CN105017538A - Degradable shape memory high polymer material of regular network structure and preparation method therefor - Google Patents
Degradable shape memory high polymer material of regular network structure and preparation method therefor Download PDFInfo
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- CN105017538A CN105017538A CN201510205953.6A CN201510205953A CN105017538A CN 105017538 A CN105017538 A CN 105017538A CN 201510205953 A CN201510205953 A CN 201510205953A CN 105017538 A CN105017538 A CN 105017538A
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Abstract
The invention relates to a degradable shape memory high polymer material of a regular network structure and a preparation method therefor. The degradable shape memory high polymer material is characterized in that the degradable shape memory high polymer material of the regular network structure is obtained through step-growth polymerization of various equal-arm-length tetrahedral structure four-arm macromonomers with different special functional groups by utilizing an efficient click chemistry method. Different components of the network and compatibility and network soft and hard area distribution can be adjusted by selecting different four-arm macromonomers, so that the material has suitable microphase separation and different phase inversion temperatures to endow the shape memory performance. The preparation method can control the microstructure, shape memory performance, thermodynamic property and degradability of the material by adjusting the contents, types and molecular weights of the four-arm macromonomers, and is an effective method for obtaining the degradable shape memory high polymer material with excellent shape memory performance and high mechanical performance.
Description
Technical field
The present invention relates to the preparation method of the degradable shape memory high molecule material with regular network structure.The various four arm macromonomers with different specific functional groups are cross-linked the degradable shape memory high molecule material obtaining regular network structure through efficient click chemistry method, belong to polymer field of new.
Background technology
Shape-memory polymer is that one can respond external stimulus, and adjusts oneself state parameter, thus is returned to a kind of intelligent macromolecule material of the state of presetting.It has that stimulation mode variation, deflection are large, performance and adjustable, the easy processing of response condition, figuration easily, light weight and the feature such as inexpensive, become a new focus of intelligent macromolecule material research, development and application in recent years, show very wide application in fields such as intelligent textile materials, bio-medical material, aeronautical and space technology, microfluidic control technology and 3D printings.
Along with the in-depth be familiar with shape-memory polymer stuctures and properties, and the development of high molecular polymer synthetic technology, become a reality with the shape-memory material obtaining expected structure and performance by molecular designing.Material can represent the special property that shape memory effect is not certain polymkeric substance, but the synergistic result of the Structure and form of material.Which provides a kind of possibility, namely some new structures and Shape memory mechanism are combined, synthesize the shape memory thing material with excellent properties by the adjustment of molecular designing and molecular structure.Colourful nature is that the discovery and application of novel texture provides good enlightenment.
Organic sphere has reached through its structure and fuction of evolution in 2,000,000,000 years and has been close to perfect degree, achieves coordination and the unification of structure and fuction and local and global deformation.To naturally learning the important source having become high performance material development, such as, " the biological steel " of the super-hydrophobic automatic cleaning coating material of bionical lotus leaf surface, bionical spider silk, the swim suit etc. of the super cohesive material of bionic gecko pin or mussel, the ceramic toughening matrix material of bionical shell pearl layer and bionical shark skin.Utilize bionic design advanced function material to become the forward position of investigation of materials, and become the tidemark of design of material.
Marine organisms jellyfish can be made response rapidly to stimulation and then can produce strong impellent to seawater, can move about by stretched and relaxed ground fast free.Why jellyfish can be made fast stimulating, the key of coherency response to be in medusa to arrange in its muscle camber order and form networking and determined by exteroceptive " pacemaker " cell, and such jellyfish can realize the synchronism of stimulating responsive on space-time and then can make responding and produce strong impellent fast.Inspire by this, we design and have prepared a kind of shape memory high molecule material with height regularity network structure, the molecular switch that to make in material enough responses stimulate (can the anti-phase) arranged distribution of regularity in material network structure, realize the synchronism of stimulating responsive on space-time, thus improve the shape-memory properties of material.Essence due to the molecule mechanism of shape memory high molecule material is the principle of entropy increase based on the change of system interior molecules chain conformation.At a certain temperature by External Force Acting figuration, be reduced to transition temperature (T
trans) high molecular sub-chain motion is frozen below, thus stoping curling of molecular chain, the shape of material is fixed; And at T
transabove, the sub-chain motion of curling molecule is activated, and make it towards the change of state of maximum conformational entropy, material is replied.Therefore, in order to obtain the fully charge of sub-chain motion, at T
transfollowing Inhibitory molecules chain is curled and higher than T
transtime complete activating molecules chain, build that to have the shape memory networks that " height regularity network structure " distribute be desirable method.Because utilize regular network structure can the interaction force of Molecular regulator interchain effectively, make it dispersed at material internal, macromolecular chain can conformingly move, and equally distributed molecular switch (can anti-phase) consistently can transmit extraneous thermal stimulus fast on space-time, so corresponding polymer segment is at T
transcan obtain completely up and down, freeze fast and activation.Therefore, more excellent shape-memory properties can be obtained by the design of regularity network structure.
On the other hand, for height regularity network structure shape memory macromolecular material, due to cross-linking set distribution, very evenly, between cross-linking set the length of molecular chain is consistent, when being out of shape stretching, network structure can cooperative bearing, internal stress is dispersed on different macromolecular chain, can improve the mechanical property of material.And the shape-memory polymer of random crosslinking, crosslink density skewness, molecular chain length are inconsistent, and when being out of shape stretching, height cross-linked areas exists irreversible molecular rupture, not only damage mechanical property but also weaken shape-memory properties.Therefore, height regularity network structure is incorporated into shape-memory material, is not only conducive to improving the shape-memory properties of shape memory high molecule material, but also can the mechanical property of strongthener.
Summary of the invention
The present invention relates to degradable shape memory high molecule material with regular network structure and preparation method thereof.Be characterized in utilizing efficient click chemistry method the various brachium tetrahedral structure four arm macromonomer that waits with different specific functional groups can be increased through step the degradable shape memory high molecule material that polymerization obtains regular network structure.By design and the adjustment of molecular structure, four different arm macromonomers can be selected to adjust different components and consistency, the network soft or hard areal distribution of these networks, make it have suitable microphase-separated and different phase transition temperatures thus give shape-memory properties.This shape-memory polymer uses different click chemistry methods according to the difference of four arm macromonomer functional groups.This preparation method, by regulating the content of four arm macromonomers, kind and molecular weight to control the microtexture of material, shape-memory properties, thermomechanical property and degradability, is a kind of effective ways obtaining the degradable shape memory high molecule material of excellent shape memory performance and high-mechanical property.As degradable shape-memory material, the shape memory high molecule material related in the present invention is particularly useful for biomedical materials field, as timbering material, operating sutures, medicine controlled releasing and Minimally Invasive Surgery device etc.
The object of the present invention is to provide and a kind ofly utilize efficient click chemistry method that the various brachium tetrahedral structure four arm macromonomer that waits with different specific functional groups to be increased the method for the degradable shape memory high molecule material of the regular network structure of polymerization preparation through step.This invention is that the degradable shape-memory material constructing regular network structure provides a kind of general method by efficient, modular click chemistry method.The microtexture of material, shape-memory properties, thermomechanical property and degradability can be controlled by the content of simple adjustment four arm unit molecule monomer, kind and molecular weight, and because of the height regularity of regular network structure, the degradable shape memory high molecule material of excellent shape memory performance and high-mechanical property can be obtained.
For reaching above-mentioned target, the invention provides a kind of method preparing the degradable shape memory high molecule material of regular network structure: there is four arm macromonomers of different functional groups, catalyzer or initiator and solvent and add in reaction flask according to certain ratio and order, stirred at ambient temperature dissolves, and injects reaction mould.By heating or illumination reaction regular hour, after the demoulding, drying at room temperature can obtain the shape-memory material of regular network structure.
In the present invention, the proportioning of the degradable shape memory high molecule material of regular network structure is:
A: four arm macromonomers (different functional group's ratios is 1: 1) 70-89wt%
B: initiator or catalyzer 0.1-1wt%, C: solvent 10%-30%
Wherein, in said ratio:
A tetra-arm macromonomer, choose the degradable four arm macromonomers with different functional groups, as four arms gather D, L-rac-Lactide, four arm polycaprolactones, four arms gather muscolactone, four arm PLLAs, four arm PGAs, four arms gather the monomers such as 2-oxepane-1,5-diketone, four arm PPDO, four arm copolymers or terpolymer one or more.
The end functional groups of B tetra-arm macromonomer, choose and can occur to click the functional group of chemical reaction, as four arm macromonomers of four arm macromonomers of azido-end-blocking and four arm macromonomers of alkynyl functionalization, four arm macromonomers of sulfydryl end-blocking and alkynyl or thiazolinyl functionalization, diene (methyl furan) functionalization four arm macromonomer and dienophile (MALEIC ANHYDRIDE) functionalization four arm macromonomer, four arm macromonomers of tetrazolium functionalization and the four arm macromonomers etc. of thiazolinyl functionalization.
C initiator or catalyzer, xitix sodium reduction CuSO selected by catalyzer
4system, CuI, Cu (I) (PPh
3)
3br etc.; Initiator selects azo or organic peroxy class initiator or various light trigger.
D solvent, chooses and can promote the dispersion of A, B and C and add appropriate solvent, requires that toxicity is little, and solvability is good.
In order to prepare shape-memory material, the second-order transition temperature of polymkeric substance, fusing point and the molecular weight that form mainly through changing B obtain the macromolecular material of a series of shape-memory properties.
Embodiment
Below in conjunction with embodiment, the invention will be further described.Subject area involved in the present invention is not limited only to this 6 examples, and should with being as the criterion of limiting in claim.
Example 1
A tetra-arm macromonomer
Azido-functionalization four arm PDLLA (M
n=23000) 3g
End alkynyl radical functionalization four arm PDLLA (M
n=23000) 3g
B catalyzer
CuI 0.06g
C solvent
Methylene dichloride 48g
Reaction formula is as follows:
Its preparation method is: azido-and end alkynyl radical functionalization four arm macromonomer, CuI and methylene dichloride add in reaction flask, and stirred at ambient temperature dissolves, and injects reaction mould.6-12 hour is reacted, the dry shape-memory material that can obtain regular network structure after the demoulding under 60 DEG C of conditions.
Product index:
Second-order transition temperature: 46 DEG C;
Shape recovery ratio at 51 DEG C: 99%;
Shape time of recovery: 5 seconds.
Example 2
A tetra-arm macromonomer
Mercapto-functionalized four arm polycaprolactone (M
n=46000) 3g
Norbornylene functionalization four arm polycaprolactone (M
n=46000) 3g
B catalyzer
Light trigger (2-hydroxyl-4 '-(2-hydroxyl-oxethyl)-2-methyl phenyl ketone) 0.06g
C solvent
Methylene dichloride 48g
Reaction formula is as follows:
Its preparation method is: sulfydryl and norbornylene functionalization four arm macromonomer, light trigger and methylene dichloride add in reaction flask, and stirred at ambient temperature dissolves, and injects reaction mould.Ultraviolet lighting reaction 1-10 minute at ambient temperature, the dry shape-memory material that can obtain regular network structure after the demoulding.
Product index:
Fusing point: 54 DEG C;
Shape recovery ratio at 70 DEG C: 99%;
Shape time of recovery: 11 seconds.
Example 3
A tetra-arm macromonomer
Methyl furan functionalization four arm polylactide-co-caprolactone (M
n=10500) 3g
MALEIC ANHYDRIDE functionalization four arm polylactide-co-caprolactone (M
n=10500) 3g
B catalyzer
Light trigger (2-hydroxyl-4 '-(2-hydroxyl-oxethyl)-2-methyl phenyl ketone) 0.06g
C solvent
Methylene dichloride 48g
Reaction formula is as follows:
Its preparation method is: methyl furan and MALEIC ANHYDRIDE functionalization four arm polylactide-co-caprolactone, light trigger and methylene dichloride add in reaction flask, and stirred at ambient temperature dissolves, and injects reaction mould.6-12 hour is reacted, the dry shape-memory material that can obtain regular network structure after the demoulding under 37 DEG C of conditions.
Product index:
Second-order transition temperature: 36 DEG C;
Shape recovery ratio at 40 DEG C: 99%;
Shape time of recovery: 14 seconds.
Example 4
A tetra-arm macromonomer
Double-bond functionalized four arm polylactide-co-2-oxepane-1,5-diketone (Mn=10000) 3g
Tetrazolium functionalization four arm polylactide-co-2-not oxygen hexane-1,5-diketone (Mn=10000) 2g
Tetrazolium functionalization four arm polycaprolactone (Mn=10000) 1g
B initiator
No initiator
C solvent
Methylene dichloride 48g
Reaction formula is as follows:
Its preparation method is: double bond and tetrazolium functionalization functionalization four arm polylactide-co-2-oxepane-1,5-diketone, tetrazolium functionalization four arm polycaprolactone, methylene dichloride add in reaction flask, and stirred at ambient temperature dissolves, and injects reaction mould.Ultraviolet lighting reaction 1-10 minute at ambient temperature, the dry shape-memory material that can obtain regular network structure after the demoulding.
This material has shape-memory properties, and primary product index is as follows:
Sparkling transition temperature: 38 DEG C;
Shape recovery ratio at 38 DEG C: 99%;
Shape time of recovery: 8 seconds.
Claims (9)
1. one kind has the degradable shape memory high molecule material of regular network structure, adopt the click chemistry between four arm degradable macromonomers to react the degradable shape memory high molecule material obtaining and have regular network structure, it is characterized in that degradable regular network structure has shape-memory properties.
2. the degradable shape memory high molecule material with regular network structure according to claim 1, it is characterized in that this macromolecular material has regularity network structure, the shape-memory properties can giving material excellence comprises replys speed and high response rate fast.
3. the degradable shape memory high molecule material with regular network structure according to claim 1, is characterized in that this macromolecular material has excellent mechanical property and degradability.
4. the degradable shape memory high molecule material based on regular network structure according to claim 1, when it is characterized in that preparing, proportioning raw materials is:
A: four arm macromonomers (different functional group's ratios is 1: 1) 70-89wt%
B: initiator or catalyzer 0.1-1wt%
C: solvent 10%-30%.
5. the degradable shape memory high molecule material with regular network structure according to claim 1, it is characterized in that its preparation method is: there is four arm macromonomers of different functional groups, catalyzer or initiator and solvent and add in reaction flask according to certain ratio and order, stirred at ambient temperature dissolves, inject reaction mould, by heating or illumination reaction regular hour, after the demoulding, drying at room temperature can obtain the shape-memory material of regular network structure.
6. the degradable shape memory high molecule material based on regular network structure according to claim 4 or 5, it is characterized in that choosing degradable four arm macromonomers, four arm macromonomers are that four arms gather D, L-rac-Lactide, four arm polycaprolactones, four arms gather muscolactone, four arm PLLAs, four arm PGAs, four arms gather 2-oxepane-1,5-diketone, four arm PPDO or four arm copolymer or terpolymers between them.
7. the degradable shape memory high molecule material based on regular network structure according to claim 6, it is characterized in that choosing the functionalized four arm macromonomers that can occur to click chemical reaction, four arm macromonomers are four arm macromonomers of azido-end-blocking and four arm macromonomers of alkynyl functionalization, four arm macromonomers of four arm macromonomers of sulfydryl end-blocking and alkynyl or thiazolinyl functionalization, diene (methyl furan) functionalization four arm macromonomer and dienophile (MALEIC ANHYDRIDE) functionalization four arm macromonomer, four arm macromonomers of tetrazolium functionalization and four arm macromonomers of thiazolinyl functionalization.
8. the degradable shape memory high molecule material based on regular network structure according to claim 7, is characterized in that four arm macromonomers of same functionalization can be dissimilar one, two or more macromonomers.
9., according to the degradable shape memory high molecule material of claim 5 based on regular network structure, it is characterized in that xitix sodium reduction CuS0 selected by catalyzer
4, CuI, Cu (I) (PPh
3)
3br; Initiator selects azo, organic peroxy class thermal initiator or light trigger.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483757A (en) * | 2019-08-27 | 2019-11-22 | 四川大学 | It is a kind of novel highly selective to click dissaving polymer and preparation method and application |
Citations (2)
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|---|---|---|---|---|
| US6388043B1 (en) * | 1998-02-23 | 2002-05-14 | Mnemoscience Gmbh | Shape memory polymers |
| CN101475677A (en) * | 2008-12-18 | 2009-07-08 | 浙江大学 | Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof |
-
2015
- 2015-04-21 CN CN201510205953.6A patent/CN105017538A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6388043B1 (en) * | 1998-02-23 | 2002-05-14 | Mnemoscience Gmbh | Shape memory polymers |
| CN101475677A (en) * | 2008-12-18 | 2009-07-08 | 浙江大学 | Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| THOMAS DEFIZE等: ""Multifunctional Polye-caprolactone)-Forming Networks by Diels-Alder Cycloaddition:Effect of the Adduct on the Shape-Memory Properties"", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
| THOMAS DEFIZE等: ""Thermoreversibly Crosslinked Poly(e-caprolactone) as Recyclable Shape-Memory Polymer Network"", 《MACROMOLECULAR RAPID COMMUNICATIONS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483757A (en) * | 2019-08-27 | 2019-11-22 | 四川大学 | It is a kind of novel highly selective to click dissaving polymer and preparation method and application |
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Application publication date: 20151104 |
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