Cationic dyeable polyester fiber and preparing method thereof

Abstract

A type of cationic dyeable polyester fiber and preparing method thereof are disclosed. The preparing method is to manufacture a fiber from a cationic modified polyester through a fully drawn yarn (FDY) process, wherein the cationic modified polyester is composed of terephthalic acid segments, ethylene glycol segments, sodium salt of diethylene ester of 5-sulfoisophthalic acid segments and tert-butyl branched diol segments and a molecular formula of tert-butyl branched diol is as following: ##STR00001## The cationic modified polyester is further dispersed with a high temperature calcined solid heteropolyacid. A final fiber has a dye uptake of 87.8-92.2% and a K/S value of 23.27-25.67 when dyed at 120° C., as well as an intrinsic viscosity drop of 13-17% when stored at 25° C. and R.H. 65% for 60 months.

Claims

1. A preparing method for a cationic dyeable polyester fiber, comprising: manufacturing a fully drawn yarn (FDY) with a cationic modified polyester; wherein the cationic modified polyester is a product of an esterification reaction and a polycondensation reaction of a uniformly mixed mixture of terephthalic acid (PTA), ethylene glycol (EG), sodium salt of diethylene ester of 5-sulfoisophthalic acid (SIPE), a tert-butyl branched diol and a high temperature calcined solid heteropolyacid powder; wherein the tert-butyl branched diol has a molecular formula of ##STR00005## wherein R stands for —H, —CH.sub.2CH.sub.3, —CH(CH.sub.3).sub.2 or —C(CH.sub.3).sub.3; wherein a solid heteropolyacid is more than one of SiO.sub.2—TiO.sub.2, SiO.sub.2—ZrO.sub.2, B.sub.2O.sub.3—Al.sub.2O.sub.3, TiO.sub.2—ZnO and SiO.sub.2—CaO, and the solid heteropolyacid is calcined under a temperature of 400-700° C.

2. The preparing method of claim 1, wherein the tert-butyl branched diol is synthesized by the steps of: 1) mixing 40-50 wt % of an aqueous potassium hydroxide solution and isobutanol in a mole ratio 5-6:1 of potassium hydroxide to the isobutanol at first to obtain a mixture, and then stirring the mixture and carrying out a first reaction under 100-110° C. for 4-5 hours to obtain potassium isobutanol; 2) removing impurities from a system of step 1) and cooling the system of step 1) to a normal temperature, then adding in xylene in a mole ratio (1.3-1.5):(2.0-3.0) of the potassium isobutanol to the xylene and furtherly reducing a temperature to 0-5° C.; 3) adding 3-methyl-3-hydroxybutyne and M into a system of step 2) with a mole ratio of the 3-methyl-3-hydroxybutyne, the M and the xylene being 1:(1.2-1.3):(2.0-3.0), then carrying out a second reaction under 40-50° C. for 3 hours, finally obtaining octynylenediol through a series of processes of a cooling crystallization, a centrifugal separation and a drying; 4) mixing the octynylenediol, alcohol and a Pd catalyst in a weight ratio of (2-3):10:(0.01-0.03) then carrying out a third reaction accompanied with a continuous hydrogen input at 40-50° C. for 50-60 minutes, finally obtaining the tert-butyl branched diol through a series of processes of a separation and a purification; wherein R is —H, —CH.sub.2CH.sub.3, —CH(CH.sub.3).sub.2 or —C(CH.sub.3).sub.3, accordingly the M refers to 2,2-dimethylpropanal, 2,2-dimethyl-3-pentanone, 2,2,4-trimethyl-3-pentanone or 2,2,4,4-tetramethyl-3-pentanone, respectively.

3. The preparing method of claim 2, wherein a calcining time of the solid heteropolyacid is 2-4 hours, and a content of TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3, ZnO and CaO in SiO.sub.2—TiO.sub.2, SiO.sub.2—ZrO.sub.2, B.sub.2O.sub.3—Al.sub.2O.sub.3, TiO.sub.2—ZnO and SiO.sub.2—CaO are 30-50 wt %, 30-50 wt %, 20-40 wt %, 20-40 wt % and 20-50 wt %, respectively, and in addition, after calcining the solid heteropolyacid, the solid heteropolyacid is ground into fine powders with an average diameter less than 0.5 micron.

4. The preparing method of claim 3, wherein the cationic modified polyester is manufactured through the following steps: 1) the esterification reaction as follows: concocting the PTA, the EG, the SIPE and the tert-butyl branched diol into a slurry, then adding in the high temperature calcined solid heteropolyacid powder, the Pd catalyst, a matting agent and a stabilizer and carrying out the esterification reaction in a nitrogen atmosphere with a pressure of 101.325 kPa 0.3 MPa at 240-250° C., finally ending the esterification reaction when a water distillation reaching more than 90% of a theoretical value; 2) the polycondensation reaction as follows: smoothly reducing a pressure of the system of step 1) to less than 500 Pa within 30-50 minutes and carrying out the polycondensation reaction at 250-260° C. for 30-50 minutes, successively, further reducing the pressure to less than 100 Pa and continuing the polycondensation reaction at 270-275° C. for 50-90 minutes.

5. The preparing method of claim 4, wherein a molar ratio of the PTA, the EG and the tert-butyl branched diol is 1:(1.2-2.0):(0.03-0.05) and a dosage of the SIPE is 1.2-1.6 mol % relative to an amount of the PTA, an amount of the SIPE is due to an incorporation of the tert-butyl branched diol to enhance dyeing performance of the cationic modified polyester, and additions of the solid heteropolyacid, the Pd catalyst, the matting agent and the stabilizer respecting to the PTA are 0.03-0.05 wt %, 0.03-0.05 wt %, 0.20-0.25 wt % and 0.01-0.05 wt %, respectively.

6. The preparing method of claim 5, wherein the Pd catalyst is selected from the group consisting of antimony trioxide, ethylene glycol antimony and antimony acetate, wherein the matting agent is titanium dioxide, and wherein the stabilizer is selected from the group consisting of triphenyl phosphate, trimethyl phosphate and trimethyl phosphite.

7. The preparing method claim 6, wherein the cationic modified polyester has a molecular weight of 24000-28000 and a molecular weight distribution index of 1.9-2.4.

8. The preparing method of claim 1, wherein an FDY technique comprises the steps of metering, spinneret extruding, cooling, oiling, stretching, heat setting and winding; wherein an FDY process involves technological parameters of a spinning temperature of 270-280° C., a cooling temperature of 18-20° C., an interlacing pressure of 0.20-0.30 MPa, godet roller 1 speed of 2200-2600 m/min, godet roller 1 temperature of 75-90° C., godet roller 2 speed of 3600-3900 m/min, godet roller 2 temperature of 105-120° C., and a winding speed of 3560-3850 m/min.

9. A cationic dyeable polyester fiber prepared by the preparing method of claim 1, comprising a cationic modified polyester FDY; wherein the cationic modified polyester has a molecular chain structure composed of PTA segments, EG segments, SIPE segments and tert-butyl branched diol segments and the cationic modified polyester is dispersed by the high temperature calcined solid heteropolyacid powder.

10. The cationic dyeable polyester fiber of claim 9, wherein the cationic dyeable polyester fiber comprises: mechanical performance indices of a monofilament fineness 0.5-1.2 dtex, a breaking strength≥3.5 cN/dtex, an elongation at break 33.0±4.0%, an interlacing degree 12±2/m, a linear density deviation rate≤1.0%, a breaking strength CV value≤5.0%, an elongation at break CV value≤8.0%, and a boiling water shrinkage rate 8.0±0.5%; a dye uptake of 87.8-92.2% and a K/S value of 23.27-25.67 when dyed under 120° C.; and an intrinsic viscosity drop of 13-17% after a storage at 25° C. and R.H. 65% for 60 months.

11. The cationic dyeable polyester fiber of claim 9, wherein the tert-butyl branched diol is synthesized by the steps of: 1) mixing 40-50 wt % of an aqueous potassium hydroxide solution and isobutanol in a mole ratio 5-6:1 of potassium hydroxide to the isobutanol at first to obtain a mixture, and then stirring the mixture and carrying out a first reaction under 100-110° C. for 4-5 hours to obtain potassium isobutanol; 2) removing impurities from a system of step 1) and cooling the system of step 1) to a normal temperature, then adding in xylene in a mole ratio (1.3-1.5):(2.0-3.0) of the potassium isobutanol to the xylene and furtherly reducing a temperature to 0-5° C.; 3) adding 3-methyl-3-hydroxybutyne and M into a system of step 2) with a mole ratio of the 3-methyl-3-hydroxybutyne, the M and the xylene being 1:(1.2-1.3):(2.0-3.0), then carrying out a second reaction under 40-50° C. for 3 hours, finally obtaining octynylenediol through a series of processes of a cooling crystallization, a centrifugal separation and a drying; 4) mixing the octynylenediol, alcohol and a Pd catalyst in a weight ratio of (2-3):10:(0.01-0.03), then carrying out a third reaction accompanied with a continuous hydrogen input at 40-50° C. for 50-60 minutes, finally obtaining the tert-butyl branched diol through a series of processes of a separation and a purification; wherein R is —H, —CH.sub.2CH.sub.3, —CH(CH.sub.3).sub.2 or —C(CH.sub.3).sub.3, accordingly the M refers to 2,2-dimethylpropanal, 2,2-dimethyl-3-pentanone, 2,2,4-trimethyl-3-pentanone or 2,2,4,4-tetramethyl-3-pentanone, respectively.

12. The cationic dyeable polyester fiber of claim 11, wherein a calcining time of the solid heteropolyacid is 2-4 hours, and a content of TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3, ZnO and CaO in SiO.sub.2—TiO.sub.2, SiO.sub.2—ZrO.sub.2, B.sub.2O.sub.3—Al.sub.2O.sub.3, TiO.sub.2—ZnO and SiO.sub.2—CaO are 30-50 wt %, 30-50 wt %, 20-40 wt %, 20-40 wt % and 20-50 wt %, respectively, and in addition, after calcining the solid heteropolyacid, the solid heteropolyacid is ground into fine powders with an average diameter less than 0.5 micron.

13. The cationic dyeable polyester fiber of claim 12, wherein the cationic modified polyester is manufactured through the following steps: 1) the esterification reaction as follows: concocting the PTA, the EG, the SIPE and the tert-butyl branched diol into a slurry, then adding in the high temperature calcined solid heteropolyacid powder, the Pd catalyst, a matting agent and a stabilizer and carrying out the esterification reaction in a nitrogen atmosphere with a pressure of 101.325 kPa 0.3 MPa at 240-250° C., finally ending the esterification reaction when a water distillation reaching more than 90% of a theoretical value; 2) the polycondensation reaction as follows: smoothly reducing a pressure of the system of step (1) to less than 500 Pa within 30-50 minutes and carrying out the polycondensation reaction at 250-260° C. for 30-50 minutes, successively, further reducing the pressure to less than 100 Pa and continuing the polycondensation reaction at 270-275° C. for 50-90 minutes.

14. The cationic dyeable polyester fiber of claim 13, wherein a molar ratio of the PTA, the EG and the tert-butyl branched diol is 1:(1.2-2.0):(0.03-0.05), and a dosage of the SIPE is 1.2-1.6 mol % relative to an amount of the PTA, an amount of the SIPE is due to an incorporation of the tert-butyl branched diol to enhance dyeing performance of the cationic modified polyester, and additions of the solid heteropolyacid, the Pd catalyst, the matting agent and the stabilizer respecting to the PTA are 0.03-0.05 wt %, 0.03-0.05 wt %, 0.20-0.25 wt % and 0.01-0.05 wt %, respectively.

15. The cationic dyeable polyester fiber of claim 14, wherein the Pd catalyst is selected from the group consisting of antimony trioxide, ethylene glycol antimony and antimony acetate, wherein the matting agent is titanium dioxide, and wherein the stabilizer is selected from the group consisting of triphenyl phosphate, trimethyl phosphate and trimethyl phosphite.

16. The cationic dyeable polyester fiber of claim 15, wherein the cationic modified polyester has a molecular weight of 24000-28000 and a molecular weight distribution index of 1.9-2.4.

17. The cationic dyeable polyester fiber of claim 9, wherein an FDY technique comprises the steps of metering, spinneret extruding, cooling, oiling, stretching, heat setting and winding; wherein an FDY process involves technological parameters of a spinning temperature of 270-280° C., a cooling temperature of 18-20° C., an interlacing pressure of 0.20-0.30 MPa, godet roller 1 speed of 2200-2600 m/min, godet roller 1 temperature of 75-90° C., godet roller 2 speed of 3600-3900 m/min, godet roller 2 temperature of 105-120° C., and a winding speed of 3560-3850 m/min.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Based on above mentioned method, the following embodiments are carried out for further demonstration in the present invention. It is to be understood that these embodiments are only intended to illustrate the invention and are not intended to limit the scope of the invention. In addition, it should be understood that after reading the contents described in the present invention, those technical personnel in this field can make various changes or modifications to the invention, and these equivalent forms also fall within the scope of the claims attached to the application.

(2) ##STR00004##

Example 1

(3) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(4) (1) Preparation of the Cationic Modified Polyester

(5) (1.1) Synthesizing 2,6,6-Trimethyl-2,5-Heptanediol

(6) (a) mixing isobutanol and 43% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 5:1, then carrying out the reaction with a stirring at 100° C. for 4 hr to obtain potassium isobutanol;

(7) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.3:2.2 and cooling the system to 1° C.;

(8) (c) adding 3-methyl-3-hydroxybutyne and 2,2-dimethylpropionaldehyde into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2-dimethylpropionaldehyde:xylene as 1:1.2:2.2, then starting the reaction at 25° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(9) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 2.2:10:0.01 and then carrying out the reaction accompanied with a continuous hydrogen input at 50° C. for 50 min, finally obtaining 2,6,6-trimethyl-2,5-heptanediol (just as demonstrated in Formula (I) with R=—H) through a series of processes of separation and purification;

(10) (1.2) Preparation of Solid Heteropolyacid SiO.sub.2—TiO.sub.2

(11) dispersing 1 phr of silica powder in 55 phr of water by fully stirring, then dripping in 2 phr of titanyl sulfate solution with concentration of 4.5 wt %. Next, adjusting the pH value of the dispersion system to neutral with 1.0 mol/L sodium hydroxide solution and then to 8 with 10 wt % sulfuric acid. after aging for 2 h, washing the dispersion system with deionized water until no SO.sub.4.sup.2− detection, and then filtering it under the vacuum and washing the filter cake with anhydrous ethanol for several times, further, drying the cake under 100° C. in an oven, finally calcining the dry cake at 500° C. for 2 h and then grinding to obtain solid heteropolyacid SiO.sub.2—TiO.sub.2 with an average diameter of 0.4 micron and a TiO.sub.2 content of 42 wt %;

(12) (1.3) Esterification

(13) concocting PTA, EG, SIPE and 2,6,6-trimethyl-2,5-heptanediol into a slurry, then adding in the calcined SiO.sub.2—TiO.sub.2 powder, antimony trioxide, titanium dioxide and triphenyl phosphate and carrying out the esterification in a nitrogen atmosphere with a pressure of normal value at 240° C., finally ending the reaction when the water distillation reaching 90% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-2,5-heptanediol being 1:1.2:0.03, and respecting to PTA the additions of SIPE, SiO.sub.2—TiO.sub.2, antimony trioxide, titanium dioxide and triphenyl phosphate are 1.3 mol %, 0.03 wt %, 0.033 wt %, 0.20 wt % and 0.04 wt %, respectively;

(14) (1.4) Polycondensation

(15) smoothly reducing the pressure of the system of (1) to less than 480 Pa within 40 min and carrying out reaction at 250° C. for 30 min, successively, further reducing the pressure to less than 80 Pa and continuing the reaction at 270° C. for 50 min. finally obtaining the cationic modified polyester with a molecular weight of 24000 and a molecular weight distribution index of 1.9;

(16) (2) Spinning of Cationic Dyeable Polyester Fiber

(17) through a FDY technological way including stages of metering, spinneret extruding (at 272° C.), cooling (at 18° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.25 MPa, godet roller 1 speed 2200 m/min, godet roller 1 temperature 75° C., godet roller 2 speed 3600 m/min, godet roller 2 temperature 110° C.), and winding (3600 m/min), converting the cationic dyeable polyester fiber.

(18) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 0.5 dtex, breaking strength 3.6 cN/dtex, elongation at break 34.0%, interlacing degree 11/m, linear density deviation rate 0.92%, breaking strength CV value 4.68%, elongation at break CV value 8.0%, boiling water shrinkage rate 8.2%.

(19) The cationic dyeable polyester fiber has a dye uptake of 87.8% and a K/S value of 24.38 when dyed under 120° C.

(20) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 17% after stored at 25° C. and R.H. 65% for 60 months.

(21) Comparison 1

(22) A method for preparing the cationic dyeable polyester fiber involved steps basically the same as those in Example1, except for no addition of 2,6,6-trimethyl-2,5-heptanediol and SiO.sub.2—TiO.sub.2, i.e., no more modification than that of SIPE for PET, and the obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 0.5 dtex, breaking strength 3.5 cN/dtex, elongation at break 33.0%, interlacing degree 11/m, linear density deviation rate 0.92%, breaking strength CV value 4.72%, elongation at break CV value 8.0%, boiling water shrinkage rate 8.0%, dye uptake 86.7%, K/S value 22.75 (dyed at 130° C.), and intrinsic viscosity drop 4.8% (after stored at 25° C. and R.H.65% for 60 months).

(23) From the analysis on the data of Example 1 and Comparison 1, it can be concluded that the cationic dyeable polyester fiber, compared with the common one, could gain a much higher dye uptake with lower dyeing temperature, shorter dyeing time and less energy consumption, as well as a fairly rapider natural degradation rate suitable for the recycling. Moreover, the additives of 2,6,6-trimethyl-2,5-heptanediol and SiO.sub.2—TiO.sub.2 just draw little effects on the other properties of the fiber such as the processablity and the mechanical performance.

(24) Comparison 2

(25) A method for preparing the cationic dyeable polyester fiber involved steps basically the same as those in Example1, except for adopting 1,2-dodecyl glycol instead of 2,6,6-trimethyl-2,5-heptanediol in step (1), and the obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 0.5 dtex, breaking strength 3.7 cN/dtex, elongation at break 33.0%, interlacing degree 11/m, linear density deviation rate 0.92%, breaking strength CV value 4.6%, elongation at break CV value 8.0%, boiling water shrinkage rate 8.1%, dye uptake 85.8%, K/S value 21.76 (dyed at 130° C.), and intrinsic viscosity drop 10.5% (after stored at 25° C. and R.H.65% for 60 months).

(26) From the analysis on the data of Example 1 and Comparison 1, it can be concluded that the tert-butyl branched diol (2,6,6-trimethyl-2,5-heptanediol), compared with 1,2-dodecyl glycol containing long alkyl chain, is more beneficial to the natural degradation of PET fibers, and the reason on one hand is that the short side chain can enlarge the void free volume whereas the long side can mainly enlarge the slit free volume, and the void free volume is more efficient than the slit one for the penetration of activator agents into the fiber, on the other hand, the short side chain with higher rigidity will seldom cause the molecular chain entanglement and gain more free volume in the molecular aggregate.

Example 2

(27) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(28) (1) Preparation of the Cationic Modified Polyester

(29) (1.1) Synthesizing 2,6,6-trimethyl-2,5-heptanediol

(30) (a) mixing isobutanol and 40% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 5.5:1, then carrying out the reaction with a stirring at 100° C. for 5 hr to obtain potassium isobutanol;

(31) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.3:2.0 and cooling the system to 3° C.;

(32) (c) adding 3-methyl-3-hydroxybutyne and 2,2-dimethylpropionaldehyde into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2-dimethylpropionaldehyde:xylene as 1:1.3:2.5, then starting the reaction at 30° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(33) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 2.5:10:0.01 and then carrying out the reaction accompanied with a continuous hydrogen input at 50° C. for 55 min, finally obtaining 2,6,6-trimethyl-2,5-heptanediol (just as demonstrated in Formula (I) with R=—H) through a series of processes of separation and purification;

(34) (1.2) Preparation of Solid Heteropolyacid SiO.sub.2—ZrO.sub.2

(35) dispersing 1 phr of silica powder in 58 phr of water by fully stirring, then dripping in 2 phr of zirconium sulfate solution with concentration of 5 wt %. Next, adjusting the pH value of the dispersion system to neutral with 1.0 mol/L sodium hydroxide solution and then to 8 with 10 wt % sulfuric acid. after aging for 1 h, washing the dispersion system with deionized water until no SO.sub.4.sup.2− detection, and then filtering it under the vacuum and washing the filter cake with anhydrous ethanol for several times, further, drying the cake under 100° C. in an oven, finally calcining the dry cake at 400° C. for 4 h and then grinding to obtain solid heteropolyacid SiO.sub.2—ZrO.sub.2 with an average diameter of 0.45 micron and a ZrO.sub.2 content of 45 wt %;

(36) (1.3) Esterification

(37) concocting PTA, EG, SIPE and 2,6,6-trimethyl-2,5-heptanediol into a slurry, then adding in the calcined SiO.sub.2—ZrO.sub.2 powder, antimony glycol, titanium dioxide and trimethyl phosphate and carrying out the esterification in a nitrogen atmosphere with a pressure of 0.1 MPa at 242° C., finally ending the reaction when the water distillation reaching 93% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-2,5-heptanediol being 1:1.3:0.035, and respecting to PTA the additions of SIPE, SiO.sub.2—ZrO.sub.2, antimony glycol, titanium dioxide and trimethyl phosphate are 1.4 mol %, 0.04 wt %, 0.03 wt %, 0.25 wt % and 0.01 wt %, respectively;

(38) (1.4) Polycondensation

(39) smoothly reducing the pressure of the system of (1) to less than 500 Pa within 44 min and carrying out reaction at 252° C. for 32 min, successively, further reducing the pressure to less than 90 Pa and continuing the reaction at 270° C. for 55 min. Finally obtaining the cationic modified polyester with a molecular weight of 24800 and a molecular weight distribution index of 1.9;

(40) (2) Spinning of Cationic Dyeable Polyester Fiber

(41) through a FDY technological way including stages of metering, spinneret extruding (at 270° C.), cooling (at 19° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.23 MPa, godet roller 1 speed 2300 m/min, godet roller 1 temperature 75° C., godet roller 2 speed 3700 m/min, godet roller 2 temperature 105° C.), and winding (3720 m/min), converting the cationic dyeable polyester fiber.

(42) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 0.8 dtex, breaking strength 3.5 cN/dtex, elongation at break 33.0%, interlacing degree 11/m, linear density deviation rate 0.95%, breaking strength CV value 4.95%, elongation at break CV value 7.9%, boiling water shrinkage rate 7.5%.

(43) The cationic dyeable polyester fiber has a dye uptake of 92.2% and a K/S value of 23.27 when dyed under 120° C.

(44) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 14% after stored at 25° C. and R.H.65% for 60 months.

Example 3

(45) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(46) (1) Preparation of the Cationic Modified Polyester

(47) (1.1) Synthesizing 2,6,6-trimethyl-5-ethyl-2,5-heptadiol

(48) (a) mixing isobutanol and 48% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 5:1, then carrying out the reaction with a stirring at 105° C. for 4.5 hr to obtain potassium isobutanol;

(49) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.5:2.5 and cooling the system to 0° C.;

(50) (c) adding 3-methyl-3-hydroxybutyne and 2,2-dimethyl-3-pentanone into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2-dimethyl-3-pentanone:xylene as 1:1.25:2.0, then starting the reaction at 30° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(51) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 2:10:0.02 and then carrying out the reaction accompanied with a continuous hydrogen input at 42° C. for 60 min, finally obtaining 2,6,6-trimethyl-5-ethyl-2,5-heptadiol (just as demonstrated in Formula (I) with R=—CH.sub.2CH.sub.3) through a series of processes of separation and purification;

(52) (1.2) Preparation of Solid Heteropolyacid B.sub.2O.sub.3—Al.sub.2O.sub.3

(53) dripping 2.5 phr of aluminum sulfate solution with concentration of 4 wt % into 1 phr of boric acid, then adjusting the pH value of the dispersion system to neutral with 1.0 mol/L sodium hydroxide solution and then to 8 with 9 wt % sulfuric acid. after aging for 1.5 h, washing the dispersion system with deionized water until no SO.sub.4.sup.2− detection, and then filtering it under the vacuum and washing the filter cake with anhydrous ethanol for several times, further, drying the cake under 100° C. in an oven, finally calcining the dry cake at 700° C. for 2 h to obtain solid heteropolyacid B.sub.2O.sub.3—Al.sub.2O.sub.3 with a Al.sub.2O.sub.3 content of 30 wt %;

(54) (1.3) Esterification

(55) concocting PTA, EG, SIPE and 2,6,6-trimethyl-5-ethyl-2,5-heptadiol into a slurry, then adding in the calcined B.sub.2O.sub.3—Al.sub.2O.sub.3 powder, antimony acetate, titanium dioxide and trimethyl phosphite and carrying out the esterification in a nitrogen atmosphere with a pressure of 0.2 MPa at 244° C., finally ending the reaction when the water distillation reaching 95% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-5-ethyl-2,5-heptadiol being 1:1.5:0.037, and respecting to PTA the additions of SIPE, B.sub.2O.sub.3—Al.sub.2O.sub.3, antimony acetate, titanium dioxide and trimethyl phosphite are 1.2 mol %, 0.04 wt %, 0.04 wt %, 0.21 wt % and 0.03 wt %, respectively;

(56) (1.4) Polycondensation

(57) smoothly reducing the pressure of the system of (1) to less than 400 Pa within 38 min and carrying out reaction at 251° C. for 33 min, successively, further reducing the pressure to less than 100 Pa and continuing the reaction at 271° C. for 60 min. finally obtaining the cationic modified polyester with a molecular weight of 25000 and a molecular weight distribution index of 2.0;

(58) (2) Spinning of Cationic Dyeable Polyester Fiber

(59) through a FDY technological way including stages of metering, spinneret extruding (at 270° C.), cooling (at 20° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.20 MPa, godet roller 1 speed 2500 m/min, godet roller 1 temperature 85° C., godet roller 2 speed 3650 m/min, godet roller 2 temperature 115° C.), and winding (3800 m/min), converting the cationic dyeable polyester fiber.

(60) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 1.2 dtex, breaking strength 3.58 cN/dtex, elongation at break 33.0%, interlacing degree 10/m, linear density deviation rate 0.92%, breaking strength CV value 5.00%, elongation at break CV value 7.92%, boiling water shrinkage rate 7.5%.

(61) The cationic dyeable polyester fiber has a dye uptake of 87.8% and a K/S value of 23.27 when dyed under 120° C.

(62) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 13% after stored at 25° C. and R.H. 65% for 60 months.

Example 4

(63) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(64) (1) Preparation of the Cationic Modified Polyester

(65) (1.1) Synthesizing 2,6,6-trimethyl-5-ethyl-2,5-heptadiol

(66) (a) mixing isobutanol and 41% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 6:1, then carrying out the reaction with a stirring at 110° C. for 4.8 hr to obtain potassium isobutanol;

(67) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.4:3.0 and cooling the system to 0° C.;

(68) (c) adding 3-methyl-3-hydroxybutyne and 2,2-dimethyl-3-pentanone into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2-dimethyl-3-pentanone:xylene as 1:1.3:2.6, then starting the reaction at 35° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(69) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 3:10:0.01 and then carrying out the reaction accompanied with a continuous hydrogen input at 40° C. for 60 min, finally obtaining 2,6,6-trimethyl-5-ethyl-2,5-heptadiol (just as demonstrated in Formula (I) with R=—CH.sub.2CH.sub.3) through a series of processes of separation and purification;

(70) (1.2) Preparation of Solid Heteropolyacid TiO.sub.2—ZnO

(71) dripping 3 phr of titanyl sulfate solution with concentration of 5 wt % into 1 phr of zinc sulfate, then adjusting the pH value of the dispersion system to neutral with 1.0 mol/L sodium hydroxide solution and then to 8 with 10 wt % sulfuric acid. after aging for 2 h, washing the dispersion system with deionized water until no SO.sub.4.sup.2− detection, and then filtering it under the vacuum and washing the filter cake with anhydrous ethanol for several times, further, drying the cake under 100° C. in an oven, finally calcining the dry cake at 600° C. for 2.5 h to obtain solid heteropolyacid TiO.sub.2—ZnO with an average diameter of 0.45 micron and a ZnO content of 35 wt %;

(72) (1.3) Esterification

(73) concocting PTA, EG, SIPE and 2,6,6-trimethyl-5-ethyl-2,5-heptadiol into a slurry, then adding in the calcined TiO.sub.2—ZnO powder, antimony acetate, titanium dioxide and triphenyl phosphate and carrying out the esterification in a nitrogen atmosphere with a pressure of the normal value at 246° C., finally ending the reaction when the water distillation reaching 99% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-5-ethyl-2,5-heptadiol being 1:1.6:0.038, and respecting to PTA the additions of SIPE, TiO.sub.2—ZnO, antimony acetate, titanium dioxide and triphenyl phosphate are 1.2 mol %, 0.03 wt %, 0.05 wt %, 0.20 wt % and 0.02 wt %, respectively;

(74) (1.4) Polycondensation

(75) smoothly reducing the pressure of the system of (1) to less than 460 Pa within 30 min and carrying out reaction at 253° C. for 35 min, successively, further reducing the pressure to less than 88 Pa and continuing the reaction at 272° C. for 65 min. finally obtaining the cationic modified polyester with a molecular weight of 25500 and a molecular weight distribution index of 2.2;

(76) (2) Spinning of Cationic Dyeable Polyester Fiber

(77) through a FDY technological way including stages of metering, spinneret extruding (at 275° C.), cooling (at 19° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.28 MPa, godet roller 1 speed 2600 m/min, godet roller 1 temperature 80° C., godet roller 2 speed 3900 m/min, godet roller 2 temperature 120° C.), and winding (3560 m/min), converting the cationic dyeable polyester fiber.

(78) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 0.7 dtex, breaking strength 3.55 cN/dtex, elongation at break 29.0%, interlacing degree 12/m, linear density deviation rate 1.00%, breaking strength CV value 4.97%, elongation at break CV value 7.95%, boiling water shrinkage rate 8.5%.

(79) The cationic dyeable polyester fiber has a dye uptake of 90.3% and a K/S value of 25.67 when dyed under 120° C.

(80) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 13% after stored at 25° C. and R.H. 65% for 60 months.

Example 5

(81) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(82) (1) Preparation of the Cationic Modified Polyester

(83) (1.1) Synthesizing 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol

(84) (a) mixing isobutanol and 50% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 5.4:1, then carrying out the reaction with a stirring at 110° C. for 5 hr to obtain potassium isobutanol;

(85) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.4:2.6 and cooling the system to 4° C.;

(86) (c) adding 3-methyl-3-hydroxybutyne and 2,2,4-trimethyl-3-pentanone into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2,4-trimethyl-3-pentanone:xylene as 1:1.2:3.0, then starting the reaction at 28° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(87) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 2.5:10:0.03 and then carrying out the reaction accompanied with a continuous hydrogen input at 44° C. for 53 min, finally obtaining 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol (just as demonstrated in Formula (I) with R=—CH(CH.sub.3).sub.2) through a series of processes of separation and purification;

(88) (1.2) Preparation of Solid Heteropolyacid SiO.sub.2—CaO

(89) dispersing 1 phr of silica powder in 50 phr of water by fully stirring, then dripping in 3 phr of calcium sulfate solution with concentration of 5 wt %. Next, adjusting the pH value of the dispersion system to neutral with 1.0 mol/L sodium hydroxide solution and then to 8 with 10 wt % sulfuric acid. after aging for 2 h, washing the dispersion system with deionized water until no SO.sub.4.sup.2− detection, and then filtering it under the vacuum and washing the filter cake with anhydrous ethanol for several times, further, drying the cake under 100° C. in an oven, finally calcining the dry cake at 650° C. for 3.5 h to obtain solid heteropolyacid SiO.sub.2—CaO with an average diameter of 0.45 micron and a CaO content of 45 wt %;

(90) (1.3) Esterification

(91) concocting PTA, EG, SIPE and 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol into a slurry, then adding in the calcined SiO.sub.2—CaO powder, antimony glycol, titanium dioxide and triphenyl phosphate and carrying out the esterification in a nitrogen atmosphere with a pressure of 0.2 MPa at 248° C., finally ending the reaction when the water distillation reaching 95% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol being 1:1.5:0.04, and respecting to PTA the additions of SIPE, SiO.sub.2—CaO, antimony glycol, titanium dioxide and triphenyl phosphate are 1.3 mol %, 0.05 wt %, 0.04 wt %, 0.24 wt % and 0.01 wt %, respectively;

(92) (1.4) Polycondensation

(93) smoothly reducing the pressure of the system of (1) to less than 470 Pa within 42 min and carrying out reaction at 255° C. for 36 min, successively, further reducing the pressure to less than 92 Pa and continuing the reaction at 272° C. for 70 min. finally obtaining the cationic modified polyester with a molecular weight of 26300 and a molecular weight distribution index of 2.4;

(94) (2) Spinning of Cationic Dyeable Polyester Fiber

(95) through a FDY technological way including stages of metering, spinneret extruding (at 280° C.), cooling (at 20° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.30 MPa, godet roller 1 speed 2300 m/min, godet roller 1 temperature 90° C., godet roller 2 speed 3700 m/min, godet roller 2 temperature 110° C.), and winding (3850 m/min), converting the cationic dyeable polyester fiber.

(96) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 0.5 dtex, breaking strength 3.5 cN/dtex, elongation at break 37.0%, interlacing degree 14/m, linear density deviation rate 0.93%, breaking strength CV value 5.00%, elongation at break CV value 7.82%, boiling water shrinkage rate 8.5%.

(97) The cationic dyeable polyester fiber has a dye uptake of 89.24% and a K/S value of 24.69 when dyed under 120° C.

(98) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 17% after stored at 25° C. and R.H. 65% for 60 months.

Example 6

(99) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(100) (1) Preparation of the Cationic Modified Polyester

(101) (1.1) Synthesizing 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol

(102) (a) mixing isobutanol and 40% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 5:1, then carrying out the reaction with a stirring at 106° C. for 4.5 hr to obtain potassium isobutanol;

(103) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.3:2.0 and cooling the system to 2° C.;

(104) (c) adding 3-methyl-3-hydroxybutyne and 2,2,4-trimethyl-3-pentanone into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2,4-trimethyl-3-pentanone:xylene as 1:1.3:2.5, then starting the reaction at 32° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(105) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 2.0:10:0.01 and then carrying out the reaction accompanied with a continuous hydrogen input at 48° C. for 50 min, finally obtaining 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol (just as demonstrated in Formula (I) with R=—CH(CH.sub.3).sub.2) through a series of processes of separation and purification;

(106) (1.2) Preparation of Solid Heteropolyacid Powder

(107) mixing SiO.sub.2—TiO.sub.2 with an average diameter of 0.45 micron and SiO.sub.2—ZrO.sub.2 with an average diameter of 0.45 micron in a weight ratio 1:1 to obtain the solid heteropolyacid powder, in which the contents of TiO.sub.2 and ZrO.sub.2 in SiO.sub.2—TiO.sub.2 and SiO.sub.2—ZrO.sub.2 are 30 wt % and 50 wt %, respectively;

(108) (1.3) Esterification

(109) concocting PTA, EG, SIPE and 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol into a slurry, then adding in the calcined solid heteropolyacid powder, antimony trioxide, titanium dioxide and trimethyl phosphate and carrying out the esterification in a nitrogen atmosphere with a pressure of 0.3 MPa at 250° C., finally ending the reaction when the water distillation reaching 94% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-5-isopropyl-2,5-heptadiol being 1:1.8:0.042, and respecting to PTA the additions of SIPE, the heteropolyacid, antimony trioxide, titanium dioxide and trimethyl phosphate are 1.5 mol %, 0.05 wt %, 0.03 wt %, 0.21 wt % and 0.05 wt %, respectively;

(110) (1.4) Polycondensation

(111) smoothly reducing the pressure of the system of (1) to less than 500 Pa within 46 min and carrying out reaction at 258° C. for 38 min, successively, further reducing the pressure to less than 95 Pa and continuing the reaction at 274° C. for 80 min. finally obtaining the cationic modified polyester with a molecular weight of 26700 and a molecular weight distribution index of 2.1;

(112) (2) Spinning of Cationic Dyeable Polyester Fiber

(113) through a FDY technological way including stages of metering, spinneret extruding (at 271° C.), cooling (at 19° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.22 MPa, godet roller 1 speed 2500 m/min, godet roller 1 temperature 75° C., godet roller 2 speed 3800 m/min, godet roller 2 temperature 105° C.), and winding (3740 m/min), converting the cationic dyeable polyester fiber.

(114) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 1.0 dtex, breaking strength 3.61 cN/dtex, elongation at break 33.0%, interlacing degree 10/m, linear density deviation rate 1.00%, breaking strength CV value 5.00%, elongation at break CV value 7.88%, boiling water shrinkage rate 8.0%.

(115) The cationic dyeable polyester fiber has a dye uptake of 92.2% and a K/S value of 25.67 when dyed under 120° C.

(116) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 15% after stored at 25° C. and R.H. 65% for 60 months.

Example 7

(117) A method for preparing the cationic dyeable polyester fiber, comprising the steps:

(118) (1) Preparation of the Cationic Modified Polyester

(119) (1.1) Synthesizing 2,6,6-trimethyl-5-tert-butyl-2,5-heptadiol

(120) (a) mixing isobutanol and 46% of KOH aqueous solution in the molar ratio of isobutanol to KOH as 5.5:1, then carrying out the reaction with a stirring at 100° C. for 4 hr to obtain potassium isobutanol;

(121) (b) removing the impurities from the system in step (a), then adding in xylene in the molar ratio of isobutanol to xylene as 1.3:2.6 and cooling the system to 5° C.;

(122) (c) adding 3-methyl-3-hydroxybutyne and 2,2,4,4-tetramethyl-3-pentanone into the system of step (b) in a molar ratio of 3-methyl-3-hydroxybutyne:2,2,4,4-tetramethyl-3-pentanone:xylene as 1:1.24:3.0, then starting the reaction at 25° C. for 3 hr, and obtaining octynyl diol after a series of processes of cooling crystallization, centrifugation and drying;

(123) (d) mixing octynyl diol, ethanol and Pd catalyst in a weight ratio of 3.0:10:0.03 and then carrying out the reaction accompanied with a continuous hydrogen input at 40° C. for 56 min, finally obtaining 2,6,6-trimethyl-5-tert-butyl-2,5-heptadiol (just as demonstrated in Formula (I) with R=—CH(CH.sub.3).sub.3) through a series of processes of separation and purification;

(124) (1.2) Preparation of Solid Heteropolyacid Powder

(125) mixing SiO.sub.2—TiO.sub.2, B.sub.2O.sub.3—Al.sub.2O.sub.3 and SiO.sub.2—ZrO.sub.2 (all with an average diameter of 0.45 micron) in a weight ratio 1:1:1 to obtain the solid heteropolyacid powder, in which the contents of TiO.sub.2, Al.sub.2O.sub.3 and ZrO.sub.2 in SiO.sub.2—TiO.sub.2, B.sub.2O.sub.3—Al.sub.2O.sub.3 and SiO.sub.2—ZrO.sub.2 are 50 wt %, 20 wt % and 20 wt %, respectively;

(126) (1.3) Esterification

(127) concocting PTA, EG, SIPE and 2,6,6-trimethyl-5-tert-butyl-2,5-heptadiol into a slurry, then adding in the calcined solid heteropolyacid powder, antimony glycol, titanium dioxide and trimethyl phosphite and carrying out the esterification in a nitrogen atmosphere with a pressure of 0.3 MPa at 250° C., finally ending the reaction when the water distillation reaching 93% of the theoretical value, wherein the molar ratio of PTA, EG and 2,6,6-trimethyl-5-tert-butyl-2,5-heptadiol being 1:2.0:0.046, and respecting to PTA the additions of SIPE, the heteropolyacid, antimony glycol, titanium dioxide and trimethyl phosphite are 1.5 mol %, 0.03 wt %, 0.04 wt %, 0.25 wt % and 0.03 wt %, respectively;

(128) (1.4) Polycondensation

(129) smoothly reducing the pressure of the system of (1) to less than 490 Pa within 35 min and carrying out reaction at 259° C. for 50 min, successively, further reducing the pressure to less than 83 Pa and continuing the reaction at 275° C. for 85 min. finally obtaining the cationic modified polyester with a molecular weight of 27000 and a molecular weight distribution index of 1.9;

(130) (2) Spinning of Cationic Dyeable Polyester Fiber

(131) through a FDY technological way including stages of metering, spinneret extruding (at 277° C.), cooling (at 20° C.), oiling, stretching as well as heat setting (carried on with the parameters of interlacing pressure 0.30 MPa, godet roller 1 speed 2400 m/min, godet roller 1 temperature 85° C., godet roller 2 speed 3830 m/min, godet roller 2 temperature 115° C.), and winding (3820 m/min), converting the cationic dyeable polyester fiber.

(132) Finally obtained cationic dyeable polyester fiber has the following performance indices: monofilament fineness 1.1 dtex, breaking strength 3.5 cN/dtex, elongation at break 37.0%, interlacing degree 14/m, linear density deviation rate 0.99%, breaking strength CV value 4.99%, elongation at break CV value 7.9%, boiling water shrinkage rate 8.5%.

(133) The cationic dyeable polyester fiber has a dye uptake of 87.8% and a K/S value of 25.12 when dyed under 120° C.

(134) The cationic dyeable polyester fiber has an intrinsic viscosity drop of 17% after stored at 25° C. and R.H. 65% for 60 months.