CN103014906B - Preparation method of inflaming retarding hydrophilic polyester fiber - Google Patents
Preparation method of inflaming retarding hydrophilic polyester fiber Download PDFInfo
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- CN103014906B CN103014906B CN201210465610.XA CN201210465610A CN103014906B CN 103014906 B CN103014906 B CN 103014906B CN 201210465610 A CN201210465610 A CN 201210465610A CN 103014906 B CN103014906 B CN 103014906B
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Abstract
The invention provides a preparation method of inflaming retarding hydrophilic polyester fiber. The preparation method is characterized by comprising the specific steps of: 1, mixing terephthalic acid with ethylene glycol to prepare slurry, adding the mixture into an esterification reaction kettle for primary esterification reaction, adding sorbitol and polyethylene glycol for carrying out secondary esterification reaction when the collecting quantity of byproducts reaches 82-95 percent of a theoretical value, after the esterification reaction is completed, carrying out a condensation polymerization on an esterification product to prepare a hydrophilic polyester slice; 2, after coffee grounds are dried, calcining to obtain coffee carbon, activating the nano-level coffee carbon powder body, adding a fire retardant to obtain a fire retardant-containing nano-level coffee carbon powder body; 3, smelting and pelleting the fire retardant-containing nano-level coffee carbon powder body and the hydrophilic polyester slice to obtain a functional master batch; and 4, smelting and spinning the functional master batch and the hydrophilic polyester slice to obtain the inflaming retarding hydrophilic polyester fiber. The inflaming retarding hydrophilic polyester fiber has the advantages of good hydrophilic performance and has a long-term continuous function of the fire retardant and the coffee carbon.
Description
Technical field
The present invention relates to a kind of preparation method of fire-retardant hydrophilic polyesters fiber.
Background technology
Since polyester and polyester fiber step into heavy industrialization from 20 century 70s, development speed is far longer than other synthetic materials and synthetic fiber, and 2,513 ten thousand tons of China's polyester fiber output in 2010, account for 81% of China's chemical fibre output;
Account for 70% of Polyester fiber production.10 years from now on, Polyester and polyester fiber will keep more than 3% speed increment, and polyester fiber will account for the more than 60% of world's fiber product total amount.The physical and mechanical properties of polyester fiber all can better meet the needs of various uses as brute force, ABRASION RESISTANCE, resilience and DIMENSIONAL STABILITY.But polyester fiber is a kind of typical hydrophobic fibre, and regain only has 0.4%, and as skintight suit material, its snugness of fit is very poor, and in high humidity, the condition of high temperature, the clothes that people wear synthetic fiber have feeling of oppression and heat, and mood is had the fidgets; Under humid tropical condition, human body and check room frictional force increase, and sense of heaviness increases, and the psychology on people and physiological change produce not very big impact.Meanwhile, polyester fiber hydrophily is very poor, also gives to weave and brings series of problems.As easily gathered static, easily to inhale dust, wipe oil stain difficult etc.For this reason, people have done a large amount of research work improving aspect polyester fiber hydrophilicity.Developed country is since the eighties in last century, polyester fiber and textiles thereof progressively catch up with or surmount the future development of natural fabric and textiles, the developing goal that the super emulation synthetic fiber with features such as high function, high-quality, low energy consumption and low emissions are synthetic fiber and textiles thereof towards performance, quality and economic indicator.Meanwhile, moisture absorption, the perspire of raising synthetic fabrics are also one of following textiles developing direction.
The hydrophilic method that changes polyester is to adopt the means of copolymerization on normal polyester, to introduce hydrophilic radical, strengthens the affinity with water.The kind of hydrophilic radical and the quantity of hydrophilic radical are very important, and polar group has stronger affinity to hydrone as hydroxyl, amino, amide groups, carboxyl etc.Have at present the water imbibition of much utilizing water-soluble polyester to improve polyester fiber, but because the manufacturing cost of " water-soluble polyester " is higher, composite spinning technology is not only complicated and yield poorly, and fiber price is higher, so limited its development and application.If domestic patent is for the preparation of polymer masterbatch and the synthetic method (patent No. 200710118744) thereof of high moisture absorption and high moisture exclusion polyester textile, preparation method's (patent No. 200710178879) of a kind of acidic dyeable polyester and this acidic dyeable polyester and fiber thereof, produce continuously the method and apparatus (patent No. 200610039096) of damp absorbent polyester, cationic dye deep dyeing copolyester at normal pressure and preparation method thereof (patent No. 200410060520.8), hygroscopicity copolyester and with the moisture-absorbing fibre (patent No. 96104374) of its manufacture, a kind of isophthalate modified poly terephthalic acid 1, preparation method's (patent No. 200910101792.0) of 2-propyl alcohol copolyesters etc.
Less about the polyester modification research containing sorbierite, as taking isobide (product after sorbierite catalytic dehydration), ethylene glycol, terephthalic acid (TPA) as raw material, adopt PTA legal system standby isobide mass fraction be 20% atactic polyester has good heat endurance and spinnability.But utilize sorbierite to prepare the research that polyester carries out micro-modification and have no report.Method of the present invention, the addition of sorbierite and polyethylene glycol is few, less on polymerization and the impact of polyester quality in ensureing modified effect.Adopt the method for in-situ polymerization, avoid due to hydrophily, the flexibility group functional defect causing of reuniting.The method cost increases few, and modified effect is good, is particularly suitable for fused mass directly spinning technique.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of fire-retardant hydrophilic polyesters fiber is provided.
In order to achieve the above object, the invention provides a kind of preparation method of fire-retardant hydrophilic polyesters fiber, it is characterized in that,
Concrete steps are:
The first step: terephthalic acid (TPA) is mixed to preparation slurry with ethylene glycol according to 1: 1.05～2.0 mol ratio; Add reaction kettle of the esterification to carry out the first esterification in the slurry preparing, accessory substance collecting amount reach theoretical value 82～95% time, add sorbierite and polyethylene glycol, carry out the second esterification, complete after esterification, carboxylate is carried out to polycondensation reaction, make hydrophilic polyester section;
Second step: after coffee grounds is dry, calcining obtains coffee charcoal; The micronizing of coffee charcoal is obtained to nanoscale coffee powdered carbon body, nanoscale coffee powdered carbon body is immersed in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3: 1; Carry out heating using microwave reaction temperature is maintained to 20～45 DEG C and stirring reaction 1～3.5h, then wash neutrality with distilled water, obtain containing the solution of the nanoscale coffee powdered carbon body after activation; Add again fire retardant, carry out ultrasonic oscillation reaction 1～2h, then dry the nanoscale coffee powdered carbon body obtaining containing fire retardant;
The 3rd step: melt pelletization is carried out in the nanoscale coffee powdered carbon body containing fire retardant that second step is obtained and the hydrophilic polyesters section that the first step obtains, and temperature is 260～300 DEG C, obtains functional agglomerate;
The 4th step: melt spinning is carried out in the hydrophilic polyesters section that the functional agglomerate that the 3rd step is obtained and the first step obtain, and finally obtains fire-retardant hydrophilic polyesters fiber.
Preferably, in the described first step, the first esterification, at 225～250 DEG C, is carried out under 0～0.4MPa condition, and the reaction time is 0.5～4h.
Preferably, in the described first step, the second esterification is carried out under 240～260 DEG C, condition of normal pressure, and the reaction time is 0.5～1h.
Preferably, in the described first step, the slurry preparing being added reaction kettle of the esterification carry out before the first esterification, first by itself and catalyst mix, described catalyst is Titanium series catalyst, antimony-based catalyst or their composition, the addition of catalyst is 120～550ppm, and radix is the quality of described terephthalic acid (TPA).
More preferably, described Titanium series catalyst is titanium dioxide or butyl titanate, and described antimony-based catalyst is antimonous oxide, antimony acetate or antimony glycol.
Preferably, in the described first step, the slurry preparing being added reaction kettle of the esterification carry out before the first esterification, first it is mixed with heat stabilizer and antioxidant, the addition of described heat stabilizer is 0.001～0.02wt% of terephthalic acid (TPA), 0.001～0.03wt% that the addition of antioxidant is terephthalic acid (TPA).
More preferably, described antioxidant is one or more the mixture in antioxidant 1010, antioxidant 168 and antioxidant 616; Described heat stabilizer is one or more the mixture in trimethyl phosphate, alkyl phosphoric acid diester and three (nonyl phenyl) phosphite ester.
Preferably, in the described first step, accessory substance is water, in the first esterification reaction process, by fractionating column, water is separated and is collected, and by graduated cylinder measurement collection amount, calculates theoretical value according to reaction equation.
Preferably, in the described first step, the addition of sorbierite is 0.1～2% of terephthalic acid (TPA) molal quantity.
Preferably, in the described first step, polyethylene glycol is PEG-2000, PEG-4000 or PEG-6000, and the addition of polyethylene glycol is 0.05～0.2% of terephthalic acid (TPA) molal quantity.
Preferably, in the described first step, the temperature of polycondensation reaction remains on 260～290 DEG C.
Preferably, in the described first step, polycondensation reaction comprises prepolymerization reaction and whole polycondensation reaction; The prepolymerization reaction time is 0.5～2h, and whole polycondensation reaction time is 1～2h.
Preferably, in described second step, the baking temperature of coffee grounds is 150～180 DEG C, and the time is 1～3 hour.
Preferably, in described second step, the calcination process of coffee grounds is: be warming up to 600～700 DEG C of calcinings 0.5～2 hour, then be warming up to 800～1000 DEG C of calcinings 1～3 hour.Discarded coffee grounds is sintered into coffee carbon, can makes the crystal of coffee grounds to presenting optimum state with hole, and remove the organic matter such as oil and starch in coffee grounds hole.
Preferably, in described second step, be to adopt ball-milling method to grind to form the nanoscale coffee powdered carbon body that particle diameter is 50～400nm coffee charcoal by micronized coffee charcoal concrete steps.Described micronizing also can adopt supercentrifugal process or nanometer technology etc.
Preferably, in described second step, the fire retardant that fire retardant is hydroxyl.
More preferably, the fire retardant of described hydroxyl is CPPA, CEPPA or hydroxyl polysiloxanes (POS-OH).Fire retardant CEPPA is the copoly type phosphorus flame retardant that contains phosphorous oxide structure, and its reactivity is high, has higher heat endurance, oxidation stability and hydrolytic resistance, purchased from Dezhou Chang Xinghua work new material development Co., Ltd; CPPA is 2-carboxyethyl phenyl phosphinic acid or 3-hydroxy benzenes phosphono propionic acid, purchased from Dongying Jia Li Chemical Co., Ltd..
Preferably, in described the 3rd step, the consumption that contains the nanoscale coffee powdered carbon body of fire retardant is 0.5～1% of functional agglomerate quality.
Preferably, in described the 4th step, spinning temperature is 240～300 DEG C, and spinning speed is 2000～3000m/min.
Preferably, in described the 4th step, the consumption of functional agglomerate is 1～5% of fire-retardant hydrophilic polyesters fiber quality.
In the strand of the hydrophilic polyester of first step gained, comprise-COC
6h
4cOOCH
2cH
2o-and
segment, and the quantitative proportion of two kinds of segments is 100: 0.1～2.0.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention adopts interpolation sorbierite to improve the hydrophilicity of polyester, and sorbierite contains six hydroxyls, adds sorbierite to ensure that the hydroxyl on its side chain does not react in the second esterification stage, generates
the segment of structure.And existing hydrophile function in formation polymer, there is again the hydrophilic-structure of conducting moisture function, greatly improve the hydrophilicity of polyester.
(2) the present invention has also added a certain amount of polyethylene glycol, and the existence of polyethylene glycol has increased the compliance of polyester macromolecule segment, reduces the fusing point of polyester, the hydrophily of polyester is increased simultaneously; Add polyethylene glycol in the second esterification stage, reduced the time of staying of polyethylene glycol in still, avoid polyethylene glycol to degrade, impact reaction, reduces the side reactions such as diethylene glycol (DEG) generation.
(3) sorbierite that the present invention adds and the addition of polyethylene glycol are little, in ensureing modified effect, do not affect polymerization process and polyester quality.
(4) method of the present invention, technique is simple, can on existing device, carry out modification production; Cost increases few, is applicable to large-scale production, is especially applicable to fused mass directly spinning technique.
(5) surface contact angle of section of the present invention is 45～60 °, and the fiber spinning also has higher regain, can be for underwear, sweat shirt, lining etc.
(6) the present invention adopts the fire retardant of nanoscale coffee powdered carbon body after activation and hydroxyl by chemical reaction occurring and utilizing the suction-operated in nanoscale coffee powdered carbon body self space, carry out two kinds of combinations, make the combination of fire retardant and coffee charcoal tightr, and bring into play effect simultaneously; Be conducive to the function with fire retardant and coffee charcoal that material continues.
Brief description of the drawings
Fig. 1 is the FTIR spectrogram of the hydrophilic polyesters section of embodiment 1;
Fig. 2 is the nuclear magnetic resonance figure of the hydrophilic polyesters section of embodiment 1.
Detailed description of the invention
Illustrate the present invention below in conjunction with embodiment.Antioxidant 1010, antioxidant 168 and antioxidant 616 used in embodiment are purchased from Nanjing Jing Tianwei Chemical Co., Ltd..
Embodiment 1
A preparation method for fire-retardant hydrophilic polyesters fiber, its concrete steps are:
(1) preparation of hydrophilic polyesters section:
Terephthalic acid (TPA) is mixed in proportion to preparation slurry with ethylene glycol.After the slurry preparing is mixed with catalyst metatitanic acid four butyl esters, add reaction kettle of the esterification to carry out the first esterification, the first esterification reaction temperature is 225 DEG C, and the time of reaction is 4h, and the relative pressure of reaction is 0MPa.By fractionating column, water byproduct is separated and collected, by graduated cylinder measurement collection amount, calculate theoretical value according to reaction equation, the collecting amount of water reach theoretical value 82% time, add in proportion sorbierite and polyethylene glycol (PEG-2000) to carry out the second esterification, the second esterification reaction temperature is 240 DEG C, and pressure is normal pressure, and reaction time of esterification is 1h.Complete after esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out precondensation and whole polycondensation reaction, prepolymerization reaction carries out under low vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation reaction remains on 260 DEG C, the prepolymerization reaction time is 2h, and whole polycondensation reaction time is 2h, makes hydrophilic polyester section; In the strand of this hydrophilic polyester, comprise-COC
6h
4cOOCH
2cH
2o-and
two kinds of segment quantitative proportions are 100: 0.1; The inherent viscosity of described hydrophilic polyester is 0.50g/dl, and melt temperature is 210 DEG C.Preparation method adopts intermittence type polymerization production technology.
Fourier's infrared tester (FTIR) of the NEXUS-670 model of Nicolet company of employing U.S. development is at wave number 500-3500cm
-1test.As can be seen from Figure 1,3435cm
-1the representation hydroxy peak, peak at place, i.e. polyhydroxy structure in sorbierite (PET is herein without any peak); 2957cm
-1the bimodal vibration absorption peak that represents C-H in polyester at place; At 1716cm
-1the strong absworption peak at place should be carbonyl (C=O) stretching vibration to be caused; 1400-1600cm
-1the characteristic absorption band spectrum that the weak peak at place is phenyl ring; At 1245cm
-1and 1096cm
-12 of place wide absworption peaks by force and are to be caused by the asymmetric stretching vibration of the C-O-C key in ester; 1017cm
-1and 873cm
-1the vibration of C-H in-plane deformation and the outer deformation vibration of face on the corresponding Isosorbide-5-Nitrae-substituted benzene ring of peak difference at place; At 725cm
-1narrow and the strong absworption peak at place is to be caused by the C-H flexural vibrations in aromatic ring.
Nuclear-magnetism characterizes and adopts the Switzerland Avance400 of Bruker company nuclear magnetic resonance chemical analyser to carry out,
1the vibration frequency of HNMR is 400mHz, tests, with the deuterated trifluoroacetic acid (CF of solvent under the condition of 25 DEG C
3cOOD) calibration.From
1in HNMR, see, as shown in Figure 2, solvent C F
3the skew peak of COOD, at 11.5ppm place, can see that in copolymer this peak is the H peak on phenyl ring at a peak of appearance, δ=8.10ppm place.The methylene H peak occurring at δ=4.70ppm is PET strand-COC
6h
4cOOCH
2cH
2h peak in methylene on O-.The H peak that δ in spectrogram=3.9-4.2ppm occurs, for
h in middle alcohol unit, and all the other H except methylene and benzene ring hydrogen in main chain.
(2) after discarded coffee grounds is dry, first, through the dry processing of 150～180 DEG C 1 hour, afterwards temperature risen to 600～700 DEG C of calcinings 0.5 hour, and then be warming up to 800～1000 DEG C of calcinings 1 hour, obtain coffee charcoal; Adopt ball-milling method to grind coffee charcoal and obtain the nanoscale coffee powdered carbon body that particle diameter is 50～100nm, nanoscale coffee powdered carbon body is immersed in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of sulfuric acid and nitric acid is 3: 1; Carry out heating using microwave reaction temperature is maintained to 20 DEG C and stirring reaction 1.5h, then wash neutrality with distilled water, obtain containing the solution of the nanoscale coffee powdered carbon body after activation; Add again fire retardant CEPPA, fire retardant is 2: 48 with the weight ratio of the solution that contains the nanoscale coffee powdered carbon body after activation, carry out ultrasonic oscillation reaction 1h, the time of ultrasonic oscillation is about 10 minutes, then dries the nanoscale coffee powdered carbon body obtaining for 45 minutes containing fire retardant for 60 DEG C;
(3) melt pelletization is carried out in the nanoscale coffee powdered carbon body containing fire retardant step (2) being obtained and the hydrophilic polyesters section that step (1) obtains, and temperature is 260～300 DEG C, obtains functional agglomerate; The consumption that contains the nanoscale coffee powdered carbon body of fire retardant is 0.5% of functional agglomerate quality.
(4) melt spinning is carried out in the hydrophilic polyesters section that functional agglomerate step (3) being obtained and step (1) obtain, wherein spinning temperature is 240～300 DEG C, spinning speed is 2000～3000m/min, process using normal polyester fibre manufacturing technique, finally obtain fire-retardant hydrophilic polyesters fiber, the consumption of functional agglomerate is 1% of fire-retardant hydrophilic polyesters fiber quality, and the contact angle of its fiber is 45 degree.
Embodiment 2
A preparation method for fire-retardant hydrophilic polyesters fiber, its concrete steps are:
(1) preparation of hydrophilic polyesters section:
Terephthalic acid (TPA) is mixed in proportion to preparation slurry with ethylene glycol.After being mixed in proportion with antimonous oxide and butyl titanate mixture, antioxidant 168 and alkyl phosphoric acid diester, the slurry preparing add reaction kettle of the esterification to carry out the first esterification, the first esterification reaction temperature is 240 DEG C, the time of reaction is 3h, and the relative pressure of reaction is 0.3MPa.By fractionating column, water byproduct is separated and collected, by graduated cylinder measurement collection amount, calculate theoretical value according to reaction equation, the collecting amount of water reach theoretical value 92% time, add in proportion sorbierite and polyethylene glycol (PEG-6000) to carry out the second esterification, the second esterification reaction temperature is 250 DEG C, and pressure is normal pressure, and reaction time of esterification is 1h.Complete after esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out precondensation and whole polycondensation reaction, prepolymerization reaction carries out under low vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation reaction remains on 280 DEG C, the prepolymerization reaction time is 1h, and whole polycondensation reaction time is 1h, makes hydrophilic polyester section; In the strand of this hydrophilic polyester, comprise-COC
6h
4cOOCH
2cH
2o-and
two kinds of segment quantitative proportions are 100: 1.0; The inherent viscosity of described hydrophilic polyester is 0.65g/dl, and melt temperature is 255 DEG C.Preparation method adopts continous mode polymerization process.
(2) after discarded coffee grounds is dry, first, through the dry processing of 150～180 DEG C 2 hours, afterwards temperature risen to 600～700 DEG C of calcinings 1.5 hours, and then be warming up to 800～1000 DEG C of calcinings 2 hours, obtain coffee charcoal; Adopt ball-milling method to grind coffee charcoal and obtain the nanoscale coffee powdered carbon body that particle diameter is 90～100nm, nanoscale coffee powdered carbon body is immersed in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of sulfuric acid and nitric acid is 3: 1; Carry out heating using microwave reaction temperature is maintained to 35 DEG C and stirring reaction 2.5h, then wash neutrality with distilled water, obtain containing the solution of the nanoscale coffee powdered carbon body after activation; Add again fire retardant 3-hydroxy benzenes phosphono propionic acid, fire retardant is 1: 49 with the weight ratio of the solution that contains the nanoscale coffee powdered carbon body after activation, carry out ultrasonic oscillation reaction 1.5h, the time of ultrasonic oscillation is about 10 minutes, then dries the nanoscale coffee powdered carbon body obtaining for 50 minutes containing fire retardant for 60 DEG C;
(3) melt pelletization is carried out in the nanoscale coffee powdered carbon body containing fire retardant step (2) being obtained and the hydrophilic polyesters section that step (1) obtains, and temperature is 260～300 DEG C, obtains functional agglomerate; The consumption that contains the nanoscale coffee powdered carbon body of fire retardant is 0.75% of functional agglomerate quality.
(4) melt spinning is carried out in the hydrophilic polyesters section that functional agglomerate step (3) being obtained and step (1) obtain, wherein spinning temperature is 240～300 DEG C, spinning speed is 2000～3000m/min, process using normal polyester fibre manufacturing technique, finally obtain fire-retardant hydrophilic polyesters fiber, the consumption of functional agglomerate is 3% of fire-retardant hydrophilic polyesters fiber quality, and the contact angle of its fiber is 50 degree.
Embodiment 3
A preparation method for fire-retardant hydrophilic polyesters fiber, its concrete steps are:
(1) preparation of hydrophilic polyesters section:
Terephthalic acid (TPA) is mixed in proportion to preparation slurry with ethylene glycol.After mixing in proportion, add reaction kettle of the esterification to carry out the first esterification with antimony acetate, antioxidant 1010, antioxidant 168 and three (nonyl phenyl) phosphite ester in the slurry preparing, the first esterification reaction temperature is 230 DEG C, the time of reaction is 3h, and the relative pressure of reaction is 0.35MPa.By fractionating column, water byproduct is separated and collected, by graduated cylinder measurement collection amount, calculate theoretical value according to reaction equation, the collecting amount of water reach theoretical value 88% time, add sorbierite and polyethylene glycol (PEG-4000) to carry out the second esterification, the second esterification reaction temperature is 250 DEG C, and pressure is normal pressure, and reaction time of esterification is 0.5h.Complete after esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out precondensation and whole polycondensation reaction, prepolymerization reaction carries out under low vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation reaction remains on 265 DEG C, the prepolymerization reaction time is 1.5h, and whole polycondensation reaction time is 1.5h, makes hydrophilic polyester section; In the strand of this hydrophilic polyester, comprise-COC
6h
4cOOCH
2cH
2o-and
two kinds of segment quantitative proportions are 100: 0.8; The inherent viscosity of described hydrophilic polyester is 0.60g/dl, and melt temperature is 235 DEG C.
(2) after discarded coffee grounds is dry, first, through the dry processing of 150～180 DEG C 3 hours, afterwards temperature risen to 600～700 DEG C of calcinings 2 hours, and then be warming up to 800～1000 DEG C of calcinings 2 hours, obtain coffee charcoal; Adopt ball-milling method to grind coffee charcoal and obtain the nanoscale coffee powdered carbon body that particle diameter is 90～100nm, nanoscale coffee powdered carbon body is immersed in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of sulfuric acid and nitric acid is 3: 1; Carry out heating using microwave reaction temperature is maintained to 45 DEG C and stirring reaction 3.5h, then wash neutrality with distilled water, obtain containing the solution of the nanoscale coffee powdered carbon body after activation; Add again fire retardant 2-carboxyethyl phenyl phosphinic acid, fire retardant is 3: 47 with the weight ratio of the solution that contains the nanoscale coffee powdered carbon body after activation, carry out ultrasonic oscillation reaction 2h, the time of ultrasonic oscillation is about 10 minutes, then dries the nanoscale coffee powdered carbon body obtaining for 60 minutes containing fire retardant for 60 DEG C;
(3) melt pelletization is carried out in the nanoscale coffee powdered carbon body containing fire retardant step (2) being obtained and the hydrophilic polyesters section that step (1) obtains, and temperature is 260～300 DEG C, obtains functional agglomerate; The consumption that contains the nanoscale coffee powdered carbon body of fire retardant is 1% of functional agglomerate quality.
(4) melt spinning is carried out in the hydrophilic polyesters section that functional agglomerate step (3) being obtained and step (1) obtain, wherein spinning temperature is 240～300 DEG C, spinning speed is 2000～3000m/min, process using normal polyester fibre manufacturing technique, finally obtain fire-retardant hydrophilic polyesters fiber, the consumption of functional agglomerate is 5% of fire-retardant hydrophilic polyesters fiber quality, and the contact angle of its fiber is 55 degree.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (7)
1. a preparation method for fire-retardant hydrophilic polyesters fiber, is characterized in that, concrete steps are:
The first step: terephthalic acid (TPA) is mixed to preparation slurry with ethylene glycol according to the mol ratio of 1:1.05～2.0; Add reaction kettle of the esterification to carry out the first esterification in the slurry preparing, accessory substance collecting amount reach theoretical value 82～95% time, add sorbierite and polyethylene glycol, carry out the second esterification, complete after esterification, carboxylate is carried out to polycondensation reaction, make hydrophilic polyester section; In the described first step, the addition of sorbierite is 0.1～2% of terephthalic acid (TPA) molal quantity; In the described first step, polyethylene glycol is PEG-2000, PEG-4000 or PEG-6000, and the addition of polyethylene glycol is 0.05～0.2% of terephthalic acid (TPA) molal quantity;
Second step: after coffee grounds is dry, calcining obtains coffee charcoal; The micronizing of coffee charcoal is obtained to nanoscale coffee powdered carbon body, nanoscale coffee powdered carbon body is immersed in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1; Carry out heating using microwave reaction temperature is maintained to 20～45 DEG C and stirring reaction 1～3.5h, then wash neutrality with distilled water, obtain containing the solution of the nanoscale coffee powdered carbon body after activation; Add again fire retardant, carry out ultrasonic oscillation reaction 1～2h, then dry the nanoscale coffee powdered carbon body obtaining containing fire retardant; In described second step, the calcination process of coffee grounds is: be warming up to 600～700 DEG C of calcinings 0.5～2 hour, then be warming up to 800～1000 DEG C of calcinings 1～3 hour;
The 3rd step: melt pelletization is carried out in the nanoscale coffee powdered carbon body containing fire retardant that second step is obtained and the hydrophilic polyesters section that the first step obtains, and temperature is 260～300 DEG C, obtains functional agglomerate;
The 4th step: melt spinning is carried out in the hydrophilic polyesters section that the functional agglomerate that the 3rd step is obtained and the first step obtain, and finally obtains fire-retardant hydrophilic polyesters fiber.
2. the preparation method of fire-retardant hydrophilic polyesters fiber as claimed in claim 1, is characterized in that, in the described first step, the first esterification, at 225～250 DEG C, is carried out under 0～0.4MPa condition, and the reaction time is 0.5～4h.
3. the preparation method of fire-retardant hydrophilic polyesters fiber as claimed in claim 1, is characterized in that, in the described first step, the second esterification is carried out under 240～260 DEG C, condition of normal pressure, and the reaction time is 0.5～1h.
4. the preparation method of fire-retardant hydrophilic polyesters fiber as claimed in claim 1, it is characterized in that, in the described first step, the slurry preparing being added reaction kettle of the esterification carry out before the first esterification, first by itself and catalyst mix, described catalyst is Titanium series catalyst, antimony-based catalyst or their composition, and the addition of catalyst is 120～550ppm, and radix is the quality of described terephthalic acid (TPA).
5. the preparation method of fire-retardant hydrophilic polyesters fiber as claimed in claim 1, it is characterized in that, in the described first step, the slurry preparing being added reaction kettle of the esterification carry out before the first esterification, first it is mixed with heat stabilizer and antioxidant, the addition of described heat stabilizer is 0.001～0.02wt% of terephthalic acid (TPA), 0.001～0.03wt% that the addition of antioxidant is terephthalic acid (TPA).
6. the preparation method of fire-retardant hydrophilic polyesters fiber as claimed in claim 1, is characterized in that, in described the 3rd step, the consumption that contains the nanoscale coffee powdered carbon body of fire retardant is 0.5～1% of functional agglomerate quality.
7. the preparation method of fire-retardant hydrophilic polyesters fiber as claimed in claim 1, is characterized in that, in described the 4th step, the consumption of functional agglomerate is 1～5% of fire-retardant hydrophilic polyesters fiber quality.
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| CN103014906B true CN103014906B (en) | 2014-10-15 |
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| CN111286050A (en) * | 2019-11-29 | 2020-06-16 | 浙江华欣新材料股份有限公司 | Preparation method of high-concentration PET color master batch |
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