CN1045452C - Carbon fiber containing chitosan composite film and its process - Google Patents
Carbon fiber containing chitosan composite film and its process Download PDFInfo
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- CN1045452C CN1045452C CN94103042A CN94103042A CN1045452C CN 1045452 C CN1045452 C CN 1045452C CN 94103042 A CN94103042 A CN 94103042A CN 94103042 A CN94103042 A CN 94103042A CN 1045452 C CN1045452 C CN 1045452C
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- carbon fiber
- chitosan
- composite membrane
- film
- composite film
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 208000031737 Tissue Adhesions Diseases 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 210000001951 dura mater Anatomy 0.000 abstract description 4
- 210000004224 pleura Anatomy 0.000 abstract description 3
- 210000003815 abdominal wall Anatomy 0.000 abstract 1
- 238000005266 casting Methods 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 13
- 229920002101 Chitin Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 4
- 238000003381 deacetylation reaction Methods 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 230000002490 cerebral effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000002980 postoperative effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 241000255789 Bombyx mori Species 0.000 description 1
- 208000003174 Brain Neoplasms Diseases 0.000 description 1
- 208000014644 Brain disease Diseases 0.000 description 1
- 102000012286 Chitinases Human genes 0.000 description 1
- 108010022172 Chitinases Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241001269524 Dura Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 206010019196 Head injury Diseases 0.000 description 1
- 108010064696 N,O-diacetylmuramidase Proteins 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 208000030886 Traumatic Brain injury Diseases 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 1
- 210000001691 amnion Anatomy 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 230000002429 anti-coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 210000002219 extraembryonic membrane Anatomy 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000007917 intracranial administration Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009772 tissue formation Effects 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
本发明公开了一种医用的含碳纤维的壳聚糖复合膜及其制备方法，该复合膜中壳聚糖与碳纤维的重量比为100∶0.5～25，膜的厚度0.04～0.20mm；用于制备上述复合膜的方法包括：将医用的壳聚糖溶解于稀酸中，去除不溶解物后的透明胶体，加入适量的碳纤维，分散均匀后倒入模中，流延展平，烘干用碱处理，水洗等过程，由此而制得的复合膜适用于硬脑膜，腹壁，胸膜及防组织粘连用途。The invention discloses a medical chitosan composite film containing carbon fiber and a preparation method thereof. The weight ratio of chitosan and carbon fiber in the composite film is 100:0.5-25, and the thickness of the film is 0.04-0.20mm; The method for preparing the above-mentioned composite film includes: dissolving medical chitosan in dilute acid, removing the transparent colloid after insoluble matter, adding an appropriate amount of carbon fiber, pouring it into a mold after dispersing evenly, casting and flattening, drying with alkali Processing, washing and other processes, the resulting composite film is suitable for dura mater, abdominal wall, pleura and anti-tissue adhesion purposes.
Description
The present invention relates to a kind of medicinal preparation, is a kind of chitosan complex film that contains carbon fiber specifically, be suitable for implanting or repair the material that human organ is used, and the preparation technology of this composite membrane.
Craniocerebral injury, dura defect often takes place in brain tumor and other brain disorder, needs in time to repair, preventing cerebrospinal leak, intracranial infection, the brain bulging, complication such as brain adhesion be the best with the frost drying human cerebral dura mater in the repair operations, but this type of are membrane derived limited; Also available animal film body, as the pig peritonaeum, fetal membrane, amnion etc., this type of film production, preservation, sterilizations etc. are all difficult.Recently, people have adopted the macromolecular material of biologically inert, as nylon, terylene, silicon rubber etc. as restorer, wherein better with terylene real silk cloth dual coating silicon rubber effect, it is big that it has a biologically inert, and the antibiont aging is strong, contact strong point such as be difficult for sticking together with tissue secretory product, but silicon rubber also has many deficiencies, and the most serious is so-called " diaphragm is carcinogenic ", just cracked the and surrounding tissue formation fibering parcel of swelling.At above deficiency, the Chinese patent Shen clear case (application number: 89106587.3 of " a kind of Carbonfibric hard meninx and treatment process thereof ", open day: March 14 nineteen ninety, publication number: CN1040318A), it provides a kind of novel endocranium preparation, and it is the film that a kind of carbon fiber is made into, it has good toolability, do not have " diaphragm is carcinogenic " effect, but exist flexibility poor, can not be absorbed deficiencies such as processed complex.United States Patent (USP) (Unitedstates Patent, Feb.14,1984) the 4th, 431, No. 601 " PROCESSFOR THE PRODUCTION OF CHITIN FIBERS ", European patent (EP0328050A2) " High strength chitosan fibers andfabrics thereof ", and the flat 2--17643 of Japanese Patent " special permission communique) ", 11～15 pages (1990) disclose employing chitin and derivative (being chitosan) thereof but the method for preparation absorption operating sutures.
The flat 3--258723 of European patent " Compositions containing derivatives ofchitin for preventing adhesion " (EP 0426368A2) and Japanese Patent " special permission communique (A) ", but tissue adhesion's film and the anti-even method of liquid prevented after only disclosing employing chitin and the operation of derivative preparation absorption thereof.The simple repairing film that uses chitin and derivative thereof to be prepared into though have good biocompatibility, and can play certain anti-effect that connects liquid, waits not enoughly but still take place to curl when having the film body hygrometric state, brings difficulty to operation.
The objective of the invention is to overcome fast the deficiencies in the prior art, a kind of composite membrane is provided, this composite membrane has good biocompatibility, and open and flat, soft when having higher dry state, wet strength and hygrometric state.
The chitosan complex film of the carbon fiber-containing described in the present invention, it is composited by chitosan and chopped carbon fiber, and its thickness is 0.04～0.20mm, and wherein the weight ratio of chitosan and carbon fiber is 100: 0.5～25.
The preparation method of the composite membrane described in the present invention comprises following processing step:
A: dissolve at least a chitosan in dilute acid soln;
B: add chopped carbon fiber;
C: the dispersion glue stirs;
D: dry glue becomes composite membrane;
E: use in the alkali and the acid in the above-mentioned composite membrane;
F: clean composite membrane to neutral.
It is multiple to adopt the carbon fiber source to have among the present invention, and it can be the fine carbon fiber of polypropylene, viscose-based carbon fiber, any in the asphalt base carbon fiber.
Carbon fiber is cut shape for short among the present invention, and its length is 1～10mm.
The acid of the dissolving chitosan that adopts among the preparation method among the present invention has multiple, for example hydrochloric acid, lactic acid or acetic acid; The alkali of above-mentioned acid of being used to neutralize also can be multiple, for example sodium hydroxide, ammoniacal liquor, yellow soda ash or its mixture.
It is the film forming matrix that the present invention adopts chitosan, is strongthener with the carbon fiber, and the film of compound back preparation is mainly used in duramater reparation thing and membranous wall, peritonaeum, pleura etc. or is used for preventing tissue adhesion after the human body operation.
Chitosan content in film can be decomposed absorption by the chitinase in the human body, N,O-Diacetylmuramidase more than 80% among the present invention, and the repairing residue is reduced significantly; Adopting carbon fiber is the strongthener of film body, and it not only can improve the doing of film, wet strength and sewing properties, curls in the time of can also preventing the film body hygrometric state.During composite membrane dry state among the present invention is dura mater, is soft film during hygrometric state, and water-intake rate reaches more than 80%, and raw material is easy to get, preparation technology is simple.
Concrete preparation method and condition are:
1. soluble chitosan (deacetylation 30～95%) is dissolved in the solution that contains acid 0.5～3%, behind the removal nonsoluble, makes the transparent glue of chitosan-containing 1～6%.Used chitosan can be by the shrimp shell, and crab shell, silkworm chrysalis shell etc. extracts contains ash less than 0.1% medical chitosan.Used acid can be acetic acid, lactic acid or hydrochloric acid.
2. carbon fiber carries out medical pyrolysis processing at 1000～1300 ℃, and short 1～10mm length that is cut into is 100: 0.5～25 by chitosan, carbon fiber weight ratio, stirs at least 2 hours, until homodisperse.
3. finely dispersed carbon fiber chitosan glue is poured in the mould, and horizontal flow spreads apart, in 20～70 ℃, and 30～60 ℃ of dryings preferably.
4. the film that makes neutralizes in the aqueous solution that contains alkali 2～4%, and used alkali can be NaOH, NH
3H
2O, Na
2CO
3In a kind of or mixed solution that several form, the treatment time was good with 8 hours more than 2 hours.
5. in and after film in hot water, desalt, treatment temp is at 40～100 ℃, best 60～80 ℃, 4 hours time was good.
6. after the film that makes being launched drying, promptly make the chitosan complex film of carbon fiber-containing of the present invention, this composite membrane can pass through alcohol disinfecting, disinfection by ultraviolet light, and oxirane disinfection, the r radiation sterilization is to satisfy the operation hygienic requirements.
The present invention confirms that through experimentation on animals certain anticoagulant effect is arranged, and does not destroy blood, excellent biological compatibility is arranged, the absorption that was decomposed in six months of chitosan in the film, remaining inertia carbon fiber remain in the newborn membrane tissue, and repairing film has good anti effect to surrounding tissue.
The composite membrane that the present invention makes is used for hard 32 examples of decreasing of clinical repairing meninx, maximum 8 * 6cm through one 0 five hospitals of PLA
2, minimum 4 * 3cm
2, postoperative blood is normal, and to body and cerebral tissue vacuum response, postoperative is followed up a case by regular visits to 3～25 monthly having no adverse reaction.Be used for peritonaeum and repair 2 example and belly anti 1 examples, result of treatment is good.The clinical carbon fiber chitosan complex film that shows is a kind of comparatively ideal human body patching material, selects different fibre contents and film thickness for use, can also be used for defect repairings such as endocranium, stomach wall, peritonaeum, pleura, and purposes such as operation rear defence tissue adhesion.
Embodiment 1
Powder shape chitosan (is that 0.28 millimeter standard sieve sieves deacetylation 92% with the aperture) 20g is added in the aqueous solution that contains acetic acid 2%, and stirring and dissolving is removed nonsoluble, 3% transparent glue.The short carbon fiber 2g that is cut into 2～4mm is added, stir and got the homodisperse glue in 4 hours, pour in the mould, horizontal flow spreads apart, and 50 ℃ of oven dry are soaked film 8 hours in 4% NaOH, be washed to neutrality, in 70 ℃ of hot water, soak 2 times again, each 5 hours, take out flattening, airing, the thickness that makes is 0.084mm, dry film intensity 95.3MPa, water-intake rate 94%, 0# surgical thread tape edge pulling force 485g.This film accords with dural particular requirement.
Embodiment 2
(with the aperture is that 0.28 millimeter standard sieve sieves to powder shape chitosan, deacetylation 72%) 20g is added in 3% the lactic acid aqueous solution, stirring and dissolving, remove nonsoluble, be made into 2% glue, the short carbon fiber 4g that is cut into 4～8mm is added, stir and got homodisperse liquid in 6 hours, pour in the film tool, being washed to neutrality embathes 2 times in 80 ℃ of hot water again, each 5 hours, take out and launch airing, the thickness 0.138mm that makes, dry strength 145MPa, wet strength 20.2MPa, water-intake rate 84%, 0# operation silk thread tape edge pulling force 862g.This composite membrane is suitable for repairing stomach wall.
Embodiment 3
Powder shape chitosan (is that 0.18 millimeter standard sieve sieves deacetylation 96% with the aperture) 20g is dissolved in 2% the aqueous hydrochloric acid, removes and does not allow to separate thing, get 4% transparent glue, add the short carbon fiber 0.4g that is cut into 2～4mm, stirred 4 hours, get the homodisperse glue, pour in the mould, horizontal flow spreads apart, 2% NaOH neutralization is gone in 40 ℃ of oven dry, example, and hot water wash is to neutral, soak 2 times, each 8 hours, oven dry made thickness 0.054mm, dry strength 8.5MPa, water-intake rate 105%.It is comparatively desirable that this film is used for Antiadhesive film.
Claims (6)
1. the chitosan complex film of a carbon fiber-containing, it is characterized in that: it is composited by chitosan and chopped carbon fiber, and its thickness is 0.04～0.20mm, and the weight ratio of chitosan and carbon fiber is 100: 0.5～25.
2. the chitosan complex film of carbon fiber-containing according to claim 1 is characterized in that: fast carbon fiber be the fine carbon fiber of polypropylene, viscose-based carbon fiber, any in the asphalt base carbon fiber.
3. the chitosan complex film of carbon fiber-containing according to claim 1 and 2, it is characterized in that: the length of described carbon fiber is 1～10mm.
4. the preparation technology of the chitosan complex film of the described carbon fiber-containing of claim 1, its processing step is as follows:
A: dissolve at least a chitosan;
B: add chopped carbon fiber;
C: the dispersion glue stirs;
D: dry glue becomes composite membrane;
E: use in the alkali and acid in the above-mentioned composite membrane;
F: clean above-mentioned composite membrane to neutral.
5. the preparation technology of composite membrane according to claim 4 is characterized in that: the described acid that is used to dissolve chitosan is: hydrochloric acid, lactic acid or acetic acid.
6. the preparation technology of composite membrane according to claim 4, it is characterized in that: the described neutral alkali that is used for is: sodium hydroxide, ammoniacal liquor, yellow soda ash or its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103042A CN1045452C (en) | 1994-03-18 | 1994-03-18 | Carbon fiber containing chitosan composite film and its process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103042A CN1045452C (en) | 1994-03-18 | 1994-03-18 | Carbon fiber containing chitosan composite film and its process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094066A CN1094066A (en) | 1994-10-26 |
| CN1045452C true CN1045452C (en) | 1999-10-06 |
Family
ID=5030913
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94103042A Expired - Fee Related CN1045452C (en) | 1994-03-18 | 1994-03-18 | Carbon fiber containing chitosan composite film and its process |
Country Status (1)
| Country | Link |
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| CN (1) | CN1045452C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301495B (en) * | 2008-06-03 | 2012-07-25 | 陕西科技大学 | Method for preparing bone screw biological compound material |
| CN102488928A (en) * | 2011-12-26 | 2012-06-13 | 重庆科技学院 | Preparation method of carbon-fiber-enhanced biological composite scaffold material |
| CN104725753A (en) * | 2015-03-31 | 2015-06-24 | 苏州维泰生物技术有限公司 | Carbon nanofiber-chitosan-polyvinyl alcohol medical composite film and preparation method thereof |
| CN108722202B (en) * | 2018-05-07 | 2021-09-21 | 东华理工大学 | Preparation method of carbon fiber reinforced sodium tripolyphosphate cross-linked chitosan/carbon nanotube composite filter membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1609795A1 (en) * | 1988-05-24 | 1990-11-30 | Ленинградский Технологический Институт Им.Ленсовета | Method of producing chitosane films |
| JPH03151976A (en) * | 1989-11-08 | 1991-06-28 | Fuji Spinning Co Ltd | Chitosan film for medical care |
-
1994
- 1994-03-18 CN CN94103042A patent/CN1045452C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1609795A1 (en) * | 1988-05-24 | 1990-11-30 | Ленинградский Технологический Институт Им.Ленсовета | Method of producing chitosane films |
| JPH03151976A (en) * | 1989-11-08 | 1991-06-28 | Fuji Spinning Co Ltd | Chitosan film for medical care |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1094066A (en) | 1994-10-26 |
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