CN104404647B - Hydrophilic polyesters fiber that a kind of Cellulose nanocrystal is modified and preparation method thereof - Google Patents
Hydrophilic polyesters fiber that a kind of Cellulose nanocrystal is modified and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to modified hydrophilic polyesters fiber of a kind of Cellulose nanocrystal and preparation method thereof.The problem that it needs to solve normal polyester hydrophilic difference.Its preparation method is according to the following steps: 1) by Cellulose nanocrystal water slurry and 75～85% ethylene glycol mixing of weight, removes the moisture in mixed liquor, is prepared as the glycolic suspension of Cellulose nanocrystal；2) glycolic suspension and the p-phthalic acid of Cellulose nanocrystal are made mixed serum；3) ethylene glycol and the catalyst of surplus are made catalyst liquid；4) mixed serum, catalyst liquid and heat stabilizer agitating heating in a kettle. carry out esterification for the first time；5) add polyhydroxy-alcohol, carry out second time esterification；6) evacuation polycondensation obtains hydrophilic polyesters melt, cooling, pelletize, obtains hydrophilic polyesters section；7) hydrophilic polyesters is cut into slices melt spinning, the hydrophilic polyesters fiber that preparation is modified.
Description
Technical field
The present invention relates to the hydrophilic polyesters section of a kind of nano modification, and relate to the hydrophilic poly-of a kind of Cellulose nanocrystal modification
The preparation method of ester fiber.
Background technology
China's chemical fibre yield accounts for the 70% of world's chemical fibre total output, is the most important raw material of textile industry.Wherein,
Polyester fiber is most important synthetic fibers kind, its state of development directly influence China's Development of Textile Industry integral level and
Competitiveness.Although China's polyester production capacity, yield occupy the first in the world, but China's polyester fiber industry still faces some need solve
Outstanding problem certainly.The production of conventional polyester fiber, scientific research have been eliminated in the exploitation of polyester fiber by developed countries at present
Strength is concentrated mainly on exploitation and the application of Speciality Pet Fiber.
The performance of polyester molecule its excellence of structures shape, PET polyester molecule structure height is regular, and molecules align is tight, molecule
Containing rigidity benzene ring structure in segment, therefore PET has good physical and mechanical property.Polyester fiber intensity is high, well-pressed,
The advantages such as wear-resisting and good stability of the dimension make it be developed rapidly.Due to the close macromolecular structure of polyester fiber and shortage
Hygroscopicity group, it is more very different than natural fibers such as cottons in terms of comfortableness.At 20 DEG C, under 65% relative humidity, polyester
The regain of fiber only has 0.4%, and cotton regain under identical humiture is up to 8.0%.Polyester hygroscopicity is poor, is easily generated quiet
Electrical phenomena, has had a strong impact on the comfortableness of clothes.Conventional polyester fiber does not has hydrophilic group due to polyester fiber, and molecular stuffing is tight
Close, therefore dyestuff hardly enters the inside of fiber, and one method can not be used in terms of dyeing to dye.Therefore to poly-
Ester fiber carries out moisture-absorption modified, improves the ability of its water management, is the importance expanding polyester fiber application further.
Specifically, can pass through copolymerization, be blended, coating, surface process, realize the functionalization of polyester fiber.For copolymerization
Or for blending and modifying, the most conventional modified component mainly has several big classes such as inorganic particle, organic monomer, polymer.Inhaling
Wet modified aspect, conventional modified method includes copolymerization and is blended, conventional modified component include polypropylene glycol, Polyethylene Glycol,
Tetramethylolmethane etc..Such as, patent WO2005019301 (A1) uses and introduces a small amount of gathering in polyethylene terephthalate
Propylene glycol, replaces diol segment structure in the way of block, and the co-polymerization modified polyester fiber obtained has good hygroscopicity.Specially
Profit US2002019508 (A1) and WO2005019301 (A1) all select Polyethylene Glycol to be modifying agent, and the hygroscopicity obtained is good
Co-polymerization modified polyester fiber.After patent WO0012793 (A1) selects Polyethylene Glycol and tetramethylolmethane modified polyester fiber, it is inhaled
Moist suitable with Cotton Gossypii and other naturally occurring or synthetic cellulose fibres.Patent CN200910101497.5 will be containing meerschaum and people
The inorganic particle making zeolite joins polyester fondant, obtains high-hydroscopicity, inhales the modified polyester fiber with blends that part response that discharges water is fast.
The silica-based inorganic particle of 1-20wt% is added in polyester by patent US6838173, obtains the good modification of hygroscopicity and gathers
Ester, has good wearing comfort.
Fewer as the research report of modification by copolymerization monomer currently with polyhydroxy-alcohol.On the basis of block copolymer, choosing
Select suitable polyhydroxy-alcohol as modified component, prepare copolyesters.Currently with polyhydroxy-alcohol as the research of modification by copolymerization monomer
It is concentrated mainly on aliphatic copolyester aspect.DOLLK et al. uses citric acid to react with sorbitol, prepares water-soluble polyester,
Ajay Kumar et al. generates copolyesters PAOS poly (apidic to the reaction of sorbitol, adipic acid and ethohexadiol
Acid-co-octanediol-co-sorbitol) studied；Ning et al. have studied polyhydroxy functional polyester, utilizes aliphatic
Suberic acid and aliphatic polyhydric alcohol synthesising biological degradable polyester.Polyhydroxy-alcohol is when polyreaction, and unnecessary hydroxyl is not participated in
Reaction, is free in polyester, and free hydroxyl has good hydrophilic.The polyhydroxy-alcohol such as sorbitol that the present invention uses,
Xylitol, tetramethylolmethane etc. is added in copolymer by trace, while not changing polyester mobility and spinning properties, again may be used
To improve the hydrophilic of polyester.
Cellulose has the characteristics such as degradable, low cost and environmental friendliness as a kind of reproducible natural polyols.Fiber
Unbodied part, remaining cellulose crystals are fallen in element hydrolysis under conditions of acid, control reaction condition and can obtain nano-scale fiber
Cellulose crystal, normally referred to as Cellulose nanocrystal.A diameter of several nanometers that Cellulose nanocrystal obtains after passing through acid hydrolysis are to tens
Nanometer, a length of 10～1000 nanometers.Cellulose nanocrystal has the characteristic that degree of crystallinity is high, hydrophilic is strong, intensity is big.Fiber
Element nanocrystal surface, rich in hydroxyl, has stronger reactivity, and hydrophilic is high, has the strongest hygroscopicity.Use the most poly-
The mode closed adds Cellulose nanocrystal, while not changing polyester construction, introduces finely disseminated cellulose in polyester matrix
Nanocrystalline, the water absorbing properties of reinforced polyester.High-specific surface area and the substantial amounts of hydroxyl of Cellulose nanocrystal can improve polyester fiber
Hydrophilic.Cellulose nanocrystal is the granule of nano-scale, good dispersion, on the premise of not affecting Direct-spinning of PET Fiber, and cellulose
Nanocrystalline addition can improve the hydrophilic of polyester.The work of presently relevant aspect also rarely has report.The method using in-situ polymerization,
Avoid Cellulose nanocrystal to reunite, and select nano level filler, it is to avoid the functional defect that common micro-scaled filler causes, it is ensured that change
The hydrophilic polyesters fiber of property has high spinnability and high-hydrophilic.Hydrophilic fibers prepared by the method, technique is simple, increases cost
Seldom, modified effect is good.
Summary of the invention
The problem that the present invention needs to solve normal polyester hydrophilic difference, it is provided that the hydrophilic polyesters fibre that a kind of Cellulose nanocrystal is modified
Dimension.
The present invention needs to solve another technical problem and is to provide the modified hydrophilic polyesters fiber of a kind of above-mentioned Cellulose nanocrystal
Preparation method.
The hydrophilic polyesters fiber that the Cellulose nanocrystal of the present invention is modified, the fibroblast hydrophilic polyesters of hydrophilic polyesters fiber is gathered by PET
Ester, Cellulose nanocrystal, polyhydroxy-alcohol and heat stabilizer composition；
Wherein, Cellulose nanocrystal content in PET polyester is 0.5～2wt%；Polyhydroxy-alcohol content in PET polyester be 0.2～
1wt%；The addition of heat stabilizer is 50ppm～200ppm, and its radix is the p-phthalic acid that PET polyester is synthesized
Quality；
Cellulose nanocrystal modified polyester fiber of the present invention has the Cellulose nanocrystal of hydrophilic moisture absorption oh group and many containing abundant
Hydroxyl alcohol.Described Cellulose nanocrystal is dispersed in hydrophilic polyesters with nano-grade size, and polyhydroxy-alcohol copolymerization is hydrophilic poly-
In ester macromolecular chain.The surface water contact angle of described fibroblast hydrophilic polyesters is 45～60 °, described hydrophilic polyesters fiber melt
Being 245～255 DEG C, regain is 0.8～3%.Other performances are identical with conventional polyester fiber.
A length of below the 500nm of described Cellulose nanocrystal, nanocrystalline diameter is in below 50nm, draw ratio L/D
It is 10～15；Described polyhydroxy-alcohol is the one in tetramethylolmethane, xylitol and sorbitol；Described heat stabilizer is phosphoric acid
Trimethyl or triphenyl phosphate.
The present invention is by introducing the nano level Cellulose nanocrystal with high-hydrophilic in polyester matrix, and ties at polyester
Structure introduces hydrophilic oh group, prepares, by the method for melt spinning, the hydrophilic polyesters fiber that Cellulose nanocrystal is modified.
The hydrophilic polyesters fiber of the Cellulose nanocrystal modification that the present invention is concretePreparation method, according to the following steps:
1) by Cellulose nanocrystal water slurry and 75～85% ethylene glycol mixing of weight, remove moisture in mixed liquor, be prepared as fiber
The glycolic suspension that element is nanocrystalline；Wherein Cellulose nanocrystal content in PET polyester is 0.5～2wt%.This step is led to
Cross solvent exchange method and Cellulose nanocrystal is dispersed in ethylene glycol the glycolic suspension being prepared as Cellulose nanocrystal；Adopt
With molecular sieve, meerschaum etc. absorbs the moisture in suspension, preferred molecular sieve.
2) by step 1) the glycolic suspension of Cellulose nanocrystal and p-phthalic acid put into making beating still and make mixed serum；
Step 1) ethylene glycol consumption and step 3) ethylene glycol surplus sum, i.e. the whole consumption of ethylene glycol and p-phthalic acid mole
Ratio is 1.2～1.8: 1；
3) ethylene glycol and the catalyst of surplus being put into preparation still, stir and make catalyst liquid, catalyst is antimony-based catalyst,
Catalyst amount is 200～500ppm, and radix is p-phthalic acid (PTA) quality；
4) by step 2) mixed serum, step 3) catalyst liquid and heat stabilizer squeeze into reactor, heating is carried out for the first time
Esterification；Wherein heat stabilizer is phosphoric acid ester stabilizer, and the addition of heat stabilizer is 50～200ppm, and radix is to benzene
Dioctyl phthalate (PTA) quality；Esterification reaction temperature is 220～250 DEG C for the first time, and pressure is 0.1～0.3MPa, esterification
Time is 1～3h.
Ester by-products is water, in the first esterification reaction process, separates water into out by fractionating column and is collected, consumption
Cylinder test collecting amount, calculates theoretical water yield according to monomer reaction equation, calculates esterification performance further according to water yield.
5) when by-product collecting amount to be esterified reaches the 85-92% of theoretical value, add polyhydroxy-alcohol, carry out second time and be esterified anti-
Should, wherein polyhydroxy-alcohol content in the polyester is 0.2～1wt%；Esterification reaction temperature is 240～260 DEG C for the second time, normal pressure
Under the conditions of carry out, reaction time of esterification is 0.5～1h；
6) by final carboxylate, further evacuation polycondensation obtains hydrophilic polyesters (this hydrophilic polyesters is fibroblast hydrophilic polyesters) melt,
Melt discharging, cooling, pelletizing are obtained hydrophilic polyesters section；Polycondensation reaction temperature is 270～290 DEG C.Conventional polycondensation reaction
Including precondensation and whole polycondensation reaction, precondensation pressure is 200～2000Pa, and the response time is 0.5～1h；During whole polycondensation reaction
For fine vacuum, pressure ＜ 100Pa, the response time is 1～2h.
7) by through modified hydrophilic polyesters section melt spinning, the hydrophilic polyesters fiber that Cellulose nanocrystal is modified is prepared.
The melt spinning of this step, spinning temperature is 260～300 DEG C, and spinning speed is 800～3000m/min, and draft temperature is
60～80 DEG C, total stretching ratio is 3～5 times.
As preferably, a length of below the 500nm of described Cellulose nanocrystal, nanocrystalline diameter at below 50nm,
Draw ratio L/D is 10～15.
As preferably, described polyhydroxy-alcohol is the one in tetramethylolmethane, xylitol and sorbitol；Antimony-based catalyst is vinegar
Acid antimony or antimony glycol, the addition of catalyst is 300～400ppm；Phosphoric acid ester stabilizer is trimethyl phosphate or phosphorus
Triphenyl phosphate ester.
Compared with prior art, the innovation effect of the present invention is:
(1) present invention uses and adds Cellulose nanocrystal as improving the hydrophilicity of polyester, uses the mode of in-situ polymerization to prepare hydrophilic
Polyester.Cellulose nanocrystal contains multiple hydroxyl, and the accessibility of hydroxyl is higher, has the highest hydrophilic ability.Cellulose is received
Meter Jing can be good at being dispersed in polyester matrix, and the polyester obtained by the way of suspended dispersed and in-situ polymerization has very well
Hydrophilicity.
(2) polyhydroxy-alcohol that the present invention adds improves the hydrophilicity of polyester, and polyhydroxy-alcohol contains multiple hydroxyl, second
The esterification stage adds polyhydroxy-alcohol alcohol and can ensure that when terminal hydroxy group reaction accesses polyester backbone section, pendant hydroxyl group does not react trip
From outside main chain, the polyester construction of formation has the performance of polyester, and has the hydrophilicity of hydroxyl.
(3) present invention adds Cellulose nanocrystal and the addition of sorbitol are the least, improve the same of hydrophilic effect in guarantee
Time do not affect the performance of polymerization process and polyester.
(4) the Cellulose nanocrystal granule that the present invention adds is Nano grade, is dispersed in polyester by the way of in-situ polymerization
In matrix, dispersity is good, does not affect the performance of polyester, can guarantee that again the spinnability of polyester.
(5) technique of the inventive method is simple, can carry out, it is not necessary to change production equipment in original polymerization equipment.
Being suitable for large-scale production, cost increases little.
(6) modified polyester fiber of the present invention has the highest hydrophilic and higher regain 0.8～3%, and fabric moisture is arranged
Antiperspirant performance is good, can be used for underwear, sweat shirt and lining.
Accompanying drawing explanation
Fig. 1 is the TEM image of Cellulose nanocrystal.
Fig. 2 is the hydrophilic polyesters SEM image that in embodiment 2, Cellulose nanocrystal is modified.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1.
The hydrophilic polyesters section of Cellulose nanocrystal modification is carried out by the mode of in-situ polymerization, and polymerization is intermittence type polymerization work
Skill, its formula is as follows:
Cellulose nanocrystal is dispersed in water in the form of a suspension in water, and the concentration in suspension is 1wt%.Nanocrystalline
Length is shown in Fig. 1 at below 500nm, diameter at below 50nm, the microscopic appearance of Cellulose nanocrystal.According to polyreaction
Material rate forms, and weighs p-phthalic acid (PTA) and ethylene glycol that good a certain amount of mol ratio is 1: 1.4.By cellulose
Nanocrystalline water slurry joins in load weighted 80% ethylene glycol solvent, utilizes the moisture in molecular sieve adsorption suspension, then
Prepare the glycolic suspension containing Cellulose nanocrystal.Cellulose nanocrystal in the glycolic suspension of Cellulose nanocrystal
Content is the 0.5wt% of final polyester quality.By above-mentioned Cellulose nanocrystal glycolic suspension with the most load weighted to benzene
Dioctyl phthalate is squeezed in making beating still and is prepared as mixed serum.Then catalyst glycol antimony (300ppm is relative to PTA) is joined
Residue ethylene glycol is prepared as catalyst mixed liquid.Finally by Cellulose nanocrystal ethylene glycol p-phthalic acid mixed serum, second two
Alcohol antimony catalyst liquid and heat stabilizer trimethyl phosphate (100ppm is relative to PTA) squeeze into reactor, and heating is carried out for the first time
Esterification.The temperature of the first esterification is 230 DEG C, and the response time is 3h, and the pressure of reaction is 0.3MPa.Pass through fractional distillation
Water byproduct is separated and is collected by tower, tests collecting amount with graduated cylinder, calculates theoretical water outlet according to monomer reaction equation
Amount, calculates esterification performance further according to water yield.When 90% that water yield is theoretical value, pressure drops to normal pressure, is subsequently adding
Polyhydroxy-alcohol sorbitol carries out the second esterification.The addition of sorbitol is the 0.2wt% of final polyester quality.Second esterification is anti-
The temperature answered is 240 DEG C, and the response time is 1h, and reaction pressure is normal pressure.After completing esterification, carry out under low vacuum state
Precondensation and high vacuum state under whole polycondensation reaction, the prepolymerization reaction time is 1h, and whole polycondensation reaction time is 2h, final minification
Poly-reaction temperature is 280 DEG C, and vacuum during whole polycondensation reaction is 80Pa.After polycondensation completes, by melt discharging, cool down, cut
Grain, prepares the hydrophilic polyesters section of modification.
(2) the hydrophilic polyesters section after modification enters melt spinning, and its spinning technique is: spinning temperature is 270 DEG C, spins
Silk speed is 900m/min, and draft temperature is 60 DEG C, and one stretching ratio is 2.2, and two road stretching ratios are 1.15；Prepare
Hydrophilic polyester fiber.
The intrinsic viscosity of the hydrophilic polyesters section that Cellulose nanocrystal palpus is modified is 0.615dL/g, and fusing point is 250.2 DEG C, section
Surface water contact angle is 58 °.The regain of Cellulose nanocrystal modified polyester fiber is 0.9%, has good hydrophilicity.
Embodiment 2:
The hydrophilic polyesters section of Cellulose nanocrystal modification is carried out by the mode of in-situ polymerization, and polymerization is batch polymerization processes, its
Formula is as follows:
Cellulose nanocrystal is dispersed in water in the form of a suspension in water, and the concentration in suspension is 1wt%.Nanocrystalline
Length is at below 500nm, and diameter is at below 50nm, and Cellulose nanocrystal form is identical with embodiment 1.According to polyreaction
Material rate composition, weigh p-phthalic acid (PTA) and ethylene glycol that good a certain amount of mol ratio is 1: 1.6.By fiber
The nanocrystalline water slurry of element joins in 80% ethylene glycol solvent weighed, and utilizes the moisture in molecular sieve adsorption suspension, so
After prepare the glycolic suspension containing Cellulose nanocrystal.Cellulose nanometer in the glycolic suspension of Cellulose nanocrystal
Brilliant content is the 1wt% of final polyester quality.By above-mentioned Cellulose nanocrystal glycolic suspension with the most load weighted to benzene
Dioctyl phthalate is squeezed in making beating still and is prepared as mixed serum.Then catalyst glycol antimony (400ppm is relative to PTA) is joined
Load weighted residue ethylene glycol is prepared as catalyst mixed liquid.Finally by Cellulose nanocrystal ethylene glycol p-phthalic acid mixing slurry
Reactor squeezed into by liquid, glycol antimony catalyst liquid and heat stabilizer triphenyl phosphate (150ppm is relative to PTA), heat into
Row esterification for the first time.The temperature of the first esterification is 240 DEG C, and the response time is 2h, and the pressure of reaction is 0.3MPa.
By fractionating column water byproduct separated and be collected, test collecting amount with graduated cylinder, calculate according to monomer reaction equation
Theoretical water yield, calculates esterification performance further according to water yield.When 85% that water yield is theoretical value, pressure drops to normal pressure,
It is subsequently adding polyhydroxy-alcohol sorbitol and carries out the second esterification.The addition of sorbitol is the 0.5wt% of final polyester quality.The
The temperature of class reaction is 250 DEG C, and the response time is 1h, and reaction pressure is normal pressure.After completing esterification, carry out low very
Precondensation under dummy status and the whole polycondensation reaction under high vacuum state, the prepolymerization reaction time is 0.5h, whole polycondensation reaction time
For 2h, the poly-reaction temperature of final minification is 290 DEG C, and vacuum during whole polycondensation reaction is 60Pa.After polycondensation completes, by melt discharging,
Cooling, pelletizing, prepare the hydrophilic polyesters section of modification.Fig. 2 is the polyester SEM pattern prepared through in-situ polymerization mode
Photo, Cellulose nanocrystal is divided in polyester matrix with nano level size, concurrently forms nano level defect.Cellulose nanometer
Brilliant containing polyhydroxy group, be conducive to absorbing hydrone.The most nanocrystalline defect destroys the crystal structure of polyester, is conducive to
The diffusion in polyester matrix of the free hydrone.Based on both above effect, it is hydrophilic that the polyester fiber through modification has had
Moisture pick-up properties.
(2) the hydrophilic polyesters section after modification enters melt spinning, and its spinning technique is: spinning temperature is 290 DEG C, spins
Silk speed is 1500m/min, and draft temperature is 70 DEG C, and one stretching ratio is 3.2, and two road stretching ratios are 1.15；Prepare
Hydrophilic polyester fiber.
The intrinsic viscosity of the hydrophilic polyesters section that Cellulose nanocrystal palpus is modified is 0.640dL/g, and fusing point is 253.7 DEG C, section
Surface water contact angle is 51 °.The regain of Cellulose nanocrystal modified polyester fiber is 1.8%, has good hydrophilicity.
Embodiment 3:
The hydrophilic polyesters section of Cellulose nanocrystal modification is carried out by the mode of in-situ polymerization, and polymerization is batch polymerization processes, its
Formula is as follows:
Cellulose nanocrystal is dispersed in water in the form of a suspension in water, and the concentration in suspension is 1wt%.Nanocrystalline
Length is at below 500nm, and diameter is at below 50nm, and Cellulose nanocrystal form is identical with embodiment 1.According to polyreaction
Material rate composition, weigh p-phthalic acid (PTA) and ethylene glycol that good a certain amount of mol ratio is 1: 1.8.By fiber
The nanocrystalline water slurry of element joins in 80% ethylene glycol solvent weighed, and utilizes the moisture in molecular sieve adsorption suspension, so
After prepare the glycolic suspension containing Cellulose nanocrystal.Cellulose nanometer in the glycolic suspension of Cellulose nanocrystal
Brilliant content is the 2wt% of final polyester quality.By above-mentioned Cellulose nanocrystal glycolic suspension with the most load weighted to benzene
Dioctyl phthalate is squeezed in making beating still and is prepared as mixed serum.Then catalyst acetic acid antimony (400ppm is relative to PTA) is joined title
Measured residue ethylene glycol is prepared as catalyst mixed liquid.Finally by Cellulose nanocrystal ethylene glycol p-phthalic acid mixed serum,
Reactor squeezed into by glycol antimony catalyst liquid and heat stabilizer triphenyl phosphate (100ppm is relative to PTA), and heating carries out the
Esterification.The temperature of the first esterification is 240 DEG C, and the response time is 3h, and the pressure of reaction is 0.2MPa.Pass through
Water byproduct is separated and is collected by fractionating column, tests collecting amount with graduated cylinder, calculates theory according to monomer reaction equation
Water yield, calculates esterification performance further according to water yield.When 92% that water yield is theoretical value, pressure drops to normal pressure, then
Add polyhydroxy-alcohol sorbitol and carry out the second esterification.The addition of sorbitol is the 1wt% of final polyester quality.Second esterification
The temperature of reaction is 250 DEG C, and the response time is 1h, and reaction pressure is normal pressure.After completing esterification, carry out low vacuum state
Under precondensation and whole polycondensation reaction under high vacuum state, the prepolymerization reaction time is 1h, and whole polycondensation reaction time is 2h, eventually
Polycondensation reaction temperature is 290 DEG C, and vacuum during whole polycondensation reaction is 50Pa.After polycondensation completes, by melt discharging, cooling,
Pelletizing, prepares the hydrophilic polyesters section of modification.
(2) the hydrophilic polyesters section after modification enters melt spinning, and POY spinning technique is: spinning temperature is 300 DEG C,
Spinning speed is 3000m/min, and draft temperature is 80 DEG C, and total stretching ratio is 5.POY is prepared as height after texturing craft
Hydrophilic DTY dacron thread.
The intrinsic viscosity of the hydrophilic polyesters section that Cellulose nanocrystal palpus is modified is 0.610dL/g, and fusing point is 248.2 DEG C, section
Surface water contact angle is 45 °.The regain of Cellulose nanocrystal modified polyester fiber is 3.0%, has good hydrophilicity.
The above is only the preferred embodiment of the present invention.
Claims (5)
1. the preparation method of the hydrophilic polyesters fiber of a Cellulose nanocrystal modification, it is characterised in that according to the following steps:
1) by Cellulose nanocrystal water slurry and 75～85% ethylene glycol mixing of weight, remove moisture in mixed liquor, be prepared as the glycolic suspension of Cellulose nanocrystal；Wherein Cellulose nanocrystal content in PET polyester is 0.5～2wt%；
2) glycolic suspension and the p-phthalic acid of the Cellulose nanocrystal of step 1) are put into making beating still and make mixed serum；
3) ethylene glycol and the catalyst of surplus being put into preparation still, stir and make catalyst liquid, catalyst is antimony-based catalyst, and catalyst amount is 200～500ppm, and radix is p-phthalic acid quality；The consumption of ethylene glycol in step 1) and the consumption sum of ethylene glycol in step 3), the i.e. whole consumption of ethylene glycol are 1.2～1.8:1 with the mol ratio of p-phthalic acid；
4) by step 2) mixed serum, the catalyst liquid of step 3) and heat stabilizer squeeze into reactor, heating carries out esterification for the first time；Wherein heat stabilizer is phosphoric acid ester stabilizer, and the addition of heat stabilizer is 50～200ppm, and radix is p-phthalic acid quality；Esterification reaction temperature is 220～250 DEG C for the first time, and pressure is 0.1～0.3MPa, and reaction time of esterification is 1～3h；
5) when by-product collecting amount to be esterified reaches the 85-92% of theoretical value, adding polyhydroxy-alcohol, carry out second time esterification, wherein polyhydroxy-alcohol content in the polyester is 0.2～1wt%；Carrying out under esterification reaction temperature is 240～260 DEG C, condition of normal pressure for the second time, reaction time of esterification is 0.5～1h；
6) by final carboxylate, further evacuation polycondensation obtains hydrophilic polyesters melt, and melt discharging, cooling, pelletizing are obtained hydrophilic polyesters section；Polycondensation reaction temperature is 270～290 DEG C；
7) by through modified hydrophilic polyesters section melt spinning, the hydrophilic polyesters fiber that Cellulose nanocrystal is modified is prepared.
The preparation method of the hydrophilic polyesters fiber that Cellulose nanocrystal the most according to claim 1 is modified, it is characterised in that a length of below the 500nm of described Cellulose nanocrystal, nanocrystalline diameter is at below 50nm, and draw ratio L/D is 10～15.
The preparation method of Cellulose nanocrystal modified hydrophilic polyester fiber the most according to claim 1 and 2, is characterized in that: described polyhydroxy-alcohol is the one in tetramethylolmethane, xylitol and sorbitol；Antimony-based catalyst is antimony acetate or antimony glycol, and the addition of catalyst is 300～400ppm；Phosphoric acid ester stabilizer is trimethyl phosphate or triphenyl phosphate.
The preparation method of Cellulose nanocrystal modified hydrophilic polyester fiber the most according to claim 1 and 2, it is characterized in that: the melt spinning described in step 7), spinning temperature is 260～300 DEG C, spinning speed is 800～3000m/min, draft temperature is 60～80 DEG C, and total stretching ratio is 3～5 times.
The preparation method of Cellulose nanocrystal modified hydrophilic polyester fiber the most according to claim 3, it is characterized in that: the melt spinning described in step 7), spinning temperature is 260～300 DEG C, and spinning speed is 800～3000m/min, draft temperature is 60～80 DEG C, and total stretching ratio is 3～5 times.
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| CN106521690B (en) * | 2016-10-27 | 2019-02-22 | 浙江恒逸高新材料有限公司 | A kind of microcrystalline cellulose modified polyester fiber and preparation method thereof |
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| CN103450643A (en) * | 2013-08-09 | 2013-12-18 | 上海交通大学 | Method for improving compatibility between cellulose nanocrystallines and aliphatic polyester by using phthalic anhydride |
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| CN103848999A (en) * | 2012-11-30 | 2014-06-11 | 中国科学院宁波材料技术与工程研究所 | Novel polymer surface modification method |
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| GB2218994B (en) * | 1988-05-26 | 1992-01-15 | Warner Lambert Co | New polymer composition |
| TW479087B (en) * | 1998-11-13 | 2002-03-11 | Kimberly Clark Co | Pulp-modified bicomponent continuous filament nonwoven webs and articles |
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|---|---|---|---|---|
| CN1513072A (en) * | 2001-04-04 | 2004-07-14 | 健康服饰公司 | Improved polymer-crafted cotton fibers and products |
| CN102641671A (en) * | 2012-04-18 | 2012-08-22 | 江南大学 | Natural nanometer crystal whisker oily polymer emulsion dispersing system and preparation method thereof |
| CN103848999A (en) * | 2012-11-30 | 2014-06-11 | 中国科学院宁波材料技术与工程研究所 | Novel polymer surface modification method |
| CN103450643A (en) * | 2013-08-09 | 2013-12-18 | 上海交通大学 | Method for improving compatibility between cellulose nanocrystallines and aliphatic polyester by using phthalic anhydride |
| CN103469427A (en) * | 2013-09-11 | 2013-12-25 | 南通金仕达超微阻燃材料有限公司 | High performance fabric and manufacturing method thereof |
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