CN105862165A - Protein-modified acrylic fiber spinning solution with phase-change temperature regulating function and preparation method thereof - Google Patents
Protein-modified acrylic fiber spinning solution with phase-change temperature regulating function and preparation method thereof Download PDFInfo
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- CN105862165A CN105862165A CN201610440883.7A CN201610440883A CN105862165A CN 105862165 A CN105862165 A CN 105862165A CN 201610440883 A CN201610440883 A CN 201610440883A CN 105862165 A CN105862165 A CN 105862165A
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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
- 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
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- 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
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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
- 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
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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
- 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
Abstract
The invention provides a protein-modified acrylic fiber spinning solution with a phase-change temperature regulating function and a preparation method thereof. The method comprises the following steps: blending and polymerizing two prefabricated solutions which are prepared in advance and are different in ingredients and a macromolecule bridging agent; and then performing filtering, defoaming and aging processes, thereby preparing the protein-modified acrylic fiber spinning solution with the phase-change temperature regulating function. According to the spinning solution, sodium thiocyanate and water are taken as solvents, the production process is relatively safe and environmentally friendly, and the recycling is relatively effective. Fiber prepared from the spinning solution through a wet-method spinning device has functions of phase-change heat absorption within a temperature range of 20-38 DEG C during a heating process, and phase-change heat emission within a range of 28-10 DEG C during a cooling process. The modified acrylic fiber has different comfort levels achieved by different modified proteins.
Description
Technical field
The invention belongs to functional high-polymer energy storage material field, particularly relate to a kind of interval in uniform temperature when heating up
The interior phase-change characteristic absorption heat leaning on material inherently, leans on when temperature is down to another low-temperature range by said temperature interval
Material phase-change characteristic inherently discharges the protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function of heat.By
The fiber that this spinning liquid produces can be widely used in textile garment and the home textile product developing and developing 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 this fibrous material
When temperature raises, fibrous material absorbs temperature energy, a kind of undulation degree of release temperature energy when ambient temperature reduces
Material.The protein modified acrylic fiber with phase-changing and temperature-regulating function is a branch of this material, and phase-changing and temperature-regulating merit to be manufactured
Can protein modified acrylic fiber, be necessary for first researching and developing and prepare the spinning liquid 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 the method that manufacture the protein modified acrylic spinning liquid with phase-changing and temperature-regulating function mainly have: 1) first
Produce the microencapsulation material with tripolycyanamide as shell with phase transition function, then with dispersant and water, microencapsulation material is divided
Dissipate, mix with the zinc oxide concentration protein modified acrylic fiber polymerization liquid with zinc chloride as solvent more than 40% afterwards, then pass through spinning
Technology of preparing is processed into the fiber accordingly with phase transition function.The manufacturing cost that this manufacturing technology has microcapsule is higher,
The elasticity of microcapsule shell is poor, and it is more difficult that microcapsule is thoroughly mixed dispersion in spray webbing liquid, and mixed spinning liquid is in spinning
Spinning process in easily cause stifled spinneret hole and the irregular phenomenon of fiber strength, production cost is the highest, and microcapsule is easy
Rupture and cause afunction and zinc chloride solvent that the molecular weight of protein can be made to diminish further, cause low molecular weight protein
The shortcoming that can not participate in the blended and building-up process of copolymerization and become waste liquid.And heterogeneity material in the waste liquid after spinning
Reclaim the most extremely difficult.2) first produce there is the microencapsulation material with tripolycyanamide as shell of phase transition function, then use dispersant
With water, microencapsulation material is disperseed, copolymerization is blended afterwards with acrylonitrile monemer, casein, zinc chloride, water, initiator and forms tool
There is the polymer base material mixed liquor of adhesion characteristic, then be processed into the fibre accordingly with phase transition function by spinning technology of preparing
Dimension.This manufacturing technology has acrylonitrile monemer and belongs to high-risk product in transportation, and freight is big, the most middle-size and small-size enterprise
Industry can not be allowed to produce because of environmental protection and safety problem, and spinning liquid polymerization process risk factor is the highest, the manufacture of microcapsule
Relatively costly, the elasticity of microcapsule shell is poor, is thoroughly mixed and disperses more difficult and be easily broken in copolymer fluid, mixed
Spinning liquid easily causes stifled spinneret hole and the irregular phenomenon of fiber strength in the spinning process of spinning, production cost the highest with
And zinc chloride solvent can make the molecular weight of protein diminish further, cause low molecular weight protein can not participate in being blended and copolymerization
Building-up process and the shortcoming that becomes waste liquid.And the recovery of heterogeneity material is the most extremely difficult in the waste liquid after spinning.
Therefore scientific research and market comsupton need to work out have higher phase change energy storage function, and processing is easier to, and produces
Cost is lower, the safer environmental protection of production process, the easier protein modified acrylon fibre with phase-changing and temperature-regulating function of devil liquor recovery
Dimension process technology.
Summary of the invention
It is an object of the invention to provide that a kind of the production as solvent has phase-changing and temperature-regulating function with sodium rhodanate and water
The synthetic method of protein modified acrylic fiber spinning liquid.Its course of processing is easier to, and production cost is lower, and production process is safer
Environmental protection, devil liquor recovery is easier to.
A kind of egg with phase-changing and temperature-regulating function produced in aforementioned manners of offer is provided
White modified acrylic fibres spinning liquid.Not only had when heating up by fiber prepared by wet spinning equipment with this spinning liquid
The function of phase transformation heat release after 20-38 DEG C of period decalescence, when cooling 28 DEG C.But also make modified acrylic fiber
Be provided with different protein modified after different comfortablenesses.Its fiber can be widely used for developing and exploitation high-performance intelligent thermoregulating
Textile garment and home textile product.
It is an object of the invention to realize by following technical solution.
A kind of protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function, the composition of described spinning liquid includes: altogether
Mixed thing A, composition B, composition C, components D and sodium rhodanate, 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 rhodanate: 10-12
Described blend A is by end hydroxy butadiene-isocyanate prepolymer, the n-alkane paraffin of carbon 18-20, Beta-methyl ring
Oxygen chloropropane or oxolane are blended composition, and the ratio of weight and number of the most each composition is:
End hydroxy butadiene-isocyanate prepolymer: 15-20
The n-alkane paraffin of carbon 18-20: 82-75
β methyl epoxy chloropropane or oxolane: 3-5；
Described composition B is: protein hydrogel body；
Described composition C is: sodium rhodanate method acrylic spinning liquid；
Described components D is: polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate.
Further, the terminal hydroxy group selected before end hydroxy butadiene-isocyanate prepolymer synthesis in described blend A
The hydroxyl value of polybutadiene end hydroxy butadiene-isocyanate prepolymer unreacted Han 4%-6% between 1 to 0.8, after synthesis
Isocyanates root.
Further, polyethyleneglycol diacrylate or the molecule of polyethylene glycol dimethacrylate in described components D
Amount is 1000-1500.
Further, described composition B protein hydrogel body molecular weight is 30-80KD.
A kind of protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function, preparation process is:
1) end hydroxy butadiene-isocyanate prepolymer, the n-alkane paraffin of carbon 18-20, β methyl epoxy chloropropane, are taken
Or oxolane, be blended formed blend A, be warmed up to 40-45 DEG C stand-by；
2), take composition B and be warming up between 65 DEG C-50 DEG C stand-by；Take composition C and heat up stand-by at 40-45 DEG C；
3), take composition B put in container with dispersion emulsifying machine between 65 DEG C-50 DEG C of constant temperature, to composition B stir situation
Under, add blend A, after having added, with 300 revs/min-500 revs/min agitations until under the microscope it can be seen that blend A
Be emulsified into 3 microns and particles below, continue agitation 5-10 minute, more uniformly reduce mixing speed to 45 revs/min-50 turns/
Continuing stirring 30 minutes after Fen, 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, in stirring, then add sodium rhodanate, and stirring makes its mixed dissolution obtain
Blended liquid E；
4), take composition C and put in container, with dispersion emulsifying machine between 40 DEG C-45 DEG C of constant temperature, with 15 revs/min-20 revs/min
Stirring composition C also adds components D and blended liquid E mixing, continues stirring 20 minutes, stops stirring, carries out filtering, deaeration and timeliness
Process, obtain the protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function.
The invention has the beneficial effects as follows:
1) present invention provides a kind of protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function.With this spinning liquid by wet
Fiber prepared by method spinning equipment not only have heat up time 20-38 DEG C period decalescence, cooling time 28 DEG C after
The function of phase transformation heat release.But also make modified acrylic fiber be provided with different protein modified after different comfortablenesses.It is fine
Dimension can be widely used for developing and developing textile garment and the home textile product of high-performance intelligent thermoregulating.
2) provide a kind of with sodium rhodanate and water the production as solvent to have the protein modified acrylon of phase-changing and temperature-regulating function fine
The synthetic method of dimension spinning liquid.Its course of processing is easier to, and production cost is lower, the safer environmental protection of production process, devil liquor recovery
It is easier to.
Accompanying drawing explanation
Fig. 1 is the process chart of preparation method of the present invention；
The phase-changing and temperature-regulating that Fig. 2 is spinning liquid of the present invention and the fiber that produces with this spinning liquid has inhales the schematic diagram of heat release.
Detailed description of the invention
A kind of protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function, the composition of described spinning liquid includes: altogether
Mixed thing A, composition B, composition C, components D and sodium rhodanate, 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 rhodanate: 10-12
Described blend A is by end hydroxy butadiene-isocyanate prepolymer, the n-alkane paraffin of carbon 18-20, Beta-methyl ring
Oxygen chloropropane or oxolane are blended composition, and the ratio of weight and number of the most each composition is:
End hydroxy butadiene-isocyanate prepolymer: 15-20
The n-alkane paraffin of carbon 18-20: 82-75
β methyl epoxy chloropropane or oxolane: 3-5；
Described composition B is: protein hydrogel body；
Described composition C is: the sulfur cyanogen being polymerized that sodium rhodanate and the Wet-spinning production standard acrylic fiber that water is solvent use
Acid sodium method acrylic spinning liquid；
Described components D is: polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate.Described blend A middle-end hydroxyl
The hydroxyl value of 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 Han 4%-6%.Polyethylene Glycol in described components D
The molecular weight of diacrylate or polyethylene glycol dimethacrylate is 1000-1500.Described composition B protein hydrogel
Body molecular weight is 30-80KD.
The preparation method of above-mentioned protein modified acrylic fiber spinning liquid, preparation process is:
A, take end hydroxy butadiene-isocyanate prepolymer, the n-alkane paraffin of carbon 18-20, β methyl epoxy chloropropane
Or oxolane, be blended formed blend A, be warmed up to 40-45 DEG C stand-by；
B, take composition B and be warming up between 65 DEG C-50 DEG C stand-by；Take composition C and heat up stand-by at 40-45 DEG C；
C, take composition B put in container with dispersion emulsifying machine between 65 DEG C-50 DEG C of constant temperature, to composition B stir in the case of,
It is gradually added blend A, after having added, with 300-500 rev/min of agitation until under the microscope it can be seen that blend A is newborn
It is melted into 3 microns and particles below, continues agitation 5-10 minute afterwards, the most uniformly reduce mixing speed to 45 rev/min-50
Continue stirring after rev/min and (make " end hydroxy butadiene-isocyanate prepolymer " in microgranule and Beta-methyl epoxy chlorine in 30 minutes
Propane or oxolane dissociate to microparticle surfaces and progressively occur interfacial polymerization shelling anti-with the protein in extracorpuscular water or water
Should), then stop stirring, static 20 minutes of constant temperature, make the microgranule of formation that interface shelling the most progressively to occur during this
The reaction thickened, then for the reunion preventing between the microgranule in this course of reaction, again with mixing speed 45 revs/min-50 turns/
Point continue stirring 30 minutes, subsequently, be naturally cooling to 35-40 DEG C static more than 48 hours, the shell making microparticle surfaces be formed enters
There is finer and close interfacial reaction in one step, is then gradually added sodium rhodanate in stirring, and stirring makes its mixed dissolution to be total to
Mixed liquid E；
D, take composition C and put in container, with dispersion emulsifying machine (such as 15 rev/min-20 between 40 DEG C-45 DEG C of constant temperature, with low speed
Rev/min) stirring composition C add components D and blended liquid E mix and makes it uniform, continue stir about 20 minutes, stop stirring,
Carry out filtering, (static placement makes the viscous consistency one of liquid for deaeration (static placement makes the air bubble in liquid escape) and timeliness
Cause) process, obtain the protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function.
Preparation method for the spray webbing liquid of wet spinning provided by the present invention refers to that one first uses synthesis point mixing
Liquid, then point mixed liquor is blended copolymerization again with crosslinking bridging agent terminates, then by filtration, deaeration, timeliness is produced has phase transformation
The synthetic method of the protein modified acrylic fiber spinning liquid of temperature adjustment function.
Its material used is: sodium rhodanate, the Wet-spinning production standard acrylic fiber as solvent with sodium rhodanate and water
The sodium rhodanate method acrylic spinning liquid being polymerized that uses, the phase transformation material being microcapsule core with the n-alkane paraffin of carbon 18-20
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, using the hydroxyl in β methyl epoxy chloropropane or oxolane and water as system
Take the interfacial polymerization auxiliary material of microcapsule shell in phase-change microcapsule and protein-colloid mixed liquor, using protein as to acrylon
Material modified, to have Polyethylene Glycol (1000-1500) diacrylate or the Polyethylene Glycol (1000-of phase transition function equally
1500) dimethylacrylate is copolymerization bridging materials during the blended copolymerization again of point mixed liquor；The terminal hydroxy group polybutadiene of its synthesis
Isocyanates in alkene-isocyanate prepolymer refers to diisocyanate (such as toluene di-isocyanate(TDI), hexa-methylene two isocyanide
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, the end hydroxy butadiene-isocyanate prepolymer after its synthesis requires containing about 4-6% unreacted isocyanates root；Its
The protein of indication is molecular weight main body fibroin protein between 30-80KD or hair protein or collagen protein.Microcapsule
With in spray webbing liquid without tripolycyanamide, microcapsules has preferable elasticity, is difficult to rupture under pressure and expansion status.
Its concrete preparation method and step are as follows in the present embodiment:
A, take hydroxyl value end hydroxy butadiene between 1 to 0.8 and hexamethylene diisocyanate or diphenyl methane two
Isocyanate prepolymers becomes the end hydroxy butadiene-isocyanate prepolymer 15-20% containing 4-6% unreacted isocyanates root,
Take n-alkane paraffin (net purchase) 82-75% of carbon 18-20, take β methyl epoxy chloropropane (net purchase) or oxolane (net purchase)
3-5%, is blended and forms blend A equal to 1.5-2 kilogram, be warmed up to 40-45 DEG C stand-by.
B, take solid content 4-6%, molecular weight protein hydrogel body (composition B) etc. between 30-80KD (thousand molecular weight)
In 15 kilograms (protein oneself preparations of the net purchase between with 30-80KD), it is warming up between 65 DEG C-50 DEG C stand-by；Take sulfur cyanogen
10-13 kilogram of sodium of acid；Take the sulfur being polymerized that the Wet-spinning production standard acrylic fiber as solvent with sodium rhodanate and water uses
Sodium cyanate (NaOCN) method acrylic spinning liquid (composition C) is equal to 150 kilograms (available in Daqing petrochemical company Acrylic Fibers Plant), consolidating of its polymer
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) is equal to 0.01-0.02 kilogram (net purchase), and room temperature is stand-by.
C, take in the wide mouth barrel that composition B puts into 40-50 kilogram, with dispersion emulsifying machine between 65 DEG C-50 DEG C of constant temperature, with
Composition B being stirred, being the most slowly gradually added blend A, until seeing 3 densely covered ц under 300 microscopes by 300-500 rev/min
Below m microcapsule (about 10 minutes).Subsequently, make speed slowly reduce to 45 revs/min-50 revs/min after stirring and continue stirring
30 minutes, then stop stirring, static 20 minutes of constant temperature.Stirring is continued under low whipping speed is 45 revs/min-50 revs/min afterwards
30 minutes.Followed by, be naturally cooling to 35-40 DEG C static more than 48 hours, be subsequently adding 10-12 kilogram of sodium rhodanate, and stir
Mix make its be thoroughly mixed dissolving stand-by, be defined as blended liquid E.
D, followed by, takes in the wide mouth barrel that composition C puts into 200-300 kilogram, with dispersion emulsifying machine 40 DEG C-45 of constant temperature
Between DEG C, to stir composition C under 15 revs/min-20 revs/min and to be slowly added into components D and blended liquid E until being sufficiently mixed, and continue
Continuous stir about 20 minutes.Followed by, stop stirring, be adjusted to filter, the temperature of deaeration timeliness carries out filtering, deaeration and timeliness.Extremely
This synthesis completing there is the protein modified acrylic fiber spinning liquid of phase-changing and temperature-regulating function.With this spinning liquid by the wettest
Fiber prepared by method spinning equipment and technique not only have heat up time 20-38 DEG C between decalescence, cooling time 28-
The function of 10 DEG C of period phase transformation heat releases.But also make modified acrylic fiber be provided with different protein modified after difference comfortable
Property.Its fiber can be widely used for developing and developing textile garment and the home textile product of high-performance intelligent thermoregulating.
The present invention is expanded on further the most by the following specific embodiments, but is not limited to the scope of the present invention.
Embodiment 1:
A, the end hydroxy butadiene taking hydroxyl value about 0.9 and hexamethylene diisocyanate are polymerized to containing about 5% unreacted in advance
End hydroxy butadiene-the isocyanate prepolymer 20% of isocyanates root, the n-alkane taking carbon 18-20 is blended paraffin 77%,
Take oxolane 3%, be blended and form blend A equal to 1.8 kilograms, be warmed up to 45 DEG C stand-by.
B, taking solid content 5%, the hair protein water gel (composition B) of mean molecule quantity 60KD is equal to 15 kilograms, heats up
Stand-by to-50 DEG C；Take sodium rhodanate 11 kilograms；Take the Wet-spinning production standard acrylic fiber as solvent with sodium rhodanate and water to make
Sodium rhodanate method acrylic spinning liquid (composition C) being polymerized 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) is equal to 0.02 kilogram, and room temperature is stand-by.
C, take in the wide mouth barrel that composition B puts into 50 kilograms, with dispersion emulsifying machine 50 DEG C of constant temperature, with 500 revs/min right
Composition B stirs, and is the most slowly gradually added composition A, until seeing the densely covered 3 following microcapsule of ц m (about 10 points under 300 microscopes
Clock).Subsequently, after making speed slowly reduce to 50 revs/min after stirring, continue stirring 30 minutes, then stop stirring, constant temperature
Static 20 minutes.Stirring 30 minutes is continued under low whipping speed is 50 revs/min afterwards.Followed by, be naturally cooling to 40 DEG C static
50 hours, it is subsequently adding 11 kilograms of sodium rhodanates, and stirs that to make it be thoroughly mixed dissolving stand-by, be defined as blended liquid E.
D, followed by, takes in the wide mouth barrel that composition C puts into 300 kilograms, with dispersion emulsifying machine between 45 DEG C of constant temperature, with
Stir composition C under 20 revs/min and be slowly added into components D and blended liquid E until being sufficiently mixed, and continuing stir about 20 minutes.Again
Afterwards, stop stirring, be adjusted to filter, the temperature of deaeration timeliness carries out filtering, deaeration and timeliness.So far complete that there is phase-changing and temperature-regulating
The synthesis of the protein modified acrylic fiber spinning liquid of function.With this spinning liquid by further wet spinning equipment and technique system
Standby fiber not only has decalescence between 20-38 DEG C when heating up, 28-10 DEG C of period phase transformation heat release when cooling
Function.But also make modified acrylic fiber be provided with the modified slickness of hairless protein and elastic comfortableness.Its fiber
Can be widely used for developing and developing textile garment and the home textile product of high-performance intelligent thermoregulating.
Embodiment 2:
A, the end hydroxy butadiene taken between hydroxyl value about 0.8 and methyl diphenylene diisocyanate are polymerized to containing about 4% the most anti-in advance
End hydroxy butadiene-the isocyanate prepolymer 15% of the isocyanates root answered, the n-alkane taking carbon 18-20 is blended paraffin
80%, take β methyl epoxy chloropropane 5%, be blended and form blend A equal to 2 kilograms, be warmed up to 40 DEG C stand-by；
B |, take solid content 6%, the fibroin protein water gel (composition B) of mean molecule quantity 50KD be equal to 15 kilograms, be warming up to
50 DEG C stand-by, takes with sodium rhodanate 12 kilograms；Take the Wet-spinning production standard acrylic fiber as solvent with sodium rhodanate and water to make
Sodium rhodanate method acrylic spinning liquid (composition C) being polymerized equal to 150 kilograms, the solid content 6% of its polymer, constant temperature exists
40 DEG C stand-by；Taking polyethylene glycol (1200 molecular weight) dimethylacrylate (components D) is equal to 0.02 kilogram, and room temperature is stand-by.
C, take in the wide mouth barrel that composition B puts into 40 kilograms, with dispersion emulsifying machine 50 DEG C of constant temperature, with 400 revs/min right
Composition B stirs, and is the most slowly gradually added blend A, until seeing the irregular micro-glue of 3 densely covered below ц m under 300 microscopes
Capsule (about 10 minutes).Subsequently, after making speed slowly reduce to 45 revs/min after stirring, continue stirring 30 minutes, then stop
Stirring, static 20 minutes of constant temperature, followed by, be naturally cooling to 35 DEG C static 48 hours, be subsequently adding 12 kilograms of sodium rhodanates, and
It is stand-by that stirring makes it be thoroughly mixed dissolving, is defined as blended liquid E.
D, followed by, takes in the wide mouth barrel that composition C puts into 300 kilograms, with dispersion emulsifying machine 45 DEG C of constant temperature, with 20
Stir composition C under rev/min and be slowly added into components D and blended liquid E until being sufficiently mixed, and continuing stir about 20 minutes；In addition
After, stop stirring, be adjusted to filter, the temperature of deaeration timeliness carries out filtering, deaeration and timeliness；So far complete that there is phase-changing and temperature-regulating merit
The synthesis of the protein modified acrylic fiber spinning liquid of energy.Prepared by further wet spinning equipment and technique with this spray webbing liquid
Fiber not only have heat up time 20-38 DEG C between decalescence, cooling time 28-10 DEG C period phase transformation heat release merit
Energy.But also make modified acrylic fiber be provided with the modified slickness of fibroin albumen and gloss and soft comfortable.Its
Fiber can be widely used for developing and developing textile garment and the home textile product of high-performance intelligent thermoregulating.
Claims (5)
1. a protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function, it is characterised in that: the one-tenth of described spinning liquid
Dividing and include: blend A, composition B, composition C, components D and sodium rhodanate, 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 rhodanate: 10-12
Described blend A is by end hydroxy butadiene-isocyanate prepolymer, the n-alkane paraffin of carbon 18-20, Beta-methyl ring
Oxygen chloropropane or oxolane are blended composition, and the ratio of weight and number of the most each composition is:
End hydroxy butadiene-isocyanate prepolymer: 15-20
The n-alkane paraffin of carbon 18-20: 82-75
β methyl epoxy chloropropane or oxolane: 3-5；
Described composition B is: protein hydrogel body；
Described composition C is: sodium rhodanate method acrylic spinning liquid；
Described components D is: polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate.
Protein modified acrylic fiber spray webbing liquid the most according to claim 1, it is characterised in that: described blend A middle-end hydroxyl
The hydroxyl value of 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 Han 4%-6%.
Protein modified acrylic fiber spray webbing liquid the most according to claim 1, it is characterised in that: poly-second two in described components D
The molecular weight of alcohol diacrylate or polyethylene glycol dimethacrylate is 1000-1500.
Protein modified acrylic fiber spinning liquid the most according to claim 1, it is characterised in that: described composition B protein water
Gelinite molecular weight is 30-80KD.
5. the preparation method of protein modified acrylic fiber spinning liquid described in any one in claim 1 ~ 4, it is characterised in that:
Preparation process is:
1) end hydroxy butadiene-isocyanate prepolymer, the n-alkane paraffin of carbon 18-20, β methyl epoxy chloropropane are taken
Or oxolane, be blended formed blend A, be warmed up to 40-45 DEG C stand-by；
2) take composition B and be warming up between 65 DEG C-50 DEG C stand-by；Take composition C and heat up stand-by at 40-45 DEG C；
3) take composition B put in container with dispersion emulsifying machine between 65 DEG C-50 DEG C of constant temperature, to composition B stir in the case of,
Add blend A, after having added, with 300 revs/min-500 revs/min agitations until under the microscope it can be seen that blend A is newborn
It is melted into 3 microns and particles below, continues agitation 5-10 minute, more uniformly reduce mixing speed to after 45 revs/min-50 revs/min
Continuing stirring 30 minutes, stop stirring, constant temperature stands 20 minutes, then continues stirring 30 minutes with 45 revs/min-50 revs/min, natural
It is cooled to 35-40 DEG C and stands more than 48 hours, in stirring, then add sodium rhodanate, and stirring makes its mixed dissolution to be blended
Liquid E；
4) take composition C and put in container, with dispersion emulsifying machine between 40 DEG C-45 DEG C of constant temperature, stir with 15 revs/min-20 revs/min
Mix point C and add components D and blended liquid E mixing, continuing stirring 20 minutes, stop stirring, carrying out filtering, at deaeration and timeliness
Reason, obtains the protein modified acrylic fiber spinning liquid with phase-changing and temperature-regulating function.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108903100A (en) * | 2018-06-27 | 2018-11-30 | 徐玉玉 | A kind of intelligence clothes new 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 |
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|---|---|---|---|---|
| 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 |
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| 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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108903100A (en) * | 2018-06-27 | 2018-11-30 | 徐玉玉 | A kind of intelligence clothes new 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 |
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| CN105862165B (en) | 2017-10-17 |
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