CN108192033A - A kind of maleic anhydride is directly grafted the preparation method of L- lactide/glycolides/6-caprolactone terpolymer - Google Patents
A kind of maleic anhydride is directly grafted the preparation method of L- lactide/glycolides/6-caprolactone terpolymer Download PDFInfo
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- CN108192033A CN108192033A CN201810155911.XA CN201810155911A CN108192033A CN 108192033 A CN108192033 A CN 108192033A CN 201810155911 A CN201810155911 A CN 201810155911A CN 108192033 A CN108192033 A CN 108192033A
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- maleic anhydride
- caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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Abstract
A kind of maleic anhydride is directly grafted the preparation method of L lactide/glycolides/ε caprolactone terpolymers：70 ~ 80 parts of L lactides, 15 ~ 20 parts of glycolides and 5 10 parts of ε caprolactones are mixed, add in a certain amount of stannous octoate；（2）12 ~ 60h of polymerisation at 120 ~ 160 DEG C, obtains crude product PLLGC；（3）Thick polymers is dissolved in chloroform, precipitating purification, dry PLLGC；（4）PLLGC is mixed with maleic anhydride, dibenzoyl peroxide, vacuumizing makes pressure less than 10.0Pa, sealing.160 DEG C shake up, and 120 DEG C are reacted to obtain thick MPLLGC；（5）It is extracted with chloroform and removes homopolymer, be dissolved in chloroform after dry, purified with ethyl alcohol precipitating, dry pure MPLLGC.Advantage：(1) mechanical property and the controllable range bigger of degradation property after being molded.（2）Hydrophilicity and biocompatibility are more preferable.（3）The introducing of anhydride bond can provide good basis for its follow-up improvement.
Description
Technical field
The present invention relates to the technologies of preparing with Biodegradable polymer material, and in particular to one kind has degradable
The direct grafting of L- lactide/glycolides/6-caprolactone terpolymer of property, excellent mechanical performances and superior bio compatibility
Technology.
Background technology
Bone tissue defect is one of clinical problem faced, although bone tissue has stronger power of regeneration in itself,
Self-regeneration can only occur under the smaller situation of defect, and bone collection is the main means for curing large volume bone defect.It is clinical
Upper bone collection mainly includes the bone grafting operations such as autologous bone, homogeneous allogenic bone and bone- xenograft, but damages or move there are supply source deficiency, for area
The deficiencies of planting rejection.Organizational engineering technology provides new method for bone defect healing, has broad application prospects.
Degradable macromolecule timbering material applied to bone tissue reparation mainly includes synthesized degradable macromolecule and natural
Degradable macromolecule.Synthesized degradable macromolecule mainly includes polylactic acid（PLA）, poly- third glycolide（PLGA）With poly- ε-oneself in
Ester（ε-PCL）Wait aliphatic polyesters.Such degradable macromolecule is because with certain mechanical strength, biological degradability and excellent
The advantages that biocompatibility, is paid more and more attention in field of tissue engineering technology, but in body degradation process middle acid substance accumulation
Implant site is led to problems such as to generate non-bacterial chronic inflammation.
Non-bacteria inflammation caused by accumulation effectively to solve the problems, such as acidic materials, it is polymer-based to PLA kind polyesters etc.
Body carries out graft modification, and it is one of effective ways to assign its basic functional group.Maleic anhydride（MAH）It is that one kind can be in organism
The polyfunctional group substance of interior eubolism has good biocompatibility.Free radical using the carbon-to-carbon double bond in MAH is anti-
It should can be grafted in polyester backbone, anhydride bond can be further introduced into functional group（Such as hydroxyl, amido）.The alkali such as amido
Property group introducing be expected effectively to neutralize the acidic materials that its internal degradation process generates, acidic materials is avoided to accumulate and lead to office
Portion's tissue generates chronic non-bacterial inflammation.
PLA after maleic anhydride is mainly grafted by domestic and foreign scholars at present improves PLA and compound resin as bulking agent（Such as
PLA/ starch, PLA/ ramies etc.）Performance, and with its graft modification for bio-medical field research it is relatively fewer.Such as
Maleic anhydride is grafted on PLLA chains by Hwang etc., can significantly reduce its glass transition temperature and crystallinity.Professor's Luo Yanfeng class
Topic group is directly grafted PLA using maleic anhydride, is further introduced into ethylenediamine, effectively improves its hydrophilicity.Maleic anhydride connects
Though can be further introduced into basic group after branch PLA, PLA compositions are single, are unfavorable for the Effective Regulation of degradation rate.
It is rarely reported in document about MAH graft copolymers PLGA.Ma etc. is grafted using radical reaction in PLGA main chains
Maleic anhydride, surface can effectively fix cationic polyethylene imines/DNA nano particles, it is expected to for gene control delivery.
This seminar uses D, and L- lactides, glycolide and maleic anhydride obtain MAH by melt polymerization and be modified poly- third glycolide
（MPLGA）（ZL2013.10564511.1）, this method is easy to operate, and acid anhydrides grafting rate may be up in the copolymer of acquisition
10.0%.Simultaneously using D, on the basis of L- lactides, glycolide prepare high molecular weight PLGA by melt polymerization, further with
MAH is directly grafted the MPLGA that high molecular weight is prepared in PLGA（ZL201510812709.6）, but its acid anhydrides grafting rate is 1.0%
Left and right.
MAH is grafted PLA or PLGA, introduces acid anhydrides isoreactivity group, and can be further introduced into basic functional group, but connect
Macromolecule brittleness before and after branch is strong, and poor toughness is unfavorable for the molding and processing of macromolecule matrix.And have in poly- 6-caprolactone
Special carbon-chain structure and good rheological performance can assign the good toughness of material and processing performance.
The present invention prepares L- lactide/glycolides/6-caprolactone terpolymer using melt phase polycondensation（PLLGC）, into
One step uses MAH graft modifications, using different component degradation rate difference in polymer, changes its composition, it is expected to obtain mechanics
The terpolymer MPLLGC that performance is good and degradation property is controllable（There is not been reported for document）.The introducing of anhydride bond can also be material
Subsequent improvement provide it is good basis and may, hydrophilicity and cellular affinity of material etc. can be further improved.
Invention content
Have both that excellent mechanical performances, degradation property be controllable and the macromolecule of acid anhydrides reactive group the purpose of the present invention is a kind of
Measure the preparation method of MPLLGC polymer.
The technical solution adopted by the present invention：A kind of maleic anhydride is directly grafted L- lactide/glycolides/6-caprolactone ternary
The preparation method of copolymer, including step：
（1）According to raw material weight number, by 70 ~ 80 parts of L- lactides, 15 ~ 20 parts of glycolides and 5-10 parts after purification process
6-caprolactone is added in the container after being dried, and adds stannous octoate/toluene solution of a certain amount of 0.1mol/L；Vacuum is done
After dry 12 ~ 24 h, at normal temperatures using 0.5 ~ 1.0 h of diffusion pump pumping high vacuum, pressure in container is made to be less than 10.0Pa, Ran Houyong
Alcohol blast burner seals；
（2）Container after tube sealing is put into insulating box, is shaken up after 100 DEG C or so meltings, then at a temperature of 120 ~ 160 DEG C
Reaction takes out after reacting 12 ~ 60 h, obtains copolymer p LLGC crude products；
（3）It breaks container into pieces, crude product is dissolved in chloroform, be configured to the solution of 3.0 ~ 5.0wt%, then instill 3 ~ 5 times of bodies
Precipitating is multiple in long-pending ethyl alcohol, by the product vacuum drying after purification to constant weight up to PLLGC polymer；
（4）PLLGC polymer after purification with a certain amount of maleic anhydride, dibenzoyl peroxide is mixed, is placed in dry place
In container after reason, vacuumizing makes pressure in container be less than 10.0Pa, alcohol blast burner sealing；Container after sealing is placed in 160
10-15min in DEG C insulating box shakes up after its melting, 2-4h is then reacted in 120 DEG C of environment obtains maleic anhydride and connect
The thick polymers MPLLGC of the PLLGC of branch；
（5）Thick polymers MPLLGC after grafting is placed in extractor, homopolymer is removed by solvent extraction of chloroform, will take out
Constant weight is dried under vacuum at 40 DEG C of copolymer after carrying.Copolymer is added in chloroform, it is configured to a concentration of 3.0 ~
The solution of 5.0wt%, it is multiple to instill precipitating in the ethyl alcohol of 3 ~ 5 times of volumes, then will be dried under vacuum to constant weight at 40 DEG C of purification,
It obtains pure maleic anhydride and is directly grafted L- lactide/glycolides/6-caprolactone terpolymer.
Preferably, the parts by weight of the raw material are：18 parts of 75 parts of L- lactides, glycolide, ε after purification process-
8 parts of caprolactone.
Preferably, step（1）In, the L- lactides are using decompression method, using Pfansteihl as raw material, 140 ~ 160
After DEG C cyclodehydration, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- lactides, repeatedly purify to obtain L- lactides crystalline substance through ethyl acetate
Body；The glycolide be using decompression method, using glycolic as raw material, after 150 ~ 170 DEG C of cyclodehydrations, 250 ~ 260 DEG C of open loops
Polymerization obtains thick glycolide, purifies to obtain the glycolide crystal of sheet through ethyl acetate；6-caprolactone distills at reduced pressure conditions
Remove contained humidity in raw material；The molar ratio of stannous octoate and three kinds of monomer total amounts is 1:2000-1:10000, preferably 1:
5000-1:7000。
Preferably, step（3）In, the concentration of chloroform soln is directly related with PLLGC molecular size ranges, molecular weight
Bigger, the chloroform soln concentration of preparation should be smaller.
Preferably, step（4）In, the amount of maleic anhydride is L- lactides, glycolide and 6-caprolactone monomer total amount
5.0 ~ 10.0 wt%, the addition of benzoyl peroxide are 1.0 ~ 5.0 wt% of maleic anhydride weight.
Preferably, the reduced pressure atmosphere is less than 0.09MPa for pressure.
The synthesis of MPLLGC is copolymerized into the melting of three kinds of L- lactides, glycolide and 6-caprolactone monomers in the present invention
On the basis of PLLGC, it is directly grafted in PLLGC skeletons by free radical polymerization at reduced pressure conditions using MAH.
Terpolymer PLLGC prepared by the present invention is pure white solid, and it is light yellow to be grafted the product MPLLGC after MAH
Solid, molecular weight is up to 1.0 × 105Da, titration measuring maleic anhydride grafting ratio are 0.5 ~ 1.0%.
The obtained MPLLGC of the present invention has the following advantages：
（1）Directly grafting MAH obtains MPLLGC again on the basis of molten monomer is copolymerized preparation high molecular weight PLLGC, passes through tune
The composition of section terpolymer can make after polymer material molding that mechanical property and degradation property modification scope are wider, can meet not
With the demand of medical material application.
（2）Hydrophilicity is improved after PLLGC grafting MAH, and the anhydride group in MPLLGC skeletons can water in degradation process
Solution two hydrophilic carboxyls of generation, so as to greatly improve the hydrophilicity of material.
（3）The introducing of anhydride bond can also be that the successive modified of material provides good basis, such as acid anhydrides bond energy and fat two
N- acylation reactions occur for amine, small peptide etc., so as to introduce amido or bioactive substance, can further improve the hydrophily of material
Energy and cellular affinity etc..
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, and the raw material number is removed and especially said
It is bright outer, it is parts by weight.
Embodiment 1：
Using Pfansteihl as raw material, under reduced pressure after 140 ~ 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- third
Lactide purifies to obtain L- lactide crystal through ethyl acetate；Using glycolic as raw material, 150 ~ 170 DEG C of cyclodehydrations under reduced pressure
Afterwards, 250 ~ 260 DEG C of ring-opening polymerisations obtain thick glycolide, purify to obtain the glycolide crystal of sheet through ethyl acetate.6-caprolactone
Moisture in raw material is distilled off in raw material at reduced pressure conditions, obtains 6-caprolactone after purification.
The dried L- lactides of 7.46g, 2.0g glycolides and 0.818mL 6-caprolactones are added in into the peace after being dried
In small jar bottle, stannous octoate/toluene solution of a concentration of 0.1mol/L of 0.766mL is added；After being dried in vacuo 24 h, in ampoule bottle
Interior pressure is sealed under conditions of being 5 .0Pa with alcohol blast burner.Ampoule bottle after sealing is placed in insulating box, it is anti-at 120 DEG C
48 h are answered, break ampoule bottle into pieces, take out to obtain crude product PLLGC.
Crude product is dissolved in chloroform, is configured to 4.0wt% solution, instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, very
Sky is dry.5.0gPLLGC, 0.5g maleic anhydride after purification and the mixing of 0.015g dibenzoyl peroxides are taken, is placed in ampoule bottle
In, alcohol blast burner seals under conditions of pressure 7.5Pa in bottle.Ampoule bottle after sealing is placed in 10min in 160 DEG C of insulating boxs,
It shakes up, 2h is then reacted in 120 DEG C of environment obtains the thick polymers of MPLLGC.Thick polymers after grafting is placed in extractor
It is interior, using chloroform as 8 h of solvent extraction, it is dissolved in chloroform, is configured to after the residue of extracting is dried in vacuo
4.0wt% solution instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, purification then is dried under vacuum to constant weight, obtains pale yellow colour purity
Graft copolymer MPLLGC.Products obtained therefrom Mn=1.06×105Da, Mw/Mn=1.21, grafting rate 0.85%.
Embodiment 2：
Using Pfansteihl as raw material, under reduced pressure after 140 ~ 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- third
Lactide purifies to obtain L- lactide crystal through ethyl acetate；Using glycolic as raw material, 150 ~ 170 DEG C of cyclodehydrations under reduced pressure
Afterwards, 250 ~ 260 DEG C of ring-opening polymerisations obtain thick glycolide, purify to obtain the glycolide crystal of sheet through ethyl acetate.6-caprolactone
Moisture in raw material is distilled off in raw material at reduced pressure conditions, obtains 6-caprolactone after purification.
The dried L- lactides of 11.2g, 3.0g glycolides and 1.2mL 6-caprolactones are added in into the ampoule after being dried
In bottle, L stannous octoates/toluene solution of a concentration of 0.1mol/ of 0.576mL is added；After being dried in vacuo 24 h, in ampoule bottle
Pressure is sealed under conditions of being 7.5Pa with alcohol blast burner.Ampoule bottle after sealing is placed in insulating box, is reacted at 120 DEG C
36h breaks ampoule bottle into pieces, takes out to obtain crude product PLLGC.
Crude product is dissolved in chloroform, is configured to 5.0wt% solution, instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, very
Sky is dry.5.0gPLLGC, 0.5g maleic anhydride after purification and the mixing of 0.015g dibenzoyl peroxides are taken, is placed in ampoule bottle
In, pressure is low in bottle seals for alcohol blast burner under conditions of 5.0Pa.Ampoule bottle after sealing is placed in 160 DEG C of insulating boxs
15min shakes up, and 4h is then reacted in 120 DEG C of environment obtains the thick polymers of MPLLGC.Thick polymers after grafting is placed in pumping
It carries in device, using chloroform as 8 h of solvent extraction, is dissolved in chloroform, is configured to after the residue of extracting is dried in vacuo
5.0wt% solution instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, purification then is dried under vacuum to constant weight, obtains pale yellow colour purity
Graft copolymer MPLLGC.Products obtained therefrom Mn=1.21×105Da, Mw/Mn=1.22, grafting rate 0.88%.
Embodiment 3：
Using Pfansteihl as raw material, under reduced pressure after 140 ~ 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- third
Lactide purifies to obtain L- lactide crystal through ethyl acetate；Using glycolic as raw material, 150 ~ 170 DEG C of cyclodehydrations under reduced pressure
Afterwards, 250 ~ 260 DEG C of ring-opening polymerisations obtain thick glycolide, purify to obtain the glycolide crystal of sheet through ethyl acetate.6-caprolactone
Moisture in raw material is distilled off in raw material at reduced pressure conditions, obtains 6-caprolactone after purification.
The dried L- lactides of 22.4g, 6.0g glycolides and 2.4mL 6-caprolactones are added in into the ampoule after being dried
In bottle, L stannous octoates/toluene solution of a concentration of 0.1mol/ of 1.15mL is added；After being dried in vacuo 24 h, in ampoule bottle
Pressure is sealed under conditions of being 10.0Pa with alcohol blast burner.Ampoule bottle after sealing is placed in insulating box, is reacted at 130 DEG C
For 24 hours, it breaks ampoule bottle into pieces, takes out to obtain crude product PLLGC.
Crude product is dissolved in chloroform, is configured to 3.0wt% solution, instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, very
Sky is dry.4.57gPLLGC, 0.457g maleic anhydride after purification and the mixing of 0.0137g dibenzoyl peroxides are taken, is placed in peace
In small jar bottle, pressure is sealed for alcohol blast burner under conditions of 7.5Pa in bottle.Ampoule bottle after sealing is placed in 160 DEG C of insulating boxs
14min shakes up, and 3h is then reacted in 120 DEG C of environment obtains the thick polymers of MPLLGC.Thick polymers after grafting is placed in pumping
It carries in device, using chloroform as 8 h of solvent extraction, is dissolved in chloroform, is configured to after the residue of extracting is dried in vacuo
3.0wt% solution instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, purification then is dried under vacuum to constant weight, obtains pale yellow colour purity
Graft copolymer MPLLGC.Products obtained therefrom Mn=8.5×104Da, Mw/Mn=1.29, grafting rate 0.92%.
Embodiment 4：
Using Pfansteihl as raw material, under reduced pressure after 140 ~ 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- third
Lactide purifies to obtain L- lactide crystal through ethyl acetate；Using glycolic as raw material, 150 ~ 170 DEG C of cyclodehydrations under reduced pressure
Afterwards, 250 ~ 260 DEG C of ring-opening polymerisations obtain thick glycolide, purify to obtain the glycolide crystal of sheet through ethyl acetate.6-caprolactone
Moisture in raw material is distilled off in raw material at reduced pressure conditions, obtains 6-caprolactone after purification.
The dried L- lactides of 28.0g, 7.5.0g glycolides and 3.0mL 6-caprolactones are added in into the peace after being dried
In small jar bottle, L stannous octoates/toluene solution of a concentration of 0.1mol/ of 3.05mL is added；After being dried in vacuo 24 h, in ampoule bottle
Interior pressure is sealed under conditions of being 5.0Pa with alcohol blast burner.Ampoule bottle after sealing is placed in insulating box, it is anti-at 150 DEG C
36h is answered, breaks ampoule bottle into pieces, takes out to obtain crude product PLLGC.
Crude product is dissolved in chloroform, is configured to 3.0wt% solution, instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, very
Sky is dry.6.0gPLLGC, 0.60g maleic anhydride after purification and the mixing of 0.018g dibenzoyl peroxides are taken, is placed in ampoule bottle
In, pressure is sealed for alcohol blast burner under conditions of 2.5Pa in bottle.Ampoule bottle after sealing is placed in 160 DEG C of insulating boxs
10min shakes up, and 3h is then reacted in 120 DEG C of environment obtains the thick polymers of MPLLGC.Thick polymers after grafting is placed in pumping
It carries in device, using chloroform as 8 h of solvent extraction, is dissolved in chloroform, is configured to after the residue of extracting is dried in vacuo
3.0wt% solution instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, purification then is dried under vacuum to constant weight, obtains pale yellow colour purity
Graft copolymer MPLLGC.Products obtained therefrom Mn=1.05×105Da, Mw/Mn=1.31, grafting rate 0.76%.
Embodiment 5：
Using Pfansteihl as raw material, under reduced pressure after 140 ~ 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- third
Lactide purifies to obtain L- lactide crystal through ethyl acetate；Using glycolic as raw material, 150 ~ 170 DEG C of cyclodehydrations under reduced pressure
Afterwards, 250 ~ 260 DEG C of ring-opening polymerisations obtain thick glycolide, purify to obtain the glycolide crystal of sheet through ethyl acetate.6-caprolactone
Moisture in raw material is distilled off in raw material at reduced pressure conditions, obtains 6-caprolactone after purification.
The dried L- lactides of 5.6g, 1.5g glycolides and 0.6mL 6-caprolactones are added in into the ampoule after being dried
In bottle, L stannous octoates/toluene solution of a concentration of 0.1mol/ of 0.288mL is added；After being dried in vacuo 24 h, in ampoule bottle
Pressure is sealed under conditions of being 5.0Pa with alcohol blast burner.Ampoule bottle after sealing is placed in insulating box, is reacted at 140 DEG C
For 24 hours, it breaks ampoule bottle into pieces, takes out to obtain crude product PLLGC.
Crude product is dissolved in chloroform, is configured to 5.0wt% solution, instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, very
Sky is dry.5.5gPLLGC, 0.55g maleic anhydride after purification and the mixing of 0.0165g dibenzoyl peroxides are taken, is placed in ampoule
In bottle, pressure is sealed for alcohol blast burner under conditions of 5.0Pa in bottle.Ampoule bottle after sealing is placed in 160 DEG C of insulating boxs
12min shakes up, and 2h is then reacted in 120 DEG C of environment obtains the thick polymers of MPLLGC.Thick polymers after grafting is placed in pumping
It carries in device, using chloroform as 8 h of solvent extraction, is dissolved in chloroform, is configured to after the residue of extracting is dried in vacuo
5.0wt% solution instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, purification then is dried under vacuum to constant weight, obtains pale yellow colour purity
Graft copolymer MPLLGC.Products obtained therefrom Mn=1.38×105Da, Mw/Mn=1.24, grafting rate 0.79%.
Embodiment 6：
Using Pfansteihl as raw material, under reduced pressure after 140 ~ 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- third
Lactide purifies to obtain L- lactide crystal through ethyl acetate；Using glycolic as raw material, 150 ~ 170 DEG C of cyclodehydrations under reduced pressure
Afterwards, 250 ~ 260 DEG C of ring-opening polymerisations obtain thick glycolide, purify to obtain the glycolide crystal of sheet through ethyl acetate.6-caprolactone
Moisture in raw material is distilled off in raw material at reduced pressure conditions, obtains 6-caprolactone after purification.
The dried L- lactides of 16.8g, 4.5g glycolides and 1.8mL 6-caprolactones are added in into the ampoule after being dried
In bottle, L stannous octoates/toluene solution of a concentration of 0.1mol/ of 0.864mL is added；After being dried in vacuo 24 h, in ampoule bottle
Pressure is sealed under conditions of being 7.5Pa with alcohol blast burner.Ampoule bottle after sealing is placed in insulating box, is reacted at 150 DEG C
For 24 hours, it breaks ampoule bottle into pieces, takes out to obtain crude product PLLGC.
Crude product is dissolved in chloroform, is configured to 3.0wt% solution, instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, very
Sky is dry.6.5gPLLGC, 0.65g maleic anhydride after purification and the mixing of 0.0195g dibenzoyl peroxides are taken, is placed in ampoule
In bottle, pressure is sealed for alcohol blast burner under conditions of 2.5Pa in bottle.Ampoule bottle after sealing is placed in 160 DEG C of insulating boxs
10min shakes up, and 3h is then reacted in 120 DEG C of environment obtains the thick polymers of MPLLGC.Thick polymers after grafting is placed in pumping
It carries in device, using chloroform as 8 h of solvent extraction, is dissolved in chloroform, is configured to after the residue of extracting is dried in vacuo
3.0wt% solution instills precipitating 3 times in the ethyl alcohol of 3 times of volumes, purification then is dried under vacuum to constant weight, obtains pale yellow colour purity
Graft copolymer MPLLGC.Products obtained therefrom Mn=8.65×104Da, Mw/Mn=1.32, grafting rate 0.81%.
Claims (6)
1. a kind of maleic anhydride is directly grafted the preparation method of L- lactide/glycolides/6-caprolactone terpolymer, feature
It is, including step：
（1）According to raw material weight number, by 70 ~ 80 parts of L- lactides, 15 ~ 20 parts of glycolides and 5-10 parts after purification process
6-caprolactone is added in the container after being dried, and adds stannous octoate/toluene solution of a certain amount of 0.1mol/L；Vacuum is done
After dry 12 ~ 24 h, at normal temperatures using 0.5 ~ 1.0 h of diffusion pump pumping high vacuum, pressure in container is made to be less than 10.0Pa, Ran Houyong
Alcohol blast burner seals；
（2）Container after tube sealing is put into insulating box, is shaken up after 100 DEG C or so meltings, then at a temperature of 120 ~ 160 DEG C
Reaction takes out after reacting 12 ~ 60 h, obtains copolymer p LLGC crude products；
（3）It breaks container into pieces, crude product is dissolved in chloroform, be configured to the solution of 3.0 ~ 5.0wt%, then instill 3 ~ 5 times of bodies
Precipitating is multiple in long-pending ethyl alcohol, by the product vacuum drying after purification to constant weight up to PLLGC polymer；
（4）PLLGC polymer after purification with a certain amount of maleic anhydride, dibenzoyl peroxide is mixed, is placed in dry place
In container after reason, vacuumizing makes pressure in container be less than 10.0Pa, alcohol blast burner sealing；Container after sealing is placed in 160
10-15min in DEG C insulating box shakes up after its melting, 2-4h is then reacted in 120 DEG C of environment obtains maleic anhydride and connect
The thick polymers MPLLGC of the PLLGC of branch；
（5）Thick polymers MPLLGC after grafting is placed in extractor, homopolymer is removed by solvent extraction of chloroform, will take out
Constant weight is dried under vacuum at 40 DEG C of copolymer after carrying,
Copolymer is added in chloroform, is configured to the solution of a concentration of 3.0 ~ 5.0wt%, instills the ethyl alcohol of 3 ~ 5 times of volumes
Middle precipitating is multiple, then will be dried under vacuum to constant weight at 40 DEG C of purification, obtain pure maleic anhydride be directly grafted L- lactides/
Glycolide/6-caprolactone terpolymer.
2. maleic anhydride according to claim 1 is directly grafted L- lactide/glycolides/6-caprolactone terpolymer
Preparation method, which is characterized in that the parts by weight of the raw material are：18 parts of 75 parts of L- lactides, glycolide after purification process,
8 parts of 6-caprolactone.
3. maleic anhydride according to claim 1 is directly grafted L- lactide/glycolides/6-caprolactone terpolymer
Preparation method, which is characterized in that step（1）In, the L- lactides be using decompression method, using Pfansteihl as raw material, 140 ~
After 160 DEG C of cyclodehydrations, 180 ~ 220 DEG C of ring-opening polymerisations obtain thick L- lactides, repeatedly purify to obtain L- third through ethyl acetate and hand over
Crystalline esters；The glycolide be using decompression method, using glycolic as raw material, after 150 ~ 170 DEG C of cyclodehydrations, 250 ~ 260 DEG C
Ring-opening polymerisation obtains thick glycolide, purifies to obtain the glycolide crystal of sheet through ethyl acetate；6-caprolactone is at reduced pressure conditions
Contained humidity in raw material is distilled off；The molar ratio of stannous octoate and three kinds of monomer total amounts is 1:2000-1:10000, preferably
1:5000-1:7000。
4. maleic anhydride according to claim 1 is directly grafted L- lactide/glycolides/6-caprolactone terpolymer
Preparation method, which is characterized in that step（3）In, the concentration of chloroform soln is directly related with PLLGC molecular size ranges, point
Son amount is bigger, and the chloroform soln concentration of preparation should be smaller.
5. maleic anhydride according to claim 1 is directly grafted L- lactide/glycolides/6-caprolactone terpolymer
Preparation method, which is characterized in that step（4）In, the amount of maleic anhydride is L- lactides, glycolide and 6-caprolactone monomer total amount
5.0 ~ 10.0 wt%, the addition of benzoyl peroxide is 1.0 ~ 5.0 wt% of maleic anhydride weight.
6. maleic anhydride according to claim 1 is directly grafted L- lactide/glycolides/6-caprolactone terpolymer
Preparation method, which is characterized in that the reduced pressure atmosphere is less than 0.09MPa for pressure.
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| CN109568649A (en) * | 2018-11-27 | 2019-04-05 | 普丽妍（南京）医疗科技有限公司 | A kind of anti-bacterial, anti-itching temperature-sensitivcomposite composite hydrogel and preparation method thereof |
| CN114478932A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Polyglycolic acid graft copolymer with high thermal stability and preparation method and application thereof |
| CN116554608A (en) * | 2023-05-04 | 2023-08-08 | 博特尔包装(江苏)有限公司 | Preparation process of degradable polystyrene packaging material |
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| CN102911347A (en) * | 2012-10-22 | 2013-02-06 | 长沙理工大学 | Method for preparing high molecular weight poly(L-lactide-co-caprolactone) random copolymer |
| CN105315412A (en) * | 2015-11-23 | 2016-02-10 | 湖南科技大学 | Technology for preparing high-molecular-weight MPLGA by directly grafting maleic anhydride onto PLGA |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102911347A (en) * | 2012-10-22 | 2013-02-06 | 长沙理工大学 | Method for preparing high molecular weight poly(L-lactide-co-caprolactone) random copolymer |
| CN105315412A (en) * | 2015-11-23 | 2016-02-10 | 湖南科技大学 | Technology for preparing high-molecular-weight MPLGA by directly grafting maleic anhydride onto PLGA |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109568649A (en) * | 2018-11-27 | 2019-04-05 | 普丽妍（南京）医疗科技有限公司 | A kind of anti-bacterial, anti-itching temperature-sensitivcomposite composite hydrogel and preparation method thereof |
| CN114478932A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Polyglycolic acid graft copolymer with high thermal stability and preparation method and application thereof |
| CN116554608A (en) * | 2023-05-04 | 2023-08-08 | 博特尔包装(江苏)有限公司 | Preparation process of degradable polystyrene packaging material |
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