CN113832719A - Preparation method of PBT (polybutylene terephthalate) elastic fiber - Google Patents
Preparation method of PBT (polybutylene terephthalate) elastic fiber Download PDFInfo
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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Abstract
The invention discloses a preparation method of PBT elastic fiber, which comprises the following steps: step 1, monomer preparation: terephthalic acid, 1, 4-butanediol and pentaerythritol are taken as raw materials to carry out esterification reaction; step 2, polycondensation preparation: putting the esterified monomer into a polycondensation reaction kettle for reaction; step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding a delustering agent and a flame retardant, and uniformly mixing to obtain a raw material mixture; step 4, spinning: preparing a PBT elastic fiber pre-product through melt spinning; step 5, modification: and (3) carrying out modification treatment on the PBT elastic fiber pre-product to obtain the PBT elastic fiber. The PBT elastic fiber obtained by the invention has better elasticity, moisture absorption and air permeability and higher heat distortion temperature, and in addition, the antistatic property of the PBT elastic fiber obtained by the invention is enhanced due to the enhanced moisture absorption.
Description
Technical Field
The invention relates to the field of PBT (polybutylene terephthalate) elastic fibers, and in particular relates to a preparation method of PBT elastic fibers.
Background
The PBT fiber (polybutylene terephthalate fiber) is different from the conventional terylene, and has the characteristics of weather resistance, stable size, crease resistance and the like of the terylene; but also has the soft hand feeling and the wear resistance of chinlon; the elastic recovery is better than that of chinlon, the dyeing performance is better than that of terylene, and the normal pressure boiling dyeing can be carried out. Particularly, the PBT fiber after deformation processing has excellent elasticity, and molecules can show reversible relaxation-tension states along with external force under low load or wet conditions. The fabric made of PBT fiber can move with, is very comfortable and close to the skin when being worn, and can be compared favorably with spandex fabric. However, the PBT fiber has the defects of poor moisture absorption and air permeability of the terylene, and the heat distortion temperature of the PBT fiber is lower than that of the terylene, so that the molding shrinkage is large, and the application of the PBT fiber is limited to a great extent by the defects.
Disclosure of Invention
Aiming at the problems of poor moisture absorption and air permeability, low thermal deformation temperature and large molding shrinkage of the PBT fiber in the prior art, the invention aims to provide a preparation method of the PBT elastic fiber.
The purpose of the invention is realized by adopting the following technical scheme:
the invention provides a preparation method of PBT elastic fiber, which comprises the following steps:
step 1, monomer preparation: terephthalic acid, 1, 4-butanediol and pentaerythritol are taken as raw materials, and esterification reaction is carried out under the action of a first catalyst to obtain an esterified monomer;
step 2, polycondensation preparation: putting an esterified monomer into a polycondensation reaction kettle, adding a stabilizer, and performing vacuum pumping reaction to obtain PBT resin;
step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding a delustering agent and a flame retardant, and uniformly mixing to obtain a raw material mixture;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing a PBT elastic fiber pre-product through melt spinning;
step 5, modification: and (3) carrying out modification treatment on the PBT elastic fiber pre-product to obtain the PBT elastic fiber.
Preferably, in the step 1, the first catalyst is one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate and tetrabutyl titanate, and the addition amount of the first catalyst is 2-6% of the mass of the terephthalic acid.
Preferably, in the step 1, the mass ratio of the terephthalic acid, the 1, 4-butanediol and the pentaerythritol is 2.6-3.2: 1: 0.2-0.4.
Preferably, the step 1 specifically comprises:
weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 160-180 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 200-220 ℃, mixing uniformly, adding a first catalyst, and carrying out heat preservation reaction for 3-5 hours to obtain an esterified monomer.
Preferably, in the step 2, the stabilizer is one of triphenyl phosphite, trimethyl phosphite and tricresyl phosphite, and the addition amount of the stabilizer is 1-3% of the mass of the esterified monomer.
Preferably, in the step 2, the reaction temperature is 250-280 ℃ and the reaction time is 3-5 h.
Preferably, in the step 3, the mass ratio of the flatting agent to the flame retardant to the PBT resin is 0.12-0.18: 0.25-0.35: 8-10.
Preferably, in the step 3, the flatting agent is anatase titanium dioxide, and the flame retardant is a phosphorus-nitrogen halogen-free flame retardant.
Preferably, in the step 4, the screw rotation speed of the screw extrusion spinning machine is 50-80 rpm, and the barrel temperature is 240-270 ℃.
Preferably, in the step 5, the method for modifying the PBT spandex comprises the following steps:
s1, dissolving orientin in alkali liquor, adding a PBT elastic fiber pre-product, stirring for 1-3 h at 50-70 ℃, standing for 3-5 h, filtering out liquid, washing with distilled water until the fiber is neutral, spreading the collected fiber, and drying under reduced pressure to obtain activated PBT fiber; wherein the mass ratio of the orientin to the PBT elastic fiber pre-product to the alkali liquor is 0.23-0.45: 1: 5-10;
s2, mixing itaconic acid and deionized water, fully stirring, adding nano boehmite, performing ultrasonic dispersion uniformly, heating to 60-80 ℃, stirring for 8-12 hours, filtering out liquid, washing with distilled water for at least three times, and performing reduced pressure drying to obtain itaconic acid/nano boehmite; wherein the mass ratio of the itaconic acid to the nano boehmite to the deionized water is 1: 2.5-4.5: 10-20;
s3, mixing the activated PBT fiber and itaconic acid/nano boehmite into DMF (dimethyl formamide), carrying out ultrasonic mixing uniformly, adding a second catalyst, heating to 135-155 ℃, carrying out stirring reaction for 4-6 h, filtering out liquid, washing with distilled water for at least three times, washing with ethanol for at least three times, and carrying out reduced pressure drying to obtain the PBT elastic fiber; the mass ratio of the activated PBT fiber to the itaconic acid/nano boehmite to the DMF is 1: 0.2-0.4: 5-10, and the mass ratio of the second catalyst to the activated PBT fiber is 0.03-0.05: 1.
Preferably, in S1, the alkali solution is sodium hydroxide solution or potassium hydroxide solution; the concentration of the alkali liquor is 0.5-0.8 mol/L.
Preferably, in S3, the second catalyst is one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
The invention has the beneficial effects that:
the invention discloses a preparation method of PBT elastic fiber, which comprises the steps of preparation, mixing, spinning and modification, wherein the preparation comprises monomer preparation and polycondensation preparation, raw materials used for preparation comprise conventional terephthalic acid and 1, 4-butanediol, and polyhydroxy pentaerythritol is added, an esterified monomer is formed through esterification and condensation, and the esterified monomer is subjected to polycondensation reaction to obtain PBT resin; the mixed raw materials are added with a delustering agent and a flame retardant besides the PBT resin, so that the effects of fiber delustering and flame retardance are improved; then spinning through a screw extrusion spinning machine to obtain a PBT elastic fiber pre-product; finally, the PBT elastic fiber pre-product is modified to finally obtain the PBT elastic fiber with better elasticity, moisture absorption and air permeability and higher heat distortion temperature, and in addition, the PBT elastic fiber prepared by the invention has enhanced antistatic property due to enhanced moisture absorption.
In the process of synthesizing the PBT resin, a small amount of pentaerythritol is added, the pentaerythritol can participate in esterification reaction, so that the finally generated esterified monomer comprises most of esterified substances combined by terephthalic acid and 1, 4-butanediol and a small amount of esterified substances combined by terephthalic acid and pentaerythritol, and the addition of the low-activity pentaerythritol can weaken the crystallinity and the orientation degree of the generated fiber, so that the fiber is easier to dye, and meanwhile, the low-activity pentaerythritol is used for laying a cushion for subsequent modification and can enhance the modification effectiveness.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The PBT fiber modification process is mainly carried out in three steps, wherein the first step is to carry out activation treatment on the PBT fibers, the PBT fibers are treated by using alkali liquor in the activation treatment step and then activated by using orientin, and the alkali liquor enables more holes to be formed on the surfaces of the PBT fibers and the orientin enables more hydroxyl functional groups to be coated on the surfaces of the fibers; the second step is to prepare nano boehmite with a large amount of itaconic acid coated on the surface by using itaconic acid and nano boehmite; and thirdly, reacting the itaconic acid/nano-boehmite with the activated PBT fiber, wherein the surface of the PBT fiber after orientin activation contains a large number of hydroxyl groups, and the PBT fiber is combined with the nano-boehmite coated with a large number of itaconic acid on the surface under the conditions of catalyst and heating, so that the nano-boehmite is fixedly adsorbed on the aperture and the surface of the PBT fiber, the fixing and adsorbing process is different from the conventional coupling and fixing process, and the itaconic acid/nano-boehmite can be combined with the PBT fiber after orientin activation to generate an ester group, so that the PBT fiber is more stable.
The invention is further described below with reference to the following examples.
Example 1
A preparation method of PBT elastic fiber comprises the following steps:
step 1, monomer preparation: weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 170 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 210 ℃, mixing uniformly, then adding tetraethyl titanate, and carrying out heat preservation reaction for 4 hours to obtain an esterified monomer; the adding amount of the tetraethyl titanate is 4 percent of the mass of the terephthalic acid; the mass ratio of terephthalic acid, 1, 4-butanediol and pentaerythritol is 2.8:1: 0.3;
step 2, polycondensation preparation: placing an esterification monomer in a polycondensation reaction kettle, adding triphenyl phosphite, and performing vacuum pumping reaction to obtain PBT resin; the addition amount of triphenyl phosphite is 2 percent of the mass of the esterification monomer, the reaction temperature is 275 ℃, and the reaction time is 4 hours;
step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding anatase titanium dioxide and a phosphorus-nitrogen halogen-free flame retardant, and uniformly mixing to obtain a raw material mixture; the mass ratio of the anatase titanium dioxide, the phosphorus-nitrogen halogen-free flame retardant to the PBT resin is 0.15:0.3: 9;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing a PBT elastic fiber pre-product through melt spinning; the screw rotating speed of the screw extrusion spinning machine is 70rpm, and the temperature of a machine barrel is 255 ℃;
step 5, modification: modifying the PBT elastic fiber pre-product to obtain the PBT elastic fiber;
the method for modifying the PBT elastic fiber comprises the following steps:
s1, dissolving orientin in a sodium hydroxide solution with the concentration of 0.6mol/L, adding a PBT elastic fiber pre-product, stirring for 2 hours at 60 ℃, standing for 4 hours, filtering out liquid, washing with distilled water until the fiber is neutral, spreading the collected fiber, and drying under reduced pressure to obtain activated PBT fiber; wherein the mass ratio of the orientin to the PBT elastic fiber pre-product to the alkali liquor is 0.32:1: 8;
s2, mixing itaconic acid and deionized water, adding nano boehmite after fully stirring, heating to 70 ℃ after uniformly dispersing by ultrasonic, stirring for 10 hours, filtering out liquid, washing with distilled water for at least three times, and drying under reduced pressure to obtain itaconic acid/nano boehmite; wherein the mass ratio of the itaconic acid to the nano boehmite to the deionized water is 1:3.5: 15;
s3, mixing the activated PBT fiber and itaconic acid/nano boehmite into DMF (dimethyl formamide), carrying out ultrasonic mixing uniformly, adding tetraethyl titanate, heating to 145 ℃, carrying out stirring reaction for 5 hours, filtering out liquid, washing with distilled water for at least three times, washing with ethanol for at least three times, and drying under reduced pressure to obtain the PBT elastic fiber; wherein the mass ratio of the activated PBT fiber to the itaconic acid/nano boehmite to the DMF is 1:0.3:8, and the mass ratio of the tetraethyl titanate to the activated PBT fiber is 0.04: 1.
Example 2
A preparation method of PBT elastic fiber comprises the following steps:
step 1, monomer preparation: weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 160 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 200 ℃, mixing uniformly, then adding tetraisopropyl titanate, and carrying out heat preservation reaction for 3 hours to obtain an esterified monomer; the addition amount of the tetraisopropyl titanate is 2 percent of the mass of the terephthalic acid; the mass ratio of terephthalic acid, 1, 4-butanediol and pentaerythritol is 2.6:1: 0.2;
step 2, polycondensation preparation: putting an esterification monomer into a polycondensation reaction kettle, adding trimethyl phosphite, and performing vacuum pumping reaction to obtain PBT resin; the addition of trimethyl phosphite accounts for 1% of the mass of the esterified monomer, the reaction temperature is 250 ℃, and the reaction time is 3 hours.
Step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding anatase titanium dioxide and a phosphorus-nitrogen halogen-free flame retardant, and uniformly mixing to obtain a raw material mixture; the mass ratio of the anatase titanium dioxide, the phosphorus-nitrogen halogen-free flame retardant to the PBT resin is 0.12:0.25: 8;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing a PBT elastic fiber pre-product through melt spinning; the screw rotating speed of the screw extrusion spinning machine is 50rpm, and the temperature of a machine barrel is 240 ℃;
step 5, modification: modifying the PBT elastic fiber pre-product to obtain the PBT elastic fiber;
the method for modifying the PBT elastic fiber comprises the following steps:
s1, dissolving orientin in a potassium hydroxide solution with the concentration of 0.5mol/L, adding a PBT elastic fiber pre-product, stirring at 50 ℃ for 1-3 h, standing for 3h, filtering out liquid, washing with distilled water until the fiber is neutral, spreading the collected fiber, and drying under reduced pressure to obtain activated PBT fiber; wherein the mass ratio of the orientin to the PBT elastic fiber pre-product to the alkali liquor is 0.23:1: 5;
s2, mixing itaconic acid and deionized water, adding nano boehmite after fully stirring, heating to 60 ℃ after uniformly dispersing by ultrasonic, stirring for 8 hours, filtering out liquid, washing with distilled water for at least three times, and drying under reduced pressure to obtain itaconic acid/nano boehmite; wherein the mass ratio of the itaconic acid to the nano boehmite to the deionized water is 1:2.5: 10;
s3, mixing the activated PBT fiber and itaconic acid/nano boehmite into DMF (dimethyl formamide), carrying out ultrasonic mixing uniformly, adding tetraisopropyl titanate, heating to 135 ℃, stirring for reaction for 4 hours, filtering out liquid, washing with distilled water for at least three times, washing with ethanol for at least three times, and drying under reduced pressure to obtain the PBT elastic fiber; wherein the mass ratio of the activated PBT fiber to the itaconic acid/nano boehmite to the DMF is 1:0.2:5, and the mass ratio of the tetraisopropyl titanate to the activated PBT fiber is 0.03: 1.
Example 3
A preparation method of PBT elastic fiber comprises the following steps:
step 1, monomer preparation: weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 180 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 220 ℃, mixing uniformly, then adding tetrapropyl titanate, and carrying out heat preservation reaction for 5 hours to obtain an esterified monomer; the addition amount of the tetrapropyl titanate is 6 percent of the mass of the terephthalic acid; the mass ratio of terephthalic acid, 1, 4-butanediol and pentaerythritol is 3.2:1: 0.4;
step 2, polycondensation preparation: putting an esterified monomer into a polycondensation reaction kettle, adding tricresyl phosphite, and performing vacuum pumping reaction to obtain PBT resin; the addition amount of the tricuspid phosphite is 3 percent of the mass of the esterified monomer, the reaction temperature is 280 ℃, and the reaction time is 5 hours.
Step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding anatase titanium dioxide and a phosphorus-nitrogen halogen-free flame retardant, and uniformly mixing to obtain a raw material mixture; the mass ratio of the anatase titanium dioxide, the phosphorus-nitrogen halogen-free flame retardant to the PBT resin is 0.18:0.35: 10;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing a PBT elastic fiber pre-product through melt spinning; the screw rotating speed of the screw extrusion spinning machine is 80rpm, and the temperature of a machine barrel is 270 ℃;
step 5, modification: modifying the PBT elastic fiber pre-product to obtain the PBT elastic fiber;
the method for modifying the PBT elastic fiber comprises the following steps:
s1, dissolving orientin in a sodium hydroxide solution with the concentration of 0.8mol/L, adding a PBT elastic fiber pre-product, stirring for 3 hours at 70 ℃, standing for 5 hours, filtering out liquid, washing with distilled water until the fiber is neutral, spreading the collected fiber, and drying under reduced pressure to obtain activated PBT fiber; wherein the mass ratio of the orientin to the PBT elastic fiber pre-product to the alkali liquor is 0.45:1: 10;
s2, mixing itaconic acid and deionized water, adding nano boehmite after fully stirring, heating to 80 ℃ after uniformly dispersing by ultrasonic, stirring for 12 hours, filtering out liquid, washing with distilled water for at least three times, and drying under reduced pressure to obtain itaconic acid/nano boehmite; wherein the mass ratio of the itaconic acid to the nano boehmite to the deionized water is 1:4.5: 20;
s3, mixing the activated PBT fiber and itaconic acid/nano boehmite into DMF (dimethyl formamide), carrying out ultrasonic mixing uniformly, adding tetrabutyl titanate, heating to 155 ℃, stirring and reacting for 6 hours, filtering out liquid, washing with distilled water for at least three times, washing with ethanol for at least three times, and drying under reduced pressure to obtain the PBT elastic fiber; wherein the mass ratio of the activated PBT fiber to the itaconic acid/nano boehmite to the DMF is 1:0.4:10, and the mass ratio of the tetrabutyl titanate to the activated PBT fiber is 0.05: 1.
Comparative example 1
A preparation method of PBT elastic fiber comprises the following steps:
step 1, monomer preparation: weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 170 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 210 ℃, mixing uniformly, then adding tetraethyl titanate, and carrying out heat preservation reaction for 4 hours to obtain an esterified monomer; the adding amount of the tetraethyl titanate is 4 percent of the mass of the terephthalic acid; the mass ratio of terephthalic acid, 1, 4-butanediol and pentaerythritol is 2.8:1: 0.3;
step 2, polycondensation preparation: placing an esterification monomer in a polycondensation reaction kettle, adding triphenyl phosphite, and performing vacuum pumping reaction to obtain PBT resin; the addition amount of triphenyl phosphite is 2 percent of the mass of the esterification monomer, the reaction temperature is 275 ℃, and the reaction time is 4 hours;
step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding anatase titanium dioxide and a phosphorus-nitrogen halogen-free flame retardant, and uniformly mixing to obtain a raw material mixture; the mass ratio of the anatase titanium dioxide, the phosphorus-nitrogen halogen-free flame retardant to the PBT resin is 0.15:0.3: 9;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing the PBT elastic fiber through melt spinning; the screw speed of the screw extrusion spinning machine was 70rpm, and the barrel temperature was 255 ℃.
Comparative example 2
A preparation method of PBT elastic fiber comprises the following steps:
step 1, monomer preparation: weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 170 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 210 ℃, mixing uniformly, then adding tetraethyl titanate, and carrying out heat preservation reaction for 4 hours to obtain an esterified monomer; the adding amount of the tetraethyl titanate is 4 percent of the mass of the terephthalic acid; the mass ratio of terephthalic acid, 1, 4-butanediol and pentaerythritol is 2.8:1: 0.3;
step 2, polycondensation preparation: placing an esterification monomer in a polycondensation reaction kettle, adding triphenyl phosphite, and performing vacuum pumping reaction to obtain PBT resin; the addition amount of triphenyl phosphite is 2 percent of the mass of the esterification monomer, the reaction temperature is 275 ℃, and the reaction time is 4 hours;
step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding anatase titanium dioxide and a phosphorus-nitrogen halogen-free flame retardant, and uniformly mixing to obtain a raw material mixture; the mass ratio of the anatase titanium dioxide, the phosphorus-nitrogen halogen-free flame retardant to the PBT resin is 0.15:0.3: 9;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing a PBT elastic fiber pre-product through melt spinning; the screw rotating speed of the screw extrusion spinning machine is 70rpm, and the temperature of a machine barrel is 255 ℃;
step 5, modification: modifying the PBT elastic fiber pre-product to obtain the PBT elastic fiber;
the method for modifying the PBT elastic fiber comprises the following steps:
s1, adding a PBT elastic fiber pre-product into a 0.6mol/L sodium hydroxide solution, stirring for 2 hours at 60 ℃, standing for 4 hours, filtering out liquid, washing with distilled water until the liquid is neutral, spreading the collected fibers, and drying under reduced pressure to obtain activated PBT fibers; wherein the mass ratio of the PBT elastic fiber pre-product to the alkali liquor is 1: 8;
s2, mixing the nano boehmite with deionized water, uniformly dispersing by ultrasonic, heating to 70 ℃, stirring for 10 hours, filtering out liquid, washing with distilled water for at least three times, and drying under reduced pressure to obtain active nano boehmite; wherein the mass ratio of the nano boehmite to the deionized water is 3.5: 15;
s3, mixing the activated PBT fiber and the active nano boehmite into DMF, uniformly mixing by ultrasonic, heating to 145 ℃, stirring for reacting for 5 hours, filtering out liquid, washing with distilled water for at least three times, washing with ethanol for at least three times, and drying under reduced pressure to obtain the PBT elastic fiber; wherein the mass ratio of the activated PBT fiber to the active nano boehmite to the DMF is 1:0.3: 8.
For more clearly explaining the invention, the PBT elastic fibers prepared in the embodiments 1-3 and the comparative examples 1-2 of the invention are compared in performance detection, wherein the breaking strength and the breaking elongation are detected according to the standard GB/T14337-.
The results are shown in Table 1.
TABLE 1 comparison of the Properties of Spandex prepared by different methods
As can be seen from Table 1, the PBT elastic fiber prepared in the embodiments 1-3 of the invention has higher breaking strength and elongation at break, which shows better mechanical strength, higher moisture regain, stronger hygroscopicity, higher heat distortion temperature and lower molding shrinkage, which shows higher high temperature resistance and more stability, and the volume specific resistance level is 107～108Meanwhile, the antistatic performance is much lower than that of comparative examples 1-2, which shows that the antistatic performance is better.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the PBT elastic fiber is characterized by comprising the following steps:
step 1, monomer preparation: terephthalic acid, 1, 4-butanediol and pentaerythritol are taken as raw materials, and esterification reaction is carried out under the action of a first catalyst to obtain an esterified monomer;
step 2, polycondensation preparation: putting an esterified monomer into a polycondensation reaction kettle, adding a stabilizer, and performing vacuum pumping reaction to obtain PBT resin;
step 3, mixing raw materials: weighing PBT resin, adding the PBT resin into a mixing stirrer, heating to be completely molten, sequentially adding a delustering agent and a flame retardant, and uniformly mixing to obtain a raw material mixture;
step 4, spinning: putting the raw material mixture into a screw extrusion spinning machine, and preparing a PBT elastic fiber pre-product through melt spinning;
step 5, modification: and (3) carrying out modification treatment on the PBT elastic fiber pre-product to obtain the PBT elastic fiber.
2. The method for preparing the PBT elastic fiber according to claim 1, wherein in the step 1, the first catalyst is one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate and tetrabutyl titanate, and the addition amount of the first catalyst is 2-6% of the mass of the terephthalic acid.
3. The preparation method of the PBT elastic fiber according to claim 1, wherein in the step 1, the mass ratio of the terephthalic acid, the 1, 4-butanediol and the pentaerythritol is 2.6-3.2: 1: 0.2-0.4.
4. The preparation method of the PBT elastic fiber according to claim 1, wherein the step 1 is specifically:
weighing terephthalic acid and 1, 4-butanediol, mixing the terephthalic acid and the 1, 4-butanediol into a reaction container, heating to 160-180 ℃, introducing nitrogen as a protective gas, stirring and dispersing uniformly, adding pentaerythritol, continuously heating to 200-220 ℃, mixing uniformly, adding a first catalyst, and carrying out heat preservation reaction for 3-5 hours to obtain an esterified monomer.
5. The method for preparing PBT elastic fiber according to claim 1, wherein in the step 2, the stabilizer is one of triphenyl phosphite, trimethyl phosphite and tricresyl phosphite, and the addition amount of the stabilizer is 1% -3% of the mass of the esterified monomer.
6. The preparation method of the PBT elastic fiber according to claim 1, wherein in the step 2, the reaction temperature is 250-280 ℃ and the reaction time is 3-5 h.
7. The preparation method of the PBT elastic fiber according to claim 1, wherein in the step 3, the mass ratio of the delustering agent to the flame retardant to the PBT resin is 0.12-0.18: 0.25-0.35: 8-10.
8. The preparation method of the PBT elastic fiber according to claim 1, wherein in the step 4, the screw rotation speed of the screw extrusion spinning machine is 50-80 rpm, and the barrel temperature is 240-270 ℃.
9. The preparation method of the PBT elastic fiber according to claim 1, wherein in the step 5, the PBT elastic fiber is modified by the following method:
s1, dissolving orientin in alkali liquor, adding a PBT elastic fiber pre-product, stirring for 1-3 h at 50-70 ℃, standing for 3-5 h, filtering out liquid, washing with distilled water until the fiber is neutral, spreading the collected fiber, and drying under reduced pressure to obtain activated PBT fiber; wherein the mass ratio of the orientin to the PBT elastic fiber pre-product to the alkali liquor is 0.23-0.45: 1: 5-10;
s2, mixing itaconic acid and deionized water, fully stirring, adding nano boehmite, performing ultrasonic dispersion uniformly, heating to 60-80 ℃, stirring for 8-12 hours, filtering out liquid, washing with distilled water for at least three times, and performing reduced pressure drying to obtain itaconic acid/nano boehmite; wherein the mass ratio of the itaconic acid to the nano boehmite to the deionized water is 1: 2.5-4.5: 10-20;
s3, mixing the activated PBT fiber and itaconic acid/nano boehmite into DMF (dimethyl formamide), carrying out ultrasonic mixing uniformly, adding a second catalyst, heating to 135-155 ℃, carrying out stirring reaction for 4-6 h, filtering out liquid, washing with distilled water for at least three times, washing with ethanol for at least three times, and carrying out reduced pressure drying to obtain the PBT elastic fiber; the mass ratio of the activated PBT fiber to the itaconic acid/nano boehmite to the DMF is 1: 0.2-0.4: 5-10, and the mass ratio of the second catalyst to the activated PBT fiber is 0.03-0.05: 1.
10. The method of claim 9, wherein in the step S3, the second catalyst is one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
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