CN108503811A - A kind of polymer assigning polylactic acid shape memory - Google Patents
A kind of polymer assigning polylactic acid shape memory Download PDFInfo
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- CN108503811A CN108503811A CN201810382287.7A CN201810382287A CN108503811A CN 108503811 A CN108503811 A CN 108503811A CN 201810382287 A CN201810382287 A CN 201810382287A CN 108503811 A CN108503811 A CN 108503811A
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- pla
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- shape memory
- ptmg
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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
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of imparting polylactic acid（PLA）Four arm polymer of shape memory, the four arms polymer is with t etram-ethyltetravinylcyclotetrasiloxane（D4vi）For core, contain allyl glycidyl ether on support arm（AGE）Segment, PolyTHF（PTMG）Block, polycaprolactone（PCL）Block, wherein PTMG blocks can improve the toughness and hydrophily of PLA, and its lower glass transition temperatures can realize that thawing and recrystallization process, PCL blocks can greatly improve it in the compatibility of PLA, avoid being separated at low temperature.The four arms polymer is at a lower temperature（20‑50℃）Thawing can be realized and recrystallize and then assign PLA shape memory effect, and shape memory recovery time is short.Four arms polymer preparation is simple and efficient, and can be improved the toughness of PLA and be reduced its processing temperature to the utmost, it is made to have shape memory function.
Description
Technical field
The present invention relates to the shape memory field of PLA, more particularly to one kind point centered on cyclosiloxane, PTMG is soft embedding
Section, PCL are four arm polymer of increase-volume block, which has shape memory function with PLA blended compound materials.
Background technology
Have effigurate solid material, plastic deformation occurs under the stimulation of certain external condition, is passing through specific ring
The phenomenon that border stimulates, and material is completely recovered to shape before deforming again is referred to as shape memory effect.PLA is a kind of ideal green
High molecular material is in plastic state, and glass transition temperature is high, and processing temperature is high, and brittleness is high, is susceptible in use
Crackle and cannot reuse.Especially few to the research of PLA shape memories at present, most of is all by blending and modifying, and there are phases
The defect of capacitive difference easily causes to be separated.
According to realizing that the environmental condition of memory function is different, a variety of notes such as response to temperature, photosensitive type and sense soda acid type can be divided into
Recall material, the mainly thermo-stimulative shape memory polymer material of research at present and application at most.
Invention content
In order to overcome above-mentioned existing technological deficiency, the present invention provides a kind of polymer making PLA shape memories, shapes
Shape recovery time is short, while can be to avoid problem of phase separation, and effectively improves the toughness of PLA.
Technical scheme of the present invention：One kind is centered on cyclosiloxane, PTMG（T g =-76℃）For soft segment, PCL（Tg=-
60℃）For four arm polymer of increase-volume block, PLLA（T g =62℃）, due to the glass transition temperature of synthetic polymer and PLA
Differ more, to realize the shape memory of thermotropic PLA composite materials.
The division center of the four arms polymer：
The structure of PCL increase-volume blocks on the four arm polymer molecule support arms is as follows：
, n is the integer more than 1.
The structure of PTMG soft segments on the four arms polymer molecule support arm is as follows：
M is the integer more than 1.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of four arm polymer.
As shown in Figure 1, in D4vi-AGE-PTMG-PCL nuclear magnetic spectrograms, between 0~0.4ppm（a）For the change of-Si-CH3 hydrogen
Displacement study, 1.4ppm（b）, 1.6~1.7ppm（c）、2.4ppm（d）、3.5ppm（e）、3.7ppm（f）、4.1ppm（g）It is
- CH in AGE, PCL and PTMG2The chemical shift of middle hydrogen, on 6 or so ppm vinyl the chemical shift disappearance of hydrogen illustrate D4vi and
AGE is in addition.Using1The result of H-NMR characterizations illustrates one kind with cyclosiloxane dendroid node, and PolyTHF is soft
Block, polycaprolactone are four arm polymer of increase-volume block（D4vi-AGE-PTMG-PCL）It has synthesized.
Fig. 2 is the process that the four arm polymer prepared according to the present invention make PLA shape memories.
Specific implementation mode
The present invention is specifically described below by embodiment.
Embodiment 1：
It weighs in azo-bis-isobutyl cyanide to the ampoule bottle equipped with magnetic stirring bar, vacuumizes logical nitrogen, one is added by syringe
Quantitative D4vi and AGE, tetrahydrofuran make solvent, ampoule bottle are placed in 12h in 80 DEG C of oil baths.Then by products therefrom and in right amount
PTMG, which is put into 250ml three-necked flasks, leads to nitrogen, prevents high-temperature oxydation, being heated after 40min makes PTMG melt, and stirs；It will urge
The agent concentrated sulfuric acid is slowly dropped in a certain amount of tetrahydrofuran, is uniformly mixed, is then added drop-wise to reaction system, is warming up to
125 DEG C, stops leading to nitrogen, vacuumize and reacted instead.Add 50ml deionized waters after 4h into system, terminates reaction, and return
1h is flowed, then with 2 catalyst neutralisations of Ca (OH) and carries out liquid separation washing, the low waste of vacuum distillation removing.Product will be appealed in right amount
It is dried it to be added the flame equipped with magnetic stirring bar with toluene, in the purged ampoule bottle of nitrogen, adds caprolactone monomer,
45min is stirred at 65 DEG C.Octoate catalyst stannous toluene solution is added by syringe in bottle, 120 DEG C of reactions are warming up to
24h.Product is settled by petroleum ether, 40 DEG C of vacuum drying 12h.
By PLLA, D4 vi- AGE-PTMG-PCL in mass ratio 1:1 is added in chloroform solvent, wherein PLLA, D4vi-
The gross mass of AGE-PTMG-PCL is the 29% of solute and solvent gross mass, is stirred overnight at room temperature.The solution being stirred overnight is poured into
On glass plate, solution is allowed freely to be cast on a glass.In room temperature（20 DEG C or so）Normal pressure volatilizees two days naturally, waits for film in air
After middle solidification, then 25 DEG C of vacuum dryings are spare.
By pure PLA film（A）And composite membrane（B）50 DEG C of deformations are separately heated to, sizing is then cooled to room temperature, is heated to
50 DEG C of recoveries.Pure PLA is difficult machining deformation, and recovery effects unobvious at 50 DEG C.And composite membrane is easily added with this condition
Work deforms, and 50 DEG C are heated sample and restore its original shape again.
Claims (1)
1. a kind of four arm polymer assigning PLA shape memories, which is characterized in that the four arms polymer is block polymer, point
Contain PTMG soft segments and PCL increase-volume blocks on sub- support arm, centered on cyclosiloxane；Its molecular structure is as follows：
The four arm polymer for assigning PLA shape memories, molecular center structure are as follows：
The four arm polymer for assigning PLA shape memories, the structure of the PCL increase-volume blocks on molecule support arm are as follows：
, n is the integer more than 1；The four arm polymer for assigning PLA shape memories, the PTMG soft segments on molecule support arm
Structure it is as follows：
, m is the integer more than 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810382287.7A CN108503811B (en) | 2018-04-26 | 2018-04-26 | Polymer for endowing polylactic acid with shape memory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810382287.7A CN108503811B (en) | 2018-04-26 | 2018-04-26 | Polymer for endowing polylactic acid with shape memory |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108503811A true CN108503811A (en) | 2018-09-07 |
| CN108503811B CN108503811B (en) | 2020-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810382287.7A Active CN108503811B (en) | 2018-04-26 | 2018-04-26 | Polymer for endowing polylactic acid with shape memory |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897348A (en) * | 2018-12-19 | 2019-06-18 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBST |
| CN111548456A (en) * | 2020-06-01 | 2020-08-18 | 长春工业大学 | Polymer for endowing polylactic acid with water-induced shape memory |
| CN113402866A (en) * | 2021-07-08 | 2021-09-17 | 长春工业大学 | Polymer for regulating and controlling drug release based on shape memory |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245642A1 (en) * | 2001-03-27 | 2002-10-02 | Samsung Electronics Co., Ltd. | Siloxane-based resin and method for forming an insulating film between interconnecting layers in wafers |
| CN106311075A (en) * | 2016-08-15 | 2017-01-11 | 常熟理工学院 | Cyclosiloxane surfactant and preparation method thereof |
| CN107022055A (en) * | 2017-04-25 | 2017-08-08 | 上海交通大学 | A kind of quick selfreparing shape-memory polymer and preparation method thereof |
-
2018
- 2018-04-26 CN CN201810382287.7A patent/CN108503811B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245642A1 (en) * | 2001-03-27 | 2002-10-02 | Samsung Electronics Co., Ltd. | Siloxane-based resin and method for forming an insulating film between interconnecting layers in wafers |
| CN106311075A (en) * | 2016-08-15 | 2017-01-11 | 常熟理工学院 | Cyclosiloxane surfactant and preparation method thereof |
| CN107022055A (en) * | 2017-04-25 | 2017-08-08 | 上海交通大学 | A kind of quick selfreparing shape-memory polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘东红 等: ""四臂聚乙二醇-聚丙交酯立体复合胶束及其药物传输性能"", 《高分子学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897348A (en) * | 2018-12-19 | 2019-06-18 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBST |
| CN109897348B (en) * | 2018-12-19 | 2021-04-13 | 长春工业大学 | PBST toughening agent-containing PBS composite material and preparation method thereof |
| CN111548456A (en) * | 2020-06-01 | 2020-08-18 | 长春工业大学 | Polymer for endowing polylactic acid with water-induced shape memory |
| CN111548456B (en) * | 2020-06-01 | 2022-05-13 | 长春工业大学 | Polymer for endowing polylactic acid with water-induced shape memory |
| CN113402866A (en) * | 2021-07-08 | 2021-09-17 | 长春工业大学 | Polymer for regulating and controlling drug release based on shape memory |
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| Publication number | Publication date |
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| CN108503811B (en) | 2020-08-07 |
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