CN107033337A - 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 PDF

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CN107033337A
CN107033337A CN201710237267.6A CN201710237267A CN107033337A CN 107033337 A CN107033337 A CN 107033337A CN 201710237267 A CN201710237267 A CN 201710237267A CN 107033337 A CN107033337 A CN 107033337A
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alternate copolymer
poly ester
functional poly
preparation
ester polyurethane
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CN107033337B (en
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游正伟
梁嘉辉
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Donghua University
National Dong Hwa University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/12Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)

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.Prepare:Under protective gas atmosphere, epoxy prapanol, hexamethylene diisocyanate, solvent are mixed, then the stirring reaction under the conditions of 30 50 DEG C of oil bath, purification, obtain own diamino acid diglyceride;Under the conditions of anhydrous and oxygen-free, after own diamino acid diglyceride, decanedioic acid, TBAB are mixed, solvent is added; continue to react 40 60h under protective gas atmosphere so that reactant all dissolves, after dissolving; sundown solution is obtained, is then purified, is produced.Ester group and carbamic acid structure are alternately present in material of the present invention, material is subsequently crosslinked the PSeHCD elastomers prepared while having polyurethane material high tenacity to have the good degradability of polyester material and biocompatibility concurrently again.

Description

A kind of functional poly ester polyurethane alternate copolymer and its preparation and application
Technical field
The invention belongs to polyester-polyurethane material and its preparation and application field, more particularly to a kind of poly- ammonia of functionalized polyester Ester alternate copolymer and its preparation and application.
Background technology
Polyester is studied most, is also the degradable biomaterial being most widely used so far.Polyester high score Contain characteristic group's ester bond in its main chain of sub- material, be the biological material that a class possesses 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 typically synthesized by alkyd polycondensation reaction.Conventional monomer has diacid, glycol, hydroxy fatty acid etc., It is monomer to commonly use its ester compounds or lactone compound.It is well known that esterification has invertibity, and this exactly causes polyester Material can be hydrolyzed, and have good biodegradability under the physiological environment of moistening.Aliphatic polyester such as PGA (PGA), polylactide (PLA), polymeric polyglycolide-polylactide copolymer (PLGA), polycaprolactone (PCL) and biological method is passed through The generally degradation property such as PHA (PHAs) of synthesis preferably, 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 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 individual polymer, relative amount and molecular weight, thus can be made it is very hard can also be very It is flexible.The content and stability of wherein hard section determine PU stability and hardness, and the content of soft segment can then influence hardness And tensile strength.
Conventional PU materials are used for the medical treatment being chronically implanted, but in 20 world's seventies it is proposed that PU material settling outs Property in vivo whether it is safe the problem of.This is due to that PU materials degradation in vivo can produce toxicity and carcinogenicity, there is mutagenicity, Produce aromatic diamines.Biomer is the degradable PU medical products in terms of applying angiocarpy in vivo at first in 1991, herein The research of the biodegradabilities about PU a large amount of afterwards is by carrying out to improve PU biological stability.On the other hand, to PU's Observational study has carried it into a brand-new field, organizational project.And this is one very dependent on controllable biodegradable Field.Since the nineties in last century, degradable PU materials are widely studied and become the general biology of regenerative medicine can One of degradable material, and the research for PU materials substantially increases its biocompatibility instantly.And degradable polyurethane Because good mechanical performance, good machinability and regulatable structure have been widely used for biomedical, tissue In terms of engineering, especially on soft tissue engineering.Its biodegradability can by select different soft and hard segments and it Relative amount change.Hard section is generally used as the material being chronically implanted in traditional PU, mainly by aromatic two Isocyanates is made, and they are typically with biological stability.And degradable PU is typically then by the isocyanide of aliphatic two Acid esters such as BDI or HDI are made.And soft segment is usually used to regulation and control PU degraded, increase the length of soft segment and the parent of material During aqueous meeting accelerated degradation, especially material hydrophilic increase, its degradation rate can be dramatically increased.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of functional poly ester polyurethane alternate copolymer and its preparation and should With ester group and carbamic acid structure are alternately present in the material, material is subsequently crosslinked the PSeHCD elastomers prepared simultaneously The good degradability of polyester material and biocompatibility are had concurrently again with polyurethane material high tenacity.
A kind of functional poly ester polyurethane alternate copolymer of the present invention, it is characterised in that:The polyester-polyurethane alternate copolymer is The poly- own diamino acid diglyceride of decanedioyl base,
Structural formula is:N scopes about exist Between 20-40.
A kind of preparation method of functional poly ester polyurethane alternate copolymer of the present invention, including:
(1) under protective gas atmosphere, epoxy prapanol, hexamethylene diisocyanate, solvent are mixed, then in oil bath Stirring reaction under the conditions of 30-50 DEG C, reaction terminates the white suspended liquid of rear system, purifies, and obtains pure white flock and consolidates Intimate diamino acid diglyceride (PSeHCD monomers);
(2) under the conditions of anhydrous and oxygen-free, by own diamino acid diglyceride, recrystallization decanedioic acid, TBAB 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 dissolves, and is kept stirring for reacting 50-70h (preferably 65h) with anhydrous and oxygen-free environment (oil bath heating condition) after dissolving, obtains shallow palm fibre Yellow solution, is then purified, and obtains functional poly ester polyurethane alternate copolymer.
Protective gas is nitrogen in the step (1), (2).
Epoxy prapanol in the step (1):Hexamethylene diisocyanate mol ratio is 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 HPLC grades of tetrahydrofurans by distillation.
Appropriate THF can be suitably supplemented in step (1) course of reaction ensures that reaction is carried out.
Step (1) preferably oil bath temperature is 35 DEG C.
Stirring reaction is in the step (1):More than sustained response 40h is stirred under conditions of 500-850rpm.
Own diamino acid diglyceride in the step (2):Mol ratio=1 of decanedioic acid:1, (oneself two for reactant quality Carbamic acid diglyceride and decanedioic acid):Solvent volume=1g:1-2mL;TBAB is that reactant feeds intake mole 0.85%);TBAB 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 The medicine weighed is added in reaction bulb successively in glove box, further encapsulation process is made to reaction tube with rubber stopper and sealed membrane Ensure the environment of reaction anhydrous and oxygen-free.
The addition of solvent adds solvent into reaction tube dropwise with needle tubing in step (2).
Stir speed (S.S.) is 800-1000rpm in the step (2).
Purification is specially in the step (2):Sundown solution is added dropwise to the heavy of rotation (rotating speed 800rpm) at a high speed In depressant prescription, due to being in uniform suspended liquid in ethyl acetate system after sedimentation, it is impossible to 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 membrane pump.
The volume ratio of sundown solution and sedimentation agent is more than or equal to 20:1;Sedimentation agent is ether.
A kind of application of functional poly ester polyurethane alternate copolymer of the present invention, polyester-polyurethane alternate copolymer is preparing PSeHCD Application in elastomer or functionalization biomaterial.
Beneficial effect
The present invention a kind of new functional poly ester polyurethane alternate copolymer --- the poly- own diamino acid of decanedioyl base is sweet Ester group in oily diester (sebacoyl-1,6-hexamethylenedicarbamate diglyceride, PSeHCD), the material It is alternately present with carbamic acid structure, material is subsequently crosslinked the PSeHCD elastomers prepared while having polyurethane material high Toughness has the good degradability of polyester material and biocompatibility concurrently again;
The side chain of material of the present invention carries substantial amounts of hydroxy functionalized site, can make further modification, be to prepare one Row functionalization biomaterial.Gathered in addition, this patent can be widened significantly using acid induction epoxy addition strategy complex functionality polyester The tactful application of urethane alternate copolymer., can be by selecting different startings because the synthesis strategy of use is very flexible Raw material (various diacid, diisocyanate etc.), obtains a series of new 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 scope.Therefore the method is expected to As the new platform technology for preparing functional material (application for including but is not limited to biomaterial).
Brief description of the drawings
The synthetic route chart of Fig. 1 functional poly ester polyurethane alternate copolymers;
Fig. 2 is the 1H NMR spectras of PSeHCD monomers;
Fig. 3 is the 13C NMR spectras of PSeHCD monomers;
Fig. 4 is PSeHCD 1H NMR spectras;
Fig. 5 is PSeHCD 13C NMR spectras;
Fig. 6 is PSeHCD monomers and PSeHCD FTIR infrared spectrums;
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 groups (D-F) and TCPs control groups (G-I) are respectively in Isosorbide-5-Nitrae, 7 The CCK-8 biocompatibility experiment figures of its culture mouse bone-forming cell;J is the increasing of PSeHCD polymer, PLGA, TCPs to cell Value influence figure.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
The synthesis of PSeHCD monomers:
Make anhydrous and oxygen-free processing after adding rotor in 25ml tool branch pipe eggplant shaped reaction bottles, whole reaction bulb is 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 tetrahydrochysene furans Mutter and water process is removed by distillation, be placed in 35 DEG C of oil bath, being stirred under conditions of 650rpm can fit in sustained response 40h, course of reaction Ensure that reaction is carried out when supplementing appropriate THF.
Reaction terminates the white suspended liquid of rear system, and pure white fluffy solid is obtained after being purified with sedimentation (PSeHCD monomers) 4.52g, yield is 50.8%.
The synthesis of PSeHCD polymer:
Take the pure own diamino acid diglyceride monomer 0.9483mmol (0.3g) of preparation and the knot again of equimolar amounts Brilliant decanedioic acid 0.1918g and 2.6mg TBAB (based on the 0.85% of the mole that fed intake by reactant), it is all to weigh Completed in the glove box environment full of nitrogen anhydrous and oxygen-free, and the medicine weighed is added into reaction bulb successively 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.Pin is used after taking-up Pipe adds 0.5mL dry DMFs into reaction tube dropwise, is stirred under nitrogen environmental protection with 900rpm rotating speed, oil bath is gradually From room temperature to 100 DEG C, this process DMF can dissolve the whole of reactant.The rotating speed and anhydrous and oxygen-free ring are kept after dissolving React 65 hours in border.
Reaction terminates rear system in sundown solution shape, separately take beaker by with reaction solution volume 20 in reaction bulb:1 ratio Example adds about 10mL ether as sedimentation agent, and the high speed for taking the glass dropper of cleaning that reaction solution is instilled into rotating speed 800rpm dropwise is revolved Turn in ether.Due to being in uniform suspended liquid in ethyl acetate system after sedimentation, it is impossible to filter, therefore centrifuge is used to react Products therefrom is placed in true with barrier film pumping at room temperature by obtained PSeHCD by centrifugal sedimentation, and after repeating the above steps three times Sky, obtains light brown viscous semisolid (PSeHCD) 0.3652g, yield is about 74.2%.
Fig. 2 is the 1H NMR spectras of PSeHCD monomers, 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 spectras of PSeHCD monomers, is matched with Fig. 2;
Fig. 4 is PSeHCD 1H NMR spectras, and δ 2.28ppm and δ 2.93ppm or so two peak areas are close, right respectively Answer in decanedioic acid fragment in hydrogen and HDI fragments of the carbonyl on two upper carbon the hydrogen on two carbon on during imino group, card It is 1 to understand the decanedioic acid fragment and PSeHCD monomer fragments ratio that contain in product PSeHCD:1, reaction are it is anticipated that design hair It is raw;
Fig. 5 is PSeHCD 13C NMR spectras;
Fig. 6 is PSeHCD monomers and PSeHCD FTIR infrared spectrums, and 1562cm-1,1639cm-1 and 3439cm-1 distinguish Correspondence amido link and free hydroxyl.
The synthesis of PSeHCD cross-linked elastomers:
Herein PSeHCD crosslinkeds are prepared using two kinds of different cross-linking methods.
1):The amount decanedioic acid that PSeHCD 1.1wt% is added in PSeHCD is dissolved in a small amount of acetone as crosslinking agent Until mixture is transferred to required given shape by dissolving just, rotary evaporation after being evaporated to most of solvent in solvent 20h is heated in tetrafluoro mould and under conditions of 120 DEG C to remove wherein all bubbles, then in vacuum condition, 120 DEG C 21h formation PSeHCD-SA elastomers are crosslinked under (1.1Torr).
2):With PSeHCD from as crosslinking agent, the high-ductility elastomer covalently combined with non-covalent bond is formed.It will directly prepare Good PSeHCD polymer is transferred in required given shape tetrafluoro mould and entered under 120 DEG C of vacuum conditions (1.1Torr) Row vacuum crosslinking 48,60,72h prepares PSeHCD-48, PSeHCD-60 and PSeHCD-72 high-ductility elastomers respectively.
Fig. 7 is a series of mechanical property of PSeHCD cross-linked elastomers, and wherein PSeHCD-48.60.72 elastomers are shown PSeHCD-SA elastomers in the case where keeping relatively low Young's modulus relatively compared to addition cross-linking agents have 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 elastomers can be one Determine to be controlled by crosslinking time in scope;
Fig. 9 is PSeHCD polymer (A-C), and PLGA control groups (D-F) and TCPs control groups (G-I) are respectively in Isosorbide-5-Nitrae, 7 The CCK-8 biocompatibility experiments of its culture mouse bone-forming cell, it can be seen that the cell number of PSeHCD cultures from data (J) No less than control experiment group, good biocompatibility is embodied.# represents to be less than 0.01 relative to previous time point value Significant difference;* the significant difference less than 0.05 relative to PLGA groups numerical value is represented.

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 is:
N=20-40.
2. a kind of preparation method of functional poly ester polyurethane alternate copolymer as claimed in claim 1, including:
(1) under protective gas atmosphere, epoxy prapanol, hexamethylene diisocyanate, solvent are mixed, then in oil bath 30- Stirring reaction under the conditions of 50 DEG C, purification, obtains own diamino acid diglyceride;
(2) under the conditions of anhydrous and oxygen-free, after own diamino acid diglyceride, decanedioic acid, TBAB are mixed, add Solvent, under protective gas atmosphere, stirs and oil bath is gradually from room temperature to 100 DEG C so that reactant all dissolves, dissolving After be kept stirring for reacting 40-60h with the conditions of anhydrous and oxygen-free environment and oil bath, obtain sundown solution, then purify, obtain Functional poly ester polyurethane alternate copolymer.
3. a kind of preparation method of functional poly ester polyurethane alternate copolymer according to claim 2, it is characterised in that:It is 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:It is described Epoxy prapanol in step (1):Hexamethylene diisocyanate mol ratio is 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:It is 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:It is described Stirring reaction is in step (1):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:It is described Own diamino acid diglyceride, decanedioic acid mol ratio are 1 in step (2):1, reactant quality:Solvent volume=1g:1- 2mL;TBAB is that reactant feeds intake the 0.85% of mole;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:It is described Stir speed (S.S.) 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:It is described Purification is specially in step (2):Sundown solution is added dropwise in the sedimentation agent of rotation, centrifugal sedimentation, repeats 3-5 times, take out Vacuum.
10. a kind of application of functional poly ester polyurethane alternate copolymer as claimed in claim 1, it is characterised in that:The poly- ammonia of polyester Application of the ester alternate copolymer in PSeHCD elastomers or functionalization biomaterial is prepared.
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CN111187393A (en) * 2020-02-19 2020-05-22 中科院广州化灌工程有限公司 Hyperbranched epoxy resin, hyperbranched epoxy resin-based building structure adhesive, preparation and application

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FR3007206B1 (en) * 2013-06-12 2016-09-02 Commissariat Energie Atomique METHOD FOR MANUFACTURING A SECONDARY BATTERY
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FR3007206B1 (en) * 2013-06-12 2016-09-02 Commissariat Energie Atomique METHOD FOR MANUFACTURING A SECONDARY BATTERY
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Publication number Priority date Publication date Assignee Title
CN111187393A (en) * 2020-02-19 2020-05-22 中科院广州化灌工程有限公司 Hyperbranched epoxy resin, hyperbranched epoxy resin-based building structure adhesive, preparation and application

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