CN107022800B - 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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- CN107022800B CN107022800B CN201710183743.0A CN201710183743A CN107022800B CN 107022800 B CN107022800 B CN 107022800B CN 201710183743 A CN201710183743 A CN 201710183743A CN 107022800 B CN107022800 B CN 107022800B
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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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 20.8-22J/g, crystallization enthalpy is 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, the modification including phase-change material micro-capsule；The modification of the phase-change material micro-capsule is modified phase-change material micro-capsule using modifier solution；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, especially 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 technique
Phase change fiber is to discharge in phase transition process using phase-change material or absorb latent heat, the spy that temperature is held essentially constant
A kind of heat-accumulation temperature-adjustment functional fibre that property developed.
Phase-change material refers to and varies with temperature and change form and can absorb or provide the substance of latent heat, phase-change material energy
It is enough undergone phase transition according to the variation of ambient temperature, and absorbs from the external world or discharge heat, formed around textile warm
Substantially invariable micro climate is spent, to realize that temperature adjusts temperature.
Blending method is generally taken to prepare phase-changing and temperature-regulating viscose rayon in the prior art:
Phase-change material is directly blended with rayon spinning stoste and carries out spinning by the first blending method, relatively simple but presence
Phase transformation heat content is low, phase-change material easily leaks the problems such as low with fibre strength；
Second of blending method, that is, microcapsule method are that first phase-change material package is closed to macromolecule, are made into micro-
Capsule prevents phase-change material from leaking, and the microcapsules containing phase-change material are carried out co-blended spinning with rayon spinning stoste and obtain phase
Become fiber.
Phase-changing and temperature-regulating viscose rayon is prepared using microcapsule method, there is also deficiencies:
(1) there are phase-change microcapsules to be largely lost, cause phase-change microcapsule greatly be lost to acid bath and cannot be complete
Portion enters fiber, and then leads to the lesser problem of fiber enthalpy of phase change；The process being specifically lost are as follows: in rayon spinning stoste, first is fine
Content between 8.2-9.2%, first fibre can coagulation forming during the spinning process, form fiber；
In spinning process, when the blend solution of rayon spinning stoste and phase-change microcapsule, coagulating bath is sprayed into a flash,
First fibre starts curing molding, then envelopes added microcapsules, but in rayon spinning stoste can curing molding substance,
Be exactly first fibre content less than 10%, the microcapsules that first fibre can coat in forming process be it is few, have a large amount of phase transformation micro-
Capsule can in spinning viscose stoste the substances such as 90% water, soluble-salt lost, cause a large amount of losses of phase-change material.
Found in actual experiment, when microcapsules solid dry powder to first fibre additive amount 10% when, phase transformation is micro- in finished fiber
For the content of capsule also less than 4.9%, a large amount of phase-change microcapsule material enters coagulating bath after being lost, and increases coagulating bath filter and tears open
Platform rate is up to 80%, while remaining phase-change microcapsule substance enters crystallizer, and stick to each other enters ten water sulfuric acid in crystallization process
In sodium product, the quality of crystal is seriously affected, 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 by-product crystal and limits application range.
(2) in addition phase-change microcapsule and fibrous matrix compatibility are poor, cause fibre strength to reduce, the moisture absorption of viscose rayon
Property reduce, the density of fiber reduces.
Summary of the invention
In view of the deficiencies 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) loss for reducing phase-change material in phase change fiber preparation process, reduces the backwash rate of pulling away a prop of coagulating bath filter,
The credit rating for improving byproduct sulfite increases substantially the crystallization enthalpy and melting enthalpy of phase-changing and temperature-regulating fiber；
(2) fibre strength, hygroscopicity and the fibre density of phase-changing and temperature-regulating viscose rayon are improved.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is that:
A kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon, comprising the following steps:
(1) phase-change material micro-capsule is prepared
A, phase-change material emulsion is prepared
Phase-change material and phase transformation auxiliary agent are mixed, 40-45 DEG C is heated to, is stirred at 500r/min, after five minutes, is increased
Emulsifier, initiator and distilled water is added to 60-65 DEG C in temperature, while revolving speed being improved with the speed of 50r/min to 1300-
1500r/min stirs 0.8-1.2 hours, forms stable emulsion；
The wherein mass ratio of phase-change material, phase transformation auxiliary agent, emulsifier, initiator and distilled water are as follows: 100:7-10:6-8:
1.7-2.2:340-370；
The emulsifier is Tween-20；The initiator is benzoyl peroxide.
, prepare melamine resin cyst material performed polymer
37% formalin is put into reaction kettle, is stirred, adjusting pH value is 7.8-8.0, by 37% formalin: three
Melamine is added in the ratio that poly cyanamid is 3:1, is warming up to 70-75 DEG C, is stirred to react 1 under constant temperature with 500-600r/min
Hour, melamine resin cyst material performed polymer is made.
, polymerization reaction
Melamine resin cyst material performed polymer is added drop-wise to dropwise in above-mentioned emulsion, in 70-75 DEG C of water-bath
In stirred with the revolving speed of 2000-2500r/min, citric acid, which is added dropwise, reduces pH to 3.5-4.0, is acidified, and acidificatoin time is 1 small
When, it is then warming up to 83-85 DEG C, is reacted 2.5-3 hours, then heats to 90-93 DEG C, is solidified 45 minutes, it after reaction, will
Gained reaction solution stands, filters and filter to obtain solid matter with ethanol washing, is washed respectively 1 time with petroleum ether, distilled water, from
Heart separation, taking precipitate obtain phase-change material micro-capsule after dry at 40 DEG C.
The partial size 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 4:1:2:
5；
The phase transformation auxiliary agent: being mixed by aluminium oxide, SBS Thermoplastic Elastomer, mass ratio 4:3；
The aluminium oxide, powdered, partial size 40-60nm, the SBS Thermoplastic Elastomer, partial size 100-120nm.
(2) modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed in modifier solution under stirring, it is then quiet
It only 30-40 minutes, then stirs 5-7 minutes, is spray-dried under the conditions of 500-600r/min, and adjust pH value to neutrality,
So that cationic polysaccharide-guar gum and chitosan on the uniform adsorption of phase-change material micro-capsule surface in modifying agent and be modified,
Obtain modified 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, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol is chip solid；
The preparation of the modifier solution, comprising the following steps:
A, the preparation of poly-vinyl alcohol solution
According to the formula of modifying agent, each raw material component is weighed, pure water is put into agitator tank, starts stirring, stirring turns
Speed is 800-1000r/min, while polyvinyl alcohol chip solid is added, and temperature is warming up to from 25 DEG C with 3 DEG C of speed per minute
98 DEG C, 30min is kept the temperature, until polyvinyl alcohol is completely dissolved, starts stirring always, crystallization is prevented to be precipitated, obtained polyvinyl alcohol is molten
The preparation of liquid；
B, the preparation of chitosan solution
Chitosan and acetic acid are mixed, dissolution, preparation obtains 4% chitosan acetic acid solution；
C, it mixes
Chitosan solution prepared by step B is placed in mixing vessel stand-by；
Guar gum is added in the poly-vinyl alcohol solution of step A preparation, after stirring and dissolving, prepares polyvinyl alcohol and guar gum
Mixed liquor, be slowly dropped in the mixing vessel containing chitosan acetic acid solution, rate of addition be 0.8-1.0 part/min, control
The temperature of mixing vessel processed is 40-45 DEG C, and speed of agitator 900-1000r/min is added dropwise, and keeps the temperature 10-15 minutes, is made
Modifier solution.
(3) modified phase-change microcapsule lotion is prepared
Ionic liquid is added in modified phase-change material micro-capsule, in 55-60 DEG C, -0.01~-0.015MPa condition
Under, it with the revolving speed of 300-350r/min, is dispersed with stirring 20-25 minutes, and adjust pH value to 7-8, prepares modified phase transformation material
Expect microcapsule emulsion.
The ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborate.
(4) co-blended spinning liquid is prepared
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by modified phase-change material
Microcapsule emulsion carries out standing and defoaming, and using injection device before spinning, viscose glue is added in the phase-change material micro-capsule lotion after deaeration
In stoste, co-blended spinning liquid is prepared；
Phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule lotion
Mass ratio be 0.095-0.10:1.
The viscose glue stoste, content of alphacellulose 8.7-9.2%, total alkali 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, the acid bath compounding agent solution of 5-7% is added in acid bath,
It stirs evenly, in the acid bath, sulfuric acid concentration 125-135g/l, sodium sulfate concentration 120-140g/l, sulfuric acid zinc concentration 3-5g/l,
The temperature of acid bath: 49-51 DEG C；Leaching length: 400-500 millimeters, spray head 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 that the present invention uses is long and spray head drawing-off can be improved and lead a linear velocity, so that strand stops in acid bath
Time is short, and then reduces the loss of phase-change microcapsule；
The present invention using specific sulfuric acid, sodium sulphate concentration and higher acid bath temperature, can make up it is molding not
Foot decreases the loss of phase-change microcapsule while improving the mechanical performance of fiber.
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, octadecyl dimethyl benzyl chlorine
Change 2 parts of ammonium, 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, comprising the following steps:
Pure water is added in filling in mixing, starts stirring, then starch tertiary amino alkyl is added in revolving speed 600-650r/min
The mixture of ether, quaternary ammonium starch ethers, charging rate are 2-2.5 parts/min, and charging finishes, and temperature is from 25 DEG C with 4 DEG C per minute
Speed is warming up to 98 DEG C, keeps the temperature 10 minutes, reuses recirculated cooling water and cools to 60-65 DEG C, poly-quaternary ammonium salt, octadecyl is added
Dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride,
It stirs evenly, cools 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 lotion is injected to coagulating bath, first fibre starts forming and hardening.
Acid bath auxiliary agent of the present invention is dispersed in coagulating bath, and during spinning moulding, coagulating bath is uniformly repelled altogether
Modified phase-change microcapsule in blended ratio liquid makes it firmly be attached to the inside or surface of rigid molding cellulose, and
Uniform distribution.
(6) it post-processes
Gained tow is refined, is dried by cutting, mitigation sulfur removal technology, finish application bath and washing, and height of the invention is obtained
Quantity of heat storage 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 help
Agent, specific spinning moulding condition technical contribution outstanding is made to the present invention.
By adopting the above-described technical solution, having the technical effect that of reaching of the present invention
(1) phase-changing and temperature-regulating viscose rayon prepared by the present invention, the content of phase-change material micro-capsule is 9.2-9.6% in fiber,
Year-on-year coagulating bath filter backwash rate of pulling away a prop reduces 50-60%, and water consumption reduces the side 500-800/day, ten water of coagulating bath crystalline product
Phase-change material is reduced to 100ppm or less in sodium sulphate.
(2) phase-changing and temperature-regulating viscose rayon prepared by the present invention, melting enthalpy be 20.8-22J/g, melting temperature 28-32
DEG C, crystallization enthalpy be 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 breaking strength of fiber is 2.70-2.75cN/dtex, wet
Breaking strength is that 1.20-1.75cN/dtex elongation at break is 20-22%, and good hygroscopicity, the regain of fiber is 14.2-15%,
Fibre density is 1.37-1.42g/cm3。
Specific embodiment
The following describes the present invention in detail with reference to examples.Following embodiment 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 those skilled in the art
For, without departing from the inventive concept of the premise, it can also make certain adjustments and improvements.These belong to guarantor of the invention
Protect range.
A kind of preparation method of the high heat storage amount phase-changing and temperature-regulating viscose rayon of embodiment 1
The following steps are included:
(1) phase-change material micro-capsule is prepared
A, phase-change material emulsion is prepared
Phase-change material and phase transformation auxiliary agent are mixed, 40 DEG C is heated to, is stirred at 500r/min, after five minutes, increases temperature
To 60 DEG C, emulsifier, initiator and distilled water is added, while revolving speed being improved with the speed of 50r/min to 1300r/min, stirs
It mixes 0.8 hour, forms stable emulsion；
The wherein mass ratio of phase-change material, phase transformation auxiliary agent, emulsifier, initiator and distilled water are as follows: 100:7:6:1.7:
340。
, prepare melamine resin cyst material performed polymer
37% formalin is put into reaction kettle, is stirred, adjusting pH value is 7.8, by 37% formalin: melamine
Melamine is added in the ratio that amine is 3:1, is warming up to 70 DEG C, is stirred to react 1 hour under constant temperature with 500r/min, is made three
Melamine-formaldehyde resin cyst material performed polymer.
, polymerization reaction
Melamine resin cyst material performed polymer is added drop-wise to dropwise in above-mentioned emulsion, in 70 DEG C of water-baths with
The revolving speed of 2000r/min stirs, and citric acid, which is added dropwise, reduces pH to 3.5, is acidified, and acidificatoin time is 1 hour, is then warming up to
It 83 DEG C, reacts 2.5 hours, then heats to 90 DEG C, solidify 45 minutes, after reaction, gained reaction solution is stood, is filtered,
And solid matter is filtered to obtain with ethanol washing, it is washed 1 time, is centrifugated, taking precipitate, 40 respectively with petroleum ether, distilled water
Phase-change material micro-capsule is obtained after drying at DEG C.
The partial size 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 4:1:2:
5；
The phase transformation auxiliary agent: being mixed by aluminium oxide, SBS Thermoplastic Elastomer, mass ratio 4:3；
The aluminium oxide, powdered, partial size 40-60nm, the SBS Thermoplastic Elastomer, partial size 100-120nm.
The emulsifier is Tween-20；The initiator is benzoyl peroxide.
(2) modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed in modifier solution under stirring, it is then quiet
It only 30 minutes, is then stirred 5 minutes under the conditions of 500r/min, be spray-dried and adjust pH value to neutrality, so that phase transformation material
Expect the cationic polysaccharide-guar gum and chitosan on surface of microcapsule uniform adsorption in modifying agent and be modified, obtains modified
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, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol is chip solid；
The preparation of the modifier solution, comprising the following steps:
A, the preparation of poly-vinyl alcohol solution
According to the formula of modifying agent, each raw material component is weighed, pure water is put into agitator tank, starts stirring, stirring turns
Speed is 800r/min, while polyvinyl alcohol chip solid is added, and temperature is warming up to 98 DEG C from 25 DEG C with 3 DEG C of speed per minute,
30min is kept the temperature, until polyvinyl alcohol is completely dissolved, starts stirring always, crystallization is prevented to be precipitated, the system of obtained poly-vinyl alcohol solution
It is standby.
B, the preparation of chitosan solution
Chitosan and acetic acid are mixed, dissolution, preparation obtains 4% chitosan acetic acid solution.
C, it mixes
Chitosan solution prepared by step B is placed in mixing vessel stand-by；
Guar gum is added in the poly-vinyl alcohol solution of step A preparation, after stirring and dissolving, prepares polyvinyl alcohol and guar gum
Mixed liquor, be slowly dropped in the mixing vessel containing chitosan acetic acid solution, rate of addition is 0.8 part/min, and control is mixed
The temperature for closing container is 40 DEG C, and speed of agitator 900r/min is added dropwise, and keeps the temperature 10 minutes, and modifier solution is made.
(3) modified phase-change material micro-capsule lotion is prepared
Ionic liquid is added in modified phase-change material micro-capsule, under the conditions of 55 DEG C, -0.01MPa, with 300r/min
Revolving speed, be dispersed with stirring 20 minutes, adjust pH value to 7-8, prepare modified phase-change material micro-capsule lotion.
(4) co-blended spinning liquid is prepared
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by modified phase-change material
Microcapsule emulsion carries out standing and defoaming, and using injection device before spinning, viscose glue is added in the phase-change material micro-capsule lotion after deaeration
In stoste, co-blended spinning liquid is prepared；
Phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule lotion
Mass ratio be 0.098:1.
The viscose glue stoste, content of alphacellulose 8.7%, total alkali 3.5%, viscosity 30s, degree of ripeness 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, stirs
It mixes uniformly, 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, spray head drawing-off: 70%；Drawing-off 14% between disk, three bath drawing-offs -2%, four bathe drawing-off 3%, spin 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, octadecyl dimethyl benzyl chlorine
Change 2 parts of ammonium, 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, comprising the following steps:
Pure water is added in filling in mixing, starts stirring, revolving speed 600r/min, then addition starch tertiary amino alkyl ether,
The mixture of quaternary ammonium starch ethers, charging rate are 2 parts/min, and charging finishes, and temperature is from 25 DEG C with 4 DEG C of speed per minute heating
To 98 DEG C, 10 minutes are kept the temperature, recirculated cooling water is reused and cools to 60 DEG C, poly-quaternary ammonium salt, octadecyl dimethyl benzyl is added
Ammonium chloride, dodecyl dimethyl benzyl ammonium chloride,
It stirs evenly, cools 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 lotion is injected to coagulating bath, first fibre starts forming and hardening.
(6) it post-processes
Gained tow is refined, is dried by cutting, mitigation sulfur removal technology, finish application bath and washing, and phase of the present invention is obtained
Become temperature-adjusting viscose.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 1, the content of phase-change material micro-capsule is 9.3% in fiber,
Year-on-year coagulating bath filter backwash rate of pulling away a prop reduces by 50%, and water consumption reduces 500 sides/day, in coagulating bath crystalline product sal glauberi
Phase-change material is reduced to 100ppm or less.
The embodiment of the present invention 1 prepare phase-changing and temperature-regulating viscose rayon, melting enthalpy be 20.8J/g, melting temperature 28-30
DEG C, crystallization enthalpy be 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 breaking strength of fiber is 2.70cN/dtex, wet
Breaking strength is that 1.20cN/dtex elongation at break is 20%, good hygroscopicity, and the regain of fiber is 14.2%, and can be changed
The wearability of kind common viscose fiber, fibre density 1.37g/cm3。
A kind of preparation method of the high heat storage amount phase-changing and temperature-regulating viscose rayon of embodiment 2
The following steps are included:
(1) phase-change material micro-capsule is prepared
A, phase-change material emulsion is prepared
Phase-change material and phase transformation auxiliary agent are mixed, 42 DEG C is heated to, is stirred at 500r/min, after five minutes, increases temperature
To 63 DEG C, emulsifier, initiator and distilled water is added, while revolving speed being improved with the speed of 50r/min to 1400r/min, stirs
It mixes 1.2 hours, forms stable emulsion；
The wherein mass ratio of phase-change material, phase transformation auxiliary agent, emulsifier, initiator and distilled water are as follows: 100:9:7:2.0:
350。
, prepare melamine resin cyst material performed polymer
37% formalin is put into reaction kettle, is stirred, adjusting pH value is 8.0, by 37% formalin: melamine
Melamine is added in the ratio that amine is 3:1, is warming up to 72 DEG C, is stirred to react 1 hour under constant temperature with 500r/min, is made three
Melamine-formaldehyde resin cyst material performed polymer.
, polymerization reaction
Melamine resin cyst material performed polymer is added drop-wise to dropwise in above-mentioned emulsion, in 70 DEG C of water-baths with
The revolving speed of 2000r/min stirs, and citric acid, which is added dropwise, reduces pH to 3.5, is acidified, and acidificatoin time is 1 hour, is then warming up to
It 84 DEG C, reacts 2.7 hours, then heats to 92 DEG C, solidify 45 minutes, after reaction, gained reaction solution is stood, is filtered,
And solid matter is filtered to obtain with ethanol washing, it is washed 1 time, is centrifugated, taking precipitate, 40 respectively with petroleum ether, distilled water
Phase-change material micro-capsule is obtained after drying at DEG C.
The partial size 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 4:1:2:
5；
The phase transformation auxiliary agent: being mixed by aluminium oxide, SBS Thermoplastic Elastomer, mass ratio 4:3；
The aluminium oxide, powdered, partial size 40-60nm, the SBS Thermoplastic Elastomer, partial size 100-120nm.
The emulsifier is Tween-20；The initiator is benzoyl peroxide.
(2) modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed in modifier solution under stirring, it is then quiet
It only 37 minutes, then stirs 5 minutes, is spray-dried under the conditions of 530r/min, and adjust pH value to neutrality, so that phase transformation material
Expect the cationic polysaccharide-guar gum and chitosan on surface of microcapsule uniform adsorption in modifying agent and be modified, obtains modified
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, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol is chip solid；
The preparation of the modifier solution, comprising the following steps:
A, the preparation of poly-vinyl alcohol solution
According to the formula of modifying agent, each raw material component is weighed, pure water is put into agitator tank, starts stirring, stirring turns
Speed is 800r/min, while polyvinyl alcohol chip solid is added, and temperature is warming up to 98 DEG C from 25 DEG C with 3 DEG C of speed per minute,
30min is kept the temperature, until polyvinyl alcohol is completely dissolved, starts stirring always, crystallization is prevented to be precipitated, the system of obtained poly-vinyl alcohol solution
It is standby.
B, the preparation of chitosan solution
Chitosan and acetic acid are mixed, dissolution, preparation obtains 4% chitosan acetic acid solution.
C, it mixes
Chitosan solution prepared by step B is placed in mixing vessel stand-by；
Guar gum is added in the poly-vinyl alcohol solution of step A preparation, after stirring and dissolving, prepares polyvinyl alcohol and guar gum
Mixed liquor, be slowly dropped in the mixing vessel containing chitosan acetic acid solution, rate of addition is 0.9 part/min, and control is mixed
The temperature for closing container is 40 DEG C, and speed of agitator 930r/min is added dropwise, and keeps the temperature 12 minutes, and modifier solution is made.
(3) modified phase-change material micro-capsule lotion is prepared
Ionic liquid is added in modified phase-change material micro-capsule, under the conditions of 57 DEG C, -0.02MPa, with 335r/min
Revolving speed, be dispersed with stirring 23 minutes, adjust pH value to 7-8, prepare modified phase-change material micro-capsule lotion.
(4) co-blended spinning liquid is prepared
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by modified phase-change material
Microcapsule emulsion carries out standing and defoaming, and using injection device before spinning, viscose glue is added in the phase-change material micro-capsule lotion after deaeration
In stoste, co-blended spinning liquid is prepared；
Phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule lotion
Mass ratio be 0.10:1.
The viscose glue stoste, content of alphacellulose 9.0%, total alkali 3.7%, viscosity 33s, degree of ripeness 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, stirs
It mixes uniformly, 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, spray head 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, octadecyl dimethyl benzyl chlorination
2 parts of ammonium, 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, comprising the following steps:
Pure water is added in filling in mixing, starts stirring, revolving speed 630r/min, then addition starch tertiary amino alkyl ether,
The mixture of quaternary ammonium starch ethers, charging rate are 2.2 parts/min, and charging finishes, and temperature is from 25 DEG C with 4 DEG C per minute of speed liter
Temperature keeps the temperature 10 minutes to 98 DEG C, reuses recirculated cooling water and cools to 60 DEG C, poly-quaternary ammonium salt, octadecyldimethyl benzyl is added
Ammonium chloride, dodecyl dimethyl benzyl ammonium chloride,
It stirs evenly, cools 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 lotion is injected to coagulating bath, first fibre starts forming and hardening.
(6) it post-processes
Gained tow is refined, is dried by cutting, mitigation sulfur removal technology, finish application bath and washing, and phase of the present invention is obtained
Become temperature-adjusting viscose.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 2, the content of phase-change material micro-capsule is 9.6% in fiber,
Year-on-year coagulating bath filter backwash rate of pulling away a prop reduces by 60%, and water consumption reduces 800 sides/day, in coagulating bath crystalline product sal glauberi
Phase-change material is reduced to 100ppm or less.
The embodiment of the present invention 2 prepare phase-changing and temperature-regulating viscose rayon, melting enthalpy be 22J/g, melting temperature 31-32
DEG C, crystallization enthalpy be 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 breaking strength of fiber is 2.75cN/dtex, wet
Breaking strength is that 1.75cN/dtex elongation at break is 22%, good hygroscopicity, and the regain of fiber is 15%, and can be improved
The wearability of common viscose fiber, fibre density 1.42g/cm3。
A kind of preparation method of the high heat storage amount phase-changing and temperature-regulating viscose rayon of embodiment 3
The following steps are included:
(1) phase-change material micro-capsule is prepared
A, phase-change material emulsion is prepared
Phase-change material and phase transformation auxiliary agent are mixed, 45 DEG C is heated to, is stirred at 500r/min, after five minutes, increases temperature
To 65 DEG C, emulsifier, initiator and distilled water is added, while revolving speed being improved with the speed of 50r/min to 1500r/min, stirs
It mixes 1.2 hours, forms stable emulsion；
The wherein mass ratio of phase-change material, phase transformation auxiliary agent, emulsifier, initiator and distilled water are as follows: 100:10:8:
2.2: 370。
, prepare melamine resin cyst material performed polymer
37% formalin is put into reaction kettle, is stirred, adjusting pH value is 8.0, by 37% formalin: melamine
Melamine is added in the ratio that amine is 3:1, is warming up to 75 DEG C, is stirred to react 1 hour under constant temperature with 600r/min, is made three
Melamine-formaldehyde resin cyst material performed polymer.
, polymerization reaction
Melamine resin cyst material performed polymer is added drop-wise to dropwise in above-mentioned emulsion, in 75 DEG C of water-baths with
The revolving speed of 2500r/min stirs, and citric acid, which is added dropwise, reduces pH to 4.0, is acidified, and acidificatoin time is 1 hour, is then warming up to
It 85 DEG C, reacts 3 hours, then heats to 93 DEG C, solidify 45 minutes, after reaction, gained reaction solution is stood, is filtered, simultaneously
Solid matter is filtered to obtain with ethanol washing, is washed respectively 1 time with petroleum ether, distilled water, is centrifugated, taking precipitate, at 40 DEG C
Phase-change material micro-capsule is obtained after lower drying.
The partial size 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 4:1:2:
5；
The phase transformation auxiliary agent: being mixed by aluminium oxide, SBS Thermoplastic Elastomer, mass ratio 4:3；
The aluminium oxide, powdered, partial size 40-60nm, the SBS Thermoplastic Elastomer, partial size 100-120nm.
The emulsifier is Tween-20；The initiator is benzoyl peroxide.
(2) modification of phase-change material micro-capsule
Phase-change material micro-capsule is added in modifier solution, is dispersed in modifier solution under stirring, it is then quiet
It only 40 minutes, then stirs 7 minutes, is spray-dried under the conditions of 600r/min, and adjust pH to neutrality, so that phase-change material
Cationic polysaccharide-guar gum and chitosan on surface of microcapsule uniform adsorption in modifying agent and be modified, obtain modified
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, pure water
30 parts, 100 parts of acetic acid.
The polyvinyl alcohol is chip solid；
The preparation of the modifier solution, comprising the following steps:
A, the preparation of poly-vinyl alcohol solution
According to the formula of modifying agent, each raw material component is weighed, pure water is put into agitator tank, starts stirring, stirring turns
Speed is 1000r/min, while polyvinyl alcohol chip solid is added, and temperature is warming up to 98 DEG C from 25 DEG C with 3 DEG C of speed per minute,
30min is kept the temperature, until polyvinyl alcohol is completely dissolved, starts stirring always, crystallization is prevented to be precipitated, the system of obtained poly-vinyl alcohol solution
It is standby.
B, the preparation of chitosan solution
Chitosan and acetic acid are mixed, dissolution, preparation obtains 4% chitosan acetic acid solution.
C, it mixes
Chitosan solution prepared by step B is placed in mixing vessel stand-by；
Guar gum is added in the poly-vinyl alcohol solution of step A preparation, after stirring and dissolving, prepares polyvinyl alcohol and guar gum
Mixed liquor, be slowly dropped in the mixing vessel containing chitosan acetic acid solution, rate of addition is 1.0 parts/min, and control is mixed
The temperature for closing container is 45 DEG C, and speed of agitator 900r/min is added dropwise, and keeps the temperature 15 minutes, and modifier solution is made.
(3) modified phase-change material micro-capsule lotion is prepared
Ionic liquid is added in modified phase-change material micro-capsule, under the conditions of 60 DEG C, -0.015MPa, with 350r/
The revolving speed of min is dispersed with stirring 25 minutes, is adjusted pH value to 7-8, is prepared modified phase-change material micro-capsule lotion.
(4) co-blended spinning liquid is prepared
Using cellulose pulp as raw material, viscose glue stoste is made through conventional viscose preparation technology, by modified phase-change material
Microcapsule emulsion carries out standing and defoaming, and using injection device before spinning, viscose glue is added in the phase-change material micro-capsule lotion after deaeration
In stoste, co-blended spinning liquid is prepared；
Phase-change material micro-capsule and alpha cellulose in viscose glue stoste in the modified phase-change material micro-capsule lotion
Mass ratio be 0.095:1.
The viscose glue stoste, content of alphacellulose 9.2%, total alkali 4.0%, viscosity 35s, degree of ripeness 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, stirs
It mixes uniformly, 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, spray head 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, octadecyl dimethyl benzyl chlorine
Change 2 parts of ammonium, 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, comprising the following steps:
Pure water is added in filling in mixing, starts stirring, revolving speed 650r/min, then addition starch tertiary amino alkyl ether,
The mixture of quaternary ammonium starch ethers, charging rate are 2.5 parts/min, and charging finishes, and temperature is from 25 DEG C with 4 DEG C per minute of speed liter
Temperature keeps the temperature 10 minutes to 98 DEG C, reuses recirculated cooling water and cools to 60 DEG C, poly-quaternary ammonium salt, octadecyldimethyl benzyl is added
Ammonium chloride, dodecyl dimethyl benzyl ammonium chloride,
It stirs evenly, cools 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 lotion is injected to coagulating bath, first fibre starts forming and hardening.
(6) it post-processes
Gained tow is refined, is dried by cutting, mitigation sulfur removal technology, finish application bath and washing, and phase of the present invention is obtained
Become temperature-adjusting viscose.
Phase-changing and temperature-regulating viscose rayon prepared by the embodiment of the present invention 3, the content of phase-change material micro-capsule is 9.2% in fiber,
Year-on-year coagulating bath filter backwash rate of pulling away a prop reduces by 56%, and water consumption reduces 600 sides/day, in coagulating bath crystalline product sal glauberi
Phase-change material is reduced to 100ppm or less.
The embodiment of the present invention 3 prepare phase-changing and temperature-regulating viscose rayon, melting enthalpy be 21.2J/g, melting temperature 29-30
DEG C, crystallization enthalpy be 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 breaking strength of fiber is 2.72cN/dtex, wet
Breaking strength is that 1.50cN/dtex elongation at break is 20%, good hygroscopicity, and the regain of fiber is 14.5%, and can be changed
The wearability of kind common viscose fiber, fibre density 1.38g/cm3。
Phase-changing and temperature-regulating viscose rayon prepared by the present invention can improve viscous due to the addition of specific phase-change material micro-capsule
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, percentage employed in the present invention is weight percent, ratio of the present invention,
For mass ratio.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (5)
1. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon, it is characterised in that: the viscose rayon melts enthalpy
It is 18.5-19.7J/g for 20.8- 22J/g, crystallization enthalpy；
The viscose rayon, the content of phase-change material micro-capsule are 9.2-9.6%；Melting temperature is 28-32 DEG C, crystallization temperature model
Enclose 15-20 DEG C；
The dry breaking strength of fiber is 2.70-2.75cN/dtex, and wet breaking strength is 1.20-1.75cN/dtex elongation at break
For 20-22%, the regain of fiber is 14.2-15%, fibre density 1.37-1.42g/cm3；
The preparation method, modification and spinning moulding including preparing phase-change material micro-capsule, phase-change material micro-capsule；The system
Standby phase-change material micro-capsule, including prepare phase-change material emulsion and prepare melamine resin cyst material performed polymer；
The wherein mass ratio of phase-change material, phase transformation auxiliary agent, emulsifier, initiator and distilled water are as follows: 100:7-10:6-8:1.7- 2.2:
340-370；The phase transformation auxiliary agent: being mixed by aluminium oxide, SBS Thermoplastic Elastomer, mass ratio 4:3；The aluminium oxide,
It is powdered, partial size 40-60nm；The SBS Thermoplastic Elastomer, partial size 100-120nm；The melamine resin capsule
The mass ratio of wall material performed polymer and phase-change material is 2:1；
The modification of the phase-change material micro-capsule is modified phase-change material micro-capsule using modifier solution；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；Institute
Stating phase-change material is by n-octadecane, n-docosane, positive certain herbaceous plants with big flowers alcohol, n-heptanol composition, mass ratio 4:1:2:5；The phase
Become the partial size D97 of material microcapsule as 1-2 μm；
The spinning moulding, is added 5-7% acid bath compounding agent solution in acid bath, 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, octadecyldimethyl benzyl
2 parts of ammonium chloride, 3 parts of dodecyl dimethyl benzyl ammonium chloride, 100 parts of pure water；
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 DEG C；Leaching length: 400-500 millimeters, spray head 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.
2. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 1, it is characterised in that: institute
State the preparation of modifier solution, comprising the following steps:
(1) preparation of poly-vinyl alcohol solution
Pure water is added to the container, speed of agitator 800-1000r/min, while polyvinyl alcohol is added, temperature from 25 DEG C with
3 DEG C of speed per minute is warming up to 98 DEG C, keeps the temperature 30min, and until polyvinyl alcohol is completely dissolved, poly-vinyl alcohol solution is made；
(2) preparation of chitosan solution
Chitosan and acetic acid are mixed, dissolution, preparation obtains 4% chitosan acetic acid solution, is placed in mixing vessel；
(3) it mixes
Guar gum is added in the poly-vinyl alcohol solution of step (1) preparation, after stirring and dissolving, prepares polyvinyl alcohol and guar gum
Mixed liquor is slowly dropped in the chitosan acetic acid solution of step (2) preparation, and rate of addition is 0.8-1.0 parts/min, and control is mixed
The temperature for closing container is 40-45 DEG C, and speed of agitator 900-1000r/min is added dropwise, and keeps the temperature 10-15 minutes, is made and is modified
Agent solution.
3. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 1, it is characterised in that: institute
State the preparation of acid bath auxiliary agent solvent, comprising the following steps: pure water is added, then speed of agitator 600-650r/min is added
The mixture of starch tertiary amino alkyl ether, quaternary ammonium starch ethers, charging rate are 2-2.5 parts/min, and charging finishes, and temperature is from 25 DEG C
98 DEG C are warming up to 4 DEG C of speed per minute, 10 minutes is kept the temperature, reuses recirculated cooling water and cool to 60-65 DEG C, poly- season is added
Amine salt, stearyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, stir evenly, and cool to 25 DEG C, mistake
Leaching filtrate obtains acid bath compounding agent solution.
4. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 1, it is characterised in that: institute
It states and prepares phase-change material emulsion, phase-change material and phase transformation auxiliary agent are mixed, 40-45 DEG C is heated to, is stirred at 500r/min
It mixes, after five minutes, increases temperature and emulsifier, initiator and distilled water is added to 60-65 DEG C, while by revolving speed with 50r/ min's
Speed is improved to 1300-1500r/min, is stirred 0.8-1.2 hours, is formed stable phase-change material emulsion.
5. a kind of preparation method of high heat storage amount phase-changing and temperature-regulating viscose rayon according to claim 1, it is characterised in that: institute
It states and prepares melamine resin cyst material performed polymer, 37% formalin is put into reaction kettle, stir, adjust
PH value is 7.8- 8.0, in 37% formalin: melamine is added in the ratio that melamine is 3:1, is warming up to 70-75 DEG C, perseverance
It is stirred to react 1 hour under the conditions of temperature with 500-600r/min, melamine resin cyst material performed polymer is made；
It is described to prepare phase-change material micro-capsule, it further include polymerization reaction；The polymerization reaction, by melamine resin cyst wall
Material performed polymer is added drop-wise to dropwise in above-mentioned phase-change material emulsion, is turned in 70-75 DEG C of water-bath with 2000-2500r/min
Speed stirring, citric acid, which is added dropwise, reduces pH to 3.5-4.0, is acidified, and 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, after reaction, gained reaction solution is stood, suction filtration,
Washing, centrifuge separation, taking precipitate obtain phase-change material micro-capsule after dry at 40 DEG C.
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| CN201710183743.0A CN107022800B (en) | 2017-03-24 | 2017-03-24 | A kind of high heat storage amount phase-changing and temperature-regulating viscose rayon 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 |
| CN109505027B (en) * | 2018-11-29 | 2021-11-30 | 上海绿薇生物科技有限公司 | High-sensitivity heat-conducting air conditioner fiber and preparation method thereof |
| CN109576808B (en) * | 2018-11-29 | 2021-08-24 | 青岛邦特生态纺织科技有限公司 | Inorganic flame-retardant intelligent temperature-adjusting cellulose fiber and preparation method thereof |
| CN110863261B (en) * | 2019-12-06 | 2022-05-27 | 大连工业大学 | Phase-change temperature-regulating composite fiber with chitosan as matrix and preparation method thereof |
| CN111455487A (en) * | 2020-04-27 | 2020-07-28 | 宁波市纤维检验所 | Phase-change temperature-regulating fiber and preparation method thereof |
| CN112251864B (en) * | 2020-09-25 | 2022-06-07 | 江西金源纺织有限公司 | Wear-resistant improved viscose composite yarn and preparation method thereof |
| CN112813516A (en) * | 2020-12-31 | 2021-05-18 | 百事基材料（青岛）股份有限公司 | Viscose macrobiological fiber containing ginkgo, rose, camellia, pomegranate and kudzu root and preparation method thereof |
| CN113529183B (en) * | 2021-06-29 | 2022-07-12 | 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 |
| CN114318571B (en) * | 2022-02-24 | 2024-03-12 | 青岛尼希米生物科技有限公司 | Mosquito-repellent microcapsule, mosquito-repellent fiber and preparation methods thereof |
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587340A (en) * | 2004-07-09 | 2005-03-02 | 清华大学 | High heat conductive fixed phase change heat storage material suitable for large scale industrial production |
| CN1732043A (en) * | 2002-12-24 | 2006-02-08 | 纳米运动技术有限公司 | Seal the method for phase transitional paraffin compounds and the microcapsules that make thus with the carbamide capsule |
| CN101037811A (en) * | 2007-04-18 | 2007-09-19 | 山东海龙股份有限公司 | Method for preparing cellulose viscose by employing sweet Chinese sorghum pole |
| CN102172502A (en) * | 2011-01-24 | 2011-09-07 | 天津工业大学 | Method for preparing functional nano capsule size by interfacial polymerization and application of functional nano capsule size |
| CN102561027A (en) * | 2011-12-23 | 2012-07-11 | 宏大研究院有限公司 | Wadding flake with function of intellectualized thermoregulation and preparation method thereof |
| CN103492062A (en) * | 2011-02-25 | 2014-01-01 | 美利肯公司 | Capsules and compositions comprising the same |
| CN105316784A (en) * | 2015-12-02 | 2016-02-10 | 山传雷 | Composite microcapsule additive containing phase change material and sarcandra glabra extract and application of composite microcapsule additive |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376800B (en) * | 2008-10-07 | 2011-02-09 | 山东省科学院新材料研究所 | High temperature resistant type phase-change material micro-capsule and preparation thereof |
| US9951294B2 (en) * | 2014-12-16 | 2018-04-24 | Noxell Corporation | Coated microcapsules |
| CN206079505U (en) * | 2016-04-21 | 2017-04-12 | 杭州吻吻鱼科技有限公司 | Insulating cup with rapid cooling function |
-
2017
- 2017-03-24 CN CN201710183743.0A patent/CN107022800B/en active Active
- 2017-03-24 CN CN201810929397.0A patent/CN109137113B/en active Active
- 2017-03-24 CN CN201810929398.5A patent/CN109137114B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732043A (en) * | 2002-12-24 | 2006-02-08 | 纳米运动技术有限公司 | Seal the method for phase transitional paraffin compounds and the microcapsules that make thus with the carbamide capsule |
| CN1587340A (en) * | 2004-07-09 | 2005-03-02 | 清华大学 | High heat conductive fixed phase change heat storage material suitable for large scale industrial production |
| CN101037811A (en) * | 2007-04-18 | 2007-09-19 | 山东海龙股份有限公司 | Method for preparing cellulose viscose by employing sweet Chinese sorghum pole |
| CN102172502A (en) * | 2011-01-24 | 2011-09-07 | 天津工业大学 | Method for preparing functional nano capsule size by interfacial polymerization and application of functional nano capsule size |
| CN103492062A (en) * | 2011-02-25 | 2014-01-01 | 美利肯公司 | Capsules and compositions comprising the same |
| CN102561027A (en) * | 2011-12-23 | 2012-07-11 | 宏大研究院有限公司 | Wadding flake with function of intellectualized thermoregulation and preparation method thereof |
| CN105316784A (en) * | 2015-12-02 | 2016-02-10 | 山传雷 | Composite microcapsule additive containing phase change material and sarcandra glabra extract and application of composite microcapsule additive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109137114B (en) | 2021-05-28 |
| CN109137113A (en) | 2019-01-04 |
| CN107022800A (en) | 2017-08-08 |
| CN109137114A (en) | 2019-01-04 |
| CN109137113B (en) | 2021-06-01 |
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