CN104404647A - Hydrophilic polyester fiber modified by cellulose nanocrystal and preparation method thereof - Google Patents
Hydrophilic polyester fiber modified by cellulose nanocrystal and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrophilic polyester fiber modified by cellulose nanocrystal and a preparation method thereof and aims to solve a problem of a poor hydrophilicity of conventional polyester. The preparation method includes following steps: (1) mixing a cellulose nanocrystal aqueous suspension liquid and 75-85% by weight of ethylene glycol and removing water from a mixed liquid to prepare an ethylene glycol suspension liquid of the cellulose nanocrystal; (2) preparing a mixed slurry liquid from the ethylene glycol suspension liquid of the cellulose nanocrystal and terephthalic acid; (3) preparing a catalyst liquid form the balanced ethylene glycol and a catalyst; (4) mixing the mixed slurry liquid, the catalyst liquid and a thermal stabilizing agent, and performing a first esterification reaction in a reaction kettle with stirring and heating; (5) performing a secondary esterification reaction with addition of a polyhydroxy-alcohol; (6) performing vacuumizing condensation polymerization to obtain a hydrophilic polyester melt, and cooling and pelleting the melt to obtain a hydrophilic polyester chip; and (7) performing melt spinning to the hydrophilic polyester chip to prepare the hydrophilic polyester fiber.
Description
Technical field
The present invention relates to a kind of hydrophilic polyesters section of nano modification, and relate to a kind of preparation method of hydrophilic polyesters fiber of Cellulose nanocrystal modification.
Background technology
China's chemical fibre output accounts for 70% of world's chemical fibre total output, is the most important raw material of textile industry.Wherein, polyester fiber is most important synthetic fiber kind, and its state of development directly has influence on integral level and the competitiveness of China's Development of Textile Industry.Although China's polyester production capacity, output occupy the first in the world, China's polyester fiber industry still faces some outstanding problems that need solve.Current developed countries has eliminated the production of conventional polyester fiber to the exploitation of polyester fiber, and scientific research strength mainly concentrates on the development & application of Speciality Pet Fiber.
The performance of its excellence of polyester molecule structures shape, PET polyester molecule structure height is regular, and molecules align is tight, and containing rigidity benzene ring structure in molecule segment, therefore PET has good physical and mechanical property.The advantages such as high, well-pressed, the wear-resisting and good stability of the dimension of polyester fiber intensity make it be developed rapidly.Due to polyester fiber macromolecular structure and shortage hygroscopicity group closely, it is more very different than natural fabrics such as cottons in comfortableness.At 20 DEG C, under 65% relative humidity, the regain of polyester fiber only has 0.4%, cotton under identical humiture regain up to 8.0%.Polyester hygroscopicity is poor, easily produces electrostatic phenomenon, has had a strong impact on the comfortableness of clothes.Conventional polyester fiber does not have hydrophilic radical due to polyester fiber, and molecular stuffing is tight, and therefore dyestuff is difficult to the inside entering into fiber, and one method can not be adopted in dyeing to dye.Therefore carrying out moisture-absorption modified to polyester fiber, improve the ability of its water management, is the importance expanding polyester fiber Application Areas further.
Specifically, by copolymerization, blended, coating, surface treatment, realize the functionalization of polyester fiber.For copolymerization or blending and modifying, modification component conventional at present mainly contains several large classes such as inorganic particle, organic monomer, polymer.In moisture-absorption modified, conventional modified method comprises copolymerization and blended, and conventional modified component comprises polypropylene glycol, polyethylene glycol, pentaerythrite etc.Such as, patent WO2005019301 (A1) adopts in polyethylene terephthalate, introduces a small amount of polypropylene glycol, and replace diol segment structure in the mode of block, the co-polymerization modified polyester fiber obtained has good hygroscopicity.Patent US2002019508 (A1) and WO2005019301 (A1) all selects polyethylene glycol to be modifier, the co-polymerization modified polyester fiber that the hygroscopicity obtained is good.After patent WO0012793 (A1) selects polyethylene glycol and pentaerythrite modified polyester fiber, its hygroscopicity and cotton and other are natural or synthetic cellulose fibres is suitable.Inorganic particle containing sepiolite and artificial zeolite is joined polyester fondant by patent CN200910101497.5, obtains high-hydroscopicity, inhales the part that discharges water and respond fast modified polyester fiber with blends.The silica-based inorganic particle of 1-20wt% adds in polyester by patent US6838173, obtains the modified poly ester that hygroscopicity is good, has good wearing comfort.
Utilize polyhydroxy-alcohol fewer as the research report of modification by copolymerization monomer at present.On the basis of block copolymer, select suitable polyhydroxy-alcohol as modified component, prepare copolyesters.Polyhydroxy-alcohol is utilized mainly to concentrate on aliphatic copolyester aspect as the research of modification by copolymerization monomer at present.The people such as DOLLK adopt citric acid and sorbierite to react, prepare water-soluble polyester, the people such as Ajay Kumar generate copolyesters PAOS poly (apidicacid-co-octanediol-co-sorbitol) to the reaction of sorbierite, adipic acid and ethohexadiol and are studied; The people such as Ning have studied polyhydroxy functional polyester, utilize aliphatic suberic acid and aliphatic polyalcohol synthesising biological degradable polyester.Polyhydroxy-alcohol is when polymerisation, and unnecessary hydroxyl does not participate in reaction, is free in polyester, and free hydroxyl has good hydrophily.The polyhydroxy-alcohol such as sorbierite that the present invention adopts, xylitol, pentaerythrite etc. are added in copolymer by trace, while not changing polyester mobility and spinning properties, can improve again the hydrophily of polyester.
Cellulose has the characteristics such as degradable, low cost and environmental friendliness as the reproducible natural polyols of one.Cellulose takes off unbodied part at the Water Under of acid, remaining cellulose crystals, controls reaction condition and can obtain nano-scale fiber cellulose crystal, be usually referred to as Cellulose nanocrystal.Cellulose nanocrystal is a few nanometer by the diameter obtained after acid hydrolysis is 10 ~ 1000 nanometers to tens nanometers, length.Cellulose nanocrystal has the characteristic that degree of crystallinity is high, hydrophily is strong, intensity is large.Cellulose nanocrystal rich surface hydroxyl, have stronger reactivity, hydrophily is high, has very strong hygroscopicity.Adopt the mode of in-situ polymerization to add Cellulose nanocrystal, while not changing polyester construction, in polyester matrix, introduce finely disseminated Cellulose nanocrystal, the water absorbing properties of reinforced polyester.The a large amount of hydroxyl of the high-ratio surface sum of Cellulose nanocrystal can improve the hydrophily of polyester fiber.Cellulose nanocrystal is the particle of nano-scale, good dispersion, under the prerequisite not affecting Direct-spinning of PET Fiber, Cellulose nanocrystal add the hydrophily improving polyester.The work of current related fields also rarely has report.Adopt the method for in-situ polymerization, avoid Cellulose nanocrystal to reunite, and select nano level filler, avoid the functional defect that common micro-scaled filler causes, ensure that the hydrophilic polyesters fiber of modification has high spinnability and high-hydrophilic.Hydrophilic fibers prepared by the method, technique is simple, and increase cost few, modified effect is good.
Summary of the invention
The present invention needs the problem solving normal polyester hydrophily difference, provides a kind of hydrophilic polyesters fiber of Cellulose nanocrystal modification.
The present invention needs to solve another technical problem, provides a kind of preparation method of hydrophilic polyesters fiber of above-mentioned Cellulose nanocrystal modification.
The hydrophilic polyesters fiber of Cellulose nanocrystal modification of the present invention, the fibroblast hydrophilic polyesters of hydrophilic polyesters fiber by PET polyester, Cellulose nanocrystal, polyhydroxy-alcohol and heat stabilizer composition;
Wherein, the content of Cellulose nanocrystal in PET polyester is 0.5 ~ 2wt%; The content of polyhydroxy-alcohol in PET polyester is 0.2 ~ 1wt%; The addition of heat stabilizer is 50ppm ~ 200ppm, and its radix is the quality of the terephthalic acid (TPA) of Reactive Synthesis PET polyester;
Containing abundant Cellulose nanocrystal and the polyhydroxy-alcohol with hydrophilic moisture absorption oh group in Cellulose nanocrystal modified polyester fiber of the present invention.Described Cellulose nanocrystal is dispersed in hydrophilic polyesters with nano-grade size, and polyhydroxy-alcohol copolymerization is in hydrophilic polyesters macromolecular chain.The surface water contact angle of described fibroblast hydrophilic polyesters is 45 ~ 60 °, and described hydrophilic polyesters fiber melt is 245 ~ 255 DEG C, and regain is 0.8 ~ 3%.Other performances are identical with conventional polyester fiber.
The length of described Cellulose nanocrystal is below 500nm, and nanocrystalline diameter is at below 50nm, and draw ratio L/D is 10 ~ 15; Described polyhydroxy-alcohol is pentaerythrite, the one in xylitol and sorbierite; Described heat stabilizer is trimethyl phosphate or triphenyl phosphate.
The present invention by introducing the nano level Cellulose nanocrystal with high-hydrophilic in polyester matrix, and introduces hydrophilic oh group in polyester construction, is prepared the hydrophilic polyesters fiber of Cellulose nanocrystal modification by the method for melt spinning.The hydrophilic polyesters fiber of the Cellulose nanocrystal modification that the present invention is concrete
preparation method, according to the following steps:
1) ethylene glycol of Cellulose nanocrystal water slurry and 75 ~ 85% weight is mixed, remove moisture in mixed liquor, be prepared into the glycolic suspension of Cellulose nanocrystal; Wherein the content of Cellulose nanocrystal in PET polyester is 0.5 ~ 2wt%.Cellulose nanocrystal is dispersed in ethylene glycol the glycolic suspension being prepared into Cellulose nanocrystal by this step by solvent exchange method; Adopt molecular sieve, sepiolite etc. absorb the moisture in suspension, preferred molecular sieve.
2) by step 1) the glycolic suspension of Cellulose nanocrystal and terephthalic acid (TPA) drop into making beating still and make mixed serum; Step 1) ethylene glycol consumption and step 3) ethylene glycol surplus sum, namely the mol ratio of the whole consumption of ethylene glycol and terephthalic acid (TPA) is 1.2 ~ 1.8: 1;
3) ethylene glycol of surplus and catalyst are dropped into preparation still, stir and make catalyst liquid, catalyst is antimony-based catalyst, and catalyst amount is 200 ~ 500ppm, and radix is terephthalic acid (TPA) (PTA) quality;
4) by step 2) mixed serum, step 3) catalyst liquid and heat stabilizer squeeze into reactor, heating carry out first time esterification; Wherein heat stabilizer is phosphoric acid ester stabilizing agent, and the addition of heat stabilizer is 50 ~ 200ppm, and radix is terephthalic acid (TPA) (PTA) quality; First time, esterification reaction temperature was 220 ~ 250 DEG C, and pressure is 0.1 ~ 0.3MPa, and reaction time of esterification is 1 ~ 3h.
Ester by-products is water, in the first esterification reaction process, to be separated by water and collects, test collecting amount, calculate theoretical water yield according to monomer reaction equation, then calculate esterification performance according to water yield with graduated cylinder by fractionating column.
5) when accessory substance collecting amount to be esterified reaches the 85-92% of theoretical value, add polyhydroxy-alcohol, carry out second time esterification, wherein polyhydroxy-alcohol content is in the polyester 0.2 ~ 1wt%; Second time esterification reaction temperature is 240 ~ 260 DEG C, and carry out under condition of normal pressure, reaction time of esterification is 0.5 ~ 1h;
6) by final carboxylate, vacuumize polycondensation further and obtain 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 comprises precondensation and whole polycondensation reaction, and precondensation pressure is 200 ~ 2000Pa, and the reaction time is 0.5 ~ 1h; Be high vacuum during whole polycondensation reaction, pressure < 100Pa, the reaction time is 1 ~ 2h.
7) by through modified hydrophilic polyesters section melt spinning, the hydrophilic polyesters fiber of Cellulose nanocrystal modification 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, and total stretching ratio is 3 ~ 5 times.
As preferably, the length of described Cellulose nanocrystal is below 500nm, and nanocrystalline diameter is at below 50nm, and draw ratio L/D is 10 ~ 15.
As preferably, described polyhydroxy-alcohol is pentaerythrite, the one in xylitol and sorbierite; Antimony-based catalyst is antimony acetate or antimony glycol, and the addition of catalyst is 300 ~ 400ppm; Phosphoric acid ester stabilizing agent is trimethyl phosphate or triphenyl phosphate.
Compared with prior art, innovation effect of the present invention is:
(1) the present invention adopts and adds Cellulose nanocrystal as the hydrophilicity improving polyester, adopts the mode of in-situ polymerization to prepare hydrophilic polyesters.Cellulose nanocrystal contains multiple hydroxyl, and the accessibility of hydroxyl is higher, has very high hydrophilic ability.Cellulose nanocrystal can be good at being dispersed in polyester matrix, and the polyester obtained by the mode of suspended dispersed and in-situ polymerization has good hydrophilicity.
(2) polyhydroxy-alcohol that the present invention adds improves the hydrophilicity of polyester, polyhydroxy-alcohol contains multiple hydroxyl, the second esterification stage add polyhydroxy-alcohol alcohol can ensure terminal hydroxy group reaction access polyester backbone section time, pendant hydroxyl group does not react and is free on outside main chain, the polyester construction formed has the performance of polyester, and has the hydrophilicity of hydroxyl.
(3) addition of the Cellulose nanocrystal that adds of the present invention and sorbierite is very little, does not affect the performance of polymerization process and polyester while ensureing to improve hydrophilic effect.
(4) the Cellulose nanocrystal particle that the present invention adds is Nano grade, is dispersed in polyester matrix by the mode of in-situ polymerization, and dispersity is good, does not affect the performance of polyester, can ensure again the spinnability of polyester.
(5) technique of the inventive method is simple, can carry out, do not need to change production equipment in original polymerization equipment.Be applicable to large-scale production, cost increases little.
(6) modified polyester fiber of the present invention has very high hydrophily and higher regain 0.8 ~ 3%, and fabric moisture perspiration discharging 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 of Cellulose nanocrystal modification in embodiment 2.
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 undertaken by the mode of in-situ polymerization, and polymerization is batch polymerization processes, and 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 the microscopic appearance of Cellulose nanocrystal is shown in Fig. 1.Form according to the material rate of polymerisation, weigh terephthalic acid (TPA) (PTA) and ethylene glycol that good a certain amount of mol ratio is 1: 1.4.Cellulose nanocrystal water slurry is joined 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 content in the glycolic suspension of Cellulose nanocrystal is the 0.5wt% of final polyester quality.Above-mentioned Cellulose nanocrystal glycolic suspension and proportionally load weighted terephthalic acid (TPA) are squeezed in still of pulling an oar and is prepared into mixed serum.Then catalyst glycol antimony (300ppm is relative to PTA) is joined in residue ethylene glycol and be prepared into catalyst mixed liquid.Finally Cellulose nanocrystal ethylene glycol terephthalic acid (TPA) mixed serum, glycol antimony catalyst liquid and heat stabilizer trimethyl phosphate (100ppm is relative to PTA) are squeezed into reactor, first time esterification is carried out in heating.The temperature of the first esterification is 230 DEG C, and the reaction time is 3h, and the pressure of reaction is 0.3MPa.By fractionating column water byproduct separated and collect, test collecting amount with graduated cylinder, calculate theoretical water yield according to monomer reaction equation, then calculate esterification performance according to water yield.When water yield is 90% of theoretical value, pressure drops to normal pressure, then adds polyhydroxy-alcohol sorbierite and carries out the second esterification.The addition of sorbierite is the 0.2wt% of final polyester quality.The temperature of the second esterification is 240 DEG C, and the reaction time is 1h, and reaction pressure is normal pressure.After completing esterification, carry out the precondensation under low vacuum state and the whole polycondensation reaction under high vacuum state, the prepolymerization reaction time is 1h, and whole polycondensation reaction time is 2h, and it is 280 DEG C that final minification gathers reaction temperature, and vacuum during whole polycondensation reaction is 80Pa.After polycondensation completes, by melt discharging, cooling, pelletizing, prepare 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, and spinning speed is 900m/min, and draft temperature is 60 DEG C, and one stretching ratio is 2.2, two road stretching ratios is 1.15; Prepare hydrophilic polyester fiber.
The inherent viscosity of the hydrophilic polyesters section of Cellulose nanocrystal palpus modification is 0.615dL/g, and fusing point is 250.2 DEG C, and slice 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 undertaken by the mode of in-situ polymerization, and polymerization is batch polymerization processes, and 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.Form according to the material rate of polymerisation, weigh terephthalic acid (TPA) (PTA) and ethylene glycol that good a certain amount of mol ratio is 1: 1.6.Cellulose nanocrystal water slurry is joined in 80% ethylene glycol solvent taken, utilizes the moisture in molecular sieve adsorption suspension, then prepare the glycolic suspension containing Cellulose nanocrystal.Cellulose nanocrystal content in the glycolic suspension of Cellulose nanocrystal is the 1wt% of final polyester quality.Above-mentioned Cellulose nanocrystal glycolic suspension and proportionally load weighted terephthalic acid (TPA) are squeezed in still of pulling an oar and is prepared into mixed serum.Then catalyst glycol antimony (400ppm is relative to PTA) is joined in load weighted residue ethylene glycol and be prepared into catalyst mixed liquid.Finally Cellulose nanocrystal ethylene glycol terephthalic acid (TPA) mixed serum, glycol antimony catalyst liquid and heat stabilizer triphenyl phosphate (150ppm is relative to PTA) are squeezed into reactor, first time esterification is carried out in heating.The temperature of the first esterification is 240 DEG C, and the reaction time is 2h, and the pressure of reaction is 0.3MPa.By fractionating column water byproduct separated and collect, test collecting amount with graduated cylinder, calculate theoretical water yield according to monomer reaction equation, then calculate esterification performance according to water yield.When water yield is 85% of theoretical value, pressure drops to normal pressure, then adds polyhydroxy-alcohol sorbierite and carries out the second esterification.The addition of sorbierite is the 0.5wt% of final polyester quality.The temperature of the second esterification is 250 DEG C, and the reaction time is 1h, and reaction pressure is normal pressure.After completing esterification, carry out the precondensation under low vacuum state and the whole polycondensation reaction under high vacuum state, the prepolymerization reaction time is 0.5h, and whole polycondensation reaction time is 2h, and it is 290 DEG C that final minification gathers reaction temperature, 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 photo prepared through in-situ polymerization mode, and Cellulose nanocrystal is divided in polyester matrix with nano level size, forms nano level defect simultaneously.Cellulose nanocrystal contains polyhydroxy group, is conducive to absorbing hydrone.Nanocrystalline defect destroys the crystal structure of polyester simultaneously, is conducive to the diffusion of hydrone in polyester matrix dissociated.Based on two kinds of effects above, through the hydrophilic moisture pick-up properties that the polyester fiber of modification has had.
(2) the hydrophilic polyesters section after modification enters melt spinning, and its spinning technique is: spinning temperature is 290 DEG C, and spinning speed is 1500m/min, and draft temperature is 70 DEG C, and one stretching ratio is 3.2, two road stretching ratios is 1.15; Prepare hydrophilic polyester fiber.
The inherent viscosity of the hydrophilic polyesters section of Cellulose nanocrystal palpus modification is 0.640dL/g, and fusing point is 253.7 DEG C, and slice 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 undertaken by the mode of in-situ polymerization, and polymerization is batch polymerization processes, and 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.Form according to the material rate of polymerisation, weigh terephthalic acid (TPA) (PTA) and ethylene glycol that good a certain amount of mol ratio is 1: 1.8.Cellulose nanocrystal water slurry is joined in 80% ethylene glycol solvent taken, utilizes the moisture in molecular sieve adsorption suspension, then prepare the glycolic suspension containing Cellulose nanocrystal.Cellulose nanocrystal content in the glycolic suspension of Cellulose nanocrystal is the 2wt% of final polyester quality.Above-mentioned Cellulose nanocrystal glycolic suspension and proportionally load weighted terephthalic acid (TPA) are squeezed in still of pulling an oar and is prepared into mixed serum.Then catalyst acetic acid antimony (400ppm is relative to PTA) is joined in load weighted residue ethylene glycol and be prepared into catalyst mixed liquid.Finally Cellulose nanocrystal ethylene glycol terephthalic acid (TPA) mixed serum, glycol antimony catalyst liquid and heat stabilizer triphenyl phosphate (100ppm is relative to PTA) are squeezed into reactor, first time esterification is carried out in heating.The temperature of the first esterification is 240 DEG C, and the reaction time is 3h, and the pressure of reaction is 0.2MPa.By fractionating column water byproduct separated and collect, test collecting amount with graduated cylinder, calculate theoretical water yield according to monomer reaction equation, then calculate esterification performance according to water yield.When water yield is 92% of theoretical value, pressure drops to normal pressure, then adds polyhydroxy-alcohol sorbierite and carries out the second esterification.The addition of sorbierite is the 1wt% of final polyester quality.The temperature of the second esterification is 250 DEG C, and the reaction time is 1h, and reaction pressure is normal pressure.After completing esterification, carry out the precondensation under low vacuum state and the whole polycondensation reaction under high vacuum state, the prepolymerization reaction time is 1h, and whole polycondensation reaction time is 2h, and it is 290 DEG C that final minification gathers reaction temperature, and vacuum during whole polycondensation reaction is 50Pa.After polycondensation completes, by melt discharging, cooling, pelletizing, prepare 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, and spinning speed is 3000m/min, and draft temperature is 80 DEG C, and total stretching ratio is 5.POY is prepared into high hydrophilic DTY terylene thread after texturing craft.
The inherent viscosity of the hydrophilic polyesters section of Cellulose nanocrystal palpus modification is 0.610dL/g, and fusing point is 248.2 DEG C, and slice 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 (7)
1. a hydrophilic polyesters fiber for Cellulose nanocrystal modification, is characterized in that: the fibroblast hydrophilic polyesters of hydrophilic polyesters fiber by PET polyester, Cellulose nanocrystal, polyhydroxy-alcohol and heat stabilizer composition; Wherein, the content of Cellulose nanocrystal in PET polyester is 0.5 ~ 2wt%; The content of polyhydroxy-alcohol in PET polyester is 0.2 ~ 1wt%; The addition of heat stabilizer is 50ppm ~ 200ppm, and its radix is the quality of the terephthalic acid (TPA) of Reactive Synthesis PET polyester;
Described Cellulose nanocrystal is dispersed in hydrophilic polyesters with nano-grade size, polyhydroxy-alcohol copolymerization is in hydrophilic polyesters macromolecular chain, the surface water contact angle of described fibroblast hydrophilic polyesters is 45 ~ 60 °, and described hydrophilic polyesters fiber melt is 245 ~ 255 DEG C, and regain is 0.8 ~ 3%.
2. the hydrophilic polyesters fiber of Cellulose nanocrystal modification according to claim 1, is characterized in that, the length of described Cellulose nanocrystal is below 500nm, and nanocrystalline diameter is at below 50nm, and draw ratio L/D is 10 ~ 15; Described polyhydroxy-alcohol is pentaerythrite, the one in xylitol and sorbierite; Described heat stabilizer is trimethyl phosphate or triphenyl phosphate.
3. a preparation method for the hydrophilic polyesters fiber of Cellulose nanocrystal modification, is characterized in that, according to the following steps:
1) ethylene glycol of Cellulose nanocrystal water slurry and 75 ~ 85% weight is mixed, remove moisture in mixed liquor, be prepared into the glycolic suspension of Cellulose nanocrystal; Wherein the content of Cellulose nanocrystal in PET polyester is 0.5 ~ 2wt%;
2) glycolic suspension of the Cellulose nanocrystal of step 1) and terephthalic acid (TPA) are dropped into making beating still and make mixed serum; The ethylene glycol surplus sum of step 1) ethylene glycol consumption and step 3), namely the mol ratio of the whole consumption of ethylene glycol and terephthalic acid (TPA) is 1.2 ~ 1.8:1;
3) ethylene glycol of surplus and catalyst are dropped into preparation still, stir and make catalyst liquid, catalyst is antimony-based catalyst, and catalyst amount is 200 ~ 500ppm, and radix is terephthalic acid (TPA) quality;
4) by step 2) mixed serum, the catalyst liquid of step 3) and heat stabilizer squeeze into reactor, first time esterification is carried out in heating; Wherein heat stabilizer is phosphoric acid ester stabilizing agent, and the addition of heat stabilizer is 50 ~ 200ppm, and radix is terephthalic acid (TPA) quality; First time, esterification reaction temperature was 220 ~ 250 DEG C, and pressure is 0.1 ~ 0.3MPa, and reaction time of esterification is 1 ~ 3h;
5) when accessory substance collecting amount to be esterified reaches the 85-92% of theoretical value, add polyhydroxy-alcohol, carry out second time esterification, wherein polyhydroxy-alcohol content is in the polyester 0.2 ~ 1wt%; Second time esterification reaction temperature is 240 ~ 260 DEG C, and carry out under condition of normal pressure, reaction time of esterification is 0.5 ~ 1h;
6) by final carboxylate, vacuumize polycondensation further and obtain hydrophilic polyesters melt, 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 of Cellulose nanocrystal modification is prepared.
4. the preparation method of Cellulose nanocrystal modified fibre according to claim 3, is characterized in that, the length of described Cellulose nanocrystal is below 500nm, and nanocrystalline diameter is at below 50nm, and draw ratio L/D is 10 ~ 15.
5. the preparation method of the Cellulose nanocrystal modified hydrophilic polyester fiber according to claim 3 or 4, is characterized in that: described polyhydroxy-alcohol is pentaerythrite, the one in xylitol and sorbierite; Antimony-based catalyst is antimony acetate or antimony glycol, and the addition of catalyst is 300 ~ 400ppm; Phosphoric acid ester stabilizing agent is trimethyl phosphate or triphenyl phosphate.
6. the preparation method of the Cellulose nanocrystal modified hydrophilic polyester fiber according to claim 3 or 4, 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.
7. the preparation method of Cellulose nanocrystal modified hydrophilic polyester fiber according to claim 5, 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.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0220564A (en) * | 1988-05-26 | 1990-01-24 | Warner Lambert Co | Novel polymer composition |
| WO2000029658A1 (en) * | 1998-11-13 | 2000-05-25 | Kimberly-Clark Worldwide, Inc. | Pulp-modified bicomponent continuous filament nonwoven webs |
| 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 |
| 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 |
| 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 |
-
2014
- 2014-10-15 CN CN201410546019.6A patent/CN104404647B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0220564A (en) * | 1988-05-26 | 1990-01-24 | Warner Lambert Co | Novel polymer composition |
| WO2000029658A1 (en) * | 1998-11-13 | 2000-05-25 | Kimberly-Clark Worldwide, Inc. | Pulp-modified bicomponent continuous filament nonwoven webs |
| 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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Effective date of registration: 20200408 Address after: 314000 no.1288, Hongye Road, Xiuzhou District, Jiaxing City, Zhejiang Province Patentee after: Jiaxing Yipeng Chemical Fiber Co., Ltd Address before: 311228 Linjiang hi tech Industrial Park, Hangzhou, Zhejiang, Xiaoshan Patentee before: ZHEJIANG HENGYI HI-TECH MATERIALS Co.,Ltd. |