CN111943846B - Octadecyl stearate, preparation method thereof, microcapsule type phase-change material, phase-change ink and application thereof - Google Patents
Octadecyl stearate, preparation method thereof, microcapsule type phase-change material, phase-change ink and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention belongs to the technical field of phase-change materials, and particularly relates to octadecyl octadecanoic acid octadecyl ether, a preparation method thereof, a microcapsule type phase-change material and phase-change ink. The invention provides octadecyl octadecanoic acid octadecyl ester octadecyl ether which is white wax at normal temperature and can be melted into transparent liquid at the temperature of more than 65 ℃. The invention also provides a microcapsule type phase-change material which comprises a core material and a wall material wrapping the core material; the core material is the octadecyl octadecanol ester in the technical scheme or the octadecyl octadecanol ester prepared by the preparation method in the technical scheme; the wall material is carbon dioxide copolymer aliphatic polycarbonate. The test result of the embodiment shows that the phase-change ink obtained from the microcapsule phase-change material provided by the invention does not need to be cleaned by wet cloth or clear water to remove marks or marks, and is decolored at high temperature and free of color reversion after being cooled.
Description
Technical Field
The invention belongs to the technical field of phase-change materials, and particularly relates to octadecyl octadecanoic acid octadecyl ether, a preparation method thereof, a microcapsule type phase-change material, phase-change ink and application thereof.
Background
When the clothes are cut, lines or marks are drawn on the cloth or the leather, so that the clothes are convenient to cut, and the conventional clothes industry draws the cloth or the leather by using the convenient cloth or leather marking pen.
The prior art leather and cloth marking pens include a mercury pen, a water disappearing pen, a temperature-sensing disappearing pen (or a high-temperature disappearing pen, a thermal disappearing pen and the like), a white non-cutting invisible marking pen and a white thermal disappearing pen improved by derivation. After the ink of the mercury pen and the ink of the water-disappearing pen are used for marking, the ink needs to be stuck by cloth, and the ink is repeatedly wiped until the marking or the writing is completely wiped; the temperature-sensitive disappearing pen (or high-temperature disappearing pen, heat colour-removing pen, etc.) is a color ink which is prepared by using a temperature-sensitive colour-changing colour-memorizing microcapsule pigment (CN 106661443) of Nippon Baile ink company, a reversible thermochromic microcapsule pigment (CN 102807853) of Beijing Moyike science and technology Limited company and a microcapsule type temperature-changing pigment (CN 109943094) of Wuhan's middle-science and technology research institute Limited company as main components, the microcapsule type pigment ink is used for marking lines or marks on leather or cloth, and after being cut, the color ink is decolored by ironing or heating and shaping, so that the marking lines or marks are removed without being washed by wet cloth or clear water, the cleaning process after processing is solved, but the marking lines or the marks return to the original colour and lose efficacy when the temperature is between minus 5 ℃ and minus 20 ℃, and the cold weather condition is not suitable; the white scratch-free invisible marker (CN 101310633) and the white heat-erasing pen ink improved by the white scratch-free invisible marker are ironed to decolor after being used, no scratch is left, but a layer of bright and transparent wax is left on leather or cloth, and when the leather or cloth is subjected to a subsequent stretching and shaping process, the layer of wax is changed back to color, and a layer of pale white mark is left.
Disclosure of Invention
In view of the above, the invention aims to provide octadecyl octadecanoic acid ester octadecyl ether and a preparation method thereof, and the octadecyl octadecanoic acid ester octadecyl ether provided by the invention forms a microcapsule type phase change material and further forms phase change ink, so that the phase change ink has the characteristics of no scrubbing, high-temperature decoloration and no color reversion when in use, and can well meet the use requirements of the clothing tailor industry on daily scribing of cloth or leather.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides octadecyl octadecanoic acid octadecyl ester octadecanol, which has a structure shown in a formula I:
the invention also provides a preparation method of the octadecyl stearate octadecyl ether in the technical scheme, which comprises the following steps:
mixing 1,18-octadecanediol solution with an alkaline catalyst, heating the obtained mixed system, mixing the heated mixed system with 1-iodooctadecane solution, preserving heat at the temperature of heating to perform substitution reaction, cooling the reaction solution to room temperature, and performing first post-treatment to obtain an intermediate;
and mixing the intermediate, octadecanoic acid, toluene and sulfuric acid, heating and refluxing to perform esterification reaction, and performing second post-treatment after the disappearance of the raw materials is detected to obtain the octadecanoic acid octadecyl ester.
Preferably, the basic catalyst is potassium carbonate or lithium bis (trimethylsilyl) amide;
when the catalyst is potassium carbonate, the solvent of the 1,18-octadecanediol solution and the 1-iodooctadecane solution is dimethylformamide; the molar ratio of 1,18-octadecanediol solution to the catalyst is 174.52:523.4, calculated as 1,18-octadecanediol;
when the catalyst is lithium bis (trimethylsilyl) amide, the solvent of the 1,18-octadecanediol solution and the 1-iodooctadecane solution is tetrahydrofuran; the molar ratio of 1,18-octadecanediol solution to the catalyst is 174.52:180.0, calculated as 1,18-octadecanediol.
Preferably, the molar ratio of the 1,18-octadecanediol solution, the 1-iodooctadecane solution and the octadecanoic acid is 1:1:1.
preferably, the temperature is increased to 50-60 ℃, and the heat preservation time is 5-8 h;
the temperature of the heating reflux is 80-95 ℃, and the time is 6-10 h.
The invention also provides a microcapsule type phase-change material which comprises a core material and a wall material wrapping the core material;
the core material is the octadecyl octadecanol ester in the technical scheme or the octadecyl octadecanol ester prepared by the preparation method in the technical scheme;
the wall material is carbon dioxide copolymer aliphatic polycarbonate.
The invention also provides a preparation method of the microcapsule type phase change material in the technical scheme, which comprises the following steps:
mixing octadecyl octadecanoate, carbon dioxide copolymer aliphatic polycarbonate and an organic solvent to obtain an oil phase;
mixing the oil phase and the water phase, and emulsifying to obtain an emulsion;
and removing the solvent from the emulsion to obtain the microcapsule type phase change material.
Preferably, the organic solvent is ethyl acetate, dichloromethane, chloroform or acetone;
the mass ratio of the octadecyl octadecanoate, the carbon dioxide copolymer aliphatic polycarbonate to the organic solvent is 3:1:2.
the invention also provides phase change ink which comprises the following components in parts by weight:
25 parts of microcapsule type phase change material; the microcapsule phase change material is the microcapsule phase change material prepared by the preparation method of the technical scheme or the microcapsule phase change material prepared by the preparation method of the technical scheme;
5 parts of a thickening agent;
1 part of a film-forming assistant;
0.5 part of nonionic fluorine-containing surfactant;
0.5 part of defoaming agent;
and 81 parts of deionized water.
The invention also provides application of the microcapsule type phase-change material in the technical scheme, or the microcapsule type phase-change material obtained by the preparation method in the technical scheme, or the phase-change ink in the technical scheme in a thermal erasable pen, a friction pen or a thermal color-erasing pen.
The invention provides octadecyl octadecanoic acid octadecyl ester octadecanol, which has a structure shown in a formula I:
The invention also provides a microcapsule type phase-change material which comprises a core material and a wall material wrapping the core material; the core material is the octadecyl octadecanol ester in the technical scheme or the octadecyl octadecanol ester prepared by the preparation method in the technical scheme; the wall material is degradable carbon dioxide copolymer aliphatic polycarbonate. In the invention, the octadecyl octadecanoic acid ester is white wax at normal temperature and can be melted into transparent liquid at the temperature of over 65 ℃; the degradable APC is transparent solid particles, has good film-forming property, and the particle shape of the microcapsule type phase change material formed by coating is a multi-concave spherical shape, and the concave-convex surface structure is beneficial to improving the color rendering property and further improving the whiteness; in addition, the obtained microcapsule type phase change material has good temperature sensitivity, the color of the white microcapsule type phase change material is transparent after being melted at the temperature higher than 65 ℃, and the color does not return after being cooled to the temperature lower than 65 ℃. The microcapsule phase change material provided by the invention is used as special white pigment color paste, the prepared phase change ink is used for scribing or marking on leather or cloth, and after ironing or heating setting, the microcapsule is not broken and can be melted and aggregated into a layer of extremely thin transparent film to be decolored, and a layer of bright and transparent wax-like substance cannot be left on the leather or cloth; meanwhile, when the leather is subjected to a subsequent stretching and shaping process, a whitish trace cannot appear, and in addition, a marking or a mark obtained by using the phase-change ink obtained from the microcapsule type phase-change material provided by the invention cannot lose efficacy due to the fact that the original color is returned in cold weather; the phase-change ink provided by the invention does not need to be cleaned by wet cloth or clear water to remove the marking or the mark.
The test result of the embodiment shows that the phase-change ink obtained from the microcapsule phase-change material provided by the invention does not need to be cleaned by wet cloth or clear water to remove marks or marks, and is decolored at high temperature and free of color reversion after being cooled.
Drawings
FIG. 1 is a hydrogen spectrum of octadecyl octadecanoic acid octadecather obtained in example 1;
FIG. 2 is a chart showing the carbon spectrum of stearyl stearate obtained in example 1;
FIG. 3 is a software simulated hydrogen spectrum of octadecyl octadecanoate, octadecyl ether;
FIG. 4 is a carbon spectrum of octadecyl octadecanoate octadecather simulated by software;
FIG. 5 is an SEM photograph of the microcapsule-type phase change material obtained in example 3.
Detailed Description
The invention provides octadecyl octadecanoic acid octadecyl ester octadecanol, which has a structure shown in a formula I:
in the present invention, the octadecyl octadecanoate is white wax-like, and the melting point is 65 ℃.
The invention also provides a preparation method of the octadecyl octadecanoic acid octadecyl ester octadecanol ester in the technical scheme, which comprises the following steps:
mixing 1,18-octadecanediol solution with an alkaline catalyst, heating the obtained mixed system, mixing the heated mixed system with 1-iodooctadecane solution, preserving heat at the temperature of heating to perform substitution reaction, cooling the reaction solution to room temperature, and performing first post-treatment to obtain an intermediate;
and mixing the intermediate, octadecanoic acid, toluene and sulfuric acid, heating and refluxing to perform esterification reaction, and performing second post-treatment after the disappearance of the raw materials is detected to obtain the octadecanoic acid octadecyl ester.
In the present invention, the components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes 1,18-octadecanediol solution with alkaline catalyst, heats the obtained mixed system and mixes with 1-iodooctadecane solution, and preserving the temperature at the temperature of the temperature rise to carry out substitution reaction, cooling the reaction liquid to room temperature, and carrying out post-treatment to obtain an intermediate.
In the present invention, the basic catalyst is preferably potassium carbonate or lithium bis (trimethylsilyl) amide.
When the catalyst is potassium carbonate, the solvent in the 1,18-octadecanediol solution and the 1-iodooctadecane solution is preferably dimethylformamide. When the catalyst is potassium carbonate, the molar ratio of 1,18-octadecanediol solution to catalyst is preferably 174.52:523.4, calculated as 1,18-octadecanediol.
When the catalyst is lithium bis (trimethylsilyl) amide, the solvent in the 1,18-octadecanediol solution and the 1-iodooctadecane solution is preferably tetrahydrofuran. When the catalyst is lithium bis (trimethylsilyl) amide, the molar ratio of 1,18-octadecanediol solution to catalyst is preferably 174.52:180.0, calculated as 1,18-octadecanediol.
In the present invention, the molar ratio of 1,18-octadecanediol solution to 1-iodooctadecane solution is preferably 1:1:1.
in the present invention, the ratio of the molar amount of 1,18-octadecanediol in the 1,18-octadecanediol solution to the volume of the solvent is preferably 174.52mmol:250mL. In the present invention, the mixing is preferably stirring; the stirring is not particularly limited in the present invention, and stirring known to those skilled in the art may be employed; the invention is stirred until the 1, 18-octadecanediol forms a clear solution in the solvent.
In the present invention, the ratio of the molar amount of 1-iodooctadecane to the volume of the solvent in the 1-iodooctadecane solution is preferably 174.52mmol:100mL.
In the invention, the mixing of the 1, 18-octadecanediol solution and the alkaline catalyst is preferably carried out by heating a mixed system obtained by mixing the 1, 18-octadecanediol solution and the catalyst and then mixing the heated mixed system with the 1-iodooctadecane solution. In the invention, the mixing of the mixed system and the 1-iodooctadecane solution is preferably to add the mixed system and the 1-iodooctadecane solution dropwise into the mixed system; the dropping speed is not particularly limited, and the dropping time is within 2h. In the present invention, the temperature of the temperature rise is preferably 50 to 60 ℃, and more preferably 50 to 55 ℃; the time for the heat preservation is preferably 5 to 8 hours, more preferably 6.5 to 8 hours.
After the heat preservation is finished, when the disappearance of the raw material substances is detected, the reaction system obtained by the invention starts to be cooled to the room temperature. In the present invention, the means for detecting whether or not the raw material substance has disappeared is preferably a Thin Layer Chromatography (TLC) detection.
In the present invention, when the basic catalyst is potassium carbonate, the first post-treatment preferably comprises: and sequentially carrying out ice water bath, filtration, washing, recrystallization and drying on the obtained reaction solution. In the present invention, the time of the ice-water bath is preferably 15 to 30min, and more preferably 20 to 25min. After filtration, the filter residue obtained by filtration is washed by water. In the present invention, the number of times of the water washing is preferably 3. In the present invention, the recrystallization reagent is preferably ethanol. In the present invention, the temperature of the drying is preferably 45 to 60 ℃, more preferably 50 to 55 ℃; the time is preferably 12 to 48 hours, more preferably 24 to 36 hours. The ice water bath, filtration, water washing, recrystallization and drying are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
When the basic catalyst is lithium bis (trimethylsilyl) amide, the first post-treatment preferably comprises: sequentially carrying out first rotary evaporation drying, purification and second rotary evaporation drying on the obtained reaction liquid; the purification is preferably silica gel chromatographic column separation purification; the silica gel chromatographic column separation and purification method is not particularly limited, and silica gel chromatographic column separation and purification known to those skilled in the art can be adopted. The temperature and time of the first rotary evaporation drying and the second rotary evaporation drying are not specially limited, the liquid evaporation is completely accurate, and specifically, the temperature of the first rotary drying is 50-60 ℃, and the time is 15-30 min; the temperature of the second rotary evaporation drying is 50-60 ℃, and the time is 15-30 min.
In the present invention, the reaction formula for preparing the intermediate is shown in formula (1)
After the intermediate is obtained, the intermediate, octadecanoic acid, toluene and sulfuric acid are mixed, heating and refluxing are carried out to carry out esterification reaction, and after the raw materials are detected to disappear, second post-treatment is carried out to obtain the octadecanoic acid octadecyl ester.
In the present invention, the sulfuric acid is preferably concentrated sulfuric acid.
In the present invention, the ratio of the molar amount of octadecanoic acid, the volume of toluene and the volume of sulfuric acid is preferably 92.7mmol:500mL:5mL. In the present invention, the molar ratio of the 1,18-octadecanediol solution to octadecanoic acid is preferably 1:1. in the invention, the temperature of the heating reflux is preferably 80-95 ℃, and more preferably 85-90 ℃; the time is preferably 6 to 10 hours, more preferably 8 to 10 hours.
In the present invention, the second post-treatment preferably includes: and sequentially carrying out ice water bath, filtration, washing, recrystallization and drying on the obtained reaction solution. In the present invention, the time of the ice-water bath is preferably 15 to 30min, and more preferably 20 to 25min. After filtration, the filter residue obtained by filtration is washed by water. In the present invention, the number of times of the water washing is preferably 3. In the present invention, the recrystallization reagent is preferably ethanol. In the present invention, the temperature of the drying is preferably 35 to 45 ℃, more preferably 38 to 42 ℃; the time is preferably 24 to 48 hours, more preferably 30 to 42 hours.
In the invention, the reaction formula for preparing the octadecyl stearate octadecyl ether from the intermediate is shown as a formula (2):
the invention also provides a microcapsule type phase-change material which comprises a core material and a wall material wrapping the core material;
the core material is the octadecyl octadecanol ester in the technical scheme or the octadecyl octadecanol ester prepared by the preparation method in the technical scheme;
the wall material is carbon dioxide copolymer aliphatic polycarbonate.
In the present invention, the ratio of the octadecyl octadecanoate and the wall material is preferably 1: (0.25 to 0.5), more preferably 1: (0.3-0.45). In the present invention, the particle size of the microcapsule-type phase change material is preferably 1 to 3 μm, and more preferably 1.5 to 2.5 μm. In the present invention, the coating thickness of the wall material in the microcapsule-type phase change material is preferably 100 to 500nm, and more preferably 150 to 450nm. In the present invention, the particle shape of the microcapsule-type phase change material is a spherical shape with a plurality of depressions.
The invention also provides a preparation method of the microcapsule phase change material in the technical scheme, which is characterized by comprising the following steps:
mixing octadecyl octadecanoate, carbon dioxide copolymer aliphatic polycarbonate and an organic solvent to obtain an oil phase;
mixing the oil phase and the water phase, and emulsifying to obtain an emulsion;
and removing the solvent from the emulsion to obtain the microcapsule type phase change material.
The method comprises the step of mixing octadecanoic acid octadecanoic ester octadecanol, carbon dioxide copolymer Aliphatic Polycarbonate (APC) and an organic solvent to obtain an oil phase.
The present invention preferably further comprises melting the stearyl octadecyl stearate, the carbon dioxide copolymer aliphatic polycarbonate, and the organic solvent prior to mixing the stearyl octadecyl stearate, the aliphatic polycarbonate, and the organic solvent; in the present invention, the temperature of the melting is preferably 65 ℃ or more.
In the present invention, the organic solvent is preferably ethyl acetate, dichloromethane, chloroform or acetone. In the present invention, the mass ratio of the octadecyl octadecanoic acid ester, the carbon dioxide copolymer aliphatic polycarbonate, and the organic solvent is preferably 3:1:2. in the present invention, the octadecyl octadecanoic acid ester, the carbon dioxide copolymer aliphatic polycarbonate and the organic solvent are preferably stirred and mixed until a clear oil phase is obtained.
After the oil phase is obtained, the oil phase and the water phase are mixed and emulsified to obtain the emulsion.
In the present invention, the aqueous phase is preferably an aqueous polyvinyl alcohol solution or an aqueous gelatin solution. In the present invention, the mass concentration of the polyvinyl alcohol aqueous solution is preferably 5%. In the present invention, the mass concentration of the gelatin aqueous solution is preferably 2.5%. In the present invention, the volume ratio of the oil phase and the aqueous phase is preferably 1: (2 to 4), more preferably 1: (2.5-3.5). In the present invention, the mixing of the oil phase and the aqueous phase is preferably performed by adding the oil phase to the aqueous phase. Before the oil phase and the water phase are mixed, the water phase is preferably heated to the emulsification temperature; the temperature of the emulsification is preferably 70 ℃. In the present invention, the time of the emulsification is preferably 30min; in the present invention, the emulsification is preferably performed under stirring; the stirring rate is preferably 5000rpm. In the present invention, the diameter of the oil droplets in the emulsion is preferably 0.5 to 2.5 μm.
After the emulsion is obtained, the solvent of the emulsion is removed to obtain the microcapsule type phase-change material. In the present invention, the solvent removal treatment is preferably evaporation. The temperature of the evaporation is preferably 95 ℃. In the present invention, the time for the evaporation treatment is not particularly limited, and the organic solvent is completely evaporated.
The invention also provides phase change ink which comprises the following components in parts by weight:
25 parts of microcapsule type phase change material; the microcapsule phase change material is the microcapsule phase change material prepared by the preparation method of the technical scheme or the microcapsule phase change material prepared by the preparation method of the technical scheme;
5 parts of a thickening agent;
1 part of a film-forming assistant;
0.5 part of nonionic fluorine-containing surfactant;
0.5 part of defoaming agent;
and 81 parts of deionized water.
In the present invention, the phase change ink includes 25 parts of the microcapsule-type phase change material. In the invention, the microcapsule type phase change material is the microcapsule type phase change material according to the technical scheme or the microcapsule type phase change material prepared by the preparation method according to the technical scheme.
The phase-change ink provided by the invention comprises 5 parts of thickening agent by taking the mass parts of the microcapsule type phase-change material as a reference. In the present invention, the thickener is preferably a polyacrylic acid emulsion or a polyurethane emulsion. In the invention, the solid content of the polyacrylic acid emulsion is preferably more than or equal to 45%, and the average particle size is preferably 0.1-0.5 μm. In the invention, the solid content of the polyurethane emulsion is preferably more than or equal to 40%, and the average particle size is preferably 0.2-0.5 μm.
Based on the mass parts of the microcapsule phase-change material, the phase-change ink provided by the invention comprises 1 part of film-forming auxiliary agent. In the present invention, the coalescent is preferably 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.
The phase change ink provided by the invention comprises 0.5 part of nonionic fluorine-containing surfactant by taking the mass parts of the microcapsule type phase change material as a reference. In the present invention, the nonionic fluorosurfactant is preferably Capstone FS-3100.
The phase change ink provided by the invention comprises 0.5 part of defoaming agent by taking the mass parts of the microcapsule type phase change material as a reference. In the present invention, the defoaming agent is preferably a silicone defoaming agent.
Based on the mass parts of the microcapsule phase-change material, the phase-change ink provided by the invention comprises 81 parts of deionized water.
The preparation method of the phase-change ink is not particularly limited, and specifically, the phase-change ink is obtained by mixing the components contained in the phase-change ink; the mixing is preferably a stirring, the stirring time is preferably 0.5h, and the speed is preferably 200 to 500rpm, more preferably 250 to 450rpm.
The invention also provides the application of the microcapsule phase-change material in the technical scheme, the microcapsule phase-change material obtained by the preparation method in the technical scheme, or the phase-change ink in the technical scheme in a thermal erasable pen, a friction pen or a thermal erase pen.
For further illustration of the present invention, the octadecyl octadecanoyl octadecanol octadecanoate and the preparation method thereof, the microcapsule type phase change material and the phase change ink and the application thereof provided by the present invention are described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Mixing 1, 18-octadecanediol (50.0g, 174.52mmol) and dimethylformamide (250 mL), stirring until the mixture is clear, adding potassium carbonate (72.4g, 523.4mmol), heating to 50 ℃, dropwise adding a dimethylformamide (100 mL) solution of 1-iodooctadecane (63.4g, 174.52mmol), after dropwise adding within 2h, keeping the temperature for 8h at 50 ℃, starting to cool to room temperature after the disappearance of the raw materials is detected by a Thin Layer Chromatography (TLC), pouring a reaction system into ice water, filtering, washing a filter cake for three times by using water, recrystallizing by using ethanol, and drying to obtain 84.6g of an intermediate;
mixing the intermediate (50g, 92.77mmol), octadecanoic acid (24.9g, 92.7mmol) and 500mL of toluene, dropwise adding 5mL of concentrated sulfuric acid, heating and refluxing for 10h at 85 ℃, pouring the reaction liquid into ice water for cooling after the disappearance of the raw materials is detected by thin layer chromatography TLC, filtering, washing a filter cake with water for three times, recrystallizing with ethanol, and drying to obtain 74.0g of white solid octadecanoic ester octadecather octadecanoic acid.
The prepared final product is sampled and subjected to nuclear magnetic resonance testing, the obtained hydrogen spectrum is shown in figure 1, the obtained carbon spectrum is shown in figure 2, and the obtained hydrogen spectrum is compared with the hydrogen spectrum (figure 3) and the carbon spectrum (figure 4) simulated by software, the peak-out positions, the peak areas and the coupling constants of all characteristic peaks are basically consistent, and the final product prepared in the embodiment can be determined to be octadecyl octadecanoyl stearate.
Example 2
Mixing 1, 18-octadecanediol (50.0g, 174.52mmol) and tetrahydrofuran (250 mL), stirring until the mixture is clear, adding lithium bis (trimethylsilyl) amide (30.1g, 180.0mmol), heating to 50 ℃, dropwise adding a tetrahydrofuran (100 mL) solution of 1-iodooctadecane (63.4g, 174.52mmol), after dropwise adding within 2h, keeping the temperature for 8h at 50 ℃, starting to cool to room temperature after a thin-layer chromatography (TLC) detects that a raw material disappears, carrying out rotary evaporation on a reaction system for 20min at 50-60 ℃ by using a rotary evaporator, and then separating and purifying by using a silica gel chromatography column. Then drying by rotary evaporation at 50-60 ℃ for 25min to obtain 84.6g of intermediate;
mixing the intermediate (50g, 92.77mmol), octadecanoic acid (24.9g, 92.7mmol) and 500mL of toluene, dropwise adding 5mL of concentrated sulfuric acid, heating and refluxing for 10h at 90 ℃, pouring the reaction liquid into ice water for cooling after the disappearance of the raw materials is detected by thin layer chromatography TLC, filtering, washing a filter cake with water for three times, recrystallizing with ethanol, and drying to obtain 74.0g of white solid octadecanoic ester octadecather octadecanoic acid.
Example 3
Heating and melting 60 parts by mass of octadecyl stearate obtained in example 1, mixing the melted octadecyl stearate with 20 parts of APC (ammonium-carbonate) and 40 parts of ethyl acetate to obtain an oil phase, uniformly stirring and mixing the oil phase to be clear, putting the clear oil phase into 70 ℃ aqueous solution containing 5wt.% of polyvinyl alcohol, emulsifying at a high speed of 5000rpm for 30min, and dispersing into micro oil drops to obtain emulsion with the diameter of the oil drops being 0.5-2.5 mu m; and heating the obtained emulsion to 95 ℃, and keeping the temperature until the ethyl acetate solvent is completely evaporated to obtain the microcapsule type phase-change material.
The obtained microcapsule phase change material was subjected to SEM test, and the obtained test chart was shown in fig. 5. As can be seen from fig. 5, the particle shape of the microcapsule-type phase-change material provided by the present invention is a spherical shape with multiple depressions. The concave-convex surface structure of the microcapsule phase change material provided by the invention is beneficial to improving the color rendering property and further improving the whiteness.
Example 4
By mass, 25 parts of the microcapsule phase-change material obtained in example 3, 5 parts of polyacrylic emulsion (solid content: not less than 45%, average particle size: 0.1 μm), 1 part of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 0.5 part of Capstone FS-3100 nonionic fluorine-containing surfactant, 81 parts of deionized water and 0.5 part of organic silicon defoamer are mixed and stirred for 0.5h, and then the white phase-change ink is obtained.
Example 5
By mass, 25 parts of the microcapsule phase-change material obtained in example 3, 5 parts of polyurethane emulsion (solid content: not less than 40%, average particle size: 0.5 μm), 1 part of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 0.5 part of Capstone FS-3100 nonionic fluorine-containing surfactant, 81 parts of deionized water and 0.5 part of organic silicon defoamer are mixed and stirred for 0.5h, and then white phase-change ink is obtained.
Application example 1
Placing the phase change ink obtained in the example 4 in a pen bag to scribe on leather to obtain white scribing marks;
ironing the leather with the marking traces at 70 ℃, and observing to obtain that the marking traces disappear; when the temperature is reduced to below 65 ℃, the marking trace is not recovered and still transparent.
Application example 2
Placing the phase change ink obtained in the example 4 in a pen bag to scribe on leather to obtain white scribing marks;
ironing the leather with the marking traces at 75 ℃, and observing to obtain that the marking traces disappear; when the temperature is reduced to below 65 ℃, the marking trace is not recovered and still transparent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. Octadecyl octadecanoate octadecather has a structure shown in a formula I:
2. a method of making the octadecyl octadecanoyl ether of claim 1 comprising the steps of:
mixing 1,18-octadecanediol solution with an alkaline catalyst, heating the obtained mixed system, mixing the heated mixed system with 1-iodooctadecane solution, preserving heat at the temperature of heating to perform substitution reaction, cooling the reaction solution to room temperature, and performing first post-treatment to obtain an intermediate;
mixing the intermediate, octadecanoic acid, toluene and sulfuric acid, heating and refluxing for esterification reaction, and performing second post-treatment after the raw materials are detected to disappear to obtain the octadecanoic acid octadecyl ester;
the alkaline catalyst is potassium carbonate or lithium bis (trimethylsilyl) amide;
when the catalyst is potassium carbonate, the solvent in the 1,18-octadecanediol solution and the 1-iodooctadecane solution is dimethylformamide; the molar ratio of 1,18-octadecanediol solution to the catalyst is 174.52:523.4, calculated as 1,18-octadecanediol;
when the catalyst is lithium bis (trimethylsilyl) amide, the solvent of the 1,18-octadecanediol solution and the 1-iodooctadecane solution is tetrahydrofuran; the molar ratio of 1,18-octadecanediol solution to the catalyst is 174.52:180.0, calculated as 1,18-octadecanediol.
3. The method as claimed in claim 2, wherein the molar ratio of 1,18-octadecanediol solution, 1-iodooctadecane solution and octadecanoic acid is 1:1:1.
4. the preparation method according to claim 2, wherein the temperature of the temperature rise is 50-60 ℃, and the time of the temperature preservation is 5-8 h;
the temperature of the heating reflux is 80-95 ℃, and the time is 6-10 h.
5. A microcapsule type phase-change material comprises a core material and a wall material wrapping the core material;
the core material is the octadecyl stearate in claim 1 or the octadecyl stearate prepared by the preparation method in any one of claims 2 to 4;
the wall material is carbon dioxide copolymer aliphatic polycarbonate.
6. The method for preparing a microcapsule-type phase change material as claimed in claim 5, comprising the steps of:
mixing octadecyl octadecanoate, carbon dioxide copolymer aliphatic polycarbonate and an organic solvent to obtain an oil phase;
mixing the oil phase and the water phase, and emulsifying to obtain an emulsion;
and removing the solvent from the emulsion to obtain the microcapsule type phase change material.
7. The method according to claim 6, wherein the organic solvent is ethyl acetate, dichloromethane, chloroform or acetone;
the mass ratio of the octadecyl octadecanoate, the carbon dioxide copolymer aliphatic polycarbonate to the organic solvent is 3:1:2.
8. the phase change ink is characterized by comprising the following components in parts by weight:
25 parts of microcapsule type phase change material; the microcapsule type phase change material is the microcapsule type phase change material as claimed in claim 5 or prepared by the preparation method as claimed in any one of claims 6 to 7;
5 parts of a thickening agent;
1 part of a film-forming assistant;
0.5 part of nonionic fluorine-containing surfactant;
0.5 part of defoaming agent;
and 81 parts of deionized water.
9. Use of the microcapsule-type phase change material of claim 5 or the microcapsule-type phase change material obtained by the preparation method of any one of claims 6 to 7 or the phase change ink of claim 8 in a thermally erasable pen, a friction pen or a thermal erase pen.
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| US20190322885A1 (en) * | 2016-06-29 | 2019-10-24 | Wap International Group Limited | A kind of temperature-sensitive erasable gel ink and its preparation method |
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