CN109381746A - A kind of preparation method and applications of lignin modification nanometer hydroxyapatite - Google Patents
A kind of preparation method and applications of lignin modification nanometer hydroxyapatite Download PDFInfo
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- CN109381746A CN109381746A CN201811193592.8A CN201811193592A CN109381746A CN 109381746 A CN109381746 A CN 109381746A CN 201811193592 A CN201811193592 A CN 201811193592A CN 109381746 A CN109381746 A CN 109381746A
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- nanometer hydroxyapatite
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- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- 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
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Abstract
The invention discloses a kind of method and its application that modifted-nano-hydroxyapatite is prepared using lignin liquor coprecipitation, this method, which refers to, is dissolved in water for lignin after purification, then inorganic phosphate saline solution is added by different proportion, reaction 0 ~ 3 hour, inorganic calcium salt is added again, keeping calcium phosphorus molar ratio is 1.67, adjust pH value between 10 ~ 13, after being stirred to react 4 ~ 6 hours at 50 ~ 80 DEG C, it stands overnight, washing, dry can be obtained can dispersibility significantly improves in methylene chloride modifted-nano-hydroxyapatite；It, which is made an addition to polylactic acid-based hydrophobic polymer mechanical property with 1 wt% ~ 15wt%, apparent reinforcing effect.The raw materials used abundance of the nanometer hydroxyapatite of the lignin modification, preparation method is simple, good biocompatibility, is expected to be developed into novel orthopaedics material.
Description
Technical field
The present invention relates to a kind of preparation method and applications of lignin modification nanometer hydroxyapatite, belong to bio-medical
Material Field.
Background technique
Nanometer hydroxyapatite [the Ca of synthesis10(PO4)6(OH)2, n-HA] because have it is identical with nature bone it is inorganic at
Point, thus there is good biocompatibility and bioactivity, it is usually used in compound to improve its osteoconductive with high polymer.But it grinds
Study carefully and show due to the intrinsic property easy to reunite of nanoparticle and poor with Study on Polymer Surfaces associativity, especially with hydrophobicity high polymer
It is difficult to obtain good interface cohesion, so that its mechanical property hardly results in improvement, it has also become urgently solve in bone material research
Problem certainly.
For the interface cohesion for solving the problems, such as n-HA inorganic particulate Yu hydrophobicity high polymer compound tense, n-HA has been carried out largely
Surface graft modification research is more, but major part n-HA may reunite before grafting, so that modified effect is little, dispersion
Property fails to be improved significantly, and grafting process is cumbersome, at high cost.And a large number of studies show that, it is introduced in n-HA preparation process
Some larger molecular organics can effectively improve its dispersibility.
Lignin (lignin, also known as lignin) is the second largest natural biomass resource abundant, is only second to cellulose, knot
Structure unit is the netted phenols high molecular polymer of the noncrystalline three-dimensional macromolecule of benzene propane, and contains hydrocarbon chain or phenyl ring parent
The hydrophilic radicals such as the lipophilic group and phenolic hydroxyl group, alcoholic extract hydroxyl group, carboxyl and sulfonic group of oil base group, and surface can be low.Lignin simultaneously
In a large amount of hydrophobic aromatic ring structure, the hydrophilic modifyings product such as sulfonation of lignosulfonates or alkali lignin, is natural
Amphiphilic macromolecule surfactant.The wooden usually modified direct utilization in the form of macromolecular, the network ball-shaped molecule energy of lignin
Enough increase the intensity of material, and prepolymer molecule chain is intertwine with each other or network interpenetrating will improve the toughness of material, therefore is expected to make
The standby material that intensity and elongation all improve out.And the Study of cytotoxicity of lignin shows the industrial lignin of purification to life
Object cell is nontoxic, but so far there are no is used for application in terms of biomedical materials field.If therefore in n-HA system
Lignin structure is introduced into n-HA structure during standby, then is expected to improve the dispersion of n-HA using the macromolecular structure of lignin
Property, while it is amphipathic to assign n-HA, to be used for and hydrophobic polymer is conductive compound with the compound obtained processus styloideus radii of different content
Material is used for bone material.
Summary of the invention
The present invention provides a kind of preparation method of the modified nano-apatite of lignin liquor co-precipitation, this method preparations
Novel nano apatite high degree of dispersion can be kept to 24 hours or more in the hydroholic solutions such as methylene chloride, thus it is available
In with polylactic acid-based high polymer with the compound obtained high strength composite of different content be used for bone material.
A kind of preparation method for the nano-apatite that lignin liquor co-precipitation is modified, includes the following steps:
Lignin is dissolved in water, concentration is 2 ~ 4 g/100 ml, then inorganic phosphorous sources aqueous solution is added by different proportion, reaction 0 ~
3 hours, then inorganic calcium salt is added, keeping calcium phosphorus molar ratio is 1.67, adjusts pH value between 10 ~ 13, stirs at 50 ~ 80 DEG C
It after reaction 4 ~ 6 hours, stands overnight, washs, for use.
In the present invention, using lignin modification nanometer hydroxyapatite, it is characterized in that referring to that lignin is after purification wooden
Element, purification process are that lignin is first dissolved in thermokalite to be filtered to remove insoluble impurities, then make lignin with sulfuric acid tune pH value
Precipitating is completely, dry after washing；
Lignin and phosphate reaction in the present invention, then add calcium source, and phosphorus source refers to that sodium phosphate, ammonium dihydrogen phosphate etc. are solvable
Property salt, calcium salt feature refers to the soluble-salts such as calcium nitrate, calcium chloride, and keeping the molar ratio of calcium and phosphorus total in solution is 1.67；
The additive amount of lignin is the % of 20 % ~ 80 of n-HA mass in the present invention.
The present invention also provides a kind of poly (glycolide-lactide) composite materials, include poly (glycolide-lactide) material and the modification hydroxyl
Base apatite；
Mass fraction of the modifted-nano-hydroxyapatite in the poly (glycolide-lactide) class composite material is 1 % ~ 15
%.After the composite material is by the way that the modifted-nano-hydroxyapatite is added into poly (glycolide-lactide) material, compound obtain is carried out
It arrives, which is ordinary skill in the art means.
At this point, the tensile strength of obtained poly (glycolide-lactide) composite material stretches by force than simple poly (glycolide-lactide) class material
Degree highest can enhance 20 % or more, it is clear that its reinforcing effect is obvious, can be used for obtaining a kind of with better bone conduction effect
High-intensitive bone material.
The preparation method of lignin modification nanometer hydroxyapatite provided by the invention is advantageous in that:
(1) for the performance of material, compared with existing n-HA, wood is introduced in nano-apatite structure prepared by the present invention
Quality macromolecular imparts the effect of its steric hindrance and realizes polymolecularity, can also assign the amphipathic of its lignin structure, make
Its with all kinds of hydrophilic and hydrophobic high polymers are compound good interfacial bonding property, solve its difficulty compound with hydrophobicity high polymer
Topic.
(2) the various raw material of the present invention are easy to get, and can make by oneself or buy in the market, preparation step is simple, reaction condition temperature
With, the equal no pollution to the environment of agents useful for same, and the reaction time is short, is suitable for being mass produced.
(3) hydrophobic structure of the nanometer hydroxyapatite of lignin modification prepared by the present invention because having lignin, can be with
Polylactic acid-based high polymer is compound to be made a kind of high-intensity absorbable composite material, can be used for bone filler particles, bone tissue engineer branch
A variety of field of orthopaedics such as frame material, inducting osseous tissue regeneration film, medicine carrying material.
Detailed description of the invention
Fig. 1 is the dispersion photo of the powder of above-described embodiment in methylene chloride.(a) n-HA, (b) solution of lignin
The modified n-HA of blending method, (c) n-HA of the solution coprecipitation preparation of lignin.
Specific embodiment
Embodiment 1: taking 2.0 g lignin to be dissolved in 100 ml water, and ten phosphate dihydrate sodium, 22.81 g is added and is dissolved in 100 ml
Water, reaction are added 23.16 g four water-calcium nitrates after 1 hour and are dissolved in 100 ml water, are 10 with the sodium hydroxide tune pH value of 10 wt%
Left and right, 70 DEG C heating stirring 4 hours, stand 48 hours after, be washed with deionized 5 times, then with ethanol washing 3 times, drying.
Take 0.5 g powder be added 50 ml methylene chloride ultrasonic disperse 30 minutes, suspension be able to maintain 10 hours or more it is not stratified.
It is 300,000 that 0.5 g of nanometer hydroxyapatite for taking the above method to be modified, which makes an addition to molecular weight in 1 wt% ratio,
Poly (glycolide-lactide) (LA and GA molar ratio be 95: 5) it is compound after, the tabletting on vulcanizing press by its composite material.This is multiple
Condensation material tensile strength is about 68.5 MPa.
Embodiment 2: taking 4.0 g lignin to be dissolved in 120 ml water, and 6.89 g of ammonium dihydrogen phosphate is added and is dissolved in 100 ml water,
23.16 g four water-calcium nitrates are added immediately and are dissolved in 100 ml water, are 10 or so, 70 DEG C with the sodium hydroxide tune pH value of 10 wt%
It heating stirring 5 hours, after standing 48 hours, is washed with deionized 5 times, then with ethanol washing 3 times, drying takes 0.3 g powder
80 ml methylene chloride ultrasonic disperse is added 20 minutes, suspension be able to maintain 12 hours or more it is not stratified.
It is 300,000 that the nanometer hydroxyapatite 2.0g for taking the above method to be modified, which makes an addition to molecular weight in 5 wt% ratios,
Poly- D, after l-polylactic acid is compound, the tabletting on vulcanizing press by its composite material.The composite material tensile strength is about 77.5
MPa。
Embodiment 3: taking 6.0 g lignin to be dissolved in 200 ml water, and 6.89 g of ammonium dihydrogen phosphate is added and is dissolved in 100 ml water,
Reaction is added 11.16 g anhydrous calcium chlorides after 3 hours and is dissolved in 100 ml water, is 10 left with the sodium hydroxide tune pH value of 10 wt%
The right side, 70 DEG C heating stirring 4 hours, stand 48 hours after, be washed with deionized 5 times, then with ethanol washing 3 times, drying.It takes
0.5 g powder be added 100 ml methylene chloride ultrasonic disperse 30 minutes, suspension be able to maintain 24 hours or more it is not stratified.
It is 300,000 that 5.0 g of nanometer hydroxyapatite for taking the above method to be modified, which makes an addition to molecular weight in 15 wt% ratios,
Poly (glycolide-lactide) (LA and GA molar ratio be 95: 5) it is compound after, the tabletting on vulcanizing press by its composite material.This is multiple
Condensation material tensile strength is about 74.8 MPa.
Embodiment 4: taking 8.0 g lignin to be dissolved in 250 ml water, and ten phosphate dihydrate sodium, 22.81 g is added and is dissolved in 100 ml
Water, reaction are added 23.16 g four water-calcium nitrates after 3 hours and are dissolved in 100 ml water, are 10 with the sodium hydroxide tune pH value of 10 wt%
Left and right, 70 DEG C heating stirring 6 hours, stand 48 hours after, be washed with deionized 5 times, then with ethanol washing 3 times, drying.
Take 0.5 g powder be added 120 ml methylene chloride ultrasonic disperse 30 minutes, suspension be able to maintain 24 hours or more it is not stratified.
It is 300,000 that 4.0 g of nanometer hydroxyapatite for taking the above method to be modified, which makes an addition to molecular weight in 10 wt% ratios,
Poly- D, after l-polylactic acid is compound, the tabletting on vulcanizing press by its composite material.The composite material tensile strength is about
79.1 MPa。
Comparative example 1: taking 4.0 g lignin to be dissolved in 120 ml water, and 9.04 g hydroxyapatites are added 200 ml of water points
Dissipate after be slowly added dropwise in above-mentioned solution, 70 DEG C heating stirring 5 hours, stand 48 hours after, be washed with deionized 5 times, then
With ethanol washing 3 times, drying.0.5 g powder is taken to be added 50 ml methylene chloride ultrasonic disperse 30 minutes, 10 minutes left sides of suspension
It is right to start to be layered.
It is 300,000 that 2.0 g of nanometer hydroxyapatite for taking the above method to be modified, which makes an addition to molecular weight in 5 wt% ratios,
Poly (glycolide-lactide) (LA and GA molar ratio be 95: 5) it is compound after, the tabletting on vulcanizing press by its composite material.This is multiple
Condensation material tensile strength is about 58.5 MPa.
Comparative example 2: taking ten phosphate dihydrate sodium, 22.81 g to be dissolved in 100 ml water, and it is molten that 23.16 g four water-calcium nitrates are added
In 100 ml water, with the sodium hydroxide tune pH value of 10 wt% be 10 or so, 70 DEG C heating stirring 5 hours, after standing 48 hours,
It is washed with deionized 5 times, then with ethanol washing 3 times, dries.Take 0.5 g powder that 50 ml methylene chloride ultrasonic disperses 30 are added
Minute, start to be layered within suspension 1 minute or so.
It is 300,000 that 2.0 g of nanometer hydroxyapatite for taking the above method to be modified, which makes an addition to molecular weight in 5 wt% ratios,
Poly- D, after l-polylactic acid is compound, the tabletting on vulcanizing press by its composite material.The composite material tensile strength is about
53.3 MPa。
Comparative example 3: taking the poly (glycolide-lactide) (LA and GA molar ratio are 95: 5) that 40 g molecular weight are 300,000, will
Its tabletting on vulcanizing press.The high polymer material tensile strength is about 57.8 MPa.
Claims (4)
1. a kind of preparation method and applications of the nanometer hydroxyapatite using lignin modification, it is characterized in that referring to lignin
It is reacted with phosphorus source, then adds calcium salt, keeping the molar ratio of calcium and phosphorus is 1.67, adjusts pH value, is stirred to react at a certain temperature
After a certain period of time, it stands overnight, washs, for use；By the modified nanometer hydroxyapatite of gained can be applied to it is polylactic acid-based
High polymer is compounded with good reinforcing effect.
2. lignin described in accordance with the claim 1, it is characterized in that referring to one kind of lignin after purification.
3. lignin described in accordance with the claim 1 is reacted with phosphorus source and calcium source, it is characterized in that referring to the additive amount of lignin for system
The % of 20 % ~ 80 of standby nanometer hydroxyapatite quality.
4. modified nanometer hydroxyapatite described in accordance with the claim 1 can be applied to be compounded with polylactic acid-based high polymer
Good reinforcing effect, it is characterized in that referring to that it is compound with polylactic acid-based high polymer with 1 wt% ~ 15wt % content addition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115025282A (en) * | 2022-04-14 | 2022-09-09 | 湖南师范大学 | Lignin/nano hydroxyapatite-based composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508429A (en) * | 2009-03-13 | 2009-08-19 | 四川大学 | Hydroxyapatite nano-complex particle, preparation and uses thereof |
| KR20110010910A (en) * | 2009-07-27 | 2011-02-08 | 국민대학교산학협력단 | Method for manufacturing organic/inorganic solvent dispersible hydroxy apatite |
| CN104292481A (en) * | 2014-10-07 | 2015-01-21 | 桂林理工大学 | Method for preparing synergetic enhanced polylactic acid biological composite material |
| CN107754019A (en) * | 2017-10-07 | 2018-03-06 | 北京林业大学 | One kind is based on Eucalyptus lignin modification hydroxyapatite/polyvinyl alcohol Biocomposite material and manufacture method |
| CN108083248A (en) * | 2018-01-23 | 2018-05-29 | 湖南师范大学 | A kind of preparation method of high dispersancy nano apatite |
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- 2018-10-15 CN CN201811193592.8A patent/CN109381746A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508429A (en) * | 2009-03-13 | 2009-08-19 | 四川大学 | Hydroxyapatite nano-complex particle, preparation and uses thereof |
| KR20110010910A (en) * | 2009-07-27 | 2011-02-08 | 국민대학교산학협력단 | Method for manufacturing organic/inorganic solvent dispersible hydroxy apatite |
| CN104292481A (en) * | 2014-10-07 | 2015-01-21 | 桂林理工大学 | Method for preparing synergetic enhanced polylactic acid biological composite material |
| CN107754019A (en) * | 2017-10-07 | 2018-03-06 | 北京林业大学 | One kind is based on Eucalyptus lignin modification hydroxyapatite/polyvinyl alcohol Biocomposite material and manufacture method |
| CN108083248A (en) * | 2018-01-23 | 2018-05-29 | 湖南师范大学 | A kind of preparation method of high dispersancy nano apatite |
Non-Patent Citations (1)
| Title |
|---|
| 汪多仁著: "《精细化工中间体》", 31 January 2008, 海洋出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115025282A (en) * | 2022-04-14 | 2022-09-09 | 湖南师范大学 | Lignin/nano hydroxyapatite-based composite material and preparation method thereof |
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