CN112457337A - Tri (2-furyl) borane-tri (2-maleimidoethyl) amine DA reaction adduct - Google Patents
Tri (2-furyl) borane-tri (2-maleimidoethyl) amine DA reaction adduct Download PDFInfo
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- CN112457337A CN112457337A CN202011400814.6A CN202011400814A CN112457337A CN 112457337 A CN112457337 A CN 112457337A CN 202011400814 A CN202011400814 A CN 202011400814A CN 112457337 A CN112457337 A CN 112457337A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
Abstract
The invention belongs to the field of synthesis, and particularly relates to a tri (2-furyl) borane-tri (2-maleimidoethyl) amine DA reaction adduct which utilizes reversible Diels-Alder reaction between furan and maleimide groups and has the characteristic of repeatability self-repair, and further provides a preparation method of the adduct. The invention solves the problem of shortage of covalent bond materials suitable for the PVC field, and forms a reversible material with thermotropic covalent bonds and repetitive self-repairing characteristics by utilizing reversible DA reaction.
Description
Technical Field
The invention belongs to the field of synthesis, and particularly relates to a tri (2-furyl) borane-tri (2-maleimidoethyl) amine DA reaction adduct.
Background
High molecular scientists have recognized, as early as half a century ago, in the performance testing of vulcanizates that the presence of dynamic covalent bonds in some polymer networks, when activated, will cause the entire network to no longer exhibit traditional thermoset behavior, but rather to exhibit a considerable degree of creep and stress relaxation behavior. In the last two decades, various types of dynamic covalent bonds have been re-activated in extensive research due to their interest in self-healing materials. In the last decade, the plastic property of the traditional thermosetting polymer is realized from the chemical structure, and the heavy processing and integral shaping based on the thermosetting polymer are carried out, and the requirement of the deformation material field for the more extensive and complicated shape of the material is generated.
The prior art of PVC labels has relatively rare introduction of dynamic covalent bonds, and no dynamic covalent bond material suitable for the PVC label field is found.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a tri (2-furyl) borane-tri (2-maleimidoethyl) amine DA reaction adduct, which solves the problem of shortage of dynamic covalent bond materials in the PVC field, and forms a reversible material with thermotropic covalent bonds and repetitive self-repairing characteristics by utilizing reversible DA reaction.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a tri (2-furyl) borane-tri (2-maleimide aminoethyl) amine DA reaction addition product utilizes furan and maleimide groups to generate reversible Diels-Alder reaction, and the addition product has the characteristic of repeatability self-repairing.
The material is a hard solid at room temperature and in a sub-room temperature environment, and the mechanical properties of the material are equivalent to those of commercial epoxy resin. At a temperature higher than 120 deg.C, about 30% of the molecules
The covalent bond is broken by the reverse reaction, so that the product has plastic processing capability and can be formed into products with various shapes by conventional processing equipment and processes. Upon cooling, the broken covalent bonds re-react to form bonds and the article regains its hard appearance and properties.
The processing method of the addition product is low-temperature crushing, and the crushing is 40 meshes.
The adduct is used for PVC heat-shrinkable label films.
The preparation steps of the adduct comprise: step 1, adding tris (2-maleimidoethyl) amine into tris (2-furyl) borane ether solution, drying with anhydrous magnesium sulfate, filtering the solution, performing vacuum exhaust treatment at normal temperature, and evaporating most of ether within 20 minutes; step 2, stirring the viscous solution for 30 minutes, removing the residual diethyl ether in high vacuum for 20 minutes, and then slowly moving the liquid which is changed into very viscous liquid into a mould to reduce bubbles as much as possible; step 3, keeping the room temperature of the die for 2 hours, then heating to 60 ℃, keeping for 4 hours, continuing heating to 75 ℃, keeping for 4 hours, then heating to 95 ℃, and keeping for 20 hours; and cooling to room temperature after the reaction is finished to obtain a reaction product.
The preparation method of the tris (2-furyl) borane ethyl ether solution comprises the following steps: step a, completely transferring n-butyl lithium ether solution to a dry three-neck flask which is filled with nitrogen and connected well, adding anhydrous ether, mixing uniformly, and cooling to-50-60 ℃ in a dry ice-n-octane bath; and step b, dropwise adding anhydrous furan, slowly heating to room temperature while stirring, stirring at room temperature for reaction for 1 hour, then dropwise adding 200mL (N, N-diethylamino) dichloroborane ether solution, continuously stirring for 0.5 hour, slowly hydrolyzing with 100 mL of 2 mol/L hydrochloric acid, separating an ether layer, and step c, extracting a water layer with ether, combining ether solutions, and washing with a proper amount of pure water and a saturated sodium bicarbonate solution to be alkalescent sequentially to obtain a tris (2-furyl) borane ether solution. Wherein the concentration of the (N, N-diethylamino) dichloroborane in the (N, N-diethylamino) dichloroborane ethyl ether solution is 129 g/L.
The preparation method of the n-butyllithium ethyl ether solution comprises the following steps: step A, under the protection of nitrogen, adding anhydrous ether and finely-divided lithium particles into a dry three-neck flask provided with a stirrer, a low-temperature thermometer, a gas-guide tube, a drying tube and a dropping funnel, and dropwise adding 1.5mL of n-bromobutane anhydrous ether solution with the concentration of 5mol/L under the stirring condition; and step B, continuously dropwise adding the n-bromobutane anhydrous ether solution until the addition of the n-bromobutane anhydrous ether solution reaches 60 percent of the volume of the anhydrous ether, keeping the temperature between minus 5 ℃ and minus 10 ℃, reacting for 1 hour, slowly self-heating to the temperature of between 0 and 10 ℃, and continuously stirring for 1.5 hours to obtain the n-butyl lithium ether solution. Wherein the n-butyl lithium ethyl ether solution is stored in a nitrogen environment.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of shortage of covalent bond materials suitable for the PVC field, and forms a reversible material with thermotropic covalent bonds and repetitive self-repairing characteristics by utilizing reversible DA reaction.
2. The invention is used for the PVC heat-shrinkable label film, forms thermal decomposition under the heating condition, and forms stable connection after covalent bond reconnection after cooling, thereby ensuring the stability of the heat-shrinkable label film.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct comprising the steps of:
step 1, preparing tris (2-furyl) borane ethyl ether solution
In an ether carrier, reacting lithium with N-bromobutane to obtain N-butyllithium, then reacting the N-butyllithium with furan to prepare 2-furyl lithium, and finally carrying out hydroxylation reaction on the 2-furyl lithium and (N, N-diethylamino) dichloroborane to obtain the tri (2-furyl) borane.
(1) Preparation of n-butyllithium Ether solution
In a nitrogen environment, a stirrer, a low-temperature thermometer, an air duct, a drying tube and a dropping funnel are arranged in a dry three-neck flask with the capacity of 500 mL; 200mL of anhydrous diethyl ether and 8.4g (1.25mol) of finely divided lithium particles; a solution of n-bromobutane in diethyl ether was prepared from 82.2g (0.6mol) of n-bromobutane and 120mL of anhydrous diethyl ether. The reaction was started by dropping 30 drops of n-bromobutane ether solution and cooling to-10 ℃ in a dry ice-acetone bath, the solution became cloudy and metallic bright spots appeared on the lithium particles. Dropwise adding the rest n-bromobutane ether solution within 30min, reacting for 1h while keeping the temperature between-5 ℃ and-10 ℃, then slowly self-heating and heating to 0-10 ℃, and keeping stirring for 1.5 h. In the process, the yield of n-butyllithium diethyl ether solution is 80-90%, and the n-butyllithium content is 0.5 mol. Filtered through a glass tube with glass filaments under nitrogen protection and stored in a nitrogen-filled container.
(2) Preparation of tris (2-furyl) borane in diethyl ether
Introducing the N-butyllithium diethyl ether prepared in the step (1) into a 1000mL dry three-neck flask which is filled with nitrogen, adding 130mL anhydrous diethyl ether, uniformly mixing, cooling to-50 to-60 ℃ in a dry ice-N-octane bath, dropwise adding 34.7 g (0.51 mol) anhydrous furan, slowly heating to room temperature under stirring, reacting for 1 hour under stirring at room temperature, dropwise adding a solution consisting of 25.8 g (0.17 mol) (N, N-diethylamino) dichloroborane and 200mL anhydrous diethyl ether, continuously stirring for 0.5 hour, slowly hydrolyzing with 100 mL 2 mol/L hydrochloric acid, and separating an ether layer. And extracting the water layer by using ether, combining ether solutions, and washing the combined ether solutions by using a proper amount of pure water and a saturated sodium bicarbonate solution in sequence until the combined ether solutions are alkalescent to obtain a tris (2-furyl) borane ether solution. The process yield was 60% with 0.1 mole of tris (2-furyl) borane etherate in solution.
Step 2, preparing a tri (2-furyl) borane/tri (2-maleimidoethyl) amine DA reaction adduct:
step a, adding 38.6 g (0.1 mol) of tris (2-maleimidoethyl) amine to the tris (2-furyl) borane ether solution prepared by (2), drying with anhydrous magnesium sulfate, filtering the solution, vacuum degassing at normal temperature, and evaporating most of the ether within 20 minutes; step b, leaving the viscous solution, stirring for 30 minutes, removing the residual diethyl ether in high vacuum for 20 minutes, and then slowly moving the viscous solution which is changed into very viscous into a mould to reduce the generation of bubbles as much as possible; step c, keeping the sample in the die at room temperature for 2 hours, then heating to 60 ℃, keeping for 4 hours, continuing heating to 75 ℃, keeping for 4 hours, then heating to 95 ℃, and keeping for 20 hours; step d, the reaction was completed, cooled to room temperature, the mold was opened, and the reaction product was taken out to obtain about 60 g (0.1 mol) of a transparent massive solid of the tris (2-furyl) borane/tris (2-maleimidoethyl) amine DA reaction adduct.
In summary, the invention has the following advantages:
1. the invention solves the shortage of dynamic covalent bond materials in the PVC field, and forms a reversible material with thermotropic covalent bonds and repetitive self-repairing characteristics by utilizing reversible DA reaction.
2. The invention is used for the PVC heat-shrinkable label film, forms thermal decomposition under the heating condition, and forms stable connection after covalent bond reconnection after cooling, thereby ensuring the stability of the heat-shrinkable label film.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct characterized by: the addition product is prepared by reversible Diels-Alder reaction of furan and maleimide group.
2. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 1, characterized in that: the adduct contains a reversible covalent bond.
3. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 1, characterized in that: the adduct adopts a low-temperature crushing mode to crush the solid into fine powder.
4. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 1, characterized in that: the adduct is used for PVC heat-shrinkable label films.
5. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 1, characterized in that: the preparation method of the adduct comprises the following steps:
step 1, adding tris (2-maleimidoethyl) amine into tris (2-furyl) borane ether solution, drying with anhydrous magnesium sulfate, filtering the solution, performing vacuum exhaust treatment at normal temperature, and evaporating most of ether within 20 minutes;
step 2, stirring the viscous solution for 30 minutes, removing the residual diethyl ether in high vacuum for 20 minutes, and then slowly moving the viscous solution into a mold to reduce bubbles as much as possible;
step 3, keeping the room temperature of the die for 2 hours, then heating to 60 ℃, keeping for 4 hours, continuing heating to 75 ℃, keeping for 4 hours, then heating to 95 ℃, and keeping for 20 hours; and cooling to room temperature after the reaction is finished to obtain a reaction product.
6. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 5, characterized in that: the preparation method of the tris (2-furyl) borane ethyl ether solution comprises the steps of obtaining N-butyl lithium through the reaction of lithium and N-bromobutane, then reacting the N-butyl lithium with furan to obtain the 2-furyl lithium, and then carrying out a alkylation reaction on the 2-furyl lithium and (N, N-diethylamino) dichloroborane to finally synthesize the tris (2-furyl) borane.
7. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 6, characterized in that: the preparation method of the n-butyllithium ethyl ether solution comprises the following steps: step A, under the protection of nitrogen, adding anhydrous ether and finely-divided lithium particles into a three-neck flask, and dropwise adding 1.5mL of n-bromobutane anhydrous ether solution with the concentration of 5mol/L under the stirring condition; and step B, continuously dropwise adding the n-bromobutane anhydrous ether solution until the addition of the n-bromobutane anhydrous ether solution reaches 60 percent of the volume of the anhydrous ether, keeping the temperature between minus 5 ℃ and minus 10 ℃, reacting for 1 hour, slowly self-heating to the temperature of between 0 and 10 ℃, and continuously stirring for 1.5 hours to obtain the n-butyl lithium ether solution.
8. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 7, characterized in that: and storing the n-butyl lithium ethyl ether solution in a nitrogen environment.
9. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 6, characterized in that: the preparation method of the tris (2-furyl) borane ethyl ether solution comprises the following steps:
step a, completely transferring n-butyl lithium ether solution to a dry three-neck flask which is filled with nitrogen and connected well, adding anhydrous ether, mixing uniformly, and cooling to-50-60 ℃ in a dry ice-n-octane bath;
step b, dropwise adding anhydrous furan, slowly heating to room temperature while stirring, stirring and reacting for 1 hour at room temperature, then dropwise adding 200mL (N, N-diethylamino) dichloroborane ethyl ether solution, continuously stirring for 0.5 hour, slowly hydrolyzing with 100 mL of 2 mol/L hydrochloric acid, and separating an ether layer;
and c, extracting the water layer by using ether, combining ether solutions, and then washing the combined ether solutions to be alkalescent by using a proper amount of pure water and a saturated sodium bicarbonate solution in sequence to obtain a tris (2-furyl) borane ether solution.
10. The tris (2-furyl) borane-tris (2-maleimidoethyl) amine DA reaction adduct of claim 9, characterized in that: the concentration of the (N, N-diethylamino) dichloroborane in the (N, N-diethylamino) dichloroborane ethyl ether solution is 129 g/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337909A (en) * | 2021-08-04 | 2021-09-03 | 江苏恒力化纤股份有限公司 | Creep-resistant polyester industrial yarn and preparation method thereof |
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| US20040014933A1 (en) * | 2002-07-12 | 2004-01-22 | Fred Wudl | Thermally re-mendable cross-linked polymers |
| CN103408684A (en) * | 2013-07-12 | 2013-11-27 | 中山大学 | Thermally-reversible crosslinked polymer film and preparation method thereof |
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- 2020-12-02 CN CN202011400814.6A patent/CN112457337A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040014933A1 (en) * | 2002-07-12 | 2004-01-22 | Fred Wudl | Thermally re-mendable cross-linked polymers |
| CN103408684A (en) * | 2013-07-12 | 2013-11-27 | 中山大学 | Thermally-reversible crosslinked polymer film and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 袁国正 等: "硼化合物的研究――XX.乙醇胺合三(2-呋喃基)硼烷的合成及其转化" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337909A (en) * | 2021-08-04 | 2021-09-03 | 江苏恒力化纤股份有限公司 | Creep-resistant polyester industrial yarn and preparation method thereof |
| CN113337909B (en) * | 2021-08-04 | 2021-10-19 | 江苏恒力化纤股份有限公司 | Creep-resistant polyester industrial yarn and preparation method thereof |
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