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    • 专利摘要:
    A type of one-step spun composite DTY and preparation method thereof are disclosed. The bi-profiled fiber is manufactured with two types of modified polyester of different viscosities through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding. Wherein those two modified polyesters have a molecular structure including terephthalic acid segments, ethylene glycol segments and branched diol segments, and the branched diol has a structural formula ofhere R<sub>1</sub>and R<sub>2</sub>are separately selected from the linear alkylene with 1-3 carbon atoms, R<sub>3</sub>from the alkyl with 1-5 carbon atoms, and R<sub>4</sub>from the alky with 2-5 carbon atoms. The obtained one-step spun composite DTY has an elastic shrinkage rate of no less than 35%. The method presented in this invention is involved in a simple and reasonable technological process for wide application range.
    公开号:EP3683339A1
    申请号:EP18889561.9
    申请日:2018-07-27
    公开日:2020-07-22
    发明作者:Hongwei FAN；Guanfan JIN；Ming Chen；Huailin REN；Yongfeng Wang；Xiangming Wang
    申请人:Jiangsu Hengli Chemical Fiber Co Ltd；
    IPC主号:C08L67-00
    专利说明:
    [0001] The present invention belongs to the field of fiber manufacture, and more particularly, relates to a type of one-step spun composite DTY and a preparation method thereof. Background
    [0002] The production of polyethylene terephthalate (PET) fiber has grown rapidly and topped out in world's synthetic fibers since its inception. Because of its excellent properties such as high breaking strength, high elastic modulus, suitable resilience, excellent heat setting performance, strong resistance to heat, light, acid, alkali and corrosion, as well as the advantages of wrinkle resistance and stiffness of the involved fabrics, PET fiber has been widely used in the fields of clothing and home textile.
    [0003] However, during the polycondensation process, the generation of linear PET polymer will also be accompanied by the linear or cyclic oligomers if the oxidative degradation is initiated by high temperature. Cyclic oligomers are those formed from the retraction and cyclization of intermediates during the condensation stage, among which more than 70% are found to be cyclic trimers. Being easy to aggregate and crystallize, stable to heat and chemical, cyclic trimers will affect the processing of PET fiber through (1) blocking the spinning pack to reduce the service life of filtering components, (2) subsiding and being deposited on the heating roller during the fiber thermal setting to increase the friction and the heating unevenness, (3) being the aggregation center of dyes to cause color stains or color specks in the surface of fiber and furtherly degrade the feel and shade of PET fabrics, or subsiding in pipelines and valves and blocking the dyeing flow to reduce the repeatability and evenness of fiber dyeing, or (4) adhering to the fiber surface and causing difficulty in yarn winding so as to result in yarn broken and unevenness, finally degrading the quality of fiber products.
    [0004] PET DTY and Nylon DTY are the two most common stretch yarn varieties. The former is of relatively low elasticity and suitable for making knitted outerwear with soft handling, considerable flexibility, dimensional stability, wrinkle resistance, wool feeling and air permeability, whereas the latter is of good extensibility and elasticity and suitable for making knitwear such as socks, underwear, sportswear and gloves. Moreover, composite fibers are those desired to combine the both fibers to obtain the best performance.
    [0005] As a matter of fact, how to prepare the one-step spun composite DTY with high elasticity and dimensional stability so as to significantly improve the quality of industrial yarn, has become an urgent problem Summary
    [0006] A primary object of the present invention is to provide a one-step spun composite DTY and preparation method thereof so as to overcome the problems such as poor heat setting effect, weak dyeability, dyeing unevenness and color stain existed in current PET fiber production.
    [0007] Another object of the present invention is to provide a one-step spun composite DTY, wherein the PET DTY possesses a fairly low content of oligomer without performance loss.
    [0008] Another object of the present invention is to provide a method for preparing one-step spun composite DTY, wherein the branched diol is incorporated in PET so as to reduce the content of oligomer generated in side reaction and enhance the stability of PET producing.
    [0009] Accordingly, to achieve the above mentioned objects, the present invention provides a technological scheme for one-step spun composite DTY in which the monofilament is composed of two modified polyester with different viscosities, wherein each modified polyester has a molecular chain structure including terephthalic acid segments, ethylene glycol segments and branched diol segments, and wherein said branched diol has a structural formula of
    [0010] Herein said one-step spun composite DTY has an elastic shrinkage rate of no less than 35%.
    [0011] As a preferred technology program, for the one-step spun composite DTY mentioned above, wherein the intrinsic viscosity ratio of two modified polyesters is 0.55-0.70:1.00-1.20, and higher one is 1.00-1.20dL/g. The intrinsic viscosity ratio determines the elastic shrinkage of fiber, and the ratio range presented above has been optimized for the best elastic effect.
    [0012] For the one-step spun composite DTY mentioned above, wherein the PET DTY has a fineness of 150-300dtex, a linear density CV of less than or equal to 1.00%, a breaking strength of greater than or equal to 2.2cN/dtex, a breaking elongation of 37.2±4.0%, a breaking strength CV of less than or equal to 5.0%, a breaking elongation CV of less than or equal to 10.0% and a boiling water shrinkage of 9.5±0.5%.
    [0013] For the one-step spun composite DTY, wherein the two modified polyesters with different viscosities have a cyclic oligomer content of less than or equal to 0.6wt%, showing a remarkable subduction relative to 1.5-2.1wt% of cyclic oligomer in the polyester prepared by the prior technology;wherein said modified polyester of low viscosity has a number average molecular weight of 17000-22000 and a molecular weight distribution index of 1.8-2.2;wherein said modified polyester of high viscosity has a number average molecular weight of 25000-30000 and a molecular weight distribution index of 1.8-2.2;wherein said two modified polyesters have a branched diol segment content of 3-5mol% respect to terephthalic acid segments, which is beneficial to maintaining the excellent performance of the polyester itself;wherein said branched diol can be one of following compounds: 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3,3-diethyl-1,5-penpentadiol, 4,4-diethyl-1,7-heptanediol, 4,4-bis(1-methyl ethyl)-1,7-heptanediol, 3,3-dipropyl-1,5-pentanediol, 4,4-dipropyl-1,7-heptanediol, 4-methyl-4-(1,1-dimethyl ethyl)-1,7-heptanediol, 3-methyl-3-amyl-1,6-hexanediol or 3,3-dipropyl-1,5-pentanediol.
    [0014] For the one-step spun composite DTY mentioned above, wherein the modified polyester of low viscosity is prepared through the steps as follows: (1) Esterification;
    [0015] Firstly, terephthalic acid, ethylene glycol and the branched diol are mixed into a slurry, then the esterification is carried out under the pressure of nitrogen after adding catalyst, extinction agent and stabilizer, wherein the pressure range from atmospheric pressure to 0.3MPa while reaction temperature is 250-260 °C, and the end point of esterification is chosen as the moment when the elimination of water reach 90% of the theoretical value; (2) Polycondensation;
    [0016] After the esterification hereinabove, the polycondensation is performed under negative pressure, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the pressure is smoothly reduced from the normal value to less than 500Pa within 30∼50min, and the reaction temperature is 260-270°C while reaction time is 30-50min, b) fine vacuum stage, wherein the pressure is furtherly reduced to less than 100Pa, and the reaction temperature is 275-285°C while reaction time is 50-90min;
    [0017] The obtained modified polyester of low viscosity will undergo an extra solid state polycondensation to produce the polyester of high viscosity.
    [0018] For the one-step spun composite DTY mentioned above, in step (1) the molar ratio of terephthalic acid, ethylene glycol and the branched diol is 1:1.2-2.0:0.03-0.06, and an amount of the catalyst is 0.01-0.05% by weight of the terephthalic acid, an amount of the extinction agent is 0.20-0.25% by weight of the terephthalic acid and an amount of the stabilizer is 0.01-0.05% by weight of the terephthalic acid;
    [0019] wherein the catalyst is one of antimony trioxide, antimony glycol or antimony acetate, the extinction agent is titanium dioxide, and the stabilizer is one of triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
    [0020] Additionally, in the present invention a method for preparing the one-step spun composite DTY mentioned above is also provided, generally including the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding;
    [0021] As a preferred technology program, for the preparing method mentioned above, wherein the weight ratio of polyester of high viscosity and polyester of low viscosity is 0.7-1.0:0.7-1.0.
    [0022] For the preparing method mentioned above, the spinning technologies for the one-step spun composite DTY could be chosen asSpinning temperature 280-290°C, Cooling temperature 20-25°C, Interlacing pressure 0.20-0.30MPa, Speed of godet roller 1 2200-2600m/min, Temperature of godet roller1 75-85°C, Speed of godet roller 2 3600-3900m/min, Temperature of godet roller 2 135-165°C, Winding speed 3580-3840m/min, Initial spinning pack pressure 120bar, Spinning pack pressure rising ΔP ≤0.6bar/day, Spinning pack life cycle ≥60days.
    [0023] The mechanism of this invention could be described as follows:
    [0024] In organic compounds, the angle between two chemical bonds formed between intramolecular atoms, called bond angle and usually expressed in degrees, is affected by the electronegativity of central atoms and coordination atoms. When the electronegativity of the coordination atoms bonded with the central atom increases, i.e., the electron absorption ability of the coordination atoms increases, the electron pairs will move toward the coordination atom whereas far away from the central atom. Therefore, the chemical bonds will move closely with each other due to the reduction of repulsion force and the bond angle will decrease. On the contrary, when the electronegativity of coordination atoms decreases, namely, their donor ability increases, the electron pairs will move close to the central atom, hence the increase of repulsion force will drive the chemical bonds away from each other and the bond angle will also increase.
    [0025] According to Pauling's electronegativity scale, the electronegativity of C, H and O atom is 2.55, 2.20 and 3.44, respectively. Furthermore, on the basis of valence electron energy balance theory, the electronegativity of an atom group can be calculated through the formula ofχ ve G = ∑ n i χ i N ve , i ∑ n i N ve , i ,
    [0026] During the esterification of terephthalic acid with diol, atom C released from the broken C-O bond of carboxyl group in terephthalic acid will combine with the atom O of hydroxyl group in the diol to form a new C-O bond in the ester group. If the angle between the bond C-C (one C belongs to the ester group and the other C to the benzene ring) and the newly formed bond C-O is marked as α, the change of the bond angle α will affect the cyclization reaction. Specifically, the cyclization will be easy if α is less than 109°, whereas the cyclizing probability will decrease when α becomes lager. In the present invention, the branched diol with a formula of
    [0027] In conclusion, the present invention providesa type of one-step spun composite DTY with the advantages of high elasticity, high dimensional stability and appreciable extensibility, etc.;the preparing method thereof, which is simple and reasonable for wide application range;the preparing method thereof, in which the branched diol has been incorporated to change the bond angles of polyester and then reduce the cyclic oligomer produced in the side reaction of polymerization. Detailed Description of the Embodiments
    [0028] 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. Example 1
    [0029] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Esterification
    [0030] Firstly, a slurry of terephthalic acid, ethylene glycol and 2-ethyl-2-methyl-1,3-propanediol with a molar ratio 1:1.2:0.03 is concocted and properly mixed with antimony trioxide, titanium dioxide and triphenyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the atmospheric pressure and the temperature of 250°C. The end point of esterification is chosen as the moment when the elimination of water reach 90% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony trioxide, titanium dioxide and triphenyl phosphate are 0.01%, 0.20% and 0.05%, respectively. Wherein the formula of branched diol is
    [0031] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 500Pa within 30min, and the reaction temperature is 260°C while reaction time is 40min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 100Pa, and the reaction temperature is 275°C while reaction time is 70min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 2-ethyl-2-methyl-1,3-propanediol segments (whose molar content is 3% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.6Wt%, a number average molecular weight of 20000 and a molecular weight distribution index of 2.0.
    [0032] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.55:1.05 and the value of higher one is 1.00dL/g, whereas the weight content ratio of two modified polyester is 0.7:0.8.
    [0033] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 35%, a fineness of 150detx, a linear density CV of 0.96%, a breaking strength of 2.5cN/dtex, a breaking elongation of 33.2%, a breaking strength CV of 4.8%, a breaking elongation CV of 9.6%, a boiling water shrinkage of 9.0%. Example 2
    [0034] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Esterification
    [0035] Firstly, a slurry of terephthalic acid, ethylene glycol and 2,2-diethyl-1,3-propanediol with a molar ratio 1:1.3:0.04 is concocted and properly mixed with antimony glycol, titanium dioxide and trimethyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the atmospheric pressure and the temperature of 260°C. The end point of esterification is chosen as the moment when the elimination of water reach 91% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony glycol, titanium dioxide and trimethyl phosphate are 0.02%, 0.21% and 0.03%, respectively. Wherein the formula of branched diol is
    [0036] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 490Pa within 35min, and the reaction temperature is 261°C while reaction time is 30min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 100Pa, and the reaction temperature is 277°C while reaction time is 85min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 2,2-diethyl-1,3-propanediol segments (whose molar content is 5% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.6Wt%, a number average molecular weight of 27000 and a molecular weight distribution index of 1.8.
    [0037] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.60:1.00 and the value of higher one is 1.05dL/g, whereas the weight content ratio of two modified polyester is 0.8:0.7.
    [0038] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 38%, a fineness of 190detx, a linear density CV of 0.96%, a breaking strength of 2.4cN/dtex, a breaking elongation of 37.2%, a breaking strength CV of 4.3%, a breaking elongation CV of 9.9%, a boiling water shrinkage of 9.0%. Example 3
    [0039] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Esterification
    [0040] Firstly, a slurry of terephthalic acid, ethylene glycol and 2-butyl-2-ethyl-1,3-propanediol with a molar ratio 1:1.4:0.05 is concocted and properly mixed with antimony acetate, titanium dioxide and trimethyl phosphite, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.1MPa and the temperature of 252°C. The end point of esterification is chosen as the moment when the elimination of water reach 92% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony acetate, titanium dioxide and trimethyl phosphite are 0.03%, 0.23% and 0.01%, respectively. Wherein the formula of branched diol is
    [0041] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the normal value to 495Pa within 40min, and the reaction temperature is 263°C while reaction time is 45min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 95Pa, and the reaction temperature is 278°C while reaction time is 60min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 2-butyl-2-ethyl-1,3-propanediol segments (whose molar content is 4% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.5Wt%, a number average molecular weight of 21000 and a molecular weight distribution index of 2.2.
    [0042] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.65:1.10 and the value of higher one is 1.08dL/g, whereas the weight content ratio of two modified polyester is 0.7:0.7.
    [0043] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 39%, a fineness of 210detx, a linear density CV of 0.99%, a breaking strength of 2.2cN/dtex, a breaking elongation of 41.2%, a breaking strength CV of 4.4%, a breaking elongation CV of 9.8%, a boiling water shrinkage of 9.5%. Example 4
    [0044] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 3,3-diethyl-1,5-pentanediol
    [0045] At first 3,3-diethyl-propionaldehyde, acetaldehyde and triethylamine are reacted for 20min under 90 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100 °C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0046] Firstly, a slurry of terephthalic acid, ethylene glycol and 3,3-diethyl-1,5-penpentadiol with a molar ratio 1:1.5:0.06 is concocted and properly mixed with antimony trioxide, titanium dioxide and triphenyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.3MPa and the temperature of 255°C. The end point of esterification is chosen as the moment when the elimination of water reach 95% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony trioxide, titanium dioxide and triphenyl phosphate are 0.04%, 0.25% and 0.01%, respectively. (c) Polycondensation
    [0047] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the normal value to 400Pa within 50min, and the reaction temperature is 265°C while reaction time is 33min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 90Pa, and the reaction temperature is 280°C while reaction time is 50min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 3,3-diethyl-1,5-penpentadiol segments (whose molar content is 3.5% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.2wt%, a number average molecular weight of 23000 and a molecular weight distribution index of 1.9.
    [0048] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.65:1.05 and the value of higher one is 1.13dL/g, whereas the weight content ratio of two modified polyester is 0.9:0.7.
    [0049] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 36%, a fineness of 250detx, a linear density CV of 0.91%, a breaking strength of 2.8cN/dtex, a breaking elongation of 40.0%, a breaking strength CV of 4.1%, a breaking elongation CV of 9.7%, a boiling water shrinkage of 9.4%. Example 5
    [0050] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 4,4-diethyl-1,7-heptanediol
    [0051] At first 4,4-diethyl-butyraldehyde, propylaldehyde and triethylamine are reacted for 20min under 92 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0052] Firstly, a slurry of terephthalic acid, ethylene glycol and 4,4-diethyl-1,7-heptanediol with a molar ratio 1:1.6:0.03 is concocted and properly mixed with antimony glycol, titanium dioxide and trimethyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the atmospheric pressure and the temperature of 257°C. The end point of esterification is chosen as the moment when the elimination of water reach 92% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony glycol, titanium dioxide and trimethyl phosphate are 0.05%, 0.20% and 0.04%, respectively. (c) Polycondensation
    [0053] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 450Pa within 33min, and the reaction temperature is 270°C while reaction time is 30min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 95Pa, and the reaction temperature is 275°C while reaction time is 60min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 4,4-diethyl-1,7-heptanediol segments (whose molar content is 5% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.5wt%, a number average molecular weight of 25000 and a molecular weight distribution index of 2.1.
    [0054] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.70:1.20 and the value of higher one is 1.18dL/g, whereas the weight content ratio of two modified polyester is 0.9:1.0.
    [0055] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 39%, a fineness of 280detx, a linear density CV of 0.93%, a breaking strength of 3.0cN/dtex, a breaking elongation of 38.2%, a breaking strength CV of 4.9%, a breaking elongation CV of 9.6%, a boiling water shrinkage of 9.9%. Example 6
    [0056] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 4,4-bis(1-methyl ethyl)-1,7-heptanediol
    [0057] At first 4,4-bis(1-methylethyl)-butyraldehyde, propylaldehyde and triethylamine are reacted for 20min under 95 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0058] Firstly, a slurry of terephthalic acid, ethylene glycol and 4,4-bis(1-methyl ethyl)-1,7-heptanediol with a molar ratio 1:1.7:0.05 is concocted and properly mixed with antimony acetate, titanium dioxide and trimethyl phosphite, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.2MPa and the temperature of 253°C. The end point of esterification is chosen as the moment when the elimination of water reach 96% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony acetate, titanium dioxide and trimethyl phosphite are 0.01%, 0.20% and 0.05%, respectively. (c) Polycondensation
    [0059] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 480Pa within 38min, and the reaction temperature is 262°C while reaction time is 38min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 98Pa, and the reaction temperature is 279°C while reaction time is 80min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 4,4-bis(1-methyl ethyl)-1,7-heptanediol segments (whose molar content is 4% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.55wt%, a number average molecular weight of 27000 and a molecular weight distribution index of 2.2.
    [0060] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.75:1.20 and the value of higher one is 1.19dL/g, whereas the weight content ratio of two modified polyester is 1.0:0.7.
    [0061] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 41%, a fineness of 300detx, a linear density CV of 0.94%, a breaking strength of 2.5cN/dtex, a breaking elongation of 34.2%, a breaking strength CV of 4.7%, a breaking elongation CV of 9.7%, a boiling water shrinkage of 9.4%. Example 7
    [0062] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 3,3-dipropyl-1,5-pentanediol
    [0063] At first 3,3-dipropyl-propionaldehyde, acetaldehyde and triethylamine are reacted for 20min under 94 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0064] Firstly, a slurry of terephthalic acid, ethylene glycol and 3,3-dipropyl-1,5-pentanediol with a molar ratio 1:1.8:0.03 is concocted and properly mixed with antimony trioxide, titanium dioxide and triphenyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.3MPa and the temperature of 250°C. The end point of esterification is chosen as the moment when the elimination of water reach 90% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony trioxide, titanium dioxide and triphenyl phosphate are 0.03%, 0.24% and 0.02%, respectively. (c) Polycondensation
    [0065] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 455Pa within 42min, and the reaction temperature is 264°C while reaction time is 45min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 85Pa, and the reaction temperature is 285°C while reaction time is 75min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 3,3-dipropyl-1,5-pentanediol segments (whose molar content is 4.5% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.45wt%, a number average molecular weight of 26500 and a molecular weight distribution index of 2.2.
    [0066] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.55:1.10 and the value of higher one is 1.00dL/g, whereas the weight content ratio of two modified polyester is 1.0:0.9
    [0067] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 43%, a fineness of 290detx, a linear density CV of 0.99%, a breaking strength of 2.7cN/dtex, a breaking elongation of 37.2%, a breaking strength CV of 5.0%, a breaking elongation CV of 9.6%, a boiling water shrinkage of 10.0%. Example 8
    [0068] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 4,4-dipropyl-1,7-heptanediol
    [0069] At first 4,4-dipropyl-butyraldehyde, acetaldehyde and triethylamine are reacted for 20min under 92 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0070] Firstly, a slurry of terephthalic acid, ethylene glycol and 4,4-dipropyl-1,7-heptanediol with a molar ratio 1:1.9:0.04 is concocted and properly mixed with antimony glycol, titanium dioxide and trimethyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.3MPa and the temperature of 260°C. The end point of esterification is chosen as the moment when the elimination of water reach 93% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony glycol, titanium dioxide and trimethyl phosphate are 0.04%, 0.21% and 0.03%, respectively. (c) Polycondensation
    [0071] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 475Pa within 45min, and the reaction temperature is 265°C while reaction time is 48min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 88Pa, and the reaction temperature is 283°C while reaction time is 80min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 4,4-dipropyl-1,7-heptanediol segments (whose molar content is 3% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.6wt%, a number average molecular weight of 23000 and a molecular weight distribution index of 2.0.
    [0072] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.65:1.15 and the value of higher one is 1.08dL/g, whereas the weight content ratio of two modified polyester is 0.8:0.7
    [0073] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 35%, a fineness of 260detx, a linear density CV of 1.00%, a breaking strength of 2.7cN/dtex, a breaking elongation of 37.2%, a breaking strength CV of 5.0%, a breaking elongation CV of 10.0%, a boiling water shrinkage of 10.0%. Example 9
    [0074] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 4-methyl-4-(1,1-dimethyl ethyl) -1,7-heptanediol
    [0075] At first 4-methyl-4-(1,1-dimethylethyl)-butyraldehyde, propylaldehyde and triethylamine are reacted for 20min under 92 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0076] Firstly, a slurry of terephthalic acid, ethylene glycol and 4-methyl-4-(1,1-dimethyl ethyl)-1,7-heptanediol with a molar ratio 1:2.0:0.05 is concocted and properly mixed with antimony acetate, titanium dioxide and trimethyl phosphate, then the esterification is carried out in the nitrogen atmosphere under the atmospheric pressure and the temperature of 251°C. The end point of esterification is chosen as the moment when the elimination of water reach 96% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony acetate, titanium dioxide and trimethyl phosphate are 0.05%, 0.22% and 0.04%, respectively. (c) Polycondensation
    [0077] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 420Pa within 30min, and the reaction temperature is 267°C while reaction time is 50min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 80Pa, and the reaction temperature is 280°C while reaction time is 90min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 4-methyl-4-(1,1-dimethyl ethyl)-1,7-heptanediol segments (whose molar content is 4% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.25wt%, a number average molecular weight of 24000 and a molecular weight distribution index of 2.2.
    [0078] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.65:1.20 and the value of higher one is 1.01 dL/g, whereas the weight content ratio of two modified polyester is 1.0:0.8.
    [0079] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 37%, a fineness of 240detx, a linear density CV of 0.98%, a breaking strength of 2.9cN/dtex, a breaking elongation of 33.2%, a breaking strength CV of 4.8%, a breaking elongation CV of 9.4%, a boiling water shrinkage of 9.5%. Example 10
    [0080] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 3-methyl-3-amyl-1,6-hexanediol
    [0081] At first 3-methyl-3-amyl-propionaldehyde, propylaldehyde and triethylamine are reacted for 20min under 90 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0082] Firstly, a slurry of terephthalic acid, ethylene glycol and 3-methyl-3-amyl-1,6-hexanediol with a molar ratio 1:1.2:0.06 is concocted and properly mixed with antimony glycol, titanium dioxide and trimethyl phosphite, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.1MPa and the temperature of 255°C. The end point of esterification is chosen as the moment when the elimination of water reach 92% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony glycol, titanium dioxide and trimethyl phosphite are 0.01%, 0.20% and 0.01%, respectively. (c) Polycondensation
    [0083] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 490Pa within 50min, and the reaction temperature is 269°C while reaction time is 30min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 100Pa, and the reaction temperature is 281°C while reaction time is 55min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 3-methyl-3-amyl-1,6-hexanediol segments (whose molar content is 3.5% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.1wt%, a number average molecular weight of 20000 and a molecular weight distribution index of 1.9.
    [0084] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.70:1.00 and the value of higher one is 1.20dL/g, whereas the weight content ratio of two modified polyester is 0.9:1.0.
    [0085] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 36%, a fineness of 230detx, a linear density CV of 0.97%, a breaking strength of 2.2cN/dtex, a breaking elongation of 33.2%, a breaking strength CV of 4.8%, a breaking elongation CV of 9.0%, a boiling water shrinkage of 9.5%. Example 11
    [0086] A method for preparing the one-step spun composite DTY, comprising the technological process of: (1) Preparation of modified polyester(a) Synthesis of 3,3-dipropyl-1,5-pentanediol
    [0087] At first 3,3-dipentyl-propionaldehyde, acetaldehyde and triethylamine are reacted for 20min under 95 °C in nitrogen atmosphere, then the concentrated solution is added into the hydrogenation reactor equipped with Raney nickel catalyst, and the reaction is furtherly carried out under 2.914MPa of hydrogen pressure at 100°C. When the reaction is completed, the reaction system is cooled to separate the catalyst out, then the solution is treated with ion exchange resin, followed by the water vacuum distillation, the separation and the purification of branched diol. The obtained diol has a formula of
    [0088] Firstly, a slurry of terephthalic acid, ethylene glycol and 3,3-dipropyl-1,5-pentanediol with a molar ratio 1:2.0:0.03 is concocted and properly mixed with antimony acetate, titanium dioxide and trimethyl phosphite, then the esterification is carried out in the nitrogen atmosphere under the pressure of 0.2MPa and the temperature of 250°C. The end point of esterification is chosen as the moment when the elimination of water reach 97% of the theoretical value. The additive contents (mass percentages relative to terephthalic acid) of antimony acetate, titanium dioxide and trimethyl phosphite are 0.01%, 0.23% and 0.05%, respectively. (c) Polycondensation
    [0089] After the esterification hereinabove, the polycondensation is performed at negative pressure to obtain modified polyester eventually, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the absolute pressure is smoothly reduced from the atmospheric pressure to 500Pa within 45min, and the reaction temperature is 260°C while reaction time is 40min, b) fine vacuum stage, wherein the pressure is furtherly reduced to 92Pa, and the reaction temperature is 277°C while reaction time is 80min. The obtained modified polyester possesses a molecular chain structure composed of terephthalic acid segments, ethylene glycol segments and 3,3-dipropyl-1,5-pentanediol segments (whose molar content is 5% respect to that of terephthalic acid segments), a cyclic oligomer content of 0.35wt%, a number average molecular weight of 25500 and a molecular weight distribution index of 1.8.
    [0090] (2) The one-step spun composite DTY is prepared from those two types of modified polyester with different viscosities mentioned above through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding, and the spinning parameters in those technology steps are listed in Table 1. Wherein the intrinsic viscosity ratio of those two modified polyester is 0.55:1.05 and the value of higher one is 1.20dL/g, whereas the weight content ratio of two modified polyester is 0.7:0.8.
    [0091] The final obtained one-step spun composite DTY has an elastic shrinkage rate of 38%, a fineness of 150detx, a linear density CV of 1.00%, a breaking strength of 2.4cN/dtex, a breaking elongation of 33.2%, a breaking strength CV of 5.0%, a breaking elongation CV of 9.2%, a boiling water shrinkage of 10.0%. Table 1. Example1 Example2 Example3 Example4 Example5 Example6 Example7 Example8 Example9 Example10 Example11 Spinning Temp.( °C) 285 283 281 280 290 285 288 290 281 283 286 Cooling Temp.(°C) 20 21 25 25 21 20 20 21 24 23 22 Interlacing Pres. (MPa) 0.22 0.21 0.25 020 0.22 0.29 0.30 0.24 0.22 0.28 0.23 Roller1 Speed (m/min) 220 0 230 0 250 0 235 0 2550 260 0 258 0 235 0 228 0 239 0 247 0 Roller1 Temp.(°C) 78 72 78 85 83 81 75 81 83 84 75 Roller2 Speed (m/min) 365 0 378 0 379 0 365 0 3800 375 0 371 0 360 0 385 0 390 0 373 0 Roller2 Temp.(°C) 118 148 135 149 135 130 120 124 165 130 152 Winding Speed (m/min) 358 0 370 0 375 0 360 0 3700 384 0 376 0 368 0 372 0 360 0 379 0 Initial Spinning Pack Pres. (bar) 120 120 120 120 120 120 120 120 120 120 120 Spinning Pack Pres. Rising ΔP (bar/day) 0.58 0.56 0.6 0.55 0.52 0.6 0.54 0.55 0.52 0.54 0.59 Spinning Pack Life Cycle (Day) 66 62 63 60 60 65 67 62 61 60 68
    权利要求:
    Claims (10)
    [0001] A one-step spun composite DTY, in which the monofilaments are made of two types of modified polyester with different viscosities;wherein those two modified polyesters have a molecular chain structure including terephthalic acid segments, ethylene glycol segments and branched diol segments, and wherein said branched diol has a structural formula of
    [0002] The one-step spun composite DTY of claim 1, wherein the intrinsic viscosity ratio of the two modified polyesters is 0.55-0.70:1.00-1.20, and the intrinsic viscosity value of the higher one is 1.00-1.20dL/g.
    [0003] The one-step spun composite DTY of claim 2, wherein the DTY has a fineness of 150-300dtex, a linear density CV of less than or equal to 1.00 and a breaking strength of greater than or equal to 2.2cN/dtex, a breaking elongation of 37.2±4.0%, a breaking strength CV of less than or equal to 5.0%, a breaking elongation CV of less than or equal to 10.0% and a boiling water shrinkage rate of 9.5±0.5%.
    [0004] The one-step spun composite DTY of any one of claims 1 to claim 3, where in the cyclic oligomer content in those two modified polyesters is less than or equal to 0.6wt%;wherein said modified polyester with low viscosity has a number average molecular weight of 17000-22000 as well as a molecular weight distribution index of 1.8-2.2;wherein said modified polyester with high viscosity has a number average molecular weight of 25000-30000 as well as a molecular weight distribution index of 1.8-2.2;wherein said two modified polyesters have a branched diol segment content of 3-5mol% respect to terephthalic acid segments;wherein said the branched diol can be one of following compounds: 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3,3-diethyl-1,5-penpentadiol, 4,4-diethyl-1,7-heptanediol, 4,4-bis(1-methyl ethyl)-1,7-heptanediol, 3,3-dipropyl-1,5-pentanediol, 4,4-dipropyl-1,7-heptanediol, 4-methyl-4-(1,1-dimethyl ethyl)-1,7-heptanediol, 3-methyl-3-amyl-1,6-hexanediol or 3,3-dipropyl-1,5-pentanediol.
    [0005] The one-step spun composite DTY of claim 4, wherein the modified polyester of low viscosity is prepared through the steps as follows:
    (1) Esterification;firstly, terephthalic acid, ethylene glycol and the branched diol are mixed into a slurry, then the esterification is carried out under the pressure of nitrogen after adding catalyst, extinction agent and stabilizer, wherein the pressure range from atmospheric pressure to 0.3MPa while reaction temperature is 250-260 °C, and the end point of esterification is chosen as the moment when the elimination of water reach 90% of the theoretical value;
    (2) Polycondensation;after the esterification hereinabove, the polycondensation is performed under negative pressure, which includes two successive stages, i.e., a) coarse vacuum stage, wherein the pressure is smoothly reduced from the normal value to less than 500Pa within 30∼50min, and the reaction temperature is 260-270°C while reaction time is 30-50min, b) fine vacuum stage, wherein the pressure is furtherly reduced to less than 100Pa, and the reaction temperature is 275-285°C while reaction time is 50-90min;the obtained modified polyester of low viscosity will undergo an extra solid state polycondensation to produce the polyester of high viscosity.
    [0006] The one-step spun composite DTY of claim 5, wherein in said step (1) the molar ratio of terephthalic acid, ethylene glycol and the branched diol is 1:1.2-2.0:0.03-0.06, and an amount of the catalyst is 0.01-0.05% by weight of the terephthalic acid, an amount of the extinction agent is 0.20-0.25% by weight of the terephthalic acid and an amount of the stabilizer is 0.01-0.05% by weight of the terephthalic acid.
    [0007] The one-step spun composite DTY of claim 5 or claim 6, wherein the catalyst is one of antimony trioxide, antimony glycol or antimony acetate, the extinction agent is titanium dioxide, and the stabilizer is one of triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
    [0008] A preparation method for the one-step spun composite DTY of any one of claims 1 to claim 7, wherein the DTY is manufactured with those two modified polyesters through the steps of melting, melt metering, composite extruding, cooling, oiling, drawing, heat setting and winding.
    [0009] The preparation method of claim 8, wherein the weight ratio of polyester of high viscosity and polyester of low viscosity is 0.7-1.0:0.7-1.0.
    [0010] The preparation method of claim 8 or claim 9, wherein the spinning technologies for the one-step spun composite DTY are chosen as:Spinning temperature 280-290°C, Cooling temperature 20-25°C, Interlacing pressure 0.20-0.30MPa, Speed of godet roller 1 2200-2600m/min, Temperature of godet roller1 75-85°C, Speed of godet roller 2 3600-3900m/min, Temperature of godet roller 2 135-165°C, Winding speed 3580-3840m/min, Initial spinning pack pressure 120bar, Spinning pack pressure rising ΔP ≤0.6bar/day, Spinning pack life cycle ≥60days.
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    同族专利:
    公开号 | 公开日
    JP2021504598A|2021-02-15|
    CN108048939A|2018-05-18|
    WO2019114277A1|2019-06-20|
    US20200190319A1|2020-06-18|
    EP3683339A4|2021-06-02|
    CN108048939B|2019-11-12|
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