CN111013506B - Microcapsule emulsion of micromolecular anti-aging agent with degradable capsule wall and preparation method and application thereof - Google Patents
Microcapsule emulsion of micromolecular anti-aging agent with degradable capsule wall and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a capsule wall degradable micromolecular antioxidant microcapsule emulsion and a preparation method and application thereof. In order to solve the problem of thermal-oxidative degradation resistance of polyether, an anti-aging agent is added in the industry, but the anti-aging agent is mostly a small molecular substance, and is easily subjected to thermodynamic migration when being directly added into emulsion particles, so that the appearance and the stability of the emulsion are influenced, and the anti-aging effect is also influenced after the migration and precipitation. The invention prepares the anti-aging agent microcapsule by a microcapsule coating technology, coats micromolecule anti-aging agent molecules inside particles, obtains a shell structure with high urea bond content by hydrazine hydrate chain extension, sets a dynamic barrier, prevents the migration of the micromolecule anti-aging agent and forms a stable anti-aging structure; the degradable antioxidant microcapsule emulsion is added into the aqueous microfiber impregnating resin, so that the use is convenient and the storage process is stable.
Description
Technical Field
The invention belongs to the field of functional microcapsules, and relates to a microcapsule emulsion of a small molecular anti-aging agent with a degradable capsule wall, and a preparation method and application thereof.
Background
The microcapsule technology is used as a new carrier technology, and solid and liquid core materials which are difficult to convey or sensitive to the environment can be coated into a microcapsule structure, so that the problem that the core materials are ineffective or ineffective too fast before being conveyed to a use scene is solved, and the targeted conveying or slow release effect is achieved. At present, the most extensive application scenes of microcapsule technology are medicine carriers, phase change material carriers, self-repairing, aromatic essential oil finishing and the like, wherein microcapsules for targeted medicine treatment mostly adopt shell materials with good biocompatibility, for example, a chitosan material is used for coating liver cell compositions disclosed by Chinese patent CN201310424282.3, and a plurality of preparation technology disclosure materials of the phase change microcapsules are provided, for example, Chinese patent CN201410056694.0 and Zhujiaping's ' phase change microcapsule preparation method research progress ', Liyanqing ' phase change microcapsule thermal conductivity and functionalization research progress ', sweet ' middle temperature phase change microcapsule research current situation and progress ' and other papers provide detailed explanation on the preparation methods of the phase change microcapsules, capsule wall materials, application fields and the like. Chinese patent CN201310548440.6 discloses an epoxy resin self-repairing microcapsule, and Chinese patent CN201410722224.3 discloses a herbal essence microcapsule. Chinese patent CN201410818500.6 discloses that a gold nano-encapsulated aromatic leather finishing agent is a nano-microcapsule aqueous solution, but the preparation process needs to use nano-gold, the cost is high, and the application range is narrow.
The polymer organic resin is easy to age and degrade when being affected by external environmental factors such as light, heat and the like, so the addition of the anti-aging agent is important, but because the anti-aging agent is mostly a small molecular substance, and has some compatibility differences with the resin, the migration of an auxiliary agent is easy to occur, in the literature which is published and reported at present, copolymerization and microencapsulation are reported, the copolymerization needs organic synthesis modification due to the limitation of raw materials, the process is complex, the production cost is higher, microencapsulation is a relatively economic and practical method, and the microcapsule containing the ultraviolet absorbent disclosed in the paper of Zhang, namely the preparation and performance research of a slow-release type microencapsulated ultraviolet absorbent is also the traditional microcapsule preparation method adopted, and the obtained microcapsule powder is added into a resin body to be melted and mixed for molding, even though the slow-release effect is mentioned, but no targeted structural design for controlled release of microcapsules is made.
The aqueous microfiber impregnating resin needs to undergo multi-step processing such as impregnation, decrement, dyeing and the like in the application and processing process, has higher requirements on weather resistance and sunlight resistance in the use process, and the adopted polyurethane resin simultaneously has multiple performances such as alkali resistance, high temperature resistance, weather resistance, sunlight resistance and the like. Starting from a polyurethane structure, it is difficult to realize all functions by changing raw materials or designing a formula, and the functions are realized by adding an auxiliary agent. The oily microfiber impregnating resin is a solvent type homogeneous system, so that the use and addition of the auxiliary agent are convenient, but the aqueous microfiber resin is emulsion type heterogeneous, so that the addition of the auxiliary agent is inconvenient, and the addition of the auxiliary agent in a traditional oily manner easily causes the precipitation and aggregation instability of the auxiliary agent. Meanwhile, the dyeing processing technology of the microfiber, particularly the dyeing of the polyester microfiber, needs to resist the high temperature of 130 ℃, and an anti-aging auxiliary agent is also needed to act in the dyeing stage.
Disclosure of Invention
The invention provides a micromolecule anti-aging agent microcapsule emulsion which can be controlled to be released in a specific link, wherein the microcapsule emulsion takes polyester polyurea polyurethane as a shell layer, a polyurea structure provides a barrier for micromolecule migration, migration of an auxiliary agent in a storage process is prevented, polyester is taken as a weak bond capable of responding to alkali, ester bond hydrolysis is triggered under the action of alkali in the process of decrement, and the microcapsule shell layer is degraded to release the auxiliary agent.
Therefore, the technical scheme adopted by the invention is as follows: a microcapsule emulsion of micromolecule anti-aging agent with degradable capsule wall comprises a degradable resin capsule shell layer and an anti-aging agent inner core.
Further, the resin capsule shell layer is made of polyester polyurea polyurethane, the anti-aging agent core comprises an antioxidant, an ultraviolet absorbent and a light stabilizer, and the mass ratio of the antioxidant to the ultraviolet absorbent is 1: 0.5-1: 2; the mass ratio of the ultraviolet absorber to the light stabilizer is 1: 0.5-1: 2. The polyester polyurea polyurethane has high cohesive energy and can prevent the migration of small molecular anti-aging agents.
The invention adopts another technical scheme that: the preparation method of the micromolecule antioxidant microcapsule emulsion comprises the following steps:
1) heating 40-120 parts by mass of one or more of polymer dihydric alcohol or polymer polyhydric alcohol with the molecular weight of 500-4000 to 90-120 ℃, performing vacuum dehydration for 30-90 min, cooling to 55-75 ℃, adding 15-35 parts by mass of diisocyanate, stirring uniformly under the protection of nitrogen, reacting for 0.5-1 h at 80-90 ℃, adding 0.01-0.05 part by mass of at least one of dibutyltin dilaurate and stannous octoate as a catalyst, and reacting for 1-3 h at 60-90 ℃ to obtain a clear and transparent reactant A;
2) at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid and ethylene diamino ethane sodium sulfonate is used as a hydrophilic chain extender, 1, 4-butanediol, diethylene glycol, 2-methylpropanediol, 3-methylpentanediol, neopentyl glycol, 1, 6-hexanediol, 2-methyl-2-ethylpropanediol, trimethylolpropane or a plurality of the above is used as a micromolecule chain extender, and acetone, butanone, N-dimethylformamide, N-methylpyrrolidone or a plurality of the above is used as a solvent; adding 2-6 parts by mass of a hydrophilic chain extender, 1.5-4 parts by mass of a micromolecular chain extender and 0.1-30 parts by mass of a solvent into the reactant A obtained in the step 1), and reacting for 1-3 hours at the temperature of 60-90 ℃; cooling to 45-70 ℃ to obtain a clear and viscous shell resin prepolymer B;
3) preparing a reactant A with a certain mass according to the step 1), fully mixing the reactant A and diisocyanate monomers according to a certain mass ratio to prepare a dissolving medium, adding an antioxidant, an ultraviolet absorbent and a light stabilizer as an auxiliary mixture, wherein the mass ratio of the reactant A to the diisocyanate monomers is 1:0.1-1:0.4, and the total mass ratio of the dissolving medium to the auxiliary mixture is controlled within the range of 1:1.5-1: 4; heating to 60-90 ℃ under the condition of stirring, and fully dissolving to obtain a mixture C serving as a microcapsule core material;
4) weighing the prepolymer B and the mixture C according to the mass ratio of 1:1-1:1.5, adding a neutralizing agent for neutralization, fully stirring for 15-300 seconds to obtain a uniform mixed prepolymer, adding the neutralizing agent corresponding to the acid value to neutralize the mixed prepolymer until the pH value is 7, and then dispersing the neutralized mixed prepolymer in deionized water under high-speed stirring at 800-2000 r/min to obtain an anti-aging agent microcapsule primary emulsion;
5) heating the primary emulsion to 45-55 ℃ under the condition of keeping stirring, dropwise adding a rear chain extender of which the molar ratio of an active functional group to NCO in the primary emulsion of the anti-aging agent microcapsule is 0.45-0.8: 1 into the primary emulsion by taking one or more of ethylenediamine, butanediamine, isophorone diamine, hexamethylene diamine, pentanediamine, piperazine, cyclohexanediamine, hydrazine hydrate and diethylenetriamine as the rear chain extender, controlling the dropwise adding time for 0.5-2 h, heating to 70 ℃ after the dropwise adding is finished, preserving heat for 4-5h, and then decompressing and removing the solvent to obtain the anti-aging agent microcapsule emulsion.
Further, the polymer polyol is selected from one or more of 1, 4-butanediol adipate, 1, 6-hexanediol adipate and polyethylene glycol adipate.
Further, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and 4, 4' -methylene dicyclohexyl diisocyanate.
Further, the neutralizing agent is one or more of triethylamine, sodium hydroxide and triethanolamine.
Further, the antioxidant is one or more of 2, 6-di-tert-butyl-4-methylphenol, tris (2, 4-di-tert-butylphenyl) phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further, the ultraviolet absorbent is one or more of benzophenone ultraviolet absorbent and benzotriazole ultraviolet absorbent.
Further, the light stabilizer is one or more of hindered amine light stabilizer and hindered amine light stabilizer.
The invention adopts another technical scheme that: the application of the micro-molecular anti-aging agent microcapsule emulsion is to add the micro-molecular anti-aging agent microcapsule emulsion into aqueous microfiber impregnating resin, wherein the addition amount of the micro-molecular anti-aging agent microcapsule emulsion is 0.5-2.0g/100 g.
The invention has the following beneficial effects:
the degradable microcapsule emulsion provided by the invention is emulsion type, is specially used for solving the problem of instability of the aqueous resin additive in shelf life, and is particularly suitable for adding aqueous microfiber impregnating resin with alkali decrement requirement. The degradable microcapsule emulsion is added into the aqueous microfiber impregnating resin, so that the use is convenient, and the storage process is stable. Compared with the common microcapsule, the microcapsule provided by the invention has alkali-responsive degradable groups, and the hydrolysis is triggered by the action of alkali in the decrement process, so that the release effect of a specified link is achieved.
Detailed Description
The present invention is illustrated by the following specific examples, which include but are not limited to these examples.
Example 1
Weighing 80g of poly (1, 6-hexanediol adipate) with molecular weight of 2000, adding the poly (1, 6-hexanediol adipate) into a four-neck flask with a stirring paddle and nitrogen protection, heating to 120 ℃, carrying out vacuum dehydration for 30min, cooling to 55 ℃, adding 33.6g of HMDI (dimethyl formamide), uniformly stirring under the nitrogen protection, reacting at 85 ℃ for 1h, adding 0.01g of stannous octoate serving as a catalyst, reacting at 60 ℃ for 3h to obtain a clear and transparent reactant A, adding 5.3g of dimethylolpropionic acid, 1.5g of neopentyl glycol, 20g of butanone, and reacting at 75 ℃ for 2 h; cooling to 45 ℃ to obtain a clear and viscous shell resin prepolymer B, preparing 32g of reactant A according to the step 1), uniformly mixing the reactant A with 13g of HMDI to be used as a dissolving medium, adding 28.8g of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionyl) hexanediamine), 57.6g of an ultraviolet absorbent CHIMASSORB 81 and 57.6g of a light stabilizer TINUVIN 770, heating to 65 ℃ under the stirring condition, and fully dissolving to obtain a mixture C as a microcapsule core material; and (3) adding 3.7g of triethylamine into the shell resin prepolymer B prepared in the step for neutralization, mixing with the mixture C, fully stirring for 30s, and dispersing in deionized water at the rotating speed of 1500r/min to obtain the microcapsule primary emulsion. Heating the microcapsule primary emulsion to 45 ℃ under the condition of maintaining stirring, dropwise adding a mixed chain extender consisting of 2.6g of butanediamine, 3g of pentanediamine and 3.1g of diethylenetriamine into the primary emulsion, controlling the dropwise adding time for 2h, heating to 70 ℃ after the dropwise adding is finished, preserving the temperature for 5h, and then decompressing and removing the solvent to obtain the antioxidant microcapsule emulsion.
Example 2
Weighing 120g of 1, 4-butanediol adipate with the molecular weight of 3000, adding the weighed 1, 4-butanediol adipate into a four-neck flask with a stirring paddle and nitrogen protection, heating to 100 ℃, carrying out vacuum dehydration for 90min, cooling to 75 ℃, adding 28.7g of IPDI (isophorone diisocyanate) by mass, uniformly stirring under the nitrogen protection, reacting at 90 ℃ for 0.5h, then adding 0.05g of dibutyltin dilaurate by mass as a catalyst, reacting at 85 ℃ for 2.5h to obtain 148.7g of clear and transparent reactant A, adding 4.5g of dimethylolpropionic acid, 2g of 1, 4-butanediol, 30g of acetone, and reacting at 75 ℃ for 2 h; cooling to 45 ℃ to obtain a clear and viscous shell resin prepolymer B, preparing 47g of reactant A according to the step 1), uniformly mixing the reactant A with 5.4g of IPDI (isophorone diisocyanate), adding 40g of antioxidant (wherein the antioxidant 2642, 6-di-tert-butyl-4-methylphenol 25g, the antioxidant 168 tris (2, 4-di-tert-butylphenyl) phosphite 15g), 20g of ultraviolet absorbent TINUVIN 328 and 20g of light stabilizer TINUVIN 622), heating to 65 ℃ under stirring, and fully dissolving to obtain 132g of mixture C as a microcapsule core material; 155g of the shell resin prepolymer B prepared in the step is added with 2.8g of triethylamine for neutralization, then mixed with 130g of the mixture C, fully stirred for 2min, and then dispersed in deionized water at the rotating speed of 800r/min to obtain the microcapsule primary emulsion. Heating the primary microcapsule emulsion to 45 ℃ under the condition of keeping stirring, dropwise adding a mixed chain extender consisting of 1.4g of ethylenediamine, 1.2g of hydrazine hydrate and 3.9g of isophorone diamine into the primary emulsion, controlling the dropwise adding time for 2h, heating to 75 ℃ after the dropwise adding is finished, preserving the temperature for 4h, and then decompressing to remove the solvent to obtain the antioxidant microcapsule emulsion.
Example 3
Weighing 40g of polyethylene glycol adipate with the molecular weight of 1000, adding the polyethylene glycol adipate into a four-neck flask with a stirring paddle and nitrogen protection, heating to 120 ℃, carrying out vacuum dehydration for 60min, cooling to 65 ℃, adding 16g of TDI (toluene diisocynate) by mass, uniformly stirring under the nitrogen protection, reacting for 0.5h at 85 ℃, adding 0.01g of dibutyltin dilaurate by mass as a catalyst, reacting for 2.5h at 85 ℃ to obtain a clear and transparent reactant A, adding 4g of hexanediol, 10g of acetone, and reacting for 2h at 75 ℃; cooling to 45 ℃, adding 2.5g of ethylenediamine ethyl sodium sulfonate to obtain a clear and viscous shell resin prepolymer B, preparing 20g of reactant A according to the step 1), uniformly mixing the reactant A with 4.2g of IPDI (isophorone diisocyanate) to be used as a dissolving medium, adding 20g of antioxidant 1010 (pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), 15g of ultraviolet absorbent TINUVIN 1577 and 15g of light stabilizer 765, heating to 65 ℃ under the stirring condition, and fully dissolving to obtain a mixture C as a microcapsule core material; and (3) mixing the shell resin prepolymer B prepared in the step with the mixture C, fully stirring for 30s, and then dispersing in deionized water at the rotating speed of 1500r/min to obtain the microcapsule primary emulsion. Heating the microcapsule primary emulsion to 45 ℃ under the condition of keeping stirring, dropwise adding a mixed chain extender consisting of 1.1g of hexamethylene diamine, 0.8g of piperazine and 1.0g of cyclohexanediamine into the primary emulsion, controlling the dropwise adding time to be 2 hours, heating to 70 ℃ after the dropwise adding is finished, preserving the temperature for 4 hours, and then decompressing to remove the solvent to obtain the antioxidant microcapsule emulsion.
Example 4
Respectively weighing 45g of polybutylene adipate with the molecular weight of 4000 and 45g of polybutylene adipate with the molecular weight of 500, adding the weighed materials into a four-neck flask provided with a stirring paddle and nitrogen protection, heating to 100 ℃, performing vacuum dehydration for 90min, cooling to 75 ℃, adding 14g of IPDI (isophorone diisocyanate) and 10.7g of HDI (hexamethylene diisocyanate), uniformly stirring under the nitrogen protection, reacting at 85 ℃ for 1h, then adding 0.03g of dibutyltin dilaurate serving as a catalyst, reacting at 85 ℃ for 2.5h to obtain a clear and transparent reactant A, adding 3.5g of dimethylolpropionic acid, 2g of diethylene glycol, 1.5g of 3-methylpentanediol, 15g of N-methylpyrrolidone, and reacting at 75 ℃ for 2 h; cooling to 45 ℃ to obtain a clear and viscous shell resin prepolymer B, preparing 30g of reactant A according to the step 1), uniformly mixing the reactant A with 9g of HDI to be used as a dissolving medium, adding 33.4g of an antioxidant 1076 (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate), 16.7g of an ultraviolet absorbent TINUVIN 231 and 66.8g of a light stabilizer 765, heating to 65 ℃ under the condition of stirring, and fully dissolving to obtain a mixture C as a microcapsule core material; and (3) mixing the shell resin prepolymer B prepared in the step with the mixture C, fully stirring for 60s, and then dispersing in deionized water at the rotating speed of 2000r/min to obtain the microcapsule primary emulsion. Heating the microcapsule primary emulsion to 55 ℃ under the condition of keeping stirring, dropwise adding a mixed chain extender consisting of 3.2g of ethylenediamine and 5.4g of diethylenetriamine into the primary emulsion, controlling the dropwise adding time to be 0.5h, heating to 70 ℃ after the dropwise adding is finished, and keeping the temperature for 4h to obtain the antioxidant microcapsule emulsion.
Example 5
Weighing 120g of 1, 4-butanediol adipate with the molecular weight of 3000, adding the weighed 1, 4-butanediol adipate into a four-neck flask with a stirring paddle and nitrogen protection, heating to 110 ℃, carrying out vacuum dehydration for 60min, cooling to 55 ℃, adding 32.3g of MDI (diphenyl-methane-diisocyanate) by mass, uniformly stirring under the protection of nitrogen, reacting at 80 ℃ for 0.5h, then adding 0.03g of dibutyltin dilaurate by mass as a catalyst, reacting at 85 ℃ for 2.5h to obtain a clear and transparent reactant A, adding 4.5g of dimethylolbutyric acid, 2g of 2-methyl 1, 3-propanediol, and reacting at 75 ℃ for 2 h; cooling to 45 ℃ to obtain a clear and viscous shell resin prepolymer B, preparing 56g of reactant A according to the step 1), uniformly mixing the reactant A with 6.4g of IPDI (isophorone diisocyanate), taking the mixture as a dissolving medium, adding 40g of antioxidant (25 g of 2, 6-di-tert-butyl-4-methylphenol and 15g of antioxidant 168 tris (2, 4-di-tert-butylphenyl) phosphite in antioxidant 264), 20g of ultraviolet absorbent TINUVIN 328 and 20g of light stabilizer TINUVIN 622, heating to 65 ℃ under the stirring condition, and fully dissolving to obtain a mixture C as a microcapsule core material; and (3) adding 5g of triethanolamine into the shell resin prepolymer B prepared in the step for neutralization, mixing with the mixture C, fully stirring for 2min, and dispersing in deionized water at the rotating speed of 800r/min to obtain the microcapsule primary emulsion. Heating the microcapsule primary emulsion to 55 ℃ under the condition of keeping stirring, dropwise adding a mixed chain extender consisting of 1.8g of ethylenediamine, 1.5g of hydrazine hydrate and 4.2g of isophorone diamine into the primary emulsion, controlling the dropwise adding time for 0.5h, heating to 75 ℃ after the dropwise adding is finished, and preserving heat for 5h to obtain the antioxidant microcapsule emulsion.
Example 6
Weighing 80g of poly (1, 6-hexanediol adipate) with molecular weight of 2000, adding the poly (1, 6-hexanediol adipate) into a four-neck flask with a stirring paddle and nitrogen protection, heating to 120 ℃, carrying out vacuum dehydration for 30min, cooling to 75 ℃, adding 33.6g of HMDI (high molecular weight polyethylene glycol) by mass, uniformly stirring under the nitrogen protection, reacting at 90 ℃ for 0.5h, adding 0.03g of dibutyltin dilaurate by mass as a catalyst, reacting at 85 ℃ for 2.5h to obtain a clear and transparent reactant A, adding 5.3g of dimethylolpropionic acid, 1.5g of neopentyl glycol, 20g of butanone, and reacting at 75 ℃ for 2 h; cooling to 45 ℃ to obtain a clear and viscous shell resin prepolymer B, preparing 32g of reactant A according to the step 1), uniformly mixing the reactant A with 13g of HMDI to be used as a dissolving medium, adding 28.8g of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionyl) hexanediamine), 57.6g of an ultraviolet absorbent CHIMASSORB 81 and 57.6g of a light stabilizer TINUVIN 770, heating to 65 ℃ under the stirring condition, and fully dissolving to obtain a mixture C as a microcapsule core material; and (3) adding 1.5g of NaOH into the shell resin prepolymer B prepared in the step for neutralization, mixing with the mixture C, fully stirring for 30s, and dispersing in deionized water at the rotating speed of 1500r/min to obtain the microcapsule primary emulsion. Heating the microcapsule primary emulsion to 55 ℃ under the condition of maintaining stirring, dropwise adding a mixed chain extender consisting of 2.6g of butanediamine, 3g of pentanediamine and 3.1g of diethylenetriamine into the primary emulsion, controlling the dropwise adding time to be 1h, heating to 70 ℃ after the dropwise adding is finished, preserving the temperature for 4h, and then decompressing and removing the solvent to obtain the antioxidant microcapsule emulsion.
Example 7
Weighing 80g of poly (1, 6-hexanediol adipate) with molecular weight of 2000, adding the poly (1, 6-hexanediol adipate) into a four-neck flask with a stirring paddle and nitrogen protection, heating to 100 ℃, carrying out vacuum dehydration for 90min, cooling to 55 ℃, adding 33.6g of HMDI (high molecular weight polyethylene glycol), uniformly stirring under the protection of nitrogen, reacting at 90 ℃ for 0.5h, adding 0.03g of dibutyltin dilaurate serving as a catalyst, reacting at 85 ℃ for 2.5h to obtain a clear and transparent reactant A, adding 5.3g of dimethylolpropionic acid, 0.6g of 2-methyl-2-ethyl propylene glycol, 0.85g of trimethylolpropane and 20g of butanone, and reacting at 75 ℃ for 2 h; cooling to 45 ℃ to obtain a clear and viscous shell resin prepolymer B, preparing 32g of reactant A according to the step 1), uniformly mixing the reactant A with 13g of HMDI to be used as a dissolving medium, adding 28.8g of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionyl) hexanediamine), 57.6g of an ultraviolet absorbent CHIMASSORB 81 and 57.6g of a light stabilizer TINUVIN 770, heating to 65 ℃ under the stirring condition, and fully dissolving to obtain a mixture C as a microcapsule core material; and (3) adding 3.7g of triethylamine into the shell resin prepolymer B prepared in the step for neutralization, mixing with the mixture C, fully stirring for 30s, and dispersing in deionized water at the rotating speed of 1500r/min to obtain the microcapsule primary emulsion. Heating the microcapsule primary emulsion to 55 ℃ under the condition of keeping stirring, dropwise adding a mixed chain extender consisting of 2.6g of butanediamine, 3g of pentanediamine and 3.1g of diethylenetriamine into the primary emulsion, controlling the dropwise adding time to be 0.5h, heating to 75 ℃ after the dropwise adding is finished, preserving the temperature for 4h, and then decompressing and removing the solvent to obtain the antioxidant microcapsule emulsion.
Application effect contrast
The microcapsule emulsion prepared in the example is added into the water-based microfiber impregnating resin produced by the company, and compared with a blank resin and a resin directly added with an auxiliary agent, the strength loss condition and the light aging resistance after a film is formed and a weight reduction dyeing process are compared.
Comparison of actual application effects of degradable auxiliary agent microcapsules
Note: a. the amounts are based on the mass of the solid substances contained in the table.
b. And (3) light aging resistance test: the test conditions were set to be carried out according to the A1 standard of 6.6 in GB/T32088-.
c. The calculation formula of the intensity loss after the weight reduction dyeing processing is as follows:
the processing strength loss of the sample is represented by X, and the value is expressed by% and is calculated by the following formula (1):
in the formula:
σ0-the initial strength of the glue film in megapascals (MPa);
σ1strength of the adhesive film after weight reduction dyeing processing in megapascals (MPa)
From the experimental results, the addition of the small-molecular auxiliary agent in the form of microcapsules can more efficiently retain the anti-aging effect of the auxiliary agent.
Claims (10)
1. A preparation method of a micro-molecular antioxidant microcapsule emulsion is characterized by comprising the following steps:
1) heating 40-120 parts by mass of polymer polyol with the molecular weight of 500-4000 to 90-120 ℃, performing vacuum dehydration for 30-90 min, cooling to 55-75 ℃, adding 15-35 parts by mass of diisocyanate, uniformly stirring under the protection of nitrogen, reacting for 0.5-1 h at 80-90 ℃, adding 0.01-0.05 part by mass of at least one of dibutyltin dilaurate and stannous octoate as a catalyst, and reacting for 1-3 h at 60-90 ℃ to obtain a clear and transparent reactant A;
2) at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid and ethylene diamino ethane sodium sulfonate is used as a hydrophilic chain extender, 1, 4-butanediol, diethylene glycol, 2-methylpropanediol, 3-methylpentanediol, neopentyl glycol, 1, 6-hexanediol, 2-methyl-2-ethylpropanediol, trimethylolpropane or a plurality of the above is used as a micromolecule chain extender, and acetone, butanone, N-dimethylformamide, N-methylpyrrolidone or a plurality of the above is used as a solvent; adding 2-6 parts by mass of a hydrophilic chain extender, 1.5-4 parts by mass of a micromolecular chain extender and 0.1-30 parts by mass of a solvent into the reactant A obtained in the step 1), and reacting for 1-3 hours at the temperature of 60-90 ℃; cooling to 45-70 ℃ to obtain a clear and viscous shell resin prepolymer B;
3) preparing a reactant A with a certain mass according to the step 1), fully mixing the reactant A and diisocyanate monomers according to a certain mass ratio to prepare a dissolving medium, adding an antioxidant, an ultraviolet absorbent and a light stabilizer as an auxiliary mixture, controlling the total mass ratio of the dissolving medium to the auxiliary mixture to be within 1:1.5-1:4, heating to 60-90 ℃ under the stirring condition, and fully dissolving to obtain a mixture C as a microcapsule core material, wherein the mass ratio of the reactant A to the diisocyanate monomers is 1:0.1-1: 0.4;
4) weighing the prepolymer B and the mixture C according to the mass ratio of 1:1-1:1.5, adding a neutralizing agent for neutralization, fully stirring for 15-300 seconds to obtain a uniform mixed prepolymer, adding the neutralizing agent corresponding to the acid value to neutralize the mixed prepolymer until the pH value is 7, and then dispersing the neutralized mixed prepolymer in deionized water under high-speed stirring at 800-2000 r/min to obtain an anti-aging agent microcapsule primary emulsion;
5) heating the primary emulsion to 45-55 ℃ under the condition of keeping stirring, dropwise adding a rear chain extender of which the molar ratio of an active functional group to NCO in the primary emulsion of the anti-aging agent microcapsule is 0.45-0.8: 1 into the primary emulsion by taking one or more of ethylenediamine, butanediamine, isophorone diamine, hexamethylene diamine, pentanediamine, piperazine, cyclohexanediamine, hydrazine hydrate and diethylenetriamine as the rear chain extender, controlling the dropwise adding time for 0.5-2 h, heating to 70 ℃ after the dropwise adding is finished, preserving heat for 4-5h, and then decompressing and removing the solvent to obtain the anti-aging agent microcapsule emulsion.
2. The method according to claim 1, wherein the polymer polyol is one or more of 1, 4-butanediol adipate, 1, 6-hexanediol adipate and polyethylene glycol adipate.
3. The method of claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and 4, 4' -methylene dicyclohexyl diisocyanate.
4. The method according to claim 1, wherein the neutralizing agent is one or more of triethylamine, sodium hydroxide and triethanolamine.
5. The method according to claim 1, wherein the antioxidant is one or more of 2, 6-di-tert-butyl-4-methylphenol, tris (2, 4-di-tert-butylphenyl) phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), and N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
6. The preparation method of claim 1, wherein the ultraviolet absorbent is one or more of benzophenone ultraviolet absorbent and benzotriazole ultraviolet absorbent.
7. The method according to claim 1, wherein the light stabilizer is a hindered amine light stabilizer.
8. The capsule wall degradable small molecular age inhibitor microcapsule emulsion prepared by the preparation method of any one of claims 1 to 7,
the anti-aging agent is characterized by comprising a degradable resin capsule shell layer and an anti-aging agent core.
9. The microcapsule emulsion of the small molecular antioxidant with degradable capsule wall according to claim 8, wherein the shell layer of the resin capsule is made of polyester polyurea polyurethane, the inner core of the antioxidant comprises an antioxidant, an ultraviolet absorbent and a light stabilizer, and the mass ratio of the antioxidant to the ultraviolet absorbent is 1: 0.5-1: 2; the mass ratio of the ultraviolet absorber to the light stabilizer is 1: 0.5-1: 2.
10. The application of the capsule wall degradable small molecular antioxidant microcapsule emulsion prepared by the preparation method of any one of claims 1 to 7 is characterized in that the small molecular antioxidant microcapsule emulsion is added into aqueous microfiber impregnating resin, and the addition amount of the small molecular antioxidant microcapsule emulsion is 0.5 to 2.0g/100 g.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1513614A (en) * | 1975-04-09 | 1978-06-07 | Minnesota Mining & Mfg | Microcapsule insecticide composition |
| CN101724392A (en) * | 2009-11-24 | 2010-06-09 | 张世智 | Multiple reversible color change microcapsule anti-counterfeiting material and preparation method and application thereof |
| CN103668764A (en) * | 2013-12-11 | 2014-03-26 | 陈曦 | Nylon lace and preparation method thereof |
| CN103897135A (en) * | 2014-04-09 | 2014-07-02 | 杭州传化精细化工有限公司 | Method for preparing waterborne polyurethane emulsion with high solid content |
| CN105925168A (en) * | 2016-05-20 | 2016-09-07 | 武汉工程大学 | Microencapsulated water-based fire retardant coating and preparation method thereof |
| CN106566477A (en) * | 2016-11-08 | 2017-04-19 | 西安工程大学 | Polyurea/polyurethane composite shell microcapsule phase-change material and preparing method thereof |
| CN109304135A (en) * | 2017-07-28 | 2019-02-05 | 捷恩智株式会社 | Liquid crystal capsule and its manufacturing method |
-
2019
- 2019-12-30 CN CN201911388504.4A patent/CN111013506B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1513614A (en) * | 1975-04-09 | 1978-06-07 | Minnesota Mining & Mfg | Microcapsule insecticide composition |
| CN101724392A (en) * | 2009-11-24 | 2010-06-09 | 张世智 | Multiple reversible color change microcapsule anti-counterfeiting material and preparation method and application thereof |
| CN103668764A (en) * | 2013-12-11 | 2014-03-26 | 陈曦 | Nylon lace and preparation method thereof |
| CN103897135A (en) * | 2014-04-09 | 2014-07-02 | 杭州传化精细化工有限公司 | Method for preparing waterborne polyurethane emulsion with high solid content |
| CN105925168A (en) * | 2016-05-20 | 2016-09-07 | 武汉工程大学 | Microencapsulated water-based fire retardant coating and preparation method thereof |
| CN106566477A (en) * | 2016-11-08 | 2017-04-19 | 西安工程大学 | Polyurea/polyurethane composite shell microcapsule phase-change material and preparing method thereof |
| CN109304135A (en) * | 2017-07-28 | 2019-02-05 | 捷恩智株式会社 | Liquid crystal capsule and its manufacturing method |
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