CN101669965A - Application of PEG-PCL-PEG triblock copolymer in preparation of medical anti-adhesion material - Google Patents
Application of PEG-PCL-PEG triblock copolymer in preparation of medical anti-adhesion material Download PDFInfo
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- CN101669965A CN101669965A CN200910304210A CN200910304210A CN101669965A CN 101669965 A CN101669965 A CN 101669965A CN 200910304210 A CN200910304210 A CN 200910304210A CN 200910304210 A CN200910304210 A CN 200910304210A CN 101669965 A CN101669965 A CN 101669965A
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Abstract
The invention relates to the field of medical high polymer materials, and in particular to an application of triblock copolymer in preparation of medical anti-adhesion material. The invention aims tosolve the technical problem of providing a new choice for medical anti-adhesion material, and has the technical scheme of providing the application of PEG-PCL-PEG triblock copolymer in preparation ofmedical anti-adhesion material, wherein the molecular weight of the PEG-PCL-PEG copolymer is from 1500 to 10000, the ratio of the molecular weight of the PEG chain to the molecular weight of the PCL chain is 0.4 to 2.6; and the triblock copolymer can be dissolved in water to form a solution and form gel after reaching a certain intensity. Experiments prove that water gel of the PEG-PCL-PEG triblock copolymer has many good characteristics, and provides a new choice for the field of medical anti-adhesion materials.
Description
Technical field
The present invention relates to pharmaceutical polymeric material field, be specifically related to a kind of water miscible, the biodegradable triblock copolymer that can form gel purposes in preparation medical anti-adhesive material.
Background technology
Tissue adhesion is the unsolved for a long time difficult problem of surgical operation circle.So far people are seeking the adhesion of the whole bag of tricks prevention of postoperative, but the clinical effectiveness of present technical scheme is all not fully up to expectations, is difficult to reach ideal clinical requirement.In recent years, the position that sticks together easily after surgery implant isolated material become prevent in the world tissue adhesion common practice.The anti thin film, anti-adhesion gel, antiblocking liquors etc., above-mentioned material have advantage separately, but also its weak point are arranged all.People wish to develop a kind of easy to use anti-adhesion gel similar to the toothpaste state, to have good adhering to and the tissue adhesion effect.
The Chinese patent application of application number 200810062241.3 discloses a kind of medical anti-adhesive gel rubber material, and this gel rubber material is to be prepared from by compositions such as poloxamer 407, hyaluronic acid or hyaluronate sodium, glycerol, propylene glycol, water.This application declares that this anti-adhesion gel material is liquid below 20 degree, 20 to 40 can be converted into solid to reach the purpose of anti when spending, but wherein do not provide any evidence that under set point of temperature, changes mutually that this material can be realized being declared, do not provide any description of test that can prevent tissue adhesion to material yet.In addition since as the poloxamer of this body of material composition (Pluronicor Poloxamer, it is higher PEG-PPG-PEG) to have a critical gel strength, gel strength a little less than, and can not biodegradation etc. shortcoming, so this material also is difficult to extensive use.
The Chinese patent application of application number 200810300757.7 discloses a kind of PEG-PCL-PEG triblock copolymer, and it is solid or thick liquid under normal operation, and water soluble has temperature sensitivity.
At present, available other medical materials or be to prepare after will being dissolved in organic solvent are unfavorable for human body safety; Be that preventing adhesiving effect is bad, and cost an arm and a leg, be difficult to transportation and preserve.
This area is badly in need of that development effectiveness is better, and cost is lower, prepares, preserves, transports and use medical anti-adhesive material more easily.
Summary of the invention:
First technical problem to be solved by this invention is for the medical anti-adhesive material provides a kind of new cost lower, effective selection of better effects if.
The technical scheme of technical solution problem of the present invention provide the PEG-PCL-PEG triblock copolymer in preparation medical anti-adhesive material new purposes and be medical anti-adhesive material of preparing of primary raw material and preparation method thereof with the PEG-PCL-PEG triblock copolymer.
Wherein, the molecular weight of above-mentioned PEG-PCL-PEG copolymer is 1500～10000, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is 0.4～2.6.This copolymer can be dissolved in water and form aqueous solution, can form colloidal sol after reaching finite concentration, can form gel under proper condition then.
Wherein, above-mentioned PEG-PCL-PEG molecular weight of copolymer is 2000～8000, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is 0.5～2.
Wherein, above-mentioned PEG-PCL-PEG (being called for short PECE) copolymer is
E
550-C
2200-E
550, E
750-C
3000-E
750, E
750-C
2500-E
750, E
750-C
750-E
750, E
2000-C
4000-E
2000Wherein E represents PEG, and C represents PCL, and subscript is represented corresponding segmental molecular weight respectively.
Medical anti-adhesive material of the present invention is by the PEG-PCL-PEG copolymer gel that forms behind the colloidal sol of making soluble in water.If cold preservation is handled after making colloidal sol, the speed that then forms gel is faster.
Wherein, above-mentioned gel is to be 1500～10000 by molecular weight, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is that 0.4～2.6 PEG-PCL-PEG copolymer is that primary raw material is prepared from.
Wherein, above-mentioned gel is to be 2000～8000 by the PEG-PCL-PEG molecular weight of copolymer, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is that 0.5～2 PEG-PCL-PEG copolymer is that primary raw material is prepared from.
Wherein, above-mentioned gel is by the PEG-PCL-PEG copolymer
E
550-C
2200-E
550, E
750-C
3000-E
750, E
750-C
2500-E
750, E
750-C
750-E
750, E
2000-C
4000-E
2000For primary raw material is prepared from.Wherein E represents PEG, and C represents PCL, and subscript is represented corresponding segmental molecular weight respectively.
Wherein, above-mentioned medical anti-adhesive material is by with the above-mentioned PEG-PCL-PEG copolymer solution that is mixed with 15～40wt% soluble in water, and this solution is warmed up to the hydrogel that 50 ℃ of processing obtain after 5 minutes more earlier after handling 24 hours below 4 ℃.
Preferably, the water-soluble concentration of the concentration of above-mentioned hydrogel is 20～30wt%.The above-mentioned words that then are preferably normal saline as aqueous solvent
Further, above-mentioned medical anti-adhesive material can also load medicines such as anti-inflammatory drug, somatomedin, analgesic or antitumor drug in preparation.
The present invention prepares the method for above-mentioned medical anti-adhesive material, it is characterized in that comprising the steps:
A, preparation PEG-PCL-PEG copolymer;
B, ready PEG-PCL-PEG triblock copolymer is dissolved in the normal saline mix homogeneously;
C, with the materials mixed aqueous solution about 5 minutes of 50 ℃ of following heated and stirred, form translucent thick liquid, be cooled to and be not higher than 4 ℃, cold preservation became gel greater than 24 hours, promptly got the medical anti-adhesive material.
If add anti-inflammatory drug, somatomedin, analgesic or antitumor drug etc. in medical anti-adhesive material of the present invention, then in step b, these medicines and PEG-PCL-PEG are dissolved in the normal saline jointly mix homogeneously.
The present invention creatively provides the purposes of water miscible PEG-PCL-PEG block copolymer in preparation medical anti-adhesive material, use have good biocompatibility, can fast degraded biologically, do not need to use the PEG-PCL-PEG block copolymer medical anti-adhesive gel of deleterious solvent to use during moderate, the preparation of gel strength as the medical anti-adhesive material.PEG-PCL-PEG block copolymer medical anti-adhesive preparing gel is easy, with low cost, be suitable for large-scale production and application, effectively overcome various prior aries defective separately, combination property is outstanding, provide a kind of new selection for needs use the field of medical anti-adhesive material, be with a wide range of applications.
Description of drawings:
Fig. 1 is a rat stomach wall caecum frictional experiment.A: modelling.B: use hydrogel as the anti barrier.C: postoperative seven days sticks together between matched group (normal saline group) rat caecum and stomach wall.D: hydrogel treatment group, caecum and stomach wall have been repaired intact, do not have adhesion to take place, and hydrogel is degraded and absorbed fully simultaneously.
Fig. 2 is a mice stomach wall caecum frictional experiment, and the water breakthrough gel does not have any toxic and side effects, can not influence wound healing.A: perform the operation one day after, a large amount of hydrogels are attached to wound face, because wound face oozes out, hydrogel is dyed redness.B: performed the operation back three days, a large amount of hydrogels are attached to wound face, and non-wound face hydrogel absorbs gradually.C: performed the operation back five days, visible hydrogel is attached to wound surface, the few D of non-wound surface hydrogel: performed the operation back seven days, the low amounts of water gel is attached to wound surface, and the hydrogel of non-wound surface part has absorbed fully.E: operation back fortnight, impaired caecum and stomach wall are repaired intact, and hydrogel absorbs fully.F: the control group mice operation is after seven days, and firmly adhesion forms.
Fig. 3 is a mice stomach wall caecum frictional experiment pathological section, and the water breakthrough gel does not have any toxic and side effects, can not influence wound healing.A: the hydrogel group was performed the operation back five days, and a large amount of hydrogels are attached to wound face, did not see that adhesion forms.B: the hydrogel group was performed the operation back seven days, and the low amounts of water gel is attached to wound face, and wound surface begins mesotheliumization.C: hydrogel group operation back fortnight, hydrogel absorbs fully, the complete mesotheliumization of wound surface.D: the caecum wound surface after the reparation, hydrogel absorbs fully, mesotheliumization fully, no adhesion produces.E: the peritoneum wound surface after the reparation, hydrogel absorbs fully, mesotheliumization fully, no adhesion produces.F: the control group mice operation is after seven days, and firmly adhesion forms.
Fig. 4 is a rat stomach wall fallopian tube frictional experiment, and the water breakthrough gel does not have any toxic and side effects, can not influence wound healing.A: modelling.B: use hydrogel as the anti barrier.C: postoperative seven days sticks together between matched group (normal saline group) rat fallopian tube and stomach wall.D: hydrogel treatment group, fallopian tube and stomach wall have been repaired intact, do not have adhesion to take place, and hydrogel is degraded and absorbed fully simultaneously.
Fig. 5 is the cell toxicity test of hydrogel material, and cell is a WISH cell.
Fig. 6 is the synthetic reaction skeleton symbol of PEG-PCL-PEG copolymer of the present invention.
Further describe by the specific embodiment below in conjunction with accompanying drawing but do not limit the present invention.
The specific embodiment:
Main agents and instrument that the embodiment of the invention is used:
6-caprolactone (ε-CL, Alfa Aesar company, analytical pure)
Poly glycol monomethyl ether (MPEG, Mn=550,750,1000, Aldrich company, analytical pure)
Stannous octoate (Stannous octoate, Sigma company, analytical pure)
Isophorone diisocyanate (IPDI, Aldrich company, analytical pure)
Toluene di-isocyanate(TDI) (Sigma company, analytical pure)
Hexamethylene diisocyanate (HDI): (Sigma company, analytical pure)
L-lysine ethyl ester diisocyanate (LDI, ethyl ester of lysine vulcabond): self-control.
Diphenyl methane-4,4 '-vulcabond (Sigma company, analytical pure)
Varian 400 type nuclear magnetic resonance analyser (U.S. Varian company)
200SXV type Fourier infrared spectrograph (Nicolet company)
Synthetic and the checking of embodiment one PEG-PCL-PEG copolymer
1) the PEG-PCL-PEG copolymer is synthetic
The synthetic reaction of PEG-PCL-PEG copolymer of the present invention is as shown in Figure 6:
Wherein X, Y are positive integer.
Synthetic route according to following formula; adding a certain amount of poly glycol monomethyl ether (MPEG) and 6-caprolactone in the there-necked flask of agitator is housed (ε-CL); with the stannous octoate is catalyst; reaction is 6 hours under 130 ℃, the condition of nitrogen protection; be cooled to 80 ℃; adding cross-linking agent isoflurane chalcone diisocyanate (IPDI) continues reaction again and obtains product after 6 hours, is cooled to room temperature and purifies, oven dry.In addition, the vulcabond that is fit to also comprises: toluene di-isocyanate(TDI), hexamethylene diisocyanate (HMDI), L-lysine ethyl ester diisocyanate (LDI, the ethyl ester of lysine vulcabond), diphenyl methane-4,4 '-vulcabond etc.When carrying out above-mentioned reaction, can substitute IPDI and carry out coupling reaction with above-mentioned vulcabond.
According to said method, synthetic
E
550-C
2200-E
550、E
750-C
3000-E
750、E
750-C
2500-E
750、E
750-C
750-E
750、E
2000-C
4000-E
2000
Deng series copolymer (seeing Table 1).
The synthetic PEG-PCL-PEG copolymer of table 1 this patent
| Sequence number | Copolymer | ??PEG/PCL? a | ??TotalMn? a | ??PEG/PCL b??( 1H-NMR) | ??Total?Mn? b??( 1H-NMR) |
| ??S1 | ??E 550-C 2200-E 550 | ??1100/2200＝0.5 | ??3300 | ??960/2448 | ??3408 |
| ? ??S2 | ? ??E 750-C 3000-E 750 | ? ??1500/3000＝0.5 | ? ??4500 | ??1518/311 ??6 | ? ??4634 |
| ? ??S3 | ? ??E 750-C 2500-E 750 | ? ??1500/2500＝0.6 | ? ??4000 | ??1481/243 ??3 | ? ??3914 |
| ??S4 | ??E 750-C 750-E 750 | ??1500/750＝2 | ??2250 | ??1505/707 | ??2212 |
| ? ??S5 | ? ??E 2000-C 4000-E 2000 | ? ??4000/4000＝1 | ? ??8000 | ??4169/402 ??9 | ? ??8198 |
aThe theoretical value of calculating according to rate of charge
bThe numerical value that comes out according to the proton nmr spectra test result calculations;
2, the checking of PEG-PCL-PEG copolymer
(1), the characterizing method of PEG-PCL-PEG copolymer of the present invention
(200SXV Nicolet), adopts the KBr pressed disc method that synthetic copolymer is carried out infrared spectrum analysis with Fourier infrared spectrograph (FTIR).
1(Varian 400, Varian) measure, and under 400MHZ, solvent is CDCl with nuclear magnetic resonance analyser for H-NMR
3, be interior mark with tetramethylsilane.The block ratio of the molecular weight of various PEG-PCL-PEG triblock copolymers and PEG and PCL detects to determine according to proton nmr spectra.Can reach a conclusion according to above-mentioned result of the test: it is E that present embodiment has successfully synthesized theoretical value
550-C
2200-E
550, E
750-C
3000-E
750, E
750-C
2500-E
750, E
750-C
750-E
750, E
2000-C
4000-E
2000The PEG-PCL-PEG triblock copolymer.
Embodiment two uses the PEG-PCL-PEG copolymer to become the medical anti-adhesive material
Use the PEG-PCL-PEG copolymer of the foregoing description preparation to become the medical anti-adhesive material: earlier with E
550-C
2200-E
550Be dissolved in the normal saline, concentration is 15-40wt%, and preferred concentration is 25wt%, fully stirs mix homogeneously.With the normal saline solution that mixes about 5 minutes of heated and stirred under 50 ℃ of degree, form translucent thick liquid, be cooled to below 4 ℃ stand-by.Using method has two kinds of a: around colloidal sol shape hydrogel injection wound surface, by the rising of temperature, form gel.B: colloidal sol shape hydrogel is handled greater than 24 hours in cold preservation below 4 ℃,, made hydrogel finish gelation, during application, directly spread upon on the abdominal cavity wound surface by crystallization.Consider the convenience of using and preserving, we select to adopt second method, that is: colloidal sol shape hydrogel is handled greater than 24 hours in cold preservation below 4 ℃, pass through crystallization, make hydrogel finish gelation, during application, directly this hydrogel is spread upon on the abdominal cavity wound surface.
The preventing adhesiving effect experiment of embodiment three medical anti-adhesive materials of the present invention
Hydrogel is used as a kind of anti barrier.Concrete grammar is that the copolymer that embodiment two prepares is dissolved in the normal saline, be mixed with the solution of 25wt%, again this colloidal sol shape hydrogel is handled greater than 24 hours in cold preservation below 4 ℃, pass through crystallization, make hydrogel finish gelation, during application, directly gel is evenly spread upon abdominal cavity wound surface wound surface and smear on every side.
1, stomach wall-caecum frictionally damage model: with Animal Anesthesia, open abdomen,,, simultaneously adjacent stomach wall is peeled off placenta percreta (mice: 1X1cm with dissecting knife with surperficial placenta percreta damage with caecum dry gauze friction; Rat: 2X2cm).Use PEG-PCL-PEG hydrogel (mice: 0.2ml at damage surface then; Rat: 1ml) smear evenly, close the abdominal cavity.
Below mainly pass through E
550-C
2200-E
550The description of hydrogel experiment is in conjunction with the concrete effect of caption as adherence preventing material.
A, rat stomach wall caecum frictional experiment result show (Fig. 1): postoperative seven days sticks together between matched group (normal saline group) rat caecum and stomach wall.Use PEG-PCL-PEG (E
550-C
2200-E
550) hydrogel is as the hydrogel treatment group of anti barrier, caecum and stomach wall have been repaired intact, do not have adhesion to take place, and hydrogel is degraded and absorbed fully simultaneously.
B, mice stomach wall caecum frictional experiment experimental result show (Fig. 2): perform the operation one day after, a large amount of hydrogels are attached to wound face, because wound face oozes out, hydrogel is dyed redness; Performed the operation back three days, a large amount of hydrogels are attached to wound face, and non-wound face hydrogel absorbs gradually; Performed the operation back five days, visible hydrogel is attached to wound surface, and non-wound surface hydrogel is few; Performed the operation back seven days, the low amounts of water gel is attached to wound surface, non-wound surface part, and hydrogel has absorbed fully; Operation back fortnight, impaired caecum and stomach wall are repaired intact, PEG-PCL-PEG (E
550-C
2200-E
550) hydrogel absorbs fully.And control group mice operation is after seven days, and firmly adhesion forms.
Simultaneously, by mice stomach wall caecum frictional experiment pathological section (Fig. 3) also not the water breakthrough gel any toxic and side effects is arranged, can not influence wound healing.
2, stomach wall-fallopian tube frictionally damage model: with Animal Anesthesia, open abdomen, with the dry gauze friction of right side fallopian tube, with surperficial placenta percreta damage, simultaneously adjacent stomach wall is peeled off placenta percreta (rat: 2X2cm), use PEG-PCL-PEG (E at damage surface then with dissecting knife
550-C
2200-E
550) hydrogel (rat: 1ml) smear evenly, close the abdominal cavity.
Rat stomach wall fallopian tube frictional experiment result shows (Fig. 4): postoperative seven days sticks together between matched group (normal saline group) rat fallopian tube and stomach wall; Use the hydrogel treatment group of hydrogel as the anti barrier, fallopian tube and stomach wall have been repaired intact, do not have adhesion to take place, and the PEG-PCL-PEG hydrogel is degraded and absorbed fully simultaneously.The water breakthrough gel does not have any toxic and side effects, can not influence wound healing.The effect of above-mentioned anti experiment also obviously is better than doing simultaneously the hyaluronate sodium adherence preventing material group of contrast.
Simultaneously, the similar experiment of other gel rubber materials of the present invention is also shown to have approaching preventing adhesiving effect, just along with the raising of molecular weight, the time of its biodegradation and absorption can prolong, such as E
2000-C
4000-E
2000Complete soak time be 3 to 4 weeks, be applicable to that the long or wound of wound healing time is influenced in the bigger surgical operation by the organ wriggling, those skilled in the art can select according to the actual requirements.
Embodiment four medical anti-adhesive material biocompatibility tests of the present invention
Biocompatibility has mainly been investigated, cytotoxicity, hemolytic test and three aspect contents of anxious poison test.Also got simultaneously the region of interest of using hydrogel material, cut into slices, its pathology effects to surrounding tissue is observed in the SABC test.
The present invention has also detected the cytotoxicity of medical anti-adhesive material of the present invention with the survival experiment of WISH cell system, the results are shown in Figure 5, and the result shows the basic no cytotoxicity of medical anti-adhesive material of the present invention.
Above-mentioned experiment synthesis result shows that it is harmless that PEG-PCL-PEG triblock copolymer of the present invention is dissolved in the medical anti-adhesive material non-toxic that makes in the normal saline, is that a kind of preventing adhesiving effect is good, the medical anti-adhesive material of good biocompatibility.
Claims (13)
1.PEG-PCL-PEG the purposes of triblock copolymer in preparation medical anti-adhesive material.
2. purposes according to claim 1 is characterized in that: described PEG-PCL-PEG copolymer, its molecular weight are 1500～10000, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is 0.4～2.6.
3. purposes according to claim 1 is characterized in that: described PEG-PCL-PEG molecular weight of copolymer is 2000～8000, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is 0.5～2.
4. purposes according to claim 3 is characterized in that: described PEG-PCL-PEG copolymer is E
550-C
2200-E
550, E
750-C
3000-E
750, E
750-C
2500-E
750, E
750-C
750-E
750Or E
2000-C
4000-E
2000Wherein E represents PEG, and C represents PCL, and subscript is represented corresponding segmental molecular weight respectively.
5. medical anti-adhesive material, it is characterized in that: described medical anti-adhesive material is by the PEG-PCL-PEG copolymer gel that forms behind the colloidal sol of making soluble in water.
6. medical anti-adhesive material according to claim 5 is characterized in that: described PEG-PCL-PEG molecular weight is 1500～10000, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is 0.4～2.6.
7. medical anti-adhesive material according to claim 6 is characterized in that: described PEG-PCL-PEG molecular weight of copolymer is 2000～8000, and wherein the ratio of segmental molecular weight of PEG and the segmental molecular weight of PCL is 0.5～2.
8. medical anti-adhesive material according to claim 5 is characterized in that: described PEG-PCL-PEG copolymer is E
550-C
2200-E
550, E
750-C
3000-E
750, E
750-C
2500-E
750, E
750-C
750-E
750Or E
2000-C
4000-E
2000Wherein E represents PEG, and C represents PCL, and subscript is represented corresponding segmental molecular weight respectively.
9. medical anti-adhesive material according to claim 5 is characterized in that: the concentration of described copolymer is 15～40wt%.
10. medical anti-adhesive material according to claim 9 is characterized in that: the concentration of described copolymer is 20～30wt%.
11. according to the described medical anti-adhesive material of claim 5～10, it is characterized in that: described water is normal saline.
12. according to each described medical anti-adhesive material of claim 5～11, it is characterized in that: described hydrogel also loads anti-inflammatory drug, somatomedin, analgesic or antitumor drug.
13. a method for preparing each described medical anti-adhesive material of claim 5～10 is characterized in that comprising the steps:
A, preparation PEG-PCL-PEG copolymer;
B, the PEG-PCL-PEG triblock copolymer of preparing is dissolved in the normal saline mix homogeneously;
C, with the materials mixed aqueous solution 50 ℃ of heated and stirred 5 minutes, form translucent thick liquid, ice bath is cooled to and is not higher than 4 ℃ and preserves after 24 hours and become gel, promptly gets the medical anti-adhesive material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837006A (en) * | 2010-04-06 | 2010-09-22 | 四川大学 | Application of PCL-PEG-PCL tri-block copolymer in preparation of medical anti-blocking material |
| CN102258813A (en) * | 2010-05-31 | 2011-11-30 | 中国科学院化学研究所 | Medical anti-adhesion material and preparation method thereof |
| CN102973941A (en) * | 2011-11-11 | 2013-03-20 | 四川大学 | Polymer hydrogel loading chemotherapy drug, and application thereof in preventing tumor recurrence and preventing and treating postoperative abdominal adhesion |
| CN113398062A (en) * | 2021-06-18 | 2021-09-17 | 苏州大学 | Absorbable hydrogel composition for promoting wound healing and preparation method and application thereof |
| CN114728099A (en) * | 2019-11-22 | 2022-07-08 | 德斯莱富股份有限公司 | Tissue repair compositions |
-
2009
- 2009-07-10 CN CN200910304210A patent/CN101669965A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837006A (en) * | 2010-04-06 | 2010-09-22 | 四川大学 | Application of PCL-PEG-PCL tri-block copolymer in preparation of medical anti-blocking material |
| CN101837006B (en) * | 2010-04-06 | 2013-04-10 | 四川大学 | Application of PCL-PEG-PCL tri-block copolymer in preparation of medical anti-blocking material |
| CN102258813A (en) * | 2010-05-31 | 2011-11-30 | 中国科学院化学研究所 | Medical anti-adhesion material and preparation method thereof |
| CN102258813B (en) * | 2010-05-31 | 2015-07-08 | 中国科学院化学研究所 | Medical anti-adhesion material and preparation method thereof |
| CN102973941A (en) * | 2011-11-11 | 2013-03-20 | 四川大学 | Polymer hydrogel loading chemotherapy drug, and application thereof in preventing tumor recurrence and preventing and treating postoperative abdominal adhesion |
| CN114728099A (en) * | 2019-11-22 | 2022-07-08 | 德斯莱富股份有限公司 | Tissue repair compositions |
| CN113398062A (en) * | 2021-06-18 | 2021-09-17 | 苏州大学 | Absorbable hydrogel composition for promoting wound healing and preparation method and application thereof |
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