KR20190042600A - Method for producing cation-exchangeable polyester fiber - Google Patents

Abstract

The present invention relates to a method for producing a cationic fluorine-containing polyester fiber. First, sodium dimethyl isophthalate-5-benzenesulfonate, ethylene glycol and a catalyst are mixed and then transesterified. After completion of the reaction, An ion regulator and sulfuric acid to prepare an esterification reaction. After the esterification reaction is carried out after mixing terephthalic acid, ethylene glycol, a catalyst and a quencher, the resulting product is added to the reaction system having reached the end of the esterification reaction And a condensation reaction is carried out to prepare a spinning melt. Finally, the spinning melt is metered, extruded, cooled, oil-ringed, stretched, heat set and wound to produce a cation-exchangeable polyester fiber. The method of the present invention reduces the pressure build-up of spinning assemblies and filters, extends the service life, reduces production costs, and ensures continuity and safety of the entire production process by reducing impurities generated during the polyester manufacturing process And has excellent economic value and dissemination value.

Description

Method for producing cation-exchangeable polyester fiber

TECHNICAL FIELD The present invention relates to the field of polyester spinning, and more particularly, to a method for producing a cationophilic polyester fiber.

Since the PET fiber has characteristics such as degree of cementation, high degree of gravity, and high vitrification temperature, it is difficult to dye the dye into the PET molecule in the absence of carrier at normal pressure, so that dyeing of the PET fiber is carried out at high temperature, Condition. Cationic Dye Phosphoric Acid PET (CDP) is a copolymer formed by introducing a third component into the polymer chain of PET overcoming the disadvantage of difficulty in dyeing with polyester, and it is now another PET variety and the third component generally contains a strongly acidic sulfonic acid sodium group -SO ₃ Na, sodium sulfonate group by an easy to dye having an affinity for the dye, and can be chemically reactive with the cationic dye is fixed to the fiber It is able to meet the various demands of modern life because the color of the dyed fabric is bright, the chromatogram is complete, the dyeing rate is high, and after washing, it is not discolored or discolored. Recently, cationic dye-transferable PET has been rapidly developed.

However, by adding the third component to the CDP melt, the apparent viscosity is relatively large, and the impurities generated in the production process also increase accordingly, so that the pressure difference of some radiator assemblies and the pressure difference of the filter quickly rise. At the same time, And this carbonized caulking material adheres to the inner wall of the pipe, so that the pipeline system is likely to be clogged and is difficult to remove, resulting in great difficulty in pipe dredging work. Also, since the use period of the filter is greatly reduced during the production of such fibers, it is generally only one week, and the usage period of some other radiation assemblies is generally only 10 days, so frequent cleaning and frequent replacement of the radiation assemblies do. This not only increases operating costs, but also affects the continuity and safety of the entire production process.

Therefore, there is a desperate need to develop a method for producing cationic flame-type polyester fiber which can effectively reduce the generation of impurities in the production process of polyester.

In the course of the production of the cationic dye-dyeable polyester, a third component having a sulfonic acid group (-SO ₃ ^- ) is often added to improve the dyeing rate of the polyester fiber. The structural characteristic of the sulfonic acid group (-SO ₃ ^- ) is As shown below. 1) The sulfonic acid group (-SO ₃ ^- ) is connected to the metal ion in different directions, so that the structural dimension forms a larger complex or accepts three hydrogen bonds in different directions simultaneously as a hydrogen bond acceptor to form divergent hydrogen bonds Having three oxygen atoms. 2) The sulfonic acid group has a strong electron withdrawing ability and can decrease the electron density of the benzene ring and can enhance the electric function of the metal complex to easily form a pore-like complex. 3) The coordination degree of the sulfonic acid group is adjustable. More than ten different coordination schemes exist between the sulfonic acid group (-SO ₃ ^- ) and the metal ion and can coordinate with the metal and the transition metal.

Cationic dyestuffs In the polymerization step of the cationic dyes, an Sb-based catalyst (ethylene glycol antimony or antimony oxide) is usually added, but the addition amount of terephthalic acid is several times as high as that of terephthalic acid, and the content of Sb in the caulking material is very high. It is obvious that it is derived. Concentration of the metal Sb is due to the fact that the antimony ion of the Sb-based catalyst easily forms a coordination compound by coordination bonding with the third component and / or the sulfonic acid group (-SO ₃ ^- ) of the polymer. Once the antimony ion and the sulfonic acid group SO ₃ ^- ) is concentrated in a binding mode, impurities in the spinning melt are increased, and carbonized caulking material is formed on the inner wall of the melt pipe, thereby clogging the pipe system. The insolubility of the carbonized caulking material causes a great difficulty in the dredging of the pipe, and at the same time, the pressure difference of some assemblies and the pressure difference of the filter increase rapidly, seriously affecting the usage period of the filter and some assemblies. The use frequency of the filter is only one week, and the use frequency of the assembly is only about 10 days. Increasing the frequency of cleaning and replacement of assemblies not only increases operating costs, but also affects the continuity and safety of the entire production process. Therefore, reducing the generation of such impurities is a key factor in radiating cationic dye-transferable polyester fibers.

It is an object of the present invention to provide a method for producing a cation-exchangeable polyester fiber which solves the above-mentioned problems existing in the prior art and effectively reduces impurities generated in the course of polyester production.

In order to solve the above problems, the present invention applies the following technical solutions.

The production method of the cationic fluorine-containing polyester fiber includes the following steps.

a) preparing a spinning melt;

(1) Sodium dimethyl isophthalate-5-benzenesulfonate, ethylene glycol, and a catalyst are mixed and ester exchange reaction is performed. After completion of the reaction, ethylene glycol, A complex ion modifier and sulfuric acid, wherein the complex ion modifier is at least one of potassium glycol, sodium glycol and calcium glycol;

The purpose of adding ethylene glycol after the transesterification reaction is to control the concentration of sodium bis hydroxyethyl isophthalate-5-sulfonate (SIPE) in the ethylene glycol solution, and sodium bishydroxyethyl isophthalate-5-sulphonate Is higher than 40 wt%, precipitation occurs and is disadvantageous to the subsequent reaction; In the prior art, the catalyst used in the cationic dye-transferable polyester polymerization step is generally ethylene glycol antimony or antimony oxide, and the sulfonic acid group in the third component introduced into the PET chip and antimony ion in the catalyst frequently undergoes coordination chemical reaction Complex is formed, and the complex also undergoes a self-polymerization reaction in accordance with the third component to produce a caulking material which is deposited on the pipe surface and the radiating plate to form a clog. In the present invention, the complex ion control agent is capable of providing a coexisting ion which is in competition with a certain amount of antimony ion, affects and weakens the coordination action of the antimony ion and the sulfonate group, and effectively decreases the complex formed by the sulfonate group and the catalyst . To reduce impurities in the spinning melt, to maintain good flow performance of the polyester, and to ensure the radioactivity of the cationic fluorophilic polyester fibers; H + in sulfuric acid reacts with the sulfonic acid group to affect the complex, and the presence of H + reduces the ability of the sulfonic acid group to cause a coordination reaction, which can be referred to as the acid effect. The higher the concentration of H + is, the more acidic the effect is, and the amount of acid can reduce the formation of the complex, but if it is too much, it affects the thermal stability of the polyester. Addition of a certain amount of sulfuric acid can reduce the formation of complexes and allow more stable flow of the polyester.

(2) an esterification reaction is performed after mixing terephthalic acid, ethylene glycol, a catalyst and a quencher, wherein the quencher is titanium dioxide particle coated with calcium oxide.

The addition of the quencher can convert the polyester from its original large brilliant state to the subsequent semi-extinction (translucent) state, which is advantageous for the progress of the subsequent reaction, the metal calcium ion can form a weak coordination with the sulfonic acid group, The metal titanium ion can form a strong coordination with the sulfonic acid group, and the titanium dioxide particle coated with calcium oxide is used to further reduce the coordination action of the titanium ion and the sulfonic acid group, and does not affect the quenching action.

(3) The product of (1) is added to (2) and a condensation reaction is carried out to prepare a spinning melt.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber.

As a preferred technical solution, the specific steps of producing the spinning melt by the above-mentioned method of producing the cationic fluorine-containing polyester fiber are as follows.

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate (SIPE)

Sodium dimethyl isophthalate-5-benzenesulfonate and ethylene glycol were added to the preparation kettle, the catalyst Zn (Ac) ₂ was added, and the ester exchange reaction was carried out at 175 to 185 ° C until the water distillation amount reached 90% To obtain sodium bis hydroxyethyl isophthalate-5-sulfonate, and adding ethylene glycol, a complex ion modifier and sulfuric acid to obtain an aqueous solution containing 30-35 wt% of sodium bis hydroxyethyl isophthalate-5-sulphonate Glycol solution.

(2) Esterification is carried out to prepare ethylene terephthalate

Terephthalic acid and ethylene glycol are slurried and then a catalyst, a stabilizer and a quencher are added to the mixture to homogeneously mix and esterify to obtain ethylene terephthalate. The esterification reaction is a pressurization reaction in a nitrogen atmosphere, Is from atmospheric pressure to 0.3 MPa, the temperature of the esterification reaction is from 250 to 260 DEG C, and the point at which the water distillation amount in the esterification reaction reaches 90% or more of the theoretical value is the end point of the esterification reaction.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) is put into step (2), and the condensation reaction in the low vacuum step is first carried out under a negative pressure condition. The pressure in the above step is pumped smoothly at atmospheric pressure to an absolute pressure of 500 Pa or less, And the reaction time is 30 to 50 min. Subsequently, by vacuum pumping, the condensation reaction in the high vacuum step is carried out to reduce the reaction pressure to an absolute pressure of 100 Pa or less, the reaction temperature is 275 to 285 ° C, 90 min to produce a spinning melt.

In the step (1) of the above-mentioned method for producing a cationic fluorophilic polyester fiber, at the beginning of the transesterification reaction, the molar ratio of sodium dimethyl isophthalate-5-benzenesulfonate to ethylene glycol is 10 to 12: The addition amount of Zn (Ac) ₂ is 0.2 to 0.5 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

In the preparation, the amount of the complex ion regulator added is 1.5 to 6 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate, the mass concentration of added sulfuric acid is 40 to 60%, and the amount of sulfuric acid added is sodium dimethyl isophthalate- Is from 1.5 to 6 wt% of the addition amount of 5-benzenesulfonate.

In the step (2) of the method for producing a cationic fluorophilic polyester fiber as described above, the molar ratio of terephthalic acid to ethylene glycol is 1.10 to 1.30: 1 at the start of the esterification reaction, and the catalyst is diantimony trioxide, Ethylene glycol antimony or antimony acetate. The amount of the catalyst to be added is 0.01 to 0.05 wt% of the addition amount of terephthalic acid. The stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite ), The addition amount of the stabilizer is 0.01 to 0.05 wt% of the addition amount of terephthalic acid, and the addition amount of the quencher is 0.05 to 0.2 wt% of the addition amount of terephthalic acid.

In the step (3) of the method for producing the cationic-fluorine-containing polyester fiber as described above, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate to ethylene terephthalate is 1 to 3: 100 .

In the above-mentioned method for producing a cationic-fluorine-containing polyester fiber, the content of calcium oxide in the quencher is 1 to 5% of the mass of titanium dioxide and the BET specific surface area is 50 to 200 m ² / g.

The method for producing the quencher is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred and ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 5 to 10% and a calcium salt was added thereto, 60 to 80 ° C, and the reaction time is 2 to 3 hours. When the reaction is completed, the titanium dioxide particles coated with calcium oxide are prepared by centrifuging, washing, drying and high-temperature treatment at 400 to 800 ° C. for 2 to 5 hours.

Here, the calcium salt is calcium chloride or calcium sulfate. At the start of the reaction, the molar ratio of calcium ions to titanium ions is 1 to 5: 100, and the pH of the reaction system is 10 to 14.

In the above-mentioned method for producing a cationic fluorine-containing polyester fiber, in order to adapt to the effect of the addition of substances such as ethylene glycol, sulfuric acid, complex ion control agent and quencher in the production process on the final spinning process, The radial process parameters should be adjusted. The controlled process parameters are as follows.

Extrusion temperature: 285 to 300 占 폚;

Cooling temperature: 20 ~ 25 ℃;

Winding speed: 4000 to 4600 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process of the cationic fluorine-containing polyester fiber fabrication method as described above, the pressure rise of the spinning assembly is? P? 1.0 bar / day, the pressure rise of the filter is? P? 3.0 bar, To 35 days, and the use period of the filter is 25 to 30 days.

In the above-mentioned method for producing a cationically-labile polyester fiber, the cationic-flame type polyester fiber has a single-fiber fineness of 0.5 to 1.5 dtex, a breaking strength of ≥3.00 cN / dtex, and a dyeing rate of more than 95%.

In the above-mentioned method for producing a cationic fluorine-containing polyester fiber, the cationic fluorine-containing polyester fiber has a fracture elongation percentage of 40.0 占 .5%, a linear density variation rate of? 0.5% and a fracture strength CV value of? 4.0% , The fracture elongation CV value is? 8.0%, and the real unevenness degree CV value is? 2.0%.

(1) The method of producing the cationically-labile polyester fiber of the present invention reduces the pressure rise of the spinning assembly and the filter, decreases the production cost by decreasing the impurities generated during the polyester production process, Thereby ensuring continuity and safety of the entire production process, and having excellent economic value and spreading value.

 (2) The addition of the complex ion control agent and the sulfuric acid in the process for producing the cationically-labile polyester fiber of the present invention reduces impurities in the spinning melt by reducing the formation of the complex in the polyester production process, Thereby maintaining the flow performance and further ensuring the radioactivity of the cation-exchangeable polyester fiber.

 (3) In the method of producing the cationically labile polyester fiber of the present invention, the quenching agent further reduces the coordination action between the titanium ion and the sulfonic acid group by using the titanium dioxide particle coated with the calcium oxide, Do not give.

Hereinafter, the present invention will be described in detail with reference to specific embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. And it is to be understood that such equivalent forms also fall within the scope defined by the claims appended hereto.

Example 1

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

First, sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 10: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto. At 176 ° C., the water distillation amount reached 91% of the theoretical value Ester exchange reaction was performed to obtain sodium bishydroxyethyl isophthalate-5-sulfonate, and after completion of the reaction, ethylene glycol, potassium glycol and sulfuric acid were added to obtain 30.4 wt% sodium bishydroxyethyl isophthalate- -Sulfonate. ≪ / RTI > The addition amount of the catalyst Zn (Ac) ₂ is 0.5 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate, and the amount of potassium glycol added during preparation is 6 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate %, The added sulfuric acid mass concentration is 40%, and the addition amount of sulfuric acid is 1.5 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 μm and deionized water were mixed and stirred and then ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 5% and calcium chloride was added thereto for reaction. At the start of the reaction, And titanium ion were 1.5: 100, the reaction temperature was 62 ° C, the reaction time was 2 hours, and the pH of the reaction system was 10. After completion of the reaction, the reaction mixture was centrifuged, washed, To prepare the coated titanium dioxide particles.

Terephthalic acid and ethylene glycol having a molar ratio of 1.10: 1 were slurried, and titanium dioxide particles coated with diantimony trioxide, triphenyl phosphate and calcium oxide were added and mixed uniformly. The esterification reaction was carried out at 260 ° C to obtain ethylene terephthalate Phthalate is produced, and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of atmospheric pressure, and the point at which the water distillation amount in the esterification reaction reaches 90% of the theoretical value is the end point of the esterification reaction. Here, the amount of addition of antimony trioxide was 0.05 wt% of the addition amount of terephthalic acid, the addition amount of triphenyl phosphate was 0.01 wt% of the addition amount of terephthalic acid, the addition amount of calcium oxide-coated titanium dioxide was 0.05 wt% of the addition amount of terephthalic acid , The content of calcium oxide in titanium dioxide particles coated with calcium oxide is 1% of the mass of titanium dioxide and the BET specific surface area is 50 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) is put into step (2) and condensation reaction is first carried out at a low vacuum stage under a negative pressure condition, and the pressure at this stage is pumped smoothly at an absolute pressure of 500 Pa or less at normal pressure. And then continuously vacuum-pumped to perform a condensation reaction in a high vacuum stage to reduce the reaction pressure to an absolute pressure of 99.5 Pa. The reaction temperature is 275 ° C and the reaction time is 50 min to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 1: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 290 DEG C;

Cooling temperature: 25 캜;

Winding speed: 4500 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, potassium glycol and sulfuric acid, effectively reducing the pressure buildup of the spinning assembly and filter. Here, the pressure rise of the radiation assembly is? P = 0.95 bar / day, the pressure rise of the filter is? P = 2.8 bar / day, the use period of the radiation assembly is 32 days, and the use period of the filter is 26 days.

The cationic fluorine-containing polyester fiber obtained by the above step had a single-yarn fineness of 1.5 dtex, a breaking strength of 2.60 cN / dtex, a dyeing rate of 97%, a elongation at break of 45.0%, a line density deviation rate of 0.2% , The fracture strength CV value is 2.3%, the fracture elongation CV value is 5.0% and the actual fracture strength CV value is 2.0%.

Comparative Example 1

In the prior art, the dyeing of the PET fibers should be carried out under the conditions of high temperature, high pressure or the presence of the carrier. The production steps are basically the same as in Example 1, except that in step (1), ethylene glycol, , The pressure rise ΔP of the spinning assembly during the spinning process is 3.43 bar / day, the pressure rise ΔP of the filter is 4.2 bar / day, the spinning assembly use period is 7 days, It is 10 days different. The produced cationic fluorine-containing polyester fiber monofilament fineness was 0.28 dtex, the breaking strength was 1.63 cN / dtex, the staining rate was 91.3%, the elongation at break was 25.0%, the linear density deviation rate was 0.75% Value of 5.2%, fracture elongation CV value of 11.05%, and real irregularity CV value of 4.8%. Compared to Example 1, the present invention significantly reduces the pressure build-up of the spinning assembly and filter during the spinning process , The use period is largely extended, the production efficiency is greatly improved, the cost is reduced, the productivity of the present invention is remarkably improved, and the economical efficiency is good.

Example 2

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

First, sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 10.5: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto, and the water distillation amount at 178 ° C was 92% Ester exchange reaction was performed to obtain sodium bishydroxyethyl isophthalate-5-sulfonate, and after completion of the reaction, ethylene glycol, sodium glycol and sulfuric acid were added to obtain 31 wt% sodium bishydroxyethyl isophthalate- To prepare an ethylene glycol solution containing a sulfonate. The addition amount of the catalyst Zn (Ac) ₂ is 0.2 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate, and the amount of sodium glycol added during preparation is 3 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate %, The added sulfuric acid mass concentration is 43%, and the addition amount of sulfuric acid is 1.8 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred and ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 5% and calcium sulfate was added thereto for reaction. At the start of the reaction, calcium Ion and titanium ion was 2: 100, the reaction temperature was 66 ° C, the reaction time was 2.2h, and the pH of the reaction system was 11. After completion of the reaction, the reaction mixture was centrifuged, Treated at a high temperature to prepare titanium dioxide particles coated with calcium oxide.

Terephthalic acid and ethylene glycol having a molar ratio of 1.15: 1 were slurried, and then titanium dioxide particles coated with ethylene glycol antimony, trimethyl phosphate and calcium oxide were added, uniformly mixed, and the esterification reaction was carried out at 253 ° C, Phthalate is produced and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of 0.1 MPa and the point at which the water distillation amount in the esterification reaction reaches 91% of the theoretical value is the end point of the esterification reaction. Here, the addition amount of ethylene glycol antimony is 0.02 wt% of the addition amount of terephthalic acid, the addition amount of trimethyl phosphate is 0.02 wt% of the addition amount of terephthalic acid, the addition amount of calcium oxide-coated titanium dioxide particles is 0.08 wt% of the addition amount of terephthalic acid , The content of calcium oxide in the titanium dioxide particle coated with calcium oxide is 2% of the mass of titanium dioxide and the BET specific surface area is 70 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) is put into step (2) and condensation reaction is first carried out at a low vacuum stage under a negative pressure condition. The pressure in the step is pumped smoothly at an absolute pressure of 490 Pa at normal pressure. 35 minutes. Subsequently, a vacuum pump is carried out to carry out a condensation reaction in a high vacuum stage to reduce the reaction pressure to an absolute pressure of 98 Pa. The reaction temperature is 277 deg. C and the reaction time is 60 min to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 1.3: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 285 DEG C;

Cooling temperature: 23 캜;

Winding speed: 4600 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, sodium glycol and sulfuric acid, effectively reducing the pressure build-up of the spinning assembly and filter. Here, the pressure rise of the radiation assembly is? P = 0.85 bar / day, the pressure rise of the filter is? P = 2.79 bar / day, the use period of the radiation assembly is 30 days, and the use period of the filter is 27 days.

The monofilament fineness of the cationic fluorine-containing polyester fiber obtained by the above step was 0.5 dtex, the breaking strength was 3.00 cN / dtex, the staining rate was 96%, the elongation at break was 45.0%, the linear density deviation rate was 0.45% , The breaking strength CV value is 4.0%, the breaking elongation CV value is 6.5%, and the yarn unevenness CV value is 1.8%.

Example 3

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

First, sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 11: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto. The mixture was stirred at 175 ° C until the water distillation amount reached 90% Ester exchange reaction was carried out to obtain sodium bishydroxyethyl isophthalate-5-sulfonate, and after completion of the reaction, ethylene glycol, calcium glycol and sulfuric acid were added to obtain 30 wt% sodium bis hydroxyethyl isophthalate- To prepare an ethylene glycol solution containing a sulfonate. The addition amount of the catalyst Zn (Ac) ₂ is 0.3 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate, and the amount of calcium glycol added during preparation is 1.5 of the amount of sodium dimethyl isophthalate-5-benzenesulfonate wt%, the added sulfuric acid mass concentration is 45%, and the addition amount of sulfuric acid is 2.0 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred and ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 10% and calcium chloride was added thereto for reaction. At the start of the reaction, And titanium ion were 3.5: 100, the reaction temperature was 80 ° C, the reaction time was 2.3 hours, the pH of the reaction system was 12, and the reaction was terminated by centrifugation, washing, drying and high temperature treatment To prepare titanium dioxide particles coated with calcium oxide.

Terephthalic acid and ethylene glycol having a molar ratio of 1.20: 1 were slurried, and titanium dioxide particles coated with antimony acetate, trimethylphosphite and calcium oxide were added thereto, uniformly mixed and esterified at 255 ° C to obtain ethylene Terephthalate is prepared and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of 0.15 MPa. The point at which the water distillation amount in the esterification reaction reaches 92% of the theoretical value is the end point of the esterification reaction. The addition amount of antimony acetate is 0.03 wt% of the addition amount of terephthalic acid, the addition amount of trimethyl phosphite is 0.03 wt% of the addition amount of terephthalic acid, the addition amount of calcium oxide-coated titanium dioxide particles is 0.11 wt% , And the content of calcium oxide in the titanium dioxide particle coated with calcium oxide is 3% of the mass of titanium dioxide and the BET specific surface area is 100 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) was put into (2) and condensation reaction was first carried out at a low vacuum stage under a negative pressure condition. The pressure at this stage was pumped smoothly at an absolute pressure of 480 Pa at normal pressure. 40 minutes. Subsequently, the reaction mixture is vacuum-pumped to carry out a condensation reaction in a high vacuum stage to reduce the reaction pressure to 98 Pa. The reaction temperature is 279 DEG C and the reaction time is 70 minutes to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 1.7: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 287 DEG C;

Cooling temperature: 22 캜;

Winding speed: 4000 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, calcium glycol and sulfuric acid, effectively reducing the pressure buildup of the spinning assembly and filter. Here, the pressure rise of the radiation assembly is? P = 1.0 bar / day, the pressure rise of the filter is? P = 2.7 bar / day, the use period of the radiation assembly is 34 days, and the use period of the filter is 25 days.

The cationic fluorine-containing polyester fiber obtained by the above step had a single-yarn fineness of 1.5 dtex, a breaking strength of 2.88 cN / dtex, a dyeing rate of 96.5%, a elongation at break of 40.0%, a linear density variation rate of 0.5% , The breaking strength CV value is 3.7%, the breaking elongation CV value is 7.3%, and the yarn unevenness CV value is 1.7%.

Example 4

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

First, sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 12: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto, and the water distillation amount at 181 캜 reached 93.5% of the theoretical value After the reaction was completed, a mixture of ethylene glycol, potassium glycol and sodium glycol (1: 1 by mass ratio) and sulfuric acid were added to obtain 32.8 wt.% Of sodium bishydroxyethyl isophthalate-5-sulfonate % Of sodium bis hydroxyethyl isophthalate-5-sulphonate is prepared. The addition amount of the catalyst Zn (Ac) ₂ is 0.35 wt% of the addition amount of sodium dimethyl isophthalate-5-benzenesulfonate. When the amount of the mixture of potassium glycol and sodium glycol is adjusted, 5 wt% of the addition amount of nitrate, the added sulfuric acid mass concentration is 47%, and the addition amount of sulfuric acid is 3.5 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred, followed by ultrasonic dispersion to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 7.5%, and calcium sulfate was added thereto for reaction. At the beginning of the reaction, calcium Ion and titanium ion was 1: 100, the reaction temperature was 70 ° C, the reaction time was 2.5h, and the pH of the reaction system was 13. After completion of the reaction, the reaction mixture was centrifuged, Treated at a high temperature to prepare titanium dioxide particles coated with calcium oxide.

After slurrying terephthalic acid and ethylene glycol having a molar ratio of 1.25: 1, titanium dioxide particles coated with diantimony trioxide, triphenyl phosphate, and calcium oxide were added, uniformly mixed, and esterified at 257 ° C to obtain ethylene terephthalate Phthalate is produced and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of 0.2 MPa. The point at which the water distillation amount in the esterification reaction reaches 93% of the theoretical value is the end point of the esterification reaction. The addition amount of terephthalic acid is 0.04 wt%, the amount of triphenyl phosphate is 0.04 wt% of the addition amount of terephthalic acid, the addition amount of calcium oxide-coated titanium dioxide is 0.13 wt% of the addition amount of terephthalic acid , The content of calcium oxide in the titanium dioxide particles coated with calcium oxide is 4% of the mass of titanium dioxide and the BET specific surface area is 120 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) was put into (2) and condensation reaction was first carried out at a low vacuum stage under a negative pressure condition. The pressure at this stage was pumped smoothly at an absolute pressure of 470 Pa at normal pressure. 30 minutes. Subsequently, the reaction mixture is vacuum pumped to carry out a condensation reaction in a high vacuum stage to reduce the reaction pressure to an absolute pressure of 96 Pa. The reaction temperature is 280 占 폚 and the reaction time is 70 minutes to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 2: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 290 DEG C;

Cooling temperature: 20 캜;

Winding speed: 4100 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, a mixture of potassium glycol and sodium glycol, and sulfuric acid, effectively reducing the pressure build-up of the spinning assembly and filter. Here, the pressure rise of the radiation assembly is? P = 0.92 bar / day, the pressure rise of the filter is? P = 3.0 bar / day, the use period of the radiation assembly is 35 days, and the use period of the filter is 28 days.

The cationic flame type polyester fiber obtained by the above step had a single fiber fineness of 0.8 dtex, a breaking strength of 3.20 cN / dtex, a dyeing rate of 97.5%, a elongation at break of 40.0%, a line density deviation rate of 0.4% , The breaking strength CV value is 4.0%, the breaking elongation CV value is 7.5%, and the yarn unevenness CV value is 2.0%.

Example 5

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

First, sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 11.5: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto. The mixture was stirred at 175 ° C until the water distillation amount reached 90.8% of the theoretical value After the reaction was completed, a mixture of ethylene glycol, potassium glycol and calcium glycol (1: 2 by mass ratio) and sulfuric acid were added to obtain 32.5 wt. Wt. % Of sodium bis hydroxyethyl isophthalate-5-sulphonate is prepared. The addition amount of the catalyst Zn (Ac) ₂ is 0.4 wt% of the addition amount of sodium dimethyl isophthalate-5-benzenesulfonate, and the addition amount of the mixture of potassium glycol and calcium glycol in the preparation is sodium dimethyl isophthalate-5-benzenesulfonate , The added sulfuric acid mass concentration is 50%, and the addition amount of sulfuric acid is 3 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred, followed by ultrasonic dispersion to prepare a titanium dioxide suspension having a solid content of 5.5% of titanium dioxide, and calcium sulfate was added thereto for reaction. At the beginning of the reaction, The reaction time was 2.7 h, the pH of the reaction system was 10, and the reaction mixture was centrifuged, washed, dried, and heated at 700 ° C To prepare titanium dioxide particles coated with calcium oxide.

Terephthalic acid and ethylene glycol having a molar ratio of 1.30: 1 were slurried, and then titanium dioxide particles coated with ethylene glycol antimony, trimethyl phosphate and calcium oxide were added, uniformly mixed, and esterified at 252 ° C to obtain ethylene terephthalate Phthalate is produced and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of 0.25 MPa. The point of time when the water distillation amount in the esterification reaction reaches 94% of the theoretical value is the end point of the esterification reaction. Here, the addition amount of ethylene glycol antimony is 0.01 wt% of the addition amount of terephthalic acid, the addition amount of trimethyl phosphate is 0.05 wt% of the addition amount of terephthalic acid, the addition amount of calcium oxide-coated titanium dioxide particles is 0.17 wt% of the addition amount of terephthalic acid , The content of calcium oxide in the titanium dioxide particles coated with calcium oxide is 4% of the mass of titanium dioxide and the BET specific surface area is 150 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) is put into (2) and condensation reaction is first carried out under a negative pressure condition and a low vacuum step, and the pressure in the above step is pumped smoothly at an absolute pressure of 500 Pa at normal pressure. 45 minutes. Subsequently, the reaction mixture was vacuum pumped to carry out a condensation reaction in a high vacuum stage to reduce the reaction pressure to 95 Pa. The reaction temperature was 282 DEG C and the reaction time was 80 minutes to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 2.5: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 293 DEG C;

Cooling temperature: 24 캜;

Winding speed: 4500 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, a mixture of potassium glycol and calcium glycol, and sulfuric acid, effectively reducing the pressure build-up of the spinning assembly and filter. Here, the pressure rise of the radiation assembly is? P = 0.85 bar / day, the pressure rise of the filter is? P = 2.8 bar / day, the use period of the radiation assembly is 32 days, and the use period of the filter is 25 days.

The cationic fluorine-containing polyester fiber obtained by the above step had a single-yarn fineness of 1.2 dtex, a breaking strength of 4.00 cN / dtex, a dyeing rate of 97.5%, a elongation at break of 45.0%, a linear density deviation rate of 0.44% , The fracture strength CV value is 4.0%, the fracture elongation CV value is 8.0%, and the actual fracture strength CV value is 1.0%.

Example 6

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

Sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 12: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto. The mixture was stirred at 183 ° C until the water distillation amount reached 92.5% After the completion of the reaction, a mixture of ethylene glycol, sodium glycol and calcium glycol (weight ratio 2: 1) and sulfuric acid were added to obtain 31 wt% of sodium bishydroxyethyl isophthalate-5-sulfonate. Of sodium bis hydroxyethyl isophthalate-5-sulphonate. The addition amount of the catalyst Zn (Ac) ₂ is 0.25 wt% of the addition amount of sodium dimethyl isophthalate-5-benzenesulfonate. The amount of addition of the mixture of sodium glycol and calcium glycol at the time of preparation is preferably sodium dimethyl isophthalate- 6 wt% of the addition amount of nitrate, the added sulfuric acid mass concentration is 55%, and the addition amount of sulfuric acid is 4.5 wt% of the added amount of sodium dimethyl isophthalate-5-benzenesulfonate.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred and ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 8% and calcium chloride was added thereto for reaction. At the start of the reaction, And titanium ion were 3: 100, the reaction temperature was 80 ° C, the reaction time was 3 hours, and the pH of the reaction system was 14. After completion of the reaction, the reaction mixture was centrifuged, washed, dried, Thereby preparing titanium dioxide particles coated with calcium oxide.

Terephthalic acid and ethylene glycol having a molar ratio of 1.25: 1 were slurried, and titanium dioxide particles coated with antimony acetate, trimethylphosphite and calcium oxide were added, uniformly mixed, and esterified at 250 ° C to obtain ethylene Terephthalate is produced and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of 0.3 MPa. The point of time when the water distillation amount in the esterification reaction reaches 90% of the theoretical value is the end point of the esterification reaction. Wherein the amount of antimony acetate added is 0.05 wt% of terephthalic acid, the amount of trimethylphosphate added is 0.03 wt% of terephthalic acid, and the amount of calcium oxide-coated titanium dioxide is 0.2 wt% , And the calcium oxide-coated titanium dioxide particles have a calcium oxide content of 5% by mass and a BET specific surface area of 200 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) was put into (2) and condensation reaction was first carried out under a negative pressure condition and a low vacuum step. The pressure in the above step was pumped smoothly at an absolute pressure of 495 Pa at normal pressure. 50 minutes. Subsequently, the reaction mixture was vacuum pumped to carry out a condensation reaction in a high vacuum stage to reduce the reaction pressure to an absolute pressure of 99 Pa. The reaction temperature was 285 deg. C and the reaction time was 90 minutes to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 3: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 295 DEG C;

Cooling temperature: 25 캜;

Winding speed: 4500 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, a mixture of sodium glycol and calcium glycol, and sulfuric acid, effectively reducing the pressure build-up of the spinning assembly and the filter. Here, the pressure rise of the radiation assembly is? P = 1.0 bar / day, the pressure rise of the filter is? P = 2.68 bar / day, the use period of the radiation assembly is 31 days, and the use period of the filter is 30 days.

The cationic fluorine-containing polyester fiber obtained by the above step had a single-fiber fineness of 1.5 dtex, a breaking strength of 2.70 cN / dtex, a dyeing ratio of 95.7%, a elongation at break of 40.0%, a linear density deviation of 0.36% , The breaking strength CV value is 2.5%, the breaking elongation CV value is 7.0%, and the yarn unevenness CV value is 2.0%.

Example 7

The steps of the production method of the cationic fluorine-containing polyester fiber are as follows.

a) preparing a spinning melt;

(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate

First, sodium dimethyl isophthalate-5-benzenesulfonate having a molar ratio of 10: 1 and ethylene glycol were placed in a preparation kettle, and the catalyst Zn (Ac) ₂ was added thereto. The temperature was raised to 185 ° C. until the water distillation amount reached 94% After the reaction was completed, a mixture of ethylene glycol and potassium glycol, sodium glycol and calcium glycol (1: 2: 1 by mass ratio) and sulfuric acid To prepare an ethylene glycol solution containing 35 wt% of sodium bishydroxyethyl isophthalate-5-sulfonate. The addition amount of the catalyst Zn (Ac) ₂ is 0.5 wt% of the addition amount of sodium dimethyl isophthalate-5-benzenesulfonate, and the addition amount of the mixture of potassium glycol, sodium glycol and calcium glycol at the time of preparation is sodium dimethyl isophthalate- -Benzenesulfonate, the added sulfuric acid mass concentration is 60%, and the addition amount of sulfuric acid is 6 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate added.

(2) Esterification reaction is carried out to prepare ethylene terephthalate

The production method of calcium oxide-coated titanium dioxide particles is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred and ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 10% and calcium chloride was added thereto for reaction. At the start of the reaction, And the titanium ion was 5: 100, the reaction temperature was 60 ° C, the reaction time was 3 hours, the reaction system pH was 14, and the reaction was terminated by centrifugation, washing, drying and high temperature treatment at 800 ° C for 5 hours Thereby preparing titanium dioxide particles coated with calcium oxide.

Tritophthalic acid and ethylene glycol having a molar ratio of 1.25: 1 were slurried, and titanium dioxide particles coated with antimony acetate, trimethylphosphite and calcium oxide were added thereto, uniformly mixed, and esterified at 260 ° C to obtain ethylene Terephthalate is produced and the esterification reaction is carried out under a nitrogen atmosphere under a pressurizing pressure of 0.3 MPa. The point of time when the water distillation amount in the esterification reaction reaches 90% of the theoretical value is the end point of the esterification reaction. Wherein the amount of antimony acetate added is 0.05 wt% of terephthalic acid, the amount of trimethylphosphate added is 0.03 wt% of terephthalic acid, and the amount of calcium oxide-coated titanium dioxide is 0.2 wt% , And the calcium oxide-coated titanium dioxide particles have a calcium oxide content of 5% by mass and a BET specific surface area of 200 m ² / g.

(3) Conducting a condensation reaction to prepare a spinning melt

The product of step (1) was put into (2) and condensation reaction was first carried out at a low vacuum stage under a negative pressure condition. The pressure in the above step was pumped smoothly at an absolute pressure of 495 Pa at normal pressure. 50 minutes. Subsequently, the reaction mixture was vacuum pumped to carry out a condensation reaction in a high vacuum stage to reduce the reaction pressure to an absolute pressure of 99 Pa. The reaction temperature was 285 deg. C and the reaction time was 90 minutes to prepare a spinning melt. At the beginning of the condensation reaction, the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate and ethylene terephthalate is 3: 100.

b) an emissive phase;

The spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The spinning process parameters are as follows.

Extrusion temperature: 300 占 폚;

Cooling temperature: 21 캜;

Winding speed: 4500 m / min;

Initial pressure of the spinning assembly: 110 bar.

In the spinning process, the amount of impurities in the melt is greatly reduced due to the preparation of ethylene glycol, potassium glycol, a mixture of sodium glycol and calcium glycol, and sulfuric acid, effectively reducing the pressure buildup of the spinning assembly and filter. Here, the pressure rise of the radiation assembly is? P = 0.82 bar / day, the pressure rise of the filter is? P = 2.76 bar / day, the use period of the radiation assembly is 35 days, and the use period of the filter is 26 days.

The cationic fluorine-containing polyester fiber obtained by the above step had a single fiber fineness of 1.1 dtex, a breaking strength of 2.40 cN / dtex, a dyeing rate of 96.1%, a elongation at break of 45.0%, a line density deviation rate of 0.4% , The breaking strength CV value is 4.0%, the breaking elongation CV value is 7.5%, and the yarn unevenness CV value is 2.0%.

Claims (10)

a) preparing a spinning melt;
(1) Sodium dimethyl isophthalate-5-benzenesulfonate, ethylene glycol, and a catalyst are mixed and ester exchange reaction is performed. After completion of the reaction, ethylene glycol, A complex ion modifier and sulfuric acid, wherein the complex ion modifier is at least one of potassium glycol, sodium glycol and calcium glycol;
(2) an esterification reaction is carried out after mixing terephthalic acid, ethylene glycol, a catalyst and a quencher, wherein the quencher is a titanium dioxide particle coated with calcium oxide;
(3) adding the product of (1) above to (2) to conduct a condensation reaction to prepare a spinning melt;
b) an emissive phase;
Wherein the spinning molten material is metered, extruded, cooled, oiled and wound to produce a cation-exchangeable polyester fiber. The method according to claim 1,
The specific steps for producing the spinning melt include,
(1) transesterification was carried out to prepare sodium bishydroxyethyl isophthalate-5-sulfonate (SIPE)
Sodium dimethyl isophthalate-5-benzenesulfonate and ethylene glycol were added to the preparation kettle, the catalyst Zn (Ac) ₂ was added, and the ester exchange reaction was carried out at 175 to 185 ° C until the water distillation amount reached 90% To obtain sodium bis hydroxyethyl isophthalate-5-sulfonate, and adding ethylene glycol, a complex ion modifier and sulfuric acid to obtain an aqueous solution containing 30-35 wt% of sodium bis hydroxyethyl isophthalate-5-sulphonate Preparing a glycol solution;
(2) Esterification is carried out to prepare ethylene terephthalate
Terephthalic acid and ethylene glycol are slurried and then a catalyst, a stabilizer and a quencher are added to the mixture to homogeneously mix and esterify to obtain ethylene terephthalate. The esterification reaction is a pressurization reaction in a nitrogen atmosphere, Is atmospheric pressure to 0.3 MPa, the temperature of the esterification reaction is 250 to 260 DEG C, and the point at which the water distillation amount in the esterification reaction reaches 90% or more of the theoretical value is the end point of the esterification reaction;
(3) Conducting a condensation reaction to prepare a spinning melt
The product of the above step (1) is introduced into the above step (2), and the condensation reaction of the low-vacuum step is first carried out under a negative pressure condition. The pressure in the above step is pumped smoothly at an absolute pressure of 500 Pa or less at normal pressure, And the reaction time is 30 to 50 min. Subsequently, by vacuum pumping, the condensation reaction in the high vacuum step is carried out to reduce the reaction pressure to an absolute pressure of 100 Pa or less, the reaction temperature is 275 to 285 DEG C, To 50 to 90 minutes to produce a spinning melt. 3. The method of claim 2,
In step (1), at the beginning of the transesterification reaction, the molar ratio of sodium dimethyl isophthalate-5-benzenesulfonate to ethylene glycol is 10-12: 1, and the amount of catalyst Zn (Ac) ₂ added is sodium dimethyl isophthalate- -Benzenesulfonate in an amount of 0.2 to 0.5 wt%;
In the preparation, the amount of the complex ion regulator added is 1.5 to 6 wt% of the amount of sodium dimethyl isophthalate-5-benzenesulfonate, the mass concentration of added sulfuric acid is 40 to 60%, and the amount of sulfuric acid added is sodium dimethyl isophthalate- Benzenesulfonate in an amount of 1.5 to 6 wt% based on the amount of 5-benzenesulfonate added. 3. The method of claim 2,
In step (2), at the beginning of the esterification reaction, the molar ratio of terephthalic acid to ethylene glycol is from 1.10 to 1.30: 1 and the catalyst is selected from diantimony trioxide, ethylene glycol antimony or antimony acetate antimony acetate), the amount of the catalyst to be added is 0.01-0.05 wt% of the addition amount of terephthalic acid, the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, and the amount of the stabilizer is 0.01-0.05 wt%, and the addition amount of the quencher is 0.05 to 0.2 wt% of the amount of terephthalic acid added. 3. The method of claim 2,
Wherein the molar ratio of sodium bishydroxyethyl isophthalate-5-sulfonate to ethylene terephthalate is 1 to 3: 100 at the beginning of the condensation reaction in step (3). 3. The method according to claim 1 or 2,
The content of calcium oxide in the quencher is 1 to 5% of the mass of titanium dioxide and the BET specific surface area is 50 to 200 m ² / g;
The method for producing the quencher is as follows. Titanium dioxide having an average particle diameter of 0.3 탆 and deionized water were mixed and stirred and ultrasonically dispersed to prepare a titanium dioxide suspension having a solid content of titanium dioxide of 5 to 10% and a calcium salt was added thereto, And the reaction time is 2 to 3 hours. When the reaction is completed, centrifugation is carried out for 2 to 5 hours, washing, drying, and high temperature treatment at 400 to 800 ° C to prepare calcium oxide-coated titanium dioxide particles;
Wherein the calcium salt is calcium chloride or calcium sulfate and the molar ratio of calcium ion to titanium ion is 1 to 5: 100 at the beginning of the reaction, and the pH of the reaction system is 10 to 14 at the start of the reaction. Gt; The method according to claim 1,
Wherein the process parameters of the radiation are
Extrusion temperature: 285 to 300 占 폚;
Cooling temperature: 20 ~ 25 ℃;
Winding speed: 4000 to 4600 m / min;
Initial pressure of the spinning assembly: 110 bar;
Wherein the cationic fluorine-containing polyester fiber is a polyester resin. 8. The method of claim 7,
In the spinning process, the pressure rise of the spinning assembly is? P? 1.0 bar / day, the pressure rise of the filter is? P? 3.0 bar, the spinning assembly use period is 30 to 35 days, the filter use period is 25 to 30 days ≪ / RTI > wherein the cationic flame-retardant polyester fiber is a polyester fiber. The method according to claim 1,
Wherein the cationic flame type polyester fiber has a monofilament fineness of 0.5 to 1.5 dtex, a breaking strength of ≥3.00 cN / dtex and a staining rate of more than 95%. 10. The method of claim 9,
The cationic flame type polyester fiber had a fracture elongation percentage of 40.0 占 .5%, a linear density variation rate of 0.5%, a fracture strength CV value of 4.0%, a fracture elongation CV value of 8.0% And the CV value is? 2.0%.