CN105949491B - A kind of preparation method of anti-adhesion medical polypropylene material - Google Patents
A kind of preparation method of anti-adhesion medical polypropylene material Download PDFInfo
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- CN105949491B CN105949491B CN201610316325.XA CN201610316325A CN105949491B CN 105949491 B CN105949491 B CN 105949491B CN 201610316325 A CN201610316325 A CN 201610316325A CN 105949491 B CN105949491 B CN 105949491B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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Abstract
The present invention provides a kind of preparation method of anti-adhesion medical polypropylene material, and this method is：Step 1：Polypropylene material is placed in dichloromethane to be cleaned by ultrasonic or stirring and washing 3~24 hours, then 25 DEG C~40 DEG C dryings in an oven；Step 2：Above-mentioned polypropylene material is passed through into oxygen plasma treatment 30 seconds~2 minutes；Step 3：It will be placed in containing in Dopamine hydrochloride monomer solution by the polypropylene material of above procedure processing；Obtain the polypropylene PP/PDA materials of surface DOPA amination；Step 4：Above-mentioned PP/PDA materials are placed in 1%~2% chitosan polymer aqueous solution, the polypropylene material PP/PDA/CS of surface chitosan is obtained；Step 5：PP/PDA/CS is taken out, the hydrophilic anti-adhesion medical polypropylene material of apparent height is obtained.The present invention makes patching material surface property change by way of surface biological modification, prevents the occurrence probability of adhesion, reduces the generation of complication to the full extent.
Description
Technical field
The present invention relates to the surface modification technology of medical polypropylene material, more particularly to it is a kind of with DOPA it is amine-modified poly- third
The preparation method of alkene film, net, particle or micro-sphere material.
Background technology
Polypropylene (PP) is a kind of thermoplastic resin, is one of current global five big general-purpose plastics, can be divided into isotactic poly- third
Alkene (isotaetic polyprolene), random polypropylene (atactic polypropylene) and syndiotactic polypropylene
Three kinds of (syndiotatic polypropylene).PP is a kind of semi-crystalline material, than polyethylene (polyethylene,
PE) there are the hardness of bigger and higher fusing point.Since the polypropylene of homopolymerization type has certain brittleness, so usually adding when polymerization
Enter 1%~4% or higher amount ethylene as comonomer to obtain the copolymer of polypropylene-polyethylene.Homopolymer type and
The PP materials of copolymer type all have excellent resistance to water soak, antiacid caustic corrosion and antilysis.Polypropylene for medical article has been made
It is widely used for medical device materials, such as other than being used as manufacturing medical catheter and blood purification filter membrane, also in hernia surgery
Hernia patching material is widely used as in operation.However under the premise of keeping its ontology mechanical property not to be remarkably decreased, how
The hydrophily, anti-adhesive and biocompatibility etc. for improving this kind of material, are still technological difficulties and research hotspot.
Chitosan (chitosan, CS), it is non-toxic and tasteless, there is higher biocompatibility.CS is easy to form a film, and film has
Good anti-tissue adhesion performance.While in operation can effectively reduce the generation of post-operation adhesion for coating corresponding position under normal circumstances.
And have the commercialized chitosan film listing that prevents adhesion now, so for from raw material, chitosan is safe and reliable.
Invention content
Technical problem：The object of the present invention is to provide providing a kind of preparation method of anti-adhesion medical polypropylene material,
Today's society, hernia incidence rise year by year, and the mode that Using prosthesis is repaired medically mainly is taken to be asked to solve this at present
Topic, most repairing prosthetic materials now are exactly propene polymer patch, but due to material self-characteristic make after Using prosthesis with
Time lengthening sticks together in patient's body and internal organs, causes patient to feel internal foreign body sensation or brings serious complication, such as
Chronic ache, intestinal obstruction, bowel narrow etc..The purpose of the present invention is by way of a kind of novel surface biological modification, make benefit
Sheet material surface property changes, and prevents the occurrence probability of adhesion, reduces the generation of complication to the full extent.
Technical solution：To solve the above-mentioned problems, the present invention provides a kind of preparation side of anti-adhesion medical polypropylene material
Method, this approach includes the following steps：
Step 1：Polypropylene material is placed in dichloromethane is cleaned by ultrasonic or stirring and washing 3~24 hours is various to remove
Additive, then 25 DEG C~40 DEG C dryings in an oven；
Step 2：Above-mentioned polypropylene material is passed through into oxygen plasma treatment 30 seconds~2 minutes；
Step 3：It will be placed in by the polypropylene material of above procedure processing containing in Dopamine hydrochloride monomer solution,
After being stirred to react 1~24 hour under the heating of 25 DEG C~40 DEG C conditions, take out surface DOPA amination polypropylene PP/PDA spend from
After sub- water is thoroughly rinsed and it is dried in vacuo；Obtain the polypropylene PP/PDA materials of surface DOPA amination；
Step 4：Above-mentioned PP/PDA materials are placed in 1%~2% chitosan polymer aqueous solution, 25 DEG C~
Heating stirring is reacted 1~24 hour under the conditions of 40 DEG C, obtains the polypropylene material PP/PDA/CS of surface chitosan；
Step 5：The polypropylene material PP/PDA/CS for taking out above-mentioned surface chitosan, is used in combination deionized water thoroughly clear
It washes, to remove unreacted chitosan, after above-mentioned processing routine, it is poly- just to obtain the hydrophilic anti-adhesion medical of apparent height
Propylene material.
Wherein：
The polypropylene material includes isotactic polypropylene (isotaeticpolyprolene), random polypropylene
(atacticpolypropylene) or syndiotactic polypropylene (syndiotaticpolypropylene) and be added 1%~4%
The blocked copolymer of the Random copolymer RCP of ethylene or more height ratio ethylene contents, polypropylene material shape used include
One or more of combinations of film, net, silk, particle or microballoon.
The Dopamine hydrochloride monomer solution is the aqueous solution or trihydroxy aminomethane solution of Dopamine hydrochloride monomer.
The heating stirring, reaction temperature are 25 DEG C~40 DEG C, and the reaction time is 1~24 hour.
Deacetylation >=80% of chitosan (chitosan) used in the chitosan polymer aqueous solution.
The chitosan polymer aqueous solution, the aqueous acetic acid that solvent for use is 1%~2%.
Advantageous effect：This method can be by simple preparation process, and reaching makes inertia polypropylene surface have resist blocking and that
The purpose of functionalization, and by this surface-functionalized polypropylene material be used for hernia paster, can effectively prevent internal organs with
The adhesion of sticking patch prosthese mitigates the generation of patient's body foreign body sensation and corresponding complication.It also can effectively reduce simultaneously corresponding
Medical burden.
Description of the drawings
Fig. 1 is the shape appearance figure on the simple surfaces PP.
Fig. 2 is the shape appearance figure through equal oxyanion precursors treated surfaces PP.
Fig. 3 is the PP surface topography maps after chitosan-modified.
Fig. 4 be it is chitosan-modified before (Fig. 4 A) afterwards (Fig. 4 B), form of the cell on the surfaces PP.
Specific implementation mode
The operating procedure of the present invention is as follows：
Step 1：Polypropylene material is placed in dichloromethane is cleaned by ultrasonic or stirring and washing 3~24 hours is various to remove
Additive, then 25 DEG C~40 DEG C dryings in an oven；
Step 2：Above-mentioned polypropylene material is passed through into oxygen plasma treatment 30 seconds~2 minutes；
Step 3：It will be placed in by the polypropylene material of above procedure processing containing in Dopamine hydrochloride monomer solution,
After being stirred to react 1~24 hour under the heating of 25 DEG C~40 DEG C conditions, take out surface DOPA amination polypropylene PP/PDA spend from
After sub- water is thoroughly rinsed and it is dried in vacuo；Obtain the polypropylene PP/PDA materials of surface DOPA amination；
Step 4：Above-mentioned PP/PDA materials are placed in 1%~2% chitosan polymer aqueous solution, 25 DEG C~
Heating stirring is reacted 1~24 hour under the conditions of 40 DEG C, obtains the polypropylene material PP/PDA/CS of surface chitosan；
Step 5：The polypropylene material PP/PDA/CS for taking out above-mentioned surface chitosan, is used in combination deionized water thoroughly clear
It washes, to remove unreacted chitosan, after above-mentioned processing routine, it is poly- just to obtain the hydrophilic anti-adhesion medical of apparent height
Propylene material.
Embodiment 1
1. by 0.5g PP GRANULESs (or microballoon), cleaned three times with dichloromethane, each 20mL, scavenging period 3 hours,
And it is 24 hours dry under the conditions of 40 DEG C.
2. above-mentioned polypropylene material is passed through oxygen plasma treatment 2 minutes.
3. by being placed in the solution containing Dopamine hydrochloride by the PP GRANULES of above procedure processing, in 25 DEG C of heating
Under the conditions of react after a certain period of time, taking-up with deionized water be thoroughly rinsed after and be dried in vacuo；Obtain the poly- of surface DOPA amination
Particulate propylene, after reaction solution become brown, PP GRANULES is taken out in filtering.
4. being stirred 24 hours for 30 DEG C in the aqueous solution for the chitosan that the obtained product of step 3 is placed on 1%, table is obtained
The PP GRANULES (PP/PDA/CS) of face-piece glycan；
5. taking out above-mentioned PP GRANULES, it is used in combination deionized water thoroughly to clean, to remove unreacted chitosan.Through above-mentioned
After processing routine, just obtains apparent height hydrophily and prevent the PP GRANULES of cell adherence.
Embodiment 2
1. PP GRANULES is laid on one piece of flake aluminum, it is heated to melting on magnetic force heating stirrer, then will
Another aluminium flake is pressed on the PP GRANULES of thawing, controls thickness, and polypropylene screen is made.Film thickness is about 0.1mm, and diameter is big
Small about 1cm~2cm.
2. by step 1 or polypropylene screen is cleaned three times with dichloromethane, each 20mL, scavenging period 3 hours, and 40
It is 24 hours dry under the conditions of DEG C.
3. above-mentioned polypropylene sheet is passed through oxygen plasma treatment 2 minutes.
4. by being placed in the solution containing Dopamine hydrochloride by the polypropylene sheet of above procedure processing, in 25 DEG C of heating
Under the conditions of react after a certain period of time, taking-up with deionized water be thoroughly rinsed after and be dried in vacuo；Obtain the poly- of surface DOPA amination
Propylene thin slice, after reaction solution become brown, polypropylene sheet is taken out in filtering.
5. being stirred 24 hours for 30 DEG C in the aqueous solution for the chitosan that the obtained product of step 4 is placed on 1%, table is obtained
The polypropylene sheet (PP/PDA/CS) of face-piece glycan；
6. taking out above-mentioned polypropylene sheet, it is used in combination deionized water thoroughly to clean, to remove unreacted chitosan.Through above-mentioned
After processing routine, just obtains apparent height hydrophily and prevent the polypropylene sheet of cell adherence.
Embodiment 3
1. under room temperature, by polypropylene net (2cm × 2cm) 50g/m2It is cleaned three times with dichloromethane or acetone, each 20mL,
Scavenging period 3 hours, and it is 24 hours dry under the conditions of 40 DEG C.
2. above-mentioned polypropylene net is passed through oxygen plasma treatment 2 minutes.
3. by being placed in the solution containing Dopamine hydrochloride by the polypropylene net of above procedure processing, 25 DEG C of items are being heated
It reacts under part after a certain period of time, after taking-up is thoroughly rinsed with deionized water and is dried in vacuo；Obtain poly- the third of surface DOPA amination
Alkene net, after reaction solution become brown, polypropylene net is taken out in filtering.
4. being stirred 24 hours for 30 DEG C in the aqueous solution for the chitosan that the obtained product of step 4 is placed on 1%, table is obtained
The polypropylene net (PP/PDA/CS) of face-piece glycan；
5. taking out above-mentioned polypropylene net, it is used in combination deionized water thoroughly to clean, to remove unreacted chitosan.Through above-mentioned place
After managing program, just obtains apparent height hydrophily and prevent the polypropylene net of cell adherence.
Embodiment 4
6. by 0.5g PP GRANULESs (or microballoon), cleaned three times with dichloromethane, each 20mL, scavenging period 3 hours,
And it is 24 hours dry under the conditions of 40 DEG C.
7. above-mentioned polypropylene material is passed through oxygen plasma treatment 1 minute.
8. by being placed in the solution containing Dopamine hydrochloride by the PP GRANULES of above procedure processing, in 25 DEG C of heating
Under the conditions of react after a certain period of time, taking-up with deionized water be thoroughly rinsed after and be dried in vacuo；Obtain the poly- of surface DOPA amination
Particulate propylene, after reaction solution become brown, PP GRANULES is taken out in filtering.
9. being stirred 24 hours for 30 DEG C in the aqueous solution for the chitosan that the obtained product of step 3 is placed on 1%, table is obtained
The PP GRANULES (PP/PDA/CS) of face-piece glycan；
10. taking out above-mentioned PP GRANULES, it is used in combination deionized water thoroughly to clean, to remove unreacted chitosan.Through upper
After stating processing routine, just obtains apparent height hydrophily and prevent the PP GRANULES of cell adherence.
The object of the present invention is to provide a kind of preparation methods of anti-adhesion medical polypropylene material, are carried out to polypropylene surface
It is modified, to obtain the performance of specific hydrophily and Anti cell adhesion.The present invention includes the following steps：1) by polypropylene material
Material is placed in dichloromethane and is cleaned by ultrasonic or stirring and washing 3~24 hours；2) at by above-mentioned polypropylene material by oxygen plasma
Reason 30 seconds~2 minutes；3) it will be placed in containing in Dopamine hydrochloride monomer solution by the polypropylene material of above procedure processing；It obtains
Obtain the polypropylene PP/PDA materials of surface DOPA amination；4) above-mentioned PP/PDA materials are placed on to 1%~2% chitosan polymerization
In object aqueous solution, the polypropylene material PP/PDA/CS of surface chitosan is obtained；5) poly- the third of above-mentioned surface chitosan is taken out
Alkene material PP/PDA/CS, is used in combination deionized water thoroughly to clean, to remove unreacted chitosan, after above-mentioned processing routine, just
Obtain the hydrophilic anti-adhesion medical polypropylene material of apparent height.
Claims (5)
1. a kind of preparation method of anti-adhesion medical polypropylene material, it is characterised in that this approach includes the following steps：
Step 1：Polypropylene material is placed in dichloromethane is cleaned by ultrasonic or stirring and washing 3~24 hours is to remove various additions
Agent, then 25 DEG C~40 DEG C dryings in an oven；
Step 2：Above-mentioned polypropylene material is passed through into oxygen plasma treatment 30 seconds~2 minutes；
Step 3：It will be placed in containing in Dopamine hydrochloride monomer solution by the polypropylene material of above procedure processing, at 25 DEG C
After being stirred to react 1~24 hour under~40 DEG C of condition heating, the polypropylene PP/PDA deionized waters of surface DOPA amination are taken out
After being thoroughly rinsed and it is dried in vacuo；Obtain the polypropylene PP/PDA materials of surface DOPA amination；
Step 4：Above-mentioned PP/PDA materials are placed in 1%~2% chitosan polymer aqueous solution, at 25 DEG C~40 DEG C
Under the conditions of heating stirring react 1~24 hour, obtain surface chitosan polypropylene material PP/PDA/CS；
Step 5：The polypropylene material PP/PDA/CS for taking out above-mentioned surface chitosan, is used in combination deionized water thoroughly to clean, with
Unreacted chitosan is removed, after above-mentioned processing routine, just obtains the hydrophilic anti-adhesion medical polypropylene of apparent height
Material；
The polypropylene material includes isotactic polypropylene, random polypropylene or syndiotactic polypropylene and 1%~4% ethylene of addition
Random copolymer RCP or more height ratio ethylene contents blocked copolymer, polypropylene material shape used include film, net,
One or more of combinations of silk, particle or microballoon.
2. the preparation method of anti-adhesion medical polypropylene material according to claim 1, which is characterized in that the hydrochloric acid
Dopamine monomer solution is the aqueous solution or trihydroxy aminomethane solution of Dopamine hydrochloride monomer.
3. the preparation method of anti-adhesion medical polypropylene material according to claim 1, which is characterized in that the heating
Stirring, reaction temperature are 25 DEG C~40 DEG C, and the reaction time is 1~24 hour.
4. the preparation method of anti-adhesion medical polypropylene material according to claim 1, which is characterized in that the shell is poly-
Deacetylation >=80% of chitosan used in glycopolymers aqueous solution.
5. the preparation method of anti-adhesion medical polypropylene material according to claim 4, which is characterized in that the shell is poly-
Glycopolymers aqueous solution, the aqueous acetic acid that solvent for use is 1%~2%.
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| CN107118305B (en) * | 2017-04-25 | 2019-04-30 | 东南大学 | A kind of preparation method of anti-adhesion medical polypropylene tissue patching material |
| CN108159508B (en) * | 2018-01-03 | 2021-01-26 | 东南大学 | Preparation method of anti-adhesion medical hydrogel material |
| CN108671271B (en) * | 2018-04-27 | 2020-12-25 | 东南大学 | Preparation method of anti-adhesion medical gel composite patch |
| CN109260528A (en) * | 2018-10-19 | 2019-01-25 | 中山大学 | A kind of bilayer prevents adhesion propene polymer patch and the preparation method and application thereof |
| CN109498835B (en) * | 2018-11-29 | 2020-08-11 | 中山大学 | Application of sodium hypochlorite in preparation of single-layer double-sided polypropylene/polydopamine patch |
| CN114106361B (en) * | 2020-08-25 | 2024-04-05 | 苏州至善新材料科技有限公司 | Polypropylene material loaded with zwitterionic polymer coating and preparation method thereof |
| CN114181421B (en) * | 2020-08-25 | 2023-09-12 | 苏州至善新材料科技有限公司 | Medical polypropylene material with highly hydrophilic surface and preparation method thereof |
| CN113041403B (en) * | 2021-03-25 | 2022-04-08 | 四川大学 | Bone repair n-HA/CS porous scaffold, preparation method and application |
| CN114163740B (en) * | 2021-12-06 | 2023-03-21 | 浙江大学 | Method for improving hydrophilicity of polyolefin elastomer |
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