CN106957416A - [PTMC GA] [PLLA GA] block polyester of adjustable degradation rate and preparation method thereof - Google Patents
[PTMC GA] [PLLA GA] block polyester of adjustable degradation rate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention belongs to technical field of polymer materials, a specially class can adjust [PTMC GA] [PLLA GA] block polyester of degradation rate and preparation method thereof.[PTMC GA] [PLLA GA] block polyester of the invention is prepared by following process：In the presence of catalyst, first by TMC）PTMC GA prepolymers are synthesized with two kinds of monomers of GA, then using PTMC GA as macromole evocating agent, with LLA and GA ring-opening polymerisations.The number-average molecular weight of the block polyester is 5.0 × 104~4.5 × 105G/mol, tensile strength is 25.2~52.4MPa, and elongation at break is 70.7%~236.5%.I.e. the block polyester toughness has significant increase, while there is more than 20% crystallinity, there is higher tensile strength.Polyester produced by the present invention has excellent mechanical property, good biocompatibility and regulatable biodegradation period, the field of medical materials such as artificial diaphysis, tissue engineering bracket, interventional medical apparatus, has broad application prospects in biomedicine.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to and [PTMC-GA] of the adjustable degradation rate of a class-
[PLLA-GA] block polyester and preparation method thereof.
Background technology
PLA (PLA) is one kind with renewable resource（Such as straw, starch）The green modeling being prepared from for raw material
Material, due to good biocompatibility and biodegradability, making it that there is great answer in biomedical materials field
With value.Phase early 1990s FDA Food and Drug Administration (FDA) have approved PLLA（PLLA）As life
Thing degraded medical material.PLLA purposes is a lot, is mainly used in medical domain as surgical sewing thread, implantable blood vessel
The medical domains such as support, medicinal control system, artificial diaphysis and tissue engineering bracket material.Meanwhile, PLLA materials have good
Mechanical property and thermoplasticity, it is adaptable to a variety of processing molding methods such as be blow molded, extrude, being molded, it is easy to process, be readily processible to
Type.
But PLLA is a kind of fragile material at normal temperatures, elongation at break is usually no more than 10%, and its pliability typically can not
Use requirement is met, this just promotes modification of the people to PLLA materials to expand further investigation.It is poly- patent document 1 discloses improving
The flexible method of lactic acid.This method is by PLLA and PLLA-polycaprolactone co-polymer solution blending, by adjusting
Save the content of flexible portion polycaprolactone in blend to regulate and control the pliability of product, modified product possesses regulatable soft
Toughness.But, the introducing of polycaprolactone reduces the crystallinity of material, causes the decline of tensile strength of material, modified material
The tensile strength of material is between 7~20MPa, it is impossible to used as structural material.Patent document 2 discloses that a kind of introduce hydroxyl
Alkanoic acid or hydroxyl alkane acid esterification derivative improve the flexible method of PLA with PLA graft copolymerization.This method is easy
In industrialization large-scale production, flexible poly resin product can be prepared on a large scale.But the polyester construction prepared using this method can not
Control, molecular weight distribution is wider, and degradation time can not regulate and control, existing defects when as bio-medical material.The disclosure of patent document 3
It is a kind of by levorotatory lactide（LLA）With trimethylene carbonate（TMC）, glycolide（GA）The method of unit modification by copolymerization improves
PLLA pliability.The method that such material uses random copolymerization, introduces TMC and GA units, TMC units in PLLA systems
Introducing can reduce the crystallinity of material, the toughness of reinforcing material.And GA monomers have the reaction higher than LLA and TMC monomers
Activity, can further upset molecular chain structure, reduce crystallinity, the pliability of reinforcing material, while PGA sheets have as one kind
There is the material of high tensile strength, introducing GA units can ensure PLLA-TMC-GA terpolymers in the relatively low situation of crystallinity
Under still have certain tensile strength.But, such material uses crystallinity after random copolymerization too low so that its degradation rate
Comparatively fast, phase molecular weight and molecular weight is too fast after degradation is unable to maintain that mechanical property, lacks when being used as medical materials such as intravascular stents
Weary stability.
The present invention is directed to above-mentioned technical problem, it is proposed that one kind [PTMC-GA]-[PLLA-GA] biodegradable polies completely
Ester preparation method, first prepares PTMC-GA bipolymers, then PTMC-GA is used as into macromolecular by TMC and GA random copolymerizations
Initiator, with LLA and GA monomer reactions, prepares [PTMC-GA]-[PLLA-GA] polyester.The polyester has well flexible
Property simultaneously also have higher tensile strength., can be by adjusting [PTMC- also, the control of such material microstructure is stronger
GA] and [PLLA-GA] segment in GA units content and to control the degradation time of polyester, accomplish degradation time controllable, this
A little by the application value of very big reinforcing material.More meet bio-medical material from principle to mechanical property and degradation property
It is required that.
Technical literature：
Patent document 1：Chinese patent, publication number CN104231578A；
Patent document 2：Chinese patent, publication number CN1908030A；
Patent document 3：Chinese patent, publication number CN103030795A.
The content of the invention
It is an object of the invention to low for existing biodegradable polyesters tensile strength, degradation rate, which can not regulate and control, etc. lacks
It is sunken that there is provided a kind of complete biodegradable block polyester and preparation method thereof.The polyester achieves great lifting in toughness,
Simultaneously as crystallinity more than 20% so as to ensure that higher tensile strength and Young's modulus；Controllable segmented structure can be more
The accurately degradation rate of controlled material.Artificial diaphysis, tissue engineering bracket and interventional medical apparatus etc. can be widely used in
Biomedical materials field.
The complete biodegradable polyesters that the present invention is provided are [PTMC-GA]-[PLLA-GA] block polyesters, its strand
Structure is as follows：
Wherein, p is the TMC and GA total chain number in macromole evocating agent PTMG-GA, and p scope is 50~400, preferably 150
~300；Total chain number that q is LLA and GA in PLLA-GA, q scope 250~1200, preferably 600~1000.
In described complete biodegradable block polyester, TMC units rubs in macromole evocating agent PTMC-GA segments
Your content is 80~98%, preferably 92~96%；The molar content of GA units is 20~2%, preferably 8~4%.Copolymer p LLA-GA
The molar content of LLA units is 80~97%, preferably 85~95% in segment；The molar content of GA units is 20%~3%, preferably 7%
~3%.
Described complete biodegradable polyester, its number-average molecular weight is 5.0 × 104~4.5 × 105, it is preferably several to divide equally
Son amount is 1.5 × 105~2.5 × 105；Molecular weight distribution index is 1.5~3.0, preferably 1.6~2.2.
The preparation side of [PTMC-GA]-[PLLA-GA] block polyesters for the above-mentioned adjustable degradation rate that the present invention is provided
Method, is concretely comprised the following steps：
（1）Initiator and catalyst and TMC, GA monomer are added in polymerization pipe by design proportioning, the addition of initiator is
The 2%~0.2% of TMC, GA monomer integral molar quantity, preferably 1%~0.5%, the addition of catalyst is the 0.2% of monomer integral molar quantity
~0.6%, melting is heated under nitrogen or argon inert gas atmosphere；It is cooled to after solid-state, persistently vacuumizes；
（2）Vacuum is less than after 100Pa, and polymerization pipe is fused, and material is in vacuum state；
（3）By polymerization pipe as in isothermal reaction case, reaction temperature is 110 DEG C~180 DEG C, preferably 130 DEG C~140 DEG C；Reaction
Time is 12~120h, preferably 48~72h, and polymerization pipe is taken out after the completion of reaction；
（4）Obtained product solvent is dissolved, then separated out with precipitating reagent, dries, is fully dried in vacuum drying oven
Product PTMC-GA；
（5）By step（4）In obtained PTMC-GA with LLA, GA monomer and catalyst by adding in polymerization pipe, macromolecular triggers
Agent PTMC-GA addition is the 1%~0.1% of LLA, GA monomer integral molar quantity, and the addition of catalyst is monomer integral molar quantity
0.2%~0.6%, under nitrogen or argon inert gas atmosphere heating melting cooling；After vacuum is less than 100Pa, fusing
Polymerization pipe, makes material be in vacuum state, polymerization pipe is placed in isothermal reaction case, and reaction temperature is 120~180 DEG C, reaction
24~120h of time, takes out after the completion of reaction；
（6）Product in polymerization pipe is pressed into step（4）In process purifying drying, that is, prepare completion biodegradable poly-
Ester, Cord blood in drier is placed in by products therefrom.
Step（1）In, described initiator is ethanol, hexanol, octanol, dodecanol, 1, ammediol, 1,4- fourths two
One or more in alcohol, glycerine；Described catalyst be stannous octoate, stannous chloride, stannic chloride, zinc lactate, zinc chloride,
One or more in zinc acetylacetonate.
Step（3）And step（5）In, vacuum is not higher than 300Pa, preferably no greater than 10Pa.
Step（4）In, described solvent is dichloromethane, chloroform, chloroethanes, 1,2- dichloroethanes, tetrahydrofuran,
One or more in N, N- dimethylformamide and DMA, described precipitating reagent is methanol, ethanol, acetic acid second
One or more in ester.
Complete biodegradable block polyester of the present invention, can be widely applied to artificial diaphysis, tissue engineering bracket
With the biomedical materials field such as interventional medical such as intravascular stent.
In the present invention, above-mentioned optimum condition can be combined on the basis of common sense in the field is combined, and be produced of the invention each
Preferred embodiment.
The raw material and reagent of the present invention is all commercially available.
Complete biodegradable [PTMC-GA] prepared by the present invention-[PLLA-GA] block polyester has excellent mechanical property
Can, compared with PLLA, great lifting is achieved in toughness, while polyester has more than 20% crystallinity so that polyester has
There is higher tensile strength.And by using macromole evocating agent prepare polyester technology can effectively controlled material degraded speed
Rate.Therefore, the block polyester that prepared by the present invention has excellent mechanical property, good biocompatibility and biodegradability
And controllable degradation rate, the medical material such as artificial diaphysis, tissue engineering bracket, interventional medical apparatus in biomedicine
Field, has broad application prospects.
Brief description of the drawings
Fig. 1 is the building-up process schematic diagram of [PTMC-GA]-[PLLA-GA] block polyesters.
Fig. 2 is macromole evocating agent PTMC-GA and [PTMC-GA]-[PLLA-GA] block polyesters1H-NMR spectrum.
Fig. 3 is the infrared spectrum of [PTMC-GA]-[PLLA-GA] block polyesters.
Fig. 4 is [PTMC-GA]-[PLLA-GA] block polyester stress-strain diagrams.
Fig. 5 is the DSC spectrograms of [PTMC-GA]-[PLLA-GA] block polyesters, and sample is from room temperature with 30 DEG C/min heating
Speed is warming up to 190 DEG C, and isothermal 2min is to eliminate thermal history；Then again with the near room temperature of 150 DEG C/min rate of temperature fall after, with
10 DEG C/min is warming up to 190 DEG C, is as a result derived from the second just DSC heating curves.
Fig. 6 is weight-loss ratio change in [PTMC-GA]-[PLLA-GA] block polyester hydrolytic processes.
Embodiment
Instantiation is given below, so that the present invention to be specifically described.But the present invention is not intended to be limited thereto, wherein：
Block polyester prepared by the present invention, passes through proton nmr spectra（1H-NMR）And FTIR spectrum（FTIR）Determine it
Chemical composition, using gel permeation chromatograph（GPC）The molecular weight of material is determined, passes through differential scanning calorimeter（DSC）Characterize
The hot property of material, using the mechanical property of extensograph testing sample.Using the experimental method of extracorporeal hydrolysis to block polyester
Degradation behavior is simulated.
Embodiment 1
（1）19.16gTMC, 0.85gGA, 0.07g octanol and 0.06g stannous octoates are added in polymerization pipe, argon filling catches up with oxygen three times,
Persistently vacuumized after molten monomer, cooling, control system vacuum is not higher than 20Pa, fuse polymerization pipe.By the polymerization after fusing
Pipe prepares PTMC-GA macromole evocating agents as 24h is reacted in 130 DEG C of constant temperature ovens.
（2）Weigh step（1）PTMC-GA5g, L-LA40.22g, GA1.16g of middle preparation, stannous octoate 0.12g are added
In polymerization pipe, argon filling catches up with oxygen three times, is persistently vacuumized after fused materials, cooling, control system vacuum is not higher than 5Pa, fusing
Polymerization pipe.By the polymerization pipe after fusing as 72h is reacted in 140 DEG C of constant temperature ovens, biodegradable [PTMC- is prepared
GA]-[PLLA-GA] polyester.Course of reaction as shown in figure 1, products therefrom is purified after determine its number-average molecular weight for 2.4 ×
105G/mol, the coefficient of dispersion is 1.9.
Fig. 2 is macromole evocating agent PTMC-GA and block polyester [PTMC-GA]-[PLLA-GA]1H-NMR spectrum, tool
Body analyzes the latter's1H-NMR spectrum, peak a corresponding is GA units-CH on PTMC-GA segments2On H；Peak b is PTMC-GA chains
O-CH in TMC units in section2On H；Peak c is-CH in TMC units on PTMC-GA segments2On H；Peak d is PLLA-GA segments
Upper LLA units-CH3On H；Peak e is the H on LLA units O-CH on PLLA-GA segments；Peak f is that GA is mono- on PLLA-GA segments
Member-CH2On H.It can be seen that in PTMC-GA segments in GA chemical shift and PLLA-GA segments GA chemical potential
Move different, this is that the chemical shift that GA units are caused by different chemistry affects is different.1H-NMR results confirm [PTMC-
GA]-[PLLA-GA] polyester successfully synthesizes.
Fig. 3 is macromole evocating agent PTMC-GA and block polyester [PTMC-GA]-[PLLA-GA] FTIR spectrograms.Analysis
PTMC-GA FTIR spectrograms, 2926cm-1Belong to-CH in TMC and GA units2Stretching vibration peak；1741cm-1Belong to TMC
With the stretching vibration of C=O on GA units；1465cm-1Belong to TMC and GA units-CH2Flexural vibrations；1224cm-1With
1191cm-1Belong to the stretching vibration of C-O-C on PTMC-GA segments；1032cm-1And 786cm-1Belong in PTMC-GA segments
C-C skeletal vibration.The FTIR spectrograms of com-parison and analysis [PTMC-GA]-[PLLA-GA] polyester, it can be found that in 2996cm-1Place goes out
- CH is showed3Stretching vibration peak, this belongs to-CH in LLA units3；And 1454 cm-1、1383 cm-1、1132 cm-1Then it is attributed to
- CH in LLA units3Flexural vibrations and skeletal vibration；2929cm-1Belong to TMC and GA units-CH in polyester2Flexible shake
It is dynamic；1754cm-1Then it is attributed to the stretching vibration of C=O in polyester；1361cm-1Belong in polyester on PLLA segments（-CH3) + (-
CH) flexural vibrations；1183cm-1Belong in polyester (COC)+(- CH on PLLA segments3) flexural vibrations；1092cm-1With
870cm-1Belong to (COC) and（C-COO）Vibration；1044cm-1Then belong to C-CH3Skeletal vibration.Above FTIR results
Illustrate, TMC, LLA, GA unit are contained in the polyester, meanwhile, the appearance of single carbonyl peak, indicating material has random copolymerization
Structure.
The stress that Fig. 4 is block polyester [PTMC-GA]-[PLLA-GA] and the control sample PLLA with identical molecular weight should
Varied curve, its mechanical property is according to GB GBT1040.1-2006《The measure general provisions of plastic tensile performance》In requirement measurement comment
Estimate, prepare dumbbell shape batten, length 20mm, width 4mm, 5 parallel battens of sample test.The tensile strength of obtained polyester is
38.9 ± 4.3MPa, elongation at break 136.7 ± 12.7%, 1153 ± 108MPa of Young's modulus.And control sample PLLA stretching is strong
Spend for 42.4 ± 3.1MPa, elongation at break is 7.4 ± 2.4%, Young's modulus is 1267 ± 154MPa.Mechanical performance data table
Bright, the block polyester material newly synthesized is compared with traditional PLLA, and elongation at break has great improvement, while also remaining
Higher tensile strength and Young's modulus.
Fig. 5 is macromole evocating agent PTMC-GA and block polyester [PTMC-GA]-[PLLA-GA] DSC spectrograms, as figure can
Know, macromole evocating agent PTMC-GA glass transition temperature（T g）For -14.1 DEG C, sample is without any crystallization and melting peak.Instead
See polyester [PTMC-GA]-[PLLA-GA] DS spectrograms, the glass transition temperature of the sample（T g）For 57.1 DEG C, 127.2
DEG C there is a wider peak crystallization, enthalpy is 40.4J/g；There is a melting peak at 166.8 DEG C, enthalpy is 30.6J/g.By calculating
The crystallinity of sample is 32.5%, and higher crystallinity is capable of the mechanical strength of effective guarantee material, and this is from the mechanics in Fig. 4
Performance data has been verified.Block polyester [PTMC-GA]-[PLLA-GA] only has one simultaneouslyT g, illustrate in material
PLLA-GA segments are good with PTMC-GA segments compatibility, in the absence of the phenomenon of phase separation.
Embodiment 2
（1）20.65gTMC, 1.58gGA, 0.09g octanol and 0.07g stannous octoates are added in polymerization pipe；Building-up process is strictly according to the facts
Apply step in example 1（1）Described in step, macromole evocating agent PTMC-GA is prepared.
（2）Weigh step（1）PTMC-GA5g, L-LA34.22g, GA1.56g of middle preparation, stannous octoate 0.12g are added
In polymerization pipe, step in building-up process such as embodiment 1（2）It is described, prepare [PTMC-GA]-[PLLA-GA] block polyesters.
It is 2.1 × 10 through measuring its number-average molecular weight5, molecular weight distribution index is 1.7.T gFor 55.4 DEG C, crystallinity is 25.8%, stretching
Intensity is 36.7 ± 4.3MPa, and elongation at break is 154.4 ± 10.7%, and Young's modulus is 1167 ± 121MPa.
Embodiment 3
（1）22.45gTMC, 2.95gGA, 0.14g octanol and 0.09g stannous octoates are added in polymerization pipe；Building-up process is strictly according to the facts
Apply step in example 1（1）Described in step, macromole evocating agent PTMC-GA is prepared.
（2）Weigh step（1）PTMC-GA5g, L-LA28.14g, GA2.56g of middle preparation, stannous octoate 0.08g are added
In polymerization pipe, step in building-up process such as embodiment 1（2）It is described, prepare [PTMC-GA]-[PLLA-GA] block polyesters.
It is 1.9 × 10 through measuring its number-average molecular weight5, molecular weight distribution index is 1.5.T gFor 54.6 DEG C, crystallinity is 24.6%, stretching
Intensity is 32.4 ± 4.3MPa, and elongation at break is 189.7 ± 15.3%, and Young's modulus is 1073 ± 110MPa.
Embodiment 4
（1）16.42gTMC, 3.58gGA, 0.09g octanol and 0.04g stannous octoates are added in polymerization pipe；Building-up process is strictly according to the facts
Apply step in example 1（1）Described in step, macromole evocating agent PTMC-GA is prepared.
（2）Weigh step（1）PTMC-GA5g, L-LA23.12g, GA3.56g of middle preparation, stannous octoate 0.08g are added
In polymerization pipe, step in building-up process such as embodiment 1（2）It is described, prepare [PTMC-GA]-[PLLA-GA] block polyesters.
It is 1.7 × 10 through measuring its number-average molecular weight5, molecular weight distribution index is 1.8.T gFor 54.6 DEG C, crystallinity is 20.6%, stretching
Intensity is 30.2 ± 3.3MPa, and elongation at break is 215.7 ± 25.3%, and Young's modulus is 960 ± 58MPa.
Fig. 6 is weight-loss ratio change curve in the sample hydrolytic process of 1~embodiment of embodiment 4, and analysis contrast is found, by adjusting
GA molar content can effectively regulate and control the degradation time of sample in section polyester.GA molar content is 3% in embodiment 1, its
Reach that 50% degraded weight-loss ratio needs 54 weeks, and the polyester GA synthesized in embodiment 4 molar content is 12%, it reaches 50% drop
Solution weight-loss ratio is only needed to 8 weeks.When illustrating effectively control the degraded of material by the molar content for adjusting GA units in sample
Between.
From above-described embodiment as can be seen that using PTMC-GA macromole evocating agents technology prepare [PTMC-GA]-
[PLLA-GA] block polyester, possesses good toughness after flexible chain TMC units are introduced, while still maintaining higher
Tensile strength, this advantage can be clearly embodied from the stress-strain diagram of sample；The material structure is controllable simultaneously.
Can be by rate of charge come the degradation cycle of controlled material, from the hydrolysis weight-loss ratio change curve of sample it can be found that changing sample
The molar content of middle GA units can significantly alter the degradation cycle of material.Therefore, polyester produced by the present invention has excellent
Mechanical property, good biocompatibility and regulatable biodegradation period, can be widely applied to artificial in biomedicine
The biomedical materials fields such as diaphysis, tissue engineering bracket, interventional medical apparatus.
Claims (7)
1. [PTMC-GA]-[PLLA-GA] block polyesters of adjustable degradation rate, it is characterised in that be prepared into by following process
Arrive：First synthesize PTMC-glycolide（PTMC-GA）Prepolymer is as macromole evocating agent, then by necessarily matching somebody with somebody
Than carrying out ring-opening polymerization after PTMC-GA is mixed with levorotatory lactide LLA and GA；
Its molecular chain structure is as follows：
Wherein, p is the TMC and GA total chain number in macromole evocating agent PTMG-GA, and p scope is for 50~400, q
LLA and GA total chain number in PLLA-GA, q scope 250~1200.
[PTMC-GA] 2. of adjustable degradation rate according to claim 1-[PLLA-GA] block polyesters, its feature exists
In the molar content of TMC units is 80~98% in described macromole evocating agent PTMC-GA segments；The molar content of GA units
For 20~2%.
[PTMC-GA] 3. of adjustable degradation rate according to claim 1-[PLLA-GA] block polyesters, its feature exists
In the molar content of LLA units is that the molar content of 80~97%, GA units is 20% in described copolymer p LLA-GA segments
~3%.
[PTMC-GA] 4. of adjustable degradation rate according to claim 1-[PLLA-GA] block polyesters, its feature exists
In its number-average molecular weight is 5.0 × 104~4.5 × 105, molecular weight distribution index is 1.5~3.0.
The preparation side of [PTMC-GA] 5. of the adjustable degradation rate as described in claim 1-4-[PLLA-GA] block polyesters
Method, it is characterised in that concretely comprise the following steps：
（1）Initiator and catalyst and dried TMC, GA monomer of purifying are added in polymerization pipe by proportioning, initiator
Addition is the 2%~0.2% of TMC, GA monomer integral molar quantity, the addition of catalyst for monomer integral molar quantity 0.2%~
0.6%, melting is heated under nitrogen or argon inert gas atmosphere；It is cooled to after solid-state, persistently vacuumizes；
（2）After vacuum is not higher than 300Pa, polymerization pipe is fused, material is in vacuum state；
（3）By polymerization pipe as in isothermal reaction case, reaction temperature is 110 DEG C~180 DEG C, and the reaction time is 12~120h, instead
Polymerization pipe is taken out after the completion of answering；
（4）Obtained product solvent is dissolved, then separated out with precipitating reagent, dries, is fully dried in vacuum drying oven
Product PTMC-GA；
（5）By step（4）In obtained PTMC-GA polymerize with purifying dried LLA, GA monomer and catalyst by proportioning addition
Guan Zhong, macromole evocating agent PTMC-GA addition are the 1%~0.1% of LLA, GA monomer integral molar quantity；The addition of catalyst
For the 0.2%~0.6% of monomer integral molar quantity, the heating melting under nitrogen or argon inert gas atmosphere；It is cooled to after solid-state, holds
Continuous to vacuumize, after vacuum is not higher than 100Pa, fuse polymerization pipe, material is in vacuum state, polymerization pipe is placed in into constant temperature
In reaction chamber, reaction temperature is 120~180 DEG C, and 24~120h of reaction time takes out after the completion of reaction；
（6）Product in polymerization pipe is pressed into step（4）In process purifying drying, that is, prepare completely it is biodegradable
[PTMC-GA]-[PLLA-GA] block polyesters.
6. preparation method according to claim 5, it is characterised in that step（1）Described in initiator for ethanol, oneself
One or more in alcohol, octanol, dodecanol, 1, ammediol, 1,4- butanediols, glycerine；Described catalyst is pungent
One or more in sour stannous, stannous chloride, stannic chloride, zinc lactate, zinc chloride, zinc acetylacetonate.
7. preparation method according to claim 5, it is characterised in that step（4）Described in solvent be dichloromethane, three
One kind in chloromethanes, chloroethanes, 1,2- dichloroethanes, tetrahydrofuran, N, N- dimethylformamides and DMAC N,N' dimethyl acetamide
Or it is a variety of, described precipitating reagent is the one or more in methanol, ethanol, ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710161604.8A CN106957416A (en) | 2017-03-17 | 2017-03-17 | [PTMC GA] [PLLA GA] block polyester of adjustable degradation rate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710161604.8A CN106957416A (en) | 2017-03-17 | 2017-03-17 | [PTMC GA] [PLLA GA] block polyester of adjustable degradation rate and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200083108A (en) * | 2018-12-28 | 2020-07-08 | 성균관대학교산학협력단 | Polyglycolic acid based block copolymer with high stiffness and bioresorbability and method of producing thereof |
| CN112175191A (en) * | 2020-09-22 | 2021-01-05 | 中山大学 | Novel crosslinkable degradable multi-block copolymer and preparation method and application thereof |
| CN115232297A (en) * | 2022-06-30 | 2022-10-25 | 中国神华煤制油化工有限公司 | Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof |
| CN116196486A (en) * | 2021-11-30 | 2023-06-02 | 韩国凡特有限公司 | Biodegradable composite material composition for manufacturing stent and preparation method thereof |
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| WO2004012780A2 (en) * | 2002-07-29 | 2004-02-12 | Poly-Med, Inc. | Composite bone cement |
| CN103030795A (en) * | 2013-01-20 | 2013-04-10 | 复旦大学 | Fully biodegradable polyester copolymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004012780A2 (en) * | 2002-07-29 | 2004-02-12 | Poly-Med, Inc. | Composite bone cement |
| CN103030795A (en) * | 2013-01-20 | 2013-04-10 | 复旦大学 | Fully biodegradable polyester copolymer and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200083108A (en) * | 2018-12-28 | 2020-07-08 | 성균관대학교산학협력단 | Polyglycolic acid based block copolymer with high stiffness and bioresorbability and method of producing thereof |
| KR102249223B1 (en) | 2018-12-28 | 2021-05-07 | 성균관대학교산학협력단 | Polyglycolic acid based block copolymer with high stiffness and bioresorbability and method of producing thereof |
| CN112175191A (en) * | 2020-09-22 | 2021-01-05 | 中山大学 | Novel crosslinkable degradable multi-block copolymer and preparation method and application thereof |
| CN112175191B (en) * | 2020-09-22 | 2022-07-26 | 中山大学 | Crosslinkable degradable multi-block copolymer and preparation method and application thereof |
| CN116196486A (en) * | 2021-11-30 | 2023-06-02 | 韩国凡特有限公司 | Biodegradable composite material composition for manufacturing stent and preparation method thereof |
| CN115232297A (en) * | 2022-06-30 | 2022-10-25 | 中国神华煤制油化工有限公司 | Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof |
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