CN107033337B - A kind of functional poly ester polyurethane alternate copolymer and its preparation and application - Google Patents
A kind of functional poly ester polyurethane alternate copolymer and its preparation and application Download PDFInfo
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- CN107033337B CN107033337B CN201710237267.6A CN201710237267A CN107033337B CN 107033337 B CN107033337 B CN 107033337B CN 201710237267 A CN201710237267 A CN 201710237267A CN 107033337 B CN107033337 B CN 107033337B
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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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The present invention relates to a kind of functional poly ester polyurethane alternate copolymer and its preparation and application, the polyester-polyurethane alternate copolymer is the own diamino acid diglyceride of poly- decanedioyl base.Preparation: under protective gas atmosphere, epoxy prapanol, hexamethylene diisocyanate, solvent is mixed, are then stirred to react under the conditions of 30-50 DEG C of oil bath, purifies, obtains own diamino acid diglyceride；Under the conditions of anhydrous and oxygen-free, after own diamino acid diglyceride, decanedioic acid, tetrabutylammonium bromide are mixed, solvent is added; under protective gas atmosphere, so that reactant all dissolves, the reaction was continued after dissolution 40-60h; obtain sundown solution, then purify to get.Ester group and carbamic acid structure are alternately present in material of the present invention, make material is subsequent to be crosslinked the PSeHCD elastomer prepared while there is polyurethane material high tenacity to have both the good degradability of polyester material and biocompatibility again.
Description
Technical field
The invention belongs to polyester-polyurethane material and its preparation and application field, in particular to a kind of poly- ammonia of functionalized polyester
Ester alternate copolymer and its preparation and application.
Background technique
Polyester is studied degradable biomaterials that are most, and being most widely used so far.Polyester high score
Contain characteristic group's ester bond in its main chain of sub- material, is a kind of biological material for having good biocompatibility and blood compatibility
Material, is widely used in modern medicine, such as Medical surgical suture, implantation internal fixation apparatus, drug controlled release.
Polyester is generally synthesized by alkyd polycondensation reaction.Common monomer has diacid, glycol, hydroxy fatty acid etc.,
It commonly uses its ester compounds or lactone compound is monomer.It is well known that esterification has invertibity, and this exactly makes polyester
Material can hydrolyze, and have good biodegradability under wet physiological environment.Aliphatic polyester such as polyglycolide
(PGA), polylactide (PLA), polymeric polyglycolide-polylactide copolymer (PLGA), polycaprolactone (PCL) and pass through biological method
The usually degradation property such as polyhydroxyalkanoates (PHAs) of synthesis is preferable, therefore is widely used.And in aromatic polyester by
In containing rigid aromatic ring structure, therefore degradation property is poor.
Polyurethane (PU) it is with a long history, be one of most important elastomer.PU be found in the 1930s and in
The sixties is applied to biomedicine field.Polyurethane elastomer mainly has good blood compatibility and excellent Mechanics of Machinery
Performance, therefore be widely used in field of biomedical materials.Its mechanical performance is mainly by each segment and whole
The influence of many factors such as the composition of a polymer, relative amount and molecular weight, therefore can be made very hard or very
It is flexible.Wherein the content of hard section and stability determine the stability and hardness of PU, and the content of soft segment then will affect hardness
And tensile strength.
The medical treatment that previous PU material be used to be chronically implanted, however in 20 world's seventies it is proposed that PU material settling out
Property in vivo whether An Quan problem.This is because PU material degradation in vivo can generate toxicity and carcinogenicity, there is mutagenicity,
Generate aromatic diamines.Biomer is in 1991 at first using the degradable PU medical product of cardiovascular aspect in vivo, herein
The research of a large amount of biodegradabilities in relation to PU is improved the biological stability of PU by carrying out later.On the other hand, to PU's
Observational study has carried it into a completely new field, organizational project.And this is one very dependent on controllable biodegradable
Field.Since the nineties in last century, degradable PU material is widely studied and becomes the general biology of regenerative medicine can
One of degradable material, and its biocompatibility is substantially increased for the research of PU material instantly.And degradable polyurethane
Because of good mechanical performance, good machinability and regulatable structure have been widely used for biomedical, tissue
Engineering etc., especially on soft tissue engineering.Its biodegradability can by select different soft and hard segments and it
Relative amount change.Hard section is usually used as the material being chronically implanted in traditional PU, mainly by aromatic two
Isocyanates is made, and they are usually to have biological stability.And degradable PU is then usually by two isocyanide of aliphatic
Acid esters such as BDI or HDI are made.And soft segment is usually used to the degradation of regulation PU, increases the length of soft segment and the parent of material
Aqueous meeting accelerated degradation, when especially material hydrophilic increases, degradation rate can be dramatically increased.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of functional poly ester polyurethane alternate copolymer and its preparation and answer
With ester group and carbamic acid structure are alternately present in the material, make material is subsequent to be crosslinked the PSeHCD elastomer prepared simultaneously
The good degradability of polyester material and biocompatibility are had both again with polyurethane material high tenacity.
A kind of functional poly ester polyurethane alternate copolymer of the invention, it is characterised in that: the polyester-polyurethane alternate copolymer is
The poly- own diamino acid diglyceride of decanedioyl base,
Structural formula are as follows:N range about exists
Between 20-40.
A kind of preparation method of functional poly ester polyurethane alternate copolymer of the invention, comprising:
(1) under protective gas atmosphere, epoxy prapanol, hexamethylene diisocyanate, solvent are mixed, then in oil bath
It is stirred to react, after reaction the white suspended liquid of system, purifies under the conditions of 30-50 DEG C, it is solid to obtain pure white flock
Intimate diamino acid diglyceride (PSeHCD monomer)；
(2) under the conditions of anhydrous and oxygen-free, by own diamino acid diglyceride, recrystallization decanedioic acid, tetrabutylammonium bromide
After mixing, solvent is added, under protective gas atmosphere, stirs and oil bath is gradually from room temperature to 100 DEG C, so that reactant is complete
Portion's dissolution, is kept stirring after dissolution and reacts 50-70h (preferably 65h) with anhydrous and oxygen-free environment (oil bath heating condition), obtain shallow palm fibre
Then yellow solution purifies, obtain functional poly ester polyurethane alternate copolymer.
Protective gas is nitrogen in the step (1), (2).
Epoxy prapanol in the step (1): hexamethylene diisocyanate molar ratio is in 2:1-2.5:1, reactant quality
(epoxy prapanol and hexamethylene diisocyanate): solvent volume=1g:1-2mL.
Solvent is tetrahydrofuran in the step (1), and tetrahydrofuran removes water process by distillation by HPLC grades of tetrahydrofurans.
Suitable THF can be suitably supplemented in step (1) reaction process to be ensured to react progress.
Step (1) preferably oil bath temperature is 35 DEG C.
It is stirred to react in the step (1) are as follows: sustained response 40h or more is stirred under conditions of 500-850rpm.
Own diamino acid diglyceride in the step (2): molar ratio=1:1 of decanedioic acid, (oneself two for reactant quality
Carbamic acid diglyceride and decanedioic acid): solvent volume=1g:1-2mL；Tetrabutylammonium bromide is that reactant feeds intake mole
0.85%)；Tetrabutylammonium bromide is the 0.85% of reactant (the own diamino acid diglyceride and decanedioic acid) mole that feeds intake；
Solvent is dimethylformamide DMF in the step (2).
The weighing of all reactants is completed in the glove box environment full of nitrogen anhydrous and oxygen-free in step (2), and
Successively weighed drug is added in reaction flask in glove box, further encapsulation process is made to reaction tube with rubber stopper and sealed membrane
Ensure to react the environment of anhydrous and oxygen-free.
Solvent is added with needle tubing in the addition of solvent into reaction tube dropwise in step (2).
Stirring rate is 800-1000rpm in the step (2).
Purification in the step (2) specifically: sundown solution is added dropwise to the heavy of high speed rotation (revolving speed 800rpm)
In depressant prescription, due to after sedimentation in ethyl acetate system in uniform suspended liquid, can not filter, therefore will be reacted using centrifuge
The PSeHCD arrived is repeated 3-5 times by centrifugal sedimentation, is placed in and is vacuumized at room temperature with diaphragm pump.
The volume ratio of sundown solution and sedimentation agent is greater than or equal to 20:1；Sedimentation agent is ether.
A kind of application of functional poly ester polyurethane alternate copolymer of the invention, polyester-polyurethane alternate copolymer is in preparation PSeHCD
Application in elastomer or functionalization biomaterial.
Beneficial effect
One kind of the invention it is novel functional poly ester polyurethane alternate copolymer --- the poly- own diamino acid of decanedioyl base is sweet
Oily diester (sebacoyl-1,6-hexamethylenedicarbamate diglyceride, PSeHCD), ester group in the material
It is alternately present with carbamic acid structure, makes material is subsequent to be crosslinked the PSeHCD elastomer prepared while there is polyurethane material height
Toughness has both the good degradability of polyester material and biocompatibility again；
The side chain of material of the present invention has a large amount of hydroxy functionalized site, can further modify, to prepare a system
Column functionalization biomaterial.Gathered in addition, this patent can be widened significantly using acid induction epoxy addition strategy synthesis functionalized polyester
The application range of the strategy of urethane alternate copolymer.It, can be by selecting different startings since the synthetic strategy of use is very flexible
Raw material (various diacid, diisocyanate etc.) obtains a series of novel functional polyurethane containing polyester construction and then obtains
A series of new material of different properties is obtained, corresponding property can also regulate and control in very big range.Therefore the method is expected to
As the new platform technology for preparing functional material (the including but not limited to application of biomaterial).
Detailed description of the invention
The synthetic route chart of Fig. 1 functional poly ester polyurethane alternate copolymer；
Fig. 2 is the 1H NMR spectra of PSeHCD monomer；
Fig. 3 is the 13C NMR spectra of PSeHCD monomer；
Fig. 4 is the 1H NMR spectra of PSeHCD；
Fig. 5 is the 13C NMR spectra of PSeHCD；
Fig. 6 is the FTIR infrared spectrum of PSeHCD monomer and PSeHCD；
Fig. 7 is a series of mechanical property figure of PSeHCD cross-linked elastomers；
Fig. 8 is a series of degradation property figure of PSeHCD cross-linked elastomers；
Fig. 9 is PSeHCD polymer (A-C), and PLGA control group (D-F) and TCPs control group (G-I) are respectively in Isosorbide-5-Nitrae, 7
The CCK-8 biocompatibility experiment figure of its culture mouse bone-forming cell；J is the increasing of PSeHCD polymer, PLGA, TCPs to cell
It is worth influence diagram.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The synthesis of PSeHCD monomer:
Make anhydrous and oxygen-free processing after rotor is added in 25ml tool branch pipe eggplant shaped reaction bottle, entire reaction flask is made to be in nitrogen
Under atmosphere, be injected separately into epoxy prapanol (4.128mL, 63.69mmol), hexamethylene diisocyanate (4.500mL,
28.09mmol), tetrahydrofuran (10mL) is into eggplant shaped reaction bottle, wherein reacting the tetrahydrofuran used by HPLC grades of tetrahydro furans
It mutters through distillation except water process, is placed in 35 DEG C of oil bath, sustained response 40h is stirred under conditions of 650rpm, can be fitted in reaction process
Ensure to react progress when supplementing suitable THF.
The white suspended liquid of system after reaction obtains pure white fluffy solid after being purified with sedimentation
(PSeHCD monomer) 4.52g, yield 50.8%.
The synthesis of PSeHCD polymer:
Take the knot again of pure own the diamino acid diglyceride monomer 0.9483mmol (0.3g) and equimolar amounts of preparation
The tetrabutylammonium bromide (based on the 0.85% of the mole that feeds intake by reactant) of brilliant decanedioic acid 0.1918g and 2.6mg, it is all to weigh
It is completed in the glove box environment full of nitrogen anhydrous and oxygen-free, and reaction flask successively is added in weighed drug in glove box
In, making further encapsulation process to reaction tube with rubber stopper and sealed membrane ensures to react the environment of anhydrous and oxygen-free.Needle is used after taking-up
0.5mL anhydrous DMF is added in pipe into reaction tube dropwise, is stirred under nitrogen protection environment with the revolving speed of 900rpm, oil bath is gradually
From room temperature to 100 DEG C, this process DMF can dissolve the whole of reactant.The revolving speed and anhydrous and oxygen-free ring are kept after dissolution
It reacts 65 hours in border.
After reaction system be in sundown solution shape, separately take beaker by and reaction flask in reaction solution volume 20:1 ratio
About 10mL ether is added as sedimentation agent in example, and clean glass dropper is taken dropwise to revolve the high speed that reaction solution instills revolving speed 800rpm
Turn in ether.Due to after sedimentation in ethyl acetate system in uniform suspended liquid, can not filter, therefore use centrifuge that will react
Obtained PSeHCD repeats the above steps three times afterwards to be placed in products therefrom and uses diaphragm pumping true at room temperature by centrifugal sedimentation
Sky obtains light brown viscous semisolid (PSeHCD) 0.3652g, and yield is about 74.2%.
Fig. 2 is the 1H NMR spectra of PSeHCD monomer, and glycerol moiety peak appears in δ 3.76-4.38ppm, decanedioyl base and
Isocyanate moiety appearance goes out peak position in δ 7.18ppm in δ 1.33 and 1.49ppm ,-NH；
Fig. 3 is the 13C NMR spectra of PSeHCD monomer, is matched with Fig. 2；
Fig. 4 is the 1H NMR spectra of PSeHCD, and two peak areas of δ 2.28ppm and δ 2.93ppm or so are close, right respectively
Answer carbonyl in decanedioic acid segment while on two upper carbon hydrogen and HDI segment in imino group while on two carbon on hydrogen, card
The decanedioic acid segment contained in product PSeHCD is illustrated and PSeHCD monomer segment ratio is 1:1, reaction is it is anticipated that design hair
It is raw；
Fig. 5 is the 13C NMR spectra of PSeHCD；
Fig. 6 is the FTIR infrared spectrum of PSeHCD monomer and PSeHCD, 1562cm-1,1639cm-1 and 3439cm-1 difference
Corresponding amido bond and free hydroxyl.
The synthesis of PSeHCD cross-linked elastomer:
PSeHCD crosslinked is prepared using two different cross-linking methods herein.
1): the amount decanedioic acid that the 1.1wt% of PSeHCD is added in PSeHCD is dissolved in a small amount of acetone as crosslinking agent
Until mixture is transferred to required specific shape after evaporating to most of solvent by dissolution, rotary evaporation just in solvent
20h is heated in tetrafluoro mold and under conditions of 120 DEG C to remove wherein all bubbles, then in vacuum condition, 120 DEG C
It is crosslinked 21h under (1.1Torr) and forms PSeHCD-SA elastomer.
2): using PSeHCD itself as crosslinking agent, forming the covalently high-ductility elastomer in conjunction with non-covalent bond.It directly will preparation
Good PSeHCD polymer be transferred in required specific shape tetrafluoro mold and under 120 DEG C of vacuum conditions (1.1Torr) into
Row vacuum crosslinking 48,60,72h prepares PSeHCD-48, PSeHCD-60 and PSeHCD-72 high-ductility elastomer respectively.
Fig. 7 is a series of mechanical property of PSeHCD cross-linked elastomers, and wherein PSeHCD-48.60.72 elastomer is shown
PSeHCD-SA elastomer in the case where keeping lower Young's modulus relatively compared to addition cross-linking agents has what is be obviously improved to break
Elongation is split, to reach the performance of high-ductility；
Fig. 8 is a series of degradation property of PSeHCD cross-linked elastomers, and embody PSeHCD cross-linked elastomer can be one
Determine to be controlled in range by crosslinking time；
Fig. 9 is PSeHCD polymer (A-C), and PLGA control group (D-F) and TCPs control group (G-I) are respectively in Isosorbide-5-Nitrae, 7
The CCK-8 biocompatibility experiment of its culture mouse bone-forming cell, it can be seen that the cell number of PSeHCD culture from data (J)
No less than control experiment group, good biocompatibility is embodied.# is indicated relative to previous time point value less than 0.01
Significant difference；* the significant difference relative to PLGA group numerical value less than 0.05 is indicated.
Claims (10)
1. a kind of functional poly ester polyurethane alternate copolymer, it is characterised in that: the polyester-polyurethane alternate copolymer is poly- decanedioyl base
Own diamino acid diglyceride,
Structural formula are as follows:N=20-40.
2. a kind of preparation method of functional poly ester polyurethane alternate copolymer as described in claim 1, comprising:
(1) under protective gas atmosphere, epoxy prapanol, hexamethylene diisocyanate, solvent are mixed, then in oil bath 30-
It is stirred to react under the conditions of 50 DEG C, purifies, obtain own diamino acid diglyceride；
(2) it under the conditions of anhydrous and oxygen-free, after own diamino acid diglyceride, decanedioic acid, tetrabutylammonium bromide are mixed, is added
Solvent stirs under protective gas atmosphere and oil bath is gradually from room temperature to 100 DEG C, so that reactant all dissolves, dissolution
After be kept stirring and react 40-60h under the conditions of anhydrous and oxygen-free environment and oil bath, obtain sundown solution, then purify, obtain
Functional poly ester polyurethane alternate copolymer；Wherein tetrabutylammonium bromide is that reactant feeds intake the 0.85% of mole.
3. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Protective gas is nitrogen in step (1), (2).
4. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Epoxy prapanol in step (1): hexamethylene diisocyanate molar ratio be 2:1-3:1, reactant quality: solvent volume=1g:
1-2mL。
5. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Solvent is tetrahydrofuran in step (1).
6. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Step is stirred to react in (1) are as follows: sustained response 40h-60h is stirred under conditions of 500-850rpm.
7. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Own diamino acid diglyceride, decanedioic acid molar ratio are 1:1, reactant quality: solvent volume=1g:1- in step (2)
2mL；Wherein solvent is dimethylformamide DMF.
8. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Stirring rate is 800-1000rpm in step (2).
9. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that: described
Purification in step (2) specifically: sundown solution is added dropwise in the sedimentation agent of rotation, centrifugal sedimentation, is repeated 3-5 times, taken out
Vacuum.
10. a kind of application of functional poly ester polyurethane alternate copolymer as described in claim 1, it is characterised in that: the poly- ammonia of polyester
Ester alternate copolymer is preparing the application in PSeHCD elastomer or functionalization biomaterial.
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