CN109320695A - The adjustable mechanical response degradation material of shape memory temperature - Google Patents
The adjustable mechanical response degradation material of shape memory temperature Download PDFInfo
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- CN109320695A CN109320695A CN201810935286.0A CN201810935286A CN109320695A CN 109320695 A CN109320695 A CN 109320695A CN 201810935286 A CN201810935286 A CN 201810935286A CN 109320695 A CN109320695 A CN 109320695A
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- shape memory
- temperature
- mechanical response
- shape
- adjustable mechanical
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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
- C08G63/02—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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Biological Depolymerization Polymers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of adjustable mechanical response degradation materials of shape memory temperature, and Polymer Synthesizing field, by L MALIC ACID and 1,8- ethohexadiol is with the mass ratio of 6:1.5~2.5, under negative pressure, temperature 120oC~140oSynthetic reaction is carried out under C, obtains moulding material, then the moulding material is placed in 120 oC~140oUnder C, by 2 ~ 36 hours subsequent heat treatments, the adjustable mechanical response degradation material of shape memory temperature is obtained.The control that the present invention passes through feed ratio, so that material has shape memory function, and further by subsequent heat treatment so that the glass transition temperature of material is stepped up, just accomplish that the region of shape memory temperature is adjustable, along with the ability for reaching mechanical response in heat treatment process by unbalanced heat supply.
Description
Technical field
The present invention relates to Polymer Synthesizing fields, and in particular to a kind of adjustable mechanical response of shape memory temperature is degradable
Material.
Background technique
L MALIC ACID also known as left-handed -2- hydroxysuccinic acid, due to there is an asymmetric carbon atom in molecule, there are two types of vertical
Body isomers.In the Nature, exist in the form of three kinds, i.e. D-malic acid, L MALIC ACID and its mixture D L MALIC ACID.White
Crystalline solid or crystalline powder have stronger hygroscopicity, soluble easily in water, ethyl alcohol.There is special pleasant tart flavour.L MALIC ACID is main
For food and medicine industry.Naturally occurring L MALIC ACID is all L-type, is almost present in all fruits, with pomaceous fruit
In at most.L MALIC ACID is colorless needle crystals or white crystalline powder, odorless, with irritant frank tart flavour, fusing point 127-
130 DEG C, soluble easily in water, 55.59/100mL (20 DEG C) is dissolved in ethyl alcohol, does not dissolve in ether.There are hygroscopicity, 1% (quality) aqueous solution
PH value 2.4.L MALIC ACID is a kind of ingredient of apple, and people is daily 1.5~3.0g by the L MALIC ACID of veterinary antibiotics intake
Left and right, never discovery adverse reaction.Apple has good degradability, and biological nontoxic, but due to poly- L MALIC ACID molecule
Very little is measured, the mechanical property of itself is also bad to cannot function as engineering material use completely.1,8- ethohexadiol is a kind of chemicals
Matter, molecular formula are C8H18O2, itself is also non-toxic.
Chinese patent CN108003330A discloses a kind of biodegradable material of high-performance shape memory, utilizes L- apple
Tartaric acid and glycerine are raw material, L MALIC ACID are first obtained polymalic acid by bulk polymerization, then react after purifying with glycerine
To obtain the material of shape memory function.In the concrete scheme of the patent, L MALIC ACID first passes through the bulk polymerization of 45h
Polymalic acid can be obtained, then is reacted with glycerine, and due to such technological design, resulting in molecular structure is with poly-
Malic acid is main chain, and glycerine is reacted as the crosslinking agent for reaction with the side group (carboxyl) on polymalic acid strand, again
Since glycerine is triol, powerful cross-linked structure is constituted, since material system is polyester, is deposited in material
In hydrogen bond, therefore material has the shape deformed at low temperature can temporarily be freezed fixation, and shape can be restored at high temperature
Appearance originally, i.e., from shape memory function.But the shape memory temperature section of material be it is fixed, can not be according to service condition
De-regulation, and the intensity of material is also not high enough, limits its application field.
Chinese patent CN108047438A discloses a kind of biodegradable material of self-healing, using L MALIC ACID and 1,
8- ethohexadiol is raw material, and L MALIC ACID is first obtained polymalic acid by bulk polymerization, then is reacted after purifying with 1,8- ethohexadiol
To obtain the material of self-healing function.In the concrete scheme of the patent, L MALIC ACID first passes through the bulk polymerization ability of 45h
Obtain polymalic acid, then reacted with 1,8- ethohexadiol, and due to such technological design, result in molecular structure be with
Polymalic acid is main chain, and 1,8- ethohexadiol is anti-as the side group (carboxyl) on the crosslinking agent and polymalic acid strand for reaction
It answers, constitutes microcosmic reticular structure, and since the control of feed ratio has so that the hydroxyl of 1,8- ethohexadiol is present in excess
Many free hydroxyls, therefore there is very powerful hydrogen bond in material, therefore after material has and is cut off, wound is docked
The ability that can be healed again, i.e. self-healing function.But this material does not have shape memory function, and the strength of materials is very low,
It can only apply to soft material use.
L MALIC ACID and 1,8- ethohexadiol are synthesized both at home and abroad at present and have both outer force-responsive and shape memory function
The report of new material, therefore this patent is of great significance.
Summary of the invention
It is an object of the present invention to provide a kind of adjustable mechanical response degradation materials of shape memory temperature.
The technical scheme is that: a kind of adjustable mechanical response degradation material of shape memory temperature, by L MALIC ACID
With 1,8- ethohexadiol with the mass ratio of 6:1.5~2.5, under negative pressure, temperature is to carry out synthetic reaction at 120 DEG C~140 DEG C,
Moulding material is obtained, then the moulding material is placed at 120 DEG C~140 DEG C, by 2~36 hours subsequent heat treatments, is obtained
To the adjustable mechanical response degradation material of shape memory temperature.
In a preferred embodiment of the invention, when the L MALIC ACID of investment and 1, the mass ratio of 8- ethohexadiol is greater than 6:
1.5, then material does not have shape memory function；And the L MALIC ACID and 1 put into, the mass ratio of 8- ethohexadiol are less than 6:2.5,
Then material does not form, the L MALIC ACID and 1, and the preferred mass ratio of 8- ethohexadiol is 6:1.5~2.5.
In a preferred embodiment of the invention, the time of synthetic reaction is 50min-70min.
In a preferred embodiment of the invention, negative pressure preferred scope is 10Pa~1000Pa.
In a preferred embodiment of the invention, by 6~36 hours subsequent heat treatments, obtaining shape memory temperature can
The mechanical response degradation material of tune.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention utilizes L MALIC ACID and 1, and 8- ethohexadiol is raw material, synthesizes high molecular material, and pass through MOLECULE DESIGN
With synthesis, the outer force-responsive of material and shape memory effect are assigned, soft material injury repair and gel biological body tissue are being solved
Between interface problem realize that soft material is intelligent, efficient and environmental-friendlyization is of great significance.
(2) for the present invention with L MALIC ACID and 1,8- ethohexadiol is that raw material is synthesized under certain temperature and pressure, is had
Standby commercial production conditions, production is simple, can obtain having mechanical property and the biodegradable material with shape memory,
It is easy to use.
Detailed description of the invention
Fig. 1 is the external force using the adjustable mechanical response degradation material of shape memory temperature made from Examples 1 to 25
Vertical responding ability shows photo.
Fig. 2 is the shape using the adjustable mechanical response degradation material of shape memory temperature made from Examples 1 to 25
Memory capability shows photo.
Specific embodiment
The adjustable mechanical response degradation material of shape memory temperature proposed by the present invention, using L MALIC ACID and 1,8- is pungent
Glycol is raw material, directly L MALIC ACID is reacted with 1,8- ethohexadiol to obtain the adjustable mechanical response of shape memory temperature can
Degradable material.In the scheme, L MALIC ACID and 1,8- ethohexadiol direct polycondensation is reacted, and since such technique is set
Meter, so that L MALIC ACID and 1,8- ethohexadiol has been reacted to a kind of block copolymer, by two carboxylics on L MALIC ACID molecule
Base and 1, two hydroxyls on 8- ethohexadiol directly form 12121212 interval block structure, then by the control of feed ratio,
So that material has shape memory function, and further by subsequent heat treatment so that the glass transition temperature of material by
Step increases, and has just accomplished that the region of shape memory temperature is adjustable, has added in heat treatment process and pass through unbalanced heat supply
Reach the ability of mechanical response.
Embodiment 1:
The L MALIC ACID and 1 for being 6:2 by mass ratio, 8- ethohexadiol are put into reaction kettle, and pressure is negative pressure: 300Pa, temperature
Degree is 130 DEG C, and reaction time 60min obtains molding material.Material is placed into again in 130 DEG C of baking oven, it is small by 2
When subsequent heat treatment, the adjustable mechanical response degradation material of shape memory temperature can be obtained.It see the table below 1.
Embodiment 2~5
Using step same as Example 1, only change L MALIC ACID and 1, the mass ratio that feeds intake of 8- ethohexadiol is specifically shown in
The following table 2.
Embodiment 6~9
Using step same as Example 1, only change synthesising reacting time, is specifically shown in the following table 3.
Embodiment 10~13:
Using step same as Example 1, only change vacuum degree, is specifically shown in the following table 4.
Embodiment 14~17:
Using step same as Example 1, only change subsequent heat treatment time (being put into the time in 130 DEG C of baking ovens), tool
Body see the table below 5.
Embodiment 18~21
Using step same as Example 1, only changes subsequent heat treatment temperature, be specifically shown in the following table 6.
Embodiment 22~25
Using step same as Example 1, only changes the temperature of synthetic reaction, be specifically shown in the following table 7.
Table 1
。
Table 2
。
Table 3
。
Table 4
。
Table 5
。
Table 6
。
Table 7
。
Comparative example 1:
The L MALIC ACID and 1 for being 6:1 by mass ratio, 8- ethohexadiol are put into reaction kettle, and pressure is negative pressure: 300Pa, temperature
Degree is 130 DEG C, and reaction time 60min obtains molding material.Material is placed into again in 130 DEG C of baking oven, it is small by 2
When subsequent heat treatment, the adjustable mechanical response degradation material of shape memory temperature can be obtained.
Comparative example 2:
The L MALIC ACID and 1 for being 6:3 by mass ratio, 8- ethohexadiol are put into reaction kettle, and pressure is negative pressure: 300Pa, temperature
Degree is 130 DEG C, and reaction time 60min obtains molding material.Material is placed into again in 130 DEG C of baking oven, it is small by 2
When subsequent heat treatment, the adjustable mechanical response degradation material of shape memory temperature can be obtained.
Table 8 is the shape memory contrast table that above each example obtains batten.
Table 8
。
As can be seen from Table 8: place the material in being cooled to 35 DEG C after 100 DEG C of deformations, shape can be fixed as temporary shapes, then
Initial shape can be restored to again by being placed in 100 DEG C of materials；Place the material in being cooled to 25 DEG C after 75 DEG C of deformations, shape can be fixed as
Temporary shapes, then be placed in 75 DEG C of materials and can be restored to initial shape again；15 DEG C are cooled to after deforming place the material in 50 DEG C, shape
Shape can be fixed as temporary shapes, then be placed in 50 DEG C of materials and can be restored to initial shape again.
Can also be seen that from upper table 8: when the mass ratio that feeds intake of L MALIC ACID and 1,8- ethohexadiol is 6:2, synthesis temperature is
130 DEG C, generated time 60min, (without influence when synthesis pressure is within the scope of 10Pa-1000Pa), the maximum intensity of material, and
And can have shape memory and mechanical response ability, when subsequent heat treatment temperature is 130 DEG C, the strength of materials is best.And
After being formed with materials synthesis, then it is placed in the time being heat-treated in baking oven and rises to 6 hours and 36 hours, the shape memory of material
Temperature range can be adjusted to best, and obtain higher mechanical strength.
Fig. 1 is to be had outer using the adjustable mechanical response degradation material of shape memory temperature made from Examples 1 to 25
The displaying photo of the vertical responding ability of power.
Fig. 2 is to have shape using the adjustable mechanical response degradation material of shape memory temperature made from Examples 1 to 25
Shape memory capability, and the displaying photo of different shape memory temperature, as shown, 15 DEG C -50 DEG C are respectively corresponded, 25 DEG C -75 DEG C,
35℃-100℃。
Claims (7)
1. a kind of adjustable mechanical response degradation material of shape memory temperature, which is characterized in that by L MALIC ACID and 1,8- is pungent
Glycol is with 6: 1.5~2.5 mass ratio, under negative pressure, temperature 120oC~140oSynthetic reaction is carried out under C, is formed
Material, then the moulding material is placed in 120 oC~140oUnder C, by 2 ~ 36 hours subsequent heat treatments, shape memory is obtained
The adjustable mechanical response degradation material of temperature.
2. material as described in claim 1, which is characterized in that the time of synthetic reaction is 50min -70min.
3. material as described in claim 1, which is characterized in that range of negative pressure is the Pa of 10 Pa ~ 1000.
4. material as described in claim 1, which is characterized in that the subsequent heat treatment for passing through 6 ~ 36 hours obtains shape memory
The adjustable mechanical response degradation material of temperature.
5. material as described in claim 1, which is characterized in that it is characterized in that, the material is placed in 100oIt is cold after C deformation
But to 35oC, shape can be fixed as temporary shapes, then be placed in 100oC-material can be restored to initial shape again；The material is set
In 75o25 are cooled to after C deformationoC, shape can be fixed as temporary shapes, then be placed in 75oC-material can be restored to initial shape again
Shape；The material is placed in 50o15 are cooled to after C deformationoC, shape can be fixed as temporary shapes, then be placed in 50oC-material again may be used
It is restored to initial shape.
6. material as described in claim 1, which is characterized in that it is characterized in that, the material has vertical direction to external force
Response: prolong radial drawing material batten, when removing external force, material can occur perpendicular to radial deformation, and remove in external force
Restore deformation after going.
7. the preparation method of the material as described in claim 1-6 is any.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810935286.0A CN109320695B (en) | 2018-08-16 | 2018-08-16 | Shape memory temperature-adjustable mechanical response degradable material |
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| CN201810935286.0A CN109320695B (en) | 2018-08-16 | 2018-08-16 | Shape memory temperature-adjustable mechanical response degradable material |
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| CN109320695B CN109320695B (en) | 2020-09-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234272A (en) * | 2020-03-05 | 2020-06-05 | 扬州大学 | Shape memory material capable of rapidly and visually identifying concentration of mixed organic solvent and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003330A (en) * | 2017-12-15 | 2018-05-08 | 扬州大学 | A kind of biodegradable material of high-performance shape memory |
-
2018
- 2018-08-16 CN CN201810935286.0A patent/CN109320695B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003330A (en) * | 2017-12-15 | 2018-05-08 | 扬州大学 | A kind of biodegradable material of high-performance shape memory |
Non-Patent Citations (2)
| Title |
|---|
| DAHU YAO: "Lipase‐catalyzed synthesis and characterization of biodegradable polyester containing l‐malic acid unit in solvent system", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| NAGATA, MINORU: "Preparation and characterization of novel biodegradable optically active", 《AMERICAN CHEMICAL SOCIETY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234272A (en) * | 2020-03-05 | 2020-06-05 | 扬州大学 | Shape memory material capable of rapidly and visually identifying concentration of mixed organic solvent and application thereof |
| CN111234272B (en) * | 2020-03-05 | 2022-09-06 | 扬州大学 | Shape memory material capable of rapidly and visually identifying concentration of mixed organic solvent and application thereof |
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