | 2008-11-07 | 2012-09-19 | 四川大学 | Polyurethane medical compound film and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109260505A (en) * | 2018-11-12 | 2019-01-25 | 上海交通大学 | A kind of multi-component bone jointing material and application method |
| CN109260505B (en) * | 2018-11-12 | 2021-02-09 | 上海交通大学 | Multi-component bone adhesive material and using method thereof |
| CN111744053A (en) * | 2020-05-19 | 2020-10-09 | 湖北大学 | Dual-network surgical adhesive and preparation method thereof |
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Inventor after: Xi Huahui Inventor before: Xi Huahui Inventor before: Zhang Yue Inventor before: Wang Xiaoxiong Inventor before: Li Zhaolong |
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Effective date of registration: 20150717 Address after: 100084 11-302, Beijing, Haidian District, Tsinghua University Applicant after: Xi Huahui Address before: 100084 11-302, Beijing, Haidian District, Tsinghua University Applicant before: Xi Huahui Applicant before: Zhang Yue Applicant before: Wang Xiaoxiong Applicant before: Li Zhaolong |
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