CN115869867A - Microcapsule containing polyurethane/urea resin wall material of siloxane and preparation method thereof - Google Patents
Microcapsule containing polyurethane/urea resin wall material of siloxane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a microcapsule containing a polyurethane/urea resin wall material of siloxane and a preparation method thereof, relating to the technical field of microcapsule materials. The microcapsule provided by the invention comprises a core material and a wall material, wherein the core material comprises a core material component and/or an organic solvent, and the organic solvent comprises solvent oil and/or a carrier solvent; the wall material is polyurethane/urea resin containing siloxane; the siloxane-containing polyurethane/urea resin is obtained by crosslinking and curing an isocyanate-terminated siloxane component with polyamine and/or polyol. The invention adopts siloxane blocked by isocyanate and an addition product thereof as a microcapsule wall material, and the siloxane is very easy to dissolve in solvent naphtha, a carrier solvent and a core material, so that corresponding functional microcapsules can be obtained, the multifunction of the microcapsules is realized, and the application field of the microcapsules is expanded; in addition, the microcapsule containing the siloxane polyurethane/urea resin wall material provided by the invention has the advantages of high mechanical strength, excellent high and low temperature resistance, acid and alkali resistance, weather resistance and the like.
Description
Technical Field
The invention relates to the technical field of microcapsule materials, in particular to a microcapsule containing a polyurethane/urea resin wall material of siloxane and a preparation method thereof.
Background
The microcapsule technology is a technology for forming fine particles by coating a solid, a liquid or a gas with a film-forming material, and has attracted extensive attention of researchers due to many unique properties of substances formed into microcapsules. Patent CN202110910510.2 and patent CN202111236885.1 adopt terminal isocyanate polyurethane prepolymer with average molecular weight of 2500-10000 and terminal hydroxyl polysiloxane with average polymerization degree of 5-10, according to a molar ratio of 2:1, polysiloxane modified polyurea-polyurethane copolymer prepolymer is synthesized at 70-90 ℃ as wall material of microcapsule; patent CN202011512568.3, a double-end hydroxyl organosilicon oligomer with a molecular weight of 1000-2000 is reacted with a diisocyanate monomer according to a certain molar ratio at a certain temperature, and amino trialkoxysilane is used for end capping to obtain an organosilicon hybrid modified polyurethane prepolymer, which is used as a wall material of a microcapsule. The polysiloxane modified polyurethane/urea copolymer prepolymer and the organosilicon hybrid modified polyurethane prepolymer have high molecular weight and high viscosity, can be dissolved in only a small part of core materials and solvent components of the core materials which are well compatible with the polysiloxane modified polyurethane/urea copolymer prepolymer and the organosilicon hybrid modified polyurethane prepolymer, such as 200# solvent oil, a solution compounded by sec-butylbenzene and tetrachloroethylene and other good solvents, and can not be dissolved in carrier solvents of higher fatty acid esters (methyl behenate, ethyl behenate, methyl arachinate, ethyl arachinate, methyl stearate, ethyl stearate, butyl stearate, methyl palmitate, ethyl palmitate and the like) and higher fatty alcohols (n-eicosanol, n-nonadecanol, n-octadecanol, n-heptadecanol, n-hexadecanol, n-tetradecanol, n-dodecanol and the like). The prepolymer as the wall material is not miscible with these solvent carriers, and microcapsules containing such solvent carriers cannot be obtained by interfacial polymerization. These solvent carriers are indispensable in the corresponding functional microcapsules. Therefore, the prepolymer (or prepolymer) used as the wall material in the patents CN202110910510.2, CN202111236885.1 and CN202011512568.3 greatly limits the application thereof in the field of microcapsule technology.
Disclosure of Invention
In view of the above, the present invention aims to provide a microcapsule containing a polyurethane/urea resin wall material of siloxane and a preparation method thereof. The microcapsule containing the polyurethane/urea resin wall material of siloxane provided by the invention is very easy to dissolve in 200# solvent naphtha, a solution compounded by sec-butylbenzene and tetrachloroethylene, phenyl dimethylethane, diarylethane, phenyl ethylphenyl ethane and other solvent naphtha; meanwhile, the microcapsule can be dissolved in core materials such as normal alkane and liquid crystal, and carrier solvents such as higher fatty acid ester and higher fatty alcohol, and further can obtain multifunctional microcapsules.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a microcapsule with a siloxane polyurethane/urea resin wall material, which comprises a core material and a wall material, wherein the core material comprises a core material component and/or an organic solvent, and the organic solvent comprises solvent oil and/or a carrier solvent; the wall material is polyurethane/urea resin containing siloxane; the siloxane-containing polyurethane/urea resin is obtained by crosslinking and curing an isocyanate-terminated siloxane component with a polyol and/or a polyamine; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct of an isocyanate-terminated siloxane and trimethylolpropane; the isocyanate-terminated siloxane has a structure represented by formula I, and the isocyanate-terminated siloxane adduct has a structure represented by formula II:
in the formulas I and II, R1, R2, R3, R4, R5 and R6 are independently selected from linear alkyl, branched alkyl, cycloalkyl, phenyl, substituted phenyl or biphenyl, and the molecular weight of the R1 or R2 group is not more than 300; the molecular weight of the R3, R4, R5 or R6 group does not exceed 200.
Preferably, the isocyanate-terminated siloxane has a structure represented by any one of formulas i 1 to i 6:
preferably, the isocyanate-terminated siloxane adduct has a structure represented by any one of formulas II 1 to II 6:
preferably, the solvent oil comprises one or more of 200# solvent oil, sec-butylbenzene-tetrachloroethylene compound solvent, phenyl dimethylethane, diarylethane and phenyl ethylphenylethane; the carrier solvent comprises one or more of higher fatty acid ester and higher fatty alcohol.
Preferably, the core material component comprises a phase change energy storage material, a thermochromic material, a photochromic material or an electrochromic material.
The invention provides a preparation method of the microcapsule in the technical scheme, which comprises the following steps:
(1) Mixing an emulsifier and water to obtain a water phase;
(2) Mixing the core material with the siloxane component blocked by isocyanate to obtain an oil phase; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct;
(3) Adding the oil phase into the water phase for emulsification to obtain an oil-in-water emulsion;
(4) Mixing the oil-in-water type emulsion with a cross-linking agent aqueous solution and a catalyst for cross-linking and curing to obtain microcapsule slurry; the cross-linking agent in the cross-linking agent aqueous solution is polyamine and/or polyalcohol;
(5) Carrying out solid-liquid separation, solid-phase washing and drying on the microcapsule slurry in sequence to obtain microcapsules;
the steps (1) and (2) are not limited in chronological order.
Preferably, the mass content of the emulsifier in the water phase is 2.5-5%.
Preferably, the mass ratio of the core material to the isocyanate-terminated siloxane component is (40 to 80): (12-20); when the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane adduct, a co-solvent is also included in the oil phase.
Preferably, the temperature of the aqueous phase is 70 ℃ when the oil phase is added to the aqueous phase; the dispersion speed of the emulsification is 2000-6000 rpm, and the emulsification time is 5-10 min.
Preferably, the mass ratio of the isocyanate-terminated siloxane component, the crosslinking agent and the catalyst is 10 to 50:2 to 20:0.01 to 1; the crosslinking and curing process comprises a first crosslinking and curing process and a second crosslinking and curing process which are sequentially carried out, wherein the temperature of the first crosslinking and curing process is 70 ℃, the heat preservation time is 1 hour, the temperature of the second crosslinking and curing process is 85 ℃, and the heat preservation time is 2 hours.
The invention provides a microcapsule with a siloxane polyurethane/urea resin wall material, which comprises a core material and a wall material, wherein the core material comprises a core material component and/or an organic solvent, and the organic solvent comprises solvent oil and/or a carrier solvent; the wall material is polyurethane/urea resin containing siloxane; the siloxane-containing polyurethane/urea resin is obtained by crosslinking and curing an isocyanate-terminated siloxane component and polyamine and/or polyol; the isocyanate-terminated siloxane component includes an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct of an isocyanate-terminated siloxane and trimethylolpropane. The invention adopts siloxane blocked by isocyanate and addition product thereof as the raw material of microcapsule wall material, which is very soluble in 200# solvent naphtha, solution compounded by sec-butylbenzene and tetrachloroethylene, phenyl dimethylethane, diarylethane, phenyl ethylphenylethane and other solvent naphtha, and simultaneously can be dissolved in core material substances such as normal alkane, liquid crystal (such as cholesterol type liquid crystal and nematic type liquid crystal) and other carrier solvents such as higher fatty acid ester and higher fatty alcohol, thereby obtaining the microcapsule containing the isocyanate-terminated siloxane and the addition product thereof by an interfacial polymerization methodThe microcapsules of the solvent further obtain corresponding functional microcapsules (such as phase change energy storage microcapsules, thermochromic microcapsules, photochromic microcapsules or electrochromic microcapsules), realize the multifunction of the microcapsules and expand the application field of the microcapsules. In addition, the invention takes siloxane blocked by isocyanate and an addition product thereof as wall material raw materials, combines the characteristics of the siloxane with the high reactivity of the isocyanate, and forms a microcapsule containing a stable polyurethane/urea shell with a Si-O-Si crosslinking net structure after being cured with polyamine and/or polyol (a crosslinking agent) in a system; because the Si-O-Si bond energy is far greater than the chemical bond energy of other structures, the microcapsule has the characteristics of high compactness, high mechanical strength, good thermal stability, good thermal conductivity, high and low temperature resistance and excellent weather resistance; si-O and Si-CH in simultaneous structure 3 Due to the existence of the microcapsule, the microcapsule has the advantages of low surface tension, excellent electrical insulation, good physiological inertia, good biocompatibility and the like, and has important application value.
Detailed Description
The invention provides a microcapsule with a siloxane polyurethane/urea resin wall material, which comprises a core material and a wall material, wherein the core material comprises a core material component and/or an organic solvent, and the organic solvent comprises solvent oil and/or a carrier solvent; the wall material is polyurethane/urea resin containing siloxane; the siloxane-containing polyurethane/urea resin is obtained by crosslinking and curing an isocyanate-terminated siloxane component and polyamine and/or polyol; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct of an isocyanate-terminated siloxane and trimethylolpropane; the isocyanate-terminated siloxane has a structure represented by formula I, and the isocyanate-terminated siloxane adduct has a structure represented by formula II:
in the formulas I and II, R1, R2, R3, R4, R5 and R6 are independently selected from linear alkyl, branched alkyl, cycloalkyl, phenyl, substituted phenyl or biphenyl, and the molecular weight of the R1 or R2 group is not more than 300; the molecular weight of the R3, R4, R5 or R6 group does not exceed 200.
In the present invention, the wall material of the microcapsule is a silicone-containing polyurethane/urea resin; the siloxane-containing polyurethane/urea resin is obtained by crosslinking and curing an isocyanate-terminated siloxane component and polyamine and/or polyol; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane having a structure represented by formula I and/or an isocyanate-terminated siloxane adduct having a structure represented by formula II. In the present invention, in said formulae i and ii, cycloalkyl is preferably cyclopropane, cyclopentane or cyclohexane; in the formulas I and II, R3 and R4 are preferably the same group, R5 and R6 are preferably the same group, and R1 and R2 may be the same group or different groups. In the present invention, the isocyanate-terminated siloxane preferably has a structure represented by any one of formulas I1 to I6:
in the present invention, the isocyanate-terminated siloxane adduct preferably has a structure represented by any one of formulas II 1 to II 6:
the source of the isocyanate-terminated siloxanes and isocyanate-terminated siloxane adducts of the present invention is not particularly critical and are commercially available or may be prepared by methods well known to those skilled in the art. In the present examples, isocyanate-terminated siloxanes having the structure shown in formula I1 have CAS numbers 37601-26-6, available from HongKongChemhere; isocyanate-terminated siloxanes having the structure shown in formula I2 have a CAS number of 62336-40-7 available from Hong Kong Chemhere; isocyanate-terminated siloxanes having the structure shown in formula I3 have CAS number 20160-69-4 available from Alfa chemistry; isocyanate-terminated siloxanes having the structure shown in formula I4 have a CAS number of 37491-41-1 available from Alfachemistry; isocyanate-terminated siloxane having a structure represented by formula I5 having CAS number of 40638-12-8, available from Zhengzhou Ruijai New Nano Material science and technology Co., ltd; isocyanate-terminated siloxanes having the structure shown in formula I6 are available from Sanfu silicon, inc. of Tang mountain. In the present examples, isocyanate terminated siloxane adducts having formula II 1 to formula II 6 were purchased from Zhengzhou Ruijai New Nano Material science and technology Co., ltd (custom synthesis).
In the invention, the polyamine is preferably one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylenepolyamine and polyethyleneimine, and the polyol is preferably one or more of ethylene glycol, polyethylene glycol, N '-dihydroxyethyl diethylenetriamine, glycerol, propylene glycol, 1,6-hexanediol and N, N' -tetrakis (2-hydroxypropyl) ethylenediamine.
In the invention, the core material of the microcapsule comprises an organic solvent, the organic solvent comprises solvent naphtha and/or a carrier solvent, and the solvent naphtha preferably comprises one or more of 200# solvent naphtha, sec-butylbenzene-tetrachloroethylene compound solvent, phenyl dimethyl ethane, diaryl ethane and phenyl ethyl phenyl ethane; the carrier solvent preferably comprises one or more of higher fatty acid ester and higher fatty alcohol; the higher fatty acid ester is preferably one or more of methyl behenate, ethyl behenate, methyl arachidate, ethyl arachidate, methyl stearate, ethyl stearate, butyl stearate, methyl palmitate and ethyl palmitate; the higher fatty alcohol is preferably one or more of n-eicosanol, n-nonadecanol, n-octadecanol, n-heptadecanol, n-hexadecanol, n-tetradecanol and n-dodecanol. The invention adopts siloxane blocked by isocyanate and addition products thereof as the raw materials of microcapsule wall materials, and the siloxane blocked by isocyanate and the addition products thereof are very easy to dissolve in 200# solvent naphtha, solution compounded by sec-butylbenzene and tetrachloroethylene, solvent naphtha such as phenyl dimethylethane, diarylethane and phenyl ethylphenylethane, and the like, and can also dissolve in carrier solvents such as higher fatty acid ester and higher fatty alcohol, so that microcapsules containing the solvents can be obtained through an interfacial polymerization method, and further the corresponding functional microcapsules can be obtained.
In the present invention, the core material includes a core material component, and the core material component preferably includes a phase change energy storage material, a thermochromic material, a photochromic material, or an electrochromic material.
In the invention, the phase change energy storage material is preferably n-alkane, and the n-alkane is preferably one or more of n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, tetracosane, pentacosane and hexacosane; when the core material component is the phase change energy storage material, no organic solvent is required in the core material. The invention adopts siloxane blocked by isocyanate and an addition product thereof as the wall material of the microcapsule, and the siloxane and the addition product thereof are very easy to dissolve in core material components such as normal alkane, thereby obtaining the phase change energy storage microcapsule.
In the present invention, the thermochromic material preferably includes a thermosensitive dye and a color developer, or includes a fluorescent dye and a color developer; the thermosensitive dye is preferably 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophenyl peptide (colorless)
Blue), N-dimethyl-4- [2- [2- (octyloxy) phenyl]-6-phenyl-4-pyridinyl]Aniline (colorless->
Yellow), 2-phenylamino-6-dibutylamino-3-methylfluoran (colorless->
Black), 1,2-benzo-6-diethylaminofluoran (colorless @)>
Dark blue), 3',6' -dimethoxyfluoran (colorless->
Bright yellow), 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide (colorless->
Green), 3,3-bis (2-methyl-1-octyl-1H-indol-3-yl) phthalide (colorless->
Rose color), 1,3-dimethyl-6-diethylaminofluoran (colorless/clear @)>
Orange) and 2 '-chloro-6' - (diethylamino) fluoran (colorless->
Red) or more; the fluorescent dye is preferably 2,6-bis (2-ethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine (colorless->
Orange), 2,6-bis (4-dimethylaminophenyl) -4- (4-methoxyphenyl) pyridine (colorless->
Orange) and 2,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (3-methylphenyl) aminophenyl) pyridine (colorless->
Yellow) or more; the developer is preferably bisphenol A, bisphenol AF, bisphenol AP, bisphenol S, bisphenol P, 4-hydroxy-4-isopropoxydiphenyl sulfone (D-8), 4,4' - (1,2-diethylethylene) diphenol, 4,4' - (2-ethylhexane-1,1-diyl) diphenol, and 4,4' - (2-methylpropylidene) diphenol. In the invention, when the core material component is the thermochromic material, the core material comprises the organic solvent, and the thermochromic microcapsule is obtained by adding the organic solvent which is suitable for the thermochromic material. In the invention, the organic solvent corresponding to the thermosensitive dye is preferably one or more of methyl behenate, methyl stearate and methyl palmitate, and the organic solvent corresponding to the fluorescent dye is preferably n-hexadecanol and methyl stearate; the mass ratio of the thermal dye, the color developer and the organic solvent is preferably 3.
In the present invention, the photochromic material is preferably a photochromic dye, and the photochromic dye is preferably 1,3-dihydro-1,3,3-trimethylspiro [ 2H-indole-2,3' - [3H ] s]Pyrido [3,2-f][1,4]Benzoxazines as herbicides](white color)
Red), 5-chloro-1,3-dihydro-1,3,3-trimethyl-6 '- (1-piperidinyl) spiro [ 2H-indole-2,3' - [ 3H-]Naphthalene [2,1-b][1,4]Oxazines](white->
Reddish purple), 1,3,3-trimethyl-9 '-hydroxy spiro [ indoline-2,3' - [3H ]]Naphtho [2,1-b](1,4) oxazines](white->
Blue), 1,3,3-trimethylindoline-6' - (1-piperidinyl) spirophenoxazine (white->
Violet), 1',3' -dihydro-1 ',3',3 '-trimethyl-6,8-dinitrospiro [ 2H-1-benzopyran-2,2' - [2H]Indoles](white->
Yellow colour) 1',3' -dihydro-1 ',3',3 '-trimethyl-6-nitro spiro [ 2H-1-benzopyran-2,2' - [2H ]]Indoles](yellow) device for selecting or keeping>
Purple), 5-chloro-1,3-dihydro-1,3,3-trimethylspiro [ 2H-indole-2,3' - (3H) naphtho [2,1-b](1,4) oxazines](white color)
Blue), 1,3-dihydro-1,3,3-trimethylspiro [ 2H-indole-2,3' - [3H ]]Naphtho [2,1-b][1,4]Oxazines (white->
Blue), 1,3-dihydro-1,3,3-trimethyl-6 '- (4-morpholinyl) -spiro [ 2H-indole-2,3' - [3H]Naphtho [2,1-b][1,4]Oxazines](white->
Violet), 1'- (2-hydroxyethyl) -3',3 '-dimethyl-6-nitrospiro [1 (2H) -benzopyran-2,2' -indoline](purple->
Mauve), 1',3',5,6,7,8-hexahydro-1 ',3',3 '-trimethylspiro [2H-1,4-benzoxazine-2,2' -2H indole](white->
Orange), 6' - (2,3-dihydro-1H-indol-1-yl) -1,3-dihydro-1,3,3-trimethylspiro [ 2H-indole-2,3 ' - [ 3H-indole-2,3 ' ]]Naphthalene [2,1-b][1,4]Oxazines](yellow) device for selecting or keeping>
Navy blue) and 3,3-diphenyl-3H-naphtho [2,1-b]Pyran (white->
Yellow) is adopted. In the present invention, when the core material component is the photochromic material, the core material includes the above-mentioned organic solventAnd the agent is added with an organic solvent which is adaptive to the photochromic material, so that the photochromic microcapsule is obtained. In the invention, the organic solvent corresponding to the photochromic dye is preferably one or more of phenyl dimethyl ethane, diaryl ethane, phenyl ethyl phenyl ethane and No. 200 solvent naphtha; the mass ratio of the photochromic dye to the organic solvent is preferably 3:100.
in the present invention, the electrochromic material is preferably a liquid crystal material, and the liquid crystal material is preferably a cholesteric liquid crystal or a nematic liquid crystal. The cholesteric liquid crystal is not particularly required, and can be prepared by a cholesteric liquid crystal well known to a person skilled in the art, and in the embodiment of the invention, the cholesteric liquid crystal is purchased from Shijia Chengxing Yonghua display materials, inc., and has the model number of ZKA10400 or ZKA10500. The nematic liquid crystal is not particularly required in the present invention, and may be a nematic liquid crystal known to those skilled in the art, and in the present embodiment, the nematic liquid crystal is obtained from Shijiacheng Yonghua display materials, inc., model number ZKA11300 (electrochromic, white/opaque state)
Colorless/transparent state). In the invention, when the core material component is the electrochromic material, the core material does not need an organic solvent, and the invention adopts isocyanate-terminated siloxane and an addition product thereof as the raw material of the microcapsule wall material, which is very easy to dissolve in the core material components such as liquid crystals, thereby obtaining the electrochromic microcapsule.
In the present invention, the particle diameter of the microcapsule is preferably 0.4 to 10 μm.
The invention provides a preparation method of the microcapsule in the technical scheme, which comprises the following steps:
(1) Mixing an emulsifier and water to obtain a water phase;
(2) Mixing the core material with the siloxane component blocked by isocyanate to obtain an oil phase; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct;
(3) Adding the oil phase into the water phase for emulsification to obtain an oil-in-water emulsion;
(4) Mixing the oil-in-water type emulsion with a cross-linking agent aqueous solution and a catalyst for cross-linking and curing to obtain microcapsule slurry; the cross-linking agent in the cross-linking agent aqueous solution is polyamine and/or polyalcohol;
(5) Carrying out solid-liquid separation, solid-phase washing and drying on the microcapsule slurry in sequence to obtain microcapsules;
the steps (1) and (2) are not limited in chronological order.
The invention mixes the emulsifier and water to obtain water phase. In the invention, the emulsifier is preferably one or more of sodium dodecyl benzene sulfonate, newcol707-SF, polyvinyl alcohol, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, polyvinylpyrrolidone and styrene maleic anhydride copolymer. In the invention, the mass content of the emulsifier in the water phase is preferably 2.5-5%, more preferably 3-4%; when the emulsifier is a styrene maleic anhydride copolymer, the styrene maleic anhydride copolymer is preferably compounded with sodium hydroxide, and the mass ratio of the styrene maleic anhydride copolymer to the sodium hydroxide is preferably 1.13. According to the invention, water is preferably added into the emulsifier for mixing, and the mixing is preferably stirring mixing.
The invention mixes the core material with the siloxane component blocked by isocyanate to obtain the oil phase. In the invention, the core material is the same as the technical scheme, and is not described again; the isocyanate-terminated siloxane component comprises isocyanate-terminated siloxane and/or isocyanate-terminated siloxane adduct, and the isocyanate-terminated siloxane adduct are the same as the technical scheme, and are not described again. In the present invention, the mass ratio of the core material to the isocyanate-terminated siloxane component is preferably (40 to 80): (12 to 20), more preferably (50 to 75): (15 to 20). In the invention, the isocyanate-terminated siloxane component is preferably added into the core material for mixing, and the mixing is preferably stirring mixing, wherein the stirring mixing time is controlled to ensure complete mutual solubility. In the present invention, when the isocyanate-terminated siloxane component includes an isocyanate-terminated siloxane adduct, the oil phase also preferably includes a co-solvent, the co-solvent is preferably ethyl acetate or butanone, and the mass ratio of the isocyanate-terminated siloxane adduct to the co-solvent is preferably (10 to 30): (20 to 30).
After obtaining the water phase and the oil phase, the invention adds the oil phase into the water phase for emulsification to obtain the oil-in-water emulsion. In the present invention, when the oil phase is added to the aqueous phase, the temperature of the aqueous phase is preferably 70 ℃, specifically, the aqueous phase is first kept at 70 ℃ for 10min, and then the oil phase is added thereto. In the invention, the dispersion rate of the emulsification is preferably 2000-6000 rpm, more preferably 3000-5000 rpm, and the time of the emulsification is preferably 5-10 min; the emulsification is preferably carried out in a high speed emulsifier. By the emulsification, a stable oil-in-water emulsion is formed.
After the oil-in-water type emulsion is obtained, the oil-in-water type emulsion, a cross-linking agent aqueous solution and a catalyst are mixed for cross-linking and solidification to obtain microcapsule slurry. In the invention, the cross-linking agent in the cross-linking agent aqueous solution is preferably polyamine and/or polyalcohol, and the polyamine and the polyalcohol are the same as the technical scheme above and are not described again; the concentration of the aqueous solution of the crosslinking agent is not particularly required in the present invention. In the invention, the catalyst is preferably one or more of stannous octoate, CUCAT-U2, dibutyltin dilaurate, CUCAT-T50 and organic zinc. In the present invention, the mass ratio of the isocyanate-terminated siloxane component, the crosslinking agent and the catalyst is preferably 10 to 50:2 to 20:0.01 to 1, more preferably 10 to 30: 3.5-10: 0.025 to 0.08. In the invention, the cross-linking agent aqueous solution is dripped into the oil-in-water emulsion preferably at the stirring speed of 1000-2500 rpm; and after the dropwise addition of the cross-linking agent aqueous solution is finished, adding a catalyst into the obtained system for cross-linking and curing. In the invention, the crosslinking curing comprises a first crosslinking curing and a second crosslinking curing which are sequentially carried out, wherein the temperature of the first crosslinking curing is preferably 70 ℃, the heat preservation time is 1h, the temperature of the second crosslinking curing is preferably 85 ℃, and the heat preservation time is preferably 2h. The interfacial polymerization method is a method for preparing microcapsules by respectively dissolving two monomers or polymers with different hydrophilicity and hydrophobicity in an immiscible water phase and an immiscible organic phase (oil phase), and after one phase of solution is dispersed into the other phase of solution (emulsification), the monomers in the two phases of solution are subjected to polymerization reaction at an oil-water interface. The interfacial polymerization method has the advantages of high reaction speed, mild conditions, low requirements on monomer purity and mixture ratio and the like. The invention takes polyamine and/or polyalcohol as a water-soluble reaction monomer (cross-linking agent), takes isocyanate-terminated siloxane and an addition product thereof as an oil-soluble reaction monomer (wall material), and the water/oil monomer diffuses to an oil/water interface through concentration to carry out polymerization reaction, thereby forming the microcapsule slurry containing the polyurethane/urea shell with a stable Si-O-Si cross-linked network structure.
After microcapsule slurry is obtained, the microcapsule slurry is subjected to solid-liquid separation, solid-phase washing and drying in sequence to obtain the microcapsule. The method for separating solid from liquid in the invention has no special requirement, and the method for separating solid from liquid, which is well known to those skilled in the art, can be adopted, such as reduced pressure filtration; the drying temperature is preferably 70 ℃, and the drying time is preferably 5-8 h.
The microcapsules containing the siloxane polyurethane/urea resin wall material and the preparation method thereof according to the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing a phase change energy storage microcapsule:
(1) Preparation of a water phase: weighing 5 g of sodium dodecyl benzene sulfonate into a beaker, adding deionized water to 100 g, stirring to completely dissolve an emulsifier, and preparing into a 5% emulsifier aqueous solution to obtain a water phase;
(2) Preparing an oil phase: adding 60 g of phase change energy storage material n-octadecane into a beaker, heating and melting into liquid, and taking the liquid as a core material; then 15 g of wall material 1,3-bis (isocyanatomethyl) -1,1,3,3-tetramethyldisiloxane (corresponding to the structural formula I1) is added, and the materials are stirred until the materials are completely dissolved to prepare an oil phase;
(3) Formation of the emulsion: keeping the temperature of the water phase at 70 ℃ for 10min, adding the oil phase into the water phase, and dispersing at a high speed of 5000rpm for 5-10 min in a high-speed emulsifying machine to form a stable oil-in-water emulsion;
(4) And (3) forming a microcapsule: and after emulsification, reducing the rotating speed, dropwise adding a cross-linking agent aqueous solution containing 5 g of diethylenetriamine into the emulsion, after dropwise adding, dropwise adding 0.04 g of catalyst stannous octoate, keeping the temperature at 70 ℃ for 1h, heating to 85 ℃, continuing to react for 2h, and finishing the reaction to obtain the phase-change energy-storage microcapsule slurry containing the siloxane polyurethane/urea resin shell, filtering and washing the slurry under reduced pressure to obtain a filter cake, and drying in a 70 ℃ drying oven for 5-8 h to obtain the phase-change energy-storage microcapsule powder (the average particle size is about 2.0 mu m) taking the siloxane-containing polyurethane/urea resin as a shell material.
In example 1, the shell reaction monomer 1,3-bis (isocyanatomethyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 1) may be wall material 1,3-bis (isocyanatomethyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 1), 1,3-bis (isocyanatomethyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula i 2), 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 3), 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula i 4), 1,3-bis (3-isocyanatophenyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 5), or a mixture of two or more thereof with structural formula i 6.
In example 1 above, the octadecane may also be tetradecane, pentadecane, hexadecane, heptadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, or hexacosane.
Example 2
Preparation of thermochromic microcapsules:
(1) Preparation of a water phase: weighing 6 g of Newcol707-SF (produced by Nippon NyukazaiCoLtd.) emulsifier in a beaker, adding deionized water to 200 g, stirring to completely dissolve the emulsifier, and preparing into 3% emulsifier aqueous solution to obtain a water phase;
(2) Preparing an oil phase: 3 g of a thermal dye 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophenylpeptide (colorless)
Blue), 6 g of color developing agent bisphenol AF, 60 g of methyl stearate and 6 g of methyl palmitate are mixed, and the core material is obtained after heating, melting and uniformly mixing; adding 20 g of wall material 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetramethyldisiloxane (corresponding to a structural formula I3) into the core material, and stirring until complete mutual dissolution to prepare an oil phase;
(3) Formation of the emulsion: keeping the temperature of the water phase at 70 ℃ for 10min, adding the oil phase into the water phase, and dispersing at a high speed of 2000rpm for 5-10 min in a high-speed emulsifying machine to form a stable oil-in-water emulsion;
(4) And (3) forming a microcapsule: after emulsification, reducing the rotation speed, dropwise adding a cross-linking agent aqueous solution containing 8 g of N, N' -dihydroxyethyl diethylenetriamine into the emulsion, after dropwise adding, dropwise adding 0.05 g of catalyst CUCAT-U2 (produced by Guangzhou Youyun synthetic materials Co., ltd.), keeping the temperature at 70 ℃ for 1h, heating to 85 ℃, continuing to react for 2h to finish the reaction to obtain thermochromic microcapsule slurry containing a siloxane polyurethane/urea resin shell, filtering and washing the slurry under reduced pressure to obtain a filter cake, and drying the filter cake in an oven at 70 ℃ for 5-8 h to obtain thermochromic microcapsule pigment powder (with the average particle size of about 5 mu m) taking the siloxane-containing polyurethane/urea resin as a shell material.
In the above example 2, the shell material reaction monomer may be 1,3-bis (isocyanatomethyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 1), 1,3-bis (isocyanatomethyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula i 2), 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 3), 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula i 4), 1,3-bis (3-isocyanatophenyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula i 5) or a mixture of two or more thereof in structural formula i 6.
In the above example 2, the thermosensitive dye may also be 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophenylpeptide (colorless)
Blue), N-dimethyl-4- [2- [2- (octyloxy) phenyl]-6-phenyl-4-pyridinyl]Aniline (colorless->
Yellow), 2-phenylamino-6-dibutylamino-3-methylfluoran (colorless `)>
Black color)
1,2-benzo-6-diethylaminofluoran (colorless)
Dark blue), 3',6' -dimethoxyfluoran (colorless->
Bright yellow), 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide (colorless->
Green), 3,3-bis (2-methyl-1-octyl-1H-indol-3-yl) phthalide (colorless->
Rose color), 1,3-dimethyl-6-
Diethylaminofluorane (colorless)
Orange) and 2 '-chloro-6' - (diethylamino) fluoran (colorless->
Red) or a mixture of two or more thereof.
In example 2 above, the developer may also be one or a mixture of two or more of bisphenol a, bisphenol AF, bisphenol AP, bisphenol S, bisphenol P, 4-hydroxy-4-isopropoxydiphenylsulfone (D-8), 4,4' - (1,2-diethylethylene) diphenol, 4,4' - (2-ethylhexane-1,1-diyl) diphenol, and 4,4' - (2-methylpropylidene) diphenol.
Example 3
Preparation of thermochromic microcapsules:
(1) Preparation of a water phase: weighing 6 g of Newcol707-SF (produced by Nippon NyukazaiCoLtd.) emulsifier in a beaker, adding deionized water to 200 g, stirring to completely dissolve the emulsifier, and preparing into 3% emulsifier aqueous solution to obtain a water phase;
(2) Preparing an oil phase: 3 g of the thermal dye 3,3-bis (2-methyl-1-octyl-1H-indol-3-yl) phthalide (colorless)
Rose), 6 g of color developing agent bisphenol A and 71 g of methyl behenate are mixed, heated, melted and mixed uniformly to obtain a melted mixture; adding 30 g of an addition product (corresponding to a structural formula II 5) of wall material trimethylolpropane and 1,3-bis (3-isocyanatophenyl) -1,1,3,3-tetramethyldisiloxane and 30 g of cosolvent ethyl acetate into the molten mixture, and stirring until the materials are completely mutually dissolved to prepare an oil phase;
(3) Formation of the emulsion: keeping the temperature of the water phase at 70 ℃ for 10min, adding the oil phase into the water phase, and dispersing at a high speed of 2000rpm for 5-10 min in a high-speed emulsifying machine to form a stable oil-in-water emulsion;
(4) And (3) forming a microcapsule: and after emulsification, reducing the rotation speed, dropwise adding a cross-linking agent aqueous solution containing 8 g of triethylene tetramine into the emulsion, after dropwise adding, dropwise adding 0.08 g of catalyst dibutyltin dilaurate, keeping the temperature at 70 ℃ for 1h, heating to 85 ℃, continuing to react for 2h, finishing the reaction to obtain thermochromic microcapsule slurry containing a siloxane polyurethane/urea resin shell, filtering and washing the slurry under reduced pressure to obtain a filter cake, and drying in an oven at 70 ℃ for 5-8 h to obtain thermochromic microcapsule pigment powder taking the siloxane polyurethane/urea resin as a shell material (the average particle size is about 4.8 mu m).
In example 3, the shell reaction monomer may be an adduct of trimethylolpropane and 1,3-bis (isocyanatomethyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula II 1), an adduct of trimethylolpropane and 1,3-bis (isocyanatomethyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula II 2), an adduct of trimethylolpropane and 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula II 3), an adduct of trimethylolpropane and 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula II 4), an adduct of trimethylolpropane and 1,3-bis (3-isocyanatophenyl) -1,1,3,3-tetramethyldisiloxane (corresponding to structural formula II 5), or a mixture of two or more thereof.
In example 3 above, the thermal sensitive dye may also be 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophenyl peptide (colorless)
Blue), N-dimethyl-4- [2- [2- (octyloxy) phenyl]-6-phenyl-4-pyridinyl]Aniline (colorless->
Yellow), 2-phenylamino-6-dibutylamino-3-methylfluoran (colorless `)>
Black), 1,2-benzo-6-diethylaminofluoran (colorless)
Dark blue), 3',6' -dimethoxyfluoran (colorless->
Bright yellow), 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide (colorless->
Green), 3,3-bis (2-methyl-1-octyl-1H-indol-3-yl) phthalide (colorless->
Rose), 1,3-dimethyl-6-diethylaminofluoran (colorless +)>
Orange) and 2 '-chloro-6' - (diethylamino) fluoran (colorless->
Red) or a mixture of two or more thereof.
In the above example 3, the developer may be one or a mixture of two or more of bisphenol a, bisphenol AF, bisphenol AP, bisphenol S, bisphenol P, 4-hydroxy-4-isopropoxydiphenyl sulfone (D-8), 4,4' - (1,2-diethylethylene) diphenol, 4,4' - (2-ethylhexane-1,1-diyl) diphenol, and 4,4' - (2-methylpropylidene) diphenol.
Example 4
Preparation of thermochromic microcapsules (fluorescent dyes):
(1) Preparation of a water phase: weighing 8 g of emulsifier polyvinyl alcohol PVA-KL-318 (produced by Nippon Coli Co., ltd.) in a beaker, adding deionized water to 200 g, stirring to completely dissolve the emulsifier, and preparing into 4% emulsifier water solution to obtain a water phase;
(2) Preparing an oil phase: 2.6 g of the fluorescent dye 2,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (3-methylphenyl) aminophenyl) pyridine (colorless
Yellow), 7 g of color developing agent bisphenol AP, 25 g of n-hexadecanol and 25 g of methyl stearate are mixed, heated, melted and uniformly mixed to obtain a core material; adding 20 g of a shell material 1,3-bis (3-isocyanatophenyl) -1,1,3,3-tetramethyldisiloxane (corresponding to a structural formula I5) into the core material, and stirring until the materials are completely dissolved to prepare an oil phase;
(3) Formation of the emulsion: keeping the temperature of the water phase at 70 ℃ for 10min, adding the oil phase into the water phase, and dispersing at 6000rpm for 5-10 min in a high-speed emulsifying machine to form a stable oil-in-water emulsion;
(4) And (3) forming a microcapsule: after emulsification, reducing the rotation speed, dropwise adding a cross-linking agent aqueous solution containing 4 g of tetraethylenepentamine and 6 g of ethylene glycol into the emulsion, after dropwise adding, dropwise adding 0.04 g of catalyst CUCAT-U2 (produced by Guangzhou Youyun synthetic materials Co., ltd.), keeping the temperature at 70 ℃ for 1h, heating to 85 ℃, continuing to react for 2h to finish the reaction to obtain the fluorescent thermochromic microcapsule slurry containing the siloxane polyurethane/urea resin shell, filtering and washing the slurry under reduced pressure to obtain a filter cake, and drying the filter cake in a 70 ℃ oven for 5-8 h to obtain the fluorescent thermochromic microcapsule pigment powder taking the siloxane-containing polyurethane/urea resin as the shell material (the average particle size is about 2 mu m).
The fluorescent dye described in example 4, which may also be 2,6-bis (2-ethyloxyphenyl) -4- (4-bis (4-methylphenyl) aminophenyl) pyridine (colorless
Orange), 2,6-bis (4-dimethylaminophenyl) -4- (4-methoxyphenyl) pyridine (colorless->
Orange) and 2,6-bis (2,4-diethyloxyphenyl) -4- (4-bis (3-methylphenyl) aminophenyl) pyridine (colorless->
Yellow) or a mixture of two or more thereof.
In example 4 above, the developer may also be one or a mixture of two or more of bisphenol A, bisphenol AF, bisphenol AP, bisphenol S, bisphenol P, 4-hydroxy-4-isopropoxydiphenyl sulfone (D-8), 4,4' - (1,2-diethylethylene) diphenol, 4,4' - (2-ethylhexane-1,1-diyl) diphenol, and 4,4' - (2-methylpropylidene) diphenol.
Example 5
Preparation of cholesterol type liquid crystal microcapsule:
(1) Preparation of a water phase: weighing 10g of emulsifier 40% acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer aqueous solution in a beaker, adding deionized water to 100 g, stirring and mixing uniformly to prepare 4% emulsifier aqueous solution to obtain a water phase;
(2) Preparing an oil phase: 40 g of cholesteric liquid crystals ZKA10400 or ZKA10500 (bistable: colorless)
Blue, produced by Shijiazhuang Chenghua display materials Co., ltd.) as a core material, and 12 g of wall material 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetraethyldisiloxane (corresponding to structural formula I4), stirring until the materials are completely mutually dissolved to prepare an oil phase;
(3) Formation of the emulsion: keeping the temperature of the water phase at 70 ℃ for 10min, adding the oil phase into the water phase, and dispersing for 5-10 min at 4200rpm in a high-speed emulsifying machine to form a stable oil-in-water emulsion;
(4) And (3) forming a microcapsule: after emulsification, reducing the rotation speed, dropwise adding a cross-linking agent aqueous solution containing 6 g of N, N, N ', N' -tetra (2-hydroxypropyl) ethylenediamine into the emulsion, stirring for 5min after dropwise adding, then adding 0.03 g of catalyst CUCAT-T50 (produced by Guangzhou Yougun synthetic materials Co., ltd.), keeping the temperature at 70 ℃ for 1h, heating to 85 ℃, continuing to react for 2h to finish the reaction to obtain electrochromic microcapsule slurry containing a siloxane polyurethane/urea resin shell, filtering and washing the slurry under reduced pressure to obtain a filter cake, and drying the filter cake in a 70 ℃ oven for 5-8 h to obtain the electrochromic microcapsule pigment powder taking the siloxane-containing polyurethane/urea resin as a shell material (the average particle size is about 3.6 mu m).
Example 6
Preparation of nematic liquid crystal microcapsules:
(1) Preparation of a water phase: weighing 3 g of emulsifier polyvinylpyrrolidone K30 in a beaker, adding deionized water to 100 g, stirring to completely dissolve the emulsifier, and preparing into 3% emulsifier aqueous solution to obtain a water phase;
(2) Preparing an oil phase: 30 g of nematic liquid crystal ZKA11300 (electrochromic, white/opaque state)
Colorless/transparent, produced by Shijiazhuang Cheng Yonghua display materials Co., ltd.) as core material, 10g of additive (corresponding to structural formula II 3) of wall material trimethylolpropane and 1,3-bis (3-isocyanatopropyl) -1,1,3,3-tetramethyldisiloxane and 20 g of cosolvent ethyl acetate, stirring until complete mutual solubility to prepare oil phase;
(3) Formation of the emulsion: keeping the temperature of the water phase at 70 ℃ for 10min, adding the oil phase into the water phase, and dispersing at a high speed of 3800rpm for 5-10 min in a high-speed emulsifying machine to form a stable oil-in-water emulsion;
(4) And (3) forming a microcapsule: after emulsification, reducing the rotation speed, dropwise adding a cross-linking agent aqueous solution containing 3.5 g of polyethylene polyamine into the emulsion, after dropwise adding, dropwise adding 0.025 g of catalyst organic zinc ZCAT-Y18 (produced by Guangzhou Youyun synthetic materials Co., ltd.), keeping the temperature at 70 ℃ for 1h, heating to 85 ℃, continuing to react for 2h to finish the reaction to obtain electrochromic microcapsule slurry containing a siloxane polyurethane/urea resin shell, filtering and washing the slurry under reduced pressure to obtain a filter cake, and drying in a 70 ℃ oven for 5-8 h to obtain the electrochromic microcapsule pigment powder (with the average particle size of about 4.2 mu m) taking the siloxane polyurethane/urea resin as a shell material.
And (3) performance testing:
(1) Appearance of the product
The microcapsule powders prepared in the above examples were visually observed to be dry powders without distinct particles, lumps, and oil stains.
(2) Dispersibility test
The test method comprises the following steps: a small amount of microcapsule powder sample prepared in the above example is put into a test tube, a proper amount of deionized water is added, shaking dispersion is carried out, and the dispersion is observed under a microscope.
And (3) testing results: the microcapsule powders prepared in the above examples are all monodisperse particles.
(3) Mechanical Property test
The test method comprises the following steps: a suitable weighing paper disc (platform area 1 cm) was laid on a standard sheeting die base platform fitted with a sleeve 2 ). 100mg of the microspheres prepared in the above examples were weighedCapsule powder samples, accurate to 1mg. Tapping the side surfaces of the base and the sleeve to uniformly spread a sample to be measured on the platform, slightly covering another weighing paper wafer on the sample to be measured, installing a die to press the top, tapping the sleeve, and rotating the top to discharge air of the sample to be measured. Placing the whole set of mould in the middle of a push-pull force test bench base, slightly pressing down a pressure tester, adjusting the position of the mould on a central line again, pressing down the tester and maintaining the pressure reading within the range of 0.45 +/-0.005 kN, lifting up the tester after lasting for 10s, taking down a standard tabletting mould, taking down a mould jacking and a sleeve, slightly taking down a powder tabletting on the mould base, uncovering an upper weighing paper wafer, and observing whether oil stains exist on the weighing paper and the tabletting. And then placing the powder tablet on a constant-temperature heating table at 80 ℃ for heating, and opening for observation. If no obvious oil stain is observed, cleaning the test bench and the standard pressure die, increasing the pressure by 0.05kN again according to the steps, and repeating the test until the oil stain appears, and recording the highest pressure when the oil stain does not appear; and if obvious oil stains are observed, cleaning the test board and the standard pressure die, reducing the pressure by 0.05kN again according to the steps, and repeating the test until the oil stains disappear, and recording the pressure.
And (3) testing results: the test pressure of the microcapsules prepared in the above examples is more than or equal to 8MPa.
(4) Acid resistance test
The test method comprises the following steps: 1g of the microcapsule powder sample prepared in the above example was weighed, 10g of a sulfuric acid solution was added by weight to 1mg. And oscillating for 10min in a water bath environment at 70 ℃, and then carrying out temperature rise and fall circulation (reducing the temperature to room temperature), comparing with the untested sample, and observing whether various performances of the sample are changed.
And (3) testing results: all the properties of the microcapsule prepared by the embodiment are kept in a stable state within 25min and are not changed.
(5) Alkali resistance test
The test method comprises the following steps: weigh 1g of the microcapsule powder sample prepared in the above example, add 10% wt of sodium hydroxide solution 10g, to 1mg. Oscillating for 3min in a water bath environment at 70 ℃, and then carrying out temperature rise and fall circulation (cooling to room temperature), comparing with the untested sample, and observing whether various performances of the untested sample are changed.
And (3) testing results: within 30min, all the properties of the microcapsule prepared by the embodiment are kept in a stable state and are not changed.
(6) Weather resistance illumination test
The test method comprises the following steps: a1 g sample of the microcapsule powder prepared in the above example was weighed and 9g of PVC blank ink was added to the nearest 1mg. And (3) uniformly mixing, scraping a PVC ink film on a white substrate with a smooth and flat surface by using a 4-surface coater, scraping the film with the thickness of 10 mu m, naturally airing or drying at 50 ℃, and testing by referring to an ISO16474-2013 colored paint and varnish-laboratory light source exposure test method. A laboratory light source exposure test method referring to ISO4892-2013 plastic is characterized in that a xenon arc lamp source is adopted, the wavelength range of the xenon arc lamp source comprises 270nm ultraviolet rays, visible spectrums and infrared rays, and as the xenon arc lamp needs to simulate sunshine, short-wave ultraviolet radiation is filtered, and the effect of ultraviolet rays with the wavelength less than 310nm is reduced. In addition, a filter capable of filtering infrared rays should be used to prevent the temperature of the sample to be measured from rising, so that the thermal strength that would not occur by actual outdoor exposure during the experiment is weakened. And then comparing with the untested sample to observe whether various properties of the sample are changed.
And (3) testing results: all the properties of the microcapsules prepared in the above examples are kept in a stable state within 10 hours and are not changed.
(7) Mechanical Strength test
The test method comprises the following steps: ultrasonic waves are generated by an ultrasonic oscillator to generate high-frequency mechanical oscillation, ultrasonic waves are formed in a medium, and the ultrasonic waves are alternately radiated and transmitted forwards in the medium at intervals by positive pressure and negative pressure high frequency, so that countless small bubbles are continuously generated in the medium and are continuously broken, namely, the cavitation effect, so that a series of explosions are generated to release huge energy, huge impact is formed on the periphery, the surface of a microcapsule shell material prepared by the embodiment is continuously impacted, and the microcapsule with weak mechanical strength is broken. Under the ultrasonic oscillation, samples are taken at intervals to carry out scanning electron microscope observation on the damage condition of the microcapsule sample, thereby achieving the purpose of testing the mechanical strength of the microcapsule.
And (3) testing results: after 30min of ultrasonic oscillation, samples were taken through a scanning electron microscope and virtually no microcapsule rupture was observed.
(8) High and low temperature resistance test
The high-temperature environment resistance test method comprises the following steps: the microcapsule powder sample prepared in the above example is put into a glass petri dish and is dried (baked) at the temperature of 1 ℃ every 15min from 100 ℃, and whether the microcapsule sample in the oven emits white smoke or not is observed through a transparent glass door of the oven, so that whether the microcapsule is resistant to a high-temperature environment or not can be roughly judged.
High temperature environment resistance test results: the microcapsule powder samples prepared in the above examples were observed to be scorched and smoky when dried (baked) at 264 ℃ according to the test method described above, indicating that the microcapsule powder samples prepared in the above examples of the present invention can endure temperatures below 264 ℃.
The method for testing the resistance to the extremely low temperature environment comprises the following steps: the microcapsule powder sample prepared in the embodiment is put into a small steel tank filled with liquid nitrogen at the temperature of 196 ℃ below zero and kept for 5 minutes, and the sample is taken out to be tested by a scanning electron microscope, so that whether the microcapsule sample is brittle or damaged can be visually observed, and whether the microcapsule is resistant to the extremely low temperature environment can be roughly judged.
The test result of the resistance to the extremely low temperature environment is as follows: scanning electron microscopy of samples taken after freezing with liquid nitrogen at-196 ℃ showed that the microcapsule powder samples prepared in the above examples were observed to have little brittle fracture or breakage.
It can be seen from the above embodiments that the isocyanate-terminated siloxane and the adduct thereof adopted by the present invention as the microcapsule wall material raw material are very soluble in solvent oil and carrier solvent, and then the corresponding functional microcapsules (phase change energy storage microcapsules, thermochromic microcapsules, photochromic microcapsules and electrochromic microcapsules) can be obtained, thereby realizing the multi-functionalization of the microcapsules and expanding the application field of the microcapsules; in addition, the microcapsule containing the polyurethane/urea resin wall material of the siloxane has the advantages of high mechanical strength, excellent high and low temperature resistance, acid and alkali resistance, weather resistance and the like.
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 (10)
1. A microcapsule containing a siloxane polyurethane/urea resin wall material comprises a core material and a wall material, wherein the core material comprises a core material component and/or an organic solvent, and the organic solvent comprises solvent oil and/or a carrier solvent; the wall material is polyurethane/urea resin containing siloxane; the siloxane-containing polyurethane/urea resin is obtained by crosslinking and curing an isocyanate-terminated siloxane component and polyamine and/or polyol; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct of an isocyanate-terminated siloxane and trimethylolpropane; the isocyanate-terminated siloxane has a structure represented by formula I, and the isocyanate-terminated siloxane adduct has a structure represented by formula II:
in the formulas I and II, R1, R2, R3, R4, R5 and R6 are independently selected from linear alkyl, branched alkyl, cycloalkyl, phenyl, substituted phenyl or biphenyl, and the molecular weight of the R1 or R2 group is not more than 300; the molecular weight of the R3, R4, R5 or R6 group does not exceed 200.
2. A microcapsule according to claim 1, characterized in that said isocyanate-terminated siloxane has the structure represented by any one of formulae i 1 to i 6:
3. a microcapsule according to claim 1, characterized in that said isocyanate-terminated
The siloxane adduct has a structure represented by any one of formulas II 1 to II 6:
4. the microcapsule of claim 1, wherein the solvent naphtha comprises one or more of 200# solvent naphtha, sec-butylbenzene-tetrachloroethylene complex solvent, phenyl dimethylethane, diarylethane and phenyl ethylphenylethane; the carrier solvent comprises one or more of higher fatty acid ester and higher fatty alcohol.
5. A microcapsule according to claim 1, wherein the core material component comprises a phase change energy storage material, a thermochromic material, a photochromic material or an electrochromic material.
6. The process for the preparation of microcapsules containing a silicone-containing polyurethane/urea resin wall material of any one of claims 1 to 5, comprising the steps of:
(1) Mixing an emulsifier and water to obtain a water phase;
(2) Mixing the core material with the siloxane component blocked by isocyanate to obtain an oil phase; the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane and/or an isocyanate-terminated siloxane adduct;
(3) Adding the oil phase into the water phase for emulsification to obtain an oil-in-water emulsion;
(4) Mixing the oil-in-water type emulsion with a cross-linking agent aqueous solution and a catalyst for cross-linking and curing to obtain microcapsule slurry; the cross-linking agent in the cross-linking agent aqueous solution is polyamine and/or polyalcohol;
(5) Carrying out solid-liquid separation, solid-phase washing and drying on the microcapsule slurry in sequence to obtain microcapsules;
the steps (1) and (2) are not limited in chronological order.
7. The preparation method according to claim 6, wherein the mass content of the emulsifier in the aqueous phase is 2.5 to 5%.
8. The production method according to claim 6, wherein the mass ratio of the core material to the isocyanate-terminated siloxane component is (40 to 80): (12-20); when the isocyanate-terminated siloxane component comprises an isocyanate-terminated siloxane adduct, the oil phase also comprises a co-solvent.
9. The method of claim 6, wherein the temperature of the aqueous phase is 70 ℃ when the oil phase is added to the aqueous phase; the dispersion speed of the emulsification is 2000-6000 rpm, and the emulsification time is 5-10 min.
10. The production method according to claim 6, wherein the isocyanate-terminated siloxane component, the crosslinking agent and the catalyst are present in a mass ratio of 10 to 50:2 to 20:0.01 to 1; the crosslinking and curing process comprises a first crosslinking and curing process and a second crosslinking and curing process which are sequentially carried out, wherein the temperature of the first crosslinking and curing process is 70 ℃, the heat preservation time is 1 hour, the temperature of the second crosslinking and curing process is 85 ℃, and the heat preservation time is 2 hours.
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