CN110028655A - Polyglycolide caprolactone copolymer ultrasonic synthetic method - Google Patents
Polyglycolide caprolactone copolymer ultrasonic synthetic method Download PDFInfo
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- CN110028655A CN110028655A CN201910319415.8A CN201910319415A CN110028655A CN 110028655 A CN110028655 A CN 110028655A CN 201910319415 A CN201910319415 A CN 201910319415A CN 110028655 A CN110028655 A CN 110028655A
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- reaction kettle
- ultrasonic
- caprolactone
- polyglycolide
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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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
- C08G63/78—Preparation processes
Abstract
The invention discloses a kind of polyglycolide caprolactone copolymer ultrasonic synthetic methods, are mixed in proportion using glycolide raw material and caprolactone raw material, using following synthesis step: 1) glycolide caprolactone being added in reaction kettle;2) inert gas is passed through into reaction kettle;3) melting of glycolide caprolactone is warming up in reaction kettle;4) 145 DEG C -155 DEG C are heated in reaction kettle;5) liquefactent in reaction kettle is transferred to ultrasonic reactor and carries out ultrasonic reaction;6) end-capping reagent is added into ultrasonic reactor and carries out end capping reaction, continue to be kept for temperature 1.0 hours;7) it is cooled to 170 DEG C -190 DEG C in ultrasonic reactor, while being vacuumized in ultrasonic reactor;8) it takes out ultrasonic reactor interpolymer and polyglycolide caprolactone polymerization composition granule is made.The present invention polymerize polyglycolide caprolactone copolymer obtained with ultrasonic method, and polymer purity is high;Product favorable reproducibility, operation is controllable, is conducive to product post-forming process, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to bio-medical material manufacturing technology fields, more particularly, to a kind of polyglycolide caprolactone copolymer
Ultrasonic synthetic method.
Background technique
Polyglycolide caprolactone copolymer (i.e. glycolide caprolactone copolymer, abbreviation PGCL) is that a kind of human body is absorbable
Aliphatic high polymer has been widely used in medical domain with the biocompatibility that its is excellent.PGCL can absorb operation stitching
Line has been widely used as second generation medical absorbable suture.Research is found by changing glycolide and caprolactone
Component ratio, can effectively adjust degradation rate, and ring-opening polymerisation is to obtain commonly using for high molecular weight glycolide caprolactone copolymer
Method.
In recent years, PGCL medical absorbable suture is widely used to medical market, compared with poly (glycolide-lactide) suture,
Polyglycolide caprolactone has better flexibility, thus more suitable for practical.Because PGCL ratio PGA provides lower solution temperature
With higher degradation temperature, so PGCL has a more good processing performance, and PGCL has a preferable drug permeability, thus
Drug controlled release field is applied, used also as bone graft substitute.
The PGCL polymer of domestic production at present still has as universality is not strong, severe reaction conditions, and product is not easy point
The defects of from purifying, being at high cost, the most key, polymerization product thermal stability is poor, is not amenable to secondary operation, such as injection molding,
The high temperature and pressure of the techniques such as melting spinning influences, the fast decoupled under high-temperature high-pressure state, is difficult to answer in actual process production
With this is also the basic reason that glycolide caprolactone copolymer cannot domesticize always.
Summary of the invention
The present invention, which is to provide for one kind, has the good security performance of bio-compatible high, can carry out post-forming process, meet
The polyglycolide caprolactone copolymer (PGCL) of medical absorbable suture items quality index, using ultrasonic method without the poly- of catalysis
Co-glycolide polymers ultrasonic synthetic method.
To achieve the goals above, the invention adopts the following technical scheme: polyglycolide caprolactone copolymer ultrasound synthesizes
Method is mixed in proportion using glycolide raw material and caprolactone raw material, and the polyglycolide caprolactone copolymer is closed using following
At step: 1) mixing glycolide raw material and caprolactone raw material and be added in reaction kettle;2) it is passed through inert gas into reaction kettle, sets
Swap out air in reaction kettle, and inert gas shielding environment is formed in reaction kettle;3) be warming up in reaction kettle glycolide raw material and
Caprolactone raw material melts;4) it is heated to 145 DEG C -155 DEG C in reaction kettle, and continues 3 hours;5) liquefactent in reaction kettle is transferred to
Ultrasonic reactor carries out ultrasonic reaction, while 200 DEG C -250 DEG C is heated in ultrasonic reactor, and continue 4-5 hours;6) Xiang Chao
End-capping reagent is added in sound reactor and carries out end capping reaction, continues to be kept for temperature 0.5 hour;7) 170 are cooled in ultrasonic reactor
DEG C -190 DEG C, while being vacuumized in ultrasonic reactor, it is kept for vacuum 1.0 hours;8) it after being cooled to room temperature in ultrasonic reactor, takes
Polyglycolide caprolactone copolymer particle is made in ultrasonic reactor interpolymer out.This programme is in glycolide, caprolactone polymerization
Polymerization is rapidly promoted using ultrasonic method, shortens polymerization time;After reaction, also with ultrasonic method unreacted small molecule
Glycolide, caprolactone, dimer and end-capping reagent remove under the conditions of sonic vacuum, avoid and various work are added in this reaction
Sprinkle metal and various initiator secondary pollution products;Using ultrasonic method, molecular weight ratio can be made with higher point of general catalysis method
Son amount, because of the reaction later period, with the increase of molecular weight, macromolecular movement is more difficult, to aggregate into bigger molecule and be bound to
Bigger energy is needed, and ultrasonic method just makes up the deficiency of catalyst method, because of the reaction later period, micro catalyst is poly-
Zoarium is fixed, does not have the effect for accelerating reaction;Increase a small amount of end-capping reagent in reaction process to block the end of polymer,
The terminal carboxyl group of polymer is replaced as hydroxyl, increases the thermal stability of polymer;After reaction, it is handed over by decompression vaporization second
Ester, caprolactone and oligomer, then vacuumize, these impurity can be reduced, achieve the effect that purified polymer.
Preferably, the caprolactone raw material is 6-caprolactone.
Preferably, the ratio that the glycolide raw material and caprolactone raw material mixes in proportion is 0.1:1-4:1.
Preferably, inert gas is argon gas or nitrogen in the step 2), it is passed through inert gas 5 into reaction kettle and divides
Clock is to displace air in reaction kettle.
Preferably, the end-capping reagent used in the step 6) for Isosorbide-5-Nitrae butanediol, ethylene glycol, pentanediol, lauryl alcohol,
At least one of hexadecanol, octadecyl alcolol.
Preferably, the relative degree of vacuum of the vacuum used in the step 7) is -100KPa.
Preferably, clear water is added into ultrasonic reactor, and open ultrasonic progress after heating up after the completion of the step 8)
Cleaning.After this programme has reacted discharging in ultrasonic reactor, proper amount of clear water is added in ultrasonic reactor, in ultrasound after heating
Middle Rapid Cleaning reactor, cleans up, because excess reactant should not stay in reactor, residue is stayed in reactor,
Lower batch materials are reacted to form cross reaction, reaction stability can be seriously affected.
The invention has the following beneficial effects: polymerize glycolide caprolactone copolymer obtained, molecule measurer with ultrasonic method
There are better controllability, narrow molecular weight distribution;Polymer is without the impurity such as catalyst, initiator, purity is high;Preparation is simple, has
Conducive to reaction kettle cleaning, product favorable reproducibility, operation is controllable, is particularly suitable for that quality is required to stablize very high biomedicine field,
Product thermal stability is good, is conducive to post-forming process, is suitable for large-scale industrial production.
Specific embodiment
Polyglycolide caprolactone copolymer ultrasonic synthetic method, is mixed in proportion using glycolide raw material and caprolactone raw material
It closes, polyglycolide caprolactone copolymer uses following synthesis step: 1) glycolide raw material and caprolactone raw material being mixed and are added instead
It answers in kettle;2) it is passed through inert gas into reaction kettle, displaces air in reaction kettle, forms inert gas shielding in reaction kettle
Environment;3) it is warming up to glycolide raw material in reaction kettle and caprolactone raw material melts;4) 145 DEG C -155 DEG C are heated in reaction kettle,
And continue 3 hours;5) liquefactent in reaction kettle is transferred to ultrasonic reactor and carries out ultrasonic reaction, while heating in ultrasonic reactor
To 200 DEG C -250 DEG C, and continue 4-5 hours;6) end-capping reagent is added into ultrasonic reactor and carries out end capping reaction, continue to keep temperature
Degree 0.5 hour;7) it is cooled to 170 DEG C -190 DEG C in ultrasonic reactor, while being vacuumized in ultrasonic reactor, keeps vacuum 1.0
Hour;8) it after being cooled to room temperature in ultrasonic reactor, takes out ultrasonic reactor interpolymer and the copolymerization of polyglycolide caprolactone is made
Object;
Caprolactone raw material is 6-caprolactone;
The ratio that glycolide raw material and caprolactone raw material mix in proportion is 0.1:1-4:1;
Inert gas is argon gas or nitrogen in step 2), inert gas is passed through into reaction kettle 5 minutes to displace reaction
Air in kettle;
The end-capping reagent used in step 6) is in Isosorbide-5-Nitrae butanediol, ethylene glycol, pentanediol, lauryl alcohol, hexadecanol, octadecyl alcolol
At least one;
The relative degree of vacuum of the vacuum used in step 7) is -100KPa;
After the completion of step 8), clear water is added into ultrasonic reactor, and open ultrasound after heating up and cleaned.
Specific implementation process is embodiment 1, weigh 1000g glycolide, 1000g caprolactone be added 3L reaction kettle in, in kettle
It is inside passed through high purity argon 5 minutes, displaces air in kettle, form inert gas shielding environment.Be rapidly heated to glycolide, oneself
Lactone melts, and after being heated to 150 DEG C of reactions 3 hours, is transferred to ultrasonic reactor, opens ultrasonic reaction, is continuously heating to 200 DEG C of reactions
After 5 hours, a small amount of 1,4-butanediol is added to be blocked, end capping reaction 0.5 hour.Reaction is finished, and reduces temperature to 180 DEG C, is taken out true
Empty (- 100KPa) 0.5 hour, it is cooling, polymer is taken out, particle is made.
Embodiment 2, weigh 1000g glycolide, 1000g caprolactone be added 3L reaction kettle in, high-purity argon is passed through in kettle
Gas 5 minutes, air in kettle is displaced, forms inert gas shielding environment.It is rapidly heated to glycolide, caprolactone melting, heating
After being reacted 3 hours to 150 DEG C, it is transferred to ultrasonic reactor, opens ultrasonic reaction, after being continuously heating to 220 DEG C of reactions 5 hours, added few
Amount 1,4-butanediol is blocked, and end capping reaction 0.5 hour.Reaction is finished, and is reduced temperature to 190 DEG C, is vacuumized (- 100KPa)
It is 1.0 hours, cooling, polymer is taken out, particle is made.
Embodiment 3, weigh 1000g glycolide, 1000g caprolactone be added 3L reaction kettle in, high-purity argon is passed through in kettle
Gas 5 minutes, air in kettle is displaced, forms inert gas shielding environment.It is rapidly heated to glycolide, caprolactone melting, heating
After being reacted 3 hours to 150 DEG C, it is transferred to ultrasonic reactor, opens ultrasonic reaction, after being continuously heating to 230 DEG C of reactions 4 hours, added few
Amount 1,4-butanediol is blocked, and end capping reaction 0.5 hour.Reaction is finished, and is reduced temperature to 190 DEG C, is vacuumized (- 100KPa)
It is 1.0 hours, cooling, polymer is taken out, particle is made.
Embodiment 4, weigh 1000g glycolide, 1000g caprolactone be added 3L reaction kettle in, high-purity argon is passed through in kettle
Gas 5 minutes, air in kettle is displaced, forms inert gas shielding environment.It is rapidly heated to glycolide, caprolactone melting, heating
After being reacted 3 hours to 150 DEG C, it is transferred to ultrasonic reactor, opens ultrasonic reaction, after being continuously heating to 240 DEG C of reactions 4 hours, added few
Amount 1,4-butanediol is blocked, and end capping reaction 0.5 hour.Reaction is finished, and is reduced temperature to 190 DEG C, is vacuumized (- 100KPa)
It is 1.0 hours, cooling, polymer is taken out, particle is made.
Embodiment 5, weigh 1000g glycolide, 1000g caprolactone be added 3L reaction kettle in, high-purity argon is passed through in kettle
Gas 5 minutes, air in kettle is displaced, forms inert gas shielding environment.It is rapidly heated to glycolide, caprolactone melting, heating
After being reacted 3 hours to 155 DEG C, it is transferred to ultrasonic reactor, opens ultrasonic reaction, after being continuously heating to 250 DEG C of reactions 4 hours, added few
Amount 1,4-butanediol is blocked, and end capping reaction 0.5 hour.Reaction is finished, and is reduced temperature to 190 DEG C, is vacuumized (- 100KPa)
It is 1.0 hours, cooling, polymer is taken out, particle is made.
Claims (7)
1. a kind of polyglycolide caprolactone copolymer ultrasonic synthetic method, which is characterized in that use glycolide raw material and caprolactone
Raw material mixes in proportion, and the polyglycolide caprolactone copolymer uses following synthesis step: 1) will be in glycolide raw material and oneself
The mixing of ester raw material is added in reaction kettle;2) it is passed through inert gas into reaction kettle, air in reaction kettle is displaced, in reaction kettle
Form inert gas shielding environment;3) it is warming up to glycolide raw material in reaction kettle and caprolactone raw material melts;4) add in reaction kettle
Heat continues 3 hours to 145 DEG C -150 DEG C;5) liquefactent in reaction kettle is transferred to ultrasonic reaction kettle and carries out ultrasonic reaction, simultaneously
It is heated to 200 DEG C -250 DEG C in ultrasonic reaction kettle, and continues 4-5 hours;6) end-capping reagent is added into ultrasonic reaction kettle to be sealed
End reaction continues to be kept for temperature 0.5 hour;7) it is cooled to 170 DEG C -190 DEG C in ultrasonic reaction kettle, while being taken out in ultrasonic reaction kettle
Vacuum is kept for vacuum 1.0 hours;8) after being cooled to room temperature in ultrasonic reaction kettle, taking-up ultrasonic reaction kettle interpolymer is made poly-
Glycolide caprolactone copolymer.
2. polyglycolide caprolactone copolymer ultrasonic synthetic method according to claim 1, characterized in that in described oneself
Ester raw material is 6-caprolactone.
3. polyglycolide caprolactone copolymer ultrasonic synthetic method according to claim 1, characterized in that the second is handed over
The ratio that ester raw material and caprolactone raw material mix in proportion is 0.1:1-4:1.
4. polyglycolide caprolactone copolymer ultrasonic synthetic method according to claim 1, characterized in that the step
2) inert gas is argon gas or nitrogen in, inert gas is passed through into reaction kettle 5 minutes to displace air in reaction kettle.
5. polyglycolide caprolactone copolymer ultrasonic synthetic method according to claim 1, characterized in that the step
6) end-capping reagent used in is at least one of 1,4- butanediol, ethylene glycol, pentanediol, lauryl alcohol, hexadecanol, octadecyl alcolol.
6. polyglycolide caprolactone copolymer ultrasonic synthetic method according to claim 1, characterized in that the step
7) relative degree of vacuum of the vacuum used in is -100KPa.
7. polyglycolide caprolactone copolymer ultrasonic synthetic method according to claim 1, characterized in that the step
8) after the completion of, clear water is added into ultrasonic reaction kettle, and open ultrasound after heating up and cleaned.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112851917A (en) * | 2021-01-28 | 2021-05-28 | 山东采采医疗科技有限公司 | Preparation method of polylactide caprolactone |
CN112920384A (en) * | 2021-01-28 | 2021-06-08 | 山东谷雨春生物科技有限公司 | Preparation method of polyglycolide caprolactone |
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CN106957412A (en) * | 2017-03-27 | 2017-07-18 | 苏州岸谷纳米技术有限公司 | It is a kind of biodegradable poly-(Glycolide ε caprolactones)The preparation method of random copolymer |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN106957412A (en) * | 2017-03-27 | 2017-07-18 | 苏州岸谷纳米技术有限公司 | It is a kind of biodegradable poly-(Glycolide ε caprolactones)The preparation method of random copolymer |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112851917A (en) * | 2021-01-28 | 2021-05-28 | 山东采采医疗科技有限公司 | Preparation method of polylactide caprolactone |
CN112920384A (en) * | 2021-01-28 | 2021-06-08 | 山东谷雨春生物科技有限公司 | Preparation method of polyglycolide caprolactone |
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