CN105949491A - Preparation method of anti-adhesion medical PP (polypropylene) material - Google Patents
Preparation method of anti-adhesion medical PP (polypropylene) material Download PDFInfo
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- CN105949491A CN105949491A CN201610316325.XA CN201610316325A CN105949491A CN 105949491 A CN105949491 A CN 105949491A CN 201610316325 A CN201610316325 A CN 201610316325A CN 105949491 A CN105949491 A CN 105949491A
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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 invention provides a preparation method of an anti-adhesion medical PP (polypropylene) material. The preparation method comprises the following steps: step 1, a PP material is subjected to ultrasonic cleaning or stirring cleaning in dichloromethane for 3-24 h and then dried in a drying oven at the temperature of 25-40 DEG C; step 2, the PP material is treated with oxygen plasma for 30 s-2 min; step 3, the treated PP material is placed in a monomer solution containing dopamine hydrochloride, and a PP/PDA material with surface reacted with dopamine is obtained; step 4, the PP/PDA material is placed in a chitosan polymer aqueous solution with the concentration of 1%-2%, and a PP/PDA/CS material with the surface reacted with chitosan is obtained; step 5, the PP/PDA/CS material is taken out, and the anti-adhesion medical PP material with highly hydrophilic surface is obtained. The surface performance of a patch material is changed in a surface bio-modification manner, the adhesion probability is reduced, and occurrence of complications is reduced to the greatest extent.
Description
Technical field
The present invention relates to the surface modification technology of medical polypropylene material, particularly to gathering that a kind of dopamine is modified
The preparation method of propylene film, net, granule or micro-sphere material.
Background technology
Polypropylene (PP) is a kind of thermoplastic resin, is one of the most global five big general-purpose plastics, can be divided into isotactic
Polypropylene (isotaetic polyprolene), random polypropylene (atactic polypropylene) and syndiotactic polypropylene
(syndiotatic polypropylene) three kinds.PP is a kind of semi-crystalline material, than polyethylene (polyethylene,
PE) there are bigger hardness and higher fusing point.Owing to the polypropylene of homopolymerization type has certain fragility, so polymerization
Often be commonly incorporated into 1%～4% or the ethylene of higher amount as comonomer thus obtain polypropylene-polyethylene
Copolymer.The PP material of homopolymer type and copolymer type all have excellent resistance to water soak, antiacid caustic corrosion and
Antilysis.Polypropylene for medical article is widely used as medical device materials, as except being used as to manufacture medical leading
Outside pipe and blood purification filter membrane etc., in hernia surgical operation, also it is widely used as hernia patching material.But keeping it
On the premise of mechanics performance is not remarkably decreased, how to improve the hydrophilic of this kind of material, anti-adhesive and life
The thing compatibilitys etc., are still that technological difficulties and study hotspot.
Chitosan (chitosan, CS), nonpoisonous and tasteless, there is higher biocompatibility.CS is prone to film forming,
Its film has good anti-tissue adhesion's performance.Generally it is used between art coating relevant position, can effectively reduce
The generation of tissue adhesion.And have now the listing of business-like anti chitosan film, so for from raw material,
Chitosan is safe and reliable.
Summary of the invention
Technical problem: it is an object of the invention to provide and a kind of anti-adhesion medical polypropylene material is provided
Preparation method, at society, hernia incidence rate rises year by year, mainly takes vacation
Body is implanted the mode repaired and is solved this problem, and present most repairing prosthetic material is just
It is propene polymer patch, but extends in time after making Using prosthesis due to material self-characteristic, suffering from
Sticks together with internal organs in person's body, cause patient feel foreign body in vivo sense or bring serious concurrent
Disease, such as chronic pain, intestinal obstruction, bowel narrow etc..It is an object of the invention to by one new
The surface biological of grain husk modifies mode, makes patching material surface property change, prevents adhesion
Occurrence probability, reduces the generation of complication to the full extent.
Technical scheme: in order to solve the problems referred to above, the present invention provides a kind of anti-adhesion medical polypropylene
The preparation method of material, the method comprises the following steps:
Step one: polypropylene material is placed in dichloromethane ultrasonic cleaning or stirring and washing 3～24 hours with
Removing various additive, 25 DEG C～40 DEG C are dried the most in an oven；
Step 2: above-mentioned polypropylene material is processed 30 seconds～2 minutes by oxygen plasma；
Step 3: the polypropylene material processed through said procedure is placed in containing in dopamine hydrochloride monomer solution,
After stirring is reacted 1～24 hour under 25 DEG C～40 DEG C of condition heating, take out the polypropylene of surface DOPA amination
PP/PDA deionized water is thoroughly rinsed rear and is vacuum dried；Obtain the polypropylene PP/PDA of surface DOPA amination
Material；
Step 4: above-mentioned PP/PDA material is placed in the chitosan polymer aqueous solution of 1%～2%,
Under the conditions of 25 DEG C～40 DEG C, heated and stirred is reacted 1～24 hour, it is thus achieved that the polypropylene of surface chitosan
Material PP/PDA/CS；
Step 5: take out the polypropylene material PP/PDA/CS of above-mentioned surface chitosan, and use deionized water
Thoroughly clean, to remove unreacted chitosan, after above-mentioned processing routine, just obtain apparent height hydrophilic
Anti-adhesion medical polypropylene material.
Wherein:
Described polypropylene material includes isotactic polypropylene (isotaeticpolyprolene), random polypropylene
(atacticpolypropylene) or syndiotactic polypropylene (syndiotaticpolypropylene) and add 1%～4%
The Random copolymer RCP of ethylene or the blocked copolymer of more height ratio ethylene contents, polypropylene material shape used
The combination of one or more including film, net, silk, granule or microsphere.
The described aqueous solution that dopamine hydrochloride monomer solution is dopamine hydrochloride monomer or trihydroxy aminomethane are molten
Liquid.
Described heated and stirred, its reaction temperature is 25 DEG C～40 DEG C, and the response time is 1～24 hour.
Deacetylation >=80% of chitosan (chitosan) used by described chitosan polymer aqueous solution.
Described chitosan polymer aqueous solution, solvent for use is the aqueous acetic acid of 1%～2%.
Beneficial effect: this method can reach to make inertia polypropylene surface have by simple preparation process
The purpose of tissue adhesion functionalization, and the polypropylene material that this is surface-functionalized is used for hernia paster, Ke Yiyou
The adhesion preventing internal organs and sticking patch prosthese of effect, alleviates foreign body sensation and the generation of corresponding complication in the patient.With
Time also can effectively reduce corresponding medical burden.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure on simple PP surface.
Fig. 2 is the shape appearance figure on the PP surface after waiting oxyanion precursor to process.
Fig. 3 is the PP surface topography map after chitosan-modified.
Fig. 4 be chitosan-modified before (Fig. 4 A) (Fig. 4 B) afterwards, cell is in the form on PP surface.
Detailed description of the invention
The operating procedure of the present invention is as follows:
Step one: polypropylene material is placed in dichloromethane ultrasonic cleaning or stirring and washing 3～24 hours with
Removing various additive, 25 DEG C～40 DEG C are dried the most in an oven；
Step 2: above-mentioned polypropylene material is processed 30 seconds～2 minutes by oxygen plasma；
Step 3: the polypropylene material processed through said procedure is placed in containing in dopamine hydrochloride monomer solution,
After stirring is reacted 1～24 hour under 25 DEG C～40 DEG C of condition heating, take out the polypropylene of surface DOPA amination
PP/PDA deionized water is thoroughly rinsed rear and is vacuum dried；Obtain the polypropylene PP/PDA of surface DOPA amination
Material；
Step 4: above-mentioned PP/PDA material is placed in the chitosan polymer aqueous solution of 1%～2%,
Under the conditions of 25 DEG C～40 DEG C, heated and stirred is reacted 1～24 hour, it is thus achieved that the polypropylene of surface chitosan
Material PP/PDA/CS；
Step 5: take out the polypropylene material PP/PDA/CS of above-mentioned surface chitosan, and use deionized water
Thoroughly clean, to remove unreacted chitosan, after above-mentioned processing routine, just obtain apparent height hydrophilic
The anti-adhesion medical polypropylene material of property.
Embodiment 1
1., by 0.5g PP GRANULES (or microsphere), clean three times with dichloromethane, each 20mL, scavenging period
3 hours, and be dried 24 hours under the conditions of 40 DEG C.
2. above-mentioned polypropylene material is processed 2 minutes by oxygen plasma.
3. the PP GRANULES processed through said procedure is placed in the solution containing dopamine hydrochloride, heating 25 DEG C
Under the conditions of react after certain time, after taking-up deionized water is thoroughly rinsed and be vacuum dried；Obtain surface DOPA
The PP GRANULES of amination, reaction terminates rear solution and becomes brown, filters and is taken out by PP GRANULES.
4. in the aqueous solution of the chitosan that the product obtained by step 3 is placed on 1%, 30 DEG C of stirrings 24 are little
Time, it is thus achieved that the PP GRANULES (PP/PDA/CS) of surface chitosan；
5. take out above-mentioned PP GRANULES, and thoroughly clean with deionized water, to remove unreacted chitosan.Through upper
After stating processing routine, just obtain apparent height hydrophilic and prevent the PP GRANULES of cell adhesion.
Embodiment 2
1. PP GRANULES is laid on one piece of flake aluminum, magnetic force heating stirrer is heated to melt, then will
Another sheet aluminium flake is pressed on the PP GRANULES of thawing, controls thickness, prepares polypropylene screen.Film thickness is about
For 0.1mm, diameter is about 1cm～2cm.
2. by step 1 or polypropylene screen with dichloromethane clean three times, each 20mL, scavenging period 3 hours,
And be dried 24 hours under the conditions of 40 DEG C.
3. above-mentioned polypropylene sheet is processed 2 minutes by oxygen plasma.
4. the polypropylene sheet processed through said procedure is placed in the solution containing dopamine hydrochloride, in heating
After reacting certain time under the conditions of 25 DEG C, taking-up deionized water is thoroughly rinsed rear and is vacuum dried；Obtain
The polypropylene sheet of surface DOPA amination, reaction terminates rear solution and becomes brown, filters and polypropylene sheet is taken
Go out.
5. in the aqueous solution of the chitosan that the product obtained by step 4 is placed on 1%, 30 DEG C are stirred 24 hours,
Obtain the polypropylene sheet (PP/PDA/CS) of surface chitosan；
6. take out above-mentioned polypropylene sheet, and thoroughly clean with deionized water, to remove unreacted chitosan.Through upper
After stating processing routine, just obtain apparent height hydrophilic and prevent the polypropylene sheet of cell adhesion.
Embodiment 3
1. under room temperature, by polypropylene net (2cm × 2cm) 50g/m2Three times are cleaned, every time with dichloromethane or acetone
20mL, scavenging period 3 hours, and be dried 24 hours under the conditions of 40 DEG C.
2. above-mentioned polypropylene net is processed 2 minutes by oxygen plasma.
3. the polypropylene net processed through said procedure is placed in the solution containing dopamine hydrochloride, heating 25 DEG C
Under the conditions of react after certain time, after taking-up deionized water is thoroughly rinsed and be vacuum dried；Acquisition surface is many
The polypropylene net of bar amination, reaction terminates rear solution and becomes brown, filters and is taken out by polypropylene net.
4. in the aqueous solution of the chitosan that the product obtained by step 4 is placed on 1%, 30 DEG C of stirrings 24 are little
Time, it is thus achieved that the polypropylene net (PP/PDA/CS) of surface chitosan；
5. take out above-mentioned polypropylene net, and thoroughly clean with deionized water, to remove unreacted chitosan.Through above-mentioned
After processing routine, just obtain apparent height hydrophilic and prevent the polypropylene net of cell adhesion.
Embodiment 4
6., by 0.5g PP GRANULES (or microsphere), clean three times with dichloromethane, each 20mL, scavenging period
3 hours, and be dried 24 hours under the conditions of 40 DEG C.
7. above-mentioned polypropylene material is processed 1 minute by oxygen plasma.
8. the PP GRANULES processed through said procedure is placed in the solution containing dopamine hydrochloride, heating 25 DEG C
Under the conditions of react after certain time, after taking-up deionized water is thoroughly rinsed and be vacuum dried；Obtain surface DOPA
The PP GRANULES of amination, reaction terminates rear solution and becomes brown, filters and is taken out by PP GRANULES.
9. in the aqueous solution of the chitosan that the product obtained by step 3 is placed on 1%, 30 DEG C of stirrings 24 are little
Time, it is thus achieved that the PP GRANULES (PP/PDA/CS) of surface chitosan；
10. take out above-mentioned PP GRANULES, and thoroughly clean with deionized water, to remove unreacted chitosan.Through upper
After stating processing routine, just obtain apparent height hydrophilic and prevent the PP GRANULES of cell adhesion.
It is an object of the invention to provide the preparation method of a kind of anti-adhesion medical polypropylene material, polypropylene surface is carried out
Modified, in order to obtain the performance of specific hydrophilic and Anti cell adhesion.The present invention comprises the following steps: 1) will
Polypropylene material is placed in dichloromethane ultrasonic cleaning or stirring and washing 3～24 hours；2) above-mentioned polypropylene material is led to
Peroxide Cement Composite Treated by Plasma 30 seconds～2 minutes；3) polypropylene material processed through said procedure is placed in containing hydrochloric acid
In dopamine monomer solution；Obtain the polypropylene PP/PDA material of surface DOPA amination；4) by above-mentioned PP/PDA material
Material is placed in the chitosan polymer aqueous solution of 1%～2%, it is thus achieved that the polypropylene material of surface chitosan
PP/PDA/CS；5) the polypropylene material PP/PDA/CS of above-mentioned surface chitosan is taken out, and thorough with deionized water
The end, is cleaned, and to remove unreacted chitosan, after above-mentioned processing routine, just obtains apparent height hydrophilic anti-
Adhesion medical polypropylene material.
Claims (6)
1. the preparation method of an anti-adhesion medical polypropylene material, it is characterised in that the method include with
Lower step:
Step one: polypropylene material is placed in dichloromethane ultrasonic cleaning or stirring and washing 3～24 hours with
Removing various additive, 25 DEG C～40 DEG C are dried the most in an oven；
Step 2: above-mentioned polypropylene material is processed 30 seconds～2 minutes by oxygen plasma；
Step 3: the polypropylene material processed through said procedure is placed in containing in dopamine hydrochloride monomer solution,
After stirring is reacted 1～24 hour under 25 DEG C～40 DEG C of condition heating, take out the polypropylene of surface DOPA amination
PP/PDA deionized water is thoroughly rinsed rear and is vacuum dried；Obtain the polypropylene PP/PDA of surface DOPA amination
Material；
Step 4: above-mentioned PP/PDA material is placed in the chitosan polymer aqueous solution of 1%～2%,
Under the conditions of 25 DEG C～40 DEG C, heated and stirred is reacted 1～24 hour, it is thus achieved that the polypropylene of surface chitosan
Material PP/PDA/CS；
Step 5: take out the polypropylene material PP/PDA/CS of above-mentioned surface chitosan, and use deionized water
Thoroughly clean, to remove unreacted chitosan, after above-mentioned processing routine, just obtain apparent height hydrophilic
Anti-adhesion medical polypropylene material.
The preparation method of anti-adhesion medical polypropylene material the most according to claim 1, it is characterised in that
Described polypropylene material includes isotactic polypropylene, random polypropylene or syndiotactic polypropylene and adds 1%～4% second
The Random copolymer RCP of alkene or the blocked copolymer of more height ratio ethylene contents, polypropylene material shape bag used
Include the combination of one or more of film, net, silk, granule or microsphere.
The preparation method of anti-adhesion medical polypropylene material the most according to claim 1, it is characterised in that
The described aqueous solution that dopamine hydrochloride monomer solution is dopamine hydrochloride monomer or trihydroxy aminomethane solution.
The preparation method of anti-adhesion medical polypropylene material the most according to claim 1, it is characterised in that
Described heated and stirred, its reaction temperature is 25 DEG C～40 DEG C, and the response time is 1～24 hour.
The preparation method of anti-adhesion medical polypropylene material the most according to claim 1, it is characterised in that
Deacetylation >=80% of chitosan used by described chitosan polymer aqueous solution.
The preparation method of anti-adhesion medical polypropylene material the most according to claim 5, it is characterised in that
Described chitosan polymer aqueous solution, solvent for use is the aqueous acetic acid of 1%～2%.
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Cited By (9)
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| CN107118305A (en) * | 2017-04-25 | 2017-09-01 | 东南大学 | A kind of preparation method of anti-adhesion medical polypropylene tissue patching material |
| CN108159508A (en) * | 2018-01-03 | 2018-06-15 | 东南大学 | A kind of preparation method of anti-adhesion medical hydrogel material |
| CN108671271A (en) * | 2018-04-27 | 2018-10-19 | 东南大学 | A kind of 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 |
| CN109498835A (en) * | 2018-11-29 | 2019-03-22 | 中山大学 | Sodium hypochlorite is preparing the application in single-layer double-side polypropylene/poly-dopamine sticking patch |
| CN113041403A (en) * | 2021-03-25 | 2021-06-29 | 四川大学 | Bone repair n-HA/CS porous scaffold, preparation method and application |
| CN114106361A (en) * | 2020-08-25 | 2022-03-01 | 苏州至善新材料科技有限公司 | Polypropylene material loaded with zwitterionic polymer coating and preparation method thereof |
| CN114163740A (en) * | 2021-12-06 | 2022-03-11 | 浙江大学 | Method for improving hydrophilicity of polyolefin elastomer |
| CN114181421A (en) * | 2020-08-25 | 2022-03-15 | 苏州至善新材料科技有限公司 | Medical polypropylene material with highly hydrophilic surface and preparation method thereof |
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Cited By (15)
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| CN107118305A (en) * | 2017-04-25 | 2017-09-01 | 东南大学 | A kind of preparation method of anti-adhesion medical polypropylene tissue patching material |
| 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 |
| CN108159508A (en) * | 2018-01-03 | 2018-06-15 | 东南大学 | A kind of preparation method of anti-adhesion medical hydrogel material |
| CN108671271A (en) * | 2018-04-27 | 2018-10-19 | 东南大学 | A kind of preparation method of anti-adhesion medical gel composite patch |
| 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 |
| CN109498835A (en) * | 2018-11-29 | 2019-03-22 | 中山大学 | Sodium hypochlorite is preparing the application in single-layer double-side polypropylene/poly-dopamine sticking patch |
| CN114106361A (en) * | 2020-08-25 | 2022-03-01 | 苏州至善新材料科技有限公司 | Polypropylene material loaded with zwitterionic polymer coating and preparation method thereof |
| CN114181421A (en) * | 2020-08-25 | 2022-03-15 | 苏州至善新材料科技有限公司 | Medical polypropylene material with highly hydrophilic surface 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 |
| 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 |
| CN113041403A (en) * | 2021-03-25 | 2021-06-29 | 四川大学 | Bone repair n-HA/CS porous scaffold, preparation method and application |
| CN114163740A (en) * | 2021-12-06 | 2022-03-11 | 浙江大学 | Method for improving hydrophilicity of polyolefin elastomer |
| CN114163740B (en) * | 2021-12-06 | 2023-03-21 | 浙江大学 | Method for improving hydrophilicity of polyolefin elastomer |
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