CN106905460A - A kind of self-healing polymers material and preparation method thereof - Google Patents
A kind of self-healing polymers material and preparation method thereof Download PDFInfo
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- CN106905460A CN106905460A CN201710090036.7A CN201710090036A CN106905460A CN 106905460 A CN106905460 A CN 106905460A CN 201710090036 A CN201710090036 A CN 201710090036A CN 106905460 A CN106905460 A CN 106905460A
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- Prior art keywords
- sulfur
- self
- slaine
- bond
- monomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
Abstract
The invention discloses a kind of self-healing polymers material and preparation method thereof, the material is using the sulfur-bearing monomer containing unsaturated double-bond and unsaturated olefin copolymerization, polymer is dissolved and slaine is added, metal cation forms coordinate bond with element sulphur, is repaired at infringement using this coordinate bond active force.Its preparation method comprises the following steps：Step 1：Sulfur-bearing monomer of the synthesis containing unsaturated double-bond, step 2：Sequentially add the sulfur-bearing monomer containing unsaturated double-bond, comonomer, initiator generation polymerizate；Step 3：The polymerizate precipitate and separate is dried, polymerizate is weighed, is dissolved in tetrahydrofuran and is prepared as polymer solution, sulfur-bearing monomer presses 1 with slaine mol ratio in polymerizate:1 to 1:4 weigh slaine, are dissolved in tetrahydrofuran, during metal salt solution dropped into above-mentioned polymer solution, stir more than 12h, obtain self-healing polymers material of the invention；Preparation process operation of the invention is simple, operates easy.
Description
Technical field
The present invention relates to a kind of self-healing polymers and its synthetic method, the sulfur-bearing polymerization more particularly to based on metal-complexing
Thing and preparation method thereof；Using sulfur-containing polymer and the coordination effect of metal, a kind of non-covalent bond effect is formed, complete to review one's lessons by oneself
It is multiple.
Background technology
Polymer self-repair material is a kind of novel high polymer material of high added value, and its selfreparing mechanism is by hydrogen bond
Or the non-covalent bond effect power such as metal-complexing key repairs breakage.The adaptation that self-reparing capability causes material is introduced in the material
Property, durability and self-maintenance are stronger.
Described polymer self-repair material belongs to thermoplastic elastomer (TPE), has preferable power compared to general self-repair material
Learn intensity.This self-healing properties have repeatability, chemical stability, and processability is preferable in itself for material.
At this stage, the reparation and the self-repair method without additive for having additional renovation agent are divided into according to the method for reviewing one's lessons by oneself.The former
Be related to material in itself with the mixing problem of non-uniform of renovation agent, the introducing of additional renovation agent is also possible to that Material Physics can be caused
The decline of energy.
The content of the invention
Technical problem：Present invention solves the technical problem that be to provide one kind can self-healing polymers material and its preparation side
Method, with the defect for overcoming prior art to exist, such as normal temperature cannot selfreparing, the introducing of additional renovation agent causes to mix inequality
Can decline etc..
Technical scheme：A kind of self-healing polymers material of the invention is using the sulfur-bearing monomer containing unsaturated double-bond and not
Saturation of olefins copolymerization, polymer is dissolved and slaine is added, and metal cation forms coordinate bond with element sulphur, is matched somebody with somebody using this
Position key active force is repaired at infringement.
Wherein：
Described polymer from from acrylic compounds, methacrylic, the ethers of phenylethylene and corresponding sulfur-bearing,
One or more groups of copolymerization in sulfone class, sulfoxide type monomer.
Described polymer chooses methyl acrylic ester and methacrylic acid thioether or esters of acrylic acid and acrylic acid
Thioether class or styryl and styryl thioether or styrene and phenyl vinyl sulfoxide combination.
Described slaine is nickeliferous, palladium, ruthenium, magnesium, the slaine of barium metal ion.
Described polymeric material is with slaine according to mol ratio 1:1 to 1:4 are weighed, and are dripped after being dissolved in tetrahydrofuran
Plus blending.
Described polymeric material and organic metal salt mol ratio are in terms of being come by sulfur-bearing monomer molar number and metal molar number
Calculate, sulfur-bearing monomer can search characteristic peak and try to achieve sulfur-bearing in polymer according to characteristic peak and initiator integration ratio by nuclear-magnetism
Monomer molar content, so that it is determined that slaine molal quantity.
The preparation method of self-healing polymers material of the invention comprises the following steps：
Step 1：Sulfur-bearing monomer of the synthesis containing unsaturated double-bond,
Step 2：Sequentially add sulfur-bearing monomer, comonomer, initiator containing unsaturated double-bond；Above each component ratio
By (100~200):(200~100):1, solvent adding amount is identical with sulfur-bearing monomer and comonomer volume, and temperature control exists
80-90 DEG C, more than 3h is reacted, generate polymerizate；
Step 3：The polymerizate precipitate and separate is dried, polymerizate is weighed, is dissolved in tetrahydrofuran and is prepared as
Polymer solution, sulfur-bearing monomer presses 1 with slaine mol ratio in polymerizate:1 to 1:4 weigh slaine, are dissolved in tetrahydrochysene furan
In muttering, during metal salt solution dropped into above-mentioned polymer solution, more than 12h is stirred,
Step 4：After being sufficiently mixed, solvent volatilization hot pressing is materialsed, temperature control will be tried at 100 DEG C -150 DEG C
Sample cuts one openning, and openning depth 80% or so supervises the reparation situation clapped at regular intervals using microscopic camera, from bat
Photograph and picture is seen can be repaired substantially.
Wherein：
Described comonomer is unsaturated double-bond class monomer, and initiator is radical initiator.
Described unsaturated double-bond class monomer is acrylic compounds, methacrylic or styrene monomer；Free radical draws
Hair agent is chlorine and bromine class, azo compounds species, organic peroxide initiator.
Beneficial effect：Compared with other published self-healing polymers materials, the invention has the advantages that：
(1) present invention carries out selfreparing using this chemical action of metal-complexing, without additional condition, strong adaptability.
(2) self-healing polymers material of the invention compared to general self-healing polymers mechanics of materials tensile property compared with
It is good.
(3) preparation process operation of the invention is simple, operates easy.
Specific embodiment
A kind of self-healing polymers material of the invention uses sulfur-bearing monomer and unsaturated olefin containing unsaturated double-bond
Copolymerization, polymer is dissolved and slaine is added, and metal cation forms coordinate bond with element sulphur, is acted on using this coordinate bond
Power is repaired at infringement.
Wherein：
Described polymer from from acrylic compounds, methacrylic, the ethers of phenylethylene and corresponding sulfur-bearing,
One or more groups of copolymerization in sulfone class, sulfoxide type monomer.
Described polymer chooses methyl acrylic ester and methacrylic acid thioether or esters of acrylic acid and acrylic acid
Thioether class or styryl and styryl thioether or styrene and phenyl vinyl sulfoxide combination.
Described slaine is nickeliferous, palladium, ruthenium, magnesium, the slaine of barium metal ion.
Described polymeric material is with slaine according to mol ratio 1:1 to 1:4 are weighed, and are dripped after being dissolved in tetrahydrofuran
Plus blending.Choose to methylthio phenyl vinyl monomer as sulfur-bearing monomer, choose styrene as comonomer, weigh 1g polymerizations
Thing, wherein being 0.005mol to methylthio phenyl ethylene molar amount, then pressesMol ratio 1:1、1:2、1:3、1:It is corresponding when 4Mole
It is 0.005mol, 0.01mol, 0.015mol, 0.02mol.
Described polymeric material and organic metal salt mol ratio are in terms of being come by sulfur-bearing monomer molar number and metal molar number
Calculate, sulfur-bearing monomer can search characteristic peak according to characteristic peak by nuclear-magnetism, special using sulfur-bearing monomeric character peak and comonomer
The mol ratio that peak area draws different monomers in copolymer is levied, sulfur-bearing monomer is actual to rub according to be calculated by alleged copolymer quality
That number, so that it is determined that slaine molal quantity.Choose to methylthio phenyl vinyl monomer as sulfur-bearing monomer, choose styrene as altogether
Polycondensation monomer, being subtracted with styrene end group peak area can obtain benzene second to the methyl characteristic peak area of methylthio phenyl ethene divided by 2
Alkene correspondence integral area 1, remembers that to 1/3rd of the methyl characteristic peak area of methylthio phenyl ethene be 0.8, then benzene in copolymer
Ethene is 1 with the mol ratio to methylthio phenyl ethylene contents：0.8.1 gram of copolymer is weighed, is tried to achieve to methylthio phenyl ethylene molar
Number is 0.00357mol, and it is then 0.001785mol that slaine molal quantity takes its half.
The preparation method of self-repair material of the invention is：
Step 1：Synthesis, as sulfur-bearing monomer, chooses styrene as comonomer to methylthio phenyl vinyl monomer.
Step 2：Sulfur-bearing monomer, styrene, solvent, initiator are sequentially added, monomer initiator rate of charge is 150:150:
1, solvent volume keeps identical with monomer volume, and temperature control reacts 7h at 80-90 DEG C.
Step 3：Copolymer precipitate and separate is dried, 1g copolymers are weighed, is dissolved in 10ml tetrahydrofurans, be computed 1g
The molal quantity of sulfur-bearing monomer is 0.00357mol in copolymer, weighs 0.001785molPdCl2, it is dissolved in 3ml tetrahydrofurans
In, during metal salt solution dropped into copolymer solution, stir more than 12h.
Step 4：After being sufficiently mixed, sample is produced into solvent volatilization, testing bar is cut into one openning, openning depth
80% or so, the reparation situation clapped at regular intervals is supervised using microscopic camera, can be repaired substantially from terms of picture of taking pictures.
Above-mentioned case describes the copolymerization of the styrene-based monomers and sulfur-bearing styrene-based monomers described in claim 2
The self-repair material that thing is constituted with slaine, remaining combination examples are as follows：
(1)NiCl2
(2)RuCl3
(3)MgCl2
(4)PdCl2
(5)BaCl2
Although detailed description has been done in general explanation and instantiation above to the present invention, in the present invention
On the basis of the present invention can be realized to the bound of cited raw material and response parameter, interval value, just do not do here
Additionally repeat.
Claims (9)
1. a kind of self-healing polymers material, it is characterised in that use sulfur-bearing monomer and ethylenic unsaturation containing unsaturated double-bond
Hydrocarbon copolymerization, polymer is dissolved and slaine is added, and metal cation forms coordinate bond with element sulphur, is made using this coordinate bond
Firmly repaired at infringement.
2. self-healing polymers material according to claim 1, it is characterised in that described polymer selects propylene
Acids, methacrylic, phenylethylene with it is one or more groups of common in ethers, sulfone class, the sulfoxide type monomer of corresponding sulfur-bearing
It is poly-.
3. self-healing polymers material according to claim 1, it is characterised in that described polymer chooses metering system
Esters of gallic acid and methacrylic acid thioether or esters of acrylic acid and acrylic acid thioether class or styryl and styryl sulphur
Ether or styrene and phenyl vinyl sulfoxide combination.
4. self-healing polymers material according to claim 1, it is characterised in that described slaine be nickeliferous, palladium,
Ruthenium, magnesium, the slaine of barium metal ion.
5. self-healing polymers material according to claim 1, it is characterised in that described polymeric material and slaine
According to mol ratio 1:1 to 1:4 are weighed, and blending is added dropwise after being dissolved in tetrahydrofuran.
6. self-healing polymers material according to claim 5, it is characterised in that described polymeric material and organic gold
Category salt mol ratio is calculated with sulfur-bearing monomer molar number with slaine molal quantity, and sulfur-bearing monomer can be searched special by nuclear-magnetism
Levy peak and try to achieve sulfur-bearing monomer molar content in polymer according to characteristic peak and initiator integration ratio, so that it is determined that slaine mole
Number.
7. a kind of preparation method of self-healing polymers material as claimed in claim 1, it is characterised in that the method is included such as
Lower step：
Step 1：Sulfur-bearing monomer of the synthesis containing unsaturated double-bond,
Step 2：Sequentially add sulfur-bearing monomer, comonomer, initiator containing unsaturated double-bond；Above each component ratio is pressed
(100~200):(200~100):1, solvent adding amount is identical with sulfur-bearing monomer and comonomer volume, and temperature control is in 80-
90 DEG C, more than 3h is reacted, generate polymerizate；
Step 3：The polymerizate precipitate and separate is dried, polymerizate is weighed, is dissolved in tetrahydrofuran and is prepared polymer
Solution, sulfur-bearing monomer presses 1 with slaine mol ratio in polymerizate:1 to 1:4 weigh slaine, are dissolved in tetrahydrofuran, will
Metal salt solution is dropped in above-mentioned polymer solution, stirs more than 12h,
Step 4：After being sufficiently mixed, solvent volatilization hot pressing is materialsed, temperature control cuts sample at 100 DEG C -150 DEG C
One openning is opened, openning depth 80% or so supervises the reparation situation clapped at regular intervals using microscopic camera, from figure of taking pictures
Piece is seen can be repaired substantially.
8. the preparation method of self-healing polymers material according to claim 7, it is characterised in that described comonomer
It is unsaturated double-bond class monomer, initiator is radical initiator.
9. the preparation method of self-healing polymers material according to claim 8, it is characterised in that described unsaturation is double
Key class monomer is acrylic compounds, methacrylic or styrene monomer；Radical initiator is chlorine and bromine class, azo compounds
Species, organic peroxide initiator.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710090036.7A CN106905460B (en) | 2017-02-20 | 2017-02-20 | A kind of self-healing polymers material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710090036.7A CN106905460B (en) | 2017-02-20 | 2017-02-20 | A kind of self-healing polymers material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106905460A true CN106905460A (en) | 2017-06-30 |
| CN106905460B CN106905460B (en) | 2019-04-30 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153108A (en) * | 2007-08-30 | 2008-04-02 | 中山大学 | Self-repaired polyalcohol composite material at room temperature |
| CN101659719A (en) * | 2009-09-18 | 2010-03-03 | 中山大学 | Room-temperature self-repairing type thermoplastic polymer material and preparation method thereof |
| EP2597110A1 (en) * | 2011-11-28 | 2013-05-29 | Fundación Cidetec | Self-healing material and method for the preparation thereof |
| CN103665696A (en) * | 2013-11-11 | 2014-03-26 | 青岛文创科技有限公司 | Self-repairing polymer |
| CN105949364A (en) * | 2016-07-22 | 2016-09-21 | 合肥工业大学 | Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof |
| CN106009702A (en) * | 2016-06-29 | 2016-10-12 | 南京大学 | Application of self-repair material in 3D printing |
-
2017
- 2017-02-20 CN CN201710090036.7A patent/CN106905460B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153108A (en) * | 2007-08-30 | 2008-04-02 | 中山大学 | Self-repaired polyalcohol composite material at room temperature |
| CN101659719A (en) * | 2009-09-18 | 2010-03-03 | 中山大学 | Room-temperature self-repairing type thermoplastic polymer material and preparation method thereof |
| EP2597110A1 (en) * | 2011-11-28 | 2013-05-29 | Fundación Cidetec | Self-healing material and method for the preparation thereof |
| CN103665696A (en) * | 2013-11-11 | 2014-03-26 | 青岛文创科技有限公司 | Self-repairing polymer |
| CN106009702A (en) * | 2016-06-29 | 2016-10-12 | 南京大学 | Application of self-repair material in 3D printing |
| CN105949364A (en) * | 2016-07-22 | 2016-09-21 | 合肥工业大学 | Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof |
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| CN106905460B (en) | 2019-04-30 |
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