WO2012116481A1 - 改性共聚酯及其制备方法和纤维 - Google Patents
改性共聚酯及其制备方法和纤维 Download PDFInfo
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- WO2012116481A1 WO2012116481A1 PCT/CN2011/071364 CN2011071364W WO2012116481A1 WO 2012116481 A1 WO2012116481 A1 WO 2012116481A1 CN 2011071364 W CN2011071364 W CN 2011071364W WO 2012116481 A1 WO2012116481 A1 WO 2012116481A1
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- copolyester
- propanediol
- methyl
- sulfonate
- sodium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/522—Polyesters using basic dyes
Definitions
- the present invention relates to a modified copolyester, in particular to a novel copolymerization of a side chain aliphatic diol blend and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium. ester. Background technique
- polyester fiber dyeing There are many methods for improving polyester fiber dyeing. It is widely used to add modified monomers for copolymerization. It can be roughly divided into the following three types: (1) Adding cationic dyes to dye monomers, such as sodium (or potassium) benzene sulfonate. (2) adding disperse dye-dyeable monomers, such as isophthalic acid with meta-structure, polyethylene glycol and sebacic acid with flexible structure; (3) adding acid dyes to dye monomers, such as Containing an amine compound.
- dye monomers such as sodium (or potassium) benzene sulfonate
- disperse dye-dyeable monomers such as isophthalic acid with meta-structure, polyethylene glycol and sebacic acid with flexible structure
- acid dyes such as Containing an amine compound.
- the present invention uses a blend of two aliphatic diols having a side chain as the fourth comonomer, and the isophthalic acid dibasic acid 5-sodium sulfonate or potassium as the third copolymer Body, obtained a new type of modified copolyester, the copolymer fiber has very good cationic dyeability, the dye uptake rate is above 95%, much higher than the copolyester fiber in the prior art .
- the Applicant has unexpectedly discovered that the fibers of the copolyester have unexpectedly good resilience.
- the copolyester can also be prepared by continuous polymerization and direct spinning or section spinning. The preparation process has no special requirements on the equipment, low cost and easy realization of industrial production.
- a first aspect of the invention provides a modified copolyester which is copolymerized from a monomer comprising: (1) terephthalic acid; (2) ethylene glycol;
- the isophthalic acid dibasic acid 5-sodium sulfonate or potassium is preferably selected from the group consisting of: ethylene isophthalate-sodium 5-sulfonate, ethylene isophthalate 5-sulfonic acid Potassium, propylene glycol isophthalate-sodium 5-sulfonate, propylene glycol isophthalate-potassium 5-sulfonate, butylene glycol isophthalate-sodium 5-sulfonate, or isophthalic acid Alcohol ester 5-sodium sulfonate.
- the molar content of the sodium or potassium monomer unit of isophthalic acid dibasic acid-5-sulfonate preferably accounts for 1.5 mol% of the molar amount of the terephthalic acid monomer unit. 7 mol%.
- the sum of the molar contents of the monomer units of 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol preferably accounts for p-phenylene
- the molar amount of the formic acid monomer unit is from 4 mol% to 20 mol%.
- the divalent or trivalent metal compound catalyst added during copolymerization is: one or more of metal Zn, Sb, Mn, Ca or Co compounds, the content of which is p-terephthalic acid
- the amount of the formic acid monomer is from 0.01% by weight to 0.08% by weight.
- trimethyl phosphate or triphenyl phosphate as a heat stabilizer in an amount of from 0.02% by weight to 0.06% by weight based on the amount of the terephthalic acid monomer.
- a second aspect of the invention relates to a process for the preparation of the copolyester of the invention, which comprises: synthesizing a copolyester on a continuous polymerization apparatus: esterification of ethylene glycol and terephthalic acid to a first esterification tank , the reaction temperature is 240 ° C ⁇ 270 ° C, time 2-4 hours; then, into the second esterification tank, while injecting 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3 - a blend of propylene glycol, and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium, further esterified, the reaction temperature is 240 ° C ⁇ 270 ° C, time 1-3 hours; then, into the polycondensation kettle , the reaction temperature is 270 ° C -300 ° C, time 2-4 hours, after the end of the reaction, discharging, dicing, drying to obtain the copolyester; wherein
- the intrinsic viscosity of the copolyester obtained by this method is preferably from 0.4 to 0.7, and the melting point is preferably from 200 ° C to 240 ° C as measured by a capillary viscosity method.
- a third aspect of the invention relates to a fiber of the above copolyester which is obtained by such a method:
- the copolyester obtained by the above method is subjected to slicing or direct spinning, wherein the spinning screw temperature in the spinning process is 270 ° C ⁇ 320 ° C, the spinning speed is 400 ⁇ 4200 m / min, the drawing temperature is 70 ° C ⁇ 160°C, the draw ratio is 1 ⁇ 4 times.
- the copolyester fiber can be dyed dark with a cationic dye at a pressure of 95 to 100 ° C under normal pressure boiling conditions.
- the dyeing rate is above 95%.
- the copolyester fiber is instantaneously stretched back at 25 ° C, a pretension of 0.5 cN/dtex, a tensile rate of 500 mm/min, and a constant elongation of 15%.
- the bomb rate is above 75%.
- the fiber of the modified copolyester of the present invention can be dyed into a dark color by a cationic dye under normal pressure boiling conditions, and the dye uptake rate is over 95%. It is also bright in color and has a wide range of chromatograms. At the same time, the copolyester fiber has a very good resilience and a soft hand.
- the invention adopts two kinds of aliphatic diol mixtures with side chains and isophthalic acid dibasic acid 5-sodium sulfonate or potassium to obtain a novel modified copolyester, the two kinds of belt sides
- the chain aliphatic diols are: 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol.
- the molar content of the isophthalic acid diester-5-sulfonic acid sodium or potassium monomer unit is 1.5 mol% to 7 mol% relative to the molar content of the terephthalic acid unit. It is preferably 1.5 mol% to 6 mol%. More preferably, it is 2 mol% to 5 mol%, more preferably 3 mol% to 4 mol%.
- the isophthalic acid dibasic acid 5-sodium sulfonate or potassium is preferably selected from the group consisting of: ethylene isophthalate-sodium 5-sulfonate, ethylene isophthalate 5-sulfonic acid Potassium, propylene glycol isophthalate-sodium 5-sulfonate, propylene glycol isophthalate-potassium 5-sulfonate, butylene glycol isophthalate-sodium 5-sulfonate, or isophthalic acid Alcohol ester 5-sodium sulfonate.
- the molar content of the aliphatic diol blend having a side chain is from 4 mol% to 20 mol%, preferably from 5 mol% to 20 mol, per mol of the terephthalic acid unit. More preferably, it is 5 mol% to 15 mol%, more preferably 5 mol% to 10 mol%.
- the molar ratio of 2-methyl-1,3-propanediol to 2,2-dimethyl-1,3-propanediol monomer is 10: 90 to 90: 10.
- the copolyester is added with one or more of the metal-containing Zn, Sb, Mn, Ca or Co compounds as a catalyst, and the content thereof is a conventional amount in the industry.
- the amount of terephthalic acid monomer is 0.01% ⁇ 0.08% (% by weight);
- the copolymerization and spinning steps are preferably carried out sequentially on a large continuous polymerization-spinning apparatus.
- the large-scale continuous polymerization-spinning apparatus preferably includes: a first esterification tank, a second esterification tank, a polycondensation tank, and a spinning device. It is also possible to carry out the polymerization on a batch polymerization apparatus, and then slice-spin to form fibers.
- the novel copolymerization of the two side chain-linked aliphatic diol blends and the isophthalic acid dibasic acid 5-sodium sulfonate or potassium modified by the present invention comprises the following steps:
- the first esterification tank is esterified with ethylene glycol and terephthalic acid, the reaction temperature is 240 ° C ⁇ 270 ° C, time 2 ⁇ 4h; then, enter the second ester
- the autoclave is simultaneously injected with an aliphatic diol blend containing a side chain and an isophthalic acid dibasic ester 5-sodium sulfonate or potassium, further esterified, and the reaction temperature is 240 ° C to 270 ° C, time l ⁇ 3h; Subsequently, entering the polycondensation kettle, the reaction temperature is 270 ° C ⁇ 300 V, time 2 ⁇ 4h, that is, a new copolyester melt; wherein terephthalic acid, ethylene glycol, aliphatic with side chains The molar ratio of the diol blend and the isophthalic acid dibasic acid 5-sodium sulfonate
- Synthesis of side chain aliphatic diol blends and isophthalic acid diester-sodium 5-sulfonate-modified new copolyesters on large continuous polymerization equipment must be optimized according to the above method Composition, feeding method, strict control of esterification, polycondensation temperature and time, to solve the above key technologies, in order to ensure a good spinnability copolyester.
- the divalent or trivalent metal compound catalyst used in the polymerization is a conventional catalyst in the industry, and preferably one or more of metal Zn, Sb, Mn, Ca or Co compounds.
- the side chain aliphatic diol blend and the meta-benzene binary synthesized on a large continuous polymerization apparatus The acid diester 5-sodium sulfonate or potassium modified copolyester melt can be directly spun to form short fibers or filaments.
- the screw temperature is 270 320 ° C, and the spinning speed is 400. ⁇ 4200m/min, the drawing temperature is 70 160 V, and the draw ratio is 1 to 4 times.
- a modified novel copolyester staple fiber or POY, FDY filament is obtained, and the enthalpy is added to obtain a stretched yarn DTY.
- the copolyester obtained by polymerization can also be sliced, and then staple fibers or filaments are spun from the chips.
- copolyester of the present invention can also be carried out on a batch polymerization apparatus by a batch process. Then slice and spin.
- novel copolyesters provided by the present invention introduce a m-besylate group in their macromolecular chain while introducing a pendant methyl group. Due to the volume effect of the side chain methyl group, the crystallization performance and glass transition temperature of the copolyester are reduced, so that the copolyester staple fiber can be dyed dark for cationic dye under normal pressure boiling conditions without alkali treatment. , bright color, wide spectrum.
- the present invention employs a specific mixture of 2-methyl-1,3-propanediol monomer and 2,2-dimethyl-1,3-propanediol monomer as the fourth comonomer to obtain a monomethyl group.
- Applicants have unexpectedly discovered that the cationic dye of this copolyester fiber has a dyeability at atmospheric pressure for boiling, compared to 2-methyl-1,3-propanediol or 2,2-dimethyl-1,3-propanediol alone.
- the copolyester fiber has a better improvement at the same fourth monomer usage.
- the copolyester fiber is in the same manner as the copolyester fiber using only 2-methyl-1,3-propanediol or 2,2-dimethyl-1,3-propanediol. Under the four monomer dosage, the resilience is greatly improved.
- the unexpectedly good performance of the copolyester fibers of the present invention may result from the particular fourth monomer employed (2-methyl-1,3-propanediol and 2,2-dimethylidene). Structural changes in the macromolecular backbone caused by a mixture of pyridine-1,3-propanediol.
- the monomethyl side chain and the dimethyl side chain are simultaneously randomly introduced into the macromolecular chain of the copolyester, resulting in a polymer chain that is larger than the introduction of only the monomethyl side chain or only the dimethyl side chain. Regularity, the average length of the crystallizable PET in the molecular chain is reduced, and the PET segment in the copolyester is hindered and tightly packed into the crystal lattice.
- the crystallinity of the polymer is low, the grain size is small, and the molecular structure Loose, ensuring that the cationic dye molecules in the dyeing process are easily diffused into the interior of the fiber and combined with the dye holder, thereby achieving the use of 2-methyl-1,3-propanediol or 2,2-dimethyl-1,3-propanediol.
- the copolyester of the fourth comonomer has a higher dye uptake rate.
- a unit of -CH 2 -C(CH 3 ) 2 -CH 2 - is present in the polymer chain, and the bis-methyl side chain is symmetrically distributed in the main chain compared to the -CH 2 -CHCH 3 -CH 2 - unit
- the electron-donating effects of the two methyl groups on the quaternary carbon atom cancel each other out, showing a freely rotatable helical conformation, and the flexibility of the molecular chain increases.
- the presence of a monomethyl side chain exacerbates the irregularity of the macromolecular chain and contributes to further enhancement of flexibility.
- the macromolecular chains in the amorphous region are arranged in the axial direction of the fiber during the tensile deformation.
- the difficulty is increased, the stress-induced crystallization during stretching is effectively suppressed, and irreversible structural changes are not formed, which contributes to the improvement of the tensile resilience of the copolyester fiber at high elongation.
- the copolyester fiber of the present invention can be dyed into a dark color under normal pressure boiling conditions with a cationic dye at a pressure of 95 to 100 ° C, and the dyeing rate thereof is 95% or more.
- the copolyester fiber of the present invention has a transient tensile resilience of more than 75% at 25 ° C, a pretension of 0.5 cN/dtex, a tensile rate of 500 mm/min and a constant elongation of 15%.
- the fiber has high resilience, good bulkiness, and can be used as a wool-like fiber, and the resulting fabric is stiff and not easy to wrinkle.
- the copolyester fiber has a small crystal grain, a low crystallinity, a very soft fiber, and can be purely spun or blended or woven with natural fibers or synthetic fibers to impart a thin, soft, smooth and smooth property to a thin fabric. Gives thick fabrics a super soft, ultra-loose style with excellent pilling resistance.
- the dyeability and resiliency of the cationic atmospheric pressure boiling of the copolyester fibers of the present invention and using only 2-methyl-1,3-propanediol or 2,2-dimethyl-1,3-propanediol as the first Compared to the copolyester fibers of the four comonomers, there is a better improvement at the same fourth monomer usage. It can also be said that the present invention employs a mixture of 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol as a fourth comonomer having a synergistic effect.
- the copolyester fiber modified by the side chain-containing aliphatic diol blend and the isophthalic acid dibasic ester 5-sodium sulfonate sodium or potassium according to the present invention has no special requirements on the equipment during the manufacturing process. It can be produced on imported or domestically produced ordinary equipment, and the cost is low, and it is easy to realize industrial production.
- PTA Terephthalic acid
- Ethylene glycol EG
- the fourth comonomer was named 2,2-dimethyl-1,3-propanediol, and the copolyester obtained by the same method as the present invention was named Pest 2, abbreviated as PARSTER2.
- the first esterification tank was charged with 1 ton of PTA, 600 kg of EG, and 0.2 kg of catalyst antimony trioxide and 0.2 kg of triphenyl phosphate were added for esterification reaction at a reaction temperature of 260 V. After 3 h, the material was transferred to a second esterification kettle while injecting a mixture of MPO and NPG equivalent to 10 mol% of the PTA (the molar ratio of MPO to NPG in the blend was 90:10) and 1.5 equivalent to PTA.
- the modified copolyester slice SULET1 is obtained by granules and drying.
- the SULET1 slice has an intrinsic viscosity of 0.650 and a melting point of 238 °C.
- the first esterification tank was charged with 1 ton of PTA, 410 kg of EG, and 0.32 kg of catalyst antimony trioxide and 0.6 kg of triphenyl phosphate were added for esterification reaction at a reaction temperature of 260 V. After 3 h, the material was transferred to a second esterification kettle while injecting a mixture of MPO and NPG equivalent to 20 mol% of PTA (the molar ratio of MPO to NPG in the blend was 50:50) and 2 mol equivalent to PTA.
- the modified copolyester slice SULET2 is dried.
- the SULET2 slice has an intrinsic viscosity of 0.620 and a melting point of 23 C.
- the first esterification tank was charged with 1 ton of PTA, 450 kg of EG, and 0.1 kg of catalyst antimony trioxide and 0.2 kg of triphenyl phosphate were added for esterification reaction at a reaction temperature of 260 V. After 3 h, the material was transferred to a second esterification kettle while injecting a 15 mol% molar amount of a mixture of MPO and NPG equivalent to PTA (the molar ratio of MPO to NPG in the blend was 10:90) and equivalent to PTA.
- the modified copolyester slice SULET3 is obtained by pelletizing and drying.
- the SULET3 slice has an intrinsic viscosity of 0.652 and a melting point of 236 °C.
- the first esterification kettle was charged with 1 ton of PTA, 800 kg of EG, and 0.2 kg of catalyst antimony trioxide and 0.4 kg of triphenyl phosphate were added for esterification reaction at a reaction temperature of 260 V. After 3 h, the material was transferred to a second esterification kettle while injecting a mixture of MPO and NPG equivalent to 10 mol% of the PTA (the molar ratio of MPO to NPG in the blend was 75:25) and 2.5 equivalent to PTA.
- the secondary drawing temperature was 80 ° C
- the relaxation temperature of each zone was 80 ° C / 80 ° C / 75 ° C / 75 ° C
- the fineness was 3.24 dt
- the breaking strength was 3.18 cN / dt
- the elongation was 30.77. , 180 ° C dry heat shrinkage 24%.
- the dyed fiber is 95-100 ° C, the dyeing rate of cationic pink X-FG dye is 97.5%; the pre-tension of 0.5 cN / dtex at 25 ° C, the tensile rate of 500 mm / min and 15% Under the condition of elongation, its instantaneous tensile rebound rate is 78%.
- the dyeing rate of PARSTER1 fiber prepared under the same conditions was 91.7%, and the instantaneous tensile rebound rate was
- PARSTER2 fiber has a dyeing rate of 90.5% and a transient tensile rebound rate of 69%.
- the first esterification tank was charged with 1 ton of PTA, 410 kg of EG, and 0.8 kg of catalyst antimony trioxide and 0.3 kg of triphenyl phosphate were added for esterification reaction at a reaction temperature of 265 V. After 3 h, the material was transferred to a second esterification kettle while injecting a mixture of MPO and NPG equivalent to 4 mol% of PTA (the molar ratio of MPO to NPG in the mixture was 25:75) and 6 mol% equivalent to PTA.
- Directly spun hollow short fibers 2.78detxX 64mm, winding speed 1100m/min, pre-stretched 1.007, first draw ratio 2.95, second draw ratio 1.14, draw speed 128m/min, stretch bath 65°C,
- the second drawing temperature was 80 ° C
- the relaxation temperature of each zone was 80 ° C / 80 ° C / 75 ° C / 75 ° C
- the fineness was 2.77 dt
- the breaking strength was 3.3 cN / dt
- the elongation was 32.67. , 180 ° C dry heat shrinkage 20%, hollowness 17.66.
- the dyed fiber was 95-100 ° C, and the dyeing rate of cationic brilliant purple X-5BLH dye was 99.2%;
- the dyeing rate of PARSTER1 fiber prepared under the same conditions was 92.3%, and the instantaneous tensile rebound rate was 71%; the SARSTER2 fiber dyeing rate was 91.5%, and the instantaneous tensile rebound rate was 72%.
- the dyed fiber is 95-100 ° C, the dyeing rate of cationic yellow 7GL dye is 99.8%; the pre-tension of 0.5cN/dtex at 25 ° C, the tensile rate of 500mm / min and the elongation of 15% Under the condition, its instantaneous tensile rebound rate is 77%.
- the spunbonded fiber had an instantaneous tensile rebound rate of 83% at 25 ° C, a pretension of 0.5 cN/dtex, a tensile rate of 500 mm/min and a tensile elongation of 15%.
- the dyed fiber is 95-100 ° C, the cationic yellow X-8GL dye has a dyeing rate of 95.8%; at 25 ° C, 0.5 cN/dtex pre-tension, 500 mm/min tensile rate and 15% Under the condition of elongation, its instantaneous tensile rebound rate is 80%.
- the dyeing rate of PARSTER1/PA6 fiber prepared under the same conditions was 91.3%, the instantaneous tensile rebound rate was 58%; the SARSTER2/PA6 fiber dyeing rate was 90.1%, and the instantaneous tensile rebound rate was 62%.
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Description
改性共聚酯及其制备方法和纤维 技术领域
本发明涉及改性的共聚酯,特别涉及一种带侧链的脂肪族二元醇共混物和间苯 二元酸二元酯一 5—磺酸钠或钾共同改性的新型共聚酯。 背景技术
改进聚酯纤维染色方法很多, 应用较为广泛的是加入改性单体进行共聚, 大致 可分为以下三种: (1 ) 加入阳离子染料可染单体, 如间苯磺酸钠 (或钾) 类; (2) 加入分散性染料可染单体, 如具有间位结构的间苯二甲酸、 具有柔性结构的聚乙二 醇和癸二酸等; (3 ) 加入酸性染料可染单体, 如含胺基化合物。
加入间苯磺酸钠 (或钾)类改性单体进行改性, 已有许多报道和研究。 这类共 聚酯 (简称 CDP) 的染色性能有改善, 但是仍有缺陷。 由于 CDP需要高温高压下 阳离子染料可染, 和棉毛丝麻等天然纤维进行混纺染色时, 会影响天然纤维性能。 另外, 也出现了常压阳离子染料易染的共聚酯 ECDP和 HCDP。 但是 ECDP的纺丝 不稳定, 纤维的耐热性差。 常压阳离子染料易染的共聚酯 HCDP和纤维, 其聚合反 应难以控制, 要增加聚合物的分子量非常困难, 使纤维加工难于进行, 而且力学性 能下降, 生产成本比较高, 影响进一步扩大生产。 发明内容
由于上述现有改性共聚酯的缺陷, 本行业仍需求新型的改性共聚酯及其纤维, 它具有更好的染色性能和其他性能, 而且易于加工。
为此, 本发明以二种带侧链的脂肪族二元醇的共混物为第四共聚单体, 以间苯 二元酸二元酯一 5—磺酸钠或钾为第三共聚单体, 得到了一种新型的改性共聚酯, 该共聚酯的纤维具有非常好的阳离子可染性, 上染率在 95%以上, 远远高于现有技 术中的共聚酯纤维。 同时, 申请人还意外地发现: 该共聚酯的纤维具有意外好的回 弹性。 而且该共聚酯还能够以连续聚合及直接纺丝或切片纺丝的方法制备。 其制备 过程对设备无特殊要求, 成本低廉, 易实现工业化生产。
本发明的第一方面提供一种改性的共聚酯, 它由包括以下的单体共聚而成: ( 1 ) 对苯二甲酸;
(2) 乙二醇;
(3 ) 间苯二元酸二元酯一 5—磺酸钠或钾;
(4) 2-甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二醇的混合物, 该混合物中 2-甲 基 -1,3-丙二醇与 2,2-二甲基 -1,3-丙二醇的摩尔比为 10: 90〜90: 10。
所述间苯二元酸二元酯一 5—磺酸钠或钾优选选自: 间苯二甲酸乙二醇酯一 5— 磺酸钠, 间苯二甲酸乙二醇酯一 5—磺酸钾, 间苯二甲酸丙二醇酯一 5—磺酸钠, 间 苯二甲酸丙二醇酯一 5—磺酸钾, 间苯二甲酸丁二醇酯一 5—磺酸钠, 或间苯二甲酸 戊二醇酯一 5—磺酸钠。
在所述共聚酯的大分子链中, 间苯二元酸二元酯 -5-磺酸钠或钾单体单元的摩尔 含量优选占对苯二甲酸单体单元摩尔量的 1.5mol%~7mol%。
在所述共聚酯的大分子链中, 2-甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二醇的单 体单元的摩尔含量之和优选占对苯二甲酸单体单元摩尔量的 4mol%~20mol%。
在所述共聚酯的制备中, 优选共聚时加入的二价或三价金属化合物催化剂为: 金属 Zn、 Sb、 Mn、 Ca或 Co化合物中的一种或几种, 其含量为对苯二甲酸单体用 量的 0.01重量%〜0.08重量%。另外,优选加入磷酸三甲酯或磷酸三苯酯作为热稳定 剂, 其含量为对苯二甲酸单体用量的 0.02重量%〜0.06重量%。
本发明的第二方面涉及一种制备本发明所述共聚酯的方法, 它包括: 在连续聚合设备上合成共聚酯: 向第一酯化釜加入乙二醇和对苯二甲酸进行酯 化, 反应温度 240°C〜270°C, 时间 2-4小时; 然后, 进入第二酯化釜, 同时注入 2- 甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二醇的共混物、和间苯二元酸二元酯一 5—磺酸 钠或钾, 进一步酯化, 反应温度 240°C〜270°C, 时间 1-3小时; 随后, 进入缩聚釜, 反应温度 270°C-300°C, 时间 2-4小时, 反应结束后出料、 切粒、 干燥即得所述共聚 酯; 其中, 对苯二甲酸、 乙二醇、 2-甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二醇共混 物、 和间苯二元酸二元酯一 5—磺酸钠或钾的投料摩尔比为 1 : 1.1〜2.4: 0.04-0.20: 0.015-0.07, 共聚反应时加入二价或三价金属化合物催化剂、 和热稳定剂磷酸三甲 酯或磷酸三苯酯,含量分别为对苯二甲酸单体用量的 0.01重量%〜0.08重量%和 0.02 重量%~0.06重量%。
由该方法得到的共聚酯的特性粘数优选为 0.4〜0.7, 由毛细管粘度法测得,熔点 优选为 200°C~240°C。
本发明的第三方面涉及一种上述共聚酯的纤维, 它由这样的方法制得: 将由本
发明上述方法制得的共聚酯进行切片纺丝或直接纺丝, 其中纺丝过程中的纺丝螺杆 温度 270°C~320°C,纺丝速度 400~4200m/min,牵伸温度 70°C~160°C,牵伸倍数 1~4 倍。
在本发明所述共聚酯纤维的一个优选实施方式中, 该共聚酯纤维在常压沸染 的条件下, 可以用阳离子染料在 95〜100°C常压下染成深色, 其上染率在 95%以上。
在另一个优选实施方式中, 所述共聚酯纤维在 25 °C、 0.5cN/dtex 的预张力、 500mm/min的拉伸速率、 和 15%的定伸长条件下, 其瞬时拉伸回弹率在 75%以上。
本发明的改性共聚酯的纤维在常压沸染条件下可用阳离子染料染成深色, 上染 率在 95%以上。 而且色泽艳丽, 色谱广泛。 同时, 该共聚酯纤维具有非常好的回弹 性、 和柔软手感。 具体实施方式
本发明采用二种带侧链的脂肪族二元醇混合物和间苯二元酸二元酯一 5—磺酸 钠或钾, 得到一种新型的改性共聚酯, 所述二种带侧链的脂肪族二元醇为: 2-甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二醇。
所述共聚酯大分子链中,间苯二元酸二元酯 -5-磺酸钠或钾单体单元的摩尔含量 相对于对苯二甲酸单元的摩尔含量为 1.5mol%~7mol%, 优选 1.5mol%~6mol%。 更 优选 2 mol%-5 mol%, 更优选 3 mol%-4 mol%。
所述间苯二元酸二元酯一 5—磺酸钠或钾优选选自: 间苯二甲酸乙二醇酯一 5— 磺酸钠, 间苯二甲酸乙二醇酯一 5—磺酸钾, 间苯二甲酸丙二醇酯一 5—磺酸钠, 间 苯二甲酸丙二醇酯一 5—磺酸钾, 间苯二甲酸丁二醇酯一 5—磺酸钠、 或间苯二甲酸 戊二醇酯一 5—磺酸钠。
含侧链的脂肪族二元醇共混物的摩尔含量相对于对苯二甲酸单元的摩尔含量 为 4mol%~20mol%,优选 5mol%~20mol。更优选 5 mol%-15 mol%,更优选 5 mol%-10 mol%。
在含侧链的脂肪族二元醇共混物中, 2-甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二 醇单体摩尔比为 10: 90〜90: 10。 优选 20: 80〜80: 20, 更优选 25 : 75〜75: 25, 更优选 40: 60〜60: 40。
所述共聚酯在共聚过程中, 添加含金属 Zn、 Sb、 Mn、 Ca或 Co化合物中的一 种或几种作为催化剂, 其含量为本行业内的常规用量。 优选占对苯二甲酸单体用量
的 0.01%〜0.08% (重量百分比) ; 添加磷酸三甲酯或磷酸三苯酯为热稳定剂, 其含 量也为本行业内的常规用量, 优选占对苯二甲酸单体用量的 0.02%〜0.06% (重量百 分比) 。
在本发明所述的共聚酯及其纤维的制备中, 共聚合和纺丝步骤优选在大型连续 聚合-纺丝设备上依序进行。 所述的大型连续聚合 -纺丝设备优选依次包括: 第一酯 化釜、 第二酯化釜、 缩聚釜、 和纺丝装置。 也可以在间歇式聚合设备上进行聚合, 然后切片纺丝, 形成纤维。
在一个优选的具体实施方式中,本发明的由二种带侧链的脂肪族二元醇共混物 和间苯二元酸二元酯一 5—磺酸钠或钾改性的新型共聚酯的共聚合方法, 包括如下 步骤:
在大型连续聚合设备上合成新型共聚酯:第一酯化釜加入乙二醇和对苯二甲酸 进行酯化, 反应温度 240°C〜270°C, 时间 2〜4h; 然后, 进入第二酯化釜, 同时注入 含有侧链的脂肪族二元醇共混物和间苯二元酸二元酯一 5—磺酸钠或钾, 进一步酯 化, 反应温度 240°C〜270°C, 时间 l〜3h; 随后, 进入缩聚釜, 反应温度 270°C〜300 V, 时间 2〜4h, 即得新型共聚酯熔体; 其中对苯二甲酸、 乙二醇、 带有侧链的脂肪 族二元醇共混物和间苯二元酸二元酯一 5—磺酸钠或钾的投料摩尔比为 1 : 1.1-2.4: 0.05-0.2: 0.015-0.07, 共聚反应时加入二价或三价金属化合物催化剂和热稳定剂磷 酸三甲酯或磷酸三苯酯, 其用量分别为对苯二甲酸单体重量的 0.01%〜0.08% (重量 百分比) 和 0.02%~0.06% (重量百分比) 。
在大型连续聚合设备上合成带侧链的脂肪族二元醇共混物和间苯二元酸二元 酯一 5—磺酸钠或钾改性的新型共聚酯, 必须按照上述方法, 优选组成、 加料方式、 严格控制酯化、 缩聚温度和时间, 解决以上关键技术, 才能保证获得可纺性良好的 共聚酯。
在大型连续聚合设备上合成带侧链的脂肪族二元醇共混物和间苯二元酸二元 酯一 5—磺酸钠或钾改性的新型共聚酯, 其优点是可以工业化大批量连续生产、 熔 体可以直接纺成短纤维或长丝。 而且, 成本低, 共聚酯分子量较高、 结构均匀、 产 品质量好、 可纺性好。
所述聚合时采用的二价或三价金属化合物催化剂为本行业内的常规催化剂,优 选金属 Zn、 Sb、 Mn、 Ca或 Co化合物中的一种或几种。
所述在大型连续聚合设备上合成的由带侧链脂肪族二元醇共混物和间苯二元
酸二元酯一 5—磺酸钠或钾改性的共聚酯熔体可以直接纺丝, 制成短纤维或长丝, 在纺丝过程中, 螺杆温度 270 320 °C, 纺丝速度 400~4200m/min, 牵伸温度 70 160 V, 牵伸倍数 1〜4倍。 由此, 得到改性的新型共聚酯短纤维或 POY、 FDY长丝, ΡΟΥ经过加弹得到加弹丝 DTY。 聚合得到的共聚酯也可以制成切片, 然后由切片 纺制短纤维或长丝。
另外, 本发明的共聚酯也可以采用间歇法, 在间歇聚合设备上进行。 然后切片 纺丝。
本发明所提供的新型共聚酯, 在其大分子链中引入间苯磺酸盐基团的同时又引 入了侧甲基基团。 由于侧链甲基的体积效应, 降低了该种共聚酯结晶性能和玻璃化 温度, 使得共聚酯短纤维能够在常压沸染条件下对于阳离子染料可染深色, 且不需 碱处理, 色泽艳丽, 色谱广泛。
尤其, 本发明采用特定的 2-甲基 -1,3-丙二醇单体和 2,2-二甲基 -1,3-丙二醇单体 的混合物作为第四共聚单体, 得到同时含有单甲基侧链和双甲基侧链的新型共聚 酯, 具有意外好的性能。 申请人意外地发现: 该共聚酯纤维的阳离子染料常压沸染 的可染性, 比仅采用 2-甲基 -1,3-丙二醇或 2,2-二甲基 -1,3-丙二醇的共聚酯纤维, 在 同样的第四单体用量下, 有更好的改善。 而且, 更意外地, 该共聚酯纤维与仅采用 2-甲基 -1,3-丙二醇或 2,2-二甲基 -1,3-丙二醇的共聚酯纤维相比, 在同样的第四单体 用量下, 回弹性有大幅度提高。
不希望受到理论的束缚, 据认为: 本发明共聚酯纤维的意外好的性能可能来自 于所采用的特定第四单体 (2-甲基 -1,3-丙二醇和 2,2-二甲基 -1,3-丙二醇的混合物) 引起的大分子主链的结构变化。
单甲基侧链和双甲基侧链同时无规地引入共聚酯的大分子链中, 导致了高分子 链比仅引入单甲基侧链或仅引入双甲基侧链更大的不规整性, 分子链中可结晶的 PET平均链段长度减小, 且阻碍了共聚酯中 PET链段规整而紧密地砌入晶格, 聚合 物中结晶度低、 晶粒尺寸小, 分子结构松散, 保证了染色过程中阳离子染料分子易 于扩散到纤维内部与染座结合, 从而达到比仅采用 2-甲基 -1,3-丙二醇或 2,2-二甲基 -1,3-丙二醇作为第四共聚单体的共聚酯更高的上染率。
其次, 高分子链中存在 -CH2-C(CH3)2-CH2-的单元, 与 -CH2-CHCH3-CH2-单元相 比, 双甲基侧链对称分布于主链中季碳原子的两侧, 季碳原子上两个甲基的推电子 效应互相抵消, 表现为可自由旋转的螺旋状构象, 分子链的柔性增加。 同时, 由于
单甲基侧链的存在, 加剧了大分子链的不规整性, 有助于进一步增强柔性。 而且, 由于单甲基侧链和双甲基侧链同时存在所引起的大分子链的更大不规整性, 使无定 形区内的大分子链在拉伸形变时沿纤维轴向有序排列的难度增加, 有效抑制了拉伸 过程中的应力诱导结晶, 未形成不可逆的结构变化, 有助于提高共聚酯纤维在高伸 长率下的拉伸回弹性能。
本发明的共聚酯纤维在常压沸染的条件下,可以用阳离子染料在 95〜100°C常压 下染成深色, 其上染率在 95%以上。
本发明的共聚酯纤维在 25°C, 0.5cN/dtex的预张力, 500mm/min的拉伸速率和 15%的定伸长条件下, 其瞬时拉伸回弹率高达 75%以上。 该纤维的回弹性高、 蓬松 性好、 可用作仿毛纤维, 制成的织物挺括、 不容易起皱。 而且, 该共聚酯纤维由于 晶粒小, 结晶度低, 纤维非常柔软, 既可纯纺, 也可与天然纤维或合成纤维混纺或 混织, 赋予薄型面料轻薄、 柔软、 爽滑的特性, 赋予厚型面料超柔软、 超蓬松的风 格, 且具有优异的抗起毛起球性能。
本发明的共聚酯纤维的阳离子常压沸染的可染性和回弹性, 与仅采用 2-甲基 -1,3-丙二醇或 2,2-二甲基 -1,3-丙二醇作为第四共聚单体的共聚酯纤维相比, 在同样 的第四单体用量下,有更好的改善。也可以说,本发明采用 2-甲基 -1,3-丙二醇和 2,2- 二甲基 -1,3-丙二醇的混合物作为第四共聚单体, 具有协效作用。
本发明的由带有侧链的脂肪族二元醇共混物和间苯二元酸二元酯一 5—磺酸钠 或钾改性的共聚酯纤维, 其制造过程对设备无特殊要求, 能在进口或国产的普通设 备上进行生产, 且***格低廉, 易实现工业化生产。
下面结合具体实施例, 进一步阐述本发明。 应理解, 这些实施例仅用于说明本 发明而不用于限制本发明的范围。 此外应理解, 在阅读了本发明讲授的内容之后, 本领域技术人员可以对本发明作各种改动或修改, 这些等价形式同样落于本申请所 附权利要求书所限定的范围。
在本发明实施例中, 所采用的物料及其名称的缩写表示如下:
对苯二甲酸: PTA;
乙二醇: EG;
2-甲基 -1,3-丙二醇: MPO;
2,2-二甲基 -1,3-丙二醇: NPG;
间苯二元酸乙二酯 -5-磺酸钠: SIPE,
间苯二甲酸二甲酯 -5-磺酸钠: SIPM, 该共聚酯也称为舒乐特, 简称为 SULET; 第四共聚单体仅用 2-甲基 -1,3-丙二醇、采用与本发明相同的方法制得的共聚酯 命名为派斯特 1, 简称为 PARSTER1 ;
第四共聚单体仅用 2,2-二甲基 -1,3-丙二醇、 采用与本发明相同的方法制得的共 聚酯命名为派斯特 2, 简称为 PARSTER2。 实施例
实施例 1
采用连续聚合设备, 第一酯化釜加入 1 吨 PTA、 600千克 EG, 同时加入 0.2 千克的催化剂三氧化二锑和 0.2千克的磷酸三苯酯,进行酯化反应,反应温度为 260 V, 反应 3h后, 物料转入第二酯化釜, 同时注入相当于 PTA的 10mol%摩尔量的 MPO与 NPG的混合物(共混物中 MPO与 NPG的摩尔比为 90: 10)和相当于 PTA 的 1.5mol%摩尔量的 SIPE, 进一步酯化, 反应温度 250°C, 反应 2h后, 物料转入缩 聚釜, 反应温度 270°C, 逐渐减压至真空度小于 130Pa, 缩聚 3h后, 出料、 切粒、 干燥即得改性的共聚酯切片 SULET1。 SULET1切片特性粘数为 0.650,熔点 238°C。 实施例 2
采用连续聚合设备, 第一酯化釜加入 1吨 PTA、 410千克 EG, 同时加入 0.32 千克的催化剂三氧化二锑和 0.6千克的磷酸三苯酯,进行酯化反应,反应温度为 260 V, 反应 3h后, 物料转入第二酯化釜, 同时注入相当于 PTA的 20mol%摩尔量的 MPO与 NPG的混合物(共混物中 MPO与 NPG的摩尔比为 50: 50)和相当于 PTA 的 2mol%摩尔量的 SIPM, 进一步酯化, 反应温度 252°C, 反应 2h后, 物料转入缩 聚釜, 反应温度 286°C, 逐渐减压至真空度小于 130Pa, 缩聚 3h后, 出料、 切粒、 干燥即得改性的共聚酯切片 SULET2。 SULET2切片特性粘数为 0.620,熔点 23 C。 实施例 3
采用连续聚合设备, 第一酯化釜加入 1 吨 PTA、 450千克 EG, 同时加入 0.1 千克的催化剂三氧化二锑和 0.2千克的磷酸三苯酯,进行酯化反应,反应温度为 260 V, 反应 3h后, 物料转入第二酯化釜, 同时注入相当于 PTA的 15mol%摩尔量的 MPO与 NPG的混合物(共混物中 MPO与 NPG的摩尔比为 10: 90)和相当于 PTA
的 3mol%摩尔量的 SIPE, 进一步酯化, 反应温度 250°C, 反应 2h后, 物料转入缩 聚釜, 反应温度 270°C, 逐渐减压至真空度小于 130Pa, 缩聚 3h后, 出料、 切粒、 干燥即得改性的共聚酯切片 SULET3。 SULET3切片特性粘数为 0.652,熔点 236°C。 实施例 4
采用连续聚合设备, 第一酯化釜加入 1 吨 PTA、 800千克 EG, 同时加入 0.2 千克的催化剂三氧化二锑和 0.4千克的磷酸三苯酯,进行酯化反应,反应温度为 260 V, 反应 3h后, 物料转入第二酯化釜, 同时注入相当于 PTA的 10mol%摩尔量的 MPO与 NPG的混合物(共混物中 MPO与 NPG的摩尔比为 75 : 25 )和相当于 PTA 的 2.5mol%摩尔量的 SIPM, 进一步酯化, 反应温度 253 °C, 停留时间 1.5h后, 反应 物进入预聚缩釜 I, 反应温度 275 °C, 反应时间为 0.5h, 进入预缩 II反应温度为 270 ,反应时间为 lh,终缩反应温度为 268°C,反应时间为 2.5h,共聚酯熔体粘度 0.580, 熔点 228°C。 直接纺制短纤维 3.33detxX 38mm, 卷绕速度 880m/min, 预拉伸 1.02, 第一拉伸比 2.85, 第二拉伸比 1.12, 拉伸速度 180m/min, 拉伸浴 65°C, 第二次牵伸 温度 80°C, 各区松弛温度 80°C/80°C/75°C/75°C, 纤度 3.24dt, 断裂强度 3.18cN/dt, 伸长 30.77。, 180°C干热收缩 24%。
纺制的纤维在 95— 100°C, 阳离子桃红 X-FG染料的上染率为 97.5%; 在 25°C, 0.5cN/dtex的预张力, 500mm/min的拉伸速率和 15%的定伸长条件下, 其瞬时拉伸 回弹率在 78%。
相同条件下制备的 PARSTER1 纤维的上染率为 91.7%, 瞬时拉伸回弹率在
63%; PARSTER2纤维的上染率为 90.5%, 瞬时拉伸回弹率在 69%。 实施例 5
采用连续聚合设备, 第一酯化釜加入 1 吨 PTA、 410千克 EG, 同时加入 0.8 千克的催化剂三氧化二锑和 0.3千克的磷酸三苯酯,进行酯化反应,反应温度为 265 V, 反应 3h后, 物料转入第二酯化釜, 同时注入相当于 PTA的 4mol%摩尔量的带 MPO与 NPG的混合物(混合物中 MPO与 NPG的摩尔比为 25 : 75 )和相当于 PTA 的 6mol%摩尔量的 SIPE, 进一步酯化, 反应温度 250°C, 停留时间 2h后, 反应物 进入预聚缩釜 I, 反应温度 275°C, 反应时间为 1.5h, 预缩 II反应温度为 276°C, 反应时间为 2.5h,终缩反应温度为 282V,反应时间为 3.5h,共聚酯熔体粘度 0.625,
熔点 230°C。 直接纺制中空短纤维 2.78detxX 64mm, 卷绕速度 1100m/min, 预拉伸 1.007, 第一拉伸比 2.95, 第二拉伸比 1.14, 拉伸速度 128m/min, 拉伸浴 65°C, 第 二次牵伸温度 80°C, 各区松弛温度 80°C/80°C/75°C/75°C, 纤度 2.77dt, 断裂强度 3.3cN/dt, 伸长 32.67。, 180°C干热收缩 20%, 中空度 17.66。
纺制的纤维在 95— 100°C, 阳离子艳紫 X-5BLH染料的上染率为 99.2%; 在 25
。C, 0.5cN/dtex的预张力, 500mm/min的拉伸速率和 15%的定伸长条件下, 其瞬时 拉伸回弹率在 80%。
相同条件下制备的 PARSTER1 纤维的上染率为 92.3%, 瞬时拉伸回弹率在 71%; PARSTER2纤维的上染率为 91.5%, 瞬时拉伸回弹率在 72%。 实施例 6
以 SULET2干燥切片为原料, 熔融高速纺 FDY, 纺丝速度: 4200m/min, 纺丝 规格 110dtex/72F, 断裂强度 2.65cN/dtex, 断裂伸长 32% , 沸水收缩 16%。
纺制的纤维在 95— 100°C, 阳离子嫩黄 7GL染料的上染率为 99.8%; 在 25°C, 0.5cN/dtex的预张力, 500mm/min的拉伸速率和 15%的定伸长条件下, 其瞬时拉伸 回弹率在 77%。
相同条件下制备的 PARSTER1 纤维的上染率为 95.5%, 瞬时拉伸回弹率在 63%; PARSTER2纤维的上染率为 90.1%, 瞬时拉伸回弹率在 69%。 实施例 7
以 SULET3干燥切片为原料, 与高温高压阳离子共聚酯 CDP (有第三种共聚 单体: 间苯二甲酸乙二醇酯一 5—磺酸钠, 但无第四种共聚单体: 2-甲基 -1,3-丙二醇 和 2,2-甲基 -1,3-丙二醇的混合物) 高速纺并列型 POY, 纺丝速度: 3000m/min, 纺 丝规格 130dtex/36f, 断裂强度 1.68cN/dtex, 断裂伸长 117%, DTY上热箱温度 152 。C, 下热箱温度 140 °C 速度 580m/min, 牵伸比: 1.67, 85 dtex/72f„ 断裂强度 2.65cN/dtex, 断裂伸长 31%, 沸水收缩 8%。
纺制的纤维在 25°C, 0.5cN/dtex的预张力, 500mm/min的拉伸速率和 15%的定 伸长条件下, 其瞬时拉伸回弹率在 83%。
相同条件下制备的 PARSTER1/CDP 纤维的瞬时拉伸回弹率在 60% ; PARSTER2/CDP纤维的瞬时拉伸回弹率在 65%。
实施例 8
以 SULET2干燥切片为原料, 与 PA6高速纺菊瓣型复合 POY ( SULET切片与 PA6质量比为 75:25 ) , 纺丝速度: 3000m/min, 326dtex/36f, 断裂强度 1.86cN/dtex, 断裂伸长 133 %, DTY上热箱温度 152°C, 下热箱温度 140°C , 速度 580m/min, 牵 伸比: 1.85, 100dtex/36f, 菊瓣型纤维加弹过程中剥离为超细纤维, 纤度为 0.26dtex, 断裂强度 2.75cN/dtex, 断裂伸长 31%, 沸水收缩 18%。
纺制的纤维在 95— 100°C,阳离子黄 X— 8GL染料的上染率为 95.8%;在 25 °C, 0.5cN/dtex的预张力, 500mm/min的拉伸速率和 15%的定伸长条件下, 其瞬时拉伸 回弹率在 80%。
相同条件下制备的 PARSTER1/ PA6纤维的上染率为 91.3%, 瞬时拉伸回弹率 在 58%; PARSTER2/ PA6纤维的上染率为 90.1%, 瞬时拉伸回弹率在 62%。
Claims
1. 一种改性的共聚酯, 由包括以下的单体共聚而成:
( 1 ) 对苯二甲酸;
(2 ) 乙二醇;
( 3 ) 间苯二元酸二元酯一 5—磺酸钠或钾;
(4 ) 2-甲基 -1,3-丙二醇和 2,2-甲基 -1,3-丙二醇的混合物, 该混合物中 2-甲基 -1,3-丙二醇与 2,2-甲基 -1,3-丙二醇的摩尔比为 10: 90〜90: 10。
2. 根据权利要求 1所述的共聚酯, 其特征在于:
所述间苯二元酸二元酯一 5—磺酸钠或钾选自: 间苯二甲酸乙二醇酯一 5—磺酸 钠, 间苯二甲酸乙二醇酯一 5—磺酸钾, 间苯二甲酸丙二醇酯一 5—磺酸钠, 间苯二 甲酸丙二醇酯一 5—磺酸钾, 间苯二甲酸丁二醇酯一 5—磺酸钠, 或间苯二甲酸戊二 醇酯一 5—磺酸钠。
3. 根据权利要求 1或 2所述的共聚酯, 其特征在于:
在共聚酯大分子链中, 间苯二元酸二元酯 -5-磺酸钠或钾单体单元的摩尔含量占 对苯二甲酸单体单元摩尔量的 1.5mol%~7mol%, 2-甲基 -1,3-丙二醇和 2,2-甲基 -1,3- 丙二醇的单体单元的摩尔含量之和占对苯二甲酸单体单元摩尔量的
4mol%~20mol%。
4. 根据权利要求 1所述的共聚酯, 其特征在于:
共聚时加入的二价或三价金属化合物催化剂为: 金属 Zn、 Sb、 Mn、 Ca或 Co 化合物中的一种或几种, 其含量为对苯二甲酸单体用量的 0.01重量%〜0.08重量%; 加入磷酸三甲酯或磷酸三苯酯作为热稳定剂, 其含量为对苯二甲酸单体用量的 0.02 重量%~0.06重量%。
5. 根据权利要求 1-3中任一项所述的共聚酯, 其特征在于:
在所述的 2-甲基 -1,3-丙二醇和 2,2-甲基 -1,3-丙二醇的混合物中, 2-甲基 -1,3-丙 二醇与 2,2-甲基 -1,3-丙二醇的摩尔比为 20 : 80〜80: 20, 更优选 25 : 75〜75: 25。
6. 根据权利要求 1所述的共聚酯,其特征在于:该共聚酯的特性粘数为 0.4〜0.7, 熔点为 200°C~240°C。
7. 一种制备权利要求 1所述共聚酯的方法, 包括:
在连续聚合设备上合成共聚酯: 向第一酯化釜加入乙二醇和对苯二甲酸进行酯 化, 反应温度 240°C〜270°C, 时间 2-4小时, 进入第二酯化釜, 同时注入 2-甲基 -1,3- 丙二醇和 2,2-甲基 -1,3-丙二醇的共混物、和间苯二元酸二元酯一 5—磺酸钠或钾, 进 一步酯化,反应温度 240°C〜270°C,时间 1-3小时,进入缩聚釜,反应温度 270°C-300 V, 时间 2-4小时, 反应结束后出料、 切粒、 干燥即得所述共聚酯; 其中, 对苯二 甲酸、 乙二醇、 2-甲基 -1,3-丙二醇和 2,2-甲基 -1,3-丙二醇共混物、 和间苯二元酸二 元酯一 5—磺酸钠或钾的投料摩尔比为 1: 1.1-2.4: 0.04-0.20: 0.015-0.07, 共聚反 应时加入二价或三价金属化合物催化剂、 和热稳定剂磷酸三甲酯或磷酸三苯酯, 含 量分别为对苯二甲酸单体用量的 0.01重量%~0.08重量%和 0.02重量%~0.06重量%。
8. 一种权利要求 1所述共聚酯的纤维, 它由这样的方法制得: 将由权利要求 7 所述方法制得的共聚酯进行切片纺丝或直接纺丝, 其中纺丝过程中的纺丝螺杆温度
270°C~320°C , 纺丝速度 400~4200m/min, 牵伸温度 70°C~160°C, 牵伸倍数 1~4倍。
9. 根据权利要求 8所述的共聚酯纤维, 其特征在于: 该共聚酯纤维在常压沸 染的条件下,可以用阳离子染料在 95〜100°C常压下染成深色,其上染率在 95%以上。
10. 根据权利要求 8所述的共聚酯纤维, 其特征在于: 该共聚酯纤维在 25°C、 0.5cN/dtex的预张力、 500mm/min的拉伸速率、 和 15%的定伸长条件下, 其瞬时拉 伸回弹率在 75%以上。
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