CN109988292A - A kind of preparation method of degradable aliphatic copolyesters - Google Patents
A kind of preparation method of degradable aliphatic copolyesters Download PDFInfo
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- CN109988292A CN109988292A CN201910245271.6A CN201910245271A CN109988292A CN 109988292 A CN109988292 A CN 109988292A CN 201910245271 A CN201910245271 A CN 201910245271A CN 109988292 A CN109988292 A CN 109988292A
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- copolyesters
- aliphatic
- degradable aliphatic
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
Abstract
The invention discloses a kind of preparation methods of degradable aliphatic copolyesters, and using aliphatic macrolide as monomer, glycol is as initiator, in the presence of a catalyst, degradable aliphatic copolyesters are prepared by open loop in situ-condensation cascade polymeric reaction；Glycol is small molecule glycol or macromolecular diol.Functional groups content with higher while copolyesters disclosed by the invention has higher molecular weight, functional groups in copolyesters mass content up to 75%；The copolyesters has degradability, and degradation speed is controlled by conditions such as temperature, enzymes.
Description
Technical field
The invention belongs to macromolecule material preparation areas, and what is involved is a kind of systems of degradable aliphatic copolyesters emphatically
It is standby.
Background technique
Currently, the polymer material based on alkene synthesis is stablized with property, it is difficult to the characteristics of degrading in nature, makes
At serious " white pollution " problem.As people are to environmental problem and to the pay attention to day by day of self health status, environment
Friendly material has obtained quick development in recent years.And in these materials, aliphatic polyester has many unique excellent
Point, such as can be prepared by reproducible biological radical derivative, it can be recycled and recycle, and there is biocompatibility, biology can drop
Solution property etc..In addition, there is the amphiphilic block copolymer based on aliphatic polyester can be self-assembly of micella in water, and can
The drug encapsulation of water will be insoluble in micella, and have the characteristics that good biocompatibility, biodegradable, therefore in medical load
The fields such as medicine and control release have broad application prospects.But the aliphatic polyester of existing synthesis there are polymer molecular weight compared with
It is low, it is more difficult to functionalization, the problems such as bioactivity is low.
Currently, aliphatic polyester mainly includes polylactic acid, polycaprolactone and aliphatic poly diacid diol ester are (as gathered
Ethylene glycol adipate) etc..Wherein, the above two are synthesized by ring-opening polymerization method, it can be difficult to preparation has higher molecular weight
And the copolyesters with higher functionality group content.In general, needing raising monomer opposite if wanting to obtain high molecular weight copolyester
Ratio of initiator, however initiator will lead to the reduction of functional groups content in copolyesters, at this with respect to the reduction of inventory
In, the demand of high molecular weight and the demand of high functionality group content are a pair of contradictory bodies.In addition, being obtained by ring-opening polymerization method
That arrive is usually two, triblock copolymer, it is difficult to form segmented copolymer；And aliphatic poly diacid diol ester is by aliphatic two
Acid and glycol carry out condensation polymerization synthesis, and side reaction is more in polymerization process, are difficult to obtain high molecular weight polyesters.
The effective ways that high level functional group is introduced in degradable copolyester are still lacked at present, and based on degradable
Aliphatic copolyester synthesis and aspect of performance research it is considerably less.In order to adapt to the development step of society, it is badly in need of exploitation one
The pervasive method of kind, functional groups are introduced in environmental-friendly degradable copolyester, can both prepare the fat of functionalization
Race's copolyesters, and aliphatic multi-block copolyesters can be prepared, and simple and easy, it is at low cost.
Summary of the invention
The present invention is intended to provide a kind of degradable aliphatic copolyesters and preparation method thereof.Use aliphatic macrolide
Astrotone (1,13- tridecandioic acid ethylene glycol lactone) passes through original position using glycol as initiator for monomer in the presence of a catalyst
Open loop-condensation cascade polymeric synthesis is copolymerized based on the degradable aliphatic of poly- (1,13- tridecandioic acid glycol ester) (PEB)
Ester.The present invention is using a kind of new polymerization, i.e., open loop-condensation cascade polymeric method in situ, by ring-opening polymerization and condensation
Polymerization reaction is carried out in the same system cascade, and synthctic fat race copolyesters, the present invention can be prepared with higher functionality base
Mass contg and with higher molecular weight aliphatic polyester, can also prepare with higher molecular weight containing the more of aliphatic polyester
Block copolymer.
To achieve the above object and effect, the invention is realized by the following technical scheme:
A kind of preparation method of degradable aliphatic copolyesters, includes the following steps, using aliphatic macrolide as monomer, two
Alcohol is as initiator, in the presence of a catalyst, degradable aliphatic is prepared by open loop in situ-condensation cascade polymeric reaction
Copolyesters.
In the present invention, aliphatic macrolide is astrotone；The present invention is for the first time using difference and prior art small molecule cyclic ester
Macrolide as monomer, degradable aliphatic copolyesters or degradable aliphatic polyester block are prepared by cascade polymeric
Copolymer makes substantive raising to molecular weight and functional groups content.
In the present invention, glycol be small molecule glycol or macromolecular diol, it is preferred that the molecular weight of small molecule glycol be 30 ~
400 grams every mole；The macromolecular diol contains polymer segment, and preferred polymer segment is polyester segment or polyether chain
Section.The chemical formula of glycol is HOROH, and when R is alkyl or fluorocarbon chain base, glycol is small molecular alcohol, preferably decanediol, 2,2,3,
3,4,4- hexafluoro -1,5- pentanediol etc.；When R is polymer segment, glycol is macromolecular alcohol, preferably polyester-diol or polyethers
Glycol.
In the present invention, the catalyst is titanate compound；Preferably tetrabutyl titanate；In mass ratio, monomer with draw
The ratio of hair agent feed ratio can be adjusted as needed, and generally in the range of 1 ~ 100, the amount of catalyst is monomer, draws
Send out the 0.03% ~ 2.00% of agent total amount of feeding.In the present invention, the temperature of open loop in situ-condensation cascade polymeric reaction is 180 ~
260 degrees Celsius；Polymerization reaction time is 10 ~ 240 minutes；Open loop in situ-condensation cascade polymeric reaction is in nitrogen atmosphere or very
It is carried out under empty condition；After reaction without purification, product degradable aliphatic copolyesters can be obtained.
The chemical structural formula of degradable aliphatic copolyesters disclosed by the invention is as follows:
Wherein, for R from initiator, x is that 10 ~ 250, y is 2 ~ 100.
Degradable aliphatic copolyesters of the invention is the degradable copolyester based on aliphatic polyester, and preparation method can
With specific as follows:
At room temperature, astrotone is added in reaction unit as monomer and glycol as initiator, leads to nitrogen, carries out mechanical stirring,
180 ~ 260 degrees Celsius are heated to, catalyst is added after mixing to reactant, continue logical nitrogen or is vacuumized, polyase 13 0
The degradable aliphatic copolyesters based on poly- (1,13- tridecandioic acid glycol ester) (PEB) can be obtained within ~ 240 minutes.Or
Person at room temperature, is added astrotone as monomer and glycol as initiator in reaction unit, catalyst is then added, is heated to
180 ~ 260 degrees Celsius, carry out mechanical stirring, logical nitrogen or vacuumize, polymerization can be obtained within 10 ~ 180 minutes based on it is poly- (1,
13- tridecandioic acid glycol ester) (PEB) degradable aliphatic copolyesters.
The aliphatic macrolide monomer used in the present invention is astrotone, i.e. 1,13- tridecandioic acid ethylene glycol lactone,
It can conveniently buy, and cheap, obtain after polymerization based on poly- (1,13- tridecandioic acid glycol ester) on the market
(PEB) copolyesters；The glycol initiator is small molecule glycol or macromolecular diol initiator, wherein small molecule glycol is excellent
Select the glycol initiator containing functional groups, such as containing the decanediol of alkyl chain, 2,2,3,3,4, the 4- hexafluoros-containing fluorocarbon chain
1,5-PD etc., and the preferred end group of macromolecular diol initiator is the polyetherdiol or polyester-diol of hydroxyl, such as polyadipate
Glycol ester glycol (PEA), polyethylene glycol (PEO), polytetrahydrofuran diol (PTMO) or polyethylene glycol-block-poly- the third two
Alcohol-block-polyethylene glycol triblock copolymer glycol (PEO-b-PPO-b- PEO) etc..It polymerize obtained copolyesters with as follows
Structure:
In the present invention, mechanism of polymerization is open loop-condensation cascade polymeric process in situ, i.e. glycol initiator first opens astrotone
Cyclopolymerization obtains the copolyesters that end group is hydroxyl, and copolyesters can continue to cause the ring-opening polymerisation of astrotone, can also carry out between each other
Condensation polymerization generates the copolyesters of higher molecular weight；Reaction product is degradable aliphatic copolyesters, is not necessarily to purification & isolation.
The molecular weight of degradable aliphatic copolyesters of the present invention can be controlled by polymerization time, polymerization temperature, and molecular weight can
Up to 70.0 kilograms every mole, functional groups mass content in copolyesters efficiently solves prior art polyester work up to 75%
It is relatively low and be difficult to the problem of introducing functional groups for biological material molecule amount.
Copolyesters of the invention has degradability, and degradation speed is controlled by conditions such as temperature, enzymes.In room temperature or 37
(pH 7.2 ~ 7.4) quality, molecular weight slowly reduce at any time in phosphate buffered saline solution under degree Celsius, in room temperature or 37
(pH 7.2 ~ 7.4) quality, molecular weight quickly reduce in the phosphate buffered saline solution of fatty enzyme under degree Celsius, Celsius 4
Quality, molecular weight are basically unchanged under degree refrigerated condition.
Original position open loop-condensation cascade polymeric method provided by the invention is intended to exist ring-opening polymerization and condensation polymerization reaction
The same system cascade carries out, and is prepared with higher functionality group content and with the aliphatic poly of higher molecular weight
Ester can also prepare the segmented copolymer containing aliphatic polyester with higher molecular weight.The prior art passes through cyclic ester open loop
Aliphatic polyester/copolyesters of polymerization preparation can not have high functionality group content while realizing high molecular weight.And
This method has reaction step simple, and molecular weight is high and controllable, without post-processing, the advantages that can largely synthesizing.System of the present invention
Standby aliphatic polyester/copolyesters has degradability, and degrades and can be adjusted by temperature, enzyme content etc., these technologies effect
Fruit is referring specifically to embodiment.To which the invention discloses the preparation methods of above-mentioned degradable aliphatic copolyesters.
The present invention has been synthesized by open loop-condensation cascade polymeric method in situ based on poly- (1,13- tridecandioic acid ethylene glycol
Ester) copolyesters, solve traditional polymerization and be difficult to synthesize the high molecular weight polyesters of high functionality group content, and be difficult to
The problem of synthesizing more blocked aliphatic copolyesters, and this method has reaction step simple, and molecular weight is high and controllable, after being not necessarily to
Processing, the advantages that can largely synthesizing；The monomer astrotone of use can largely be bought, extremely cheap, thus what is synthesized is total to
Polyester cost is very low；And by introducing functional groups in glycol, prepare feed fat powder race copolyesters with can be convenient；
When using polyetherdiol or polyester-diol as macromole evocating agent, multi-block copolyesters are synthesized with can be convenient；Synthesis
Copolyesters is a kind of biological poly ester material, has degradability, is a kind of green environment friendly materials, has biggish answer
With value.
The above description is only an overview of the technical scheme of the present invention.In order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following are specific embodiments of the present invention and attached drawing is cooperated to be described in detail.
Detailed description of the invention
Fig. 1 is the synthetic route chart of degradable aliphatic copolyesters of the present invention；
Fig. 2 is to carry out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing, is reacted not under nitrogen at 200 degrees Celsius
The volume removing chromatogram figure of the copolyesters (PEBDB) obtained with the time；
Fig. 3 is to carry out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing, is reacted not under nitrogen at 200 degrees Celsius
Copolyesters (PEBDB) molecular weight obtained with the time changes over time figure；
Fig. 4 is to carry out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing, is reacted not under nitrogen at 240 degrees Celsius
Copolyesters (PEBDB) molecular weight obtained with the time changes over time figure；
Fig. 5 is to carry out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing, vacuumizes down and reacts at 200 degrees Celsius
The volume removing chromatogram figure of the copolyesters (PEBDB) obtained for 30 minutes；
Fig. 6 is by 2, and 2,3,3,4,4- hexafluoros -1,5-PD and astrotone mixing carry out open loop-condensation cascade polymeric in situ, nitrogen
The molecular weight for reacting the copolyesters (PEBFB) that different time obtains at 220 degrees Celsius under gas changes over time figure；
Fig. 7 is to carry out open loop-condensation cascade polymeric in situ, nitrogen by polyethylene glycol adipate glycol (PEA) and astrotone mixing
Under at 220 degrees Celsius react the obtained multi-block copolyesters (PEB- of different timesb-PEA-b-PEB)nMolecular weight become at any time
Change figure；
Fig. 8 is to carry out open loop-condensation cascade polymeric in situ by polyethylene glycol (PEO) and astrotone mixing, vacuumizes down and takes the photograph 220
Multi-block copolyesters (the PEB- that family name's degree reaction different time obtainsb-PEO-b-PEB)nVolume removing chromatogram figure；
Fig. 9 is to carry out open loop-condensation cascade polymeric in situ by polytetrahydrofuran diol (PTMO) and astrotone mixing, is vacuumized down
In 220 degrees Celsius of reactions, 30 minutes obtained multi-block copolyesters (PEB-b-PTMO-b-PEB)nVolume removing chromatogram figure；
Figure 10 is by polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer glycol (PEO-b-PPO-b-
PEO) and astrotone mixing carries out open loop-condensation cascade polymeric in situ, reacts what different time obtained at 220 degrees Celsius under nitrogen
Multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nMolecular weight change over time figure；
Figure 11 is by polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer glycol (PEO-b-PPO-b-
PEO it) is mixed with astrotone and carries out open loop-condensation cascade polymeric in situ, vacuumized down to react at 220 degrees Celsius and obtain for 45 minutes
Multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nVolume removing chromatogram figure；
Figure 12 is aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nQuality at 37 degrees Celsius not
The degradation curve figure changed over time in phosphate buffered saline solution under the conditions of fatty enzyme and fatty enzyme；
Figure 13 is aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nIt is not fatty at 20 degrees Celsius
The degradation curve figure that the molecular weight in phosphate buffered saline solution under the conditions of enzyme and fatty enzyme changes over time；
Figure 14 is aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nIt is not fatty at 37 degrees Celsius
The degradation curve figure that the molecular weight in phosphate buffered saline solution under the conditions of enzyme and fatty enzyme changes over time.
Specific embodiment
The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with example.
It is shown in Figure 1, it is the preparation method of degradable aliphatic copolyesters of the present invention, that is, passes through open loop-condensation in situ
Cascade polymeric method prepares copolyesters, including two processes, 1) it is anti-to carry out ring-opening polymerisation to macrolide monomer astrotone for glycol
Answer, generate copolymerization esterdiol, 2) copolymerization esterdiol can continue to astrotone carry out ring-opening polymerization, can also be mutual
Condensation polymerization is carried out, a series of aliphatic copolyesters based on poly- (1,13- tridecandioic acid glycol ester) are obtained.
Embodiment 1 carries out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing and generates degradable aliphatic
Copolyesters (PEBDB)
Decanediol (0.05 gram) and astrotone (5.00 grams) are added in 100 milliliters of three-necked flask, leads to nitrogen and removes oxygen, it will
Three-necked flask, which is placed in salt bath, is heated to 200 degrees Celsius, and mechanical stirring, is then slowly added by microsyringe
10.1 microlitres of tetrabutyl titanate carries out open loop in situ-condensation cascade polymeric reaction under nitrogen atmosphere, generates corresponding polymerization
Object.It was sampled in reaction process every 30 minutes, stops reaction after 120 minutes.
Volume removing chromatogram figure and copolyesters molecular weight change over time figure and see Fig. 2, Fig. 3, it was demonstrated that target product at
Function synthesis, molecular weight can be controlled by controlling polymerization time.By can be calculated, functional groups quality in copolyesters contains
Amount about 1%.
Embodiment 2 carries out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing and generates degradable aliphatic
Copolyesters (PEBDB)
Decanediol (0.50 gram) and astrotone (5.00 grams) are added in 100 milliliters of three-necked flask, leads to nitrogen and removes oxygen, it will
Three-necked flask, which is placed in salt bath, is heated to 240 degrees Celsius, and mechanical stirring, is then slowly added by microsyringe
11.0 microlitres of tetrabutyl titanate carries out open loop in situ-condensation cascade polymeric reaction under nitrogen atmosphere, generates corresponding polymerization
Object.It was sampled in reaction process every 30 minutes, stops reaction after 120 minutes.
Copolyesters molecular weight changes over time figure and sees Fig. 4, it was demonstrated that the successful synthesis of target product, molecular weight can pass through
It controls polymerization time and controls.By can be calculated, functional groups mass content in copolyesters is about 9%.
Embodiment 3 carries out open loop-condensation cascade polymeric in situ by decanediol and astrotone mixing and generates degradable aliphatic
Copolyesters (PEBDB)
Decanediol (3.00 grams) and astrotone (10.0 grams) are added in 100 milliliters of single-necked flask, it is slow by microsyringe
26.0 microlitres of tetrabutyl titanate is added in ground.Single-necked flask is placed in salt bath and is heated to 200 degrees Celsius, and mechanical stirring,
It reacts 10 minutes under nitrogen atmosphere, then vacuumizes polyase 13 0 minute, ultimately generate corresponding polymer.
Volume removing chromatogram figure is shown in Fig. 5, and measuring molecular weight is 20.3 kilograms every mole, it was demonstrated that the successful conjunction of target product
At.By can be calculated, functional groups mass content in copolyesters is about 23%.
Embodiment 4 carries out open loop-condensation in situ by 2,2,3,3,4,4- hexafluoro -1,5- pentanediol and astrotone mixing and cascades
Polymerization generates degradable aliphatic copolyesters (PEBFB)
2,2,3,3,4,4- hexafluoro -1,5- pentanediol (0.25 gram) and astrotone (5.00 are added in 100 milliliters of three-necked flask
Gram), lead to nitrogen and remove oxygen, three-necked flask is placed in salt bath and is heated to 220 degrees Celsius, and mechanical stirring, is then passed through
Microsyringe is slowly added into 10.5 microlitres of tetrabutyl titanate, and it is poly- to carry out open loop in situ-condensation cascade under nitrogen atmosphere
Reaction is closed, corresponding polymer is generated.It was sampled in reaction process every 30 minutes, stops reaction after 180 minutes.
Copolyesters molecular weight changes over time figure and sees Fig. 6, it was demonstrated that the successful synthesis of target product.By can be calculated, function
Energy property group mass content in copolyesters is about 5%.
Embodiment 5 carries out open loop in situ-condensation cascade by polyethylene glycol adipate glycol (PEA) and astrotone mixing and gathers
Symphysis is at degradable aliphatic multi-block copolyesters (PEB-b-PEA-b-PEB)n
In 100 milliliters of three-necked flask be added polyethylene glycol adipate glycol (molecular weight be 3.81 kilograms every mole, 1.00
Gram) and astrotone (1.00 grams), lead to nitrogen and removes oxygen.Three-necked flask is placed in salt bath and is heated to 220 degrees Celsius, and machine
Tool stirring, is then slowly added into 4.00 microlitres of tetrabutyl titanate by microsyringe, carries out under nitrogen atmosphere in situ
Open loop-condensation cascade polymeric reaction, generates corresponding polymer.It sampled in reaction process every 30 minutes, stops after 120 minutes
Reaction.
Copolyesters molecular weight changes over time figure and sees 7, it was demonstrated that the successful synthesis of target product.By can be calculated, function
Property group mass content in copolyesters is about 50%.
Embodiment 6 is generated degradable by polyethylene glycol (PEO) and astrotone mixing progress open loop-condensation cascade polymeric in situ
Aliphatic multi-block copolyesters (PEB-b-PEO-b-PEB)n
Polyethylene glycol (molecular weight is 2.00 kilograms every mole, 1.00 grams) and astrotone are added in 100 milliliters of single-necked flask
(1.00 grams), 4.00 microlitres of tetrabutyl titanate is slowly added by microsyringe.Single-necked flask is placed in salt bath
Be heated to 220 degrees Celsius, and mechanical stirring, under nitrogen atmosphere react 5 minutes, then vacuumize polymerization 20 minutes, 30 minutes,
90 minutes, ultimately generate corresponding polymer.
Volume removing chromatogram figure is shown in Fig. 8, and polymerizeing 20 minutes molecular weight measured is 18.4 kilograms every mole, measures within 30 minutes
Molecular weight be 25.7 kilograms every mole, 90 minutes molecular weight measured are 50.3 kilograms every mole, it was demonstrated that target product
Success synthesizes.By can be calculated, functional groups mass content in copolyesters is about 50%.
Embodiment 7 carries out open loop-condensation cascade polymeric in situ by polytetrahydrofuran diol (PTMO) and astrotone mixing and generates
Degradable aliphatic multi-block copolyesters (PEB-b-PTMO-b-PEB)n
Be added in 100 milliliters of single-necked flask polytetrahydrofuran diol (molecular weight be 2.90 kilograms every mole, 7.50 grams) and
Astrotone (2.50 grams), 20.0 microlitres of tetrabutyl titanate is slowly added by microsyringe.Single-necked flask is placed in salt bath
It is heated to 220 degrees Celsius, and mechanical stirring in pot, reacts 15 minutes under nitrogen atmosphere, then vacuumizes polyase 13 0 minute, most
Throughout one's life at corresponding polymer.
Volume removing chromatogram figure is shown in Fig. 9, and the molecular weight measured is 68.7 kilograms every mole, it was demonstrated that the success of target product
Synthesis.By can be calculated, functional groups mass content in copolyesters is about 75%.
Embodiment 8 is by polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer glycol (PEO-b-
PPO-b- PEO) and astrotone mixing progress open loop in situ-condensation cascade polymeric generation degradable aliphatic multi-block copolyesters
(PEB-b-PEO-b-PPO-b-PEO-b-PEB)n
Polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer is added in 100 milliliters of three-necked flask
Glycol (molecular weight is 2.00 kilograms every mole, and PEO content is 10%, 5.00 grams) and astrotone (5.00 grams) leads to nitrogen except deoxygenating
Gas.Three-necked flask is placed in salt bath and is heated to 220 degrees Celsius, and mechanical stirring, then slowly by microsyringe
20.0 microlitres of tetrabutyl titanate is added, carries out open loop in situ-condensation cascade polymeric reaction under nitrogen atmosphere, generates corresponding
Polymer.It was sampled in reaction process every 30 minutes, stops reaction after 150 minutes.
Copolyesters molecular weight changes over time figure and sees Figure 10, it was demonstrated that the successful synthesis of target product.By can be calculated, function
Energy property group mass content in copolyesters is about 50%.
Embodiment 9 is by polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer glycol (PEO-b-
PPO-b- PEO) and astrotone mixing progress open loop in situ-condensation cascade polymeric generation degradable aliphatic multi-block copolyesters
(PEB-b-PEO-b-PPO-b-PEO-b-PEB)n
Polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer is added in 100 milliliters of single-necked flask
Glycol (molecular weight is 2.90 kilograms every mole, and PEO content is 30%, 15.0 grams) and astrotone (15.0 grams), passes through micro-sampling
Device is slowly added into 60.0 microlitres of tetrabutyl titanate.Single-necked flask is placed in salt bath and is heated to 220 degrees Celsius, and is mechanical
Stirring is reacted 15 minutes under nitrogen atmosphere, is then vacuumized polymerization 45 minutes, is ultimately generated corresponding polymer.
Volume removing chromatogram figure is shown in Figure 11, and the molecular weight measured is 40.6 kilograms every mole, it was demonstrated that target product at
Function synthesis.By can be calculated, functional groups mass content in copolyesters is about 50%.
10 aliphatic multi-block copolyesters (PEB- of embodimentb-PEO-b-PPO-b-PEO-b-PEB)nUnder 37 degrees Celsius
Degradation test in phosphate buffered saline solution
Phosphate buffered saline solution pH 7.2 ~ 7.4, wherein ingredient includes that sodium chloride, 2.00 grams that concentration is 80.0 gram per liters are every
Potassium chloride, 36.3 gram per liters of the disodium hydrogen phosphate dodecahydrate, 2.40 gram per liters of potassium dihydrogen phosphate risen；Phosphate-buffered salt is molten
Liquid is divided into without lipase group and fatty enzyme (lipase title: Pseudomonas cepacia lipase, enzyme activity: 30.0 × 103Unit
Every gram, optimal pH: 7.0) group.
It is the aliphatic multi-block copolyesters (PEB- of 10.0 milligrams or so disc-shapeds (about 5.00 millimeters of diameter) by qualityb-
PEO-b-PPO-b-PEO-b-PEB)nSample (prepared by embodiment 9, sample starting molecule amount is 40.6 kilograms every mole) is submerged to
In the phosphate buffered saline solution of 1.00 milliliters or so fatty enzymes (concentration: 1.00 milligrams every milliliter), sample is placed on 37 and is taken the photograph
Degradation experiment is carried out in the environment of family name's degree.Separately setting one group of control experiment, without lipase phosphate buffered saline solution in into
Row, other conditions are constant.When it reaches predetermined number of days, sample is taken out, is eluted, filtered, dried with distilled water, utilize electronics day
It is flat to weigh its mass change.
Aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nThe quality of degradation changes over time
Degradation curve figure see Figure 12.As seen from the figure, aliphatic copolyester (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nIt is taken the photograph 37
In family name's degree phosphate buffered saline solution, do not reduced without quality under conditions of lipase；And its quality under the action of lipase
It is smaller and smaller, quality/initial mass × 100% after residual mass about 43%(degradation when degrading 8 days).And polylactic acid is in the same terms
Residual mass about 75% at lower degradation 8 days.Illustrate aliphatic copolyester (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nWith good
Good degradability.
11 aliphatic multi-block copolyesters (PEB- of embodimentb-PEO-b-PPO-b-PEO-b-PEB)nAt 20 degrees celsius
In phosphate buffered saline solution, without the degradation test under the conditions of lipase and fatty enzyme
Weigh 10.0 milligrams or so of aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nSample is (real
The preparation of example 8 is applied, sample starting molecule amount is 21.3 kilograms every mole) it is submerged to 1.00 milliliters or so fatty enzyme (concentration: 1.00
Milligram every milliliter) phosphate buffered saline solution in, carry out degradation experiment in the environment of sample is placed on 20 degrees Celsius.Another setting
One group of control experiment carries out in the phosphate buffered saline solution without lipase, and other conditions are constant.Reach predetermined number of days to it
When, sample is taken out, is eluted, filtered, dried with distilled water, test its molecular weight using gel permeation chromatograph.
Aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nResidue not soluble in water after degradation
The degradation curve figure that the molecular weight of sample segment changes over time is shown in Figure 13.As seen from the figure, aliphatic copolyester (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nIt is very slow without degradation speed under conditions of lipase in 20 degrees Celsius of phosphate buffered saline solutions,
Molecular weight is declined slightly, and its degradation speed is accelerated under the action of lipase, and molecular weight is often rubbed by 21.3 kilograms in 8 day time
You are reduced to 15.1 kilograms every mole.Under same experimental conditions, sample is placed 30 days under 4 degrees Celsius of refrigerated conditions, molecule
Amount remains unchanged in apparatus measures error range, illustrates that the aliphatic copolyester has good stability at this temperature.
12 aliphatic multi-block copolyesters (PEB- of embodimentb-PEO-b-PPO-b-PEO-b-PEB)nIn 37 degrees Celsius of phosphorus
In acid buffering salting liquid, without the degradation test under the conditions of lipase and fatty enzyme
Weigh 10.0 milligrams or so of aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nSample is (real
The preparation of example 8 is applied, sample starting molecule amount is 21.3 kilograms every mole) it is submerged to 1.00 milliliters or so fatty enzyme (concentration: 1.00
Milligram every milliliter) phosphate buffered saline solution in, carry out degradation experiment in the environment of sample is placed on 37 degrees Celsius.Another setting
One group of control experiment carries out in the phosphate buffered saline solution without lipase, and other conditions are constant.Reach predetermined number of days to it
When, sample is taken out, is eluted, filtered, dried with distilled water, test its molecular weight using gel permeation chromatograph.
Aliphatic multi-block copolyesters (PEB-b-PEO-b-PPO-b-PEO-b-PEB)nThe molecular weight of degradation becomes at any time
The degradation curve figure of change is shown in Figure 14.As seen from the figure, aliphatic copolyester (PEB-b-PEO-b-PPO-b-PEO-b-PEB)n37
In degree Celsius phosphate buffered saline solution, slightly reduced without molecular weight under conditions of lipase, and energy under the action of lipase
Enough fast degradations.Comparison diagram 13, illustrates the degradation speed for changing the adjustable aliphatic multi-block copolyesters of temperature, and temperature increases
To after 37 degrees Celsius, degradation is faster.
The foregoing is merely the preferred embodiments of invention, are not intended to restrict the invention, for the technology of this field
For personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Decorations, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of degradable aliphatic copolyesters, which is characterized in that using aliphatic macrolide as monomer, two
Alcohol is as initiator, in the presence of a catalyst, degradable aliphatic is prepared by open loop in situ-condensation cascade polymeric reaction
Copolyesters；Glycol is small molecule glycol or macromolecular diol.
2. the preparation method of degradable aliphatic copolyesters according to claim 1, which is characterized in that aliphatic macrolide
For astrotone；The molecular weight of small molecule glycol is 30~400 grams every mole；The macromolecular diol contains polymer segment；It is described
Catalyst is titanate compound.
3. the preparation method of degradable aliphatic copolyesters according to claim 2, which is characterized in that the macromolecular diol
The polymer segment contained is polyester segment or polyether segment；The titanate compound is tetrabutyl titanate or metatitanic acid isobutyl
Ester.
4. the preparation method of degradable aliphatic copolyesters according to claim 1, which is characterized in that the degradable aliphatic
The chemical structural formula of race's copolyesters is as follows:
Wherein, for R from initiator, x is that 10~250, y is 2~100.
5. the preparation method of degradable aliphatic copolyesters according to claim 1, which is characterized in that open loop-condensation in situ
Cascade polymeric reaction carries out under nitrogen atmosphere or vacuumized conditions；After reaction without purification.
6. the preparation method of degradable aliphatic copolyesters according to claim 1, which is characterized in that open loop-condensation in situ
The temperature of cascade polymeric reaction is 180~260 degrees Celsius, and polymerization reaction time is 10~240 minutes.
7. the preparation method of degradable aliphatic copolyesters according to claim 1, which is characterized in that monomer and initiator are thrown
Material than being 1~100, the amount of catalyst be monomer, initiator total amount of feeding 0.03%~2%.
8. the preparation method of degradable aliphatic copolyesters according to claim 1, which is characterized in that the copolyesters has
Functional groups content with higher while higher molecular weight, functional groups in copolyesters mass content up to 75%；
The copolyesters has degradability, and degradation speed is controlled by conditions such as temperature, enzymes.
9. degradable aliphatic copolyesters, chemical structural formula are as follows:
Wherein, for R from initiator, x is that 10~250, y is 2~100.
10. degradable aliphatic copolyesters according to claim 9, which is characterized in that the copolyesters has higher molecular
Functional groups content with higher while amount, functional groups in copolyesters mass content up to 75%；The copolymerization
Ester has degradability, and degradation speed is controlled by conditions such as temperature, enzymes.
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| CN111019126A (en) * | 2019-12-06 | 2020-04-17 | 苏州大学 | Polyester amide and preparation method thereof |
| CN115260460A (en) * | 2022-09-26 | 2022-11-01 | 苏州大学 | Copolyester and preparation method thereof |
| CN116425983A (en) * | 2023-06-14 | 2023-07-14 | 苏州大学 | High-impact polyether ester amide thermoplastic elastomer and preparation method thereof |
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| CN107567471A (en) * | 2014-12-17 | 2018-01-09 | Sabic环球技术有限责任公司 | For the product for preparing the method comprising the first polyolefin block and second polymer block and being obtained from methods described |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019126A (en) * | 2019-12-06 | 2020-04-17 | 苏州大学 | Polyester amide and preparation method thereof |
| WO2021110182A3 (en) * | 2019-12-06 | 2021-07-29 | 苏州大学 | Polyesteramide and preparation method therefor |
| CN115260460A (en) * | 2022-09-26 | 2022-11-01 | 苏州大学 | Copolyester and preparation method thereof |
| WO2024066194A1 (en) * | 2022-09-26 | 2024-04-04 | 苏州大学 | Copolyester and preparation method therefor |
| CN116425983A (en) * | 2023-06-14 | 2023-07-14 | 苏州大学 | High-impact polyether ester amide thermoplastic elastomer and preparation method thereof |
| CN116425983B (en) * | 2023-06-14 | 2023-09-29 | 苏州大学 | High-impact polyether ester amide thermoplastic elastomer and preparation method thereof |
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