CN103848979B - P-Dioxane ketone polymer and synthetic method thereof and application - Google Patents
P-Dioxane ketone polymer and synthetic method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of P-Dioxane ketone polymer, further give the synthetic method of this P-Dioxane ketone polymer.Of the present inventionly contain following technical scheme: pdioxane ketone polymer binary polymer, is formed by the pdioxane ketone polymer of 10%-50% molar composition and the rac-Lactide polyreaction of 50%-90% molar composition.The invention has the beneficial effects as follows: the medical anti-adhesive film adopting this P-Dioxane ketone polymer to make has good snappiness.
Description
The application is patent application: the divisional application of P-Dioxane ketone polymer and synthetic method 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, particularly relate to biology medical material technical field.
Background technology
Surgical site infections tissue adhesion be clinical in common phenomenon, as brain surgery, abdominal surgery, Obstetric and Gynecologic Department, orthopedics and cardiovascular Post operation, if generation adhesion, what have causes serious complication, as intestinal obstruction, abdomen pelvic pain, infertility, dysfunction etc., add the difficulty of again performing the operation and have the potentially dangerous producing 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 needs to carry out second time operation, adds misery and the economical load of patient; (3), after gynaecology and obstetrics operation, serious adhesion person has because ovary peritonaeum uterus " is glued " together, and occurs pain dysfunction; (4) thoracic surgery is as heart valve xenograft, pericardium Post operation, needs 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 paid close attention to.
Previously report that the method for Film with Preventing Adhesion mainly uses medicine to reduce clinically ooze out and be suppressed to fibrocellular formation, but uncertain therapeutic efficacy is cut, side effect large, can widespread use.Nearly ten years, report is had to use Absorbable rod fluid to reach the object of isolation both at home and abroad clinically, prevention and minimizing adhesion, though achieve certain curative effect, but absorb fast, easy loss because fluid (as hyaluronate sodium etc.) has, the defects such as effectively isolation can not be reached in the Adhesion formation later stage, thus have impact on its marketing.
Sight concentrated on bioabsorbable membrane by medical expert and materials specialist both at home and abroad in recent years, and " physical barriers " effect utilizing film to play, reaches the object preventing tissue adhesion.The material forming film has good biocompatibility and blood compatibility, effectively can isolate the histoorgan of easy adhesion after surgery, do not affect the reparation of wound healing and wound uneven surface, and second operation can not needed to take out by human body degraded and absorbed after completing isolation object.But Antiadhesive film leading in the market, such as poly(lactic acid) (PolyLacticAcid, english abbreviation PLA, poly(lactic acid) is polymerized by intermediate lactide C6H8O4) Antiadhesive film and chitosan Antiadhesive film, all there is the defect that film flexibility is not good enough, operate inconvenience, and cannot adapt to the tissue that some has complicated interface.Also to have degradation rate comparatively slow for rac-Lactide film in addition, degraded product poor biocompatibility, the defect of secondary adhesion of easily causing.Therefore, the absorbent antiseize film that can overcome above-mentioned defect of Development of New Generation, effectively can improve the performance of existing market product, and is conducive to absorbable medical film further genralrlization in market.
Poly-para-dioxanone (PPDO) is the polymkeric substance that a class has good biocompatibility and degradability, potential extensive use is had in bio-medical field, also ester bond-diether linkage structure specific to PPDO in addition, give the snappiness that this material is good, it is by food and drug administration (FoodandDrugAdministration, FDA) approval is applied to gynecilogical operation suture, the existing material for gynecilogical operation suture is made up of the homopolymer of single pdioxane ketone polymer, , yet there are no about by this pdioxane ketone polymer homopolymer or be used for the report of medical surgery Antiadhesive film with the multipolymer of other component.
Summary of the invention
The object of the invention is the deficiency in order to overcome existing medical anti-adhesive film snappiness difference, proposing a kind of P-Dioxane ketone polymer, further give 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 following technical scheme is contained:
Scheme one: pdioxane ketone polymer binary polymer, is characterized in that, is formed by the pdioxane ketone polymer (PDO) of 10%-50% molar composition and the rac-Lactide polyreaction of 50%-90% molar composition.
Scheme two: a kind of manufacture method of pdioxane ketone polymer 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% molar composition and the P-Dioxane one monomers of 10%-50% molar composition, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use high pure nitrogen replacement(metathesis)reaction system at regular intervals, so repeated multiple times, under set temperature, for some time is carried out with post-polymerization, after question response, resulting polymers methylene dichloride is dissolved, and then with a large amount of freezing ether sedimentation, in purification final vacuum baking oven, drying obtains P-Dioxane ketone polymer.
Scheme three: a kind of manufacture method of pdioxane ketone polymer binary polymer, is characterized in that, polymkeric substance is formed by two step reactive polymerics, and concrete steps comprise:
In reaction vessel, add the P-Dioxane one monomers of 10%-50% molar composition, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use high pure nitrogen replacement(metathesis)reaction system at regular intervals, so repeated multiple times, under set temperature, carry out for some time with post-polymerization; Then system is dropped to room temperature, add the lactide monomer of 50%-90% molar composition under nitrogen protection, then system is warmed up to suitable temp, continue the reaction some time; Reaction resulting polymers methylene dichloride dissolves, and then precipitates in a large amount of freezing ether, to remove unreacted monomer and catalyzer, in vacuum drying oven, is dried to constant weight.
Scheme four: pdioxane ketone polymer ter-polymers, it is characterized in that, formed by the polyoxyethylene glycol copolymerization of the pdioxane ketone polymer of 80%-95% weight ratio and the mix monomer of rac-Lactide and 5%-20% weight ratio, wherein mix monomer is made up of the pdioxane ketone polymer of 10%-30% molar composition and the rac-Lactide of 70%-90% molar composition.
Scheme five: a kind of manufacture method of pdioxane ketone polymer 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 pdioxane ketone polymer of 80%-95% weight ratio and the mix monomer of rac-Lactide and 5%-20% weight ratio, wherein mix monomer contains the pdioxane ketone polymer of 10%-30% molar composition and the rac-Lactide of 70%-90% molar composition, and then add stannous octoate solution, at room temperature reaction system decompression is evacuated, use high pure nitrogen replacement(metathesis)reaction system at regular intervals, so repeated multiple times, under set temperature, for some time is carried out with post-polymerization, question response is complete, resulting polymers methylene dichloride is dissolved, and then with a large amount of freezing ether sedimentation, in purification final vacuum baking oven, drying obtains P-Dioxane ketone polymer.
Scheme six: a kind of medical anti-adhesive film, 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: adopt the P-Dioxane ketone polymer that pdioxane ketone polymer (PDO) is polymerized, ester bond-diether linkage structure specific to pdioxane ketone polymer, and the feature of the lower glass transition temperatures that has of its homopolymer PPDO (second-order transition temperature is-10 DEG C), the medical anti-adhesive film therefore adopting this P-Dioxane ketone polymer to make has good snappiness.In addition, because PPDO degradation rate is greatly faster than Biodegradable Material Polylactic Acid (PolyLacticeAcid, english abbreviation PLA) feature, by the monomer of pdioxane ketone polymer and the monomer copolymerization of rac-Lactide, or under the monomer existent condition of polyoxyethylene glycol with rac-Lactide copolymerization, effectively can reduce the second-order transition temperature of poly-lactic acid material, greatly accelerate its degradation speed, the such as degradation cycle of existing polylactic acid anti-adhesion film is approximately 6-12 month, adopts the degradation cycle of poly-para-dioxanone Antiadhesive film of the present invention to be about 1-3 month.
Accompanying drawing explanation
Fig. 1 is the pdioxane ketone polymer of one-step synthesis method of the present invention and the limiting viscosity of the lactide copolymer film variation relation figure with degradation time.
Fig. 2 is the pdioxane ketone polymer 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 contain following technical scheme in the present embodiment:
Scheme one: pdioxane ketone polymer binary polymer, is characterized in that, is formed by the pdioxane ketone polymer (PDO) of 10%-50% molar composition and the rac-Lactide polyreaction of 50%-90% molar composition.
Scheme two: a kind of manufacture method of pdioxane ketone polymer 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 as formation poly(lactic acid) intermediate as following table ratio and P-Dioxane one monomers, and then inject 0.5 milliliter of stannous octoate solution (concentration is 0.1 grams per milliliter) with microsyringe.At room temperature reaction system decompression is evacuated, replaces system every half an hour with high pure nitrogen, so repeated multiple times.Polyreaction carries out 12 hours under the oil bath of l50 DEG C and agitation condition.After completion of the reaction, resulting polymers methylene dichloride dissolves, and then with a large amount of freezing ether sedimentation, after purification in 70 DEG C of vacuum drying ovens dry 24 hours.
Further on the data basis of above-mentioned specific embodiment, in above-mentioned one-step synthesis method method, the condition of ring-opening polymerization can also expand to: reaction system vacuum tightness is at 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, 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 select between 0.03-0.06 millimeter or between 0.10-0.30 millimeter.Those of ordinary skill in the art it should be appreciated that 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.
The pdioxane ketone polymer adopting the method (single stage method) in such scheme two to synthesize and lactide copolymer feed 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, as P (LA90-co-PDO10) represents that the LA of 90% mol ratio and the PDO of 10% mol ratio carries out copolyreaction; " 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 synthesis 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 synthesis is shown in " molecular weight " list, and the molecular weight distributing index of the multipolymer after synthesis is shown in " molecular weight distribution " list.
First, analyze useful range during aforesaid method synthesis copolymer: by the multipolymer of the different ratios of above-mentioned synthesis and organic solvent combined experiments, we find, when PDO molar content in above table is than the multipolymer of synthesis during more than 70%, be difficult to dissolve in organic solvent, be not suitable for by solvent evaporation method film forming, therefore in order to above-mentioned polymkeric substance is made film forming, the mol ratio of PDO participation polyreaction can not more than 70%, and the molar content of effective pdioxane ketone polymer and rac-Lactide disclosed in table is than between 10/90-70/30; Learn by experiment, more suitable molar content is than between 10/90 – 50/50.
Secondly, the medical anti-adhesive film manufactured by polymkeric substance choosing three kinds of synthesis ratios in the polymkeric substance of above-mentioned synthesis does further Mechanics Performance Testing.The mechanical property of medical anti-adhesive film measures on SANS instrument, and the shape of film is rectangle (5 × 40mm2, N=5), and mensuration temperature is room temperature, and rate of extension is 10mm/min, and 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 is between (612-788%) 650-750%, and showing that the film adopting the polymkeric substance of aforementioned proportion to prepare has good snappiness, is desirable Antiadhesive film material.
Finally, degradation property test is carried out to the medical anti-adhesive film of the multipolymer manufacture choosing three kinds of proportioning synthesis from table 1.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 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 fresh buffered soln.Be 2,4 at degradation time, 6,8,10, during 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 the variation relation figure of limiting viscosity with degradation time of scheme two (single stage method) pdioxane ketone polymer of synthesizing and lactide copolymer film.As can be seen from this figure, along with the increase of PDO content in multipolymer, its degradation property is significantly accelerated, illustrate pdioxane ketone polymer add the speed significantly can accelerated film and be absorbed by the body.
Embodiment 2: specifically contain following technical scheme in the present embodiment:
Scheme one: pdioxane ketone polymer binary polymer, is characterized in that, is formed by the pdioxane ketone polymer (PDO) of 10%-50% molar composition and the rac-Lactide polyreaction of 50%-90% molar composition.
Scheme three: a kind of manufacture method of pdioxane ketone polymer binary polymer, the method is two 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 P-Dioxane one monomers of following table ratio, and then inject 0.5 milliliter of stannous octoate solution (concentration is 0.1 grams per milliliter) with microsyringe.At room temperature reaction system decompression is evacuated, replaces system every half an hour with high pure nitrogen, so repeated multiple times.Polyreaction carries out 12 hours under the oil bath of l20 DEG C and agitation condition.Then reaction system is reduced to room temperature, adds the lactide monomer as forming poly(lactic acid) intermediate under nitrogen protection, then system is warmed up to l50 DEG C, continue reaction 12 hours.After completion of the reaction, resulting polymers methylene dichloride dissolves, and then with a large amount of freezing ether sedimentation, to remove unreacted monomer and catalyzer, and after purification in 70 DEG C of vacuum drying ovens dry 24 hours.
In above-mentioned two step synthetic method method, the condition of the first step ring-opening polymerization is: reaction system vacuum tightness is at 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, 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 select between 0.03-0.06 millimeter or between 0.10-0.30 millimeter.Those of ordinary skill in the art it should be appreciated that filming technology here can adopt the common practise of this area to carry out, and is therefore not described in detail.
The pdioxane ketone polymer of two step synthetic method 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, analyze useful range during aforesaid method synthesis copolymer: by the multipolymer of the different ratios of above-mentioned synthesis and organic solvent combined experiments, we find, when PDO molar content in above table all can effectively be dissolved in organic solvent than the multipolymer synthesized during at 10%-50%, be applicable to by solvent evaporation method film forming.
Secondly, the mechanical property of the pdioxane ketone polymer of above-mentioned two step synthesis and the medical anti-adhesive film of lactide copolymer is tested.The mechanical property of film measures on SANS instrument, and the shape of film is rectangle (5 × 40mm2, N=5), and mensuration temperature is room temperature, and rate of extension is 10mm/min, and 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, carry out degradation property test to the medical anti-adhesive film of the multipolymer manufacture choosing four kinds of proportioning synthesis from table 3, 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 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 fresh buffered soln.Be 2,4 at degradation time, 6,8,10, during 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 pdioxane ketone polymer of two step synthesis and the limiting viscosity of the lactide copolymer film variation relation figure with degradation time.As can be seen from this figure, the residual weight per-cent of copolymer film and composition have substantial connection.Along with the increase of PDO content in multipolymer, its degradation property is significantly accelerated, illustrate pdioxane ketone polymer add the speed significantly can accelerated film and be absorbed by the body.
Embodiment 3: specifically contain following technical scheme in the present embodiment:
Scheme four: pdioxane ketone polymer ter-polymers, it is characterized in that, by the polyoxyethylene glycol (polyethyleneglycol of the pdioxane ketone polymer 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 pdioxane ketone polymer of 10%-30% molar composition and the rac-Lactide of 70%-90% molar composition.
During terpolymer synthesis, polyoxyethylene glycol raw material has at least an end group to be hydroxyl, and another end group can be hydroxyl, also can be methyl or other functional group.The molecular weight of polyoxyethylene glycol is between 1000-20000; More suitable molecular weight is between 4000-10000; Molecular weight the most suitable is 6000.
Scheme five: a kind of manufacture method of pdioxane ketone polymer 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 inject 0.5 milliliter of stannous octoate solution (concentration is 0.1 grams per milliliter) with microsyringe.At room temperature reaction system decompression is evacuated, replaces system every half an hour with high pure nitrogen, so repeated multiple times.Polyreaction carries out 12 hours under the oil bath of l50 DEG C and agitation condition.After completion of the reaction, resulting polymers methylene dichloride dissolves, and then with a large amount of freezing ether sedimentation, after purification in 70 DEG C of vacuum drying ovens dry 24 hours.
Scheme six: a kind of medical anti-adhesive film, 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 select between 0.03-0.06 millimeter or between 0.10-0.30 millimeter.Those of ordinary skill in the art it should be appreciated that filming technology here can adopt the common practise of this area to carry out, and is therefore not described in detail.
The pdioxane ketone polymer of one-step synthesis method, rac-Lactide and polyoxyethylene glycol terpolymer feed intake when characterization data as shown in following table five:
Table five
In above table, the copolymerization ratios of each component of LA, PDO and PEG is shown in " multipolymer abbreviation " list, as P (LA90-co-PDO10)-PEG (5%) represents that terpolymer occurs the PEG of 5% weight ratio and mix monomer LA and PDO of 95% weight ratio, wherein in mix monomer, the mol ratio of LA is 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 synthesis 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 synthesis is shown in " molecular weight " list, and the molecular weight distributing index of the multipolymer after synthesis is shown in " molecular weight distribution " list.
First, analyze the useful range of the terpolymer of aforesaid method synthesis: by the multipolymer of the different ratios of above-mentioned synthesis and organic solvent combined experiments, we find, when PDO molar content in above table is than during at 10%-30%, the mass ratio of PEG is when 5-20%, synthesized multipolymer all can effectively dissolve in organic solvent, is applicable to by solvent evaporation method film forming.
Secondly, the mechanical property of the medical anti-adhesive film of the pdioxane ketone polymer of above-mentioned one-step synthesis method, rac-Lactide and polyoxyethylene glycol terpolymer is tested.The mechanical property of film measures on SANS instrument, and the shape of film is rectangle (5 × 40mm2, N=5), and mensuration temperature is room temperature, and rate of extension is 10mm/min, and 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 (polyethyleneglycol, be called for short PEG) water-absorbent and water soluble nature, the film of above-mentioned terpolymer, under hygrometric state and human body temperature, further can accelerate 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 more than human body temperature, such as between human body temperature and 45 DEG C, also can below human body temperature, and such as between 5-37 DEG C.Better second-order transition temperature can be selected between 25-37 DEG C or between 5-25 DEG C, further to adapt to different application scenarios.
In three embodiments, 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 embodiments, the degradation cycle of copolymer film is between the 1-12 month.Be adapted to different application scenarios and the thickness of film, can further between the 1-3 month, select between the 3-6 month or between the 6-12 month, degradation time depends primarily on the ratio of properties of materials viscosity and polyoxyethylene glycol, limiting viscosity is higher, and degrade slower, polyoxyethylene glycol ratio is higher, PDO content is more, degrades faster.
In three embodiments, the elongation at break of copolymer film is between 200-2000%.Be adapted to different application scenarios and the thickness of film, further between 200-400%, can select between 400-800%, 800-1500%.
Antiadhesive film in three embodiments 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., also may be used for nerve, bone, joint, blood vessel etc. needs the occasion with the barrier film being wound around function to use.
Those of ordinary skill in the art will appreciate that, embodiment described here is 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 so special statement and embodiment.Those of ordinary skill in the art can make various other various concrete distortion and combination of not departing from essence of the present invention according to these technology enlightenment disclosed by the invention, and these distortion and combination are still in protection scope of the present invention.
Claims (1)
1. for a pdioxane ketone polymer binary polymer for medical anti-adhesive film, it is characterized in that, formed by the pdioxane ketone polymer of 20%-30% molar composition and the rac-Lactide polyreaction of 70%-80% molar composition;
The manufacture method of described dioxane ketone binary polymer is single step reaction polymerization or two step reactive polymerics;
The concrete steps of described single step reaction polymerization comprise:
In reaction vessel, add the lactide monomer of 70%-80% molar composition and the P-Dioxane one monomers of 20%-30% molar composition, and then add the stannous octoate solution that 0.5mL concentration is 0.1 grams per milliliter, at room temperature reaction system decompression is evacuated, every half an hour by high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, under the oil bath of l50 DEG C and agitation condition, 12 hours are carried out with post-polymerization, after question response, resulting polymers methylene dichloride is dissolved, and then with a large amount of freezing ether sedimentation, vacuum drying oven is put into dry after being purified by gained throw out, obtain P-Dioxane ketone polymer,
The concrete steps of described two step reactive polymerics comprise:
In reaction vessel, add the P-Dioxane one monomers of 20%-30% molar composition, and then add the stannous octoate solution that 0.5mL concentration is 0.1 grams per milliliter, at room temperature reaction system decompression is evacuated, every half an hour by high pure nitrogen replacement(metathesis)reaction system, so repeated multiple times, under the oil bath of l20 DEG C and agitation condition, 12 hours are carried out with post-polymerization, then system is dropped to room temperature, add the lactide monomer of 70%-80% molar composition under nitrogen protection, again system is warmed up to l50 DEG C, continues reaction 12 hours; Reaction resulting polymers methylene dichloride dissolves, and then precipitates in a large amount of freezing ether, to remove unreacted monomer and catalyzer, puts into 70 DEG C of vacuum drying ovens dry 24 hours after being purified by gained throw out.
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| JP4548623B2 (en) * | 1999-02-24 | 2010-09-22 | 多木化学株式会社 | Biomaterial |
| KR100451910B1 (en) * | 2000-10-05 | 2004-10-08 | 주식회사 바이오폴리테크 | A water soluble and biodegradable polymer gel, and a process of preparing for the same |
| US8580307B2 (en) * | 2006-06-22 | 2013-11-12 | Ethicon, Inc. | High glass transition temperature absorbable microspheres |
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| CN102344557A (en) | 2012-02-08 |
| CN103848979A (en) | 2014-06-11 |
| CN102344557B (en) | 2014-08-13 |
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