CN102344558A - Polyester-polyether copolymer and its synthesis method and use - Google Patents
Polyester-polyether copolymer and its synthesis method and use Download PDFInfo
- Publication number
- CN102344558A CN102344558A CN2011101857916A CN201110185791A CN102344558A CN 102344558 A CN102344558 A CN 102344558A CN 2011101857916 A CN2011101857916 A CN 2011101857916A CN 201110185791 A CN201110185791 A CN 201110185791A CN 102344558 A CN102344558 A CN 102344558A
- Authority
- CN
- China
- Prior art keywords
- lactide
- polyester
- weight ratio
- copolyether
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
- Polyesters Or Polycarbonates (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to a polyester-polyether copolymer and its synthesis method and use. The invention comprises a technical scheme 1, wherein the technical scheme 1 is characterized in that the polyester-polyether copolymer is prepared from 75 to 90 wt% of lactide and 10 to 25 wt% of polyethylene glycol by polymerization, a technical scheme 3, wherein the technical scheme 3 is characterized in that the polyester-polyether copolymer is prepared from 75 to 90 wt% of a mixture of lactide and glycolide and 10 to 25 wt% of polyethylene glycol by polymerization and a molar ratio of lactide to glycolide in the mixture is in a range of (65: 35) to (95: 5), and a technical scheme 5, wherein the technical scheme 5 is characterized in that the polyester-polyether copolymer is prepared from 90 to 99 wt% of a mixture of lactide and caprolactone and 1 to 10 wt% of polyethylene glycol by polymerization and a molar ratio of lactide to caprolactone in the mixture is in a range of (60: 40) to (80: 20). A medical anti-adhesion membrane prepared from the polyester-polyether copolymer has good flexibility.
Description
Technical field
The invention belongs to technical field of polymer chemistry, relate in particular to the bio-medical material technical field.
Background technology
Tissue adhesion is clinical middle common phenomena after the surgical operation; After brain surgery, abdominal surgery, Obstetric and Gynecologic Department, orthopedics and cardiovascular operation; If produce adhesion; The caused severe complications that has; Like intestinal obstruction, abdomen pelvic pain, infertility, dysfunction etc., increased the difficulty of performing the operation once more and the potentially dangerous that produces further complication has been arranged.Such as: (1) brain surgery post-craniotomy dura mater is damaged, and cicatricial adhesion can cause postoperative epilepsy; (2) adhesion after the abdomen operation on pelvis can cause intestinal obstruction, and severe patient need be carried out operation for the second time, has increased patient's misery and economical load; (3) behind the gynaecology and obstetrics operation, serious adhesion person has because of " gluing " together in ovary peritonaeum uterus, and the pain dysfunction occurs; (4) after thoracic surgery such as heart valve implantation, the pericardium operation, 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.
The previous method of reporting Film with Preventing Adhesion clinically mainly is to use medicine to reduce to ooze out and is suppressed to fibrocellular formation, but uncertain therapeutic efficacy is cut, side effect is big, can widespread use.Over past ten years; But there is report to use absorption fluids to reach isolated purpose both at home and abroad clinically; Prevention and minimizing adhesion; Though obtained certain curative effect; But because of fluid (like hyaluronate sodium etc.) have absorb fast, be prone to run off, can not form the later stage in adhesion and reach defectives such as effective isolation, thereby influenced its marketing.
Medical expert and material expert concentrated on sight on the bioabsorbable membrane both at home and abroad in recent years, and " physical barriers " effect that utilizes film to bring into play reaches the purpose that prevents tissue adhesion.The film forming material of structure has excellent biological compatibility and blood compatibility; After operation, can effectively isolate the histoorgan that is prone to adhesion; Do not influence the reparation of wound healing and wound uneven surface, and after accomplishing the isolation purpose, can not needed second operation to take out by the human body degraded and absorbed.Yet leading in the market Antiadhesive film such as polylactic acid membrane and chitosan film, all exists the not good enough defective of flexibility, inconvenient operation, and can't adapt to the tissue that some has complicated interface.It is slower that polylactic acid membrane also has degradation rate in addition, the defective that the degraded product biocompatibility is poor, be prone to cause secondary adhesion.Therefore, the absorbent antiseize film that can overcome above-mentioned defective of Development of New Generation can effectively improve the existing market performance of products, and helps absorbable medical film and aspect market, further promote.
Polyoxyethylene glycol (PEG) is a kind of material with good biocompatibility, good water solubility.When its molecular weight greater than 1000 the time, nontoxic; Molecular weight is 4000 o'clock, and its 10% solution injectable uses; Molecular weight can be filtered by animal kidney less than 30000 and excrete.Polyoxyethylene glycol has purposes widely at biomedicine field, in order to modifying various insoluble drugs, or is used for the component of biological device or pharmaceutical carrier.Because polyoxyethylene glycol has second-order transition temperature low (60 ℃), hydrophilic characteristics,, can effectively reduce the latter's second-order transition temperature, and accelerate its degradation speed greatly itself and biodegradable polyesters copolymerization.
In Chinese patent CN 1532216A, reported the medical film that 90% blend that gathers the polyoxyethylene glycol of (D, L-lactic acid) and 10% forms Wei etc.Since polyoxyethylene glycol not with other lactone or lactide monomers copolymerization; Both consistencies are poor; The polyoxyethylene glycol easy and crystalline; And under aqueous environments, be easy in film, run off; Lost its purpose as softening agent; Can't fundamentally solve and gather (D, L-lactic acid) film and in degradation process, be easy to generate the relatively poor fragment product of biocompatibility, cause problems such as secondary adhesion.
Teng Cun is strong to control to wait in international monopoly WO2006/100895 and corresponding Chinese patent CN 101052425A to have reported with rac-Lactide and caprolactone copolymer to be the medical film of component, has splendid flexibility, can be used for the occasion of needs winding function.Yet this multipolymer does not include the polyoxyethylene glycol component, and degradation rate is slower, in human body by complete soak time above six months.
Xiao etc. once mentioned with the polyethylene glycol-ester copolymer in Chinese patent CN 101461966 in Chinese patent CN 101274104, Tang etc. and using as the component of Antiadhesive film.Yet these patents all do not show substantive progress, fail to this specific end use of anti, how effectively to regulate and control with the effect of softening that increases that realizes polyoxyethylene glycol to give to specify to the concrete application strategy of multipolymer and on component or composition.Particularly the range of application of polyoxyethylene glycol is too wide in these patents, when its content is low, then may not necessarily plays medical film and increasing gentle effect, and when content is higher, then can damage other performances such as molecular weight and mechanical strength of mould material.
In sum; Though the polyethylene glycol-ester copolymer has potential advantages as the component of Antiadhesive film in theory; But can polyoxyethylene glycol particularly effectively play a role aspect the improvement of flexibility to the lifting of the over-all properties of mould material, is prerequisite not damage other performances.Therefore, seek out significantly flexible and the good medical film of over-all properties, need further investigate the application strategy of polyethylene glycol-ester copolymer.
Summary of the invention
The objective of the invention is that existing medical anti-adhesive film snappiness is poor in order to overcome, degradation rate is slow and the defective of degraded product biocompatibility difference, has proposed a kind of polyester-copolyether and synthesis method thereof and application.
To achieve these goals, the following technical scheme that comprises of the present invention:
Scheme one: polyester-copolyether, it is characterized in that, form by the rac-Lactide of 75%-90% weight ratio and the polyethylene glycol polymeric reaction of 10%-25% weight ratio.
Scheme two: a kind of method of manufacture of polyester-copolyether, it is characterized in that, comprise step:
In reaction vessel; Add the rac-Lactide of 75%-90% weight ratio and the polyoxyethylene glycol of 10%-25% weight ratio; Add stannous octoate solution then; At room temperature the reaction system decompression is evacuated; Whenever at a distance from a set time with high pure nitrogen replacement(metathesis)reaction system; Repeated multiple times like this; Carry out for some time being provided with under the temperature with post-polymerization; After question response finishes; Resulting polymers is dissolved with methylene dichloride; And then with a large amount of freezing ether sedimentations, the back drying in vacuum drying oven of purifying obtains polyester-copolyether.
Scheme three: polyester-copolyether; It is characterized in that; Formed by the mixture of the rac-Lactide of 75%-90% weight ratio and glycollide and the polyethylene glycol polymeric reaction of 10%-25% weight ratio, the mole component ratio of the mixture of said rac-Lactide and glycollide is between 65/35 to 95/5.
Scheme four: a kind of method of manufacture of polyester-copolyether, it is characterized in that, comprise step:
In reaction vessel; Adding is by lactide and the mixture of glycolide and the polyethylene glycol of 10%-25% weight ratio of 75%-90% weight ratio; The mole component ratio of the mixture of said lactide and glycolide is between 65/35 to 95/5; Add stannous octoate solution then; At room temperature the reaction system decompression is evacuated; Whenever use high pure nitrogen displacement reaction system at a distance from a set time; Repeated multiple times like this; Carry out a period of time being provided with under the temperature with post-polymerization; After question response finishes; Resulting polymers is dissolved with carrene, and then with a large amount of freezing ether sedimentations, the back drying in vacuum drying oven of purifying obtains polyester-copolyether.
Scheme five: polyester-copolyether; It is characterized in that; Formed by the mixture of the rac-Lactide of 90%-99% weight ratio and caprolactone and the polyethylene glycol polymeric reaction of 1%-10% weight ratio, the mole component ratio of the mixture of said rac-Lactide and caprolactone is between 60/40 to 80/20.
Scheme six: a kind of method of manufacture of polyester-copolyether, it is characterized in that, comprise step:
In reaction vessel; The lactide and the mixture of caprolactone and the polyethylene glycol of 1%-10% weight ratio that add the 90%-99% weight ratio; The mole component ratio of the mixture of said lactide and caprolactone is between 60/40 to 80/20; Add stannous octoate solution then; At room temperature the reaction system decompression is evacuated; Whenever use high pure nitrogen displacement reaction system at a distance from a set time; Repeated multiple times like this; Carry out a period of time being provided with under the temperature with post-polymerization; After question response finishes; Resulting polymers is dissolved with carrene, and then with a large amount of freezing ether sedimentations, the back drying in vacuum drying oven of purifying obtains polyester-copolyether.
Scheme seven: a kind of medical anti-adhesive film, it is characterized in that said medical anti-adhesive film adopts aforementioned polyester-polyethers binary or ter-polymers to be made, the thickness of said Antiadhesive film is between the 0.03-0.5 millimeter.
The invention has the beneficial effects as follows: polyester-copolyether that lactone or lactide and polyoxyethylene glycol copolymerization are obtained; Because polyoxyethylene glycol has the characteristics (second-order transition temperature is for-60 ℃) of lower glass transition temperatures, therefore the medical anti-adhesive film that adopts this multipolymer to make has good snappiness.In addition, because polyoxyethylene glycol possess hydrophilic property and water miscible characteristics can improve the water-absorbent of mould material, and accelerate it by the speed of corrosion.At last, polyester of the present invention-copolyether Antiadhesive film is keeping the good flexible while, and the content through the control polyoxyethylene glycol also has good mechanical intensity concurrently.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done further explanation.
Embodiment 1: specifically comprised following technical scheme in the present embodiment:
Scheme one: polyester-copolyether, it is characterized in that, form by the rac-Lactide of 75%-90% weight ratio and the polyethylene glycol polymeric reaction of 10%-25% weight ratio.
To have an end group at least be hydroxyl to the polyoxyethylene glycol raw material when multipolymer was synthetic, and another end group can be a 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; The most suitable molecular weight is 6000.
Scheme two: a kind of method of manufacture of polyester-copolyether, this method is an one-step synthesis, an one of which concrete example may further comprise the steps:
Be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, the molecular weight that adds different proportionings is 6000 polyoxyethylene glycol and rac-Lactide totally 50 grams, and then injects 0.5 milliliter of stannous octoate solution (concentration is 0.1g/ml) with microsyringe.At room temperature the reaction system decompression is evacuated, replace system with high pure nitrogen every separated half an hour, so repeated multiple times.Polyreaction was carried out 12 hours under 150 ℃ oil bath and agitation condition.After reaction finished, resulting polymers dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, the back drying 24 hours in 70 ℃ of vacuum drying ovens of purifying.
The condition of ring-opening polymerization is in the above-mentioned synthesis method: 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 ℃, and more suitable temperature is 80-200 ℃, and optimal reaction temperature is 110-180 ℃; 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.
Scheme seven: a kind of medical anti-adhesive film, it is characterized in that said medical anti-adhesive film adopts aforementioned polyester-copolyether to be made, the thickness of said Antiadhesive film is between the 0.03-0.5 millimeter.Further can select between the 0.03-0.06 millimeter or between the 0.10-0.30 millimeter.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 therefore is not described in detail.
Below, through experiment and test data to above-mentioned polymkeric substance and adopt the medical anti-adhesive film of this polymer formation to make checking and analysis.
That adopts method synthetic polyoxyethylene glycol and lactide copolymer in the such scheme two feeds intake when characterization data shown in following table one:
Table one
In the above table, " multipolymer is called for short row " expression rac-Lactide and polyoxyethylene glycol copolymerization ratio carried out copolyreaction like the rac-Lactide of PLA-PEG (95/5) expression 95% weight ratio and the polyoxyethylene glycol of 5% weight ratio; The actual charging capacity of the rac-Lactide of copolyreaction is shown in " rac-Lactide feed ratio " tabulation; The actual charging capacity of the polyoxyethylene glycol of copolyreaction is shown in " polyoxyethylene glycol feed ratio " tabulation; " polyethyleneglycol content " tabulation shows that the theoretical weight of polyoxyethylene glycol in the gained multipolymer is than forming; The weight-average molecular weight of the multipolymer after synthesizing is shown in " molecular weight " tabulation.
Medical anti-adhesive film to the manufacturing of above-mentioned synthetic polymkeric substance is done mechanical property and thermal performance test.Be equipped with the film of multipolymer through the solution evaporation legal system, the control film thickness is in 0.1 millimeter.Measure the thermal characteristics of film through DSC; Mechanical properties in films is measured on the SANS instrument, film be shaped as rectangle (5 * 40mm2, N=5), the mensuration temperature is a room temperature, rate of extension is 10mm/min.The second-order transition temperature of film and mechanical performance data see the following form two:
Table two
Can be found out that by last table the content of PEG is at 75-90wt% in the control multipolymer, the mechanical strength of copolymer film satisfies the demand of anti, and its elongation at break is all greater than 200%, and the flexibility of film is able to remarkable improvement.In addition, the second-order transition temperature of the flexibility of the film material that is able to significantly to improve is between 25-45oC.
Performance data by Comparative Examples PLA-PEG (95/5) can find out, when the content of PEG in the multipolymer is 5wt%, and film flexible relatively poor.
Performance data by Comparative Examples PLA-PEG (50/50) can find out that when the content of PEG in the multipolymer was 50wt%, molecular weight of copolymer was low excessively, and second-order transition temperature is low excessively, and the non-constant of the mechanical strength of film can't satisfy the service requirements of anti.
Embodiment 2: specifically comprised following technical scheme in the present embodiment:
Scheme three: polyester-copolyether; It is characterized in that; Formed by the mixture of the rac-Lactide of 75%-90% weight ratio and glycollide and the polyethylene glycol polymeric reaction of 10%-25% weight ratio, the mole component ratio of the mixture of said rac-Lactide and glycollide is between 65/35 to 95/5.
To have an end group at least be hydroxyl to the polyoxyethylene glycol raw material when multipolymer was synthetic, and another end group can be a 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; The most suitable molecular weight is 6000.
Scheme four: a kind of method of manufacture of polyester-copolyether, this method is an one-step synthesis, an one of which concrete example may further comprise the steps:
Be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, the molecular weight that adds different proportionings is 6000 polyoxyethylene glycol, rac-Lactide, glycollide totally 50 grams, and then injects 0.5 milliliter of stannous octoate solution (concentration is 0.1g/ml) with microsyringe.At room temperature the reaction system decompression is evacuated, replace system with high pure nitrogen every separated half an hour, so repeated multiple times.Polyreaction was carried out 12 hours under 150 ℃ oil bath and agitation condition.After reaction finished, resulting polymers dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, the back drying 24 hours in 70 ℃ of vacuum drying ovens of purifying.
The condition of ring-opening polymerization is in the above-mentioned synthesis method: 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 ℃, and more suitable temperature is 80-200 ℃, and optimal reaction temperature is 110-180 ℃; 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.
Scheme seven: a kind of medical anti-adhesive film, it is characterized in that said medical anti-adhesive film adopts aforementioned polyester-copolyether to be made, the thickness of said Antiadhesive film is between the 0.03-0.5 millimeter.Further can select between the 0.03-0.06 millimeter or between the 0.10-0.30 millimeter.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 therefore is not described in detail.
Below, through experiment and test data to above-mentioned polymkeric substance and adopt the medical anti-adhesive film of this polymer formation to make checking and analysis.
That adopts method synthetic polyoxyethylene glycol and rac-Lactide and glycolide copolymer in the such scheme four feeds intake when characterization data shown in following table three:
Table three
In the above table; " multipolymer is called for short row " expression rac-Lactide, glycollide and polyoxyethylene glycol copolymerization ratio; Represent that like PLGA (95/5)-PEG (10%) rac-Lactide of 90% weight ratio and the mixture of glycollide and the polyoxyethylene glycol of 10% weight ratio carry out copolyreaction; Wherein in the mix monomer, the mol ratio of rac-Lactide and glycollide is 95/5; The actual charging capacity of the rac-Lactide of copolyreaction is shown in " rac-Lactide feeds intake " tabulation; The actual charging capacity of the glycollide of copolyreaction is shown in " glycollide feeds intake " tabulation; The actual charging capacity of the polyoxyethylene glycol of copolyreaction is shown in " polyoxyethylene glycol feeds intake " tabulation; The theoretical molar ratio of rac-Lactide and glycollide in the gained multipolymer is shown in " lactide/glycolides " tabulation; " polyethyleneglycol content " tabulation shows that the theoretical weight of polyoxyethylene glycol in the gained multipolymer is than forming; The weight-average molecular weight of the multipolymer after synthesizing is shown in " molecular weight " tabulation.
Medical anti-adhesive film to the manufacturing of above-mentioned synthetic polymkeric substance is done mechanical property and thermal performance test.Be equipped with the film of multipolymer through the solution evaporation legal system, the control film thickness is in 0.1 millimeter.Measure the thermal characteristics of film through DSC; Mechanical properties in films is measured on the SANS instrument, film be shaped as rectangle (5 * 40mm2, N=5), the mensuration temperature is a room temperature, rate of extension is 10mm/min.The second-order transition temperature of film and mechanical performance data see the following form four:
Table four
Can find out by last table; The content of PEG is at 75-90wt% in the control multipolymer, and the mol ratio of lactide/glycolides is between 95/5-65/35, and the mechanical strength of copolymer film satisfies the demand of anti; And its elongation at break is all greater than 200%, and the flexibility of film is able to remarkable improvement.In addition, the second-order transition temperature of the flexibility of the film material that is able to significantly to improve is between 25-45oC.
Embodiment 3: specifically comprised following technical scheme in the present embodiment:
Scheme five: polyester-copolyether; It is characterized in that; Formed by the mixture of the rac-Lactide of 90%-99% weight ratio and caprolactone and the polyethylene glycol polymeric reaction of 1%-10% weight ratio, the mole component ratio of the mixture of said rac-Lactide and caprolactone is between 60/40 to 80/20.
To have an end group at least be hydroxyl to the polyoxyethylene glycol raw material when multipolymer was synthetic, and another end group can be a 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; The most suitable molecular weight is 6000.
Scheme six: a kind of method of manufacture of polyester-copolyether, this method is an one-step synthesis, an one of which concrete example may further comprise the steps:
Be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, the molecular weight that adds different proportionings is 6000 polyoxyethylene glycol, rac-Lactide, caprolactone totally 50 grams, and then injects 0.5 milliliter of stannous octoate solution (concentration is 0.1g/ml) with microsyringe.At room temperature the reaction system decompression is evacuated, replace system with high pure nitrogen every separated half an hour, so repeated multiple times.Polyreaction was carried out 12 hours under 150 ℃ oil bath and agitation condition.After reaction finished, resulting polymers dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, the back drying 24 hours in 70 ℃ of vacuum drying ovens of purifying.Be equipped with in 100 milliliters of reaction vessels of magnetic stirring apparatus one, the molecular weight that adds different proportionings is 6000 polyoxyethylene glycol, rac-Lactide, glycollide totally 50 grams, and then injects 0.5 milliliter of stannous octoate solution (concentration is 0.1g/ml) with microsyringe.At room temperature the reaction system decompression is evacuated, replace system with high pure nitrogen every separated half an hour, so repeated multiple times.Polyreaction was carried out 12 hours under 150 ℃ oil bath and agitation condition.After reaction finished, resulting polymers dissolved with methylene dichloride, and then with a large amount of freezing ether sedimentations, the back drying 24 hours in 70 ℃ of vacuum drying ovens of purifying.
The condition of ring-opening polymerization is in the above-mentioned synthesis method: 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 ℃, and more suitable temperature is 80-200 ℃, and optimal reaction temperature is 110-180 ℃; 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.
Scheme seven: a kind of medical anti-adhesive film, it is characterized in that said medical anti-adhesive film adopts aforementioned polyester-copolyether to be made, the thickness of said Antiadhesive film is between the 0.03-0.5 millimeter.Further can select between the 0.03-0.06 millimeter or between the 0.10-0.30 millimeter.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 therefore is not described in detail.
Below, through experiment and test data to above-mentioned polymkeric substance and adopt the medical anti-adhesive film of this polymer formation to make checking and analysis.
That adopts method synthetic polyoxyethylene glycol and rac-Lactide and caprolactone copolymer in the such scheme five feeds intake when characterization data shown in following table five:
Table five
In the above table; " multipolymer is called for short row " expression rac-Lactide, caprolactone and polyoxyethylene glycol copolymerization ratio; Represent that like PLACL (80/20)-PEG (5%) rac-Lactide of 95% weight ratio and the mixture of caprolactone and the polyoxyethylene glycol of 5% weight ratio carry out copolyreaction; Wherein in the mix monomer, the mol ratio of rac-Lactide and caprolactone is 80/20; The actual charging capacity of the rac-Lactide of copolyreaction is shown in " rac-Lactide feeds intake " tabulation; The actual charging capacity of the glycollide of copolyreaction is shown in " caprolactone feeds intake " tabulation; The actual charging capacity of the polyoxyethylene glycol of copolyreaction is shown in " polyoxyethylene glycol feeds intake " tabulation; The theoretical molar ratio of rac-Lactide and caprolactone in the gained multipolymer is shown in " rac-Lactide/caprolactone " tabulation; " polyethyleneglycol content " tabulation shows that the theoretical weight of polyoxyethylene glycol in the gained multipolymer is than forming; The weight-average molecular weight of the multipolymer after synthesizing is shown in " molecular weight " tabulation.
Medical anti-adhesive film to the manufacturing of above-mentioned synthetic polymkeric substance is done mechanical property and thermal performance test.Be equipped with the film of multipolymer through the solution evaporation legal system, the control film thickness is in 0.1 millimeter.Measure the thermal characteristics of film through DSC; Mechanical properties in films is measured on the SANS instrument, film be shaped as rectangle (5 * 40mm2, N=5), the mensuration temperature is a room temperature, rate of extension is 10mm/min.The second-order transition temperature of film and mechanical performance data see the following form six:
Table six
Can find out by last table; The content of PEG is at 1-10wt% in the control multipolymer, and the mol ratio of rac-Lactide and caprolactone is between 80/20-60/40, and the mechanical strength of copolymer film satisfies the demand of anti; And its elongation at break is all greater than 400%, and the flexibility of film is able to remarkable improvement.In addition, the second-order transition temperature of the flexibility of the film material that is able to significantly to improve is between 5-30oC.
The suitable second-order transition temperature of the foregoing description 1 and embodiment 2 medical anti-adhesive films is between 25-45 ℃, and the suitable second-order transition temperature of embodiment 3 medical anti-adhesive films is between 5-30 ℃.
The suitable molecular weight of the foregoing description 1 and embodiment 2 medical anti-adhesive films is between 3-10 ten thousand, and the suitable molecular weight of embodiment 3 medical anti-adhesive films is between 6-50 ten thousand.
The suitable elongation at break of the foregoing description 1 and embodiment 2 medical anti-adhesive films is between 200-800%, and the suitable elongation at break of embodiment 3 medical anti-adhesive films is between 600-1500%.
The barrier film that above-mentioned three embodiment medical anti-adhesive films can be used for the post-operation adhesion preventing of multiple operation uses; Wherein embodiment 1 is particularly suitable for abdominal operation, heart operation etc. with embodiment 2 medical anti-adhesive films, and embodiment 3 is particularly suitable for the occasion use that nerve, bone, joint, blood vessel etc. need have the winding function
The degradation cycle of copolymer film is at 1-12 between the month among above-mentioned three embodiment.Be adapted to the different application scenarios and the thickness of film, can be further at 1-3 between the month, 3-6 between the month or 6-12 select between the month; Degradation time depends primarily on the ratio of the molecular weight and the polyoxyethylene glycol of material, and molecular weight is high more, and it is slow more to degrade; The polyoxyethylene glycol ratio is high more, and it is fast more to degrade.
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 to be understood 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 break away from essence of the present invention according to these teachings disclosed by the invention, and these distortion and combination are still in protection scope of the present invention.
Claims (7)
1. polyester-copolyether is characterized in that, is formed by the rac-Lactide of 75%-90% weight ratio and the polyethylene glycol polymeric reaction of 10%-25% weight ratio.
2. the method for manufacture of a polyester-copolyether is characterized in that, comprises step:
In reaction vessel; Add the rac-Lactide of 75%-90% weight ratio and the polyoxyethylene glycol of 10%-25% weight ratio; Add stannous octoate solution then; At room temperature the reaction system decompression is evacuated; Whenever at a distance from a set time with high pure nitrogen replacement(metathesis)reaction system; Repeated multiple times like this; Carry out for some time being provided with under the temperature with post-polymerization; After question response finishes; Resulting polymers is dissolved with methylene dichloride; And then with a large amount of freezing ether sedimentations, the back drying in vacuum drying oven of purifying obtains polyester-copolyether.
3. polyester-copolyether; It is characterized in that; Formed by the mixture of the rac-Lactide of 75%-90% weight ratio and glycollide and the polyethylene glycol polymeric reaction of 10%-25% weight ratio, the mole component ratio of the mixture of said rac-Lactide and glycollide is between 65/35 to 95/5.
4. the method for manufacture of a polyester-copolyether is characterized in that, comprises step:
In reaction vessel; Adding is by lactide and the mixture of glycolide and the polyethylene glycol of 10%-25% weight ratio of 75%-90% weight ratio; The mole component ratio of the mixture of said lactide and glycolide is between 65/35 to 95/5; Add stannous octoate solution then; At room temperature the reaction system decompression is evacuated; Whenever use high pure nitrogen displacement reaction system at a distance from a set time; Repeated multiple times like this; Carry out a period of time being provided with under the temperature with post-polymerization; After question response finishes; Resulting polymers is dissolved with carrene, and then with a large amount of freezing ether sedimentations, the back drying in vacuum drying oven of purifying obtains polyester-copolyether.
5. polyester-copolyether; It is characterized in that; Formed by the mixture of the rac-Lactide of 90%-99% weight ratio and caprolactone and the polyethylene glycol polymeric reaction of 1%-10% weight ratio, the mole component ratio of the mixture of said rac-Lactide and caprolactone is between 60/40 to 80/20.
6. the method for manufacture of a polyester-copolyether is characterized in that, comprises step:
In reaction vessel; The lactide and the mixture of caprolactone and the polyethylene glycol of 1%-10% weight ratio that add the 90%-99% weight ratio; The mole component ratio of the mixture of said lactide and caprolactone is between 60/40 to 80/20; Add stannous octoate solution then; At room temperature the reaction system decompression is evacuated; Whenever use high pure nitrogen displacement reaction system at a distance from a set time; Repeated multiple times like this; Carry out a period of time being provided with under the temperature with post-polymerization; After question response finishes; Resulting polymers is dissolved with carrene, and then with a large amount of freezing ether sedimentations, the back drying in vacuum drying oven of purifying obtains polyester-copolyether.
7. a medical anti-adhesive film is characterized in that, said medical anti-adhesive film adopts aforementioned claim 1,3 or 5 described polyester-polyethers binary or ter-polymers to be made, and the thickness of said Antiadhesive film is between the 0.03-0.5 millimeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101857916A CN102344558A (en) | 2011-07-05 | 2011-07-05 | Polyester-polyether copolymer and its synthesis method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101857916A CN102344558A (en) | 2011-07-05 | 2011-07-05 | Polyester-polyether copolymer and its synthesis method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102344558A true CN102344558A (en) | 2012-02-08 |
Family
ID=45543653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101857916A Pending CN102344558A (en) | 2011-07-05 | 2011-07-05 | Polyester-polyether copolymer and its synthesis method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102344558A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055354A (en) * | 2013-01-17 | 2013-04-24 | 中国科学院长春应用化学研究所 | Biodegradable medical surgery anti-adhesion membrane and preparation method thereof |
| CN103936973A (en) * | 2013-01-23 | 2014-07-23 | 中国科学院化学研究所 | Multi-functional-group polyethylene oxide-b-aliphatic polyester block copolymers, preparing method thereof and applications thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101052425A (en) * | 2005-03-23 | 2007-10-10 | 株式会社Jms | Antiadhesive film |
| CN101461966A (en) * | 2007-12-21 | 2009-06-24 | 唐伟锋 | Method for preparing degradable flexible medical film material |
| US20090294049A1 (en) * | 2008-06-02 | 2009-12-03 | Medtronic Vascular, Inc. | Biodegradable Adhesive Hydrogels |
| CN102058909A (en) * | 2011-01-18 | 2011-05-18 | 复旦大学 | Polyethylene glycol-copolyester segmented copolymer material capable of preventing adhesion, a preparation method and application thereof |
| CN102107018A (en) * | 2011-01-11 | 2011-06-29 | 上海鼎华医械有限责任公司 | Postoperative anti-adhesion membrane and application thereof |
-
2011
- 2011-07-05 CN CN2011101857916A patent/CN102344558A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101052425A (en) * | 2005-03-23 | 2007-10-10 | 株式会社Jms | Antiadhesive film |
| CN101461966A (en) * | 2007-12-21 | 2009-06-24 | 唐伟锋 | Method for preparing degradable flexible medical film material |
| US20090294049A1 (en) * | 2008-06-02 | 2009-12-03 | Medtronic Vascular, Inc. | Biodegradable Adhesive Hydrogels |
| CN102107018A (en) * | 2011-01-11 | 2011-06-29 | 上海鼎华医械有限责任公司 | Postoperative anti-adhesion membrane and application thereof |
| CN102058909A (en) * | 2011-01-18 | 2011-05-18 | 复旦大学 | Polyethylene glycol-copolyester segmented copolymer material capable of preventing adhesion, a preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055354A (en) * | 2013-01-17 | 2013-04-24 | 中国科学院长春应用化学研究所 | Biodegradable medical surgery anti-adhesion membrane and preparation method thereof |
| CN103055354B (en) * | 2013-01-17 | 2015-10-07 | 中国科学院长春应用化学研究所 | A kind of biodegradable medical surgery anti-adhesion membrane and preparation method thereof |
| CN103936973A (en) * | 2013-01-23 | 2014-07-23 | 中国科学院化学研究所 | Multi-functional-group polyethylene oxide-b-aliphatic polyester block copolymers, preparing method thereof and applications thereof |
| CN103936973B (en) * | 2013-01-23 | 2015-12-23 | 中国科学院化学研究所 | A kind of polyfunctional group polyethylene oxide-b-aliphatic poly ester block copolymer and preparation method thereof and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2262182T3 (en) | METHODS AND COMPOSITIONS TO REDUCE OR ELIMINATE THE FORMATION OF POSTOPERATIVE ADHERENCES. | |
| US6699940B2 (en) | Cyanoacrylate-capped heterochain polymers and tissue adhesives and sealants therefrom | |
| EP0693294B1 (en) | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom | |
| US7321008B2 (en) | Bioabsorbable branched polymers end-capped with diketene acetals | |
| US8927001B2 (en) | Bioswellable, crystalline, amphiphilic, block/graft polymers and applications thereof | |
| RU2640817C2 (en) | Segmented, semi-crystal soluble compounds of lactide and epsilon-caprolactone | |
| JPH0859811A (en) | Biocompatible block copolymer | |
| CN103055354B (en) | A kind of biodegradable medical surgery anti-adhesion membrane and preparation method thereof | |
| CN103992465B (en) | biodegradable terpolymer | |
| US7754233B2 (en) | Method of preventing post-operative surgical adhesion | |
| Yuan et al. | 5-Fluorouracil loaded thermosensitive PLGA–PEG–PLGA hydrogels for the prevention of postoperative tendon adhesion | |
| JP2986498B2 (en) | Bioabsorbable polyester and method for producing the same | |
| EP2203500A1 (en) | Absorbable polymer formulations | |
| CN102344558A (en) | Polyester-polyether copolymer and its synthesis method and use | |
| CN103951950B (en) | Flexible biological degradable composite material | |
| US9433639B2 (en) | Synthetic mechanical hemostatic composition, method of making and use thereof | |
| CN1569261A (en) | Novel use of ploy-L-lactic acid as medical shape memory material | |
| CN103848979B (en) | P-Dioxane ketone polymer and synthetic method thereof and application | |
| US10160831B2 (en) | Astaxanthin based polymer and uses thereof | |
| EP0837084A2 (en) | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom | |
| CN103495211A (en) | Absorbable anti-adhesive membrane for cardiac surgery and preparation method of absorbable anti-adhesive membrane | |
| US20020032298A1 (en) | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom | |
| CN109970957B (en) | Controllable biodegradable copolymer with alkaline copolymerization center | |
| JP4548644B2 (en) | Biomaterial | |
| KR20210067089A (en) | Biodegradable block-copolymer for and preparation method the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120208 |