CN112440359B - Sulfonation modification method of willow branches and application of willow branches as bone repair material - Google Patents

Sulfonation modification method of willow branches and application of willow branches as bone repair material Download PDF

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CN112440359B
CN112440359B CN202011277173.XA CN202011277173A CN112440359B CN 112440359 B CN112440359 B CN 112440359B CN 202011277173 A CN202011277173 A CN 202011277173A CN 112440359 B CN112440359 B CN 112440359B
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willow
willow branches
branches
soaking
drying
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CN112440359A (en
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姚福君
刘勋
吴超群
伍波
李兆乾
裴重华
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Southwest University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K9/00—Chemical or physical treatment of reed, straw, or similar material
    • B27K9/002—Cane, bamboo
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/001—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/04—Combined bleaching or impregnating and drying of wood
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2002/3093—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth for promoting ingrowth of bone tissue

Abstract

The invention provides a sulfonation modification method of willow branches, which comprises the following steps: (1) peeling willow branches, cutting the willow branches into small sections, cleaning the willow branches, and drying the willow branches; (2) putting the dried willow branches into 0.2-2.0 mol/L sulfuric acid, heating to 50-90 ℃, stirring for reaction for 1-6 hours, cooling, taking out, cleaning and drying; (3) soaking the willow branches treated in the step (2) in 0.1-0.5 mol/L calcium chloride solution for 18-24 h, then soaking in 0.1-0.5 mol/L sodium phosphate solution for 18-24 h, taking out the willow branches and drying; (4) and (3) carrying out high-temperature calcination treatment on the willow branches, wherein the calcination temperature is 850-950 ℃, the heating rate is 1-3 ℃/min, and furnace cooling is carried out after calcination. The modification method can promote the osteogenesis capacity of the willow branches and can be stably used as a bone fracture repair material.

Description

Sulfonation modification method of willow branches and application of willow branches as bone repair material
Technical Field
The invention belongs to the technical field of natural material modification and medical application thereof, and particularly relates to a willow branch modification method, in particular to a willow branch sulfonation modification method and application thereof as a bone repair material.
Background
The transmission of the willow branch to the setting of bone is a technique used by ancient Chinese medical orthopedics and traumatology doctors to treat open fracture, which has been circulating in Jiangsu, Guangxi, Sichuan and Hunan places for a long time. The "Liuzhi Jiegu" is to replace the unrecoverable bone with Liuzhi. Willow is not only a common plant, but also has medicinal value in a plurality of parts of the willow. The Ming Dynasty Chinese materia medica works recorded in Ben Cao gang mu records that willow catkin, willow leaf, willow branch, willow root bark and even willow glue, willow parasitic, willow ear and willow stupid can be used as medicines for treating various common diseases such as hematemesis, hemoptysis, incised wound bleeding, facial malignant boil, early jaundice, tooth open swelling and pain, toothache due to wind-evil, ear pain with pus and the like, and are mostly single-prescription and very simple and convenient to use. The record of the use of willow branches in the traditional Chinese medicine fracture treatment can be traced to the Song Dynasty officer's doctor book ' Taiping Shenghui Fang ' at the earliest, and the record of the book includes that the willow branches are clamped by rice sanders and cotton ropes, and the willow branches are clamped by strips in summer. "however, it is described here only the use of willow branches as a splint material for external fixation, which is a common practice among orthopedics and traumatologists, and has been still followed up to the 60 s, and is completely different from the properties of the willow branch osteosynthesis. (Chengyong. Nanjing university school newspaper, 2017, 5, 120-.
In recent times, with the gradual popularization of western medical technology and medical education in China, Chinese traditional medicine, namely traditional Chinese medicine, has to strive to find a reasonable development path, and Chinese medicine scientization is regarded as a unique path in a certain sense. It is described that Liudafu was subjected to the willow branch setting test on 9 dogs in 8 months from 10 months in 1957 to 6 months in 1958 with the help of Western medical colleagues, wherein 8 are right tibia and 1 is left tibia. The surgical process comprises the following steps: cutting off the backbone, embedding willow branches, sewing and wrapping, X-ray shooting and the like, and has achieved certain success. However, there are also a considerable number of failure cases. One of the main reasons for the failure is that the wicker is not easy to ossify, which reflects the inherent defect of the wicker-branch coaptation technology, i.e. the problem that the plant tissue is difficult to combine with the human body and is transformed into the human tissue. (Chengyong. Nanjing university school newspaper, 2017, 5, 120-. So far, despite sporadic reports on this technology, negative attitudes are still the mainstream.
From the perspective of modern science, ancient Chinese medicine selects wicker as a medium for bone repair, and still has certain scientific basis. From the structural point of view, taking weeping willow as an example, willow branches have perfect pore connectivity compared with other woods: on one hand, the wicker has a secondary pore structure, wherein the pore diameter of a large pore is about 30 microns, the pore diameter of a small pore is about 1.5 microns, and the large pore and the small pore are uniformly distributed, are cylindrical and are well distributed along the long diameter direction; on the other hand, there are channels (Ma Yongjun, Yin Zhenquan, Pei Chonghua, et al. journal of ports Materials, 2016, 23, 225-. This excellent pore structure facilitates cell attachment and transport of nutrients and metabolites. In the aspect of mechanical property, the wicker has better toughness and strength and can meet certain biomechanical requirements. In addition, willow branches are rich in acetylsalicylic acid, can prevent thrombosis and inhibit platelet aggregation, have antibacterial activity, and can be beneficial to wound healing and prevention of other adverse reactions to a certain extent.
In view of the above structural characteristics of willow branches and the advantages of low price and easy availability, if the problem that willow branches are difficult to ossify is fundamentally changed, the willow branches have wide application prospects in the field of bone repair. Therefore, there is a need in the art to develop a method capable of promoting the mineralization (osteogenesis) of Hydroxyapatite (HA) on the surface of willow branches, so that the willow branches can be really applied to the bone-knitting repair technology in a large amount.
Disclosure of Invention
Aiming at the problem of insufficient bone forming capability of willow branches, the invention aims to provide a sulfonation modification method of willow branches and application of the sulfonation modification method of willow branches as a bone repair material.
One of the purposes of the invention is to provide a sulfonated modification method of willow branches, which comprises the following steps:
(1) peeling willow branches, cutting the willow branches into small sections, cleaning the willow branches, and drying the willow branches;
(2) putting the dried willow branches into 0.2-2.0 mol/L sulfuric acid, heating to 50-90 ℃, stirring for reaction for 1-6 hours, cooling, taking out, cleaning with distilled water, and drying;
(3) soaking the willow branches treated in the step (2) in 0.1-0.5 mol/L calcium chloride solution for 18-24 hours, then soaking in 0.1-0.5 mol/L sodium phosphate solution for 18-24 hours, taking out the willow branches after soaking treatment, and drying;
(4) and (4) carrying out high-temperature calcination treatment on the willow branches obtained in the step (3), wherein the calcination temperature is 850-950 ℃, the calcination time is 1-5 hours, the heating rate is 1-3 ℃/min, and furnace cooling is carried out on the calcined willow branches.
The present inventors have determined the above-mentioned modification method of willow branches after extensive studies based on the specific composition of willow branches, and have found that HSO can be introduced onto the surface of willow branches by the above-mentioned modification method3 -The group can greatly improve the induced osteogenesis capacity of the modified willow branches. Placing modified willow branches in CaCl2And Na3PO4The products obtained by respectively soaking in the solution are all HA, and the test result shows that the HA generation amount and the soaking times (mineralization time) are in a direct proportion relation.
Willow branches are mainly composed of cellulose, hemicellulose and lignin. Wherein the cellulose accounts for 40-50%, the hemicellulose accounts for 10-30%, and the lignin accounts for 20-30%. Cellulose is a linear polymer formed by connecting beta-D-glucose through 1-4-beta-glycosidic bonds. Hemicellulose is a heterogeneous polymer composed of several different types of monosaccharides (pentoses and hexoses), such as xylose, arabinose and galactose. Both cellulose and hemicellulose are polysaccharides, collectively referred to as holocellulose. They are carbohydrates, so the reactive groups in the molecule are hydroxyl groups. Lignin is a typical aromatic compound with the basic structural features of phenyl propane. The main reactive groups on the polymer chain are methoxy and hydroxy. Therefore, ordinary willow branches are not easy to react with Ca2+Or PO4 3-The binding occurs, and thus osteogenesis is difficult. The inventor verifies the osteogenic capacity of willow branches, and willow branches which are not subjected to modification treatment are placed in CaCl2And Na3PO4Soaking in the solution respectively to obtain NaCaPO4And not HA (comparative example of the invention).
The modification method of willow branches mainly introduces HSO on the surfaces of willow branches through sulfonation reaction3 -A group which can react with Ca2+Binding and ultimately producing HA involves the following chemical reaction:
CB-OH+SO3H++OH-→CB-O…SO3H+H2O (1)
CB-O…SO3H+10Ca2++6PO4 3-+3H2O→CB-OH…Ca10(PO4)6(OH)2+SO4 2-+4H+ (2)
CB-OH+10Ca2++6PO4 3-+2H2O→CB-OH…Ca10(PO4)6(OH)2+2H+ (3)
in the formula, CB represents a cellulose main chain, and "…" represents a hydrogen bond formed by a hydroxyl group on a cellulose molecule and a hydroxyl group on HA.
On the basis of the reaction formula, the preparation method can introduce HSO on the surface of willow branch molecules3 -The group is added, so that the induced osteogenesis capacity of the modified willow branches is greatly improved. The inventor verifies the osteogenic capacity of willow branches, and modified willow branches are placed in CaCl2And Na3PO4The products obtained by respectively and continuously soaking in the solution are HA, but not NaCaPO4The modification method provided by the invention is proved to greatly improve the osteogenesis inducing capability of the willow branches.
Further, absolute ethyl alcohol is adopted for cleaning in the step (1).
Further, the drying manner in the step (1) is freeze drying.
Further, the heating in the step (2) is carried out in an oil bath.
Further, after washing with distilled water for 3-6 times in the step (2), the willow branches are freeze-dried.
Further, in the step (3), repeated soaking treatment of calcium chloride solution and sodium phosphate solution is carried out on the willow branches, and the number of repeated soaking treatment is 2-12.
Further, taking out the willow branches for freeze drying after repeated soaking treatment (1-12 rounds) is finished.
Further, the high-temperature calcination in the step (4) is performed at normal temperature and normal pressure in an air atmosphere.
The invention also aims to provide the application of the willow branch obtained by the sulfonation modification method as a bone repair material. In particular, the sulfonated and modified willow branch is used for replacing common willow branches in the traditional Chinese medicine 'willow branch bonesetting' to induce and promote the growth of bones.
The invention has the following beneficial effects:
1. the invention provides a sulfonation modification method of willow branches, and the willow branches subjected to sulfonation modification have the comprehensive advantages of strong osteogenesis inducing capability and low cost, and can be well used as bone repair materials.
2. The method has the advantages of simple process, strong controllability, good stability, mild reaction conditions, wide raw material sources, low cost and the like, and the whole process is beneficial to large-scale industrial treatment.
Drawings
Fig. 1 is an XRD pattern, in which: (a) XRD patterns of original willow branches and willow branches (sulfonated and acidified willow branches) modified by examples; (b) the modified wicker is soaked and mineralized in different rounds to prepare the XRD pattern of the sample.
FIG. 2 is a SEM image, in which: (a) SEM image of raw material willow branch; (b) soaking 6 rounds of willow branches SEM images; (c) enlarged image of fig. b; (d) soaking 8 rounds of willow branches in SEM images; (e) enlarged image of fig. d; (f) SEM images of 10 soaking cycles.
FIG. 3 is an IR diagram, wherein: (a) IR spectra of original willow branches and HA powder; (b) and soaking and mineralizing the modified wickers in different rounds to prepare the IR spectrum of the sample.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The sulfonated modification method of willow branches comprises the following processing steps:
taking a plurality of willow branches, removing leaves and peels, cutting the willow branches with the diameter of about 1mm into samples with the lengths of 0.5 cm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm and 10cm, wherein the number of the cut samples is as large as possible so as to ensure that the samples can be taken out for multiple times in the experimental process. And repeatedly washing the intercepted sample with absolute ethyl alcohol for 3 times, and then putting the sample into a freeze dryer for freeze drying. Taking out the well freeze-dried willow branches, putting the well freeze-dried willow branches into prepared sulfuric acid with the concentration of 0.2mol/L, putting the well freeze-dried willow branches into an oil bath pan with the temperature reaching 50 ℃, enabling the willow branches to carry out sulfonation reaction, recording the reaction time to be 1h, stirring all the time in the reaction process, cooling the willow branches which are subjected to sulfonation treatment and carbonization to room temperature after reaction for 1h, taking out the willow branches, washing the willow branches with distilled water for 3 times, and then carrying out freeze drying on the cleaned willow branch samples.
The preparation of the hydroxyapatite is researched by adopting an alternate immersion method, and a calcium chloride solution and a sodium phosphate solution of 0.2mol/L are respectively prepared before the experiment. The freeze-dried willow branches are placed into a calcium chloride solution with the concentration of 0.2mol/L for soaking for one day, then sodium phosphate solution with the concentration of 0.2mol/L is used for soaking for 24 hours, and soaking is repeated for 12 rounds (one round is formed every two days from the first day of soaking). And (2) calcining the willow branches obtained by soaking in different rounds at high temperature under normal temperature and normal pressure, setting the carbonization temperature and the oxidation temperature of the willow branches to 900 ℃, meanwhile, in order to keep the original shape of the willow branches, slowly sintering the willow branches in the air atmosphere, setting the heating rate to be 1 ℃/min, removing the template from the hydroxyapatite to obtain the ordered porous hydroxyapatite, wherein the obtained hydroxyapatite can well keep the shape and the size of the willow branches. The morphology of the mineralized material was observed by SEM (JSM-6360 LV, Japan electronic Co., Ltd.), and the phase of the mineralized material was observed by XRD (D/max-RB, Japan science Co., Ltd.). The composition of the mineralized material was analyzed by IR (BRUKER spectroscopy instruments, germany). The result shows that a small amount of white HA is generated on the outer surface and in the inner hole of the modified willow branch, and HA particles are in a blocky shape and mixed with a small amount of fibers.
Example 2
The sulfonated modification method of willow branches comprises the following processing steps:
taking a plurality of willow branches, removing leaves and peels, cutting the willow branches with the diameter of about 1.5mm into samples with the lengths of 0.5 cm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm and 10cm, wherein the number of the cut samples is as large as possible so as to ensure that the samples can be taken out for multiple times in the experimental process. And repeatedly washing the intercepted sample with absolute ethyl alcohol for 4 times, and then putting the sample into a freeze dryer for freeze drying. And taking out the freeze-dried willow branches, putting the willow branches into prepared sulfuric acid with the concentration of 0.5mol/L, putting the willow branches into an oil bath kettle with the temperature reaching 60 ℃, performing sulfonation reaction on the willow branches, recording the reaction time to be 2 hours, and stirring all the time in the reaction process. After reacting for 2h, cooling the sulfonated and carbonized willow branches to room temperature, taking out the willow branches, washing the willow branches for 4 times by using distilled water, and then freezing and drying the washed willow branch samples.
The experiment and the characterization method for the capability of inducing salix twig into bone are the same as those in example 1. The result shows that white HA is generated on the outer surface and in the inner hole of the modified willow branch. The HA particles are mainly in a block shape, but the proportion of fibrous particles is obviously increased compared with the example 1.
Example 3
The sulfonated modification method of willow branches comprises the following processing steps:
taking a plurality of willow branches, removing leaves and peels, cutting the willow branches with the diameter of about 2.0mm into samples with the lengths of 0.5 cm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm and 10cm, wherein the number of the cut samples is as large as possible so as to ensure that the samples can be taken out for multiple times in the experimental process. And repeatedly washing the intercepted sample with absolute ethyl alcohol for 5 times, and then putting the sample into a freeze dryer for freeze drying. And taking out the freeze-dried willow branches, putting the willow branches into prepared sulfuric acid with the concentration of 1.0mol/L, putting the willow branches into an oil bath kettle with the temperature reaching 70 ℃ to perform sulfonation reaction, recording the reaction time to be 3 hours, and stirring all the time in the reaction process. After reacting for 3h, cooling the sulfonated and carbonized willow branches to room temperature, taking out the willow branches, washing the willow branches for 5 times by using distilled water, and then freezing and drying the washed willow branch samples.
The experiment and the characterization method for the capability of inducing salix twig into bone are the same as those in example 1. The results show that: after the modification, the micropores in the template are still orderly arranged, except that the powdery substance is attached to the surface of the pores, so that the scanned image of the sample looks very rough, part of the micropores are filled and extruded by the substance to be deformed, and part of the micropores are changed into ellipses, different from the previous circular pores.
Example 4
The sulfonated modification method of willow branches comprises the following processing steps:
taking a plurality of willow branches, removing leaves and peels, cutting the willow branches with the diameter of about 2.5mm into samples with the lengths of 0.5 cm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm and 10cm, wherein the number of the cut samples is as large as possible so as to ensure that the samples can be taken out for multiple times in the experimental process. And repeatedly washing the intercepted sample with absolute ethyl alcohol for 5 times, and then putting the sample into a freeze dryer for freeze drying. And taking out the freeze-dried willow branches, putting the willow branches into prepared sulfuric acid with the concentration of 1.0mol/L, putting the willow branches into an oil bath kettle with the temperature reaching 80 ℃, performing sulfonation reaction on the willow branches, recording the reaction time to be 4 hours, and stirring all the time in the reaction process. After 4h of reaction, cooling the sulfonated and carbonized willow branches to room temperature, taking out the willow branches, washing the willow branches for 5 times by using distilled water, and then freezing and drying the washed willow branch samples.
The experiment and the characterization method for the capability of inducing salix twig into bone are the same as those in example 1. The results show that: the modified willow branches are generated with a large amount of powdery and blocky substances, the powdery and blocky substances are attached to the willow branch template to fill gaps of the willow branches, and obviously, the gaps of the willow branches soaked for 8 rounds are far less than those of the willow branches soaked for 6 rounds, which shows that more and more compositions are accumulated in the gaps of the willow branches along with the increase of the soaking time, so that the porosity of the willow branches is greatly reduced.
Example 5
The sulfonated modification method of willow branches comprises the following processing steps:
taking a plurality of willow branches, removing leaves and peels, cutting the willow branches with the diameter of about 2.5mm into samples with the lengths of 0.5 cm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm and 10cm, wherein the number of the cut samples is as large as possible so as to ensure that the samples can be taken out for multiple times in the experimental process. And repeatedly washing the intercepted sample with absolute ethyl alcohol for 6 times, and then putting the sample into a freeze dryer for freeze drying. And taking out the freeze-dried willow branches, putting the willow branches into prepared sulfuric acid with the concentration of 1.5mol/L, putting the willow branches into an oil bath kettle with the temperature of 90 ℃, performing sulfonation reaction on the willow branches, recording the reaction time to be 5 hours, and stirring all the time in the reaction process. After 5h of reaction, cooling the willow branches carbonized by sulfonation treatment to room temperature, taking out and washing the willow branches by using distilled water for 6 times, and then freezing and drying the washed willow branch samples.
The experiment and the characterization method for the capability of inducing salix twig into bone are the same as those in example 1. The results show that: white HA is generated on the outer surface and in the inner hole of the willow branch after modification, and HA particles are in a block shape.
Example 6
The sulfonated modification method of willow branches comprises the following processing steps:
taking a plurality of willow branches, removing leaves and peels, cutting the willow branches with the diameter of about 3mm into samples with the lengths of 0.5 cm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm and 10cm, wherein the number of the cut samples is as large as possible so as to ensure that the samples can be taken out for multiple times in the experimental process. And repeatedly washing the intercepted sample with absolute ethyl alcohol for 6 times, and then putting the sample into a freeze dryer for freeze drying. And taking out the freeze-dried willow branches, putting the willow branches into prepared sulfuric acid with the concentration of 2mol/L, putting the willow branches into an oil bath kettle with the temperature of 90 ℃ to perform sulfonation reaction, recording the reaction time to be 6 hours, and stirring all the time in the reaction process. After 6h of reaction, cooling the sulfonated and carbonized willow branches to room temperature, taking out the willow branches, washing the willow branches for 6 times by using distilled water, and then freezing and drying the washed willow branch samples.
The experiment and the characterization method for the capability of inducing salix twig into bone are the same as those in example 1. The results show that: a large amount of white HA is generated on the outer surface and in the inner hole of the willow branch after modification. The HA particles are fibrous and mixed with a small amount of lumps.

Claims (7)

1. The application of the willow branch obtained by the sulfonation modification method as a bone repair material is characterized in that the willow branch obtained by sulfonation modification replaces the common willow branch in the traditional Chinese medicine 'willow branch coaptation' for inducing and promoting the growth of bones; the sulfonation modification method comprises the following steps: (1) peeling willow branches, cutting the willow branches into small sections with the length of 0.5-10 cm, cleaning the willow branches, and drying the willow branches; putting the dried willow branches into 0.2-2.0 mol/L sulfuric acid, heating to 50-90 ℃, stirring for reaction for 1-6 hours, cooling, taking out, cleaning with distilled water, and drying; (3) putting the willow branches treated in the step (2) into 0.1-0.5 mol/L calcium chloride solution for soaking for 18-24 hours, then soaking for 18-24 hours by using 0.1-0.5 mol/L sodium phosphate solution, and repeatedly soaking the willow branches by using the calcium chloride solution and the sodium phosphate solution according to the method, wherein the repeated soaking is performed for 2-12 times; taking out the willow branches after soaking treatment and drying; (4) and (4) carrying out high-temperature calcination treatment on the willow branches obtained in the step (3), wherein the calcination temperature is 850-950 ℃, the calcination time is 1-5 hours, the heating rate is 1-3 ℃/min, and furnace cooling is carried out on the calcined willow branches.
2. The use of claim 1, wherein in step (1), the intercepted fragments are washed with absolute ethanol.
3. Use according to claim 1, wherein the drying in step (1) is carried out by freeze-drying.
4. Use according to claim 1, wherein the heating in step (2) is carried out in an oil bath.
5. The use according to claim 1, wherein the willow branch is freeze-dried after 3-6 times of washing with distilled water in the step (2).
6. The use of claim 5, wherein the willow branches are taken out after the repeated soaking treatment and freeze-dried.
7. The use according to claim 1, wherein the high-temperature calcination in step (4) is carried out at normal temperature and pressure and in an air atmosphere.
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