CN114177850B - Air microcapsule and preparation method thereof, thermal cellulose fiber and preparation method and application thereof - Google Patents
Air microcapsule and preparation method thereof, thermal cellulose fiber and preparation method and application thereof Download PDFInfo
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- CN114177850B CN114177850B CN202110400204.4A CN202110400204A CN114177850B CN 114177850 B CN114177850 B CN 114177850B CN 202110400204 A CN202110400204 A CN 202110400204A CN 114177850 B CN114177850 B CN 114177850B
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- air
- formaldehyde resin
- microcapsule
- melamine formaldehyde
- modified melamine
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 121
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 100
- -1 benzoguanamine modified melamine formaldehyde Chemical class 0.000 claims abstract description 60
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 47
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002775 capsule Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 239000000839 emulsion Substances 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 52
- 238000009987 spinning Methods 0.000 claims description 41
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000004132 cross linking Methods 0.000 claims description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 19
- 229920002866 paraformaldehyde Polymers 0.000 claims description 19
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 230000003009 desulfurizing effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 9
- 239000004753 textile Substances 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 5
- RVHPJLCXULJZOU-UHFFFAOYSA-N furan-2,5-dione;sodium;styrene Chemical compound [Na].O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 RVHPJLCXULJZOU-UHFFFAOYSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 89
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 239000006185 dispersion Substances 0.000 description 23
- 239000000835 fiber Substances 0.000 description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000004359 castor oil Substances 0.000 description 7
- 235000019438 castor oil Nutrition 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000008098 formaldehyde solution Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000002166 wet spinning Methods 0.000 description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 6
- 229960001763 zinc sulfate Drugs 0.000 description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000008041 oiling agent Substances 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 102220042174 rs141655687 Human genes 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 208000011231 Crohn disease Diseases 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the technical field of cellulose fibers, and particularly relates to an air microcapsule, a preparation method thereof, a warm-keeping cellulose fiber, and a preparation method and application thereof. The air microcapsule provided by the invention comprises a capsule core and a capsule wall, wherein the capsule core is air, and the capsule wall material is modified melamine formaldehyde resin; the modified melamine formaldehyde resin comprises a first modified melamine formaldehyde resin and a second modified melamine formaldehyde resin, wherein the first modified melamine formaldehyde resin is a cross-linked product of polyvinyl alcohol and a benzoguanamine modified melamine formaldehyde resin, and the second modified melamine formaldehyde resin is a cross-linked product of a benzoguanamine modified melamine formaldehyde resin and a benzoguanamine modified melamine formaldehyde resin. The modified melamine formaldehyde resin is used as the capsule wall material, so that the toughness of the capsule wall material is improved, the air microcapsule has higher compressive strength, and the air microcapsule is prevented from breaking and losing effect under the action of external force.
Description
Technical Field
The invention belongs to the technical field of cellulose fibers, and particularly relates to an air microcapsule, a preparation method thereof, a warm-keeping cellulose fiber, and a preparation method and application thereof.
Background
With the improvement of the living standard of people and the development of scientific technology, consumers are not only required to keep warm for clothing raw materials, but also required to be light, soft and comfortable while keeping warm. Along with market demands, development of variable thermal clothes is continuously developed, and most importantly, thermal performance of the clothes is improved in development of novel thermal fibers. Therefore, the heat insulation and heat preservation effects of the fiber materials are researched, the promotion of the industrial upgrading of the clothing fabric is facilitated, and the purposes of low-carbon life, energy conservation and emission reduction are achieved.
In the prior art, most of traditional textile fibers and textiles are heated by increasing the consumption of the fibers and increasing the thickness and the weight of the fiber textiles, but the comfort of wearing is affected, and the problems of larger weight and thicker thickness exist. With the development of research, scientific researchers add air microcapsules into fibers to improve the warmth retention property of the fibers, but the air microcapsules in the existing warmth retention fibers have lower compressive strength and are easy to break in the use process so as to lose warmth retention effect.
Disclosure of Invention
In view of the above, the invention provides an air microcapsule, which has higher compressive strength, and the thermal cellulose fiber prepared by the air microcapsule provided by the invention has good thermal property and reduces the density of the thermal cellulose fiber.
In order to solve the technical problems, the invention provides an air microcapsule, which comprises a capsule core and a capsule wall, wherein the capsule core is air, and the capsule wall material is modified melamine formaldehyde resin;
the modified melamine formaldehyde resin comprises a first modified melamine formaldehyde resin and a second modified melamine formaldehyde resin, wherein the first modified melamine formaldehyde resin is a cross-linked product of polyvinyl alcohol and a benzoguanamine modified melamine formaldehyde resin prepolymer, and the second modified melamine formaldehyde resin is a cross-linked product of a benzoguanamine modified melamine formaldehyde resin prepolymer and a benzoguanamine modified melamine formaldehyde resin prepolymer.
Preferably, the average degree of polymerization of the polyvinyl alcohol is 300 to 600;
The particle size of the air microcapsule is D90 which is less than or equal to 2.538 mu m.
The invention also provides a preparation method of the air microcapsule, which comprises the following steps:
mixing polyvinyl alcohol, an emulsifying agent, water and air to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and performing polycondensation reaction to obtain benzoguanamine modified melamine formaldehyde resin prepolymer;
Mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and performing cross-linking polymerization reaction to obtain the air microcapsule.
Preferably, the emulsifier comprises styrene maleic anhydride sodium salt, sodium dodecylbenzene sulfonate, sodium dodecylsulfate or sodium hexametaphosphate; the mass concentration of the emulsifier in the air emulsion is 1-2.5%;
the mass concentration of the polyvinyl alcohol in the air emulsion is 5-10%.
Preferably, the mixing comprises the steps of:
Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
Dispersing an emulsifying agent in the polyvinyl alcohol solution to obtain emulsion;
Introducing air into the emulsion to obtain an air emulsion;
The flow rate of the air is 0.8-1.5L/min, and the time is 40-60 min.
Preferably, the pH value of the reaction solution of the polycondensation reaction is 7.5-8.5, the temperature is 60-90 ℃ and the time is 60-90 min.
Preferably, the pH value of the reaction solution of the crosslinking polymerization reaction is 3.5-5.0, the temperature is 75-85 ℃ and the time is 100-180 min.
The invention also provides a warm-keeping cellulose fiber, which comprises cellulose fiber and air microcapsules uniformly distributed in the cellulose fiber or on the surface of the cellulose fiber, wherein the air microcapsules are prepared by the air microcapsules according to the technical scheme or the preparation method according to the technical scheme;
The mass ratio of the cellulose fiber to the air microcapsule is 100:20.8-29.6.
The invention also provides a preparation method of the warm-keeping cellulose fiber, which comprises the following steps:
Mixing the air microcapsule and the cellulose spinning solution to obtain cellulose fiber blending spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass ratio of the air microcapsule to the alpha cellulose is 25-35:100;
And (3) spinning, drafting, cutting off, desulfurizing, oiling, drying and opening the cellulose fiber blending spinning solution in sequence to obtain the thermal cellulose fiber.
The invention also provides application of the thermal cellulose fiber prepared by the technical scheme or the preparation method of the technical scheme in textiles.
The invention provides an air microcapsule, which comprises a capsule core and a capsule wall, wherein the capsule core is air, and the capsule wall material is modified melamine formaldehyde resin; the modified melamine formaldehyde resin comprises a first modified melamine formaldehyde resin and a second modified melamine formaldehyde resin, wherein the first modified melamine formaldehyde resin is a cross-linked product of polyvinyl alcohol and a benzoguanamine modified melamine formaldehyde resin prepolymer, and the second modified melamine formaldehyde resin is a cross-linked product of a benzoguanamine modified melamine formaldehyde resin prepolymer and a benzoguanamine modified melamine formaldehyde resin prepolymer. The modified melamine formaldehyde resin is used as the wall material, and the modified melamine formaldehyde resin is modified by using the polyvinyl alcohol and the benzomelamine, so that the toughness of the wall material is improved, the wall of the air microcapsule has higher compressive strength, the air microcapsule is prevented from being broken under the action of external force so as to lose the function, and the warmth retention property of the warmth retention cellulose fiber is further improved.
The invention also provides a warm-keeping cellulose fiber, which comprises cellulose fiber and an air microcapsule attached to the inside or the surface of the cellulose fiber, wherein the air microcapsule is prepared by the air microcapsule according to the technical scheme or the preparation method according to the technical scheme; the mass ratio of the cellulose fiber to the air microcapsule is 100:20.8-29.6. The thermal cellulose fiber provided by the invention has good thermal property under the action of the air microcapsule, and simultaneously reduces the density of the thermal cellulose fiber, so that the thermal cellulose fiber has thermal property and is not uncomfortable; meanwhile, the air microcapsule provided by the invention has good toughness, and the air microcapsule in the thermal-insulation cellulose fiber is prevented from being broken, so that the service life of the thermal-insulation cellulose fiber is prolonged.
Detailed Description
The invention provides an air microcapsule, which comprises a capsule core and a capsule wall, wherein the capsule core is air, and the capsule wall material is modified melamine formaldehyde resin;
the modified melamine formaldehyde resin comprises a first modified melamine formaldehyde resin and a second modified melamine formaldehyde resin, wherein the first modified melamine formaldehyde resin is a cross-linked product of polyvinyl alcohol and a benzoguanamine modified melamine formaldehyde resin prepolymer, and the second modified melamine formaldehyde resin is a cross-linked product of a benzoguanamine modified melamine formaldehyde resin prepolymer and a benzoguanamine modified melamine formaldehyde resin prepolymer.
In the present invention, the average polymerization degree of the polyvinyl alcohol is preferably 300 to 600, more preferably 450 to 500. In the present invention, the particle diameter of the air microcapsule is preferably D90.ltoreq. 2.538. Mu.m, more preferably 2.215. Mu.m.ltoreq.D90.ltoreq.2.439. Mu.m.
In the present invention, the compressive strength of the air microcapsule is preferably 0.52 to 0.6MPa, more preferably 0.55 to 0.58MPa. In the invention, the air microcapsule has better temperature resistance, acid resistance and alkali resistance, and can stably exist in a sulfuric acid solution with the mass concentration of 90-125 g/L or a sodium hydroxide solution with the mass concentration of 4.3-8.8 percent at 130-150 ℃.
The invention also provides a preparation method of the air microcapsule, which comprises the following steps:
mixing polyvinyl alcohol, an emulsifying agent, water and air to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and performing polycondensation reaction to obtain benzoguanamine modified melamine formaldehyde resin prepolymer;
Mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and performing cross-linking polymerization reaction to obtain the air microcapsule.
The invention mixes the polyvinyl alcohol, the emulsifying agent, the water and the air to obtain the air emulsion. In the present invention, the mixing preferably includes the steps of:
Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
Dispersing an emulsifying agent in the polyvinyl alcohol solution to obtain emulsion;
And (3) introducing air into the emulsion to obtain an air emulsion.
The invention dissolves polyvinyl alcohol in water to obtain polyvinyl alcohol solution. In the present invention, the water is preferably deionized water; the average degree of polymerization of the polyvinyl alcohol is preferably 300 to 600, more preferably 450 to 500. In the present invention, the polyvinyl alcohol solution preferably has a mass concentration of 5 to 10%, more preferably 6 to 9%. In the present invention, the temperature of the dissolution is preferably 60 to 85 ℃, more preferably 70 to 80 ℃. The time of dissolution is not particularly limited as long as the dissolution is complete. In the present invention, the dissolution is preferably performed under stirring, and the stirring speed is preferably 900 to 1200r/min, more preferably 1000 to 1100r/min. In the invention, the polyethylene glycol can improve the viscosity of the air emulsion, slow down the overflow time of bubbles, avoid the rapid overflow of the bubbles in the air emulsion, and maintain the stability of the bubbles in the emulsion.
After the polyvinyl alcohol solution is obtained, the invention disperses the emulsifying agent in the polyvinyl alcohol solution to obtain emulsion. In the present invention, the emulsifier preferably includes styrene maleic anhydride sodium salt, sodium dodecylbenzenesulfonate, sodium dodecylsulfate or sodium hexametaphosphate, more preferably ethylene maleic anhydride sodium salt, sodium dodecylbenzenesulfonate or sodium dodecylsulfate. In the present invention, the mass percentage of the emulsifier in the emulsion is preferably 1 to 2.5%, more preferably 1.5 to 2%. In the present invention, the temperature of the dispersion is preferably 50 to 70 ℃, more preferably 55 to 65 ℃. The time of the dispersion is not particularly limited as long as the emulsifier can be uniformly dispersed. In the present invention, the dispersion is preferably performed under stirring, and the stirring speed is preferably 1800 to 2500r/min, more preferably 1900 to 2300r/min.
After the emulsion is obtained, air is introduced into the emulsion to obtain an air emulsion. In the present invention, the air flow rate is preferably 0.8 to 1.5L/min, more preferably 1 to 1.2L/min; the time is preferably 40 to 60 minutes, more preferably 49 to 55 minutes. In the present invention, stirring is accompanied by air-introducing, and the rotation speed of the stirring is preferably consistent with that of the stirring during dispersion.
The invention mixes paraformaldehyde, formaldehyde, melamine, benzoguanamine and water to carry out polycondensation reaction to obtain benzoguanamine modified melamine formaldehyde resin prepolymer. In the present invention, the formaldehyde is preferably added in the form of an aqueous formaldehyde solution. In the present invention, the mass concentration of the aqueous formaldehyde solution is preferably 37%. In the invention, the mass ratio of the paraformaldehyde to the formaldehyde is preferably 1:1-3, more preferably 1:1.5-2; the mass ratio of the melamine to the benzomelamine is preferably 1-3:1, more preferably 1.5-2:1; the ratio of the total mass of paraformaldehyde and formaldehyde to the total mass of melamine and benzomelamine is preferably 2 to 4:1, more preferably 2.5 to 3:1. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring is not particularly limited as long as the mixing can be uniformly performed.
In the present invention, the pH of the reaction liquid of the polycondensation reaction is preferably 7.5 to 8.5, more preferably 7.8 to 8. In the present invention, the pH adjustor for adjusting the pH value preferably includes triethanolamine or sodium hydroxide, more preferably triethanolamine; the amount of the pH adjustor to be used in the present invention is not particularly limited as long as the above-defined pH can be attained. In the present invention, the temperature of the polycondensation reaction is preferably 60 to 90 ℃, more preferably 70 to 80 ℃; the time is preferably 60 to 90 minutes, more preferably 70 to 80 minutes.
In the present invention, the polycondensation reaction preferably further comprises: and cooling the polycondensation reaction product, filtering, and taking filtrate to obtain the benzoguanamine modified melamine formaldehyde resin prepolymer. In the present invention, the temperature after the temperature reduction is preferably 30 to 50 ℃, more preferably 38 to 44 ℃. The invention is not particularly limited to the filtration, and the filtration is carried out by adopting the technical means conventional in the field.
After the air emulsion and the benzoguanamine modified melamine formaldehyde resin prepolymer are obtained, the benzoguanamine modified melamine formaldehyde resin prepolymer and the air emulsion are mixed and subjected to cross-linking polymerization reaction to obtain the air microcapsule. In the present invention, the mixing is preferably to add a benzoguanamine modified melamine formaldehyde resin prepolymer to the air emulsion. In the present invention, the mass percentage of the benzoguanamine modified melamine formaldehyde resin prepolymer in the mixed solution is preferably 40 to 65%, more preferably 51 to 58%. In the present invention, the temperature of the mixing is preferably 75 to 85 ℃, more preferably 78 to 82 ℃. In the present invention, the mixing is preferably performed under stirring, and the stirring speed is preferably 1800 to 2500r/min, more preferably 2000 to 2250r/min. In the invention, primary air microcapsule is obtained after mixing, and the wall of the primary air microcapsule is benzoguanamine modified melamine formaldehyde resin prepolymer. In the present invention, the primary air microcapsules preferably have a particle size of D90.ltoreq.2.135. Mu.m, more preferably 1.890. Mu.m.ltoreq.D90.ltoreq.2.008. Mu.m. The stirring time is not particularly limited in the present invention, as long as the particle size of the primary air microcapsule can be brought into the above range.
In the present invention, the pH of the reaction solution of the crosslinking polymerization reaction is preferably 3.5 to 5.0, more preferably 4 to 4.5. In the present invention, the pH adjustor for adjusting the pH preferably includes citric acid or acetic acid more preferably citric acid; the amount of the pH adjustor of the present invention is not particularly limited as long as the above-defined pH can be attained. In the present invention, the temperature of the crosslinking polymerization reaction is preferably 75 to 85 ℃, more preferably 80 to 83 ℃; the time is preferably 100 to 180 minutes, more preferably 120 to 160 minutes. In the present invention, the crosslinking polymerization reaction is preferably carried out under stirring at a rotation speed of preferably 600 to 1000r/min, more preferably 700 to 850r/min. In the present invention, it is preferable that the crosslinking polymerization reaction further comprises: filtering the product of the cross-linking polymerization reaction to obtain the air microcapsule. The invention is not particularly limited to the filtration, and the filtration is carried out by adopting the conventional technical means in the field.
In the invention, cross-linking polymerization can occur between polyvinyl alcohol and a benzoguanamine modified melamine formaldehyde resin prepolymer in the cross-linking polymerization reaction, and cross-linking polymerization can also occur between the benzoguanamine modified melamine formaldehyde resin prepolymer and the benzoguanamine modified melamine formaldehyde resin prepolymer; according to the invention, the melamine formaldehyde resin is modified by polyethylene glycol and benzomelamine, and the toughness of the modified melamine formaldehyde resin is improved by increasing the distance between triazine rings in the melamine and reducing the density of crosslinking points, so that the compressive strength of the air microcapsule is improved. The invention can wrap air in air emulsion into cross-linked polymer product during cross-linked polymerization.
The invention also provides a warm-keeping cellulose fiber, which comprises cellulose fiber and air microcapsules uniformly distributed in the cellulose fiber or on the surface of the cellulose fiber, wherein the air microcapsules are prepared by the air microcapsules according to the technical scheme or the preparation method according to the technical scheme;
the mass ratio of the cellulose fiber to the air microcapsule is 100:20.8-29.6, preferably 100:23.5 to 27.3.
The invention also provides a preparation method of the warm-keeping cellulose fiber, which comprises the following steps:
Mixing the air microcapsule and the cellulose spinning solution to obtain cellulose fiber blending spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass ratio of the air microcapsule to the alpha cellulose is 25-35:100;
And (3) spinning, drafting, cutting off, desulfurizing, oiling, drying and opening the cellulose fiber blending spinning solution in sequence to obtain the thermal cellulose fiber.
The invention mixes air microcapsule and cellulose spinning solution to obtain cellulose fiber blending spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass percentage of alpha cellulose in the cellulose spinning solution is preferably 8.2-9.25%, more preferably 8.58-9.05%; the mass concentration of sodium hydroxide in the fiber spinning solution is preferably 4.3-5.5%, more preferably 4.65-5.16%. In the present invention, the falling ball viscosity of the cellulose dope is preferably 36 to 55s, more preferably 41 to 50s. In the invention, the mass ratio of the air microcapsule to the alpha cellulose is 25-35:100, preferably 27.6-31.5%.
In the present invention, the mixing step further preferably comprises: and dispersing the air microcapsule in water, and then adjusting the pH value to obtain an air microcapsule dispersion liquid. In the present invention, the mass percentage of the air microcapsules in the air microcapsule dispersion liquid is preferably 25 to 35%, more preferably 28 to 31%. In the present invention, the pH of the dispersion after the pH adjustment is preferably 7 to 8.5, more preferably 7.5 to 8; the pH adjusting agent for adjusting the pH is preferably sodium hydroxide, and the amount of the sodium hydroxide is not particularly limited in the present invention, as long as the above-defined pH can be achieved. The purpose of the invention is to adjust the pH value of the dispersion liquid to match the alkaline condition of the cellulose spinning dope.
The invention aims to reduce the preparation steps and directly adjust the dispersion liquid of the air microcapsule and the cellulose spinning solution after the pH value of the cross-linked polymerization reaction product. The present invention is not particularly limited as long as the mixing can be uniformly performed.
After the cellulose fiber blending spinning solution is obtained, the cellulose fiber blending spinning solution is sequentially subjected to spinning, drafting, cutting, desulfurization, oiling, drying and opening to obtain the thermal cellulose fiber. In the present invention, the spinning is preferably wet spinning, the coagulation bath for wet spinning is preferably a solution of sulfuric acid, sodium sulfate, zinc sulfate, and the mass concentration of sulfuric acid in the coagulation bath is preferably 90 to 100g/L, more preferably 96 to 103g/L; the mass concentration of the sodium sulfate is preferably 260-310 g/L, more preferably 275-296 g/L; the mass concentration of zinc sulfate is preferably 8 to 12g/L, more preferably 9.5 to 10.6g/L. The temperature of the coagulation bath in the present invention is preferably 40 to 50 ℃, more preferably 43 to 48 ℃.
The invention is not particularly limited to the drafting and cutting, and the conventional technical means in the field can be adopted.
In the present invention, the desulfurization bath for desulfurization is preferably a sodium sulfite solution having a mass concentration of 5 to 8.5g/L, more preferably 6.5 to 7.3g/L; the temperature of the desulfurization bath is preferably 70 to 85 ℃, more preferably 6.5 to 7.3 ℃.
In the invention, the oiling oil agent preferably comprises a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate, wherein the mass ratio of the 13# spindle oil to the polyoxyethylene castor oil ester to the alkyl phosphate is 65:10:25; the total mass concentration of the 13# spindle oil, the polyoxyethylene castor oil ester and the alkyl phosphate ester salt in the oiling agent is preferably 2.5-6 g/L, more preferably 3.8-5.5 g/L; the temperature of the oil is preferably 55 to 70 ℃, more preferably 60 to 65 ℃.
In the invention, the drying is preferably microwave drying, and the microblog frequency of the microwave drying is preferably 1260-1550 MHz, more preferably 1350-1490 MHz; the time is preferably 25 to 40 minutes, more preferably 30 to 36 minutes; the moisture content of the dried fiber is preferably 9.35 to 12.5%, more preferably 10.2 to 11.9%.
The invention is not particularly limited to the opening, and the conventional technical means in the field can be adopted.
The invention also provides application of the thermal cellulose fiber prepared by the technical scheme or the preparation method of the technical scheme in textiles.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
The embodiment of the invention has no limitation on the grade of the dosage of each raw material, and can be prepared by adopting any weight grade as long as the raw material is mixed according to specific raw material ratio.
Preparation of air microcapsules
Example 1
Dissolving polyvinyl alcohol with the average polymerization degree of 300 in deionized water at the temperature of 60 ℃ and the rotating speed of 900r/min to obtain a polyvinyl alcohol solution with the mass concentration of 5%; dispersing styrene maleic anhydride sodium salt in a polyvinyl alcohol solution at the temperature of 50 ℃ and the rotating speed of 1800r/min to obtain emulsion with the mass percent of the styrene maleic anhydride sodium salt of 1%; introducing air into the emulsion (40 min) at a flow rate of 1.5L/min and a rotation speed of 1800r/min to obtain an air emulsion;
Mixing paraformaldehyde, formaldehyde solution with the mass concentration of 37%, melamine and benzomelamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; regulating the pH value of the reaction solution to 7.5 by using triethanolamine, carrying out polycondensation reaction at 60 ℃ for 90min, cooling to 30 ℃ and filtering to obtain a benzoguanamine modified melamine formaldehyde resin prepolymer; wherein the mass ratio of the paraformaldehyde to the formaldehyde is 1:1, the mass ratio of the melamine to the benzomelamine is 3:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzomelamine is 1:1;
Adding the benzoguanamine modified melamine formaldehyde resin prepolymer into the air emulsion at the temperature of 75 ℃ and the rotating speed of 1800r/min to obtain a reaction liquid of crosslinking polymerization reaction (the particle size of primary air microcapsules in the reaction liquid is D90=2.135 mu m, and the mass percentage of the benzoguanamine modified melamine formaldehyde resin prepolymer in the reaction liquid is 65 percent); adjusting the pH value of the reaction liquid to 3.5 by utilizing citric acid, and carrying out crosslinking polymerization for 180min under the conditions of 75 ℃ and 1000r/min of rotating speed to obtain an air microcapsule dispersion liquid with the mass percent of 35% of air microcapsules; the air microcapsule dispersion was filtered to obtain air microcapsules having a particle diameter D90 of 2.538 μm.
Example 2
Dissolving polyvinyl alcohol with average polymerization degree of 450 in deionized water at the temperature of 72 ℃ and the rotating speed of 1000r/min to obtain a polyvinyl alcohol solution with the mass concentration of 6.8%; dispersing sodium dodecyl benzene sulfonate into a polyvinyl alcohol solution at 57 ℃ and a rotating speed of 1950r/min to obtain an emulsion with the mass percentage of sodium dodecyl benzene sulfonate of 1.5%; introducing air into the emulsion (49 min) at a flow rate of 1.2L/min under the condition of a rotating speed of 1950r/min to obtain an air emulsion;
Mixing paraformaldehyde, formaldehyde solution with the mass concentration of 37%, melamine and benzomelamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; regulating the pH value of the reaction solution to 8 by using triethanolamine, carrying out polycondensation reaction at 72 ℃ for 80min, cooling to 38 ℃ and filtering to obtain a benzoguanamine modified melamine formaldehyde resin prepolymer; wherein the mass ratio of the paraformaldehyde to the formaldehyde is 1:2, the mass ratio of the melamine to the benzomelamine is 2:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzomelamine is 4:1;
Adding the benzoguanamine modified melamine formaldehyde resin prepolymer into the air emulsion at the temperature of 78 ℃ and the rotating speed of 2000r/min to obtain a reaction liquid of crosslinking polymerization reaction (the particle size of primary air microcapsules in the reaction liquid is D90=2.008 mu m, and the mass percentage of the benzoguanamine modified melamine formaldehyde resin prepolymer in the reaction liquid is 58 percent); adjusting the pH value of the reaction solution to 4 by using citric acid, and performing crosslinking polymerization for 155min under the conditions of the temperature of 80 ℃ and the rotating speed of 850r/min to obtain an air microcapsule dispersion liquid with the mass percent of 31.5% of air microcapsules; the air microcapsule dispersion was filtered to obtain air microcapsules having a particle diameter D90 of 2.439 μm.
Example 3
Dissolving polyvinyl alcohol with the average polymerization degree of 500 in deionized water at the temperature of 80 ℃ and the rotating speed of 1100r/min to obtain a polyvinyl alcohol solution with the mass concentration of 8.5%; dispersing sodium dodecyl sulfate into a polyvinyl alcohol solution at 65 ℃ and the rotating speed of 2300r/min to obtain an emulsion with the mass percent of sodium dodecyl sulfate of 2%; introducing air into the emulsion (53 min) at a speed of 2300r/min at a flow rate of 1L/min to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde solution with the mass concentration of 37%, melamine and benzomelamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; adjusting the pH value of the reaction solution to 8.5 by using sodium hydroxide, carrying out polycondensation reaction at 80 ℃ for 70min, cooling to 44 ℃ and filtering to obtain a benzoguanamine modified melamine formaldehyde resin prepolymer; wherein the mass ratio of the paraformaldehyde to the formaldehyde is 1:3, the mass ratio of the melamine to the benzomelamine is 1:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzomelamine is 3:1;
Adding the benzoguanamine modified melamine formaldehyde resin prepolymer into the air emulsion at the temperature of 82 ℃ and the rotating speed of 2250r/min to obtain a reaction liquid of crosslinking polymerization reaction (the particle size of primary air microcapsules in the reaction liquid is D90= 1.890 mu m, and the mass percentage of the benzoguanamine modified melamine formaldehyde resin prepolymer in the reaction liquid is 51 percent); regulating the pH value of the reaction solution to 4.5 by utilizing acetic acid, and carrying out crosslinking polymerization for 120min under the conditions of the temperature of 80 ℃ and the rotating speed of 700r/min to obtain an air microcapsule dispersion liquid with the mass percent of 27.6 percent of air microcapsules; the air microcapsule dispersion was filtered to obtain air microcapsules having a particle diameter D90 of 2.215 μm.
Example 4
Dissolving polyvinyl alcohol with the average polymerization degree of 600 in deionized water at the temperature of 85 ℃ and the rotating speed of 1200r/min to obtain a polyvinyl alcohol solution with the mass concentration of 10%; dispersing sodium hexametaphosphate in a polyvinyl alcohol solution at the temperature of 70 ℃ and the rotating speed of 2500r/min to obtain emulsion with the mass percent of sodium hexametaphosphate of 2.5%; introducing air into the emulsion (60 min) at a flow rate of 0.8L/min and a rotation speed of 2500r/min to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde solution with the mass concentration of 37%, melamine and benzomelamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; adjusting the pH value of the reaction solution to 8.5 by using sodium hydroxide, carrying out polycondensation reaction at 90 ℃ for 60min, cooling to 50 ℃ and filtering to obtain a benzoguanamine modified melamine formaldehyde resin prepolymer; wherein the mass ratio of the paraformaldehyde to the formaldehyde is 1:3, the mass ratio of the melamine to the benzomelamine is 1:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzomelamine is 2:1;
Adding the benzoguanamine modified melamine formaldehyde resin prepolymer into the air emulsion at the temperature of 85 ℃ and the rotating speed of 2500r/min to obtain a reaction liquid of crosslinking polymerization reaction (the particle size of primary air microcapsules in the reaction liquid is D90=1.968 mu m, and the mass percentage of the benzoguanamine modified melamine formaldehyde resin prepolymer in the reaction liquid is 40 percent); regulating the pH value of the reaction solution to 5 by utilizing acetic acid, and carrying out crosslinking polymerization reaction for 100min under the condition that the temperature is 85 ℃ and the rotating speed is 600r/min to obtain an air microcapsule dispersion liquid with the mass percent of the air microcapsule of 25%; the air microcapsule dispersion was filtered to obtain air microcapsules having a particle diameter D90 of 2.316 μm.
The compressive strength testing method comprises the following steps: the air microcapsule is dried (the water content is 2.0-5.0%) and then is horizontally spread on a horizontal object stage, different pressures are applied, static pressure is carried out for 20min, and the air microcapsule is placed under a microscope to observe the perfect condition of the air microcapsule. The pressure that can destroy the air microcapsule is the compressive strength.
Acid resistance test method: preparing sulfuric acid solution with a certain concentration, wherein the mass of the dried air microcapsule (the water content is 2.0% -5.0%) and the volume ratio of the sulfuric acid solution are 1g: and adding the air microcapsule into the sulfuric acid solution according to the proportion of 30mL, soaking for 24 hours, observing whether the defects of foaming, decomposition, dissolution and the like exist, and if not, continuing to increase the concentration of sulfuric acid until the phenomena of foaming, decomposition and dissolution occur, wherein the concentration of the corresponding sulfuric acid solution is acid resistance.
Alkali resistance testing method: preparing sodium hydroxide solution with a certain concentration, wherein the mass of the dried air microcapsule (the water content is 2.0% -5.0%) and the volume ratio of the sodium hydroxide solution are 1g: and adding the dried air microcapsule into the sodium hydroxide solution according to the proportion of 30mL, immersing for 24 hours, observing whether the defects of foaming, decomposition, dissolution and the like exist, and if not, continuing to increase the concentration of sodium hydroxide until the phenomena of foaming, decomposition and dissolution occur, wherein the concentration of the corresponding sodium hydroxide solution is alkali resistance.
The air microcapsules prepared in examples 1 to 4 were tested for compressive strength, acid resistance and alkali resistance according to the above-described methods, and the results are shown in Table 1.
TABLE 1 compressive Strength, acid resistance and alkali resistance of air microcapsules prepared in examples 1 to 4
| Examples | Compressive Strength (MPa) | Acid resistance | Alkali resistance |
| Example 1 | 0.6 | 125G/L sulfuric acid solution | 8.8% Sodium hydroxide solution |
| Example 2 | 0.58 | 125G/L sulfuric acid solution | 8.8% Sodium hydroxide solution |
| Example 3 | 0.55 | 125G/L sulfuric acid solution | 8.8% Sodium hydroxide solution |
| Example 4 | 0.52 | 125G/L sulfuric acid solution | 8.8% Sodium hydroxide solution |
As can be seen from the data in table 1, the air microcapsule provided by the invention has good compressive strength, acid resistance and alkali resistance; the compressive strength of the air microcapsule is 0.52-0.6 MPa; the air microcapsule can stably exist in a sulfuric acid solution with the mass concentration of 125g/L or a sodium hydroxide solution with the mass concentration of 8.8%, which indicates that the air microcapsule provided by the invention can stably exist in a viscose system.
Preparation of warm-keeping cellulose fiber
Example 5
Adjusting the pH value of the air microcapsule dispersion liquid prepared in the example 1 to 7 by using sodium hydroxide, and mixing with a fiber spinning solution (the mass percentage content of alpha cellulose is 8.20%, the mass concentration of sodium hydroxide is 4.30%, and the falling ball viscosity is 36 s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 25:100;
The cellulose fiber blending spinning solution is subjected to wet spinning (a coagulating bath is a solution with the temperature of 50 ℃, the mass concentration of sulfuric acid is 90g/L, the mass concentration of sodium sulfate is 260g/L, the mass concentration of zinc sulfate is 8 g/L), drafting, cutting off and desulfurizing (a desulfurizing bath is a sodium sulfite solution with the temperature of 85 ℃ and the mass concentration of sodium sulfite of 5 g/L), oiling (an oiling agent is a mixed solution of 13# spindle oil with the temperature of 70 ℃ and the total mass concentration of 2.5g/L, polyoxyethylene castor oil ester and alkyl phosphate (the mass ratio is 65:10:25)), microwave drying (the frequency is 1260MHz, the time is 40min, the water content after microwave drying is 12.5%) and opening in sequence, and the warm-keeping cellulose fiber with the specification of 1.67dtex 38mm is obtained.
Example 6
Adjusting the pH value of the air microcapsule dispersion liquid prepared in the example 2 to 7.5 by using sodium hydroxide, and then mixing the air microcapsule dispersion liquid with a fiber spinning solution (the mass percentage of alpha cellulose is 8.58%, the mass concentration of sodium hydroxide is 4.65%, and the falling ball viscosity is 41 s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 28:100;
The cellulose fiber blending spinning solution is subjected to wet spinning (a coagulating bath is a solution with the temperature of 48 ℃, the mass concentration of sulfuric acid is 96g/L, the mass concentration of sodium sulfate is 275g/L, the mass concentration of zinc sulfate is 9.5 g/L), drafting, cutting, desulfurizing (a desulfurizing bath is a sodium sulfite solution with the temperature of 82 ℃ and the mass concentration of sodium sulfite of 6.5 g/L), oiling (an oiling agent is a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate (with the mass concentration of 3.8g/L, the mass ratio of 65:10:25) with the temperature of 65 ℃), microwave drying (with the frequency of 1350MHz, the time of 36min, the water content of 11.9 percent after microwave drying) and opening in sequence, so that the warm-keeping cellulose fiber with the specification of 1.67dtex 38mm is obtained.
Example 7
Adjusting the pH value of the air microcapsule dispersion liquid prepared in the example 3 to 8 by using sodium hydroxide, and mixing with a fiber spinning solution (the mass percentage content of alpha cellulose is 9.05%, the mass concentration of sodium hydroxide is 5.16%, and the falling ball viscosity is 50 s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 31:100;
the cellulose fiber blending spinning solution is subjected to wet spinning (a coagulating bath is a solution with the temperature of 43 ℃, the mass concentration of sulfuric acid is 103g/L, the mass concentration of sodium sulfate is 296g/L, the mass concentration of zinc sulfate is 10.6 g/L), drafting, cutting, desulfurizing (a desulfurizing bath is a sodium sulfite solution with the temperature of 75 ℃ and the mass concentration of sodium sulfite of 7.5 g/L), oiling (an oiling agent is a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate (with the mass concentration of 5.5g/L, the mass ratio of 65:10:25) with the temperature of 60 ℃), microwave drying (with the frequency of 1490MHz for 30min, the water content of 10.2 percent after microwave drying) and opening in sequence, so that the warm-keeping cellulose fiber with the specification of 1.67dtex 38mm is obtained.
Example 8
Adjusting the pH value of the air microcapsule dispersion liquid prepared in the example 4 to 8.5 by using sodium hydroxide, and then mixing the air microcapsule dispersion liquid with a fiber spinning solution (the mass percentage of alpha cellulose is 9.25%, the mass concentration of sodium hydroxide is 5.5%, and the falling ball viscosity is 55 s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 35:100;
The cellulose fiber blending spinning solution is subjected to wet spinning (a coagulating bath is a solution with the temperature of 40 ℃, the mass concentration of sulfuric acid is 110g/L, the mass concentration of sodium sulfate is 310g/L, the mass concentration of zinc sulfate is 12 g/L), drafting, cutting off, desulfurizing (a desulfurizing bath is a sodium sulfite solution with the temperature of 70 ℃ and the mass concentration of sodium sulfite of 8.5 g/L), oiling (an oiling agent is a mixed solution of 13# spindle oil with the mass concentration of 6.0g/L, polyoxyethylene castor oil ester and alkyl phosphate (the mass ratio is 65:10:25), microwave drying (the frequency is 1550MHz, the time is 25min, the water content after microwave drying is 9.35%) and opening in sequence, so that the thermal cellulose fiber with the specification of 1.67dtex x 38mm is obtained.
Comparative example
The preparation of cellulose fibers was carried out according to the preparation methods of examples 5 to 8, respectively, without changing the spinning conditions used, except that air microcapsules were not added during the preparation.
The thermal insulation rate and the Crohn's value of the thermal insulation cellulose fibers prepared in examples 5 to 8 were measured according to the method A-flat plate type fabric thermal insulation instrument method in the national standard GB/T11048-1989, test method for thermal insulation property of textiles, and the results are shown in Table 2.
The thermal cellulose fibers prepared in examples 5 to 8 were examined for dry break strength, wet modulus and elongation at break according to the methods in GB/T14337-2008 "method for testing tensile Property of short chemical fiber", and the results are shown in Table 2.
The fiber weight reduced by the addition of air microcapsules was calculated according to the formula shown in formula 1, and the results are shown in table 2.
M= (M1-M2)/M1 formula 1;
Wherein M is the fiber weight (%) with reduced addition of air microcapsules;
m1 is the mass of cellulose fiber per unit length prepared under the same spinning condition without adding air microcapsules;
m2 is the mass of cellulose fibers per unit length prepared when air microcapsules are added under the same spinning conditions.
Table 2 properties of the thermal cellulosic fibers prepared in examples 5 to 8
As can be seen from the data in Table 2, the thermal cellulose fiber provided by the invention has good thermal insulation performance, wherein the thermal insulation rate is 39.35-52.5%, and the Crohn value is 0.2612-0.5680; the thermal cellulose fiber provided by the invention has good physical and mechanical properties, wherein the dry breaking strength is 1.86-2.16 cN/dtex, the wet breaking strength is 0.98-1.18 cN/dtex, and the breaking elongation is 16.5-19.2%.
Compared with cellulose fibers without air microcapsules, the thermal cellulose fibers provided by the invention have lower weight, so that the thermal insulation property is improved, the density of the fibers is reduced, and the comfort is improved.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (9)
1. An air microcapsule comprises a capsule core and a capsule wall, wherein the capsule core is air, and the capsule wall material is modified melamine formaldehyde resin;
The modified melamine formaldehyde resin comprises a first modified melamine formaldehyde resin and a second modified melamine formaldehyde resin, wherein the first modified melamine formaldehyde resin is a cross-linked product of polyvinyl alcohol and a benzoguanamine modified melamine formaldehyde resin prepolymer, and the second modified melamine formaldehyde resin is a cross-linked product of a benzoguanamine modified melamine formaldehyde resin prepolymer and a benzoguanamine modified melamine formaldehyde resin prepolymer;
The preparation method of the air microcapsule comprises the following steps:
Mixing polyvinyl alcohol, an emulsifying agent, water and air to obtain an air emulsion; the mixing comprises the following steps:
Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
Dispersing an emulsifying agent in the polyvinyl alcohol solution to obtain emulsion;
Introducing air into the emulsion to obtain an air emulsion; the flow rate of the air is 0.8-1.5L/min, and the time is 40-60 min;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and performing polycondensation reaction to obtain benzoguanamine modified melamine formaldehyde resin prepolymer;
Mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and performing cross-linking polymerization reaction to obtain the air microcapsule.
2. The air microcapsule according to claim 1, wherein the polyvinyl alcohol has an average degree of polymerization of 300 to 600;
The particle size of the air microcapsule is D90 which is less than or equal to 2.538 mu m.
3. A method of preparing the air microcapsule according to claim 1 or 2, comprising the steps of:
Mixing polyvinyl alcohol, an emulsifying agent, water and air to obtain an air emulsion; the mixing comprises the following steps:
Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
Dispersing an emulsifying agent in the polyvinyl alcohol solution to obtain emulsion;
Introducing air into the emulsion to obtain an air emulsion; the flow rate of the air is 0.8-1.5L/min, and the time is 40-60 min;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and performing polycondensation reaction to obtain benzoguanamine modified melamine formaldehyde resin prepolymer;
Mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and performing cross-linking polymerization reaction to obtain the air microcapsule.
4. A method of preparation according to claim 3, wherein the emulsifier comprises styrene maleic anhydride sodium salt, sodium dodecylbenzene sulfonate, sodium dodecylsulfate or sodium hexametaphosphate; the mass concentration of the emulsifier in the air emulsion is 1-2.5%;
the mass concentration of the polyvinyl alcohol in the air emulsion is 5-10%.
5. The method according to claim 3, wherein the pH of the reaction solution of the polycondensation reaction is 7.5 to 8.5, the temperature is 60 to 90 ℃ and the time is 60 to 90min.
6. The method according to claim 3, wherein the pH of the reaction solution of the crosslinking polymerization reaction is 3.5-5.0, the temperature is 75-85 ℃ and the time is 100-180 min.
7. A thermal cellulose fiber, comprising cellulose fiber and air microcapsules uniformly distributed in the cellulose fiber or on the surface of the cellulose fiber, wherein the air microcapsules are prepared by the air microcapsules in claim 1 or 2 or the preparation method in any one of claims 3-6;
the mass ratio of the cellulose fiber to the air microcapsule is 100:20.8-29.6.
8. The method for preparing the thermal cellulose fiber according to claim 7, comprising the following steps:
mixing the air microcapsule and the cellulose spinning solution to obtain cellulose fiber blending spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass ratio of the air microcapsule to the alpha cellulose is 25-35:100;
And (3) spinning, drafting, cutting off, desulfurizing, oiling, drying and opening the cellulose fiber blending spinning solution in sequence to obtain the thermal cellulose fiber.
9. Use of the thermal cellulose fiber of claim 7 or the thermal cellulose fiber prepared by the preparation method of claim 8 in textiles.
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