CN107022800A - A kind of high heat storage amount phase-changing and temperature-regulating viscose rayon and preparation method thereof - Google Patents
A kind of high heat storage amount phase-changing and temperature-regulating viscose rayon and preparation method thereof Download PDFInfo
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- CN107022800A CN107022800A CN201710183743.0A CN201710183743A CN107022800A CN 107022800 A CN107022800 A CN 107022800A CN 201710183743 A CN201710183743 A CN 201710183743A CN 107022800 A CN107022800 A CN 107022800A
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- 229920000297 Rayon Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 238000005338 heat storage Methods 0.000 title claims abstract description 21
- 239000012782 phase change material Substances 0.000 claims abstract description 114
- 239000003094 microcapsule Substances 0.000 claims abstract description 87
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 40
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001661 Chitosan Polymers 0.000 claims abstract description 34
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 229920002907 Guar gum Polymers 0.000 claims abstract description 20
- 239000000665 guar gum Substances 0.000 claims abstract description 20
- 229960002154 guar gum Drugs 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 235000010417 guar gum Nutrition 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 52
- 238000009987 spinning Methods 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 39
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 39
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 229920000877 Melamine resin Polymers 0.000 claims description 30
- 239000003292 glue Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 206010011732 Cyst Diseases 0.000 claims description 21
- 208000031513 cyst Diseases 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- 229920002472 Starch Polymers 0.000 claims description 20
- 239000008107 starch Substances 0.000 claims description 20
- 235000019698 starch Nutrition 0.000 claims description 20
- 230000009466 transformation Effects 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 238000013329 compounding Methods 0.000 claims description 18
- 239000004640 Melamine resin Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- -1 tertiary amino alkyl ether Chemical class 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 10
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 10
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 10
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 6
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 239000000498 cooling water Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- OOSUHIIJYDMCCW-UHFFFAOYSA-N cyanamide;formaldehyde Chemical compound O=C.NC#N OOSUHIIJYDMCCW-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 48
- 230000001112 coagulating effect Effects 0.000 abstract description 24
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 75
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000002775 capsule Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002964 rayon Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 229920001213 Polysorbate 20 Polymers 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000000116 mitigating effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- HPAVSHLOCSRBQS-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCCl(C)(C)CC1=CC=CC=C1 Chemical compound CCCCCCCCCCCCCCCCCCCl(C)(C)CC1=CC=CC=C1 HPAVSHLOCSRBQS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Artificial Filaments (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present invention provides a kind of high heat storage amount phase-changing and temperature-regulating viscose rayon, the viscose rayon, and melting enthalpy is that 20.8 22J/g, crystallization enthalpy are 18.5 19.7J/g；The present invention also provides a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon, includes the modification of phase-change material micro-capsule；The modification of the phase-change material micro-capsule, is modified using modifier solution to phase-change material micro-capsule；The modifier solution, in parts by weight, including 2 parts of guar gum, 4 parts of chitosan, 1 part of polyvinyl alcohol, 30 parts of pure water, 100 parts of acetic acid.The present invention reduces the loss of phase-change material in phase change fiber preparation process, reduces the backwash rate of pulling away a prop of coagulating bath filter, improves the credit rating of byproduct sulfite, increases substantially the crystallization enthalpy and melting enthalpy of phase-changing and temperature-regulating fiber；Improve fibre strength, hygroscopicity and the fibre density of phase-changing and temperature-regulating viscose rayon.
Description
Technical field
The present invention relates to a kind of phase change fiber, particularly a kind of high heat storage amount phase-changing and temperature-regulating viscose rayon and its preparation side
Method, belongs to textile technology field.
Background technology
Phase change fiber be discharged using phase-change material in phase transition process or absorb latent heat, the spy that temperature is held essentially constant
A kind of heat-accumulation temperature-adjustment functional fibre that property is developed.
Phase-change material, refers to vary with temperature and change form and can absorb or provide the material of latent heat, phase-change material energy
It is enough to be undergone phase transition according to the change of ambient temperature, and absorbed or release heat from the external world, temperature is formed around textile
Substantially invariable micro climate is spent, so as to realize temperature adjustment temperature.
Blending method is typically taken to prepare phase-changing and temperature-regulating viscose rayon in the prior art：
The first blending method, carry out spinning is directly blended by phase-change material and rayon spinning stoste, relatively simple but there is phase transformation
Heat content is low, phase-change material is easily leaked and the low problem of fibre strength；
Second of blending method, that is, microcapsule method, are that first phase-change material parcel is closed to macromolecule, make micro- glue
Capsule, prevents phase-change material from leaking, and the microcapsules containing phase-change material and rayon spinning stoste are carried out into co-blended spinning obtains phase transformation
Fiber.
Phase-changing and temperature-regulating viscose rayon is prepared using microcapsule method, there is also deficiency：
（1）There is phase-change microcapsule to be largely lost in, cause phase-change microcapsule to be greatly lost to acid bath and can not all enter
Enter fiber, and then cause the less problem of fiber enthalpy of phase change；The process being specifically lost in is：In rayon spinning stoste, first fibre content
Between 8.2-9.2%, first fibre can in spinning process coagulation forming, formed fiber；
In spinning process, when rayon spinning stoste and the blend solution of phase-change microcapsule, coagulating bath is sprayed into a flash, first is fine
Start curing molding, then coat residence addition microcapsules, but in rayon spinning stoste can curing molding material, that is,
The fine content of first is less than 10%, and the microcapsules that first fibre can be coated in forming process are few, there is substantial amounts of phase-change microcapsule
Understand as the material such as 90% water, soluble-salt lost in spinning viscose stoste, cause a large amount of losses of phase-change material.
Found in actual experiment, when microcapsules solid dry powder to the fine addition of first 10% when, phase transformation is micro- in finished fiber
The content of capsule is also less than 4.9%, and substantial amounts of phase-change microcapsule material enters coagulating bath after being lost in, and adds coagulating bath filter and tears open
Platform rate is up to 80%, while the phase-change microcapsule material of residual enters crystallizer, it is inter-adhesive in crystallization process to enter ten water sulfuric acid
In sodium product, the quality of crystal has been badly influenced, after being tested and analyzed using instrument, phase in crystal sal glauberi
Become material content to reach as high as in 2.6g/kg saltcake, seriously reduce the quality of accessory substance crystal and limit application.
（2）Other phase-change microcapsule and fibrous matrix compatibility are poor, cause fibre strength to reduce, the moisture absorption of viscose rayon
Property reduction, fiber density reduction.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of high heat storage amount phase-changing and temperature-regulating viscose rayon and its preparation side
Method, to realize following goal of the invention：
（1）The loss of phase-change material in phase change fiber preparation process is reduced, the backwash rate of pulling away a prop of coagulating bath filter is reduced, improved
The credit rating of byproduct sulfite, increases substantially the crystallization enthalpy and melting enthalpy of phase-changing and temperature-regulating fiber；
（2）Improve fibre strength, hygroscopicity and the fibre density of phase-changing and temperature-regulating viscose rayon.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
A kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon, comprises the following steps：
（1）Prepare phase-change material micro-capsule
A, prepare phase-change material emulsion
Phase-change material and phase transformation auxiliary agent are mixed, 40-45 DEG C is heated to, stirred under 500r/min, after 5 minutes, temperature is raised
To 60-65 DEG C, emulsifying agent, initiator and distilled water are added, while rotating speed is improved to 1300- with 50r/min speed
1500r/min, is stirred 0.8-1.2 hours, forms stable emulsion；
The mass ratio of wherein phase-change material, phase transformation auxiliary agent, emulsifying agent, initiator and distilled water is:100:7-10：6-8:1.7-
2.2:340-370；
The emulsifying agent is Tween-20；The initiator is benzoyl peroxide.
, prepare melamine resin cyst material performed polymer
37% formalin is put into reactor, stirred, regulation pH value is 7.8-8.0, by 37% formalin：Melamine
Amine is 3:1 ratio adds melamine, is warming up to small with 500-600r/min stirring reactions 1 under 70-75 DEG C, constant temperature
When, melamine resin cyst material performed polymer is made.
, polymerisation
Melamine resin cyst material performed polymer is added drop-wise in above-mentioned emulsion dropwise, in 70-75 DEG C of water-bath with
2000-2500r/min rotating speed stirring, citric acid, which is added dropwise, reduces pH to 3.5-4.0, is acidified, and acidificatoin time is 1 hour,
Then 83-85 DEG C is warming up to, is reacted 2.5-3 hours, 90-93 DEG C is then heated to, solidified 45 minutes, after reaction terminates, by institute
Reaction solution stands, suction filtration and wash suction filtration with ethanol and obtain solid matter, washed respectively with petroleum ether, distilled water 1 time, centrifugation
Separation, taking precipitate obtains phase-change material micro-capsule after being dried at 40 DEG C.
The particle diameter D97 of the phase-change material micro-capsule is 1-2 μm.
The mass ratio of the melamine resin cyst material performed polymer and phase-change material is 2:1；
The phase-change material, by n-octadecane, n-docosane, positive certain herbaceous plants with big flowers alcohol, n-heptanol composition, mass ratio is 4:1:2：5；
The phase transformation auxiliary agent：Mixed by aluminum oxide, SBS Thermoplastic Elastomer, mass ratio is 4:3；
The aluminum oxide, powdered, particle diameter is 40-60nm, and the SBS Thermoplastic Elastomer, particle diameter is 100-120nm.
（2）The modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed under stirring in modifier solution, then static 30-
40 minutes, then stir 5-7 minutes, be spray-dried, and adjust pH value to neutrality so that phase under the conditions of 500-600r/min
Become the cationic polysaccharide-guar gum and chitosan on the uniform adsorption of material microcapsule surface in modifying agent and be modified, changed
Phase-change material micro-capsule after property.
The modifier solution, in parts by weight, including 2 parts of guar gum, 4 parts of chitosan, 1 part of polyvinyl alcohol, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol, is chip solid；
The preparation of the modifier solution, comprises the following steps：
A, poly-vinyl alcohol solution preparation
According to the formula of modifying agent, each raw material components are weighed, pure water is put into agitator tank, start stirring, speed of agitator is
800-1000r/min, while adding polyvinyl alcohol chip solid, temperature is warming up to 98 DEG C from 25 DEG C with 3 DEG C per minute of speed,
30min is incubated, until polyvinyl alcohol is completely dissolved, stirring is started always, prevents crystallization from separating out, the system of poly-vinyl alcohol solution is made
It is standby；
B, chitosan solution preparation
Chitosan and acetic acid are mixed, dissolving, preparation obtains 4% chitosan acetic acid solution；
C, mixing
Chitosan solution prepared by step B, is placed in stand-by in stainless steel；
Guar gum is added in poly-vinyl alcohol solution prepared by step A, after stirring and dissolving, the mixed of polyvinyl alcohol and guar gum is prepared
Liquid is closed, is slowly dropped in the stainless steel containing chitosan acetic acid solution, rate of addition is 0.8-1.0 parts/min, control is mixed
The temperature for closing container is 40-45 DEG C, and speed of agitator is 900-1000r/min, and completion of dropping is incubated 10-15 minutes, is made and is modified
Agent solution.
（3）Prepare modified phase-change microcapsule emulsion
Modified phase-change material micro-capsule is added into ionic liquid, under the conditions of 55-60 DEG C, -0.01~-0.015MPa, with
300-350r/min rotating speed, dispersed with stirring 20-25 minutes, and pH value is adjusted to 7-8, prepare the micro- glue of modified phase-change material
Capsule emulsion.
The ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborates.
（4）Prepare co-blended spinning liquid
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by the modified micro- glue of phase-change material
Capsule emulsion carries out standing and defoaming, and using injection device before spinning, the phase-change material micro-capsule emulsion after deaeration is added into viscose glue stoste
In, prepare co-blended spinning liquid；
The matter of phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule emulsion
Amount is than being 0.095-0.10:1.
The viscose glue stoste, content of alphacellulose is 8.7-9.2%, and total alkali is 3.5-4.0%, viscosity 30-35s,
Degree of ripeness is 15-17ml (10% ammonium chloride value).
（5）Spinning moulding
Co-blended spinning liquid is added to the coagulating bath adjusted and carries out spinning, 5-7% acid bath compounding agent solution, stirring are added in acid bath
Uniformly, in the acid bath, sulfuric acid concentration 125-135g/l, sodium sulfate concentration 120-140g/l, sulfuric acid zinc concentration 3-5g/l, acid bath
Temperature：49-51℃；Leaching length：400-500 millimeters, shower nozzle drawing-off：70-85%；Drawing-off 14-20% between disk, three bath drawing-offs -2~
12%, four bath drawing-off 3-10%, spin speed 25-30m/min.
The specific leaching length and shower nozzle drawing-off that the present invention is used can be improved and lead a linear velocity so that strand is stopped in acid bath
Time is short, and then reduces the loss of phase-change microcapsule；
The present invention can make up the deficiency of shaping using specific sulfuric acid, the concentration of sodium sulphate, and higher acid bath temperature,
While the mechanical performance of fiber is improved, the loss of phase-change microcapsule is decreased.
The acid bath compounding agent solution, in parts by weight, including following raw material components：
8 parts of starch tertiary amino alkyl ether, 10 parts of quaternary ammonium starch ethers, 7 parts of poly-quaternary ammonium salt, stearyl dimethyl benzyl ammonium chloride 2
Part, 3 parts of dodecyl dimethyl benzyl ammonium chloride, 100 parts of pure water.
The poly-quaternary ammonium salt is poly-quaternary ammonium salt 10；
The preparation method of acid bath compounding agent solution, comprises the following steps：
Mixing adds pure water in filling, and starts stirring, rotating speed is 600-650r/min, then addition starch tertiary amino alkyl ether,
The mixture of quaternary ammonium starch ethers, charging rate is 2-2.5 parts/min, and charging is finished, and temperature is from 25 DEG C with 4 DEG C per minute of speed
98 DEG C are warming up to, 10 minutes are incubated, recirculated cooling water is reused and cools to 60-65 DEG C, add poly-quaternary ammonium salt, hexadecyldimethylamine
Base benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride,
Stir, cool to 25 DEG C, filter to take filtrate, obtain acid bath compounding agent solution.
When the co-blended spinning liquid of spinning solution and phase-change microcapsule emulsion is injected to coagulating bath, first fibre starts forming and hardening.
Acid bath auxiliary agent of the present invention is dispersed in coagulating bath, during spinning moulding, and coagulating bath is uniformly repelled altogether
Modified phase-change microcapsule in blended ratio liquid, the inside or surface for it is firmly attached to the cellulose being just molded, and
Uniform distribution.
（6）Post processing
Gained tow is refined, dried by cut-out, mitigation sulfur removal technology, finish application bath and washing, obtains high heat storage of the present invention
Measure phase-changing and temperature-regulating viscose rayon.
Combination, phase transformation auxiliary agent, the modifying agent of phase-change material micro-capsule, the acid bath of specific phase-change material in the present invention are helped
Agent, the condition of specific spinning moulding make prominent technical contribution to the present invention.
By adopting the above-described technical solution, the present invention reach have the technical effect that：
（1）The content of phase-change material micro-capsule is 9.2-9.6% in phase-changing and temperature-regulating viscose rayon prepared by the present invention, fiber, on year-on-year basis
Coagulating bath filter pull away a prop backwash rate reduction 50-60%, water consumption reduce 500-800 side/day, the water sulfuric acid of coagulating bath crystalline product ten
Phase-change material is reduced to below 100ppm in sodium.
（2）Phase-changing and temperature-regulating viscose rayon prepared by the present invention, melting enthalpy is that 20.8-22J/g, melting temperature are 28-32
DEG C, crystallization enthalpy is 18.5-19.7J/g, 15-20 DEG C of crystallization range.
（3）Phase-changing and temperature-regulating viscose rayon prepared by the present invention, the dry fracture strength of fiber is 2.70-2.75cN/dtex, wet
Fracture strength is that 1.20-1.75cN/dtex elongation at breaks are 20-22%, good hygroscopicity, and the regain of fiber is 14.2-15%,
Fibre density is 1.37-1.42g/cm3。
Embodiment
With reference to embodiment, the present invention is described in detail.Following examples will be helpful to those skilled in the art
The present invention is further understood, but the invention is not limited in any way.It should be pointed out that to one of ordinary skill in the art
For, without departing from the inventive concept of the premise, it can also make certain adjustments and improvements.These belong to the guarantor of the present invention
Protect scope.
A kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon of embodiment 1
Comprise the following steps：
（1）Prepare phase-change material micro-capsule
A, prepare phase-change material emulsion
Phase-change material and phase transformation auxiliary agent are mixed, 40 DEG C are heated to, stirred under 500r/min, after 5 minutes, rise temperature to 60
DEG C, emulsifying agent, initiator and distilled water are added, while rotating speed is improved to 1300r/min, stirring 0.8 with 50r/min speed
Hour, form stable emulsion；
The mass ratio of wherein phase-change material, phase transformation auxiliary agent, emulsifying agent, initiator and distilled water is:100:7：6:1.7:340.
, prepare melamine resin cyst material performed polymer
37% formalin is put into reactor, stirred, regulation pH value is 7.8, by 37% formalin：Melamine is
3:1 ratio adds melamine, is warming up to 70 DEG C, and with 500r/min stirring reactions 1 hour under constant temperature, melamine is made
Amine-formaldehyde resins cyst material performed polymer.
, polymerisation
Melamine resin cyst material performed polymer is added drop-wise in above-mentioned emulsion dropwise, in 70 DEG C of water-baths with
2000r/min rotating speed stirring, citric acid, which is added dropwise, reduces pH to 3.5, is acidified, acidificatoin time is 1 hour, is then warming up to
83 DEG C, react 2.5 hours, then heat to 90 DEG C, solidify 45 minutes, after reaction terminates, by gained reaction solution standing, suction filtration,
And wash suction filtration with ethanol and obtain solid matter, washed 1 time, centrifuged, taking precipitate, 40 respectively with petroleum ether, distilled water
Phase-change material micro-capsule is obtained after being dried at DEG C.
The particle diameter D97 of the phase-change material micro-capsule is 1-2 μm.
The mass ratio of the melamine resin cyst material performed polymer and phase-change material is 2:1；
The phase-change material, by n-octadecane, n-docosane, positive certain herbaceous plants with big flowers alcohol, n-heptanol composition, mass ratio is 4:1:2：5；
The phase transformation auxiliary agent：Mixed by aluminum oxide, SBS Thermoplastic Elastomer, mass ratio is 4:3；
The aluminum oxide, powdered, particle diameter is 40-60nm, and the SBS Thermoplastic Elastomer, particle diameter is 100-120nm.
The emulsifying agent is Tween-20；The initiator is benzoyl peroxide.
（2）The modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed under stirring in modifier solution, then static 30
Minute, then stirred 5 minutes under the conditions of 500r/min, be spray-dried and adjust pH value to neutrality so that phase-change material is micro-
Cationic polysaccharide-guar gum and chitosan on capsule surface uniform adsorption in modifying agent and be modified, obtain modified phase
Become material microcapsule.
The modifier solution, in parts by weight, including 2 parts of guar gum, 4 parts of chitosan, 1 part of polyvinyl alcohol, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol, is chip solid；
The preparation of the modifier solution, comprises the following steps：
A, poly-vinyl alcohol solution preparation
According to the formula of modifying agent, each raw material components are weighed, pure water is put into agitator tank, start stirring, speed of agitator is
800r/min, while adding polyvinyl alcohol chip solid, temperature is warming up to 98 DEG C, insulation from 25 DEG C with 3 DEG C per minute of speed
30min, until polyvinyl alcohol is completely dissolved, starts stirring always, prevents crystallization from separating out, and the preparation of poly-vinyl alcohol solution is made.
B, chitosan solution preparation
Chitosan and acetic acid are mixed, dissolving, preparation obtains 4% chitosan acetic acid solution.
C, mixing
Chitosan solution prepared by step B, is placed in stand-by in stainless steel；
Guar gum is added in poly-vinyl alcohol solution prepared by step A, after stirring and dissolving, the mixed of polyvinyl alcohol and guar gum is prepared
Liquid is closed, is slowly dropped in the stainless steel containing chitosan acetic acid solution, rate of addition is 0.8 part/min, control mixing is held
The temperature of device is 40 DEG C, and speed of agitator is 900r/min, and completion of dropping is incubated 10 minutes, modifier solution is made.
（3）Prepare modified phase-change material micro-capsule emulsion
Modified phase-change material micro-capsule is added into ionic liquid, under the conditions of 55 DEG C, -0.01MPa, with turning for 300r/min
Speed, dispersed with stirring 20 minutes, adjustment pH value prepares modified phase-change material micro-capsule emulsion to 7-8.
（4）Prepare co-blended spinning liquid
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by the modified micro- glue of phase-change material
Capsule emulsion carries out standing and defoaming, and using injection device before spinning, the phase-change material micro-capsule emulsion after deaeration is added into viscose glue stoste
In, prepare co-blended spinning liquid；
The matter of phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule emulsion
Amount is than being 0.098:1.
The viscose glue stoste, content of alphacellulose is 8.7%, and total alkali is 3.5%, and viscosity 30s, degree of ripeness is 15ml
(10% ammonium chloride value).
（5）Spinning moulding
Co-blended spinning liquid is added to the coagulating bath adjusted and carries out spinning, 5% acid bath compounding agent solution is added in acid bath, stirring is equal
It is even, in the acid bath, sulfuric acid concentration 125g/l, sodium sulfate concentration 120g/l, sulfuric acid zinc concentration 3g/l, the temperature of acid bath：50℃；
Leaching length：400 millimeters, shower nozzle drawing-off：70%；Drawing-off 14% between disk, three bath drawing-off -2%, four bath drawing-offs 3%, spins speed 25m/min.
The acid bath compounding agent solution, in parts by weight, including following raw material components：
8 parts of starch tertiary amino alkyl ether, 10 parts of quaternary ammonium starch ethers, 7 parts of poly-quaternary ammonium salt, stearyl dimethyl benzyl ammonium chloride 2
Part, 3 parts of dodecyl dimethyl benzyl ammonium chloride, 100 parts of pure water.
The poly-quaternary ammonium salt is poly-quaternary ammonium salt 10；
The preparation method of acid bath compounding agent solution, comprises the following steps：
Mixing adds pure water in filling, and starts stirring, rotating speed is 600r/min, then adds starch tertiary amino alkyl ether, quaternary ammonium
The mixture of starch ether, charging rate is 2 parts/min, and charging is finished, and temperature is warming up to 98 from 25 DEG C with 4 DEG C per minute of speed
DEG C, 10 minutes are incubated, recirculated cooling water is reused and cools to 60 DEG C, add poly-quaternary ammonium salt, octadecyl dimethyl benzyl chlorination
Ammonium, dodecyl dimethyl benzyl ammonium chloride,
Stir, cool to 25 DEG C, filter to take filtrate, obtain acid bath compounding agent solution.
When the co-blended spinning liquid of spinning solution and phase-change microcapsule emulsion is injected to coagulating bath, first fibre starts forming and hardening.
（6）Post processing
Gained tow is refined, dried by cut-out, mitigation sulfur removal technology, finish application bath and washing, is obtained the present invention and is mutually modified tone
Warm viscose rayon.
The content of phase-change material micro-capsule is 9.3% in phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 1, fiber,
Year-on-year coagulating bath filter is pulled away a prop backwash rate reduction by 50%, and water consumption is reduced in 500 sides/day, coagulating bath crystalline product sal glauberi
Phase-change material is reduced to below 100ppm.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 1, melting enthalpy is that 20.8J/g, melting temperature are 28-30
DEG C, crystallization enthalpy is 18.5J/g, 15-17 DEG C of crystallization range.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 1, the dry fracture strength of fiber is 2.70cN/dtex, wet
Fracture strength is that 1.20cN/dtex elongation at breaks are 20%, good hygroscopicity, and the regain of fiber is 14.2%, and can be changed
The wearability of kind common viscose fiber, fibre density is 1.37g/cm3。
A kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon of embodiment 2
Comprise the following steps：
（1）Prepare phase-change material micro-capsule
A, prepare phase-change material emulsion
Phase-change material and phase transformation auxiliary agent are mixed, 42 DEG C are heated to, stirred under 500r/min, after 5 minutes, rise temperature to 63
DEG C, emulsifying agent, initiator and distilled water are added, while rotating speed is improved to 1400r/min, stirring 1.2 with 50r/min speed
Hour, form stable emulsion；
The mass ratio of wherein phase-change material, phase transformation auxiliary agent, emulsifying agent, initiator and distilled water is:100:9：7:2.0:350.
, prepare melamine resin cyst material performed polymer
37% formalin is put into reactor, stirred, regulation pH value is 8.0, by 37% formalin：Melamine is
3:1 ratio adds melamine, is warming up to 72 DEG C, and with 500r/min stirring reactions 1 hour under constant temperature, melamine is made
Amine-formaldehyde resins cyst material performed polymer.
, polymerisation
Melamine resin cyst material performed polymer is added drop-wise in above-mentioned emulsion dropwise, in 70 DEG C of water-baths with
2000r/min rotating speed stirring, citric acid, which is added dropwise, reduces pH to 3.5, is acidified, acidificatoin time is 1 hour, is then warming up to
84 DEG C, react 2.7 hours, then heat to 92 DEG C, solidify 45 minutes, after reaction terminates, by gained reaction solution standing, suction filtration,
And wash suction filtration with ethanol and obtain solid matter, washed 1 time, centrifuged, taking precipitate, 40 respectively with petroleum ether, distilled water
Phase-change material micro-capsule is obtained after being dried at DEG C.
The particle diameter D97 of the phase-change material micro-capsule is 1-2 μm.
The mass ratio of the melamine resin cyst material performed polymer and phase-change material is 2:1；
The phase-change material, by n-octadecane, n-docosane, positive certain herbaceous plants with big flowers alcohol, n-heptanol composition, mass ratio is 4:1:2：5；
The phase transformation auxiliary agent：Mixed by aluminum oxide, SBS Thermoplastic Elastomer, mass ratio is 4:3；
The aluminum oxide, powdered, particle diameter is 40-60nm, and the SBS Thermoplastic Elastomer, particle diameter is 100-120nm.
The emulsifying agent is Tween-20；The initiator is benzoyl peroxide.
（2）The modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed under stirring in modifier solution, then static 37
Minute, then stir 5 minutes, be spray-dried, and adjust pH value to neutrality so that phase-change material is micro- under the conditions of 530r/min
Cationic polysaccharide-guar gum and chitosan on capsule surface uniform adsorption in modifying agent and be modified, obtain modified phase
Become material microcapsule.
The modifier solution, in parts by weight, including 2 parts of guar gum, 4 parts of chitosan, 1 part of polyvinyl alcohol, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol, is chip solid；
The preparation of the modifier solution, comprises the following steps：
A, poly-vinyl alcohol solution preparation
According to the formula of modifying agent, each raw material components are weighed, pure water is put into agitator tank, start stirring, speed of agitator is
800r/min, while adding polyvinyl alcohol chip solid, temperature is warming up to 98 DEG C, insulation from 25 DEG C with 3 DEG C per minute of speed
30min, until polyvinyl alcohol is completely dissolved, starts stirring always, prevents crystallization from separating out, and the preparation of poly-vinyl alcohol solution is made.
B, chitosan solution preparation
Chitosan and acetic acid are mixed, dissolving, preparation obtains 4% chitosan acetic acid solution.
C, mixing
Chitosan solution prepared by step B, is placed in stand-by in stainless steel；
Guar gum is added in poly-vinyl alcohol solution prepared by step A, after stirring and dissolving, the mixed of polyvinyl alcohol and guar gum is prepared
Liquid is closed, is slowly dropped in the stainless steel containing chitosan acetic acid solution, rate of addition is 0.9 part/min, control mixing is held
The temperature of device is 40 DEG C, and speed of agitator is 930r/min, and completion of dropping is incubated 12 minutes, modifier solution is made.
（3）Prepare modified phase-change material micro-capsule emulsion
Modified phase-change material micro-capsule is added into ionic liquid, under the conditions of 57 DEG C, -0.02MPa, with turning for 335r/min
Speed, dispersed with stirring 23 minutes, adjustment pH value prepares modified phase-change material micro-capsule emulsion to 7-8.
（4）Prepare co-blended spinning liquid
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by the modified micro- glue of phase-change material
Capsule emulsion carries out standing and defoaming, and using injection device before spinning, the phase-change material micro-capsule emulsion after deaeration is added into viscose glue stoste
In, prepare co-blended spinning liquid；
The matter of phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule emulsion
Amount is than being 0.10:1.
The viscose glue stoste, content of alphacellulose is 9.0%, and total alkali is 3.7%, and viscosity 33s, degree of ripeness is 16ml
(10% ammonium chloride value).
（5）Spinning moulding
Co-blended spinning liquid is added to the coagulating bath adjusted and carries out spinning, 6% acid bath compounding agent solution is added in acid bath, stirring is equal
It is even, in the acid bath, sulfuric acid concentration 130g/l, sodium sulfate concentration 122g/l, sulfuric acid zinc concentration 3g/l, the temperature of acid bath：49℃；
Leaching length：470 millimeters, shower nozzle drawing-off：75%；Speed 27m/min is spun in drawing-off 17% between disk, three bath drawing-offs 6%, four bath drawing-offs 7%.
The acid bath compounding agent solution, in parts by weight, including following raw material components：
8 parts of starch tertiary amino alkyl ether, 10 parts of quaternary ammonium starch ethers, 7 parts of poly-quaternary ammonium salt, stearyl dimethyl benzyl ammonium chloride 2
Part, 3 parts of dodecyl dimethyl benzyl ammonium chloride, 100 parts of pure water.
The poly-quaternary ammonium salt is poly-quaternary ammonium salt 10；
The preparation method of acid bath compounding agent solution, comprises the following steps：
Mixing adds pure water in filling, and starts stirring, rotating speed is 630r/min, then adds starch tertiary amino alkyl ether, quaternary ammonium
The mixture of starch ether, charging rate is 2.2 parts/min, and charging is finished, and temperature is warming up to from 25 DEG C with 4 DEG C per minute of speed
98 DEG C, 10 minutes are incubated, recirculated cooling water is reused and cools to 60 DEG C, add poly-quaternary ammonium salt, octadecyl dimethyl benzyl chlorine
Change ammonium, dodecyl dimethyl benzyl ammonium chloride,
Stir, cool to 25 DEG C, filter to take filtrate, obtain acid bath compounding agent solution.
When the co-blended spinning liquid of spinning solution and phase-change microcapsule emulsion is injected to coagulating bath, first fibre starts forming and hardening.
（6）Post processing
Gained tow is refined, dried by cut-out, mitigation sulfur removal technology, finish application bath and washing, is obtained the present invention and is mutually modified tone
Warm viscose rayon.
The content of phase-change material micro-capsule is 9.6% in phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 2, fiber,
Year-on-year coagulating bath filter is pulled away a prop backwash rate reduction by 60%, and water consumption is reduced in 800 sides/day, coagulating bath crystalline product sal glauberi
Phase-change material is reduced to below 100ppm.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 2, melting enthalpy is that 22J/g, melting temperature are 31-32
DEG C, crystallization enthalpy is 19.7J/g, 19-20 DEG C of crystallization range.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 2, the dry fracture strength of fiber is 2.75cN/dtex, wet
Fracture strength is that 1.75cN/dtex elongation at breaks are 22%, good hygroscopicity, and the regain of fiber is 15%, and can be improved
The wearability of common viscose fiber, fibre density is 1.42g/cm3。
A kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon of embodiment 3
Comprise the following steps：
（1）Prepare phase-change material micro-capsule
A, prepare phase-change material emulsion
Phase-change material and phase transformation auxiliary agent are mixed, 45 DEG C are heated to, stirred under 500r/min, after 5 minutes, rise temperature to 65
DEG C, emulsifying agent, initiator and distilled water are added, while rotating speed is improved to 1500r/min, stirring 1.2 with 50r/min speed
Hour, form stable emulsion；
The mass ratio of wherein phase-change material, phase transformation auxiliary agent, emulsifying agent, initiator and distilled water is:100: 10： 8: 2.2:
370。
, prepare melamine resin cyst material performed polymer
37% formalin is put into reactor, stirred, regulation pH value is 8.0, by 37% formalin：Melamine is
3:1 ratio adds melamine, is warming up to 75 DEG C, and with 600r/min stirring reactions 1 hour under constant temperature, melamine is made
Amine-formaldehyde resins cyst material performed polymer.
, polymerisation
Melamine resin cyst material performed polymer is added drop-wise in above-mentioned emulsion dropwise, in 75 DEG C of water-baths with
2500r/min rotating speed stirring, citric acid, which is added dropwise, reduces pH to 4.0, is acidified, acidificatoin time is 1 hour, is then warming up to
85 DEG C, react 3 hours, then heat to 93 DEG C, solidify 45 minutes, after reaction terminates, by gained reaction solution standing, suction filtration, simultaneously
Suction filtration is washed with ethanol and obtains solid matter, is washed respectively with petroleum ether, distilled water 1 time, is centrifuged, taking precipitate, at 40 DEG C
Phase-change material micro-capsule is obtained after lower drying.
The particle diameter D97 of the phase-change material micro-capsule is 1-2 μm.
The mass ratio of the melamine resin cyst material performed polymer and phase-change material is 2:1；
The phase-change material, by n-octadecane, n-docosane, positive certain herbaceous plants with big flowers alcohol, n-heptanol composition, mass ratio is 4:1:2：5；
The phase transformation auxiliary agent：Mixed by aluminum oxide, SBS Thermoplastic Elastomer, mass ratio is 4:3；
The aluminum oxide, powdered, particle diameter is 40-60nm, and the SBS Thermoplastic Elastomer, particle diameter is 100-120nm.
The emulsifying agent is Tween-20；The initiator is benzoyl peroxide.
（2）The modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed under stirring in modifier solution, then static 40
Minute, then stir 7 minutes, be spray-dried, and adjust pH to neutrality so that the micro- glue of phase-change material under the conditions of 600r/min
Cationic polysaccharide-guar gum and chitosan on the uniform adsorption of capsule surface in modifying agent and be modified, obtain modified phase transformation
Material microcapsule.
The modifier solution, in parts by weight, including 2 parts of guar gum, 4 parts of chitosan, 1 part of polyvinyl alcohol, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol, is chip solid；
The preparation of the modifier solution, comprises the following steps：
A, poly-vinyl alcohol solution preparation
According to the formula of modifying agent, each raw material components are weighed, pure water is put into agitator tank, start stirring, speed of agitator is
1000r/min, while adding polyvinyl alcohol chip solid, temperature is warming up to 98 DEG C, insulation from 25 DEG C with 3 DEG C per minute of speed
30min, until polyvinyl alcohol is completely dissolved, starts stirring always, prevents crystallization from separating out, and the preparation of poly-vinyl alcohol solution is made.
B, chitosan solution preparation
Chitosan and acetic acid are mixed, dissolving, preparation obtains 4% chitosan acetic acid solution.
C, mixing
Chitosan solution prepared by step B, is placed in stand-by in stainless steel；
Guar gum is added in poly-vinyl alcohol solution prepared by step A, after stirring and dissolving, the mixed of polyvinyl alcohol and guar gum is prepared
Liquid is closed, is slowly dropped in the stainless steel containing chitosan acetic acid solution, rate of addition is 1.0 parts/min, control mixing is held
The temperature of device is 45 DEG C, and speed of agitator is 900r/min, and completion of dropping is incubated 15 minutes, modifier solution is made.
（3）Prepare modified phase-change material micro-capsule emulsion
Modified phase-change material micro-capsule is added into ionic liquid, under the conditions of 60 DEG C, -0.015MPa, with 350r/min's
Rotating speed, dispersed with stirring 25 minutes, adjustment pH value prepares modified phase-change material micro-capsule emulsion to 7-8.
（4）Prepare co-blended spinning liquid
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by the modified micro- glue of phase-change material
Capsule emulsion carries out standing and defoaming, and using injection device before spinning, the phase-change material micro-capsule emulsion after deaeration is added into viscose glue stoste
In, prepare co-blended spinning liquid；
The matter of phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule emulsion
Amount is than being 0.095:1.
The viscose glue stoste, content of alphacellulose is 9.2%, and total alkali is 4.0%, and viscosity 35s, degree of ripeness is 17ml
(10% ammonium chloride value).
（5）Spinning moulding
Co-blended spinning liquid is added to the coagulating bath adjusted and carries out spinning, 7% acid bath compounding agent solution is added in acid bath, stirring is equal
It is even, in the acid bath, sulfuric acid concentration 135g/l, sodium sulfate concentration 140g/l, sulfuric acid zinc concentration 5g/l, the temperature of acid bath： 51
℃；Leaching length：500 millimeters, shower nozzle drawing-off： 85%；Speed 30m/ is spun in drawing-off 20% between disk, three bath drawing-offs 12%, four bath drawing-offs 10%
min。
The acid bath compounding agent solution, in parts by weight, including following raw material components：
8 parts of starch tertiary amino alkyl ether, 10 parts of quaternary ammonium starch ethers, 7 parts of poly-quaternary ammonium salt, stearyl dimethyl benzyl ammonium chloride 2
Part, 3 parts of dodecyl dimethyl benzyl ammonium chloride, 100 parts of pure water.
The poly-quaternary ammonium salt is poly-quaternary ammonium salt 10；
The preparation method of acid bath compounding agent solution, comprises the following steps：
Mixing adds pure water in filling, and starts stirring, rotating speed is 650r/min, then adds starch tertiary amino alkyl ether, quaternary ammonium
The mixture of starch ether, charging rate is 2.5 parts/min, and charging is finished, and temperature is warming up to from 25 DEG C with 4 DEG C per minute of speed
98 DEG C, 10 minutes are incubated, recirculated cooling water is reused and cools to 60 DEG C, add poly-quaternary ammonium salt, octadecyl dimethyl benzyl chlorine
Change ammonium, dodecyl dimethyl benzyl ammonium chloride,
Stir, cool to 25 DEG C, filter to take filtrate, obtain acid bath compounding agent solution.
When the co-blended spinning liquid of spinning solution and phase-change microcapsule emulsion is injected to coagulating bath, first fibre starts forming and hardening.
（6）Post processing
Gained tow is refined, dried by cut-out, mitigation sulfur removal technology, finish application bath and washing, is obtained the present invention and is mutually modified tone
Warm viscose rayon.
The content of phase-change material micro-capsule is 9.2% in phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 3, fiber,
Year-on-year coagulating bath filter is pulled away a prop backwash rate reduction by 56%, and water consumption is reduced in 600 sides/day, coagulating bath crystalline product sal glauberi
Phase-change material is reduced to below 100ppm.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 3, melting enthalpy is that 21.2J/g, melting temperature are 29-30
DEG C, crystallization enthalpy is 18.8J/g, 17-18 DEG C of crystallization range.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 3, the dry fracture strength of fiber is 2.72cN/dtex, wet
Fracture strength is that 1.50cN/dtex elongation at breaks are 20%, good hygroscopicity, and the regain of fiber is 14.5%, and can be changed
The wearability of kind common viscose fiber, fibre density is 1.38g/cm3。
Phase-changing and temperature-regulating viscose rayon prepared by the present invention, due to the addition of specific phase-change material micro-capsule, can improve viscous
The wearability of glue fiber.
The content of phase-change material in viscose rayon prepared by the present invention, is calculated relative to first fibre；
Coagulating bath of the present invention, is acid bath.
Unless otherwise indicated, the percentage employed in the present invention is percetage by weight, ratio of the present invention,
For mass ratio.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of high heat storage amount phase-changing and temperature-regulating viscose rayon, it is characterised in that：The viscose rayon, melting enthalpy is 20.8-
22J/g, crystallization enthalpy are 18.5-19.7J/g.
2. a kind of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 1, it is characterised in that：The viscose glue is fine
Dimension, the content of phase-change material micro-capsule is 9.2-9.6%；Melting temperature is 28-32 DEG C, 15-20 DEG C of crystallization range.
3. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon, it is characterised in that：Including phase-change material micro-capsule
It is modified；The modification of the phase-change material micro-capsule, is modified using modifier solution to phase-change material micro-capsule；The modification
Agent solution, in parts by weight, including 2 parts of guar gum, 4 parts of chitosan, 1 part of polyvinyl alcohol, 30 parts of pure water, 100 parts of acetic acid.
4. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 3, it is characterised in that：Institute
It is that mass ratio is 4 by n-octadecane, n-docosane, positive certain herbaceous plants with big flowers alcohol, n-heptanol composition to state phase-change material:1:2：5；The phase
Become the particle diameter D97 of material microcapsule into 1-2 μm.
5. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 3, it is characterised in that：Institute
The preparation of modifier solution is stated, is comprised the following steps：
（1）The preparation of poly-vinyl alcohol solution
By pure water add container in, speed of agitator is 800-1000r/min, at the same add polyvinyl alcohol, temperature from 25 DEG C with
3 DEG C per minute of speed is warming up to 98 DEG C, is incubated 30min, and until polyvinyl alcohol is completely dissolved, poly-vinyl alcohol solution is made；
（2）The preparation of chitosan solution
Chitosan and acetic acid are mixed, dissolving, preparation obtains 4% chitosan acetic acid solution, is placed in stainless steel；
（3）Mixing
Guar gum is added into step（1）In the poly-vinyl alcohol solution of preparation, after stirring and dissolving, polyvinyl alcohol and guar gum are prepared
Mixed liquor, is slowly dropped to step（2）In the chitosan acetic acid solution of preparation, rate of addition is 0.8-1.0 parts/min, control
The temperature of stainless steel is 40-45 DEG C, and speed of agitator is 900-1000r/min, and completion of dropping is incubated 10-15 minutes, is made and changes
Property agent solution.
6. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 3, it is characterised in that：Institute
State preparation method, in addition to spinning moulding；The spinning moulding, adds 5-7% acid bath compounding agent solutions in acid bath, the acid bath is helped
Agent solution, in parts by weight, including following raw material components：8 parts of starch tertiary amino alkyl ether, 10 parts of quaternary ammonium starch ethers, poly- quaternary amine
7 parts of salt, 2 parts of stearyl dimethyl benzyl ammonium chloride, 3 parts of dodecyl dimethyl benzyl ammonium chloride, 100 parts of pure water.
7. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 6, it is characterised in that：Institute
The preparation of acid bath auxiliary agent solvent is stated, is comprised the following steps：Pure water is added, speed of agitator is 600-650r/min, is then added
Starch tertiary amino alkyl ether, the mixture of quaternary ammonium starch ethers, charging rate are 2-2.5 parts/min, and charging is finished, and temperature is from 25 DEG C
98 DEG C are warming up to 4 DEG C per minute of speed, 10 minutes are incubated, recirculated cooling water is reused and cools to 60-65 DEG C, add poly- season
Amine salt, stearyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, stir, and cool to 25 DEG C, mistake
Leaching filtrate, obtains acid bath compounding agent solution.
8. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 3, it is characterised in that：Institute
Preparation method is stated, in addition to prepares phase-change material micro-capsule, it is described to prepare phase-change material micro-capsule, including prepare phase-change material breast
Change liquid；It is described to prepare phase-change material emulsion, phase-change material and phase transformation auxiliary agent are mixed, 40-45 DEG C is heated to, in 500r/min
Lower stirring, after 5 minutes, rise temperature adds emulsifying agent, initiator and distilled water, while by rotating speed with 50r/ to 60-65 DEG C
Min speed is improved to 1300-1500r/min, is stirred 0.8-1.2 hours, forms stable phase-change material emulsion；
The mass ratio of wherein phase-change material, phase transformation auxiliary agent, emulsifying agent, initiator and distilled water is:100:7-10：6-8:1.7-
2.2:340-370。
9. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 8, it is characterised in that：Institute
State phase transformation auxiliary agent：Mixed by aluminum oxide, SBS Thermoplastic Elastomer, mass ratio is 4:3；The aluminum oxide, powdered, grain
Footpath is 40-60nm；The SBS Thermoplastic Elastomer, particle diameter is 100-120nm.
10. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 8, it is characterised in that：
It is described to prepare phase-change material micro-capsule, in addition to prepare melamine resin cyst material performed polymer；It is described to prepare trimerization
Cyanamide formaldehyde resin cyst material performed polymer, 37% formalin is put into reactor, stirring, and regulation pH value is 7.8-
8.0, by 37% formalin：Melamine is 3:1 ratio adds melamine, be warming up under 70-75 DEG C, constant temperature with
500-600r/min stirring reactions 1 hour, are made melamine resin cyst material performed polymer；
It is described to prepare phase-change material micro-capsule, in addition to polymerisation；The polymerisation, by melamine resin cyst wall
Material performed polymer is added drop-wise in above-mentioned phase-change material emulsion dropwise, the turning with 2000-2500r/min in 70-75 DEG C of water-bath
Speed stirring, citric acid, which is added dropwise, reduces pH to 3.5-4.0, is acidified, acidificatoin time is 1 hour, is then warming up to 83-85 DEG C,
Reaction 2.5-3 hour, then heats to 90-93 DEG C, solidifies 45 minutes, reacts after terminating, by gained reaction solution standing, suction filtration,
Washing, centrifugation, taking precipitate obtain phase-change material micro-capsule after being dried at 40 DEG C；
The mass ratio of the melamine resin cyst material performed polymer and phase-change material is 2:1.
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| CN201810929397.0A CN109137113B (en) | 2017-03-24 | 2017-03-24 | Phase-change thermoregulation viscose fiber with good hygroscopicity and preparation method thereof |
| CN201810929398.5A CN109137114B (en) | 2017-03-24 | 2017-03-24 | Phase-change temperature-regulating viscose fiber and preparation method thereof |
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| CN109137115A (en) * | 2018-08-29 | 2019-01-04 | 中科纺织研究院（青岛）有限公司 | A kind of intelligent temperature adjusting fiber cellulose fiber and preparation process |
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| CN113529183A (en) * | 2021-06-29 | 2021-10-22 | 吉祥三宝高科纺织有限公司 | Gel preparation process of heating fiber |
| CN114381824A (en) * | 2022-02-17 | 2022-04-22 | 上海麦酷酷电子商务有限公司 | Constant-temperature mite-killing antibacterial fiber and preparation method thereof |
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| CN115747992A (en) * | 2022-11-21 | 2023-03-07 | 江苏康溢臣生命科技有限公司 | High-protein-content antibacterial thermoregulation cellulose fiber and preparation method thereof |
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| CN109137114A (en) | 2019-01-04 |
| CN109137114B (en) | 2021-05-28 |
| CN109137113B (en) | 2021-06-01 |
| CN109137113A (en) | 2019-01-04 |
| CN107022800B (en) | 2019-06-07 |
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