CN103848979A - P-dioxanone polymer as well as synthetic method and application thereof - Google Patents
P-dioxanone polymer as well as synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a p-dioxanone polymer and further provides a synthetic method of the p-dioxanone polymer. The technical scheme provided by the invention is as follows: the p-dioxanone polymer is obtained through a polymerization reaction on 10-50% of p-dioxanone and 50-90% of lactide in molar ratio. The invention has the beneficial effect that an anti-adhesive membrane prepared by the p-dioxanone polymer has good flexibility.
Description
The application is patent application: the divisional application of P-Dioxane ketone polymer and synthetic method thereof and application, and the applying date of former patent application is: 2011-07-04; Application number is: 2011101855751; Name is called: P-Dioxane ketone polymer and synthetic method thereof and application.
Technical field
The invention belongs to technical field of polymer chemistry, relate in particular to bio-medical material technical field.
Background technology
After surgical operation tissue adhesion be clinical in common phenomenon, after brain surgery, abdominal surgery, Obstetric and Gynecologic Department, orthopedics and cardiovascular operation, if generation adhesion, what have causes serious complication, as intestinal obstruction, abdomen pelvic pain, infertility, dysfunction etc., increase the difficulty of again performing the operation and had the potentially dangerous that produces further complication.Such as: (1) brain surgery post-craniotomy dura defect, cicatricial adhesion can cause postoperative epilepsy; (2) adhesion after abdomen operation on pelvis can cause intestinal obstruction, and severe patient need to be carried out operation for the second time, has increased patient's misery and economical load; (3), after gynaecology and obstetrics operation, serious adhesion person has because " gluing " together in ovary peritonaeum uterus, and occurs pain dysfunction; (4) thoracic surgery as the operation of heart valve xenograft, pericardium after, need Film with Preventing Adhesion to improve success rate of operation.Therefore, how to prevent and reduce postoperative adhesion and become current medical expert and biomaterial expert and need the urgent problem of paying close attention to.
Previously report that clinically the method for Film with Preventing Adhesion is mainly to reduce and ooze out and be suppressed to fibrocellular formation with medicine, but uncertain therapeutic efficacy is cut, side effect is large, can widespread use.Nearly ten years, there is clinically both at home and abroad the object that can absorption fluids reaches isolation for report, prevention and minimizing adhesion, though obtained certain curative effect, but because of fluid (as hyaluronate sodium etc.) have absorb fast, easily run off, can not reach the defects such as effective isolation in the Adhesion formation later stage, thereby affected its marketing.
Medical expert and material expert concentrated on sight on bioabsorbable membrane both at home and abroad in recent years, and " physical barriers " effect that utilizes film to bring into play, reaches the object that prevents tissue adhesion.The material that forms film has good biocompatibility and blood compatibility, after operation, can effectively isolate the histoorgan of easy adhesion, do not affect the reparation of wound healing and wound uneven surface, and complete after isolation object and can not needed second operation to take out by human body degraded and absorbed.But leading Antiadhesive film in the market, such as poly(lactic acid) (PolyLactic Acid, english abbreviation PLA, poly(lactic acid) is to be polymerized by intermediate lactide C6H8O4) Antiadhesive film and chitosan Antiadhesive film, all exist the not good enough defect of film flexibility, the inconvenience that operates, and cannot adapt to some and have the tissue of complicated interface.It is slower that rac-Lactide film also has degradation rate in addition, the defect that degraded product biocompatibility is poor, easily cause secondary adhesion.Therefore, the absorbent antiseize film that can overcome above-mentioned defect of Development of New Generation, can effectively improve the performance of existing market product, and is conducive to absorbable medical film and further promotes aspect market.
Poly-para-dioxanone (PPDO) is the polymkeric substance that a class has good biocompatibility and degradability, there is potential extensive use in bio-medical field, in addition also due to the peculiar ester bond-diether linkage structure of PPDO, give the snappiness that this material is good, it is by (the Food and Drug Administration of food and drug administration, FDA) approval is applied to gynecilogical operation suture, the existing material for gynecilogical operation suture is to be made up of the homopolymer of single P-Dioxane ketone, , yet there are no about by this P-Dioxane ketone homopolymer or with the multipolymer of other component report for medical surgery Antiadhesive film.
Summary of the invention
The object of the invention is, in order to overcome the poor deficiency of existing medical anti-adhesive film snappiness, to have proposed a kind of P-Dioxane ketone polymer, further provided the synthetic method of this P-Dioxane ketone polymer and a kind of application of medical anti-adhesive film.
To achieve these goals, of the present inventionly comprised following technical scheme:
Scheme one: P-Dioxane ketone binary polymer, it is characterized in that, formed by the P-Dioxane ketone (PDO) of 10%-50% mole of component and the rac-Lactide polyreaction of 50%-90% mole of component.
Scheme two: a kind of manufacture method of P-Dioxane ketone binary polymer, it is characterized in that, polymkeric substance is polymerized by single step reaction, and concrete steps comprise:
In reaction vessel, add the lactide monomer of 50%-90% mole of component and the P-Dioxane one monomers of 10%-50% mole of component, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use at regular intervals high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, carry out for some time under set temperature with post-polymerization, after question response, resulting polymers is dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, in purification final vacuum baking oven, be dried and obtain P-Dioxane ketone polymer.
Scheme three: a kind of manufacture method of P-Dioxane ketone binary polymer, it is characterized in that, polymkeric substance forms by two step reactive polymerics, and concrete steps comprise:
In reaction vessel, add the P-Dioxane one monomers of 10%-50% mole of component, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use at regular intervals high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, carry out for some time under set temperature with post-polymerization; Then system is dropped to room temperature, under nitrogen protection, add the lactide monomer of 50%-90% mole of component, then system is warmed up to suitable temp, continue the reaction some time; Reaction resulting polymers dissolves with methylene dichloride, then in a large amount of freezing ether, precipitates, and to remove unreacted monomer and catalyzer, is dried to constant weight in vacuum drying oven.
Scheme four: P-Dioxane ketone ter-polymers, it is characterized in that, polyoxyethylene glycol copolymerization by the P-Dioxane ketone of 80%-95% weight ratio and the mix monomer of rac-Lactide and 5%-20% weight ratio forms, and wherein mix monomer is made up of the P-Dioxane ketone of 10%-30% mole of component and the rac-Lactide of 70%-90% mole of component.
Scheme five: a kind of manufacture method of P-Dioxane ketone ter-polymers, it is characterized in that, polymkeric substance is polymerized by single step reaction, and concrete steps comprise:
In reaction vessel, add the polyoxyethylene glycol of the P-Dioxane ketone of 80%-95% weight ratio and the mix monomer of rac-Lactide and 5%-20% weight ratio, the P-Dioxane ketone that wherein mix monomer contains 10%-30% mole of component and the rac-Lactide of 70%-90% mole of component, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use at regular intervals high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, carry out for some time under set temperature with post-polymerization, question response is complete, resulting polymers is dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, the dry P-Dioxane ketone polymer that obtains in purification final vacuum baking oven.
Scheme six: a kind of medical anti-adhesive film, it is characterized in that, described medical anti-adhesive film adopts aforementioned dioxane ketone binary polymer or ter-polymers to be made, and the thickness of described Antiadhesive film is between 0.03-0.5 millimeter.
The invention has the beneficial effects as follows: the P-Dioxane ketone polymer that adopts P-Dioxane ketone (PDO) to be polymerized, due to the peculiar ester bond-diether linkage structure of P-Dioxane ketone, taking and the feature (second-order transition temperature is as-10 DEG C) of the lower glass transition temperatures that had of homopolymer PPDO, the medical anti-adhesive film that therefore adopts this P-Dioxane ketone polymer to make has good snappiness.In addition, because PPDO degradation rate is greatly faster than Biodegradable Material Polylactic Acid (PolyLactice Acid, english abbreviation PLA) feature, by the monomer copolymerization of the monomer of P-Dioxane ketone and rac-Lactide, or under the condition existing at the monomer of polyoxyethylene glycol with rac-Lactide copolymerization, can effectively reduce the second-order transition temperature of poly-lactic acid material, greatly accelerate its degradation speed, the for example degradation cycle of existing anti-sticking poly lactic acid film is approximately 6-12 month, and the degradation cycle that adopts poly-para-dioxanone Antiadhesive film of the present invention is about 1-3 month.
Brief description of the drawings
Fig. 1 is that the limiting viscosity of the synthetic P-Dioxane ketone of single stage method of the present invention and lactide copolymer film is with the variation relation figure of degradation time.
Fig. 2 is the P-Dioxane ketone of two step synthesis of the present invention and the limiting viscosity of the lactide copolymer film variation relation figure with degradation time.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
Embodiment 1: specifically comprised following technical scheme in the present embodiment:
Scheme one: P-Dioxane ketone binary polymer, it is characterized in that, formed by the P-Dioxane ketone (PDO) of 10%-50% mole of component and the rac-Lactide polyreaction of 50%-90% mole of component.
Scheme two: a kind of manufacture method of P-Dioxane ketone binary polymer, the method is one-step synthesis, an one concrete example comprises the following steps: be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, add the lactide monomer and the P-Dioxane one monomers that form poly(lactic acid) intermediate as the conduct of following table ratio, and then with microsyringe 0.5 milliliter of stannous octoate solution of injection (concentration is 0.1 grams per milliliter).At room temperature reaction system decompression is evacuated, replaces system every half an hour with high pure nitrogen, so repeated multiple times.Polyreaction is carried out 12 hours under the oil bath of l50 DEG C and agitation condition.After completion of the reaction, resulting polymers dissolves with methylene dichloride, and then with a large amount of freezing ether sedimentations, after purification, in 70 DEG C of vacuum drying ovens, is dried 24 hours.
Further, on the data basis of above-mentioned specific embodiment, in above-mentioned single stage method synthetic method, the condition of ring-opening polymerization can also expand to: reaction system vacuum tightness is below 1mmHg; Catalyst content is 0.005-0.5wt%, and more suitable content is 0.01-0.2wt%; Polymeric reaction temperature is 60-240 DEG C, and more suitable temperature is 80-200 DEG C, and optimal reaction temperature is 110-180 DEG C; Polymerization reaction time is between 1-48 hour, and the more suitable time is 4-36 hour, and Best Times is 8-24 hour; Catalyzer generally uses stannous octoate, tin protochloride or triethyl aluminum.In this programme, various parameters required in the manufacture method of binary polymer are as poly-
Scheme six: a kind of medical anti-adhesive film, it is characterized in that, described medical anti-adhesive film adopts the dioxane ketone binary polymer of the single stage method of aforementioned schemes one to be made, and the thickness of described Antiadhesive film is between 0.03-0.5 millimeter.Further can between 0.03-0.06 millimeter or between 0.10-0.30 millimeter, select.Those of ordinary skill in the art should be appreciated that the filming technology here can adopt the common practise of this area to carry out, and is therefore not described in detail.
Below, by experiment with test data to above-mentioned polymkeric substance and adopt the medical anti-adhesive film of this polymer formation make checking and analyze.
What adopt the synthetic P-Dioxane ketone of method (single stage method) in such scheme two and lactide copolymer feeds intake when characterization data as shown in following table one:
Table one
In above table, " multipolymer is called for short row " represents LA and PDO monomer copolymerization ratio, carries out copolyreaction as P (LA90-co-PDO10) represents the LA of 90% mol ratio and the PDO of 10% mol ratio; " PDO feed ratio " list shows that the theoretical molar ratio of copolyreaction feeds intake, and the mol ratio composition of real income multipolymer is shown in " PDO actual content " list; The characteristic degree of being stained with of the multipolymer after synthesizing is shown in " characteristic degree of being stained with " list, and dl/g is viscosity unit; The weight-average molecular weight of the multipolymer after synthesizing is shown in " molecular weight " list, and the molecular weight distributing index of the multipolymer after synthesizing is shown in " molecular weight distribution " list.
First, useful range while analyzing the synthetic copolymer of aforesaid method: by the multipolymer of above-mentioned synthetic different ratios and organic solvent combined experiments, we find, when the synthetic multipolymer when exceeding 70% of PDO molar content in above table, be difficult to be dissolved in organic solvent, be not suitable for by solvent evaporation method film forming, therefore for above-mentioned polymkeric substance is made to film forming, the mol ratio that PDO participates in polyreaction can not exceed 70%, and in table, the molar content of disclosed effective P-Dioxane ketone and rac-Lactide is than between 10/90-70/30; Learn by experiment, more suitable molar content is than between 10/90 – 50/50.
Secondly, in above-mentioned synthetic polymkeric substance, choose three kinds of medical anti-adhesive films that close proportional polymkeric substance manufacturing and do further Mechanics Performance Testing.The mechanical property of medical anti-adhesive film is measured on SANS instrument, film be shaped as rectangle (5 × 40mm2, N=5), mensuration temperature is room temperature, rate of extension is 10mm/min, the thickness of film and mechanical performance data see the following form two:
Table two
In table, " elongation at break " represents the longest ratio that this film can stretch.As seen from table, the elongation at break of the copolymer film of above-mentioned composition, between (612-788%) 650-750%, shows that the film that adopts the polymkeric substance of aforementioned proportion to prepare has good snappiness, is desirable Antiadhesive film material.
Finally, the medical anti-adhesive film of choosing the synthetic multipolymer manufacture of three kinds of proportionings from table 1 is carried out to degradation property test.The degradation property of copolymer film carries out in potassium primary phosphate-disodium hydrogen phosphate buffer solution (1/15M, pH=7.41).The sample of having weighed is placed in to 10ml centrifuge tube, seals after adding 6ml buffered soln, be placed in isothermal vibration case (temperature 37 ± 0.1oC, hunting speed 60r/min).Every two weeks, the buffered soln of all samples is replaced as to fresh buffered soln.Be 2,4,6,8 at degradation time, when 10,12 time-of-week, take out its three parallel sample with regard to each copolymerization composition, washing, dry, weigh, be then stored in-20oC, for the test of limiting viscosity.Fig. 1 is that the limiting viscosity of the synthetic P-Dioxane ketone of scheme two (single stage method) and lactide copolymer film is with the variation relation figure of degradation time.Can be found out by this figure, along with the increase of PDO content in multipolymer, its degradation property is significantly accelerated, illustrate P-Dioxane ketone add and can significantly accelerate the speed that film is absorbed by the body.
Embodiment 2: specifically comprised following technical scheme in the present embodiment:
Scheme one: P-Dioxane ketone binary polymer, it is characterized in that, formed by the P-Dioxane ketone (PDO) of 10%-50% mole of component and the rac-Lactide polyreaction of 50%-90% mole of component.
Scheme three: a kind of manufacture method of P-Dioxane ketone binary polymer, the method is that two steps are synthetic, an one concrete example comprises the following steps: be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, add the P-Dioxane one monomers of following table ratio, and then with microsyringe inject 0.5 milliliter of stannous octoate solution (concentration is 0.1 grams per milliliter).At room temperature reaction system decompression is evacuated, replaces system every half an hour with high pure nitrogen, so repeated multiple times.Polyreaction is carried out 12 hours under the oil bath of l20 DEG C and agitation condition.Then reaction system is reduced to room temperature, under nitrogen protection, adds as the lactide monomer that forms poly(lactic acid) intermediate, then system is warmed up to l50 DEG C, continue reaction 12 hours.After completion of the reaction, resulting polymers dissolves with methylene dichloride, and then with a large amount of freezing ether sedimentations, to remove unreacted monomer and catalyzer, after purification, in 70 DEG C of vacuum drying ovens, is dried 24 hours.
In above-mentioned two step method synthetic method, the condition of the first step ring-opening polymerization is: reaction system vacuum tightness is below 1mmHg; Catalyst content is 0.005-0.5wt%, and more suitable content is 0.01-0.2wt%; Polymeric reaction temperature is 60-240 DEG C, and more suitable temperature is 80-200 DEG C, and optimal reaction temperature is 110-180 DEG C; Polymerization reaction time is between 1-48 hour, and the more suitable time is 4-36 hour, and Best Times is 8-24 hour; Catalyzer generally uses stannous octoate, tin protochloride or triethyl aluminum.The condition of second step ring-opening polymerization is: polymeric reaction temperature is 60-240 DEG C, and more suitable temperature is 80-200 DEG C, and optimal reaction temperature is 110-180 DEG C; Polymerization reaction time is between 1-48 hour, and the more suitable time is 4-36 hour, and Best Times is 8-24 hour.
Scheme six: a kind of medical anti-adhesive film, it is characterized in that, described medical anti-adhesive film adopts the dioxane ketone binary polymer of aforementioned two step method to be made, and the thickness of described Antiadhesive film is between 0.03-0.5 millimeter.Further can between 0.03-0.06 millimeter or between 0.10-0.30 millimeter, select.Those of ordinary skill in the art should be appreciated that the filming technology here can adopt the common practise of this area to carry out, and is therefore not described in detail.
The P-Dioxane ketone that two step method is synthetic and lactide copolymer feed intake when characterization data as shown in following table three:
Table three
In above table three, each row implication is with table one.First, useful range while analyzing the synthetic copolymer of aforesaid method: by the multipolymer of above-mentioned synthetic different ratios and organic solvent combined experiments, we find, in the time that in above table, PDO molar content ratio is at 10%-50%, synthetic multipolymer all can effectively be dissolved in organic solvent, is applicable to by solvent evaporation method film forming.
Secondly, the mechanical property of the P-Dioxane ketone to above-mentioned two step synthesis and the medical anti-adhesive film of lactide copolymer is tested.The mechanical property of film is measured on SANS instrument, film be shaped as rectangle (5 × 40mm2, N=5), mensuration temperature is room temperature, rate of extension is 10mm/min, the thickness of film and mechanical performance data see the following form four:
Table four
The elongation at break of the copolymer film of above-mentioned composition, between 250-600%, shows that film has good snappiness, is desirable adherence preventing material.
Finally, the medical anti-adhesive film of choosing the synthetic multipolymer manufacture of four kinds of proportionings from table 3 is carried out to degradation property test, the degradation property of copolymer film carries out in potassium primary phosphate-disodium hydrogen phosphate buffer solution (1/15M, pH=7.41).The sample of having weighed is placed in to 10ml centrifuge tube, seals after adding 6ml buffered soln, be placed in isothermal vibration case (temperature 37 ± 0.1oC, hunting speed 60r/min).Every two weeks, the buffered soln of all samples is replaced as to fresh buffered soln.Be 2,4,6,8 at degradation time, when 10,12 time-of-week, take out its three parallel sample with regard to each copolymerization composition, washing, dry, weigh, be then stored in-20oC, for the test of limiting viscosity.
Fig. 2 is the P-Dioxane ketone of two step synthesis and the limiting viscosity of the lactide copolymer film variation relation figure with degradation time.Can be found out by this figure, remaining weight percent and the composition of copolymer film have substantial connection.Along with the increase of PDO content in multipolymer, its degradation property is significantly accelerated, illustrate P-Dioxane ketone add and can significantly accelerate the speed that film is absorbed by the body.
Embodiment 3: specifically comprised following technical scheme in the present embodiment:
Scheme four: P-Dioxane ketone ter-polymers, it is characterized in that, by polyoxyethylene glycol (the polyethylene glycol of the P-Dioxane ketone of 80%-95% weight ratio and the mix monomer of rac-Lactide and 5%-20% weight ratio, being called for short PEG) copolymerization forms, and wherein mix monomer is made up of the P-Dioxane ketone of 10%-30% mole of component and the rac-Lactide of 70%-90% mole of component.
When terpolymer is synthetic, to have an end group at least be hydroxyl to polyoxyethylene glycol raw material, and another end group can be hydroxyl, can be also methyl or other functional group.The molecular weight of polyoxyethylene glycol is between 1000-20000; More suitable molecular weight is between 4000-10000; The most suitable molecular weight is 6000.
Scheme five: a kind of manufacture method of P-Dioxane ketone ter-polymers, the method is one-step synthesis, an one concrete example comprises the following steps: be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, add as the lactide monomer of following table ratio, P-Dioxane one monomers and polyoxyethylene glycol, and then with microsyringe inject 0.5 milliliter of stannous octoate solution (concentration is 0.1 grams per milliliter).At room temperature reaction system decompression is evacuated, replaces system every half an hour with high pure nitrogen, so repeated multiple times.Polyreaction is carried out 12 hours under the oil bath of l50 DEG C and agitation condition.After completion of the reaction, resulting polymers dissolves with methylene dichloride, and then with a large amount of freezing ether sedimentations, after purification, in 70 DEG C of vacuum drying ovens, is dried 24 hours.
Scheme six: a kind of medical anti-adhesive film, it is characterized in that, described medical anti-adhesive film adopts aforementioned dioxane ketone ter-polymers to be made, and the thickness of described Antiadhesive film is between 0.03-0.5 millimeter.Further can between 0.03-0.06 millimeter or between 0.10-0.30 millimeter, select.Those of ordinary skill in the art should be appreciated that the filming technology here can adopt the common practise of this area to carry out, and is therefore not described in detail.
Synthetic P-Dioxane ketone, rac-Lactide and the polyoxyethylene glycol terpolymer of single stage method feed intake when characterization data as shown in following table five:
Table five
In above table, the copolymerization ratio of LA, PDO and the each component of PEG is shown in " multipolymer abbreviation " list, as representing the PEG of 5% weight ratio and the mix monomer LA of 95% weight ratio and PDO, P (LA90-co-PDO10)-PEG (5%) there is terpolymer, wherein in mix monomer, the mol ratio of LA is that the mol ratio of 90%, PDO is 10%; " PDO feed ratio " list shows that the theoretical molar ratio of copolyreaction feeds intake; " PEG feed ratio " list shows that the Theoretical Mass ratio of copolyreaction feeds intake; The mol ratio composition of real income multipolymer is shown in " PDO actual content " list; The mass ratio composition of real income multipolymer is shown in " PEG actual content " list; The characteristic degree of being stained with of the multipolymer after synthesizing is shown in " characteristic degree of being stained with " list, and dl/g is viscosity unit; The weight-average molecular weight of the multipolymer after synthesizing is shown in " molecular weight " list, and the molecular weight distributing index of the multipolymer after synthesizing is shown in " molecular weight distribution " list.
First, analyze the useful range of the synthetic terpolymer of aforesaid method: by the multipolymer of above-mentioned synthetic different ratios and organic solvent combined experiments, we find, in the time that in above table, PDO molar content ratio is at 10%-30%, the mass ratio of PEG is in the time of 5-20%, the multipolymer of synthesized all can effectively be dissolved in organic solvent, is applicable to by solvent evaporation method film forming.
Secondly, the mechanical property of the medical anti-adhesive film to the synthetic P-Dioxane ketone of above-mentioned single stage method, rac-Lactide and polyoxyethylene glycol terpolymer is tested.The mechanical property of film is measured on SANS instrument, film be shaped as rectangle (5 × 40mm2, N=5), mensuration temperature is room temperature, rate of extension is 10mm/min, the thickness of film and mechanical performance data see the following form six:
The elongation at break of the copolymer film of above-mentioned composition, between 670-1250%, shows that film has good snappiness, is desirable adherence preventing material.Due to polyoxyethylene glycol (polyethylene glycol, be called for short PEG) water-absorbent and water-soluble feature, the film of above-mentioned terpolymer, under hygrometric state and human body temperature, can further be accelerated the degradation rate of material under the prerequisite that still can show flexible nature.
The medical anti-adhesive film second-order transition temperature of above-described embodiment 1, embodiment 2 and embodiment 3 can be more than human body temperature, such as between human body temperature and 45 DEG C, and also can be below human body temperature, between 5-37 DEG C.Better second-order transition temperature can be further selecting between 25-37 DEG C or between 5-25 DEG C, to adapt to different application scenarios.
In three embodiment, the suitable molecular weight of multipolymer is between 1-100 ten thousand, and more suitably molecular weight is between 3-30 ten thousand, and most suitable molecular weight is between 3-10 ten thousand.
In three embodiment, the degradation cycle of copolymer film is between the 1-12 month.Be adapted to different application scenarios and the thickness of film, can be further between the 1-3 month, between the 3-6 month or between the 6-12 month, select, degradation time depends primarily on the ratio of properties of materials viscosity and polyoxyethylene glycol, limiting viscosity is higher, degrades slower, and polyoxyethylene glycol ratio is higher, PDO content is more, degrades faster.
In three embodiment, the elongation at break of copolymer film is between 200-2000%.Be adapted to different application scenarios and the thickness of film, can be further between 200-400%, 400-800%, selects between 800-1500%.
Antiadhesive film in three embodiment can be used for that the barrier film of the post-operation adhesion preventing of multiple operation uses, and such as abdominal operation, heart operation etc., the occasion that also can need to have a barrier film that is wound around function for nerve, bone, joint, blood vessel etc. is used.
Those of ordinary skill in the art will appreciate that, embodiment described here is in order to help reader understanding's principle of the present invention, should be understood to that protection scope of the present invention is not limited to such special statement and embodiment.Those of ordinary skill in the art can make various other various concrete distortion and combinations that do not depart from essence of the present invention according to these technology enlightenments disclosed by the invention, and these distortion and combination are still in protection scope of the present invention.
Claims (3)
1. P-Dioxane ketone binary polymer, is characterized in that, is formed by the P-Dioxane ketone (PDO) of 10%-50% mole of component and the rac-Lactide polyreaction of 50%-90% mole of component.
2. the manufacture method to dioxane ketone binary polymer described in claim 1, is characterized in that, polymkeric substance is polymerized by single step reaction, and concrete steps comprise:
In reaction vessel, add the lactide monomer of 50%-90% mole of component and the P-Dioxane one monomers of 10%-50% mole of component, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use at regular intervals high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, carry out for some time under set temperature with post-polymerization, after question response, resulting polymers is dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, in purification final vacuum baking oven, be dried and obtain P-Dioxane ketone polymer.
3. the manufacture method to dioxane ketone binary polymer claimed in claim 1, is characterized in that, polymkeric substance forms by two step reactive polymerics, and concrete steps comprise:
In reaction vessel, add the P-Dioxane one monomers of 10%-50% mole of component, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use at regular intervals high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, carry out for some time under set temperature with post-polymerization; Then system is dropped to room temperature, under nitrogen protection, add the lactide monomer of 50%-90% mole of component, then system is warmed up to suitable temp, continue the reaction some time; Reaction resulting polymers dissolves with methylene dichloride, then in a large amount of freezing ether, precipitates, and to remove unreacted monomer and catalyzer, is dried to constant weight in vacuum drying oven.
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| CN103848979B (en) | 2016-01-20 |
| CN102344557B (en) | 2014-08-13 |
| CN102344557A (en) | 2012-02-08 |
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