CN114351278A - Method for reducing polyester melt spinning temperature - Google Patents

Method for reducing polyester melt spinning temperature Download PDF

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CN114351278A
CN114351278A CN202111583542.2A CN202111583542A CN114351278A CN 114351278 A CN114351278 A CN 114351278A CN 202111583542 A CN202111583542 A CN 202111583542A CN 114351278 A CN114351278 A CN 114351278A
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polyester
anhydride
melt
polymer
acid
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CN114351278B (en
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马逸凡
马正升
董红霞
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Shanghai Yiyu Industry And Trade Development Co ltd
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Abstract

The application provides a method capable of reducing the melt spinning temperature of polyester, which comprises the following steps: spinning a polyester melt, wherein a cooling master batch exists in the polyester melt, the cooling master batch at least comprises a polymer containing a branched structure, the branched structure contains a cyclic structure, and the cyclic structure is an aromatic ring or an aliphatic ring. The polyester melt spinning process can reduce the viscosity activation energy of polyester by 10-30%, lower the melt spinning temperature of the polyester by 5-20 ℃, slowly raise the pressure of a spinning assembly, and prolong the replacement period by 20-40%. The viscosity of the polyester melt can be effectively controlled, the inherent viscosity of the oil-free yarn is reduced to at least 0.05dL/g, the melt spinning speed of the polyester is increased by 10-30%, and the stretchability of the fiber is increased by 20-40%.

Description

Method for reducing polyester melt spinning temperature
Technical Field
The application relates to the technical field of polyester melt spinning, in particular to a method capable of reducing polyester melt spinning temperature.
Background
The polyester fiber is a textile basic raw material, has the characteristics of high strength, high modulus and low water absorption, and is widely applied to civil textiles. Among them, the polyester variety represented by PET (polyethylene terephthalate, polyester) fiber has a yield of over 5000 ten thousand tons in 2020, and is in the world's absolute leading position.
Polyester fibers are generally melt spun, for example, chip spinning: drying polyester chips, heating and melting the polyester chips in a screw, extruding the polyester chips into each spinning part of a spinning box, spraying the polyester chips from spinneret orifices of a spinneret plate, and cooling and solidifying the sprayed melt trickle by cooling air flow to form filaments.
The melting point of polyester fibers is generally above 250 ℃, which requires higher spinning temperatures. From the development of the polyester fiber industry, the development direction mainly takes energy conservation, consumption reduction, green and low carbon as the main development direction, wherein the polyester fiber is more efficient and energy-saving in melt spinning and forming, which is the key point of research at home and abroad.
The Chinese invention patent CN103741258A discloses a hydrophilic polyester fiber and a preparation method thereof, which comprises the following steps: (1) a chelate formed by dissolving polyvinyl alcohol in a calcium chloride aqueous solution; (2) mixing and granulating polyester chips, a molecular weight regulator, an antioxidant and a lubricant to obtain cooling master batches; (3) and carrying out blending melt spinning on the obtained modified polyvinyl alcohol, the cooling master batch and the polyester chips, and finally preparing the cotton-like polyester fiber after treatment. The hydrophilic cotton-like polyester fiber prepared by the method comprises 0.1-5 wt% of modified polyvinyl alcohol, 0.005-0.05 wt% of molecular weight regulator, 0.002-0.02 wt% of antioxidant and 0.002-0.02 wt% of lubricant; the moisture regain of the fiber is more than or equal to 2.0 percent, the water absorption of the fiber is more than or equal to 250 percent, and the evaporation rate is more than or equal to 0.18 g/hr; the breaking strength of the fiber is more than or equal to 2.5cN/dtex, the elongation at break is more than or equal to 20 percent, and the volume specific resistance is less than or equal to 108 omega cm. In the patent, polyester chips, a molecular weight regulator, an antioxidant and a lubricant are mixed and then granulated to obtain the cooling master batch.
Chinese patent CN101798422A discloses a production method of polypropylene cooling masterbatch, which comprises the following steps: (1) 50-90 parts of polypropylene resin, 0.5-9.5 parts of dispersant, 0.1-0.6 part of surface modifier, 0.1-2.7 parts of lubricant and 0.2-0.8 part of flow regulator are mixed for 10-20 minutes, then 0.1-0.9 part of light stabilizer, 0.1-1.6 part of antioxidant and 0.2-7 parts of molecular weight regulator are sequentially added, and the mixture is continuously mixed for 5-15 minutes; (2) and melting and extruding the mixed materials at the temperature of 180 +/-50 ℃, and then granulating. The method adopts the composite peroxide as the molecular weight regulator and adopts the composite antioxidant, the composite dispersant, the composite light stabilizer and the composite lubricant, and the produced polypropylene cooling master batch has the advantages of high initiator content, good dispersibility, obvious cooling effect and modification effect.
The above patent technology is that a lubricant or a cooling master batch containing a lubricant (master batch for reducing the melt spinning temperature) is added into polyester, the cooling master batch has to have the effect of obviously reducing the melt spinning temperature of the polyester, and simultaneously, the master batch needs to be dried and dehumidified before being used, and the master batch is difficult to be bonded with each other in the stage, so that the master batch cannot be used; this puts strict requirements on the added masterbatch.
Chinese invention patent CN108660537A discloses a method for preparing heat-sensitive copolyester fiber, mixing terephthalic acid, aliphatic diol I, a guide and a titanium-silicon-cobalt composite catalyst uniformly, then carrying out esterification reaction, pre-polycondensation reaction and final polycondensation reaction in sequence to obtain heat-sensitive copolyester, and then directly spinning the melt to obtain the heat-sensitive copolyester fiber; the aliphatic diol I is propylene glycol or butanediol, the guide substance is an esterified substance generated by the reaction of dibasic acid and aliphatic diol II, the molar ratio of terephthalic acid to the aliphatic diol I is 1: 1.05-1.10, the titanium-silicon-cobalt composite catalyst is formed by compounding a titanium-silicon composite catalyst and a cobalt catalyst, the titanium-silicon composite catalyst is obtained by loading a titanium catalyst on a silicon catalyst, and polysiloxane and a copolymerization component are added in the final polycondensation reaction process. To improve the heat-sensitive polyester spin-forming, a certain amount of large polysiloxanes is introduced to improve the flow characteristics, but this reduces the melt quality.
Disclosure of Invention
The application provides a method capable of reducing polyester melt spinning temperature, and the method can be used for overcoming the defects of the method for reducing the polyester melt spinning temperature in the prior art under the condition of ensuring the melt quality.
The method capable of reducing the melt spinning temperature of polyester comprises the following steps: spinning a polyester melt, wherein a cooling master batch exists in the polyester melt, the cooling master batch at least comprises a polymer containing a branched structure, the branched structure contains a cyclic structure, and the cyclic structure is an aromatic ring or an aliphatic ring.
Preferably, in the branched structure, a branch or a side chain is at least partially linked into the cyclic structure.
More preferably, the cyclic structure is selected from:
Figure BDA0003426939860000031
Figure BDA0003426939860000032
and the like.
In a preferred embodiment, the cyclic structure may also have a C1-C12 hydrocarbon group (especially preferably an alkyl group) and/or a group having the following structure: -CO-, -NH-CO-, -O-,
Figure BDA0003426939860000033
-S-、-SO2-。
in a preferred embodiment, the polyester melt can be a polymer melt obtained by polymerization reaction, and can also be a melt obtained by heating and melting polyester chips.
In a preferred embodiment, the temperature-reducing masterbatch can be added during the polymerization of the polyester, can be added during the spinning process, can be present in the polyester chip, can be melted together with the polyester chip, or can be added after the polyester chip is melted.
In a preferred embodiment, the number average molecular weight of the polymer containing a branched structure is preferably 5000-.
In a preferred embodiment, the molecular weight distribution coefficient of the polymer containing a branched structure is preferably 1.5 to 5, more preferably 2 to 4, more preferably 2.5 to 3.5.
In a preferred embodiment, the cooling crystallization temperature of the cooling masterbatch is preferably 50-250 ℃, more preferably 80-220 ℃, and more preferably 100-200 ℃.
In a preferred embodiment, the crystallization time of the cooling masterbatch is preferably 1-15min, more preferably 2-10min, and more preferably 3-8 min.
In a preferred embodiment, the dynamic viscosity of the cooling masterbatch is preferably 10-150 pas, more preferably 20-120 pas, and more preferably 50-100 pas.
In a preferred embodiment, the temperature-reducing masterbatch herein has a thermal decomposition temperature (the temperature corresponding to the mass loss of 5%) of preferably at least 300 ℃, more preferably 300-500 ℃, and more preferably 350-400 ℃.
In a preferred embodiment, the crystallinity of the cooling masterbatch is preferably at least 5%, more preferably 5-50%, more preferably 10-40%, more preferably 20-30%.
In a preferred embodiment, the crystallization enthalpy of the cooling masterbatch is preferably 5 to 50J/g, more preferably 10 to 40J/g, and even more preferably 20 to 30J/g.
In a preferred embodiment, the polymer containing a branched structure is a polymer containing a polyester structure, or a polymer containing a polyester and polyether structure.
More preferably, the polymer containing a branched structure is a polymer containing a polyester structure obtained from at least a trihydric alcohol, at least a trihydric carboxylic acid and/or an anhydride thereof, or a polymer containing a polyester and a polyether structure.
More preferably, the polymer containing a branched structure is a polymer containing a polyester structure obtained from a diol, a dicarboxylic acid, an at least triol, an at least tricarboxylic acid and/or an anhydride thereof, or a polymer containing a polyester and a polyether structure.
More preferably, the polymer containing a branched structure is a condensation polymer of a first esterification reaction product and a second esterification reaction product, wherein the first esterification reaction product is a diol terminated oligomer and the second esterification reaction product is a diol terminated oligomer containing a branched structure.
In a preferred embodiment, the weight ratio of the second esterification reaction product in the temperature-reducing masterbatch is preferably at least 30 wt%, such as may be no more than 80 wt%, and preferably 40-60 wt%.
In a preferred embodiment, the first esterification reaction product is obtained by esterification of dicarboxylic acid and/or anhydride and diol I.
In a preferred embodiment, the second esterification reaction product is obtained by esterification of a polyol, a diol II and a polycarboxylic acid and/or anhydride, wherein the polycarboxylic acid and/or anhydride is at least a tricarboxylic acid and/or anhydride and the polyol is at least a triol.
In a preferred embodiment, the diols I and II may be the same or different diols and may each be independently selected from HO-R1-OH, wherein R1 is a C2-C10 aliphatic hydrocarbon group, such as-CH2-CH2-、-CH(CH3)-CH2-、-CH(CH2CH3)-CH2-、-CH(CH3)-CH(CH3)-、-CH2-CH2-CH2-、-CH(CH3)-CH2-CH2-、-CH(CH2CH3)-CH2-CH2-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3)2-CH2-、-CH2-C(CH2CH3)2-CH2-、-CH2-C(CH3)(CH2CH3)-CH2-、-CH2-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-CH2-and the like.
Specifically, the diol I and the diol II may be one or more selected from ethylene glycol, propylene glycol, butylene glycol, and pentylene glycol, respectively and independently.
In a preferred embodiment, the dicarboxylic acid and/or anhydride refers to any one or more of dicarboxylic acid and anhydride formed by dehydrating dicarboxylic acid, for example, HOOC-R2-COOH or anhydride formed by dehydrating dicarboxylic acid, wherein R2 is C2-C16, more preferably C4-C12 aliphatic hydrocarbon group or C3-C20 cyclic group (e.g., cycloalkyl group, aryl group, cycloalkyl group with aliphatic hydrocarbon group, aromatic hydrocarbon group with aliphatic hydrocarbon group), and specifically, the polycarboxylic acid and/or anhydride may be terephthalic acid, phthalic anhydride, isophthalic acid, phthalic anhydride, oxalic acid, malonic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, suberic acid, sebacic acid, maleic anhydride, cyclopentane-1, 2-dicarboxylic anhydride, 1, 2-cyclohexane dicarboxylic anhydride, 4-methyl phthalic anhydride, 2, 3-naphthalene dicarboxylic anhydride and 1, 2-naphthalene dicarboxylic anhydride.
In a preferred embodiment, the molar ratio of dicarboxylic acid and/or anhydride to diol I is 1:1 (1.1-2.0), more preferably 1:1 (1.2-1.8), more preferably 1:1 (1.4-1.6).
In a preferred embodiment, the polycarboxylic acid and/or anhydride refers to at least a tricarboxylic acid, an anhydride formed by dehydrating a tricarboxylic acid, such as a tricarboxylic acid, a tetracarboxylic acid, and an anhydride formed by dehydrating a tricarboxylic acid, an anhydride formed by dehydrating a tetracarboxylic acid, and particularly preferably a polycarboxylic acid containing the cyclic structure and/or an anhydride formed by dehydrating a polycarboxylic acid containing the cyclic structure, wherein the cyclic structure may be an aliphatic ring or an aromatic ring, and preferably, the cyclic structure is selected from:
Figure BDA0003426939860000051
Figure BDA0003426939860000061
Figure BDA0003426939860000062
and the like.
In a preferred embodiment, the cyclic structure may also have a C1-C12 hydrocarbon group (especially preferably an alkyl group) and/or a group having the following structure: -CO-, -NH-CO-, -O-,
Figure BDA0003426939860000063
-S-、-SO2-。
for example, the polycarboxylic acid and/or anhydride may be one or more of pyromellitic anhydride, cyclopentanetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, trimellitic anhydride, trimellitic dianhydride, pyromellitic acid, cyclopentanetetracarboxylic acid, benzophenone tetracarboxylic acid, trimellitic acid (1,2, 4-benzenetricarboxylic acid), trimesic acid, 1,2, 3-benzenetricarboxylic acid, and trimellitic acid.
In a preferred embodiment, the polyol is preferably one or more of a triol, tetraol, pentaol, hexaol, such as pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol, tween and the like. More preferably, the polyol is preferably TWEEN, wherein the TWEEN (TWEEN) may be any one or more selected from TWEEN 20, TWEEN 21, TWEEN 40, TWEEN 60, TWEEN 61, TWEEN 8, TWEEN 81 and TWEEN 85.
In a preferred embodiment, the molar ratio of polyol to polycarboxylic acid and/or anhydride is preferably 1: 1.2-4.0, more preferably 1: 1.5-3.0, more preferably 1: 2-2.5.
In a preferred embodiment, the molar ratio of polycarboxylic acid and/or anhydride to glycol II is preferably 1:1 (1.2-4.0), more preferably 1:1 (1.5-3.0), more preferably 1: 2-2.5.
In a preferred embodiment, the second esterification reaction product is obtained by further esterification reaction of the diol II with the esterification reaction product of the polyol and the polycarboxylic acid and/or the anhydride.
In a preferred embodiment, the cooling masterbatch further contains a nucleating agent, and preferably, the nucleating agent is an inorganic particle, such as silica, talc, calcium carbonate, titanium dioxide, magnesium oxide, calcium oxide, carbon black, mica, kaolin, barium sulfate, and the like.
In a preferred embodiment, the nucleating agent is a nanoparticle, preferably, the particle diameter of the nucleating agent particle is between 10 nm and 300nm, preferably between 20nm and 200nm, more preferably between 30 nm and 150nm, and more preferably between 50nm and 100 nm.
In a preferred embodiment, the addition amount of the nucleating agent is 0.1-5 wt%, more preferably 0.5-3 wt%, and more preferably 1-2 wt% of the total weight of the cooling masterbatch.
In a preferred embodiment, the cooling masterbatch further contains a heat stabilizer. Preferably, the heat stabilizer may be any one or more of phosphate, phosphite, preferably any one or more of phosphate and phosphite. Such as any one or more of a phosphoric acid diester, a phosphoric acid triester, a phosphorous acid diester, which may be any one or more of an alkyl ester, an aryl ester, an alkyl aryl mixed ester, such as any one or more of trimethyl phosphite, trimethyl phosphate, tris (nonylphenyl) phosphite, triethyl phosphate, triphenyl phosphite, trioctyl phosphate, triphenyl phosphate, tris (2-chloroethyl) phosphate, bisphosphite, triphosphite.
In a preferred embodiment, the thermal stabilizer is added in an amount of 0.1-1000ppm, preferably 1-800ppm, more preferably 5-500ppm, and more preferably 10-100ppm based on the weight of the cooling masterbatch.
In a preferred embodiment, the cooling masterbatch is 1-15 wt%, more preferably 2-10 wt%, and more preferably 5-8 wt% of the polyester.
In a preferred embodiment, the spinning may be any one or more of preparing POY (pre-oriented yarn), FDY (fully drawn yarn), short fiber, and non-woven fabric.
The technical scheme of this application has following beneficial effect:
1) the polyester melt spinning process can reduce the viscosity activation energy of polyester by 10-30%, lower the melt spinning temperature of the polyester by 5-20 ℃, slowly raise the pressure of a spinning assembly, and prolong the replacement period by 20-40%.
2) The method can realize effective control of the viscosity of the polyester melt, the intrinsic viscosity of the non-oil yarns is reduced to be less than or equal to 0.05dL/g, the polyester melt spinning speed is increased by 10-30%, and the stretchability of the fiber is increased by 20-40%.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
0.15mol of ethylene glycol was added to the flask, heated to 200 ℃ and 0.1mol of terephthalic acid was added dropwise. After the addition is finished, keeping the temperature at 200 ℃ and the pressure in the flask at 0.1MPa, continuing the reaction, and finishing the esterification reaction when the water yield of the esterification reaction reaches 90-98% of the theoretical water yield. Because of the excess of ethylene glycol, the first esterification reaction product obtained in this step is an ethylene glycol-terminated oligomer.
0.005mol of water is used as an initiator, 0.1mol of Tween 60 and 0.15mol of cyclopentane tetracarboxylic dianhydride are mixed and heated to 180 ℃, the temperature is kept for reaction for 3 hours, then 0.3mol of propylene glycol is added, the temperature is kept at 180 ℃, and the reaction is continued until no water is generated. Both the tween and the cyclopentanetetracarboxylic dianhydride can form a branched structure, so that the second esterification reaction product obtained in this step is a compound having a branched structure, or a prepolymer having a branched structure, and an excess of propylene glycol is added last, so that the second esterification reaction product is terminated with propylene glycol.
In the presence of an inorganic nano nucleating agent (such as barium sulfate, the particle size is 50nm), a titanium composite catalyst is used, a first esterification reaction product and a second esterification reaction product are mixed according to the weight ratio of 5:5 (10 g respectively), 100ppm of trimethyl phosphate serving as a thermal stabilizer is added, the reaction temperature is kept at 250 ℃, and a polycondensation reaction is carried out, wherein the polycondensation reaction mainly comprises the etherification reaction of alcohol between end-capping groups. The polycondensation reaction can be carried out under negative pressure conditions, for example at a reaction pressure of 100Pa, in order to remove small molecules, accelerate the reaction and achieve molecular weight build-up. The heat stabilizer can be added into the reaction system independently or added in a way of being supported in a catalyst.
Adding the obtained functional master batch into polyester chips, wherein the adding amount is 7 wt% of the polyester, and carrying out melt spinning.
Example 2
0.12mol of 1, 4-butanediol was added to the flask, the mixture was heated to 200 ℃ and 0.1mol of adipic acid was added dropwise. After the addition is finished, keeping the temperature at 160 ℃, keeping the pressure in the flask at 0.1MPa, continuing the reaction, and finishing the esterification reaction when the water yield of the general esterification reaction reaches 90-98% of the theoretical water yield. Because of the excess of butanediol, the first esterification reaction product obtained in this step is a butanediol-terminated oligomer.
0.005mol of water is used as an initiator, 0.1mol of Tween 40 and 0.2mol of pyromellitic anhydride are mixed and heated to 180 ℃, the temperature is kept for reaction for 3 hours, then 0.4mol of ethylene glycol is added, the temperature is kept at 180 ℃, and the reaction is continued until no water is generated. Both the exocarpium and the pyromellitic anhydride can form a branched structure, so that the second esterification reaction product obtained in the step is a compound with a branched structure or a prepolymer with a branched structure, and the excessive ethylene glycol is added finally, so that the second esterification reaction product is terminated by the ethylene glycol.
In the presence of an inorganic nano nucleating agent (such as barium sulfate, the particle size is 80nm), a titanium composite catalyst is used, a first esterification reaction product and a second esterification reaction product are mixed according to the weight ratio of 5:5 (10 g respectively), a thermal stabilizer of trimethyl phosphate is added for 200ppm, the reaction temperature is kept at 250 ℃, and a polycondensation reaction is carried out, wherein the polycondensation reaction mainly comprises the etherification reaction of alcohol between end-capping groups. The polycondensation reaction can be carried out under negative pressure conditions, for example at a reaction pressure of 100Pa, in order to remove small molecules, accelerate the reaction and achieve molecular weight build-up. The heat stabilizer can be added into the reaction system independently or added in a way of being supported in a catalyst.
Adding the obtained functional master batch into polyester chips, wherein the adding amount is 5 wt% of the polyester, and carrying out melt spinning.
Example 3
0.18mol of 1, 3-propanediol is added into a flask, the flask is heated to 200 ℃, and 0.1mol of terephthalic acid is added dropwise. After the addition is finished, keeping the temperature at 200 ℃ and the pressure in the flask at 0.1MPa, continuing the reaction, and finishing the esterification reaction when the water yield of the esterification reaction reaches 90-98% of the theoretical water yield. Because of the excess propylene glycol, the first esterification reaction product obtained in this step is a propylene glycol-terminated oligomer.
0.005mol of water is used as an initiator, 0.1mol of Tween 61 and 0.25mol of trimellitic anhydride are mixed and heated to 170 ℃, the temperature is kept for reaction for 3 hours, then 0.5mol of ethylene glycol is added, the temperature is kept at 180 ℃, and the reaction is continued until no water is generated. Both the exocarpium and the trimellitic anhydride can form a branched structure, so that the second esterification reaction product obtained in the step is a compound with a branched structure or a prepolymer with a branched structure, and excessive glycol is added finally, so that the second esterification reaction product is terminated by glycol.
In the presence of an inorganic nano nucleating agent (such as barium sulfate, the particle size is 20nm), a titanium composite catalyst is used, a first esterification reaction product and a second esterification reaction product are mixed according to the weight ratio of 5:5 (10 g respectively), a thermal stabilizer triphenyl phosphate is added, the reaction temperature is kept at 250 ℃, and a polycondensation reaction is carried out, wherein the polycondensation reaction mainly comprises the etherification reaction of alcohol between end-capping groups. The polycondensation reaction can be carried out under negative pressure conditions, for example at a reaction pressure of 100Pa, in order to remove small molecules, accelerate the reaction and achieve molecular weight build-up. The heat stabilizer can be added into the reaction system independently or added in a way of being supported in a catalyst.
Adding the obtained functional master batch into polyester chips, wherein the adding amount is 3 wt% of the polyester, and carrying out melt spinning.
Example 4
0.2mol of 1, 2-pentanediol was added to the flask, the mixture was heated to 200 ℃ and 0.1mol of sebacic acid was added dropwise. After the addition is finished, keeping the temperature at 180 ℃ and the pressure in the flask at 0.1MPa, continuing the reaction, and finishing the esterification reaction when the water yield of the general esterification reaction reaches 90-98% of the theoretical water yield. Because of the excess of pentanediol, the first esterification reaction product obtained in this step is a pentanediol end-capped oligomer.
0.005mol of water is used as an initiator, 0.1mol of Tween 80 and 0.25mol of benzophenone tetracarboxylic dianhydride (3,3',4,4' -benzophenone tetracarboxylic anhydride) are mixed and heated to 180 ℃, the temperature is kept for reaction for 3 hours, then 0.6mol of 1, 4-butanediol is added, the temperature is kept at 180 ℃, and the reaction is continued until no water is generated. Both tween and benzophenone tetracarboxylic dianhydride can form a branched structure so that the second esterification reaction product obtained in this step is a compound with a branched structure or a prepolymer with a branched structure, and an excess of butanediol is added last, so that the second esterification reaction product is terminated by butanediol.
In the presence of an inorganic nano nucleating agent (such as barium sulfate, the particle size is 20nm), a titanium composite catalyst xxg is used for mixing a first esterification reaction product and a second esterification reaction product according to the weight ratio of 5:5 (10 g respectively), a thermal stabilizer of trioctyl phosphate of 450ppmg is added, the reaction temperature is kept at 250 ℃, and a polycondensation reaction is carried out, wherein the polycondensation reaction is mainly that alcohol between end-capping groups is subjected to etherification reaction. The polycondensation reaction can be carried out under negative pressure conditions, for example at a reaction pressure of 100Pa, in order to remove small molecules, accelerate the reaction and achieve molecular weight build-up. The heat stabilizer can be added into the reaction system independently or added in a way of being supported in a catalyst.
Adding the obtained functional master batch into polyester chips, wherein the adding amount is 10 wt% of the polyester, and carrying out melt spinning.
Table 1 shows the results of testing the functional master batches and the application properties obtained in the above examples of the present application
Figure BDA0003426939860000101
Figure BDA0003426939860000111
The dynamic viscosity test conditions were: the temperature is 10-20 ℃ above the melting point of the polyester, and the shear rate is 50s-1Tested under the condition.
The applicant believes that the temperature-reducing master batches cannot be thermally degraded in the drying and dehumidifying stage and have good crystallizability, so that the master batches are prevented from being bonded to each other and cannot be used. In the published data, there is no research and report on how the master batch has the cooling performance and the crystallizability.
The functional master batch for reducing the polyester melt spinning temperature is based on the principle of copolymerization, a high-content branched structure modification component is introduced into a polyester molecular chain, the prepared master batch is good in flowability, plays a role in plasticizing and promoting flow in melt blending with polyester, obviously reduces the viscous flow activation energy of polyester melt, and can realize the flow of the melt at a lower temperature, so that the temperature required by spinning forming is reduced. The prepared functional master batch can play a role in melt surface self-lubricating in the polyester blending extrusion process, greatly reduces the friction force between the master batch and a pipeline and between the master batch and a spinning assembly, is more favorable for plastic stretching, and therefore the spinning speed is also obviously improved.
Compared with PET directly synthesized by polyethylene glycol and terephthalic anhydride, the spinning temperature can be reduced by 5-20 ℃, the inherent viscosity of oil-free yarn is reduced by at least 0.05dL/g, the polyester melt spinning speed is increased by 10-30%, the fiber stretchability is increased by 20-40%, and the polyester viscosity activation energy is reduced by 10-30%, so that the pressure of a spinning assembly is slowly increased, and the replacement period can be prolonged by 20-40%.
The embodiments of the present invention have been described in detail, but the present invention is only by way of example and is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, it is intended that all equivalent alterations and modifications be included within the invention, without departing from the spirit and scope of the invention.

Claims (10)

1. A method of reducing the melt spinning temperature of a polyester, comprising: spinning a polyester melt, wherein a cooling master batch exists in the polyester melt, the cooling master batch at least comprises a polymer containing a branched structure, the branched structure contains a cyclic structure, and the cyclic structure is an aromatic ring or an aliphatic ring; in the branched structure, a branch or a side chain is at least partially linked to the cyclic structure.
2. The method according to claim 1, wherein the polyester melt is a polymer melt obtained by polymerization reaction, and/or a melt obtained by heating and melting polyester chips;
the cooling master batch is added in the polyester polymerization process, or added in the spinning process, or exists in the polyester chip, or is melted together with the polyester chip, or is added after the polyester chip is melted.
3. The method as claimed in claim 1, wherein the number average molecular weight of the polymer having a branched structure is 5000-50000g/mol, and the molecular weight distribution coefficient of the polymer having a branched structure is 1.5-5; the cooling crystallization temperature of the cooling master batch is 50-250 ℃, the semi-crystallization time is 1-15min, the dynamic viscosity is 10-150 Pa.S, the thermal decomposition temperature is at least 300 ℃, the crystallinity is at least 5%, and the crystallization enthalpy is preferably 5-50J/g.
4. The method according to claim 1, wherein the cooling masterbatch further comprises a nucleating agent, wherein the nucleating agent is an inorganic particle; the nucleating agent is a nano particle, and the particle size of the nucleating agent particle is 10-300 nm; the addition amount of the nucleating agent accounts for 0.1-5 wt% of the total weight of the cooling master batch.
5. The method according to claim 1, wherein the cooling masterbatch further comprises a heat stabilizer, the heat stabilizer is any one or more of phosphate, phosphite, phosphate and phosphite, and the amount of the heat stabilizer added is 0.1-1000ppm of the weight of the cooling masterbatch.
6. The method of claim 1, wherein the temperature-reducing masterbatch is present in an amount of 1-15 wt% based on the weight of the polyester.
7. The method of claim 1, wherein the spinning is any one or more of POY, FDY, staple fiber and non-woven fabric.
8. The method according to claim 1, wherein the polymer having a branched structure is a polymer having a polyester structure obtained from at least a trihydric alcohol, at least a trihydric carboxylic acid and/or an anhydride thereof, or a polymer having a polyester and polyether structure; or
The polymer containing the branched structure is a polymer containing a polyester structure obtained by dihydric alcohol, dicarboxylic acid, at least trihydric alcohol, at least trihydric carboxylic acid and/or anhydride thereof, or a polymer containing a polyester and polyether structure.
9. The method of claim 8, wherein the polymer comprising a branched structure is a condensation polymer of a first esterification product and a second esterification product, wherein the first esterification product is a diol terminated oligomer and the second esterification product is a diol terminated oligomer comprising a branched structure;
the first esterification reaction product is obtained by esterification reaction of dicarboxylic acid and/or anhydride and dihydric alcohol I;
the second esterification reaction product is obtained by esterification reaction of polyhydric alcohol, dihydric alcohol II and polycarboxylic acid and/or anhydride, wherein the polycarboxylic acid and/or anhydride is at least tricarboxylic acid and/or anhydride, and the polyhydric alcohol is at least triol;
the dihydric alcohol I and the dihydric alcohol II are respectively and independently selected from HO-R1-OH, wherein R1 is C2-C10 aliphatic hydrocarbon,
the dicarboxylic acid and/or anhydride refers to any one or more of dicarboxylic acid and anhydride formed by dehydrating dicarboxylic acid, and is selected from HOOC-R2-COOH or anhydride formed by dehydrating dicarboxylic acid, wherein R2 is C2-C16, more preferably C4-C12 aliphatic hydrocarbon group or C3-C20 cyclic group;
the polycarboxylic acid and/or the anhydride is formed by dehydrating the polycarboxylic acid containing the cyclic structure and/or the polycarboxylic acid containing the cyclic structure;
the polyalcohol is preferably one or more of trihydric alcohol, tetrahydric alcohol, pentahydric alcohol and hexahydric alcohol;
the mole ratio of the dicarboxylic acid and/or the anhydride to the diol I is 1: 1.1-2.0;
the molar ratio of the polyhydric alcohol to the polycarboxylic acid and/or anhydride is preferably 1: 1.2 to 4.0;
the molar ratio of polycarboxylic acid and/or anhydride to diol II is preferably 1: 1.2-4.0.
10. The method of claim 9, wherein the second esterification reaction product is present in the temperature-reducing masterbatch in an amount of at least 30 wt%.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010163722A (en) * 2009-01-19 2010-07-29 Toray Ind Inc Method of melt-spinning
CN109180918A (en) * 2018-10-14 2019-01-11 东华大学 A kind of copoly type high flow polyester master batch basis material and preparation method thereof
CN109456469A (en) * 2018-10-14 2019-03-12 东华大学 A kind of preparation method of the cation-modified copolyesters of high fluidity
CN113668092A (en) * 2021-10-25 2021-11-19 苏州宝丽迪材料科技股份有限公司 Polyester fiber and method for producing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010163722A (en) * 2009-01-19 2010-07-29 Toray Ind Inc Method of melt-spinning
CN109180918A (en) * 2018-10-14 2019-01-11 东华大学 A kind of copoly type high flow polyester master batch basis material and preparation method thereof
CN109456469A (en) * 2018-10-14 2019-03-12 东华大学 A kind of preparation method of the cation-modified copolyesters of high fluidity
CN113668092A (en) * 2021-10-25 2021-11-19 苏州宝丽迪材料科技股份有限公司 Polyester fiber and method for producing same

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