CN105862165B - A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof - Google Patents
A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof Download PDFInfo
- Publication number
- CN105862165B CN105862165B CN201610440883.7A CN201610440883A CN105862165B CN 105862165 B CN105862165 B CN 105862165B CN 201610440883 A CN201610440883 A CN 201610440883A CN 105862165 B CN105862165 B CN 105862165B
- Authority
- CN
- China
- Prior art keywords
- composition
- spinning solution
- modified acrylic
- acrylic fiber
- revs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
Landscapes
- Chemical & Material Sciences (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)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof, copolymerization again is blended by using the preparation liquid and a kind of macromolecule bridging agent of prefabricated two kinds different components, again by filtering, deaeration, ag(e)ing process, the protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function is prepared.The spinning solution is using sodium sulfocyanate and water as solvent, the safer environmental protection of production process, reclaims more effective.The fiber prepared with the spinning solution by wet spinning equipment have decalescence between 20 38 DEG C in heating, during 28 10 DEG C in cooling phase transformation heat release function.But also make modified acrylic fiber be provided with it is different it is protein modified after different comfortablenesses.
Description
Technical field
The invention belongs to functional high-polymer energy storage material field, more particularly to one kind are interval in certain temperature in heating
It is interior to absorb heat by the phase-change characteristic of material inherently, leaned on when temperature is down to another low-temperature range by said temperature interval
The phase-change characteristic of material inherently discharges the protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function of heat.By
The fiber of spinning solution production can be widely used in the textile garment and home textile product developed and develop high-performance intelligent thermoregulating.
Background technology
Phase-change energy-storage temperature adjustment fiber refers to a kind of to work as external environment in the range of the phase transformation transformation of the fibrous material
Fibrous material absorbs temperature energy, a kind of undulation degree of release temperature energy when ambient temperature is reduced when temperature is raised
Material.Protein modified acrylic fiber with phase-changing and temperature-regulating function is a branch of this material, and to manufacture phase-changing and temperature-regulating work(
The protein modified acrylic fiber of energy, just must first research and develop the spinning solution for preparing and manufacturing this fiber, then could pass through wet method
Spinning equipment and technique prepare this protein modified acrylic fiber with phase-changing and temperature-regulating function.
At present, the technology and method of protein modified acrylic spinning liquid of the manufacture with phase-changing and temperature-regulating function mainly have：1）First
The microencapsulation material using melamine as shell with phase transition function is produced, then with dispersant and water microencapsulation material point
Dissipate, the protein modified acrylic fiber polymerization liquid by solvent of zinc chloride for being more than 40% with zinc oxide concentration afterwards is mixed, then passes through spinning
Technology of preparing is processed into the corresponding fiber with phase transition function.This manufacturing technology has the manufacturing cost of microcapsules higher,
Microcapsule shell it is elastic poor, microcapsules are thoroughly mixed scattered more difficult in spinneret liquid, and mixed spinning solution is in spinning
Spinning process in easily cause stifled spinneret hole and the irregular phenomenon of fiber strength, production cost is also higher, and microcapsules are easy
Rupture causes function forfeiture and zinc chloride solvent that the molecular weight of protein can be made further to diminish, and causes low molecular weight protein
The building-up process of blending and copolymerization can not be participated in and be changed into the shortcoming of waste liquid.And heterogeneity material in the waste liquid after spinning
Reclaim also extremely difficult.2）The microencapsulation material using melamine as shell with phase transition function is first produced, then uses dispersant
Microencapsulation material is disperseed with water, tool is formed with acrylonitrile monemer, casein, zinc chloride, water, initiator blending copolymerization afterwards
There is the polymer base material mixed liquor of adhesion characteristic, then the corresponding fibre with phase transition function is processed into by spinning technology of preparing
Dimension.There is this manufacturing technology acrylonitrile monemer to belong to high-risk product in transportation, and freight is big, particularly middle-size and small-size enterprise
Industry can not be allowed to production because of environmental protection and safety problem, and spinning solution polymerization process hazards are also high, microcapsules manufactures
Cost is higher, microcapsule shell it is elastic poor, be thoroughly mixed scattered more difficult and be easily broken in copolymer fluid, it is mixed
Spinning solution easily causes stifled spinneret hole and the irregular phenomenon of fiber strength in the spinning process of spinning, production cost also it is higher with
And zinc chloride solvent can make the molecular weight of protein further diminish, low molecular weight protein is caused to participate in blending and copolymerization
Building-up process and be changed into the shortcoming of waste liquid.And in the waste liquid after spinning heterogeneity material recovery it is also extremely difficult.
Therefore scientific research and market comsupton are needed to work out with higher phase change energy storage function, and processing is easier, and are produced
Cost is lower, the safer environmental protection of production process, and the easier protein modified acrylic fibers with phase-changing and temperature-regulating function of devil liquor recovery are fine
Tie up process technology.
The content of the invention
It is an object of the invention to provide a kind of producing with phase-changing and temperature-regulating function as solvent using sodium sulfocyanate and water
The synthetic method of protein modified acrylic fiber spinning solution.Its process is easier, and production cost is lower, and production process is safer
Environmental protection, devil liquor recovery is easier.
It is another object of the present invention to provide a kind of egg with phase-changing and temperature-regulating function produced in aforementioned manners
White modified acrylic fibres spinning solution.The fiber prepared with the spinning solution by wet spinning equipment not only has in heating
Decalescence during 20-38 DEG C, the function of phase transformation heat release after 28 DEG C in cooling.But also make modified acrylic fiber
Be provided with it is different it is protein modified after different comfortablenesses.Its fiber can be widely used for developing and developing high-performance intelligent thermoregulating
Textile garment and home textile product.
The purpose of the present invention is achieved by the following technical solution.
A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function, the composition of the spinning solution includes：Altogether
Thing A, composition B, composition C, components D and sodium sulfocyanate are mixed, the ratio of weight and number of each composition is：
Blend A：1.5-2
Composition B：14.5-15.5
Composition C：148-152
Components D：0.01-0.02
Sodium sulfocyanate：10-12
The blend A is by end hydroxy butadiene-isocyanate prepolymer, carbon 18-20 n-alkane paraffin, β-first
Base epoxychloropropane or tetrahydrofuran blending composition, wherein the ratio of weight and number of each composition is：
End hydroxy butadiene-isocyanate prepolymer：15-20
Carbon 18-20 n-alkane paraffin：82-75
β methyl epoxy chloropropane or tetrahydrofuran：3-5；
The composition B is：Protein hydrogel body；
The composition C is：Sodium sulfocyanate method acrylic spinning liquid；
The components D is：Polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate.
Further, the terminal hydroxy group selected in the blend A before end hydroxy butadiene-isocyanate prepolymer synthesis
The hydroxyl value of polybutadiene is between 1 to 0.8, end hydroxy butadiene-isocyanate prepolymer unreacted containing 4%-6% after synthesis
Isocyanates root.
Further, in the components D polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate molecule
Amount is 1000-1500.
Further, the composition B protein hydrogel bodies molecular weight is 30-80KD.
A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function, preparation process is：
1）, take end hydroxy butadiene-isocyanate prepolymer, carbon 18-20 n-alkane paraffin, Beta-methyl epoxy chlorine
Propane or tetrahydrofuran, blending form blend A, be warming up to 40-45 DEG C it is stand-by；
2）, take composition B stand-by between being warming up to 65 DEG C -50 DEG C；Take composition C heatings stand-by at 40-45 DEG C；
3）, take composition B be put into container with dispersion emulsifying machine between 65 DEG C -50 DEG C of constant temperature, to composition B stir feelings
Under condition, blend A is added, after having added, with 300 revs/min of -500 revs/min of agitations until under the microscope it can be seen that blend
A is emulsified into 3 microns and following particulate, continues to stir 5-10 minute, then uniformly reduce mixing speed to 45 revs/min -50 turns/
Continue stirring 30 minutes after point, stop stirring, constant temperature stands 20 minutes, then continues stirring 30 minutes with 45 revs/min -50 revs/min,
It is naturally cooling to 35-40 DEG C and stands more than 48 hours, sodium sulfocyanate is then added in stirring, and stirring obtains its mixed dissolution
Blended liquid E；
4）, take composition C to be put into container, with dispersion emulsifying machine between 40 DEG C -45 DEG C of constant temperature, with 15 rev/min -20
Rev/min stirring composition C simultaneously adds components D and blended liquid E mixing, continues to stir 20 minutes, stops stirring, filtered, deaeration
And Ageing Treatment, obtain the protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function.
The beneficial effects of the invention are as follows：
1）The present invention provides a kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function.Use the spinning solution
The fiber prepared by wet spinning equipment is not only with the 20-38 DEG C of period decalescence in heating, 28 in cooling
The function of phase transformation heat release after DEG C.But also make modified acrylic fiber be provided with it is different it is protein modified after difference it is comfortable
Property.Its fiber can be widely used for the textile garment and home textile product for developing and developing high-performance intelligent thermoregulating.
2）There is provided a kind of fine by protein modified acrylic fibers of the production with phase-changing and temperature-regulating function of solvent of sodium sulfocyanate and water
Tie up the synthetic method of spinning solution.Its process is easier, and production cost is lower, the safer environmental protection of production process, devil liquor recovery
Easily.
Brief description of the drawings
Fig. 1 is the process chart of preparation method of the present invention；
Fig. 2 is the schematic diagram that the phase-changing and temperature-regulating that spinning solution of the present invention and the fiber produced with the spinning solution have inhales heat release.
Embodiment
A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function, the composition of the spinning solution includes：Altogether
Thing A, composition B, composition C, components D and sodium sulfocyanate are mixed, the ratio of weight and number of each composition is：
Blend A：1.5-2
Composition B：14.5-15.5
Composition C：148-152
Components D：0.01-0.02
Sodium sulfocyanate：10-12
The blend A is by end hydroxy butadiene-isocyanate prepolymer, carbon 18-20 n-alkane paraffin, β-first
Base epoxychloropropane or tetrahydrofuran blending composition, wherein the ratio of weight and number of each composition is：
End hydroxy butadiene-isocyanate prepolymer：15-20
Carbon 18-20 n-alkane paraffin：82-75
β methyl epoxy chloropropane or tetrahydrofuran：3-5；
The composition B is：Protein hydrogel body；
The composition C is：Sodium sulfocyanate and water are having polymerize of using of the Wet-spinning production standard acrylic fiber of solvent
Sodium sulfocyanate method acrylic spinning liquid；
The components D is：Polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate.In the blend A
The hydroxyl value for the end hydroxy butadiene selected before end hydroxy butadiene-isocyanate prepolymer synthesis is closed between 1 to 0.8
End hydroxy butadiene-isocyanate prepolymer unreacted isocyanates root containing 4%-6% after.Poly- second in the components D
The molecular weight of omega-diol diacrylate or polyethylene glycol dimethacrylate is 1000-1500.The composition B protein water
Gelinite molecular weight is 30-80KD.
The preparation method of above-mentioned protein modified acrylic fiber spinning solution, preparation process is：
A, take end hydroxy butadiene-isocyanate prepolymer, carbon 18-20 n-alkane paraffin, Beta-methyl epoxy chlorine
Propane or tetrahydrofuran, blending form blend A, be warming up to 40-45 DEG C it is stand-by；
B, take composition B stand-by between being warming up to 65 DEG C -50 DEG C；Take composition C heatings stand-by at 40-45 DEG C；
C, take composition B be put into container with dispersion emulsifying machine between 65 DEG C -50 DEG C of constant temperature, to composition B stir feelings
Under condition, blend A is gradually added, after having added, with 300-500 revs/min of agitation until under the microscope it can be seen that blend A
Be emulsified into 3 microns and following particulate, afterwards continue stir 5-10 minute, followed by uniformly reduce mixing speed to 45 turns/
Divide after -50 revs/min and continue to stir 30 minutes（Make " end hydroxy butadiene-isocyanate prepolymer " and the Beta-methyl in particulate
Epoxychloropropane or tetrahydrofuran, which dissociate to the protein or water in microparticle surfaces and extracorpuscular water, progressively occurs interfacial polymerization
Shelling is reacted）, then stop stirring, static 20 minutes of constant temperature makes the particulate to be formed that boundary further progressively occur during this
The reaction that face shelling is thickened, then to prevent the reunion between the particulate in this course of reaction, and with 45 turns of mixing speed/
Points -50 revs/min continue to stir 30 minutes, subsequently, be naturally cooling to 35-40 DEG C it is static more than 48 hours, make microparticle surfaces shape
Into shell further occur finer and close interfacial reaction, sodium sulfocyanate is then gradually added in stirring, and stirring mixes it
Dissolve to obtain blended liquid E；
D, composition C is taken to be put into container, with dispersion emulsifying machine between 40 DEG C -45 DEG C of constant temperature, with low speed（Such as 15 turns/
Divide -20 revs/min）Stirring composition C simultaneously adds components D and blended liquid E mix and made it uniform, continues stir about 20 minutes, stopping
Stirring, is filtered, (static placement makes the viscosity of liquid equal for deaeration (static placement escapes the air bubble in liquid) and timeliness
It is even consistent) processing, obtain the protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function.
The preparation method of spinneret liquid provided by the present invention for wet spinning refers to a kind of first using synthesis point mixing
Liquid, then point mixed liquor, copolymerization is terminated again with the blending of crosslinking bridging agent, is then produced by filtering, deaeration, timeliness with phase transformation
The synthetic method of the protein modified acrylic fiber spinning solution of temperature adjustment function.
Its material used is：Sodium sulfocyanate, using sodium sulfocyanate and water as the Wet-spinning production standard acrylic fiber of solvent
The sodium sulfocyanate method acrylic spinning liquid having polymerize that uses, using carbon 18-20 n-alkane paraffin as the phase transformation material of microcapsules core
Material, using end hydroxy butadiene-isocyanate prepolymer and protein as producing phase-change microcapsule and protein-colloid mixing
The interfacial polymerization main material of microcapsule shell in liquid, system is used as using the hydroxyl in β methyl epoxy chloropropane or tetrahydrofuran and water
Take the interfacial polymerization auxiliary material of microcapsule shell in phase-change microcapsule and protein-colloid mixed liquor, using protein as to acrylic fibers
Polyethylene glycol (1000-1500) diacrylate or polyethylene glycol (1000- material modified, equally to have phase transition function
1500) dimethylacrylate is copolymerization bridging materials when copolymerization again is blended in point mixed liquor；Its terminal hydroxy group polybutadiene synthesized
Isocyanates in alkene-isocyanate prepolymer refers to diisocyanate（Such as toluene di-isocyanate(TDI), the isocyanide of hexa-methylene two
Acid esters, methyl diphenylene diisocyanate）, the hydroxyl value of the end hydroxy butadiene (HTPB) before the synthesis of its prepolymer is 1 to 0.8
Between, end hydroxy butadiene-isocyanate prepolymer requirement after its synthesis is containing about the unreacted isocyanates roots of 4-6%；Its
Signified protein is fibroin protein or hair protein or collagen of the molecular weight main body between 30-80KD.Microcapsules
With tripolycyanamide is free of in spinneret liquid, microcapsules have preferable elasticity, are difficult to rupture under pressure and expansion status.
Its specific preparation method and step are as follows in the present embodiment：
A, take end hydroxy butadiene and hexamethylene diisocyanate or diphenylmethyl of the hydroxyl value between 1 to 0.8
End hydroxy butadiene-isocyanate prepolymer 15- of the alkane diisocyanate prepolymer into the unreacted isocyanates root containing 4-6%
20%, take carbon 18-20 n-alkane paraffin（Net purchase）82-75%, takes β methyl epoxy chloropropane（Net purchase）Or tetrahydrofuran（Net
Purchase）3-5%, blending forms blend A equal to 1.5-2 kilograms, be warming up to 40-45 DEG C it is stand-by.
B, take solid content 4-6%, protein hydrogel body of the molecular weight between 30-80KD (thousand molecular weight)（Composition B）Deng
In 15 kilograms（Prepared with the protein oneself of the net purchase between 30-80KD）, it is stand-by between being warming up to 65 DEG C -50 DEG C；Take sulphur cyanogen
Sour 10-13 kilograms of sodium；Take the sulphur having polymerize used using sodium sulfocyanate and water as the Wet-spinning production standard acrylic fiber of solvent
Zassol method acrylic spinning liquid（Composition C）Equal to 150 kilograms（It is available in Daqing petrochemical company Acrylic Fibers Plant）, its polymer consolidates
Content 4-6%, constant temperature is stand-by at 40-45 DEG C；Taking polyethylene glycol (1000-1500) diacrylate or polyethylene glycol (1000-
1500 molecular weight) dimethylacrylate（Components D）Equal to 0.01-0.02 kilograms（Net purchase）, normal temperature is stand-by.
C, composition B is taken to be put into 40-50 kilograms of wide mouth barrel, with dispersion emulsifying machine between 65 DEG C -50 DEG C of constant temperature, with
300-500 revs/min stirs to composition B, is then slowly gradually added blend A, until seeing 3 densely covered ц under 300 microscopes
Below m microcapsules（About 10 minutes）.Subsequently, make speed slowly be reduced to 45 revs/min -50 revs/min after stirring to continue to stir
30 minutes, then stop stirring, static 20 minutes of constant temperature.Low whipping speed is continuation stirring under 45 revs/min -50 revs/min afterwards
30 minutes.Followed by, it is naturally cooling to 35-40 DEG C of static more than 48 hours, then 10-12 kilograms of sodium sulfocyanate of addition, and stirring
Mix make its be thoroughly mixed dissolving it is stand-by, be defined as blended liquid E.
D, followed by, takes composition C to be put into 200-300 kilograms of wide mouth barrel, with dispersion emulsifying machine at 40 DEG C -45 of constant temperature
Between DEG C, to stir composition C under 15 revs/min -20 revs/min and be slowly added into components D and blended liquid E until being sufficiently mixed, and after
Continuous stir about 20 minutes.Followed by, stop stirring, be adjusted to filtering, the temperature of deaeration timeliness filtered, deaeration and timeliness.Extremely
This completes the synthesis of the protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function.Passed through with the spinning solution further wet
Fiber prepared by method spinning equipment and technique is not only with decalescence, the 28- in cooling between 20-38 DEG C in heating
The function of phase transformation heat release during 10 DEG C.But also make modified acrylic fiber be provided with it is different it is protein modified after difference it is comfortable
Property.Its fiber can be widely used for the textile garment and home textile product for developing and developing high-performance intelligent thermoregulating.
The present invention is now expanded on further by the following specific embodiments, but is not limited to the scope of the present invention.
Embodiment 1：
A, take the end hydroxy butadiene and hexamethylene diisocyanate that hydroxyl value is about 0.9 and be polymerized in advance containing about 5% not anti-
End hydroxy butadiene-the isocyanate prepolymer 20% for the isocyanates root answered, takes carbon 18-20 n-alkane that paraffin is blended
77%, take tetrahydrofuran 3%, blending forms blend A equal to 1.8 kilograms, be warming up to 45 DEG C it is stand-by.
B, take solid content 5%, mean molecule quantity 60KD hair protein water gel（Composition B）Equal to 15 kilograms, heating
It is stand-by to -50 DEG C；Take 11 kilograms of sodium sulfocyanate；Taking by the Wet-spinning production standard acrylic fiber of solvent of sodium sulfocyanate and water makes
The sodium sulfocyanate method acrylic spinning liquid having polymerize（Composition C）Equal to 150 kilograms, the solid content 5% of its polymer, constant temperature exists
40 DEG C stand-by；Taking polyethylene glycol (1500 molecular weight) diacrylate（Components D）Equal to 0.02 kilogram, normal temperature is stand-by.
C, take composition B to be put into 50 kilograms of wide mouth barrel, with dispersion emulsifying machine at 50 DEG C of constant temperature, with 500 revs/min
Composition B is stirred, composition A is then slowly gradually added, until seeing the 3 densely covered following microcapsules of ц m under 300 microscopes（About 10
Minute）.Subsequently, speed is slowly reduced to after 50 revs/min after stirring, continue to stir 30 minutes, then stop stirring, it is permanent
Static 20 minutes of temperature.Low whipping speed is stirred 30 minutes for continuation under 50 revs/min afterwards.Followed by, be naturally cooling to 40 DEG C it is quiet
Only 50 hours, then add 11 kilograms of sodium sulfocyanates, and stir make its be thoroughly mixed dissolving it is stand-by, be defined as blended liquid E.
D, followed by, takes composition C to be put into 300 kilograms of wide mouth barrel, with dispersion emulsifying machine between 45 DEG C of constant temperature, with
Composition C is stirred under 20 revs/min and components D and blended liquid E is slowly added into until being sufficiently mixed, and continues stir about 20 minutes.Again
Afterwards, stop stirring, be adjusted to filtering, the temperature of deaeration timeliness filtered, deaeration and timeliness.So far complete that there is phase-changing and temperature-regulating
The synthesis of the protein modified acrylic fiber spinning solution of function.Pass through further wet spinning equipment and technique system with the spinning solution
Standby fiber not only has decalescence between 20-38 DEG C in heating, phase transformation heat release during 28-10 DEG C in cooling
Function.But also modified acrylic fiber is provided with the modified slickness of hairless protein and elastic comfortableness.Its fiber
The textile garment and home textile product for developing and developing high-performance intelligent thermoregulating can be widely used for.
Embodiment 2：
A, the end hydroxy butadiene and methyl diphenylene diisocyanate taken between hydroxyl value about 0.8 are polymerized to contain about 4% in advance
End hydroxy butadiene-isocyanate prepolymer 15% of unreacted isocyanates root, takes carbon 18-20 n-alkane to be blended
Paraffin 80%, takes β methyl epoxy chloropropane 5%, and blending forms blend A equal to 2 kilograms, be warming up to 40 DEG C it is stand-by；
B |, take solid content 6%, mean molecule quantity 50KD fibroin protein water gel（Composition B）Equal to 15 kilograms, rise
Temperature to 50 DEG C it is stand-by, take with 12 kilograms of sodium sulfocyanate；Take fine by the Wet-spinning production standard acrylic fibers of solvent of sodium sulfocyanate and water
Tie up the sodium sulfocyanate method acrylic spinning liquid having polymerize used（Composition C）Equal to 150 kilograms, the solid content 6% of its polymer is permanent
Temperature is stand-by at 40 DEG C；Taking polyethylene glycol (1200 molecular weight) dimethylacrylate（Components D）Equal to 0.02 kilogram, normal temperature is treated
With.
C, composition B is taken to be put into 40 kilograms of wide mouth barrel, with dispersion emulsifying machine at 50 DEG C of constant temperature, with 400 revs/min right
Composition B is stirred, and is then slowly gradually added blend A, until seeing the irregular micro- glue of densely covered below 3 ц m under 300 microscopes
Capsule（About 10 minutes）.Subsequently, speed is slowly reduced to after 45 revs/min after stirring, continue to stir 30 minutes, then stop
Stirring, static 20 minutes of constant temperature, followed by, be naturally cooling to 35 DEG C it is static 48 hours, then add 12 kilograms of sodium sulfocyanates, and
Stirring make its be thoroughly mixed dissolving it is stand-by, be defined as blended liquid E.
D, followed by, takes composition C to be put into 300 kilograms of wide mouth barrel, with dispersion emulsifying machine at 45 DEG C of constant temperature, with 20
Composition C is stirred under rev/min and components D and blended liquid E is slowly added into until being sufficiently mixed, and continues stir about 20 minutes；In addition
Afterwards, stop stirring, be adjusted to filtering, the temperature of deaeration timeliness filtered, deaeration and timeliness；So far complete that there is phase-changing and temperature-regulating work(
The synthesis of the protein modified acrylic fiber spinning solution of energy.Prepared with the spinneret liquid by further wet spinning equipment and technique
Fiber not only have heating when 20-38 DEG C between decalescence, cooling when 28-10 DEG C during phase transformation heat release work(
Energy.But also modified acrylic fiber is provided with the modified slickness of fibroin albumen and gloss and soft comfortable.Its
Fiber can be widely used for the textile garment and home textile product for developing and developing high-performance intelligent thermoregulating.
Claims (5)
1. a kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function, it is characterised in that：The spinning solution into
Dividing includes：Blend A, composition B, composition C, components D and sodium sulfocyanate, the ratio of weight and number of each composition is：
Blend A：1.5-2
Composition B：14.5-15.5
Composition C：148-152
Components D：0.01-0.02
Sodium sulfocyanate：10-12
The blend A is by end hydroxy butadiene-isocyanate prepolymer, carbon 18-20 n-alkane paraffin, Beta-methyl ring
Oxygen chloropropane or tetrahydrofuran blending composition, wherein the ratio of weight and number of each composition is：
End hydroxy butadiene-isocyanate prepolymer：15-20
Carbon 18-20 n-alkane paraffin：82-75
β methyl epoxy chloropropane or tetrahydrofuran：3-5；
The composition B is：Protein hydrogel body；
The composition C is：Sodium sulfocyanate method acrylic spinning liquid；
The components D is：Polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate.
2. protein modified acrylic fiber spinning solution according to claim 1, it is characterised in that：The blend A middle-end hydroxyls
The hydroxyl value for the end hydroxy butadiene selected before base polybutadiene-isocyanate prepolymer synthesis is between 1 to 0.8, after synthesis
End hydroxy butadiene-isocyanate prepolymer unreacted isocyanates root containing 4%-6%.
3. protein modified acrylic fiber spinning solution according to claim 1, it is characterised in that：Poly- second two in the components D
The molecular weight of alcohol diacrylate or polyethylene glycol dimethacrylate is 1000-1500.
4. protein modified acrylic fiber spinning solution according to claim 1, it is characterised in that：The composition B protein water
Gelinite molecular weight is 30-80KD.
5. the preparation method of the protein modified acrylic fiber spinning solution in claim 1 ~ 4 described in any one, it is characterised in that：
Preparation process is：
1）Take end hydroxy butadiene-isocyanate prepolymer, carbon 18-20 n-alkane paraffin, β methyl epoxy chloropropane
Or tetrahydrofuran, blending form blend A, be warming up to 40-45 DEG C it is stand-by；
2）Take composition B stand-by between being warming up to 65 DEG C -50 DEG C；Take composition C heatings stand-by at 40-45 DEG C；
3）Composition B is taken to be put into container with dispersion emulsifying machine between 65 DEG C -50 DEG C of constant temperature, in the case of being stirred to composition B,
Blend A is added, after having added, with 300 revs/min of -500 revs/min of agitations until under the microscope it can be seen that blend A is newborn
3 microns and following particulate are melted into, continues to stir 5-10 minute, then uniformly reduces mixing speed to after 45 revs/min -50 revs/min
Continue stirring 30 minutes, stop stirring, constant temperature stands 20 minutes, then continue stirring 30 minutes with 45 revs/min -50 revs/min, it is natural
It is cooled to 35-40 DEG C and stands more than 48 hours, sodium sulfocyanate is then added in stirring, and stirring makes its mixed dissolution to be blended
Liquid E；
4）Take composition C to be put into container, stirred with dispersion emulsifying machine between 40 DEG C -45 DEG C of constant temperature, with 15 revs/min -20 revs/min
Mix point C and add components D and blended liquid E mixing, continue to stir 20 minutes, stop stirring, filtered, at deaeration and timeliness
Reason, obtains the protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610440883.7A CN105862165B (en) | 2016-06-20 | 2016-06-20 | A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610440883.7A CN105862165B (en) | 2016-06-20 | 2016-06-20 | A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105862165A CN105862165A (en) | 2016-08-17 |
| CN105862165B true CN105862165B (en) | 2017-10-17 |
Family
ID=56650997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610440883.7A Active CN105862165B (en) | 2016-06-20 | 2016-06-20 | A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105862165B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108903100B (en) * | 2018-06-27 | 2021-04-09 | 上海明制实业有限公司 | Novel intelligent clothing material and preparation method thereof |
| CN110067134A (en) * | 2019-05-23 | 2019-07-30 | 叶盛 | The preparation method of intelligent thermoregulating microcapsules cyst membrane and its application in textile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1851072A (en) * | 2006-05-26 | 2006-10-25 | 天津工业大学 | Polyacrylonitrile temperature-regulating fiber, and its manufacturing method |
| CN1900413A (en) * | 2005-07-23 | 2007-01-24 | 山东理工大学 | Acrylic fiber surface graft protein modified fiber and its producing method |
| CN102002771A (en) * | 2010-10-21 | 2011-04-06 | 大连工业大学 | Phase-change microcapsule heat storage and temperature adjustment polyacrylonitrile fiber and wet spinning preparation method thereof |
-
2016
- 2016-06-20 CN CN201610440883.7A patent/CN105862165B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900413A (en) * | 2005-07-23 | 2007-01-24 | 山东理工大学 | Acrylic fiber surface graft protein modified fiber and its producing method |
| CN1851072A (en) * | 2006-05-26 | 2006-10-25 | 天津工业大学 | Polyacrylonitrile temperature-regulating fiber, and its manufacturing method |
| CN102002771A (en) * | 2010-10-21 | 2011-04-06 | 大连工业大学 | Phase-change microcapsule heat storage and temperature adjustment polyacrylonitrile fiber and wet spinning preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 智能调温负离子牛奶蛋白纤维的试制研究;苗晓光;《毛纺科技》;20051231(第7期);第9-12页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105862165A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9713801B2 (en) | Self-healing material and preparation process thereof | |
| EP3819410A2 (en) | Plant-based functional polyester filament and preparation method thereof | |
| US4321173A (en) | Method for the preparation of finely dispersed polyurethane ureas | |
| CN105860025B (en) | Functional cross-links agent-isocyanate microcapsule and preparation method thereof | |
| CN105381767B (en) | A kind of polyurethane microcapsule encapsulating phase-change material and preparation method thereof | |
| CN105862165B (en) | A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof | |
| JP2014514400A (en) | Microcapsule curing agent | |
| CN108690223A (en) | A kind of layered double hydroxide/fibrination hole composite material and preparation method thereof | |
| CN106943969A (en) | A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate | |
| CN106884330B (en) | A kind of emulsion type carbon fiber sizing agent and its preparation method and application | |
| CN106480545B (en) | A kind of preparation method colouring alginate fiber | |
| DE60105021T2 (en) | COLOR-RESISTANT POLYMERIC DYES WITH A LOW VISCOSITY | |
| CN107794770B (en) | Method for preparing temperature-adjusting fabric by in-situ ultraviolet light initiated polymerization | |
| CN109576808A (en) | A kind of inorganic fire-retarded intelligent temperature adjusting fiber cellulose fiber and preparation method thereof | |
| CN110079279A (en) | A method of wax phase change microcapsules are prepared using lignin emulsified particle | |
| CN106751718A (en) | A kind of lubricant particles intelligently discharge high-abrasive material and preparation method thereof | |
| CN1459330A (en) | High temp. resistance capsule, and its prepn. method | |
| CN103966673A (en) | Fine-denier nylon raw material blend spinning masterbatch | |
| CN112940305A (en) | Preparation method of aramid pulp masterbatch, masterbatch obtained by preparation method and application of masterbatch | |
| CN109322008A (en) | A method of improving spandex properties of product stability | |
| CN112574549B (en) | Flame-retardant polyurethane microcapsule and preparation method and use method thereof | |
| DE102004041684A1 (en) | Molded body used as a fiber for clothing comprises polymers which form a network produced from the chemical coupling of functional groups, hydrogen bridges or polymeric or oligomeric structures helically combined with each other | |
| US3757004A (en) | Gelatin coacervate fibers | |
| CN108517128A (en) | A kind of liquid SBS modified pitch and preparation method thereof | |
| CN107419358A (en) | Selfreparing regeneration spandex based on microcapsules and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180711 Address after: 719000, Shenyang City, Shenyang City, Shaanxi, Shenyang City, Shenyang City, Yulin, Shennan Industrial Development Co., Ltd., office building, room 9, 913. Patentee after: Shaanxi fiber tempering materials research and Development Co., Ltd. Address before: 100101 No. 1, No. 1, century village, No. 8 Yuhui North Road, Chaoyang District, Beijing. Co-patentee before: Wu Chengqin Patentee before: Miao Xiaoguang |