CN110790937A - Repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and preparation method thereof - Google Patents
Repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and preparation method thereof Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 polysiloxane Polymers 0.000 claims abstract description 33
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 14
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 125000003172 aldehyde group Chemical group 0.000 claims description 14
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 229940015043 glyoxal Drugs 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 5
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 229940118019 malondialdehyde Drugs 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000004970 Chain extender Substances 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- 239000002262 Schiff base Substances 0.000 abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- JNFRNXKCODJPMC-UHFFFAOYSA-N aniline;boric acid Chemical compound OB(O)O.NC1=CC=CC=C1 JNFRNXKCODJPMC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000002441 reversible effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZSKXYSCQDWAUCM-UHFFFAOYSA-N 1-(chloromethyl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCl ZSKXYSCQDWAUCM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Silicon Polymers (AREA)
Abstract
The invention relates to a repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and a preparation method thereof. According to the invention, the amino-containing polysiloxane derivative A, the chain extender aldehyde-containing monomer derivative B and the 3-aminobenzene boric acid C react with Schiff base through condensation reaction of boron and hydroxyl to generate the organic polysiloxane with a main chain containing boron-oxygen bonds and dynamic imine bonds, and multiple hydrogen bonds are formed by amino and hydroxyl to prepare the repairable and easily-soluble organic silicon elastomer. The organic silicon elastomer prepared by the invention has good mechanical property, dissolution property, self-repairing property in hot water and high self-repairing efficiency, and can be applied to the fields of flexible display, flexible sensing, wearable electronic products, electronic skins and the like.
Description
Technical Field
The invention belongs to the field of flexible materials, and particularly relates to a repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the continuous development of polymer materials and electronic science, the demand of various flexible electronic devices in daily life is increasing, wherein the most prominent research field is from directions such as flexible display, flexible sensing, wearable electronic products, electronic skin, and the like, and various flexible electronic devices often need an ideal stretchable elastomer as a substrate. Among them, the silicone elastomer is an ideal polymer material for various flexible electronic devices because it has excellent chemical stability and thermodynamic stability, is non-toxic and non-flammable, and has excellent flexibility in a wide temperature range. The traditional methods of peroxide crosslinking, hydrosilylation crosslinking and the like of the organic silicon elastomer form a permanent covalent bond crosslinking network, so that the self-repairing performance is lost, and the dissolving capacity is poor. How to make the damaged silicone elastomer self-repair and recover the mechanical properties is a difficult problem. And the organic silicon elastomer prepared based on dynamic chemical bonds, such as disulfide bonds, reversible acylhydrazone, metal coordination bonds and reversible D-A reaction, can easily realize self-repair of the material through reversible damage of the dynamic chemical bonds. For example, patent CN 109749086 a discloses a preparation method of a self-repairing silicone elastomer, which comprises the following steps: synthesizing polysiloxane containing 1, 2-dithiocyclopentyl by a chain extension reaction of the 1, 2-dithiocyclopentyl-containing derivative A and an amino-containing polysiloxane derivative B; reversible crosslinking of the silicone elastomer is realized by utilizing the dynamic disulfide bond function of disulfide cyclopentyl groups at the tail ends of polysiloxane, and a self-repairable silicone elastomer is prepared, but the inventor finds that: the mechanical properties and degradability of the material have also been investigated.
Disclosure of Invention
In order to overcome the problems, the invention provides a repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and a preparation method thereof. The reversible crosslinking of the organic silicon elastomer is realized by adopting a dynamic imine bond generated by the reaction of a boron-oxygen bond formed by the polycondensation of 3-aminophenylboronic acid and Shiff alkali, and the self-repairing performance of the organic silicon elastomer is further endowed under the action of various hydrogen bonds, so that the organic silicon elastomer has high tensile strength and is easy to be quickly dissolved by amino and methylamino reagents; the preparation method is simple, efficient, high in practicability and easy to popularize.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds comprises the steps of dispersing an amino-containing polysiloxane derivative A, an aldehyde-containing monomer derivative B and 3-aminophenylboronic acid in an organic solvent, reacting for 12-16 h at 25-40 ℃, and casting to obtain the repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds;
the structural unit formula of the amino-containing polysiloxane derivative A is as follows:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formula
Wherein y is 0-10;
the aldehyde group-containing monomer derivative B has the following general formula:
OHC-R3-CHO
wherein R is3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
The research of the invention finds that: although the organic silicon elastomer covalent bond crosslinking network prepared by peroxide crosslinking, hydrosilylation crosslinking and other modes has better mechanical property, the material is insoluble and only swells, the self-repairing performance is poor, and the preparation process is complex. For this purpose, the invention utilizes the condensation of 3-aminophenylboronic acid to form boron-oxygen bonds and the reaction of Shiff base to form dynamic imine bonds to achieve reversible crosslinking of the silicone elastomer. The introduction of the boron-oxygen bond can not only carry out self-repairing under the conventional condition, but also carry out self-repairing in water; the introduction of dynamic imine bonds can endow the material with self-repairing and dissolving properties at high temperature. In addition, the 3-aminophenylboronic acid can construct a ternary structure through the formation of boron-oxygen bonds, so that a ternary crosslinking network is formed, the crosslinking density of the organic elastomer is increased, and the mechanical property of the material can be regulated and controlled by regulating the dosage and the size of the crosslinking density.
In some embodiments, the molar content ratio of amino groups to aldehyde groups in the amino group-containing polysiloxane derivative a to the aldehyde group-containing monomer derivative B is 1: 1, Schiff base reaction can be effectively carried out, and complete amino and aldehyde group reaction is ensured. 3-aminophenylboronic acid C with the weight percent of 3-5 percent is added to enable the polymer to generate a three-dimensional crosslinking structure, and multiple hydrogen bonds can be formed between unreacted amino and hydroxyl and between hydroxyl and hydroxyl.
The research of the application finds that: if the amount of the 3-aminophenylboronic acid is too large, solid precipitation may be caused, and if the amount of the 3-aminophenylboronic acid is too small, the effect may not be obvious, so in some embodiments, the amount of the 3-aminophenylboronic acid is 3 wt% to 5 wt%, so that the silicone elastomer has good repairing performance and dissolution performance, and also has good mechanical properties and stability.
The 3-aminophenylboronic acid can form boron-oxygen bonds through dehydration to achieve a crosslinking effect, so that a polymer can generate a three-dimensional structure, the processability of the polymer is improved, the self-repairing capability of the polymer in water is endowed, the crosslinking density is increased, and the mechanical property is improved.
The structure of the amino-containing polysiloxane derivative a is not particularly limited in this application, and in some embodiments, the amino-containing polysiloxane derivative a is at least one of α, ω -diaminopropyl polydimethylsiloxane, α, ω -diaminopropyl polymethylphenylsiloxane or α, ω -diaminopropyl polymethyltrifluoropropylsiloxane, which can achieve superior self-repairing and easy-dissolving properties.
In some embodiments, the amino-containing polysiloxane derivative A has a molecular weight of 1000 to 30000, preferably 2000 to 20000.
When synthesizing the silicone elastomer, a chain extender is commonly used to carry out a chain extension reaction on the prepolymer to increase the relative molecular mass, and therefore,
in some embodiments, the chain extender containing the aldehyde group monomer derivative B is glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, or terephthalaldehyde, and the amine group and the aldehyde group are subjected to Schiff base reaction to form an imine bond, so that the silicone elastomer has good thermal repair performance and solubility.
The invention also provides the repairable and easily-soluble organic silicon elastomer containing the boron-oxygen bond, which is prepared by any one of the methods.
The invention also provides a repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds, which has the following structural formula:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formula
Wherein y is 0-10; r3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
In some embodiments, the molecular weight of the repairable, readily soluble silicone elastomer containing boron-oxygen bonds ranges from: 3000-90000.
The invention also provides application of any one repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds in manufacturing flexible displays, flexible sensors, wearable electronic products or electronic skins.
The invention has the beneficial effects that:
(1) compared with the prior art, the reversible crosslinking of the organic silicon elastomer is realized by utilizing the boron-oxygen bond formed by the polycondensation of 3-aminophenylboronic acid and the dynamic imine bond generated by the reaction of Shiff alkali, and the content of 3-aminophenylboronic acid C is regulated and controlled to regulate the crosslinking density, so that the organic silicon elastomer has good mechanical property, solubility and self-repairing property in water.
(2) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a FT-IR plot of a silicone elastomer prepared in example 1;
FIG. 2 is an optical microscope photograph of the silicone elastomer prepared in example 1 before and after self-healing;
FIG. 3 is a stress-strain curve for silicone elastomers of example 1 having varying amounts of 3-aminophenylboronic acid;
FIG. 4 is a stress-strain curve of the silicone elastomer prepared in example 1 before and after it has been self-repaired under different conditions;
FIG. 5 is a photograph of the easy degradability process of the silicone elastomer prepared in example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the problems of poor mechanical property, poor dissolution property and the like still exist in the current self-repairing organic silicon elastomer material. The invention provides a repairable and easily-degradable organic silicon elastomer containing boron-oxygen bonds, which comprises amino-containing polysiloxane derivatives A, chain extenders containing aldehyde group monomer derivatives B and 3-amino phenylboronic acid, wherein reversible dynamic imine bonds, boron-oxygen bonds and hydrogen bonds are formed through condensation reaction of amino groups and aldehyde groups, and the repairable and easily-degradable organic silicon elastomer is prepared.
The method comprises the following specific steps:
the method comprises the following steps: dissolving the amino-containing polysiloxane derivative A, the chain extender, the aldehyde-containing monomer derivative B and the 4-aminophenylboronic acid C in tetrahydrofuran, fully mixing under normal pressure, heating and reacting.
Step two: and (3) heating and drying the prepolymer until the weight is constant, thus obtaining the prepolymer.
The structural unit formula of the amino-containing polysiloxane derivative A is as follows:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formula
Wherein y is 0-10;
the general formula of the aldehyde group-containing monomer derivative B chain extender is as follows:
OHC-R3-CHO
wherein R is3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number. Such as glyoxal: OHCCHO, malondialdehyde:
succinaldehyde:
glutaraldehyde:
terephthalaldehyde:
the structural formula of the 3-aminophenylboronic acid C is respectively as follows:
the invention also provides a preparation method of the repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds, which is characterized in that a reversible dynamic imine bond, boron-oxygen bonds and hydrogen bonds are formed to construct a reversible cross-linking network by condensation reaction and Shiff alkali reaction of amino-containing polysiloxane derivatives A, chain extenders and aldehyde-containing monomer derivatives B and 3-aminophenylboronic acid.
In order to realize the self-repairing performance of the organic silicon elastomer, aldehyde groups are introduced on amino groups blocked by an organic polysiloxane main chain, and a reversible dynamic imine bond is formed by Shiff base reaction; introducing 3-aminophenylboronic acid into a system to form a reversible boron-oxygen bond; the self-repairing performance of the organic silicon elastomer is realized by utilizing multiple hydrogen bonds formed by unreacted amino and hydroxyl and between hydroxyl and hydroxyl. In addition, imine bonds and boron-oxygen bonds on the main chain form a cross-linked network, so that the repair performance of the organic silicon elastomer is further improved.
Preferably, A is one or more of α, omega-diaminopropyl polydimethylsiloxane, α, omega-diaminopropyl polymethylphenylsiloxane and α, and omega-diaminopropyl polymethyltrifluoropropylsiloxane.
Preferably, the molecular weight of A is 1000-30000, preferably 2000-20000.
Preferably, the chain extender B is one or more of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and terephthalaldehyde.
Preferably, the using amount of the 3-aminophenylboronic acid C is 3-5% of the total mass of the system.
Preferably, the condensation polymerization reaction of the amino and aldehyde groups is carried out at the reaction temperature of 25-40 ℃.
Preferably, the studies have found that the usual organic synthesis reactions are employed: the condensation reaction of the 3-aminophenylboronic acid and the Shiff alkali reaction have simple and mild reaction conditions and convenient operation.
The invention also provides polysiloxane which is prepared by any one method and has an imine bond and a boron-oxygen bond in a main chain.
The polysiloxane with the main chain containing imine bonds and boron-oxygen bonds can be used for preparing an organic silicon elastomer material, and has good mechanical properties, dissolution properties and self-repairing properties in heat and water.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
In the following examples, α, omega-aminopropylpolysiloxane (Mn: 2000, 5000, 10000) is a commercially available polymer from Jiashan south textile materials, Inc., all other materials being commercially available products.
Example 1
Dissolving α g of omega-aminopropylpolysiloxane (Mn: 2000), 0.67g of terephthalaldehyde (purity: 98%), 0.53g of 3-aminobenzeneboronic acid in a proper amount of tetrahydrofuran (monomer concentration is kept about 0.1g/ml), mixing uniformly at 40 ℃, reacting for 12h, pouring into a polytetrafluoroethylene mold, drying at constant temperature until constant weight is achieved to obtain the silicone elastomer, cutting the silicone elastomer into dumbbells (length x width x thickness: 50 x 4 x 0.8 mm)3) After the sample is pulled off at room temperature at a tensile rate of 50mm/min by using an Instron3343 electronic universal tester, the fracture surfaces of the sample are fully contacted, and then the sample is placed into a 100 ℃ vacuum drying oven for repairing for 15min and then is tested or repaired under certain pressure at room temperature for 12h or repaired in water at room temperature for 30 min.
Fig. 1 to 5 are FT-IR diagrams of the silicone elastomer, optical microscopic diagrams before and after self-repair under different self-repair conditions, stress-strain curves of the silicone elastomer having different 3-aminophenylboronic acid contents, stress-strain curves before and after self-repair under different self-repair conditions, and material-object display photographs of the dissolution process.
As shown in FIG. 1, wherein the silicone elastomer was present at 1624cm-1Imine bonds (C ═ N) are shown, illustrating the formation of dynamic imine bonds in the elastomer. As shown in fig. 2, the upper part is an optical microscope image of the surface of the silicone elastomer with the cut crack, and the lower part is an optical microscope image of the silicone elastomer with the cut crack after being repaired for 12 hours at room temperature, 30 minutes in water at room temperature and 15 minutes at high temperature of 100 ℃ from left to right, and the high self-repairing capability of the silicone elastomer is accurately and clearly observed through the optical microscope. As shown in FIG. 3, the tensile properties of the elastomers obtained from 3 different 3-aminophenylboronic acid contents were different, wherein the elongation at break of the elastomer with 3-aminophenylboronic acid accounting for 3 wt% of the total system mass could reach 295%, and the tensile strength of the elastomer with 3-aminophenylboronic acid accounting for 5 wt% of the total system mass could reach 2.84 MPa. As shown in FIG. 4, the silicone elastomer can be self-repaired for 15min at 100 ℃, and the repair efficiency of the silicone elastomer can reach 95%. As shown in FIG. 5, when 1 silicone elastomer having a mass of 0.1g was put into an excess amount of aniline due to the presence of dynamic imine bonds, it was clearly seen that the sample after 15min had been completely dissolved, showing its good dissolution properties.
Example 2
The procedure described in example 1 was repeated except that 0.67g of terephthalaldehyde was replaced with 1.0g of glutaraldehyde (50 wt%).
Example 3
The procedure described in example 1 was repeated, except that 10g of α, omega-aminopropylpolysiloxane (Mn: 2000) was replaced by 27.5g of α, omega-aminopropylpolysiloxane (Mn: 5000).
Example 4
The procedure described in example 1 was repeated, except that 10g of α,. omega. -aminopropylpolysiloxane (Mn: 2000) was replaced by 55g of α,. omega. -aminopropylpolysiloxane (Mn: 10000).
Example 5
The procedure described in example 1 was repeated except that 0.67g of terephthalaldehyde was replaced with 0.725g of glyoxal (40 wt%).
Example 6
The procedure described in example 1 was repeated except that 0.67g of terephthalaldehyde was replaced with 0.36g of malondialdehyde (purity: 98%).
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. A preparation method of a repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds is characterized in that an amino-containing polysiloxane derivative A, an aldehyde-containing monomer derivative B and 3-aminophenylboronic acid are dispersed in an organic solvent, react for 12-16 h at 25-40 ℃, and are molded by casting, so that the repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds is obtained;
the structural unit formula of the amino-containing polysiloxane derivative A is as follows:
wherein n is a natural number greater than zero; r1Is methyl, phenyl or trifluoropropyl; r2Has the structural formula
Wherein y is 0-10;
the aldehyde group-containing monomer derivative B has the following general formula:
OHC-R3-CHO
wherein R is3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
2. The method for preparing the repairable and easily-dissolvable silicone elastomer containing boron-oxygen bonds according to claim 1, wherein the molar content ratio of amino groups to aldehyde groups in the amino-containing polysiloxane derivative a to the aldehyde-containing monomer derivative B is 1: 1 to 1.1.
3. The method for preparing the repairable and easily-dissolvable silicone elastomer containing boron-oxygen bonds according to claim 1, wherein the amount of the 3-aminophenylboronic acid is 3% to 5% of the total mass of the system.
4. The method for preparing the repairable and easily-dissolvable silicone elastomer containing boron-oxygen bonds according to claim 1, wherein the amino-containing polysiloxane derivative a is one or more of α, ω -diaminopropyl polydimethylsiloxane, α, ω -diaminopropyl polymethylphenylsiloxane or α, ω -diaminopropyl polymethyltrifluoropropylsiloxane.
5. The method for preparing the repairable and easily soluble silicone elastomer containing boron-oxygen bonds according to claim 1, wherein the molecular weight of the amino-containing polysiloxane derivative A is 1000 to 30000, preferably 2000 to 20000.
6. The method for preparing the repairable and easily-dissolvable silicone elastomer containing boron-oxygen bonds according to claim 1, wherein the aldehyde group-containing monomer derivative B is at least one of glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, and terephthalaldehyde.
7. The repairable, easily dissolvable silicone elastomer containing boron-oxygen bonds prepared by the method of any one of claims 1-6.
8. The repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds is characterized by having the following structural formula:
wherein n is a natural number greater than zero; r1Is methyl, phenyl or trifluoropropyl; r2Has the structural formula
Wherein y is 0-10; r3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
9. The repairable easily dissolvable silicone elastomer containing boron-oxygen bonds according to claim 8, wherein the molecular weight of the repairable easily dissolvable silicone elastomer containing boron-oxygen bonds ranges from: 3000-90000.
10. Use of the repairable, easily soluble silicone elastomer containing boron-oxygen bonds as claimed in any one of claims 7 to 9 in the manufacture of flexible displays, flexible sensors, wearable electronics or electronic skins.
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