CN107033338A - One kind is poly-（Decanedioyl base glycerol diester）The preparation method of shape memory elastic body - Google Patents

One kind is poly-（Decanedioyl base glycerol diester）The preparation method of shape memory elastic body Download PDF

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CN107033338A
CN107033338A CN201710249299.8A CN201710249299A CN107033338A CN 107033338 A CN107033338 A CN 107033338A CN 201710249299 A CN201710249299 A CN 201710249299A CN 107033338 A CN107033338 A CN 107033338A
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poly
shape memory
decanedioyl base
glycerol diester
elastic body
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CN107033338B (en
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游正伟
耿聪颖
轩慧霞
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Donghua University
National Dong Hwa University
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • 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
    • C08G2280/00—Compositions for creating shape memory
    • 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

Abstract

The present invention relates to a kind of preparation method of poly- (decanedioyl base glycerol diester) shape memory elastic body, including：(1) monomer decanedioyl base ethylene oxidic ester is prepared；(2) prepare poly- (decanedioyl base glycerol diester)；(3) poly- (decanedioyl base glycerol diester) shape memory elastic body is prepared.The degree of cross linking of the invention by adjusting PSeD, make the PSeD after crosslinking simultaneously flexible, SME and thermoplasticity, PSeD after crosslinking has good shape-memory properties, and transfer of shapes temperature is between room temperature and human body temperature, it is expected to develop into the intellectual material (having been achieved with the shape-memory properties near human body temperature) of the shape memory of body temperature response.

Description

A kind of preparation method of poly- (decanedioyl base glycerol diester) shape memory elastic body
Technical field
The invention belongs to shape memory elastic body field, more particularly to a kind of poly- (decanedioyl base glycerol diester) shape memory Method for producing elastomers.
Background technology
After so-called " shape memory " refers to that the product with original shape is fixed through deformation, pass through heat energy, luminous energy, electric energy It can be made extensive again etc. the processing that the chemical factor such as physical factor and acid-base value, phase in version reaction and chelatropic reaction is stimulation means The phenomenon of multiple original shape.Shape-memory material includes marmem, shape memory ceramics and shape-memory polymer.With Marmem and ceramic phase ratio, shape-memory polymer have deformation quantity big, and deformation temperature is adjustable and can functionalization Advantage, some polymer also have biocompatibility and biological degradability, it is had very big application in bio-medical field Potentiality.
Bioelastomer (elastomer degradable and with biocompatibility) is widely used in bio-medical field, Such as medicament slow release, the support for organizational project.Bioelastomer would generally be divided into two major classes：Thermoplastic elastomer (TPE) and thermosetting Elastomer.Poly- decanedioic acid glyceride (PGS) is a kind of typical thermosetting bioelastomer, its good elasticity, bio-compatible Property and biodegradability it is had many potential applications, such as cardiac patch in bio-medical field, tissue engineering bracket, operation Glue.Shape memory elastic body is a kind of new stimulating responsive material, under extraneous certain stimulation, and it can be from one temporarily When recovery of shape to original-shape, this characteristic has very big application potential in bio-medical field, and such as bone is filled, blood vessel branch Application on frame, particularly medicament slow release, Minimally Invasive Surgery.The porous support reduced after deformation is implanted into human body by Minimally Invasive Surgery After interior, under the stimulation of body temperature, porous support is returned to original shape, this process simplification surgical procedure, subtracts Small operation risk, it is both simple and effective.Therefore, the transfer of shapes temperature (Ttrans) for the material of Minimally Invasive Surgery need to be in people Near temperature.PGS has also been studied in the application potential of intelligent response, for example, PGS SME.But report PGS transfer of shapes temperature below room temperature, no Practical significance.Accordingly, it would be desirable to by improving PGS molecular structures, improving it Crystalline method, makes PGS materials have excellent SME near human body temperature (37 DEG C).
PGS prepolymers are semi-crystalline polymer at room temperature, its fusing point (Tm) near human body temperature, it can just make For transfer of shapes temperature, but after PGS crosslinkings, its fusing point there occurs obvious decline.The PGS of document report transfer of shapes temperature Degree is near 10.8 DEG C (fusing point), and this temperature makes its temporary shapes can not keep at room temperature, limits it in practice Application.Therefore, it is necessary to prepare the PGS with higher melt for actual internal medical application.And poly- decanedioyl Diglyceride (PSeD) is synthesized by epoxy ring opening reaction, with the new polyester with PGS strand similar structures, and With good biological degradability and biocompatibility, there is very big application potential in organizational project.Compared with PGS, PSeD tools There is more regular structure, so as to make it have the crystallization temperature and crystallinity higher than PGS.Meanwhile, PSeD still has PGS's Biodegradability and biocompatibility.Therefore, PSeD is a good selection for the shape-memory material in human body.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of poly- (decanedioyl base glycerol diester) shape memory elastic body Preparation method, this method makes flexible, the SMEs simultaneously of the PSeD after crosslinking by adjusting the PSeD degree of cross linking And thermoplasticity, the PSeD after crosslinking has good shape-memory properties, and transfer of shapes temperature is between room temperature and human temperature Between degree, it is expected to develop into the intellectual material of the shape memory of body temperature response.
A kind of preparation method of poly- (decanedioyl base glycerol diester) shape memory elastic body of the present invention, including：
(1) glycidol, triethylamine and toluene are mixed in the container handled through anhydrous and oxygen-free, treats that temperature drops to -10 After~5 DEG C, 5~10 hours of sebacoyl chloride keeping temperature stirring reaction are added；Reaction steams reacting liquid filtering, rotation after terminating Hair removes solvent, and decanedioyl base ethylene oxidic ester is obtained by column chromatography；Wherein, sebacoyl chloride, glycidol and triethylamine Mol ratio is 1:1.2:1-8；
(2) decanedioyl base ethylene oxidic ester, decanedioic acid and TBAB are mixed in organic solvent, 90~180 DEG C, the lower stirring reaction 10min~30min of protective atmosphere protection；Reaction washs reaction solution after terminating, and vacuumizes, obtains the poly- (last of the ten Heavenly stems Diacylglycerol diester)；Wherein, the mol ratio of decanedioyl base ethylene oxidic ester and decanedioic acid is 1:0.7-1.5；
(3) by poly- (decanedioyl base glycerol diester) at 120~130 DEG C, 6-12h is not vacuumized, 3-9h progress is vacuumized Crosslinking, produces poly- (decanedioyl base glycerol diester) shape memory elastic body.
The solvent that column chromatography in the step (1) is used is the mixed solution of ethyl acetate and petroleum ether；Wherein, second The volume ratio of acetoacetic ester and petroleum ether is 1:3-1:15.
Decanedioic acid in the step (2) first passes through purifying in advance.
The addition of TBAB in the step (2) is the 0.1- of decanedioyl base ethylene oxidic ester consumption 3mol%.
Organic solvent in the step (2) is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, dichloro One or more in methane, chloroform, tetrahydrofuran.
The transfer of shapes temperature of poly- (the decanedioyl base glycerol diester) shape memory elastic body obtained in the step (3) exists Human body temperature nearby (37 DEG C) and with remodeling performance, and remold after poly- (decanedioyl base glycerol diester) still have shape remember Recall performance.
Cross linking conditions of the invention by controlling PSeD, make crosslink part be enough to maintain permanent shape and elasticity, and not enough To fetter the motion of whole system strand, and crystalline portion is enough to maintain temporary shapes, so as to prepare a kind of response temperature The thermoplasticity PSeD elastomers with SME spent near body temperature.In glass transition temperature (Tg) and viscosity flow temperature Spend in (Tf) this temperature range, the PSeD after crosslinking is in elastomeric state, shape recovery process is carried out in this temperature range.One Denier temperature be higher than flow temperature, strand setting in motion, disentanglement between chain and chain, because the degree of cross linking is relatively low, crosslink part Strand still can be moved in the presence of uncrosslinked part, so that whole system is in viscosity flow state, can be easily Remolded.In addition, on PSeD strand main chains with residual hydroxyl can with multiple biological activities molecular action so that PSeD functionalization is realized, the application field of PSeD shape memories has been widened.In PSeD SME, strand it Between crosslinking points and tangle provide permanent shape, and crystalline portion provide temporary shapes.After PSeD is implanted into the human body, crystallization Partial melting, PSeD returns back to original shape.
Beneficial effect
The present invention makes the PSeD after crosslinking simultaneously flexible by adjusting the PSeD degree of cross linking, SME with And thermoplasticity, the PSeD after crosslinking has good shape-memory properties, and transfer of shapes temperature is (37 near human body temperature DEG C), it is expected to develop into the shape memory intellectual material of body temperature response.
Brief description of the drawings
Fig. 1 is the DSC curve of the PSeD shape memory elastic bodies of different crosslinking times；
Fig. 2 is that PSeD circulates stress-strain-Temperature-time X-Y scheme that shape memory is characterized；
Fig. 3 is the displaying of the macroshape memory effect of PSeD shape memory elastic bodies；
Fig. 4 is the remodelled shape of PSeD shape memory elastic bodies；
Fig. 5 is the displaying of shape memory after PSeD is remolded.
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
(1) purifying of raw material
The recrystallization of decanedioic acid：50g decanedioic acid to be purified is weighed, in the three neck round bottom flask for adding 500ml, adds and turns Son, connects condensation reflux unit, in the oil bath pan that flask is placed in 80 DEG C, is gradually added into ethanol stirring, until solution clarification, the last of the ten Heavenly stems Diacid is completely dissolved, and the solution in flask is poured into beaker, room temperature cooling, and standing makes decanedioic acid crystallization precipitation, carries out afterwards Suction filtration.Above step in triplicate after, by product be placed in 60 DEG C of vacuum drying oven dry 24h.
(2) synthesis of PSeD monomers decanedioyl base ethylene oxidic ester
The water in toluene is removed with sodium silk, dry toluene is obtained after backflow standby.Removed with sodium hydroxide in triethylamine It is standby that anhydrous triethylamine is obtained after water, backflow.500ml three neck round bottom flask is subjected to anhydrous and oxygen-free processing, respectively with injection Device extracts 4ml glycidols, and 15ml anhydrous triethylamines and 90ml dry toluenes are added in flask, and flask is put into ice and second afterwards In alcohol mixing bath (- 10 DEG C).Then 5ml sebacoyl chloride is added drop-wise in flask dropwise, 7h is reacted.After reaction terminates, by institute Obtained product is filtered with diatomite, after filtrate concentrated by rotary evaporation, by petroleum ether and ethyl acetate with 3:The ratio of 1 (volume ratio) The mixed solvent being mixed to get is purified as solvent by column chromatography to product.With1H NMR determine resulting The structure of PSeD monomers.
(3) PSeD synthesis
Reaction tube is subjected to anhydrous and oxygen-free processing, PSeD monomers (0.2006g), decanedioic acid are sequentially added under nitrogen atmosphere (0.3149g), TBAB (0.0043g) and 1ml N '-N '-dimethyl formamide (DMF).Under nitrogen protection, 100 DEG C stirring 10min, is warming up to 180 DEG C, stirs 16min, reaction terminates.Products therefrom is washed 3 times with ether, 24h is vacuumized and removes Excess of solvent is removed, PSeD white solids are obtained.
(4) PSeD fusing point can be adjusted by controlling the degree of cross linking：It will be seen from figure 1 that constant in crosslinking temperature In the case of, with the increase of crosslinking time, PSeD fusing point is gradually reduced, and melting enthalpy is gradually reduced.Need to choose a conjunction Suitable crosslinking time, makes PSeD battens both have sufficiently elasticity, has enough crystallinity again to fix temporary shapes, and melt Point need to be near human body temperature, in Fig. 1, and the pumpdown time between 4h and 8h, after trial, is chosen at 120 DEG C, no 12h is vacuumized, 7h cross linking conditions are vacuumized.Crosslinking PSeD used below is prepared according to this cross linking conditions.
(5) shape memory effect of different crosslinking times is characterized：
Table 1 is the shape fixed rate and recovery rate in the PSeD batten loop tests after crosslinking
Cycle 1st 2nd 3rd 4th 5th 6th
(%) 99.98 99.97 99.97 99.97 99.98 99.97
(%) 93.29 91.97 95.82 96.58 96.23 97.75
The SME of PSeD after crosslinking is characterized by DMA.Should from the crosslinking typical shape memories of PSeD Stress-strain can be seen that in the temperature rise period with temperature curve (Fig. 2), at about 30 DEG C, that is, at the fusing point of the PSeD after being crosslinked, PSeD battens after crosslinking start to reply, and illustrate that the temporary shapes of PSeD after crosslinking are provided by PSeD crystalline portion.In addition, from Table 1 can show that the shape fixed rate and shape recovery rate of the batten are respectively 99.98% and 93.29%, illustrate after crosslinking PSeD has good shape-memory properties, and transfer of shapes temperature is between room temperature and human body temperature, is expected to develop into body The intellectual material of the shape memory of temperature response.
In addition, loop test has been carried out to the shape-memory properties of PSeD battens, as shown in Fig. 2 the test is circulated altogether Six times, the shape fixed rate circulated every time is close to 100%, and shape recovery rate (table 1) more than 90% illustrates after circulation, crosslinking The shape-memory properties of PSeD battens afterwards can still be kept.For with the increase of cycle-index, in the work of identical power Under, the elongation of batten is gradually reduced, it should mainly due to batten with stretching, and strand more easily rearranges knot Crystalline substance, so that crystallinity increase, crystallizes at 37 DEG C and be not wholly absent, batten is not in, entirely without stabilized condition, making elongation Reduce.Finally, it can be kept at room temperature to probe into the temporary shapes after batten is fixed, the heating tested in shape memory Cheng Zhong, temperature is risen to after 25 DEG C, insulation 20min, then is warming up on transfer of shapes temperature, because cyclic tension ties it Brilliant degree increase, so final temperature is risen into 45 DEG C from 37 DEG C.As a result show, in 25 DEG C of holding stages, the shape of batten is kept Rate is 100%, illustrates the temporary shapes of batten at room temperature and can keep well (Fig. 2).
As shown in figure 3, the PSeD battens after the crosslinking of strip are stretched at 37 DEG C, stretching retrotorsion or curling, afterwards 10min solid shapes are placed in the environment of -20 DEG C, temporary shapes can stably be kept after taking-up, finally by after deformation Batten is placed into 37 DEG C of water-bath, batten shape Quick-return, and its original-shape can be returned back in 10s.Illustrate after crosslinking PSeD there is the SME of quick response.As shown in figure 4, the PSeD battens after the crosslinking of strip can be remolded into not Similar shape, still has shape-memory properties (Fig. 5) with the PSeD battens remolded after performance, and remodeling.

Claims (6)

1. a kind of preparation method of poly- (decanedioyl base glycerol diester) shape memory elastic body, including：
(1) glycidol, triethylamine and toluene are mixed in the container handled through anhydrous and oxygen-free, after temperature drops to -10 DEG C, Add 5~10 hours of sebacoyl chloride keeping temperature stirring reaction；Reacting liquid filtering, rotary evaporation are removed molten by reaction after terminating Agent, decanedioyl base ethylene oxidic ester is obtained by column chromatography；Wherein, the mol ratio of sebacoyl chloride, glycidol and triethylamine is 1:1.2:1-8；
(2) decanedioyl base ethylene oxidic ester, decanedioic acid and TBAB are mixed in organic solvent, 90~180 DEG C, guarantor Protect stirring reaction 10min~30min under atmosphere protection；Reaction washs reaction solution after terminating, and vacuumizes, obtains poly- (decanedioyl Base glycerol diester)；Wherein, the mol ratio of decanedioyl base ethylene oxidic ester and decanedioic acid is 1:0.7-1.5；
(3) by poly- (decanedioyl base glycerol diester) at 120~130 DEG C, 6-12h is not vacuumized, 3-9h is vacuumized and is crosslinked, Produce poly- (decanedioyl base glycerol diester) shape memory elastic body.
2. the preparation method of poly- (the decanedioyl base glycerol diester) shape memory elastic body of one kind according to claim 1, its It is characterised by：The solvent that column chromatography in the step (1) is used is the mixed solution of ethyl acetate and petroleum ether；Wherein, The volume ratio of ethyl acetate and petroleum ether is 1:3~1:15.
3. the preparation method of poly- (the decanedioyl base glycerol diester) shape memory elastic body of one kind according to claim 1, its It is characterised by：Decanedioic acid in the step (2) first passes through purifying in advance.
4. the preparation method of poly- (the decanedioyl base glycerol diester) shape memory elastic body of one kind according to claim 1, its It is characterised by：The addition of TBAB in the step (2) is the 0.1- of decanedioyl base ethylene oxidic ester consumption 3mol%.
5. the preparation method of poly- (the decanedioyl base glycerol diester) shape memory elastic body of one kind according to claim 1, its It is characterised by：Organic solvent in the step (2) is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, dichloro One or more in methane, chloroform, tetrahydrofuran.
6. the preparation method of poly- (the decanedioyl base glycerol diester) shape memory elastic body of one kind according to claim 1, its It is characterised by：The transfer of shapes temperature of poly- (the decanedioyl base glycerol diester) shape memory elastic body obtained in the step (3) Still there is good shape near human body temperature and with poly- (the decanedioyl base glycerol diester) remolded after performance, and remodeling Memory performance.
CN201710249299.8A 2017-04-14 2017-04-17 A kind of preparation method of poly- (decanedioyl base glycerol diester) shape memory elastic body Active CN107033338B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109503822A (en) * 2018-12-04 2019-03-22 东华大学 A kind of preparation method of organic photo-thermal macromolecular with biocompatibility
CN110859996A (en) * 2019-10-18 2020-03-06 叶晓峰 Heart patch
CN109621002B (en) * 2018-12-04 2021-08-31 东华大学 Self-healing shape memory porous scaffold with bioactivity and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109503822A (en) * 2018-12-04 2019-03-22 东华大学 A kind of preparation method of organic photo-thermal macromolecular with biocompatibility
CN109503822B (en) * 2018-12-04 2019-12-31 东华大学 Preparation method of organic photo-thermal macromolecule with biocompatibility
CN109621002B (en) * 2018-12-04 2021-08-31 东华大学 Self-healing shape memory porous scaffold with bioactivity and preparation method and application thereof
CN110859996A (en) * 2019-10-18 2020-03-06 叶晓峰 Heart patch

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