CN110862507B - Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane - Google Patents
Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane Download PDFInfo
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
Abstract
The invention provides a preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane. The prepared hydroxyl rhodamine can be chemically reacted with isocyanate and is permanently bonded on a polyurethane chain, the defects that an external addition type force-induced fluorescent material is poor in dispersibility and easy to aggregate in polyurethane are overcome, the fluorescence quenching phenomenon can be prevented, the polyurethane has a lasting fluorescence characteristic, strong yellow fluorescence is emitted under ultraviolet rays and the like, C-N bonds in the rhodamine are broken under the action of mechanical force, the fluorescence color is changed, and after the action of the mechanical force disappears, broken C-N are recovered, and the fluorescence is gradually self-recovered to the original yellow color. And the water is used as a dispersion medium, so that the use of an organic solvent can be reduced, the environmental pollution is reduced, and meanwhile, the preparation method is simple and effective, has a simple process and easily controlled operation conditions, and is suitable for large-scale production, popularization and application.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane.
Background
The functional materials are developed into various purposes according to the characteristics of the functional materials, and the intelligent color-changing fluorescent materials responding to external stimuli have very wide application prospects in the actual life of people, for example, the intelligent color-changing fluorescent materials have potential application values in the fields of optical recording, trademark anti-counterfeiting, sensors, memory chips, data safety protection and the like. The material with the mechanochromic fluorescence property can change the optical property of the material under the stimulation of mechanical external force (shearing, stretching, pressure and the like), and the color change is visible to the naked eye in most cases. To date, there are two approaches to achieving the mechanochromic phenomenon that have been reported in the literature: one is the action of external force to change the chemical structure of the molecule, and the other is the action of external force to change the physical aggregation state of the substance. The former is the action of external force, so that the material molecules are subjected to chemical reaction, namely, the breakage of old bonds and the formation of new bonds are carried out, and the material molecules are basically light with different colors emitted by different molecules formed before and after the material molecules are stressed; the latter is that under the action of external force, the intermolecular interaction force of the material molecules, the accumulation mode of the molecules and the like are changed, and finally the fluorescence color is changed. The mechanochromic material is used as a novel stimulus response material, and research related to the mechanochromic material has become a very important research hotspot in the field of intelligent materials.
Rhodamine fluorescent agents are visible fluorescent agents that emit intense fluorescence under ultraviolet light. As shown in the following figure, when the force is applied to the molecule, the C-N bond in the molecule can be broken, the electron transfer is generated, another structure is obtained, the color of the fluorescence is changed, and after the force is removed, the C-N in the molecule is restored again, so that the self-recoverable force to the color-changing fluorescence effect is generated
Because of the advantages of excellent friction resistance, mechanical property, low-temperature flexibility and the like, the polyurethane is widely applied to the industries of leather finishing, synthetic leather manufacturing, fabric coating, building road coating, adhesives, medical treatment and the like. With the continuous rising of the demand of people for high-performance, high-quality and high-environmental-protection ecological polyurethane, the demand that a single-performance polyurethane product cannot meet is met, and in recent years, functional polyurethane products such as fluorescence, color change, wave absorption, electromagnetic shielding and the like are favored by consumers.
The rhodamine mechaochromic fluorescent material is introduced into polyurethane, and obvious color change can occur before and after mechanical force stimulation, so that the rhodamine mechaochromic fluorescent material is expected to be used for pressure sensing in daily life of people, and has important significance for preparing the obvious color change material after mechanical force stimulation.
Disclosure of Invention
The invention aims to provide a preparation method of self-recoverable force-induced color-changing fluorescent water-based polyurethane, which has the advantages of lasting fluorescence characteristic, self-recovering force-induced color-changing property, environmental friendliness, simple and effective preparation method, simple process, easily-controlled operation condition and suitability for large-scale production and popularization and application.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane comprises the following steps:
(1) preparation of hydroxy rhodamine
Dissolving rhodamine compounds in acetonitrile, adding monoethanolamine, controlling the temperature of the system to be constant, refluxing and stirring for a certain time, filtering after stirring to obtain a filter cake, fully washing the filter cake with deionized water until the color of the filtrate is clear, and drying the filter cake in a vacuum drying oven to obtain hydroxyl rhodamine;
(2) preparation of self-recoverable mechanochromic fluorescent water-based polyurethane
Adding polymer diol, diisocyanate, a small molecular weight diol chain extender and a catalyst which are dried in a vacuum oven with drying conditions overnight into a reaction container, reacting for 2-3h at 65-85 ℃ under the protection of continuous stirring and nitrogen atmosphere to obtain a prepolymer, adding an organic solvent in which a hydrophilic chain extender and the hydroxyl rhodamine prepared in the step (1) are dissolved into the obtained prepolymer, maintaining the system temperature at 65-85 ℃ and continuing to react for 2-3h, then adding triethylamine to neutralize the prepolymer, adding deionized water under the action of high shear force, and emulsifying at high speed to obtain the self-recoverable mechanochromic fluorescent water-based polyurethane;
wherein the dosage ratio of the components is as follows by weight: 0.1-0.5 part of hydroxyl rhodamine, 60-100 parts of polymer dihydric alcohol, 30-50 parts of diisocyanate, 2-5 parts of micromolecular dihydric alcohol chain extender, 0.01-0.2 part of catalyst, 5-20 parts of solvent, 5-7 parts of hydrophilic chain extender and 4-5 parts of triethylamine.
In the scheme, the rhodamine compound used in the step (1) is the rhodamine compound with the structural formula shown in the following figure:
in the above scheme, the polymer diol in step (2) is any one or combination of polypropylene glycol, polyethylene glycol or polytetrahydrofuran glycol with number average molecular weight of 1000-2000-.
In the above embodiment, the diisocyanate in the step (2) is any one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 1, 6-hexyl diisocyanate, diphenylmethane diisocyanate, or 4,4' -dicyclohexylmethane diisocyanate.
In the above scheme, the small molecule diol chain extender in step (2) is any one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, or diethylene glycol.
In the scheme, the catalyst in the step (2) is any one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, bis-dimethylaminoethylether or dimethylcyclohexylamine.
In the above scheme, the organic solvent in step (2) is any one of acetone, butanone N, N-dimethylformamide, N-dimethylacetamide, or N-methylpyrrolidone.
In the above scheme, the hydrophilic chain extender in step (2) is any one of dimethylolpropionic acid or dimethylolbutyric acid.
In the scheme, the drying conditions in the step (2) are 120 ℃ and 0.1 atm.
In the scheme, the specific route for modifying the rhodamine fluorescent compound is as follows:
the invention has the following innovation points and beneficial effects:
(1) hydroxyl and imino in the hydroxyl rhodamine provided by the invention can chemically react with isocyanic acid radical in isocyanate, and are permanently bonded with a polyurethane chain, so that the defects that an external addition type force-induced fluorescent material is poor in dispersibility and easy to aggregate in polyurethane are overcome, the fluorescence quenching phenomenon can be prevented, and the hydroxyl rhodamine has a lasting fluorescence characteristic;
(2) the self-recoverable force-induced color-changing fluorescent water-based polyurethane has the fluorescent characteristic of self-recovering force-induced color-changing property, emits strong yellow fluorescent light under ultraviolet rays and the like, changes the color of the fluorescent light after the action of mechanical force, and gradually self-recovers to the original yellow color after the action of the mechanical force disappears;
(3) the self-recoverable mechanochromic fluorescent water-based polyurethane provided by the invention takes water as a dispersion medium, can reduce the use of organic solvents and reduce environmental pollution, is environment-friendly, and has the advantages of simple and effective preparation method, simple process, easily-controlled operation conditions and suitability for large-scale production, popularization and application.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The rhodamine compounds used in the following examples are rhodamine compounds of which the structural formula is shown in the following figure:
example 1
(1) Preparation of hydroxy rhodamine
Dissolving 10g of rhodamine compound in 160mL of acetonitrile, adding 3.7mL of monoethanolamine, controlling the temperature of the system at 90 ℃, refluxing and stirring for 2h, filtering after stirring to obtain a filter cake, fully washing the filter cake with deionized water until the color of the filtrate is clear, and drying the filter cake in a vacuum drying oven to obtain the hydroxyl rhodamine.
(2) Preparation of self-recoverable mechanochromic fluorescent water-based polyurethane
Adding 100 parts of polypropylene glycol (120 ℃, 0.1atm vacuum oven drying overnight) with the average molecular weight of 2000, 50 parts of 4,4' -dicyclohexylmethane diisocyanate, 4 parts of 1, 4-butanediol and 0.2 part of bismuth laurate catalyst into a reaction container, heating to 85 ℃ under the protection of continuous stirring and nitrogen atmosphere, reacting for 2 hours to obtain a prepolymer, adding 20 parts of N, N-dimethylformamide-dissolved 7 parts of dimethylolpropionic acid and 0.5 part of the hydroxyl rhodamine prepared in the step (1), continuously reacting for 2 hours at 85 ℃, then adding 5 parts of triethylamine to neutralize the prepolymer, adding deionized water under the action of high shearing force, and emulsifying for 1 hour at high speed to obtain the self-recoverable mechanosensitive color-changing fluorescent water-based polyurethane.
Example 2
(1) Preparation of hydroxy rhodamine
Dissolving 10g of rhodamine compound in 160mL of acetonitrile, adding 3.7mL of 2-monoethanolamine, controlling the temperature of the system at 90 ℃, refluxing and stirring for 2h, filtering after stirring to obtain a filter cake, fully washing the filter cake with deionized water until the color of the filtrate is clear, and drying the filter cake in a vacuum drying oven to obtain the hydroxyl rhodamine.
(2) Preparation of self-recoverable mechanochromic fluorescent water-based polyurethane
Adding 20 parts of polyethylene glycol with the average molecular weight of 2000, 40 parts of polytetrahydrofuran glycol with the average molecular weight of 1000 (120 ℃, 0.1atm vacuum oven drying overnight), 30 parts of 2, 4-toluene diisocyanate, 2 parts of ethylene glycol and 0.01 part of bismuth neodecanoate catalyst into a reaction container, heating to 65 ℃ under the continuous stirring and nitrogen atmosphere protection to react for 2 hours to obtain a prepolymer, adding 5 parts of acetone-dissolved dimethylolbutyric acid and 0.1 part of hydroxyl rhodamine prepared in the step (1) into the obtained prepolymer, keeping at 65 ℃ for continuous reaction for 3 hours, then adding 4 parts of triethylamine to neutralize the prepolymer, adding deionized water under the action of high shearing force, and emulsifying at high speed for 1 hour to obtain the self-recoverable mechanochromic fluorescent water-based polyurethane.
Example 3
(1) Preparation of hydroxy rhodamine
Dissolving 10g of rhodamine compound in 160mL of acetonitrile, adding 3.7mL of 2-monoethanolamine, controlling the temperature of the system at 90 ℃, refluxing and stirring for 2h, filtering after stirring to obtain a filter cake, filtering, fully washing the filter cake with deionized water until the color of the filtrate is clear, and drying the filter cake in a vacuum drying oven to obtain the hydroxyl rhodamine.
(2) Preparation of self-recoverable mechanochromic fluorescent water-based polyurethane
Adding 80 parts of polytetrahydrofuran diol (120 ℃, 0.1atm vacuum oven drying overnight) with the average molecular weight of 2000, 40 parts of isophorone diisocyanate, 5 parts of diethylene glycol and 0.1 part of dimethylcyclohexylamine catalyst into a reaction container, heating to 80 ℃ under the protection of continuous stirring and nitrogen atmosphere, reacting for 3 hours to obtain a prepolymer, adding 15 parts of N, N-dimethylacetamide-dissolved 6 parts of dimethylolbutyric acid and 0.3 part of the hydroxyl rhodamine prepared in the step (1), keeping at 80 ℃, continuing to react for 2.5 hours, then adding 5 parts of triethylamine to neutralize the prepolymer, adding deionized water under the action of high shear force, and emulsifying at high speed for 1 hour to obtain the self-recoverable mechanosensitive color-changing fluorescent water-based polyurethane.
Example 4
(1) Preparation of hydroxy rhodamine
Dissolving 10g of rhodamine compound in 160mL of acetonitrile, adding 3.7mL of 2-monoethanolamine, controlling the temperature of the system at 90 ℃, refluxing and stirring for 2h, filtering after stirring to obtain a filter cake, fully washing the filter cake with deionized water until the color of the filtrate is clear, and drying the filter cake in a vacuum drying oven to obtain the hydroxyl rhodamine.
(2) Preparation of self-recoverable mechanochromic fluorescent water-based polyurethane
Adding 50 parts of polypropylene glycol with the average molecular weight of 2000, 20 parts of polyethylene glycol with the average molecular weight of 1000 (dried overnight in a vacuum oven at 120 ℃ under 0.1 atm), 40 parts of diphenylmethane diisocyanate, 2 parts of 1, 6-hexanediol and 0.05 part of bis-dimethylamino ethyl ether catalyst into a reaction container, heating to 65 ℃ under the protection of continuous stirring and nitrogen atmosphere, reacting for 2.5 hours to obtain a prepolymer, adding 10 parts of acetone-dissolved 6 parts of dimethylolpropionic acid and 0.2 part of the hydroxy rhodamine prepared in the step (1), keeping the temperature at 65 ℃ for continuous reaction for 3 hours, then adding 4.5 parts of triethylamine to neutralize the prepolymer, adding deionized water under the action of high shear force, and emulsifying for 1 hour at high speed to obtain the self-recoverable thermochromic fluorescent waterborne polyurethane.
In examples 1 to 4, isophorone diisocyanate, 2, 4-toluene diisocyanate, diphenylmethane diisocyanate, or 4,4' -dicyclohexylmethane diisocyanate can be replaced with 1, 6-hexyl diisocyanate; ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol or diethylene glycol can be replaced by any one of 1, 3-propanediol or neopentyl glycol; the bismuth neodecanoate, the bismuth laurate, the bis-dimethylaminoethyl ether or the dimethylcyclohexylamine can be replaced by any one of bismuth isooctanoate or bismuth naphthenate; acetone, N-dimethylformamide or N, N-dimethylacetamide may be replaced by any of butanone or N-methylpyrrolidone.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (1)
1. A preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane is characterized by comprising the following steps:
(1) preparation of hydroxy rhodamine
Dissolving rhodamine compounds in acetonitrile, adding monoethanolamine, controlling the temperature of the system to be constant, refluxing and stirring for a certain time, filtering after stirring to obtain a filter cake, fully washing the filter cake with deionized water until the color of the filtrate is clear, and drying the filter cake in a vacuum drying oven to obtain hydroxyl rhodamine; the rhodamine compound is the rhodamine compound with the structural formula shown in the following figure:
(2) preparation of self-recoverable mechanochromic fluorescent water-based polyurethane
Adding polymer diol, diisocyanate, a small molecular weight diol chain extender and a catalyst which are dried in a vacuum oven with drying conditions overnight into a reaction container, reacting for 2-3h at 65-85 ℃ under the protection of continuous stirring and nitrogen atmosphere to obtain a prepolymer, adding an organic solvent in which a hydrophilic chain extender and the hydroxyl rhodamine prepared in the step (1) are dissolved into the obtained prepolymer, maintaining the system temperature at 65-85 ℃ and continuing to react for 2-3h, then adding triethylamine to neutralize the prepolymer, adding deionized water under the action of high shear force, and emulsifying at high speed to obtain the self-recoverable mechanochromic fluorescent water-based polyurethane;
the polymer diol in the step (2) is any one or the combination of polypropylene glycol, polyethylene glycol or polytetrahydrofuran glycol with the number average molecular weight of 1000-;
the diisocyanate in the step (2) is any one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 1, 6-hexyl diisocyanate, diphenylmethane diisocyanate or 4,4' -dicyclohexylmethane diisocyanate;
the micromolecular diol chain extender in the step (2) is any one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol or diethylene glycol;
the catalyst in the step (2) is any one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, bis-dimethylamino ethyl ether or dimethyl cyclohexylamine;
the organic solvent in the step (2) is any one of acetone, butanone, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the hydrophilic chain extender in the step (2) is any one of dimethylolpropionic acid or dimethylolbutyric acid;
the drying condition in the step (2) is 120 ℃ and 0.1 atm; wherein the dosage ratio of the components is as follows by weight: 0.1-0.5 part of hydroxyl rhodamine, 60-100 parts of polymer dihydric alcohol, 30-50 parts of diisocyanate, 2-5 parts of micromolecular dihydric alcohol chain extender, 0.01-0.2 part of catalyst, 5-20 parts of solvent, 5-7 parts of hydrophilic chain extender and 4-5 parts of triethylamine.
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| CN113354789B (en) * | 2021-07-21 | 2022-09-27 | 江南大学 | Force-induced color-changing polyurethane elastomer material, and preparation method and application thereof |
| IL285884B2 (en) * | 2021-08-05 | 2023-04-01 | Kornit Digital Ltd | Digital ink composition |
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