CN114177850A - Air microcapsule and preparation method thereof, and thermal insulation cellulose fiber and preparation method and application thereof - Google Patents
Air microcapsule and preparation method thereof, and thermal insulation cellulose fiber and preparation method and application thereof Download PDFInfo
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- CN114177850A CN114177850A CN202110400204.4A CN202110400204A CN114177850A CN 114177850 A CN114177850 A CN 114177850A CN 202110400204 A CN202110400204 A CN 202110400204A CN 114177850 A CN114177850 A CN 114177850A
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- CN
- China
- Prior art keywords
- air
- formaldehyde resin
- modified melamine
- microcapsule
- benzoguanamine
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Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 126
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000009413 insulation Methods 0.000 title description 5
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 97
- -1 benzoguanamine modified melamine-formaldehyde Chemical class 0.000 claims abstract description 57
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 43
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 43
- 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 33
- 239000002775 capsule Substances 0.000 claims abstract description 26
- 239000003570 air Substances 0.000 claims description 170
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 239000000839 emulsion Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 42
- 238000009987 spinning Methods 0.000 claims description 41
- 238000004132 cross linking Methods 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 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 20
- 239000000835 fiber Substances 0.000 claims description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 19
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 18
- 229920002866 paraformaldehyde Polymers 0.000 claims description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 18
- 229920002678 cellulose Polymers 0.000 claims description 16
- 239000001913 cellulose Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 230000003009 desulfurizing effect Effects 0.000 claims description 7
- 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 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
- 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 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 83
- 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 25
- 239000012295 chemical reaction liquid Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 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 18
- 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 12
- 239000003921 oil Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 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
- 238000004090 dissolution Methods 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
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000008041 oiling agent Substances 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 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
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YYXLGGIKSIZHSF-UHFFFAOYSA-N ethene;furan-2,5-dione Chemical compound C=C.O=C1OC(=O)C=C1 YYXLGGIKSIZHSF-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 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 and a preparation method thereof, and heat-preservation cellulose fibers 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 is made of 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 the benzoguanamine modified melamine-formaldehyde resin and the 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 being broken 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 and a preparation method thereof, and heat-preservation cellulose fibers and a preparation method and application thereof.
Background
With the improvement of living standard of people and the development of science and technology, consumers do not only require warm keeping but also require light weight, softness and comfort while keeping warm. Along with market demands, the development of warm-keeping clothes is continuously developed, and the most important is to improve the warm-keeping performance of the clothes in the aspect of development of novel warm-keeping fibers. Therefore, the study on the heat insulation and heat preservation effects of the fiber material is beneficial to promoting the upgrading of the garment fabric industry and realizing the purposes of low-carbon life, energy conservation and emission reduction.
In the prior art, the heat preservation performance of most of traditional textile fibers and textiles is improved by increasing the using amount of the fibers and improving the thickness and the weight of the textile fibers, but the wearing comfort is affected, and the problems of large weight and thick thickness exist. With the development of research, scientific researchers add air microcapsules into fibers to improve the heat retention of the fibers, but the air microcapsules in the existing heat retention fibers are low in compressive strength and easy to break in the using process, so that the heat retention effect is lost.
Disclosure of Invention
In view of the above, the invention provides an air microcapsule, which has high compressive strength, and the thermal cellulose fiber prepared by using the air microcapsule provided by the invention has good thermal property and reduced density.
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 is made of 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-linking product of polyvinyl alcohol and a performed polymer of a benzoguanamine modified melamine-formaldehyde resin, and the second modified melamine-formaldehyde resin is a cross-linking product of a performed polymer of the benzoguanamine modified melamine-formaldehyde resin and a performed polymer of the benzoguanamine modified melamine-formaldehyde resin.
Preferably, the average polymerization degree of the polyvinyl alcohol is 300-600;
the particle size of the air microcapsule is D90 not more than 2.538 mu m.
The invention also provides a preparation method of the air microcapsule in the technical scheme, which comprises the following steps:
mixing polyvinyl alcohol, an emulsifier, water and air to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and carrying out polycondensation reaction to obtain benzoguanamine modified melamine-formaldehyde resin prepolymer;
and mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and carrying out cross-linking polymerization reaction to obtain the air microcapsule.
Preferably, the emulsifier comprises sodium styrene maleic anhydride, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or sodium hexametaphosphate; the mass concentration of the emulsifier in the air emulsion is 1-2.5%;
the mass concentration of 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 emulsifier in the polyvinyl alcohol solution to obtain an 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 liquid 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 liquid 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 thermal cellulose fiber, which comprises cellulose fibers and air microcapsules uniformly distributed in or on the cellulose fibers, wherein the air microcapsules are the air microcapsules in the technical scheme or the air microcapsules prepared by the preparation method in the technical scheme;
the mass ratio of the cellulose fibers to the air microcapsules is 100: 20.8-29.6.
The invention also provides a preparation method of the thermal cellulose fiber in the technical scheme, which comprises the following steps:
mixing the air microcapsule and the cellulose spinning solution to obtain cellulose fiber blended spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass ratio of the air microcapsules to the alpha cellulose is 25-35: 100;
and (3) spinning, drafting, cutting, desulfurizing, oiling, drying and opening the cellulose fiber blended spinning solution in sequence to obtain the thermal cellulose fiber.
The invention also provides application of the thermal cellulose fiber in the technical scheme or the thermal cellulose fiber prepared by the preparation method in 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 is made of 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-linking product of polyvinyl alcohol and a performed polymer of a benzoguanamine modified melamine-formaldehyde resin, and the second modified melamine-formaldehyde resin is a cross-linking product of a performed polymer of the benzoguanamine modified melamine-formaldehyde resin and a performed polymer of the benzoguanamine modified melamine-formaldehyde resin. The modified melamine-formaldehyde resin is used as the capsule wall material, and the polyvinyl alcohol and the benzoguanamine are used for modifying the melamine-formaldehyde resin, so that the toughness of the capsule wall material is improved, the capsule wall of the air microcapsule has higher compressive strength, the air microcapsule is prevented from being broken under the action of external force and losing the effect, and the heat retention property of the heat retention cellulose fiber is further improved.
The invention also provides a thermal cellulose fiber, which comprises cellulose fibers and air microcapsules attached to the inside or the surface of the cellulose fibers, wherein the air microcapsules are the air microcapsules in the technical scheme or the air microcapsules prepared by the preparation method in the technical scheme; the mass ratio of the cellulose fibers to the air microcapsules 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 the density of the thermal cellulose fiber is reduced, 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 cellulose fiber is prevented from being broken, so that the service life of the thermal 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 is made of 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-linking product of polyvinyl alcohol and a performed polymer of a benzoguanamine modified melamine-formaldehyde resin, and the second modified melamine-formaldehyde resin is a cross-linking product of a performed polymer of the benzoguanamine modified melamine-formaldehyde resin and a performed polymer of the benzoguanamine modified melamine-formaldehyde resin.
In the present invention, the polyvinyl alcohol preferably has an average polymerization degree of 300 to 600, more preferably 450 to 500. In the present invention, the particle size of the air microcapsule is preferably D90 ≦ 2.538 μm, more preferably 2.215 μm ≦ D90 ≦ 2.439 μm.
In the present invention, the air microcapsule preferably has a compressive strength of 0.52 to 0.6MPa, more preferably 0.55 to 0.58 MPa. In the invention, the air microcapsule has good 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%.
The invention also provides a preparation method of the air microcapsule in the technical scheme, which comprises the following steps:
mixing polyvinyl alcohol, an emulsifier, water and air to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and carrying out polycondensation reaction to obtain benzoguanamine modified melamine-formaldehyde resin prepolymer;
and mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and carrying out cross-linking polymerization reaction to obtain the air microcapsule.
The air emulsion is obtained by mixing polyvinyl alcohol, an emulsifier, water and air. In the present invention, the mixing preferably comprises the steps of:
dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
dispersing an emulsifier in the polyvinyl alcohol solution to obtain an emulsion;
and introducing air into the emulsion to obtain the 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 polymerization degree of the polyvinyl alcohol is preferably 300 to 600, and more preferably 450 to 500. In the present invention, the mass concentration of the polyvinyl alcohol solution is preferably 5 to 10%, and more preferably 6 to 9%. In the invention, the dissolving temperature is preferably 60-85 ℃, and more preferably 70-80 ℃. The time for the dissolution is not particularly limited in the present invention, as long as the dissolution can be completed. In the invention, the dissolution is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 900-1200 r/min, and more preferably 1000-1100 r/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 emulsifier is dispersed in the polyvinyl alcohol solution to obtain the emulsion. In the present invention, the emulsifier preferably includes a sodium salt of styrene maleic anhydride, sodium dodecylbenzene sulfonate, sodium dodecylsulfate or sodium hexametaphosphate, more preferably a sodium salt of ethylene maleic anhydride, sodium dodecylbenzene sulfonate or sodium dodecylsulfate. In the invention, the mass percentage of the emulsifier in the emulsion is preferably 1-2.5%, and more preferably 1.5-2%. In the invention, the temperature of the dispersion is preferably 50-70 ℃, and more preferably 55-65 ℃. The time for the dispersion is not particularly limited as long as the emulsifier can be uniformly dispersed. In the present invention, the dispersion is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 1800 to 2500r/min, more preferably 1900 to 2300 r/min.
After the emulsion is obtained, the air is introduced into the emulsion to obtain the air emulsion. In the invention, the air flow rate is preferably 0.8-1.5L/min, and more preferably 1-1.2L/min; the time is preferably 40 to 60min, and more preferably 49 to 55 min. In the present invention, the aeration is accompanied by stirring, and the rotation speed of the stirring is preferably the same as that of the stirring during the dispersion.
The invention mixes paraformaldehyde, formaldehyde, melamine, benzoguanamine and water to carry out polycondensation reaction, and obtains 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, and more preferably 1: 1.5-2; the mass ratio of the melamine to the benzoguanamine is preferably 1-3: 1, and more preferably 1.5-2: 1; the ratio of the total mass of the paraformaldehyde and the formaldehyde to the total mass of the melamine and the benzoguanamine is preferably 2-4: 1, and more preferably 2.5-3: 1. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring is not particularly limited in the present invention as long as the uniform mixing is possible.
In the present invention, the pH of the reaction solution in the polycondensation reaction is preferably 7.5 to 8.5, and more preferably 7.8 to 8. In the present invention, the pH adjusting agent for adjusting pH preferably includes triethanolamine or sodium hydroxide, more preferably triethanolamine; the amount of the pH adjuster used in the present invention is not particularly limited as long as the above-mentioned pH can be attained. In the invention, the temperature of the polycondensation reaction is preferably 60-90 ℃, and more preferably 70-80 ℃; the time is preferably 60 to 90min, and more preferably 70 to 80 min.
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 invention, the temperature after temperature reduction is preferably 30-50 ℃, and more preferably 38-44 ℃. The filtration is not particularly limited in the invention, and the conventional technical means in the field can be selected.
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 for cross-linking polymerization reaction to obtain the air microcapsule. In the present invention, the mixing is preferably performed by adding the benzoguanamine modified melamine formaldehyde resin prepolymer to the air emulsion. In the invention, the mass percentage content of the benzoguanamine modified melamine formaldehyde resin prepolymer in the mixed solution is preferably 40-65%, and more preferably 51-58%. In the invention, the mixing temperature is preferably 75-85 ℃, and more preferably 78-82 ℃. In the invention, the mixing is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 1800-2500 r/min, and more preferably 2000-2250 r/min. In the invention, the primary air microcapsule is obtained after the mixing, and the capsule 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 ≦ 2.135 μm, more preferably 1.890 μm ≦ D90 ≦ 2.008 μm. The stirring time in the present invention is not particularly limited as long as the particle size of the primary air microcapsule can be brought to the above range.
In the present invention, the pH of the reaction solution of the cross-linking polymerization reaction is preferably 3.5 to 5.0, more preferably 4 to 4.5. In the present invention, the pH adjusting agent for adjusting pH preferably includes citric acid or acetic acid, more preferably citric acid; the amount of the pH regulator used in the present invention is not particularly limited as long as the above-mentioned pH is attained. In the invention, the temperature of the cross-linking polymerization reaction is preferably 75-85 ℃, and more preferably 80-83 ℃; the time is preferably 100 to 180min, and more preferably 120 to 160 min. In the invention, the crosslinking polymerization reaction is preferably carried out under the condition of stirring, and the rotation speed of the stirring is preferably 600-1000 r/min, and more preferably 700-850 r/min. In the present invention, it is preferable that the crosslinking polymerization reaction further includes, after completion of the crosslinking polymerization reaction: and filtering the product of the crosslinking polymerization reaction to obtain the air microcapsule. The filtration is not particularly limited in the present invention, and conventional technical means in the art can be adopted.
In the invention, in the cross-linking polymerization reaction, cross-linking polymerization can occur between the polyvinyl alcohol and the benzoguanamine modified melamine-formaldehyde resin prepolymer, 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 benzoguanamine, and the toughness of the modified melamine formaldehyde resin is improved by increasing the distance between triazine rings in melamine and reducing the density of cross-linking points, so that the compressive strength of the air microcapsule is improved. The present invention will encapsulate air in the air emulsion within the crosslinked polymeric product during the crosslinking polymerization process.
The invention also provides a thermal cellulose fiber, which comprises cellulose fibers and air microcapsules uniformly distributed in or on the cellulose fibers, wherein the air microcapsules are the air microcapsules in the technical scheme or the air microcapsules prepared by the preparation method in the technical scheme;
the mass ratio of the cellulose fibers to the air microcapsules is 100: 20.8-29.6, preferably 100: 23.5 to 27.3.
The invention also provides a preparation method of the thermal cellulose fiber in the technical scheme, which comprises the following steps:
mixing the air microcapsule and the cellulose spinning solution to obtain cellulose fiber blended spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass ratio of the air microcapsules to the alpha cellulose is 25-35: 100;
and (3) spinning, drafting, cutting, desulfurizing, oiling, drying and opening the cellulose fiber blended spinning solution in sequence to obtain the thermal cellulose fiber.
Mixing an air microcapsule and a cellulose spinning solution to obtain a cellulose fiber blending spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass percentage content of alpha cellulose in the cellulose spinning solution is preferably 8.2-9.25%, and more preferably 8.58-9.05%; the mass concentration of the sodium hydroxide in the fiber spinning solution is preferably 4.3-5.5%, and more preferably 4.65-5.16%. In the invention, the falling ball viscosity of the cellulose spinning solution is preferably 36-55 s, and more preferably 41-50 s. 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, it is preferable that the mixing further comprises: and (3) dispersing the air microcapsule in water, and then adjusting the pH value to obtain the air microcapsule dispersion liquid. In the invention, the mass percentage of the air microcapsules in the air microcapsule dispersion liquid is preferably 25-35%, and more preferably 28-31%. In the invention, the pH value of the dispersion liquid after the pH value is adjusted is preferably 7-8.5, and more preferably 7.5-8; the pH adjuster for adjusting pH is preferably sodium hydroxide, and the amount of sodium hydroxide used in the present invention is not particularly limited as long as the pH can be adjusted to the above-mentioned limit. The purpose of the present invention to adjust the pH of the dispersion is to match the alkaline conditions of the cellulose dope.
The invention aims to reduce the preparation steps and mix the dispersion liquid of the air microcapsule and the cellulose spinning solution after directly adjusting the pH value of a cross-linking polymerization reaction product. The mixing is not particularly limited in the present invention as long as it can be mixed uniformly.
After the cellulose fiber blended spinning solution is obtained, the cellulose fiber blended spinning solution is sequentially subjected to spinning, drafting, cutting, desulfurization, oiling, drying and opening to obtain the thermal cellulose fiber. In the invention, the spinning is preferably wet spinning, the coagulating bath for the wet spinning is preferably a solution of sulfuric acid, sodium sulfate and zinc sulfate, and the mass concentration of the sulfuric acid in the coagulating bath is preferably 90-100 g/L, and more preferably 96-103 g/L; the mass concentration of the sodium sulfate is preferably 260-310 g/L, and more preferably 275-296 g/L; the mass concentration of the zinc sulfate is preferably 8-12 g/L, and more preferably 9.5-10.6 g/L. In the invention, the temperature of the coagulating bath is preferably 40-50 ℃, and more preferably 43-48 ℃.
In the present invention, the drawing and cutting are not particularly limited, and a conventional technique in the art may be used.
In the invention, the desulfurization bath for desulfurization is preferably a sodium sulfite solution with the mass concentration of 5-8.5 g/L, and more preferably 6.5-7.3 g/L; the temperature of the desulfurization bath is preferably 70-85 ℃, and more preferably 6.5-7.3 ℃.
In the invention, the oiling oil agent preferably comprises a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate ester salt, wherein the mass ratio of the 13# spindle oil, the polyoxyethylene castor oil ester and the alkyl phosphate ester salt is 65:10: 25; the total mass concentration of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate ester in the oil agent is preferably 2.5-6 g/L, and more preferably 3.8-5.5 g/L; the temperature of the oil agent is preferably 55-70 ℃, and more preferably 60-65 ℃.
In the invention, the drying is preferably microwave drying, and the frequency of microblogs dried by microwave is preferably 1260-1550 MHz, and more preferably 1350-1490 MHz; the time is preferably 25-40 min, and more preferably 30-36 min; the moisture content of the dried fiber is preferably 9.35-12.5%, and more preferably 10.2-11.9%.
The opening is not specially limited in the invention, and the conventional technical means in the field can be adopted.
The invention also provides application of the thermal cellulose fiber in the technical scheme or the thermal cellulose fiber prepared by the preparation method in the technical scheme in textiles.
In order to further illustrate the present invention, the following embodiments are described in detail, 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 the raw materials can be prepared by adopting any weight grade as long as the raw materials are mixed according to a specific 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 sodium styrene maleic anhydride into a polyvinyl alcohol solution at the temperature of 50 ℃ and the rotating speed of 1800r/min to obtain an emulsion with the mass percentage of the sodium styrene maleic anhydride of 1%; introducing air into the emulsion at a flow rate of 1.5L/min and a rotation speed of 1800r/min for 40min to obtain an air emulsion;
mixing paraformaldehyde, a formaldehyde solution with the mass concentration of 37%, melamine and benzoguanamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; regulating the pH value of the reaction liquid 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 benzoguanamine is 3:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzoguanamine is 1: 1;
adding the benzoguanamine modified melamine-formaldehyde resin prepolymer into air emulsion at the temperature of 75 ℃ and the rotating speed of 1800r/min to obtain a reaction liquid of a cross-linking polymerization reaction (the particle size of a primary air microcapsule in the reaction liquid is D90-2.135 mu m; and the mass percentage content of the benzoguanamine modified melamine-formaldehyde resin prepolymer in the reaction liquid is 65%); adjusting the pH value of the reaction solution to 3.5 by using citric acid, and carrying out cross-linking polymerization reaction for 180min under the conditions that the temperature is 75 ℃ and the rotating speed is 1000r/min to obtain an air microcapsule dispersion liquid with the mass percentage of 35% of air microcapsules; and filtering the air microcapsule dispersion liquid to obtain the air microcapsule with the particle size D90 of 2.538 mu m.
Example 2
Dissolving polyvinyl alcohol with the 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 in polyvinyl alcohol solution at the temperature of 57 ℃ and the rotation speed of 1950r/min to obtain emulsion with the mass percentage of the sodium dodecyl benzene sulfonate of 1.5 percent; introducing air into the emulsion at a flow rate of 1.2L/min at 1950r/min (49min) to obtain air emulsion;
mixing paraformaldehyde, a formaldehyde solution with the mass concentration of 37%, melamine and benzoguanamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; regulating the pH value of the reaction liquid 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 benzoguanamine is 2:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzoguanamine is 4: 1;
adding the benzoguanamine modified melamine-formaldehyde resin prepolymer into an air emulsion at the temperature of 78 ℃ and the rotating speed of 2000r/min to obtain a reaction liquid of a cross-linking polymerization reaction (the particle size of a primary air microcapsule in the reaction liquid is D90-2.008 mu m; and the mass percentage content of the benzoguanamine modified melamine-formaldehyde resin prepolymer in the reaction liquid is 58%); adjusting the pH value of the reaction solution to 4 by using citric acid, and carrying out cross-linking polymerization reaction for 155min at the temperature of 80 ℃ and the rotating speed of 850r/min to obtain an air microcapsule dispersion liquid with the mass percentage of 31.5% of air microcapsules; and filtering the air microcapsule dispersion liquid to obtain the air microcapsule with the particle size D90 of 2.439 mu m.
Example 3
Dissolving polyvinyl alcohol with average polymerization degree of 500 in deionized water at 80 ℃ and rotation speed of 1100r/min to obtain polyvinyl alcohol solution with mass concentration of 8.5%; dispersing sodium dodecyl sulfate in a polyvinyl alcohol solution at the temperature of 65 ℃ and the rotation speed of 2300r/min to obtain an emulsion with the mass percentage of the sodium dodecyl sulfate of 2%; introducing air into the emulsion at a flow rate of 1L/min (53min) at a rotation speed of 2300r/min to obtain an air emulsion;
mixing paraformaldehyde, a formaldehyde solution with the mass concentration of 37%, melamine and benzoguanamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; adjusting the pH value of the reaction liquid 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 benzoguanamine is 1:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzoguanamine is 3: 1;
adding the benzoguanamine modified melamine-formaldehyde resin prepolymer into air emulsion at the temperature of 82 ℃ and the rotating speed of 2250r/min to obtain a reaction liquid for crosslinking polymerization (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%); adjusting the pH value of the reaction liquid to 4.5 by using acetic acid, and carrying out cross-linking polymerization reaction for 120min under the conditions that the temperature is 80 ℃ and the rotating speed is 700r/min to obtain an air microcapsule dispersion liquid with the mass percentage of 27.6% of air microcapsules; and filtering the air microcapsule dispersion liquid to obtain the air microcapsule with the particle size D90 of 2.215 mu m.
Example 4
Dissolving polyvinyl alcohol with the average polymerization degree of 600 in deionized water at the temperature of 85 ℃ and the rotation 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 an emulsion with the mass percentage of the sodium hexametaphosphate being 2.5 percent; introducing air into the emulsion at a flow rate of 0.8L/min and a rotation speed of 2500r/min for 60min to obtain an air emulsion;
mixing paraformaldehyde, a formaldehyde solution with the mass concentration of 37%, melamine and benzoguanamine under the condition of stirring to obtain a reaction solution of polycondensation reaction; adjusting the pH value of the reaction liquid 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 benzoguanamine is 1:1, and the total mass ratio of the paraformaldehyde to the formaldehyde to the total mass ratio of the melamine to the benzoguanamine is 2: 1;
adding the benzoguanamine modified melamine-formaldehyde resin prepolymer into air emulsion at the temperature of 85 ℃ and the rotating speed of 2500r/min to obtain a reaction liquid of a crosslinking polymerization reaction (the particle size of a primary air microcapsule in the reaction liquid is D90-1.968 mu m; and the mass percentage content of the benzoguanamine modified melamine-formaldehyde resin prepolymer in the reaction liquid is 40%); adjusting the pH value of the reaction liquid to 5 by using acetic acid, and carrying out cross-linking polymerization reaction for 100min under the conditions that the temperature is 85 ℃ and the rotating speed is 600r/min to obtain an air microcapsule dispersion liquid with the mass percentage of 25% of air microcapsules; and filtering the air microcapsule dispersion liquid to obtain the air microcapsule with the particle size D90 of 2.316 mu m.
The compression strength test method comprises the following steps: and (3) after drying the air microcapsule (the water content is 2.0-5.0%), spreading the air microcapsule on a horizontal objective table, applying different pressures, carrying out static pressure for 20min, and then placing the air microcapsule under a microscope to observe the perfect condition of the air microcapsule. The pressure capable of destroying the air microcapsules is the compressive strength thereof.
The acid resistance test method comprises the following steps: preparing a sulfuric acid solution with a certain concentration, wherein the mass ratio of the dried air microcapsules (the water content is 2.0-5.0%) to the sulfuric acid solution is 1 g: and adding the air microcapsules into the sulfuric acid solution at a ratio of 30mL, soaking for 24 hours, observing whether defects such as foaming, decomposition and dissolution exist, and if not, continuously increasing the sulfuric acid concentration until foaming, decomposition and dissolution occur, wherein the concentration of the corresponding sulfuric acid solution is acid resistance.
Alkali resistance test method: preparing a sodium hydroxide solution with a certain concentration, wherein the mass ratio of the dried air microcapsules (the water content is 2.0-5.0%) to the sodium hydroxide solution is 1 g: and adding the dried air microcapsules into the sodium hydroxide solution in a proportion of 30mL, soaking for 24 hours, observing whether defects such as foaming, decomposition and dissolution exist, and if not, continuously increasing the concentration of the sodium hydroxide until foaming, decomposition and dissolution occur, wherein the concentration of the corresponding sodium hydroxide solution is alkali-resistant.
The air microcapsules prepared in examples 1 to 4 were tested for their compressive strength, acid resistance and alkali resistance according to the methods described above, 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 |
| Practice ofExample 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 present invention has good compressive strength, acid resistance and alkali resistance; the compression 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 shows that the air microcapsule provided by the invention can stably exist in an adhesive system.
Preparation of thermal cellulose fiber
Example 5
Adjusting the pH value of the air microcapsule dispersion liquid prepared in the example 1 to be 7 by using sodium hydroxide, and mixing the air microcapsule dispersion liquid with a fiber spinning solution (the mass percentage of the A cellulose is 8.20%, the mass concentration of the sodium hydroxide is 4.30%, and the falling ball viscosity is 36s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 25: 100;
and (2) sequentially carrying out wet spinning (the coagulation bath is a solution with the temperature of 50 ℃, the mass concentration of sulfuric acid of 90g/L, the mass concentration of sodium sulfate of 260g/L and the mass concentration of zinc sulfate of 8 g/L), drafting, cutting, desulfurizing (the desulfurization bath is a sodium sulfite solution with the temperature of 85 ℃ and the mass concentration of sodium sulfite of 5 g/L), oiling (the oiling agent is a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate ester salt (the mass ratio is 65:10:25) with the temperature of 70 ℃ and the total mass concentration of 2.5 g/L), microwave drying (the frequency is 1260MHz, the time is 40min, and the water content is 12.5 percent after microwave drying) and opening on the cellulose fiber blending spinning solution to obtain the heat-insulating cellulose fiber with the specification of 1.67dtex 38 mm.
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 mixing the air microcapsule dispersion liquid with a fiber spinning solution (the mass percentage of the A cellulose is 8.58%, the mass concentration of the sodium hydroxide is 4.65%, and the falling ball viscosity is 41s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 28: 100;
and (2) sequentially carrying out wet spinning (the coagulation bath is a solution with the temperature of 48 ℃, the mass concentration of sulfuric acid of 96g/L, the mass concentration of sodium sulfate of 275g/L and the mass concentration of zinc sulfate of 9.5 g/L), drafting, cutting, desulfurizing (the desulfurization bath is a sodium sulfite solution with the temperature of 82 ℃ and the mass concentration of sodium sulfite of 6.5 g/L), oiling (the oiling agent is a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate ester salt (the mass ratio is 65:10:25) with the temperature of 65 ℃ and the mass concentration of 3.8 g/L), microwave drying (the frequency is 1350MHz, the time is 36min, and the moisture content after microwave drying is 11.9%) and opening on the cellulose fiber blending spinning solution to obtain the thermal cellulose fiber with the specification of 1.67dtex 38 mm.
Example 7
Adjusting the pH value of the air microcapsule dispersion liquid prepared in the example 3 to be 8 by using sodium hydroxide, and mixing the air microcapsule dispersion liquid with a fiber spinning solution (the mass percentage of the A cellulose is 9.05%, the mass concentration of the sodium hydroxide is 5.16%, and the falling ball viscosity is 50s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 31: 100;
and (2) sequentially carrying out wet spinning (the coagulation bath is a solution with the temperature of 43 ℃, the mass concentration of sulfuric acid of 103g/L, the mass concentration of sodium sulfate of 296g/L and the mass concentration of zinc sulfate of 10.6 g/L), drafting, cutting, desulfurizing (the desulfurization bath is a sodium sulfite solution with the temperature of 75 ℃ and the mass concentration of sodium sulfite of 7.5 g/L), oiling (the oiling agent is a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate ester (the mass ratio is 65:10:25) with the temperature of 60 ℃ and the mass concentration of 5.5 g/L), microwave drying (the frequency is 1490MHz, the time is 30min, and the water content is 10.2% after microwave drying) and opening on the cellulose fiber blending spinning solution to obtain the thermal cellulose fiber with the specification of 1.67dtex 38 mm.
Example 8
Adjusting the pH value of the air microcapsule dispersion liquid prepared in example 4 to 8.5 by using sodium hydroxide, and mixing the air microcapsule dispersion liquid with a fiber spinning solution (the mass percentage of the A cellulose is 9.25%, the mass concentration of the sodium hydroxide is 5.5%, and the falling ball viscosity is 55s) to obtain a cellulose fiber blending spinning solution; wherein the mass ratio of the air microcapsule to the alpha cellulose is 35: 100;
and (2) sequentially carrying out wet spinning (the coagulation bath is a solution with the temperature of 40 ℃, the mass concentration of sulfuric acid of 110g/L, the mass concentration of sodium sulfate of 310g/L and the mass concentration of zinc sulfate of 12 g/L), drafting, cutting, desulfurizing (the desulfurization bath is a sodium sulfite solution with the temperature of 70 ℃ and the mass concentration of sodium sulfite of 8.5 g/L), oiling (the oiling agent is a mixed solution of 13# spindle oil, polyoxyethylene castor oil ester and alkyl phosphate ester salt (the mass ratio is 65:10:25) with the temperature of 55 ℃ and the mass concentration of 6.0 g/L), microwave drying (the frequency is 1550MHz, the time is 25min, and the water content is 9.35% after microwave drying) and opening on the cellulose fiber blending spinning solution to obtain the thermal cellulose fiber with the specification of 1.67dtex 38 mm.
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 no air microcapsules were added during the preparation.
The heat preservation rate and the clo value of the heat preservation cellulose fibers prepared in the examples 5-8 are detected according to a method A-a flat-plate type fabric heat preservation instrument method in a national standard GB/T11048-1989 textile heat preservation performance test method, and the results are listed in Table 2.
The dry breaking strength, wet modulus and elongation at break of the thermal cellulose fibers prepared in examples 5 to 8 were measured according to the method in GB/T14337-2008 "test method for tensile properties of chemical fiber staple fibers", and the results are listed in table 2.
The weight of the fiber reduced by the addition of the 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 (%) reduced by the addition of the air microcapsules;
m1 is the mass per unit length of cellulose fiber prepared without the addition of air microcapsules under the same spinning conditions;
m2 is the mass per unit length of cellulose fiber produced when air microcapsules are added under the same spinning conditions.
Table 2 properties of the thermal cellulose 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 warm-keeping 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 elongation at break is 16.5-19.2%.
Compared with the cellulose fiber without the air microcapsule, the heat-insulating cellulose fiber provided by the invention has lower weight, improves heat-insulating property, reduces fiber density and improves comfort.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. An air microcapsule comprises a capsule core and a capsule wall, wherein the capsule core is air, and the capsule wall is made of 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-linking product of polyvinyl alcohol and a performed polymer of a benzoguanamine modified melamine-formaldehyde resin, and the second modified melamine-formaldehyde resin is a cross-linking product of a performed polymer of the benzoguanamine modified melamine-formaldehyde resin and a performed polymer of the benzoguanamine modified melamine-formaldehyde resin.
2. The air microcapsule according to claim 1, wherein the polyvinyl alcohol has an average polymerization degree of 300 to 600;
the particle size of the air microcapsule is D90 not more than 2.538 mu m.
3. A process for the preparation of an air microcapsule according to claim 1 or 2 comprising the steps of:
mixing polyvinyl alcohol, an emulsifier, water and air to obtain an air emulsion;
mixing paraformaldehyde, formaldehyde, melamine, benzoguanamine and water, and carrying out polycondensation reaction to obtain benzoguanamine modified melamine-formaldehyde resin prepolymer;
and mixing the benzoguanamine modified melamine formaldehyde resin prepolymer with air emulsion, and carrying out cross-linking polymerization reaction to obtain the air microcapsule.
4. The method of claim 3, wherein the emulsifier comprises sodium styrene maleic anhydride, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, or sodium hexametaphosphate; the mass concentration of the emulsifier in the air emulsion is 1-2.5%;
the mass concentration of polyvinyl alcohol in the air emulsion is 5-10%.
5. The method of claim 3, wherein the mixing comprises the steps of:
dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
dispersing an emulsifier in the polyvinyl alcohol solution to obtain an 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.
6. The method according to claim 3, wherein the reaction solution of the polycondensation reaction has a pH of 7.5 to 8.5, a temperature of 60 to 90 ℃ and a time of 60 to 90 min.
7. The method according to claim 3, wherein the reaction solution of the cross-linking polymerization reaction has a pH of 3.5 to 5.0, a temperature of 75 to 85 ℃ and a time of 100 to 180 min.
8. A thermal cellulose fiber, comprising cellulose fiber and air microcapsules uniformly distributed in or on the cellulose fiber, wherein the air microcapsules are the air microcapsules described in claim 1 or 2 or the air microcapsules prepared by the preparation method described in any one of claims 3 to 7;
the mass ratio of the cellulose fibers to the air microcapsules is 100: 20.8-29.6.
9. A method of making the thermal cellulosic fibers of claim 8 comprising the steps of:
mixing the air microcapsule and the cellulose spinning solution to obtain cellulose fiber blended spinning solution; the cellulose spinning solution comprises alpha cellulose and sodium hydroxide; the mass ratio of the air microcapsules to the alpha cellulose is 25-35: 100;
and (3) spinning, drafting, cutting, desulfurizing, oiling, drying and opening the cellulose fiber blended spinning solution in sequence to obtain the thermal cellulose fiber.
10. Use of the thermal cellulose fibers according to claim 8 or the thermal cellulose fibers produced by the method according to claim 9 in textiles.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115748260A (en) * | 2022-10-20 | 2023-03-07 | 浙江理工大学桐乡研究院有限公司 | Super-hydrophobic and super-light-weight lifesaving filling fiber and preparation method thereof |
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| CN114177850B (en) | 2024-04-26 |
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