CN114351278B - Method for reducing polyester melt spinning temperature - Google Patents

Method for reducing polyester melt spinning temperature Download PDF

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CN114351278B
CN114351278B CN202111583542.2A CN202111583542A CN114351278B CN 114351278 B CN114351278 B CN 114351278B CN 202111583542 A CN202111583542 A CN 202111583542A CN 114351278 B CN114351278 B CN 114351278B
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polyester
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reaction
temperature
esterification reaction
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CN114351278A (en
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马逸凡
马正升
董红霞
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Shanghai Yifan New Materials Co ltd
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Shanghai Yifan New Materials Co ltd
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Abstract

The present application provides a method capable of reducing the melt spinning temperature of a polyester comprising: spinning the polyester melt, wherein a cooling master batch exists in the polyester melt, the cooling master batch at least comprises a polymer with a branched structure, the branched structure contains a cyclic structure, and the cyclic structure is an aromatic ring or an aliphatic ring. The application can reduce the viscosity activation energy of the polyester by 10-30%, reduce the melt spinning temperature of the polyester by 5-20 ℃, slowly increase the pressure of the spinning component and prolong the replacement period by 20-40%. And can realize the effective control of the melt viscosity of the polyester, the intrinsic viscosity of the oil-free filaments is reduced by at least 0.05dL/g, the melt spinning speed of the polyester is improved by 10 to 30 percent, and the stretchability of the fiber is improved by 20 to 40 percent.

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 the temperature of polyester melt spinning.
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. The polyester variety represented by PET (polyethylene terephthalate, polyester) fiber has a yield of over 5000 ten thousand tons in 2020, and is in absolute leading position in the world.
Polyester fibers are generally melt spun, for example, by chip spinning: the polyester chips are heated and melted in a screw rod after being dried, extruded and sent into each spinning position of a spinning box body, ejected from spinning holes of a spinneret plate, and the ejected melt trickles are cooled and solidified into filaments by cooling air flow.
Polyester fibers typically have a melting point above 250 ℃, which requires a relatively high spinning temperature. From the development of the polyester fiber industry, the development direction of energy conservation, consumption reduction and green low carbon is mainly adopted, wherein the polyester fiber is more efficient and energy-saving in melt spinning forming, and is the focus of research at home and abroad.
Chinese patent No. 103741258A discloses a hydrophilic polyester fiber and a preparation method thereof, comprising the following steps: (1) A chelate compound formed by dissolving polyvinyl alcohol in a calcium chloride aqueous solution; (2) Mixing and granulating the polyester chips, a molecular weight regulator, an antioxidant and a lubricant to obtain cooling master batches; (3) And (3) blending and melt spinning the obtained modified polyvinyl alcohol, the cooling master batch and the polyester chips, and finally preparing the cotton-like polyester fiber through treatment. The hydrophilic cotton-like polyester fiber prepared by the method comprises 0.1 to 5 weight percent of modified polyvinyl alcohol, 0.005 to 0.05 weight percent of molecular weight regulator, 0.002 to 0.02 weight percent of antioxidant and 0.002 to 0.02 weight percent 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 0.18g/hr; the breaking strength of the fiber is more than or equal to 2.5cN/dtex, the breaking elongation is more than or equal to 20 percent, and the volume specific resistance is less than or equal to 108 Ω & cm. In the patent, polyester chips, a molecular weight regulator, an antioxidant and a lubricant are mixed and granulated to obtain the cooling master batch.
Chinese patent No. CN101798422a discloses a method for producing polypropylene cooling master batch, which comprises the following steps: (1) 50-90 parts of polypropylene resin, 0.5-9.5 parts of dispersing agent, 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 parts 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 (3) carrying out melt extrusion on the mixed materials at 180+/-50 ℃ and then granulating. The method adopts the compound peroxide as a molecular weight regulator, and adopts the compound antioxidant, the compound dispersant, the compound light stabilizer and the compound lubricant, and the produced polypropylene cooling master batch has the advantages of high initiator content, good dispersibility, obvious cooling effect and modification effect.
The technology of the patent is that a lubricant or a cooling master batch containing the lubricant (master batch for reducing the melt spinning temperature) is added into polyester, the cooling master batch has the effect of obviously reducing the melt spinning temperature of the polyester, and meanwhile, the master batch needs to be dried and dehumidified before being used, and the bonding between the master batches is easy to occur at the stage, so that the master batch cannot be used; this places stringent requirements on the masterbatch added.
Chinese patent No. 108660537A discloses a preparation method of heat-sensitive copolyester fiber, which comprises uniformly mixing terephthalic acid, aliphatic dihydric alcohol I, a guide and a titanium-silicon-cobalt composite catalyst, sequentially carrying out esterification reaction, pre-polycondensation reaction and final polycondensation reaction to obtain heat-sensitive copolyester, and directly spinning the heat-sensitive copolyester fiber through melt; the aliphatic diol I is propylene glycol or butanediol, the guide is an esterified product generated by the reaction of the dibasic acid and the aliphatic diol II, the mol ratio of terephthalic acid to the aliphatic diol I is 1:1.05-1.10, the titanium-silicon-cobalt composite catalyst is formed by compositing a titanium-silicon composite catalyst and a cobalt-based catalyst, the titanium-silicon composite catalyst is obtained by loading a titanium-based catalyst with a silicon-based catalyst, and polysiloxane and a copolymerization component are added in the final polycondensation reaction process. To enhance heat sensitive polyester spin formation, a large amount of polysiloxane is introduced to enhance its flow characteristics, but this reduces melt quality.
Disclosure of Invention
The application provides a method capable of reducing the melt spinning temperature of polyester, which solves the defects of the method for reducing the melt spinning temperature of polyester in the prior art under the condition of ensuring the quality of melt.
The method capable of reducing the melt spinning temperature of the polyester comprises the following steps: spinning the polyester melt, wherein a cooling master batch exists in the polyester melt, the cooling master batch at least comprises a polymer with 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 side chain is at least partially linked into the cyclic structure.
More preferably, the cyclic structure is selected from:
etc.
In a preferred embodiment, the cyclic structure may also bear C1-C12 hydrocarbon radicals (in particular preferably alkyl radicals) and/or radicals containing the following structures: -CO-, -NH-CO-, -O-,-S-、-SO 2 -。
in a preferred embodiment, the polyester melt may be a polymer melt obtained by polymerization reaction or a melt obtained by heating and melting a polyester chip.
In a preferred embodiment, the temperature-reducing masterbatch may be added during the polymerization of the polyester, during the spinning process, in the polyester chips, may be melted with the polyester chips, or may be added after the melting of the polyester chips.
In a preferred embodiment, the number average molecular weight of the branched structure containing polymer is preferably 5000-50000g/mol, more preferably 10000-40000g/mol, more preferably 20000-30000g/mol.
In a preferred embodiment, the molecular weight distribution coefficient of the branched structure-containing polymer is preferably 1.5 to 5, more preferably 2 to 4, and still more preferably 2.5 to 3.5.
In a preferred embodiment, the cooling master batch described herein has a cooling crystallization temperature of preferably 50-250 ℃, more preferably 80-220 ℃, more preferably 100-200 ℃.
In a preferred embodiment, the cooling down masterbatch described herein has a crystallization half time of preferably 1 to 15 minutes, more preferably 2 to 10 minutes, and even more preferably 3 to 8 minutes.
In a preferred embodiment, the cooling master batch described herein has a dynamic viscosity of preferably 10 to 150 Pa.S, more preferably 20 to 120 Pa.S, and even more preferably 50 to 100 Pa.S.
In a preferred embodiment, the temperature-reduced masterbatch described herein preferably has a thermal decomposition temperature (the temperature corresponding to a mass loss of 5%) of at least 300 ℃, more preferably 300-500 ℃, more preferably 350-400 ℃.
In a preferred embodiment, the temperature-reduced masterbatch described herein preferably has a crystallinity of at least 5%, more preferably 5-50%, more preferably 10-40%, more preferably 20-30%.
In a preferred embodiment, the cooling master batch described herein has a crystallization enthalpy of preferably 5-50J/g, more preferably 10-40J/g, more preferably 20-30J/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 triol, at least a 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 polymer containing a polyester structure obtained by a diol, a dicarboxylic acid, at least a triol, at least a tricarboxylic acid and/or an anhydride thereof, or a polymer containing a polyester and a polyether structure.
More preferably, the branched structure containing polymer is a polycondensate 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 branched structure containing oligomer.
In a preferred embodiment, the weight ratio of the second esterification reaction product in the temperature-reduced masterbatch is preferably at least 30 wt.%, such as may be no more than 80 wt.%, preferably 40-60 wt.%.
In a preferred embodiment, the first esterification reaction product is obtained from the esterification of dicarboxylic acids and/or anhydrides, diol I.
In a preferred embodiment, the second esterification reaction product is derived from the esterification reaction 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 radical, such as-CH 2 -CH 2 -、-CH(CH 3 )-CH 2 -、-CH(CH 2 CH 3 )-CH 2 -、-CH(CH 3 )-CH(CH 3 )-、-CH 2 -CH 2 -CH 2 -、-CH(CH 3 )-CH 2 -CH 2 -、-CH(CH 2 CH 3 )-CH 2 -CH 2 -、-CH 2 -CH(CH 3 )-CH 2 -、-CH 2 -C(CH 3 ) 2 -CH 2 -、-CH 2 -C(CH 2 CH 3 ) 2 -CH 2 -、-CH 2 -C(CH 3 )(CH 2 CH 3 )-CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -and the like.
Specifically, the dihydric alcohol I and the dihydric alcohol II can be one or more selected from ethylene glycol, propylene glycol, butanediol and pentanediol respectively and independently.
In a preferred embodiment, the dicarboxylic acid and/or anhydride refers to any one or more of dicarboxylic acid, anhydride formed by dehydration of dicarboxylic acid, and may be HOOC-R2-COOH or anhydride formed by dehydration thereof, wherein R2 is a C2-C16, more preferably a C4-C12 aliphatic hydrocarbon group or a C3-C20 cyclic group (such as a naphthene group, an aromatic group, a naphthene group with an aliphatic hydrocarbon group, an aromatic hydrocarbon group with an aliphatic hydrocarbon group), and in particular the polycarboxylic acid and/or anhydride may be any one or more of 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-cyclohexanedicarboxylic anhydride, 4-methylphthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, and 1, 2-naphthalenedicarboxylic anhydride.
In a preferred embodiment, the molar ratio of dicarboxylic acid and/or anhydride to diol I is 1: (1.1-2.0), more preferably 1: (1.2-1.8), and still more preferably 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 dehydration of at least a tricarboxylic acid, such as a tricarboxylic acid, a tetracarboxylic acid, and an anhydride formed by dehydration of a tricarboxylic acid, an anhydride formed by dehydration of a tetracarboxylic acid, especially preferably a polycarboxylic acid containing the cyclic structure and/or an anhydride formed by dehydration of a polycarboxylic acid containing the cyclic structure, the cyclic structure may be an aliphatic ring or an aromatic ring, preferably the cyclic structure is selected from the group consisting of:
etc.
In a preferred embodiment, the cyclic structure may also bear C1-C12 hydrocarbon radicals (in particular preferably alkyl radicals) and/or radicals containing the following structures: -CO-, -NH-CO-, -O-,-S-、-SO 2 -。
for example, the polycarboxylic acid and/or anhydride may be one or more of pyromellitic anhydride, cyclopentanetetra-acid dianhydride, benzophenone tetraoic acid dianhydride, trimellitic anhydride, pyromellitic acid, cyclopentanetetra-acid, benzophenone tetraoic acid, trimellitic acid (1, 2, 4-trimellitic acid), trimellitic acid, 1,2, 3-trimellitic acid, and trimellitic acid.
In a preferred embodiment, the polyol is preferably one or more of a triol, a tetrol, a penta, a hexa, such as pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol, tween, and the like. More preferably, the polyhydric alcohol 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, TWEEN 85.
In a preferred embodiment, the molar ratio of the polyhydric alcohol to the polycarboxylic acid and/or anhydride is preferably 1: (1.2-4.0), more preferably 1: (1.5-3.0), and still more preferably 1: (2-2.5).
In a preferred embodiment, the molar ratio of polycarboxylic acid and/or anhydride to diol II is preferably 1: (1.2-4.0), more preferably 1: (1.5-3.0), and still more preferably 1: (2-2.5).
In a preferred embodiment, the second esterification product is the result of a further esterification of diol II with a polycarboxylic acid and/or anhydride.
In a preferred embodiment, the cooling master batch further comprises a nucleating agent, 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 size of the nucleating agent particle is between 10 and 300nm, preferably between 20 and 200nm, more preferably between 30 and 150nm, more preferably between 50 and 100 nm.
In a preferred embodiment, the nucleating agent is added in an amount of 0.1 to 5wt%, more preferably 0.5 to 3wt%, and still more preferably 1 to 2wt% based on the total weight of the cooling master batch.
In a preferred embodiment, the cooling master batch further comprises 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 phosphodiester, a phosphotriester, a phosphite triester, a phosphodiester, and an alkylaryl mixed ester, such as any one or more of a trimethyl phosphite, a trimethyl phosphate, a tris (nonylphenyl) phosphite, a triethyl phosphate, a triphenyl phosphite, a trioctyl phosphate, a triphenyl phosphate, a tris (2-chloroethyl) phosphate, a bisphosphite, and a triphosphite.
In a preferred embodiment, the heat stabilizer is added in an amount of 0.1 to 1000ppm, preferably 1 to 800ppm, more preferably 5 to 500ppm, still more preferably 10 to 100ppm based on the weight of the cooling master batch.
In a preferred embodiment, the cooling master batch comprises 1 to 15wt%, more preferably 2 to 10wt%, and even more preferably 5 to 8wt% of the weight of the polyester.
In a preferred embodiment, the spinning may be any one or more of preparation of POY (pre-oriented yarn), FDY (fully drawn yarn), staple fiber and nonwoven fabric.
The technical scheme of the application has the following beneficial effects:
1) The application can reduce the viscosity activation energy of the polyester by 10-30%, reduce the melt spinning temperature of the polyester by 5-20 ℃, slowly increase the pressure of the spinning component and prolong the replacement period by 20-40%.
2) The method can effectively control the melt viscosity of the polyester, the intrinsic viscosity of the oil-free filaments is reduced to be less than or equal to 0.05dL/g, the melt spinning speed of the polyester is improved by 10-30%, and the stretchability of the fiber is improved by 20-40%.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Example 1
Into the flask, 0.15mol of ethylene glycol was added, and the flask was heated to 200℃and 0.1mol of terephthalic acid was added dropwise. After the material is fed, the temperature is kept at 200 ℃, the pressure in the flask is 0.1MPa, the reaction is continued, and the water yield of the esterification reaction reaches 90-98% of the theoretical water yield, so that the esterification reaction can be completed. 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 spitting and the cyclopentane tetra-acid dianhydride 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 propylene glycol is finally added, so that the second esterification reaction product is terminated by propylene glycol.
In the presence of inorganic nano nucleating agent (such as barium sulfate with the particle size of 50 nm), a titanium composite catalyst is used, the first esterification reaction product and the second esterification reaction product are mixed according to the weight ratio of 5:5 (10 g respectively), and a heat stabilizer trimethyl phosphate of 100ppm is added, the reaction temperature is kept at 250 ℃, and the polycondensation reaction is carried out, wherein the polycondensation reaction is mainly the etherification reaction of alcohol between end sealing groups. In order to remove small molecules, accelerate the reaction speed and achieve an increase in molecular weight, the polycondensation reaction may be carried out under negative pressure, for example at a reaction pressure of 100Pa. The heat stabilizer may be added to the reaction system alone or supported on a catalyst.
The obtained functional master batch was added to a polyester chip in an amount of 7wt% of polyester for melt spinning.
Example 2
Into the flask, 0.12mol of 1, 4-butanediol was charged, heated to 200℃and 0.1mol of adipic acid was added dropwise. After the material is fed, the temperature is kept at 160 ℃, the pressure in the flask is 0.1MPa, the reaction is continued, and the water yield of the esterification reaction reaches 90-98% of the theoretical water yield, so that the esterification reaction can be completed. 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 glycol is added, the temperature is kept at 180 ℃, and the reaction is continued until no water is generated. The pyromellitic anhydride 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 excessive ethylene glycol is finally added, so that the second esterification reaction product is end capped by the ethylene glycol.
In the presence of inorganic nano nucleating agent (such as barium sulfate with the particle size of 80 nm), a titanium composite catalyst is used, the first esterification reaction product and the second esterification reaction product are mixed according to the weight ratio of 5:5 (10 g respectively), and a heat stabilizer trimethyl phosphate of 200ppm is added, the reaction temperature is kept at 250 ℃, and the polycondensation reaction is carried out, wherein the polycondensation reaction is mainly the etherification reaction of alcohol between end sealing groups. In order to remove small molecules, accelerate the reaction speed and achieve an increase in molecular weight, the polycondensation reaction may be carried out under negative pressure, for example at a reaction pressure of 100Pa. The heat stabilizer may be added to the reaction system alone or supported on a catalyst.
The obtained functional master batch is added into polyester chips, the addition amount is 5 weight percent of the polyester, and melt spinning is carried out.
Example 3
Into the flask, 0.18mol of 1, 3-propanediol was added, heated to 200℃and 0.1mol of terephthalic acid was added dropwise. After the material is fed, the temperature is kept at 200 ℃, the pressure in the flask is 0.1MPa, the reaction is continued, and the water yield of the esterification reaction reaches 90-98% of the theoretical water yield, so that the esterification reaction can be completed. Because of the excess of propylene glycol, the first esterification reaction product obtained in this step is a propylene glycol end-capped 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 glycol is added, the temperature is kept at 180 ℃, and the reaction is continued until no water is generated. 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 ethylene glycol is finally added, so that the second esterification reaction product is end capped by ethylene glycol.
In the presence of inorganic nano nucleating agent (such as barium sulfate with the particle size of 20 nm), a titanium composite catalyst is used, the first esterification reaction product and the second esterification reaction product are mixed according to the weight ratio of 5:5 (10 g respectively), and 250ppm of heat stabilizer triphenyl phosphate is added, the reaction temperature is kept at 250 ℃, and the polycondensation reaction is carried out, wherein the polycondensation reaction is mainly the etherification reaction of alcohol between end sealing groups. In order to remove small molecules, accelerate the reaction speed and achieve an increase in molecular weight, the polycondensation reaction may be carried out under negative pressure, for example at a reaction pressure of 100Pa. The heat stabilizer may be added to the reaction system alone or supported on a catalyst.
The obtained functional master batch is added into polyester chips, the addition amount is 3 weight percent of the polyester, and melt spinning is carried out.
Example 4
Into the flask, 0.2mol of 1, 2-pentanediol was added, and the flask was heated to 200℃to dropwise add 0.1mol of decanedicarboxylic acid. After the material is fed, the temperature is kept at 180 ℃, the pressure in the flask is 0.1MPa, the reaction is continued, and the water yield of the esterification reaction reaches 90-98% of the theoretical water yield, so that the esterification reaction can be completed. Because of the excess of pentanediol, the first esterification reaction product obtained in this step is a pentanediol-terminated 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' -benzophenone tetracarboxylic anhydride) are mixed, then the mixture is 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. The first esterification reaction product obtained in the step is a compound with a branched structure or a prepolymer with a branched structure, and excessive butanediol is finally added, so that the first esterification reaction product is a butanediol end cap.
In the presence of inorganic nano nucleating agent (such as barium sulfate with the particle size of 20 nm), using titanium composite catalyst xxg, mixing the first esterification reaction product and the second esterification reaction product according to the weight ratio of 5:5 (10 g respectively), adding heat stabilizer trioctyl phosphate 450ppmg, keeping the reaction temperature at 250 ℃, and carrying out polycondensation reaction, wherein the polycondensation reaction is mainly alcohol between end sealing groups for etherification reaction. In order to remove small molecules, accelerate the reaction speed and achieve an increase in molecular weight, the polycondensation reaction may be carried out under negative pressure, for example at a reaction pressure of 100Pa. The heat stabilizer may be added to the reaction system alone or supported on a catalyst.
The obtained functional master batch is added into polyester chips, the addition amount is 10 weight percent of the polyester, and melt spinning is carried out.
TABLE 1 functional masterbatch and application Performance test results obtained in the above examples of the present application
The dynamic viscosity test conditions were: the temperature is 10-20 ℃ above the melting point of the polyester, and the shearing rate is 50s -1 And testing under the condition.
The applicant believes that the cooling master batch cannot be thermally degraded in the drying and dehumidifying stage and has good crystallinity, so that the master batch can be prevented from being bonded and being unusable. There is no study or report on how to provide crystallinity while the masterbatch has cooling properties in the presently disclosed materials.
The functional master batch for reducing the melt spinning temperature of the polyester 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 has good fluidity, plays a role in plasticizing and flow promotion in melt blending with the polyester, remarkably reduces the viscous flow activation energy of the polyester melt, and can realize the flow of the melt at a lower temperature, thereby reducing the temperature required by spinning formation. The prepared functional master batch can play a role in self-lubricating the surface of a melt in the process of blending and extruding the polyester, greatly reduces the friction force between the melt and the metal of a pipeline and a spinning component, is more beneficial to plastic stretching, and therefore, the spinning speed is also obviously improved.
Compared with PET directly synthesized by polyethylene glycol and terephthalic anhydride, the temperature of spinning can be reduced by 5-20 ℃, the intrinsic viscosity of the oil-free silk is reduced by at least 0.05dL/g, the melt spinning speed of the polyester is improved by 10-30%, the stretchability of the fiber is improved by 20-40%, and the activation energy of the viscosity of the polyester is reduced by 10-30%, so that the pressure of a spinning component is slowly increased, and the replacement period can be prolonged by 20-40%.
The above description of the specific embodiments of the invention is given by way of example only, and the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, it is intended to cover such equivalent alterations and modifications as fall within the spirit and scope of the invention.

Claims (6)

1. A method of reducing the melt spinning temperature of a polyester comprising:
1, 3-propanediol 0.18mol was added to the flask, heated to 200℃and terephthalic acid 0.1mol was added dropwise;
after the material is fed, keeping the temperature at 200 ℃ and the pressure in the flask at 0.1MPa, continuing to react, and finishing the esterification reaction when the water yield of the esterification reaction reaches 90-98% of the theoretical water yield, wherein a first esterification reaction product is obtained in the step, and is a propylene glycol end-capped oligomer;
0.005mol of water is used as an initiator, 0.1mol of Tween 61 and 0.25mol of trimellitic anhydride are mixed and then heated to 170 ℃, the temperature is kept for reaction for 3 hours, then 0.5mol of glycol is added, the temperature is kept at 180 ℃, the reaction is continued until no water is generated, 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 finally added, so that the second esterification reaction product is terminated by glycol;
in the presence of an inorganic nano nucleating agent, a titanium composite catalyst is used, a first esterification reaction product and a second esterification reaction product are mixed according to a weight ratio of 5:5, a heat stabilizer is added, the reaction temperature is kept at 250 ℃, and polycondensation reaction is carried out, wherein the polycondensation reaction is mainly carried out by etherification reaction of alcohol between end sealing groups, and a polymer containing a branched structure, namely, a cooling master batch is obtained;
the heat stabilizer is added into the reaction system independently or loaded into the catalyst;
the cooling master batch is added into the polyester chip, the addition amount of the cooling master batch is 3% of that of the polyester, and melt spinning is carried out.
2. The process according to claim 1, wherein the polycondensation reaction is carried out under negative pressure.
3. The process according to claim 2, wherein the polycondensation is carried out under 100Pa.
4. The method of claim 1, wherein the inorganic nano-nucleating agent is barium sulfate.
5. The method of claim 4, wherein the barium sulfate particle size is 20nm.
6. The method of claim 1, wherein the spinning is producing any one or more of POY, FDY, staple fiber, and nonwoven fabric.
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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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