CN111363128A - PTT polyester with intensively distributed molecular weight and preparation method thereof - Google Patents
PTT polyester with intensively distributed molecular weight and preparation method thereof Download PDFInfo
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- CN111363128A CN111363128A CN202010342770.XA CN202010342770A CN111363128A CN 111363128 A CN111363128 A CN 111363128A CN 202010342770 A CN202010342770 A CN 202010342770A CN 111363128 A CN111363128 A CN 111363128A
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- reaction
- ptt polyester
- molecular weight
- ptt
- polyester
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- 229920000728 polyester Polymers 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 79
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005886 esterification reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- GSHLZLUAXZTEDF-UHFFFAOYSA-N [Ti].[Co].[Sn] Chemical compound [Ti].[Co].[Sn] GSHLZLUAXZTEDF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000265 homogenisation Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims description 82
- 238000009826 distribution Methods 0.000 claims description 43
- 238000009987 spinning Methods 0.000 claims description 35
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000013329 compounding Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000004804 winding Methods 0.000 claims description 12
- 238000002074 melt spinning Methods 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002932 luster Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- 229940035437 1,3-propanediol Drugs 0.000 claims description 5
- 241001589086 Bellapiscis medius Species 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 152
- 229920000642 polymer Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010036 direct spinning Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- -1 Polytrimethylene terephthalate Polymers 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G63/785—Preparation processes characterised by the apparatus used
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a PTT polyester with a concentratedly distributed molecular weight and a preparation method thereof. The preparation method comprises the following steps: the method comprises the following steps: mixing terephthalic acid and 1, 3-propylene glycol according to the molar ratio of 1:1.1-1.5, pulping, then adding a titanium-tin-cobalt composite catalyst for esterification reaction, discharging the reaction pressure to normal pressure after the esterification water yield reaches 95% of the theoretical esterification water yield, and continuing the reaction for 15-45min to obtain a PTT polyester prepolymer; step two: mixing the PTT polyester prepolymer and 1, 3-propylene glycol monomer according to the molar ratio of 1:1.05-1.10 to perform homogenization reaction, and then sequentially performing stirring pre-polycondensation reaction and final polycondensation reaction to obtain PTT polyester with the centrally distributed molecular weight; wherein the intrinsic viscosity of the PTT polyester prepolymer is less than or equal to 0.15dl/g, and the addition amount of the titanium-tin-cobalt composite catalyst is 100-200ppm of the mass fraction of the terephthalic acid.
Description
Technical Field
The invention belongs to the field of chemical fiber processing, and relates to PTT polyester with a centralized molecular weight distribution and a preparation method thereof.
Background
Polytrimethylene terephthalate (PTT), and PET and PBT belong to a novel organic high-molecular aromatic polyester product of the same polymer series. PTT as a novel polyester product has excellent characteristics. The PTT has good processing performance, electrical performance, mechanical performance and dimensional stability. The PTT fiber keeps the excellent crease resistance and chemical resistance of the PET fiber, and the strength meets the textile requirement. The excellent dyeing property has great attraction to the dyeing and finishing processing of fiber textiles, and is powerful in improving economic benefits and environmental benefits. In addition, it has excellent flexibility, sunlight resistance, stain resistance, low static electricity, low water absorption, etc. In the application field of chemical fiber, PTT fiber integrates the softness of nylon and has better color fastness and bulkiness of acrylic fiber. The viscosity of the PTT polyester greatly affects the performance and the post-processing such as spinning, and therefore, the PTT polyester obtained by polymerization needs to be further thickened.
The existing PTT polyester increases the viscosity of the product by prolonging the polycondensation reaction time. However, in the actual operation process, as the viscosity of the reaction system increases with the progress of the reaction, the discharge of low molecular by-products generated by the reaction is more difficult, local overheating is likely to occur, so that the degradation reaction increases, the further increase of the molecular weight is limited, and the high-viscosity PTT polyester is difficult to obtain. As the molecular weight of the polyester increases, fluid transport conditions become more stringent. The melt polycondensation requires a long polycondensation time, and the degradation of the PTT polyester is increased under the high-temperature reaction condition of more than 270 ℃, various side reactions are caused, the color of the resin is increased, and the quality is poor. The prior art system mainly increases the molecular weight distribution of the prepared PTT polyester chip to 0.90-1.00dl/g through a polycondensation stage after obtaining higher viscosity (all reported in literature is above 0.20 dl/g), and the prepared PTT polyester chip has wide molecular weight distribution and causes bad influence on fiber forming process such as broken ends, broken filaments and the like.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a PTT polyester having a concentrated molecular weight distribution and a process for producing the same. The PTT polyester prepared by the preparation method has good color phase, concentrated molecular weight distribution and beneficial color, can be directly used for melt spinning, and has low spinning waste silk rate.
In order to achieve the aforementioned object, the present invention provides a method for producing a PTT polyester having a centrally distributed molecular weight, comprising the steps of:
the method comprises the following steps: mixing terephthalic acid and 1, 3-propylene glycol according to the molar ratio of 1:1.1-1.5, pulping, then adding a titanium-tin-cobalt composite catalyst for esterification reaction, discharging the reaction pressure to normal pressure after the esterification water yield reaches 95% of the theoretical esterification water yield, and continuing the reaction for 15-45min to obtain a PTT polyester prepolymer;
step two: mixing the PTT polyester prepolymer and 1, 3-propylene glycol monomer according to the molar ratio of 1:1.05-1.10 to perform homogenization reaction, and then sequentially performing stirring pre-polycondensation reaction and stirring final polycondensation reaction to obtain PTT polyester with the centrally distributed molecular weight;
wherein the intrinsic viscosity of the PTT polyester prepolymer is less than or equal to 0.15dl/g,
the addition amount of the titanium-tin-cobalt composite catalyst is 100-200ppm of the mass fraction of the terephthalic acid.
Meanwhile, the molecular weight distribution of the PTT polyester is concentrated, and the time cost and the capital cost of the production of the PTT polyester melt are greatly reduced. In addition, the melt has the characteristics of high viscosity, concentrated molecular weight distribution, excellent color and luster and the like, can be directly subjected to melt direct spinning to obtain the PTT polyester fiber, has good product performance, high added value and easy process realization, is beneficial to large-scale production, and has wide application prospects in elastic fabrics of clothes, home textiles and the like.
At present, in the preparation process of PTT polyester, a prepolymer with higher intrinsic viscosity is formed firstly, and then the viscosity is further increased through a polycondensation stage, and the following problems exist in the polycondensation process and the solid-phase tackifying process of the PTT polyester: the PTT polyester has long retention time under high temperature condition in the solid-phase tackifying and gradual polycondensation stage, so that the molecular weight is slowly increased, the PTT polyester is easy to generate side reactions such as thermal degradation and the like, the color difference and the molecular weight distribution of the PTT polyester are wide, the prepared PTT polyester has poor color and luster, and the subsequent forming processing is influenced. Generally speaking, solid phase polycondensation tackifying is a widely applied production method for tackifying PTT polyester at present due to the advantages of mild conditions and good product quality, but the production process of solid phase polycondensation is long in time, needs to consume a large amount of inert gas, and is high in consumed time and energy. According to the preparation method of the PTT polyester with the intensively distributed molecular weight, provided by the invention, the inherent viscosity of prepolymerization is not more than 0.15dl/g after the esterification reaction is finished, the homogenization reaction of a prepolymer with low viscosity is realized by supplementing 1, 3-propylene glycol, the chain segment structures of the prepolymers are all terminated by 1, 3-propylene glycol, and the low-viscosity prepolymers have consistent structures and consistent reaction activity. And then horizontal pre-polycondensation and horizontal final polycondensation are carried out by a horizontal series double kettle with a material stirring device to realize polymerization kinetic enhancement, the PTT polyester prepolymer with low intrinsic viscosity is quickly tackified to be more than 0.95dl/g in a short time to reach the PTT polyester intrinsic viscosity required by spinning, quick tackification is realized, the PTT polyester molecular weight distribution is concentrated, the hue is good, the color is excellent, the PTT polyester can be directly used for melt spinning, and the fibrilization of the PTT polyester is greatly improved.
According to the specific embodiment of the present invention, preferably, the temperature of the esterification reaction is 220-240 ℃, the reaction pressure is 50-200kPa, and the reaction time is 1.5-3.5 h.
According to the specific embodiment of the present invention, preferably, in the first step, the addition amount of the titanium-tin-cobalt composite catalyst is 100-200ppm of the mass fraction of the terephthalic acid.
According to an embodiment of the present invention, preferably, the titanium-tin-cobalt composite catalyst is formed by combining a titanium-based catalyst, a tin-based catalyst and a cobalt-based catalyst in a molar ratio of 1:0.1:0.1-1:10:10, wherein the titanium-based catalyst comprises tetrabutyl titanate or metatitanic acid; the tin-based catalyst comprises dibutyl tin oxide or indium tin oxide; the cobalt-based catalyst comprises cobalt acetate. More preferably, the titanium-tin-cobalt composite catalyst is prepared by compounding tetrabutyl titanate, dibutyltin oxide and cobalt acetate according to the molar ratio of 1:1: 1.
In the esterification and polycondensation reaction process of PTT synthesis, the catalytic system plays a role in playing a role in carrying out the reaction. The catalyst in the PTT synthesis process has a wide selection range, and titanium compounds and tin compounds, titanium tin mixed catalysts, ethylene glycol titanium and the like can be used as catalysts for reaction. In the preparation process of PTT, the heat degradation or the thermo-oxidative degradation of PTT inevitably exists in the melt polycondensation reaction process, so that the hue of the product is deteriorated, and simultaneously the heat resistance is reduced, because the quality is reduced. The titanium-tin-cobalt composite catalyst is prepared by compounding a titanium catalyst, a tin catalyst and a cobalt catalyst according to a certain molar ratio, has certain reaction activity, avoids inactivation caused by titanium dioxide produced by hydrolysis of the traditional titanium catalyst, and can remarkably improve the color phase of PTT by introducing the cobalt salt.
According to the specific embodiment of the present invention, preferably, the reaction temperature of the homogenization reaction is 200-220 ℃, the reaction time is 0.5-1.5h, and the reaction pressure is 0.1-0.3 MPa.
According to the specific embodiment of the present invention, preferably, the catalyst for the homogenization reaction is methyl benzene sulfonic acid, and the amount of the methyl benzene sulfonic acid added is 100-200ppm of the content of the PTT polyester prepolymer.
According to the specific embodiment of the present invention, preferably, the reaction temperature of the pre-polycondensation reaction is 230 ℃ to 250 ℃, the pressure is 0 to 10kPa, and the time is 60 to 80 min.
According to a specific embodiment of the present invention, the stirring speed during the pre-polycondensation reaction is preferably 5-20 rpm/min.
According to the specific embodiment of the present invention, it is preferable that the reaction temperature of the final polycondensation reaction is 240-260 ℃, the pressure is 0-1kPa, and the time is 90-180 min.
According to the specific embodiment of the present invention, the stirring speed in the final polycondensation is preferably 5 to 10 rpm/min.
According to a specific embodiment of the present invention, preferably, the first step further comprises the step of adding an ether inhibitor to the mixed system of terephthalic acid and 1, 3-propanediol before the esterification reaction.
According to the specific embodiment of the invention, the addition amount of the ether inhibitor is preferably 1000ppm of 100-1000ppm of the mass fraction of the terephthalic acid; preferably, the anti-ether agent comprises sodium acetate.
According to a specific embodiment of the present invention, preferably, the second step further comprises a step of adding an antioxidant and/or an antioxidant to the homogeneous reacted PTT polyester prepolymer, which comprises the following steps:
and adding an anti-thermal oxidant and/or an antioxidant into the PTT polyester prepolymer by using a syringe pump in the process of conveying the PTT polyester prepolymer after the homogeneous reaction to the horizontal pre-polycondensation reaction kettle.
The invention also provides a PTT polyester with the concentrated molecular weight distribution, which is prepared by the preparation method of the PTT polyester with the concentrated molecular weight distribution.
According to a specific embodiment of the present invention, it is preferred that the PTT polyester having a concentrated molecular weight distribution has an intrinsic viscosity of 0.95 to 1.15dl/g, a weight-average molecular weight of 55000-70000 and a molecular weight distribution of 1.1 to 1.2.
According to the specific embodiment of the invention, preferably, the content of 1, 3-propanediol in the PTT polyester with the concentrated molecular weight distribution is less than or equal to 1.0%, and the color degree of the PTT polyester with the concentrated molecular weight distribution is less than or equal to 10.
According to the specific embodiment of the invention, preferably, the yarn evenness rate of the PTT polyester with the intensively distributed molecular weight is less than or equal to 1.0 percent, and the processing waste yarn rate is less than or equal to 10 kg/t.
According to a specific embodiment of the present invention, it is preferred that the PTT polyester having a concentrated molecular weight distribution has dispersed therein an antioxidant and/or an antioxidant.
According to an embodiment of the present invention, preferably, the anti-thermal oxidizer comprises one or more of phosphoric acid, phosphorous acid, trimethyl phosphate, trimethyl phosphite and triphenyl phosphate.
According to a specific embodiment of the present invention, preferably, the antioxidant comprises one or a combination of several of antioxidant 1010, antioxidant 168 and antioxidant 616. The antioxidant 1010, antioxidant 168 and antioxidant 616 are all conventional in the art.
According to an embodiment of the present invention, preferably, the content of the anti-thermal oxygen agent is 0.005 to 0.05% by mass.
According to a specific embodiment of the present invention, preferably, the antioxidant is contained in an amount of 0.001 to 0.01% by mass.
The invention also provides a composite POY fiber which is prepared by melt spinning the PTT polyester with the intensively distributed molecular weight and the PET polyester according to the mass ratio of 40:60-60: 40. The composite POY fiber has the strength obviously higher than that of single horizontal liquid-phase tackified POY fiber, and has low yarn evenness and uniform fiber thickness.
The invention also provides a preparation method of the composite POY fiber, which comprises the following steps: putting PET polyester into a PET spinning box, wherein the temperature of the PET spinning box is 240-300 ℃; putting the PTT polyester with the molecular weight distributed in a concentrated way into a PTT spinning box, wherein the temperature of the PTT spinning box is 200-300 ℃; placing the PET polyester and the PTT polyester with the molecular weight intensively distributed in a public box body according to the mass ratio of 40:60-60:40 for compounding, and after cooling, sequentially stretching by a GR1 roller, shaping by a GR2 roller, and winding to form a composite POY fiber; the temperature of the public box body is 220-300 ℃, the cooling blowing temperature is 10-50 ℃, the blowing wind speed is 0.1-1.5m/s, and the relative humidity is 55-95%; the roll speed of the GR1 roll is 2500-3500m/min, the roll speed of the GR2 roll is 2500-3500m/min, and the roll speed of the winding is 2500-3500 m/min.
The invention also provides a composite elastic DTY fiber which is prepared from the composite POY fiber.
The invention also provides a preparation method of the composite POY fiber, which comprises the following steps: feeding the composite POY fiber into a first roller, preparing the DTY fiber through a first yarn guide porcelain, a hot box, a second yarn guide porcelain, a false twister, a second roller, a netlike device, a third roller, an oil tanker, a winding roller and coiling, and drawing and shaping the DTY fiber through a yarn spindle to prepare the composite elastic DTY fiber.
The invention has the beneficial effects that:
(1) the intrinsic viscosity of the PTT polyester with the intensively distributed molecular weight reaches 0.95dl/g-1.15dl/g, the molecular weight is intensively distributed between 1.1 and 1.2, the content of DPG (1, 3-propylene glycol) is less than or equal to 1.0ppm, the fiber forming property of the PTT polyester is greatly improved, and the spinning waste silk rate is reduced to be less than 8kg/t or even to reach 4kg/t from the level of more than or equal to 10kg/t at present;
(2) the preparation method of the PTT polyester with the intensively distributed molecular weight, which is provided by the invention, adopts the titanium-tin-cobalt composite catalyst, so that the reaction activity of the catalyst is ensured, the inactivation caused by titanium dioxide produced by hydrolysis of the traditional titanium catalyst is avoided, the introduction of the cobalt salt can obviously improve the hue of the PTT polyester, and the hue is less than or equal to 10;
(3) according to the preparation method of the PTT polyester with the centrally distributed molecular weight, provided by the invention, the PTT polyester prepolymer is subjected to homogenization reaction to realize consistent prepolymer structure and consistent reaction activity, and then sequentially passes through the horizontal prepolymerization reaction kettle and the horizontal polycondensation reaction kettle with stirring, so that the PTT polyester with low intrinsic viscosity is quickly tackified in a short time to meet the spinning requirement, the reaction energy consumption is greatly reduced, and the quality of the PTT polyester is improved. The mechanical strength of the fiber is more than or equal to 4.0cN/dtex, and the fiber irregularity is less than or equal to 1.0 percent;
(4) the PTT polyester with the concentrated distribution of molecular weight can be directly formed by melt spinning, has stable fiber quality, and can be compounded with conventional PET polyester and the like for spinning to prepare elastic composite fibers.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited thereto.
Example 1
The embodiment provides a production method of PTT polyester with centrally distributed molecular weight, which comprises the following steps:
(1) preparing a PTT polyester prepolymer: mixing terephthalic acid and 1, 3-propylene glycol according to a molar ratio of 1:1.1, pulping, mixing, adding a titanium-tin-cobalt composite catalyst and an anti-ether agent sodium acetate for esterification until the esterification water yield reaches 95% of the theoretical esterification water yield, discharging the pressure of a reaction kettle to normal pressure, and continuing to react for 15min to obtain a PTT polyester prepolymer with low intrinsic viscosity;
the titanium-tin-cobalt composite catalyst is prepared by compounding tetrabutyl titanate, dibutyltin oxide and cobalt acetate according to the molar ratio of 1:0.5:0.5, and the addition amount of the titanium-tin-cobalt composite catalyst is 100ppm of the mass fraction of terephthalic acid (PTA); the addition amount of sodium acetate is 100ppm of the mass fraction of terephthalic acid (PTA); the temperature of the esterification reaction is 220 ℃, the pressure of the esterification reaction is 200kPa, and the time of the esterification reaction is 3.5 h; the intrinsic viscosity of the low intrinsic viscosity PTT polyester prepolymer was 0.12 dl/g.
(2) Homogenizing a PTT polyester prepolymer: performing homogenization reaction on the PTT polyester prepolymer with low intrinsic viscosity and 1, 3-propylene glycol according to the molar ratio of 1:1.05 to realize consistent prepolymer structure and consistent reaction activity of further polycondensation, wherein the temperature of the homogenization reaction is 220 ℃, the reaction time is 0.5h, the pressure is controlled at 0.1MPa, the catalyst of the homogenization reaction of the prepolymer and the 1, 3-propylene glycol is toluenesulfonic acid, and the addition amount of the toluenesulfonic acid is 100ppm relative to the prepolymer.
(3) And (3) performing polycondensation reaction of the PTT polyester prepolymer: guiding the homogenized PTT polyester prepolymer into a horizontal series double kettle to sequentially perform horizontal prepolymerization reactor and horizontal final polycondensation for tackifying to prepare PTT polyester with centrally distributed molecular weight;
wherein, the temperature of the homogenized PTT polyester prepolymer is controlled at 230 ℃, the pressure is 10kPa, the time is 60min, and the stirring speed is 20rpm/min in the process of pre-polycondensation and tackifying in a horizontal pre-polymerization reactor; the PTT polyester tackified by the pre-polycondensation reaction enters a horizontal polycondensation reactor for tackification, the tackification temperature of the horizontal tackification is controlled at 240 ℃, the pressure is 1kPa, the time is 90min, and the stirring speed is 10 r/min; introducing heat-resistant oxygen agent phosphoric acid and an antioxidant 1010 into the homogenized PTT polyester prepolymer in a horizontal series double-kettle polycondensation reaction process, wherein the addition amount of the heat-resistant oxygen agent phosphoric acid is 0.005%, and the addition amount of the antioxidant 1010 is 0.001%;
after the PTT polyester prepolymer is subjected to polycondensation reaction, the intrinsic viscosity is 0.95dl/g, the molecular weight distribution is 1.1, and the DPG content is 1.0 ppm. The PTT polyester with the concentrated molecular weight distribution reaches the spinning level. The PTT polyester fiber obtained by spinning has the advantages of color 4, excellent color, low breakage rate and 8kg/t of spinning waste yarn rate.
The embodiment also provides a composite POY fiber, which is compounded by the PTT polyester with the centralized molecular weight distribution and the PET polyester prepared in the embodiment, and the compounding steps are as follows:
and carrying out melt spinning forming on the PTT polyester subjected to the polycondensation reaction, wherein the melt spinning forming of the PTT polyester is mainly carried out by a composite spinning process. The PTT/PET composite fiber is prepared by a composite spinning component together with conventional PET, and the method comprises the following specific steps: in the forming process, the temperature of a PET spinning box body is 280 ℃, the temperature of a PTT spinning box body is 260 ℃, the temperature of a public box body is 300 ℃, and PET and PTT are added into a spinning component for composition according to the mass ratio of 50:50 under the accurate measurement of a metering pump in the box body. The cooling air blowing temperature is 30 ℃, the air speed is 1.0m/s, and the relative humidity is 65%. The POY fiber is prepared by a GR1 roller with the roller speed of 2500m/min and a GR2 roller with the roller speed of 2550m/min and the winding speed of 2600 m/min.
The embodiment also provides a composite elastic DTY fiber, which is obtained by processing the composite POY fiber prepared in the embodiment, and the specific steps are as follows: and feeding the prepared POY composite fiber into a first roller, and preparing the POY composite fiber into a composite elastic DTY fiber through a yarn guide porcelain, a hot box, another yarn guide porcelain, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot.
Tests prove that the composite POY fiber prepared by the embodiment has good color phase, excellent color and luster, low end breakage rate, the strength of the fiber is 2.2cN/dtex, and the yarn evenness is 1.0%. The strength of the composite elastic DTY fiber prepared in the embodiment is 4.0 cN/dtex.
The PTT polyester with the molecular weight distributed in a centralized way and the production method thereof carry out the polycondensation reaction through the horizontal series double kettles, thereby solving the problems that the residence time of the step-by-step polycondensation stage under the high-temperature condition is long, the molecular weight rises slowly, the PTT polyester is easy to generate side reactions such as thermal degradation and the like, the color difference and the molecular weight distribution of the PTT polyester are poor, and the subsequent forming processing is influenced. The melt after polycondensation has the characteristics of high viscosity, concentrated molecular weight distribution, excellent color and the like, can be directly subjected to melt direct spinning to obtain PTT polyester fibers, and has good product performance.
Example 2
The embodiment provides a production method of PTT polyester with centrally distributed molecular weight, which comprises the following steps:
(1) preparing a PTT polyester prepolymer: mixing terephthalic acid and 1, 3-propylene glycol according to a molar ratio of 1:1.5, pulping, mixing, adding a titanium-tin-cobalt composite catalyst and an anti-ether agent sodium acetate for esterification until the esterification water yield reaches 95% of the theoretical esterification water yield, discharging the pressure of a reaction kettle to normal pressure, and continuing to react for 30min to obtain a PTT polyester prepolymer with low intrinsic viscosity;
the titanium-tin-cobalt composite catalyst is prepared by compounding tetrabutyl titanate, indium tin oxide and cobalt acetate according to a molar ratio of 1:0.5:0.5, and the addition amount of the titanium-tin-cobalt composite catalyst is 150ppm of the mass fraction of terephthalic acid (PTA); the addition amount of sodium acetate is 500ppm of the mass fraction of terephthalic acid (PTA); the temperature of the esterification reaction is 230 ℃, the pressure of the esterification reaction is 100kPa, and the time of the esterification reaction is 2.5 h; the intrinsic viscosity of the low intrinsic viscosity PTT polyester prepolymer was 0.14 dl/g.
(2) Homogenizing a PTT polyester prepolymer: performing homogenization reaction on the PTT polyester prepolymer with low intrinsic viscosity and 1, 3-propylene glycol according to the molar ratio of 1:1.10 to realize consistent prepolymer structure and consistent reaction activity of further polycondensation, wherein the temperature of the homogenization reaction is 200 ℃, the reaction time is 1.5h, and the pressure is controlled at 0.2 MPa. The catalyst for the homogenization reaction of the prepolymer and the 1, 3-propylene glycol is methyl benzene sulfonic acid, and the addition amount of the methyl benzene sulfonic acid is 150ppm relative to the prepolymer.
(3) And (3) performing polycondensation reaction of the PTT polyester prepolymer: introducing the homogenized PTT polyester prepolymer into the horizontal series double kettles in the embodiment 1 to sequentially perform horizontal pre-polycondensation reaction and horizontal final polycondensation reaction for tackifying to prepare PTT polyester with the centrally distributed molecular weight;
wherein, the temperature is controlled at 240 ℃, the pressure is 5kPa, the time is 70min, and the stirring speed is 15rpm/min in the process of carrying out pre-polycondensation and tackifying on the homogenized PTT polyester prepolymer in a horizontal pre-polymerization reactor; the PTT polyester tackified by the pre-polycondensation enters a horizontal polycondensation reactor for tackification, the temperature of the horizontal tackification is controlled at 250 ℃, the pressure is 0.5kPa, the time is 120min, and the stirring speed is 8 r/min; introducing heat-resistant antioxidant phosphorous acid and antioxidant 168 into the homogenized PTT polyester prepolymer in a horizontal series double-kettle polycondensation reaction process, wherein the addition amount of the heat-resistant antioxidant phosphorous acid is 0.005-0.05%, and the addition amount of the antioxidant 168 is 0.005%;
after the PTT polyester prepolymer is subjected to polycondensation reaction, the intrinsic viscosity is 0.98dl/g, the molecular weight distribution is 1.15, the DPG content is 0.8ppm, and the hue is 6. The PTT polyester with the centralized distribution of molecular weight reaches the spinning level, and the waste silk rate is 6 kg/t.
The embodiment also provides a composite POY fiber, which is compounded by the PTT polyester with the centralized molecular weight distribution and the PET polyester prepared in the embodiment, and the compounding steps are as follows:
and carrying out melt spinning forming on the PTT polyester after the polymerization kinetics is strengthened, wherein the melt spinning forming of the PTT polyester is mainly carried out by a composite spinning process. The PTT/PET composite fiber is prepared by a composite spinning component together with conventional PET, and the method comprises the following specific steps: in the forming process, the temperature of a PET spinning box body is 280 ℃, the temperature of a PTT spinning box body is 250 ℃, the temperature of a common box body is 290 ℃, and PET and PTT are added into a spinning assembly for composition compounding according to the mass ratio of 40:60 under the accurate metering of a metering pump in the box body. The cooling air blowing temperature is 25 ℃, the air speed is 1.2m/s, and the relative humidity is 65 percent. The composite POY fiber is prepared by a GR1 roller with the roller speed of 2600m/min and a GR2 roller with the roller speed of 2650m/min and the winding speed of 2700 m/min.
The embodiment also provides a composite elastic DTY fiber, which is obtained by processing the composite POY fiber prepared in the embodiment, and the specific steps are as follows: and feeding the prepared POY composite fiber into a first roller, and preparing the POY composite fiber into a composite elastic DTY fiber through a yarn guide porcelain, a hot box, another yarn guide porcelain, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot.
Tests prove that the composite POY fiber prepared by the embodiment has good color phase, excellent color and luster, low end breakage rate, the strength of the fiber is 2.4cN/dtex, and the yarn evenness is 0.8%. The strength of the composite elastic DTY fiber prepared in the embodiment is 4.2 cN/dtex.
Example 3
The embodiment provides a production method of PTT polyester with centrally distributed molecular weight, which comprises the following steps:
(1) preparing a PTT polyester prepolymer: mixing terephthalic acid and 1, 3-propylene glycol according to a molar ratio of 1:1.3, pulping, mixing, adding a titanium-tin-cobalt composite catalyst and an anti-ether agent sodium acetate for esterification until the esterification water yield reaches 95% of the theoretical esterification water yield, discharging the pressure of a reaction kettle to normal pressure, and continuing to react for 35min to obtain a PTT polyester prepolymer with low intrinsic viscosity;
the titanium-tin-cobalt composite catalyst is prepared by compounding metatitanic acid, indium tin oxide and cobalt acetate according to a molar ratio of 1:1:1, and the addition amount of the titanium-tin-cobalt composite catalyst is 150ppm of the mass fraction of terephthalic acid (PTA); the addition amount of sodium acetate is 600ppm of the mass fraction of terephthalic acid (PTA); the temperature of the esterification reaction is 230 ℃, the pressure of the esterification reaction is 100kPa, and the time of the esterification reaction is 3.0 h; the intrinsic viscosity of the low intrinsic viscosity PTT polyester prepolymer was 0.15 dl/g.
(2) Homogenizing a PTT polyester prepolymer: performing homogenization reaction on the PTT polyester prepolymer with low intrinsic viscosity and 1, 3-propylene glycol according to the molar ratio of 1:1.08, and realizing consistent prepolymer structure and consistent reaction activity of further polycondensation, wherein the temperature of the homogenization reaction is 210 ℃, the reaction time is 1.0h, the pressure is controlled at 0.25MPa, the catalyst of the homogenization reaction of the prepolymer and the 1, 3-propylene glycol is methyl benzenesulfonic acid, and the addition amount of the methyl benzenesulfonic acid is 200ppm relative to the prepolymer.
(3) And (3) performing polycondensation reaction of the PTT polyester prepolymer: introducing the homogenized PTT polyester prepolymer into the horizontal series double kettles in the embodiment 1 to sequentially perform horizontal pre-polycondensation reaction and horizontal final polycondensation reaction for tackifying to prepare PTT polyester with the centrally distributed molecular weight;
wherein, the temperature is controlled at 250 ℃, the pressure is 0kPa, the time is 90min, and the stirring speed is 10rpm/min in the process of carrying out pre-polycondensation and tackifying on the homogenized PTT polyester prepolymer in a horizontal pre-polymerization reactor; the PTT polyester subjected to horizontal pre-polycondensation tackifying enters a horizontal final polycondensation reactor for tackifying, the temperature of horizontal tackifying is controlled to be 240 ℃ and 260 ℃, the pressure is 0kPa, the time is 180min, and the stirring speed is 5 r/min; introducing a thermal-oxidation-resistant agent trimethyl phosphate and an antioxidant 616 into the homogenized PTT polyester prepolymer in a horizontal series double-kettle polycondensation reaction process, wherein the addition amount of the thermal-oxidation-resistant agent trimethyl phosphate is 0.05 percent, and the addition amount of the antioxidant 616 is 0.01 percent;
the intrinsic viscosity of the PTT polyester prepolymer after polycondensation is 1.05dl/g, and the molecular weight distribution is 1.2. DPG content is 0.6ppm, hue is 8, the PTT polyester with the centralized distribution of molecular weight reaches spinning level, and waste silk rate is 4 kg/t.
The embodiment also provides a composite POY fiber, which is compounded by the PTT polyester with the centralized molecular weight distribution and the PET polyester prepared in the embodiment, and the compounding steps are as follows:
and carrying out melt spinning forming on the PTT polyester after the polymerization kinetics is strengthened, wherein the melt spinning forming of the PTT polyester is mainly carried out by a composite spinning process. The PTT/PET composite fiber is prepared by a composite spinning component together with conventional PET, and the method comprises the following specific steps: in the forming process, the temperature of a PET spinning box body is 280 ℃, the temperature of a PTT spinning box body is 240 ℃, the temperature of a public box body is 300 ℃, and PET and PTT are added into a spinning assembly for composition compounding according to the mass ratio of 60:40 under the accurate metering of a metering pump in the box body. The cooling air blowing temperature is 25 ℃, the air speed is 0.5m/s, and the relative humidity is 55 percent. The composite POY fiber is prepared by a GR1 roller with the roller speed of 2800m/min and a GR2 roller with the roller speed of 2850m/min and the winding speed of 2900 m/min.
The embodiment also provides a composite elastic DTY fiber, which is obtained by processing the composite POY fiber prepared in the embodiment, and the specific steps are as follows: and feeding the prepared POY composite fiber into a first roller, and preparing the POY composite fiber into a composite elastic DTY fiber through a yarn guide porcelain, a hot box, another yarn guide porcelain, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot.
Tests prove that the composite POY fiber prepared by the embodiment has good color phase, excellent color and luster, low end breakage rate, the strength of the fiber is 2.6cN/dtex, and the yarn evenness is 0.6%. The strength of the composite elastic DTY fiber prepared in the embodiment is 4.4 cN/dtex.
Comparative experiment:
in this comparison experiment, the performances of the PTT polyesters prepared in examples 1 to 3 were compared with those of the conventional horizontal liquid-phase tackified PTT polyester, and the terephthalic acid and 1, 3-propanediol, antioxidant, and anti-ether agent used in the comparison experiments were the same, the charge ratio was the same, the time of the esterification reaction was the same, and the difference was that the catalyst for synthesizing the oligomer (PTT) used in the conventional horizontal liquid-phase tackification in each ratio in the comparison experiments was tetrabutyl titanate, and the catalyst was not subjected to the homogenization treatment before the conventional horizontal liquid-phase tackification, and the comparison results are shown in table 1 (see national standard GB/T14190-2008).
TABLE 1
As can be seen from Table 1, in comparative experiment I, comparative example 1 gradually tackifies the oligomer (PTT) with the intrinsic viscosity of 0.20dl/g into the final Polymer (PTT) with the intrinsic viscosity of 0.90dl/g, and the molecular weight distribution of the final polymer obtained by tackification is high, mainly concentrated on 1.40, the color difference is high, the end breakage rate of waste filaments is nearly 16kg/t, the evenness of yarn levelness is not high, and the strength of DTY fibers is not high, compared with example 1, the oligomer (PTT) with the intrinsic viscosity of 0.12dl/g is gradually tackified into the final Polymer (PTT) with the intrinsic viscosity of 0.95dl/g, the molecular weight distribution of the final polymer obtained by tackification is low, mainly concentrated on 1.10, the color phase is good, the content of DPG is small, the waste filaments rate is reduced by nearly 50%, the evenness of yarn levelness is also reduced by nearly 37.5%, the strength of DTY fibers is obviously improved by nearly 14.3%; as can be seen from comparative experiment I, example 1 can increase the viscosity of the Polymer (PTT) with lower intrinsic viscosity to a higher intrinsic viscosity Polymer (PTT), and the final polymer molecular weight distribution is lower, which can make the fiber have better strength, and the evenness of the fiber is below 1.0, greatly improving the thickness uniformity of the fiber.
Similarly, it is seen from comparative experiments II and III that examples 2-3 also tackify lower intrinsic viscosity Polymers (PTT) to higher intrinsic viscosity Polymers (PTT) and that the final reduced polymer molecular weight distribution obtained is lower than that obtained by the horizontal liquid phase tackification alone.
In conclusion, the preparation method of the PTT polyester with the intensively distributed molecular weight, which is provided by the invention, adopts the titanium-tin-cobalt composite catalyst, so that the reaction activity of the catalyst is ensured, the inactivation caused by titanium dioxide produced by hydrolysis of the traditional titanium catalyst is avoided, and the color phase of the PTT is obviously improved by introducing the cobalt salt; in addition, the PTT polyester prepolymer is tackified sequentially through the horizontal pre-polycondensation reactor and the horizontal final polycondensation reactor after the homogenization reaction, so that the PTT polyester with low intrinsic viscosity is tackified rapidly in a short time, the spinning requirement is met, the reaction energy consumption is greatly reduced, and the quality of the PTT polyester is improved. The intrinsic viscosity of the PTT polyester with the concentratedly distributed molecular weight prepared by the preparation method reaches 0.95-1.15dl/g, the concentratedly distributed molecular weight is 1.1-1.2, the DPG is less than or equal to 1.0ppm, the hue is less than or equal to 10, the evenness of the fiber is less than or equal to 1.0 percent, the fiber forming property of the PTT polyester is greatly improved, the waste silk rate is reduced to be less than 8kg/t, the viscosity reduction caused by thermal degradation is greatly reduced, and the waste silk rate, the evenness of the finally obtained PTT polyester fiber and the strength of the fiber are obviously improved.
Claims (14)
1. A preparation method of PTT polyester with centralized molecular weight distribution comprises the following steps:
the method comprises the following steps: mixing terephthalic acid and 1, 3-propylene glycol according to the molar ratio of 1:1.1-1.5, pulping, then adding a titanium-tin-cobalt composite catalyst for esterification reaction, discharging the reaction pressure to normal pressure after the esterification water yield reaches 95% of the theoretical esterification water yield, and continuing the reaction for 15-45min to obtain a PTT polyester prepolymer;
step two: mixing the PTT polyester prepolymer and 1, 3-propylene glycol monomer according to the molar ratio of 1:1.05-1.10 to perform homogenization reaction, and then sequentially performing stirring pre-polycondensation reaction and stirring final polycondensation reaction to obtain PTT polyester with the centrally distributed molecular weight;
wherein the intrinsic viscosity of the PTT polyester prepolymer is less than or equal to 0.15dl/g,
the addition amount of the titanium-tin-cobalt composite catalyst is 100-200ppm of the mass fraction of the terephthalic acid.
2. The method of claim 1, wherein: the temperature of the esterification reaction is 220-240 ℃, the reaction pressure is 50-200kPa, and the reaction time is 1.5-3.5 h;
preferably, in the first step, the addition amount of the titanium-tin-cobalt composite catalyst is 100-200ppm of the mass fraction of the terephthalic acid;
preferably, the titanium-tin-cobalt composite catalyst is prepared by compounding a titanium catalyst, a tin catalyst and a cobalt catalyst according to a molar ratio of 1:0.1:0.1-1:10:10, wherein the titanium catalyst comprises tetrabutyl titanate or metatitanic acid; the tin-based catalyst comprises dibutyl tin oxide or indium tin oxide; the cobalt catalyst comprises cobalt acetate;
preferably, the titanium-tin-cobalt composite catalyst is prepared by compounding tetrabutyl titanate, dibutyltin oxide and cobalt acetate according to the molar ratio of 1:1: 1.
3. The method of claim 1, wherein: the reaction temperature of the homogenization reaction is 200-220 ℃, the reaction time is 0.5-1.5h, and the reaction pressure is 0.1-0.3 MPa;
preferably, the catalyst for the homogenization reaction is methyl benzene sulfonic acid, and the addition amount of the methyl benzene sulfonic acid is 100-200ppm of the content of the PTT polyester prepolymer.
4. The method of claim 1, wherein: the reaction temperature of the pre-polycondensation reaction is 230-250 ℃, the pressure is 0-10kPa, and the time is 60-80 min;
preferably, the stirring speed in the pre-polycondensation reaction is 5-20 rpm/min.
5. The method of claim 1, wherein: the reaction temperature of the final polycondensation reaction is 240-260 ℃, the pressure is 0-1kPa, and the time is 90-180 min;
preferably, the stirring speed in the final polycondensation reaction is 5-10 rpm/min.
6. The method of claim 1, wherein: the first step also comprises the step of adding an ether inhibitor into the mixed system of terephthalic acid and 1, 3-propanediol before esterification reaction;
preferably, the addition amount of the ether inhibitor is 100-1000ppm of the mass fraction of the terephthalic acid;
preferably, the anti-ether agent comprises sodium acetate.
7. The method of claim 1, wherein: the second step also comprises the step of adding an anti-thermal oxidizer and/or an antioxidant into the PTT polyester prepolymer after the homogeneous reaction, and the step comprises the following specific steps:
and adding an anti-thermal oxidant and/or an antioxidant into the PTT polyester prepolymer by using a syringe pump in the process of conveying the PTT polyester prepolymer after the homogeneous reaction to the horizontal pre-polycondensation reaction kettle.
8. A PTT polyester with a concentrated molecular weight distribution, which is produced by the process for producing a PTT polyester with a concentrated molecular weight distribution according to any one of claims 1 to 7.
9. The PTT polyester having a concentrated molecular weight distribution according to claim 8, characterized in that: the intrinsic viscosity of the PTT polyester with the molecular weight centralized distribution is 0.95-1.15dl/g, the weight-average molecular weight is 55000-70000, and the molecular weight distribution is 1.1-1.2;
preferably, the content of 1, 3-propanediol in the PTT polyester with the concentrated molecular weight distribution is less than or equal to 1.0 percent, and the color and luster degree of the PTT polyester with the concentrated molecular weight distribution is less than or equal to 10;
preferably, the yarn evenness of the PTT polyester with the intensively distributed molecular weight is less than or equal to 1.0 percent, and the processing waste yarn rate is less than or equal to 10 kg/t.
10. The PTT polyester having a concentrated molecular weight distribution according to claim 8, characterized in that: the PTT polyester with the centralized distribution of molecular weight is dispersed with an anti-thermal oxidizer and/or an antioxidant;
preferably, the anti-thermal oxidation agent comprises one or a combination of several of phosphoric acid, phosphorous acid, trimethyl phosphate, trimethyl phosphite and triphenyl phosphate;
preferably, the antioxidant comprises one or more of an antioxidant 1010, an antioxidant 168 and an antioxidant 616;
preferably, the content of the anti-thermal oxygen agent is 0.005-0.05 percent by mass;
preferably, the content of the antioxidant is 0.001-0.01% by mass.
11. A composite POY fiber, characterized in that: the composite POY fiber is prepared by melt spinning the PTT polyester with the concentrated molecular weight distribution and the PET polyester according to the mass ratio of 40:60-60:40, wherein the PTT polyester and the PET polyester are as defined in any one of claims 8-10.
12. A method of making the composite POY fiber of claim 11, comprising the steps of: putting PET polyester into a PET spinning box, wherein the temperature of the PET spinning box is 240-300 ℃; putting the PTT polyester with the molecular weight distributed in a concentrated way into a PTT spinning box, wherein the temperature of the PTT spinning box is 200-300 ℃; placing the PET polyester and the PTT polyester with the molecular weight intensively distributed in a public box body according to the mass ratio of 40:60-60:40 for compounding, and after cooling, sequentially stretching by a GR1 roller, shaping by a GR2 roller, and winding to form a composite POY fiber; the temperature of the public box body is 220-300 ℃, the cooling blowing temperature is 10-50 ℃, the blowing wind speed is 0.1-1.5m/s, and the relative humidity is 55-95%; the roll speed of the GR1 roll is 2500-3500m/min, the roll speed of the GR2 roll is 2500-3500m/min, and the roll speed of the winding is 2500-3500 m/min.
13. A composite elastic DTY fiber characterized by: the composite elastic DTY fiber is made from the composite POY fiber of claim 11.
14. The method of making a composite elastic DTY fiber of claim 13, comprising the steps of: feeding the composite POY fiber into a first roller, preparing the DTY fiber through a first yarn guide porcelain, a hot box, a second yarn guide porcelain, a false twister, a second roller, a netlike device, a third roller, an oil tanker, a winding roller and coiling, and drawing and shaping the DTY fiber through a yarn spindle to prepare the composite elastic DTY fiber.
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| CN202010342770.XA CN111363128B (en) | 2020-04-27 | 2020-04-27 | PTT polyester with concentratedly distributed molecular weight and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110156970A (en) * | 2019-06-26 | 2019-08-23 | 西北师范大学 | A method of the Lewis Acids and Bases that are obstructed are to catalysis cyclic acid anhydride and epoxide copolymerization aliphatic polyester |
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| JP2003171539A (en) * | 2001-12-09 | 2003-06-20 | Efutekkusu Kk | Polyolefin-polyester block copolymer composition and method for producing its molded article |
| CN107118339A (en) * | 2016-02-25 | 2017-09-01 | 中国纺织科学研究院 | A kind of continuous method for preparing modified poly ester |
| CN108559068A (en) * | 2018-05-21 | 2018-09-21 | 东华大学 | A kind of PTT polyester or copolyesters and preparation method thereof |
| CN108610477A (en) * | 2018-05-21 | 2018-10-02 | 东华大学 | A method of inhibiting polymerization side reactions |
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| JP2003171539A (en) * | 2001-12-09 | 2003-06-20 | Efutekkusu Kk | Polyolefin-polyester block copolymer composition and method for producing its molded article |
| CN107118339A (en) * | 2016-02-25 | 2017-09-01 | 中国纺织科学研究院 | A kind of continuous method for preparing modified poly ester |
| CN108559068A (en) * | 2018-05-21 | 2018-09-21 | 东华大学 | A kind of PTT polyester or copolyesters and preparation method thereof |
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| CN110156970A (en) * | 2019-06-26 | 2019-08-23 | 西北师范大学 | A method of the Lewis Acids and Bases that are obstructed are to catalysis cyclic acid anhydride and epoxide copolymerization aliphatic polyester |
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