CN114232127B - Ultralow-thermal-shrinkage polyester staple fiber and preparation method thereof - Google Patents
Ultralow-thermal-shrinkage polyester staple fiber and preparation method thereof Download PDFInfo
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- CN114232127B CN114232127B CN202210087187.8A CN202210087187A CN114232127B CN 114232127 B CN114232127 B CN 114232127B CN 202210087187 A CN202210087187 A CN 202210087187A CN 114232127 B CN114232127 B CN 114232127B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
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- 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
Abstract
The invention discloses an ultralow-heat-shrinkage polyester staple fiber and a preparation method thereof. The in-situ polymerization modifier is mainly nano-level polymeric carbon and metal salt, the modifier does not affect the appearance and dyeing performance of the fiber, the linear density of the single fiber can be adjusted within the range of 0.88 to 9.99detx, and the dry heat shrinkage rate can be controlled within the range of 0.1 to 1.0 percent when the linear density is measured at 180 +/-1 ℃ and 0.075 +/-0.0075 cN/dtex for 30 minutes.
Description
Technical Field
The invention belongs to the technical field of spinning, and particularly relates to a polyester staple fiber with ultralow thermal shrinkage and a preparation method thereof.
Background
Polyethylene terephthalate (PET) fibers have become the most important source of textile fibers worldwide, accounting for over 50% of textile fibers. 90% of polyester filaments and staple fibers were used for traditional woven and non-woven textiles and 10% for industrial textiles. The technology of directly esterifying terephthalic acid and ethylene glycol and continuously condensing and polymerizing the terephthalic acid and the ethylene glycol to form PET is an industrial means generally adopted since 1995, and the direct spinning of civil filaments and short fibers also becomes a main process route for environment-friendly, energy-saving and low-cost production. Good performance and relatively low manufacturing cost, which makes the application field continuously open.
The polyester staple fiber is obviously different from the filament in that the total fiber concentration of the fiber bundle in the manufacturing process greatly exceeds that of the polyester filament, the total fiber concentration in the processing process is 4 hundred to 2 ten thousand times of that of the filament no matter in the spinning forming and the subsequent drawing, curling and heat setting processes, and the drawing speed is 10 to 20 percent of that of the filament. Therefore, the technical difficulty of improving the uniformity of the physical and mechanical properties of the short fibers is relatively high.
The polyester staple fiber is mainly used for blending with cotton in the initial stage, and with the progress of process production technology, the technologies including copolymerization, blending, surface modification and the like are gradually applied in practical production, and the application field is expanded to various fields such as super cotton imitation, wool imitation, viscose imitation fiber, non-woven fabric, sewing thread, industrial super short fiber and the like. From the aspect of product variety development, the melt spinning of the modified polyester chip is relatively simple, but the manufacturing energy consumption, the material consumption, the management cost and the product quality are not uniform. Therefore, copolymerized, blended modified staple fibers that are directly spun by continuous polymerization are not common.
The expansion of new application fields puts forward higher technical requirements of the polyester staple fibers, including lower thermal shrinkage, higher uniformity and the like. The means for meeting the technical requirements mainly relate to two aspects, one is that the existing direct spinning polyester staple fiber production device is adjusted and implemented through processes such as spinning, post-stretching, heat treatment and the like; and the second is the copolymerization, blending modification or melt blending implementation in the process of synthesizing the polyester.
The first approach is relatively simple to implement, but is limited at present by the characteristics of the polyethylene terephthalate polyester material with the intrinsic viscosity of 0.64-0.67 dl/g, and most of the process adjustment closely related to the microstructure of the material is difficult to realize breakthrough. Such as macroscopic thermal shrinkage associated with macromolecular orientation, crystallization, amorphous domain orientation, and stress relaxation within the fiber.
The thermal shrinkage rate is related to the application and processing process of the fiber and the use requirement of the final product to a great extent, and the short fiber with the thermal shrinkage rate of more than 50 percent is used as the base fabric of the raw material high-density artificial leather as the non-woven fabric; the heat shrinkage rate of less than 5 percent is the basic requirement of short fiber for civil sewing thread; for the technical processing requirements of composite materials such as non-woven fabrics, the fiber shrinkage rate at the processing temperature of 180 ℃ is expected to be less than 1% so as to meet the final technical requirements of the composite materials.
The second means mainly relates to the technical and economic feasibility of a large-capacity continuous production device, in particular to direct spinning, and along with the industrialization of novel monomers, copolymerization modification has wider monomer selection and precedent of industrialization, such as direct spinning of acid-modified low-melting-point polyester, direct spinning of acid-modified cationic dye-dyeable polyester and the like; but the relative blending modification still has the defects of higher cost, long variety switching transition period and the like, and the continuous technical progress is still needed.
The blending modification has the advantage of relatively flexible means, and the selected blend does not participate in the polyester chemical reaction, can participate in blending in the polyester synthesis reaction process and can also participate in blending before spinning. The fiber performance can be greatly changed on the premise of not changing the basic characteristics of the polyester.
Generally, blending of organics can be selected from melt processes, such as dyes and the like; the mixing difficulty of the inorganic substance in a melt state is high, and two main reasons are mainly involved, namely, the dynamic viscosity of the polyester melt is high, extra energy consumption is caused by mechanical stirring, and the melt is heated, so that the degradation of a polymer can be caused; secondly, the inorganic substance of the superfine powder has agglomeration effect, and the non-implementation of dispersion means can cause the extreme non-uniform distribution of the modifier in the melt, even cause the instability of the spinning and post-stretching processes, and is the main reason of the non-uniform quality of the final product.
Therefore, the technical problems of blending modification are that the screening does not change the polymerization reaction process, does not influence the catalytic effect of the catalyst, can realize good dispersion effect in the process embodiment, and has the requirements of available raw materials and acceptable cost.
The addition of the modifier in the process of preparing PTA/EG slurry and the process of pre-polycondensation molten mass has the advantage of fully utilizing the mechanical and chemical thermal kinetic energy dispersing and stirring means existing in the original design.
In recent years, the research on ultrafine particles and the dispersibility thereof has been advanced greatly, the industrialization is mature basically, and with the progress of the sustainable development concept, the cost of the polyester and the fiber manufactured by selecting the additives and the dispersing agent is removed, and the influence on the environment in the processing, using and regenerating processes and the safety in the production and using processes must be considered.
The technical attempts and industrialization for reducing shrinkage of polyester filament, polyester film plastic, film and the additives for reducing shrinkage are also advanced at home and abroad.
Chinese patent CN 108130743B "ultra-low shrinkage sunshade cloth and its preparation method" adopts terephthalic acid, ethylene glycol and dihydric alcohol with branched chain to copolymerize, and then the ultra-low shrinkage polyester industrial yarn is prepared by solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding, and the dry heat shrinkage rate of the ultra-low shrinkage polyester industrial yarn is 2.2 +/-0.35% under the conditions of 190 ℃,15 min and 0.01 cN/dtex.
Chinese patent CN 109750363B "preparation method of ultra-low shrinkage polyester industrial yarn" adopts FDY process, and adds a relaxation heat treatment process between tension heat-setting process and winding process, and the relaxation heat treatment is that the polyester yarn bundle is passed through a space with a certain temperature in a proper relaxation state, and the proper relaxation state, overfeed rate is 3.0-5.0%, 200-240 deg.C, and the space is between a pair of parallel arranged and non-coplanar hot plates. The dry heat shrinkage under the load test conditions of 190 ℃ for 15 minutes and 4.0cN/dtex is 1.8 plus or minus 0.25 percent.
Chinese patent CN 105839207A "production method of ultra-low shrinkage bright FDY", is composed of a double-roller heating and shaping device, a main network and a rear heating plate, wherein the heating temperature of the hot plate is 300-350 ℃, and the shrinkage of obtained boiling water is below 3%.
Chinese patent CN 107663665B "a method for preparing a high-strength low-shrinkage extra-bright embroidery thread polyester drawn yarn" discloses a method for preparing a high-strength low-shrinkage extra-bright embroidery thread polyester drawn yarn, wherein polyester chips with the viscosity of 0.70-0.80 dl/g are selected as raw materials, graphene is added as an additive of modified polyester, and the lowest boiling water shrinkage rate is 2% after processes of melt spinning, stretch forming and the like.
Chinese patent CN 111875941A "use of hyperbranched polyester as a low shrinkage additive and a toughening agent for polyester molding compounds" discloses use of hyperbranched polyester as a low shrinkage additive and a toughening agent for polyester molding compounds.
Chinese patent CN 113480761A "a high-toughness low-shrinkage polyester film and a preparation method thereof" discloses a high-toughness low-shrinkage polyester film, which is composed of 60-90 parts of PET, 10-40 parts of PEN, 5-20 parts of a functional toughening component, 2-6 parts of a chain extender, 1-5 parts of a composite anti-shrinkage agent and 0.1-1 part of a heat stabilizer. The composite anti-shrinkage agent is prepared by mixing glyceryl monostearate, trilauryl phosphite, fumed silica and titanate coupling agent according to the mass ratio of 10-5:1-2. The minimum heat shrinkage after the application was 0.4% at 150 ℃ for 30 minutes.
The above-mentioned patents mainly relate to melt spinning with high-viscosity polyester, and the minimum dry heat shrinkage of the filament obtained by high-temperature heat setting is 1.8 plus or minus 0.25%, although the shrinkage value is very close to the requirement of processing polyester staple fiber non-woven fabric composite material, the transportation of the high-viscosity melt is difficult to realize in the direct spinning process of polyester staple fiber, and the high-temperature processing equipment is not suitable for the form of staple fiber; the addition of graphene is not obvious in reducing the thermal shrinkage of the filament, and the addition of the composite anti-shrinkage agent formed by mixing hyperbranched polyester, glyceryl monostearate, trilauryl phosphite, fumed silica and titanate coupling agent according to the mass ratio of 10-5:1-2 of 0.2-0.5 is effective in reducing the molding of polyester molding materials and the shrinkage of films, but is also not suitable for being added in the polyester synthesis process, and the hydroxyl and carboxyl of the hyperbranched polyester participate in the reaction of terephthalic acid and ethylene glycol, so that the smooth proceeding of the spinning and post-stretching processes is hindered.
Therefore, it is desirable to provide a polyester staple fiber with ultra-low thermal shrinkage, and at the same time, the in-situ polymerization modifier is added in the polyester synthesis process, and the in-situ polymerization modifier does not participate in the high-molecular synthesis reaction of esterification and polycondensation, and does not affect the catalytic effects of polyethylene terephthalate esterification, titanium-based polycondensation and antimony-based catalysts.
Disclosure of Invention
The invention aims to solve the technical problem of providing the polyester short fiber with the ultralow heat shrinkage rate and the preparation method thereof aiming at the defects of the prior art.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the polyester staple fiber with the ultralow heat shrinkage rate is formed by melt spinning of polyethylene glycol terephthalate subjected to in-situ polymerization modification, wherein the polyethylene glycol terephthalate subjected to in-situ polymerization modification contains an in-situ polymerization modifier, and the in-situ polymerization modifier comprises polymerized carbon and barium sulfate.
In order to achieve the technical purpose, the invention adopts another technical scheme as follows:
a preparation method of polyester staple fiber with ultralow heat shrinkage rate comprises the following steps:
conveying the melt of the polyethylene glycol terephthalate subjected to in-situ polymerization modification to a spinning manifold, metering, extruding, quenching to form filaments, spinning the filaments at the speed of 1000-1350 m/min, balancing for more than 24 hours under the environmental conditions that the relative humidity is 60 +/-5 RH% and the temperature is 20-28 ℃, drawing and curling the filaments after bundling, treating the filaments by adopting a metal hot roller or hot air and additionally arranging a far infrared heat radiation device under the conditions of high temperature of 190-240 ℃ and long time of 20-60 minutes, and then cutting the filaments into short fibers, wherein the short fibers are polyester short fibers with ultralow heat shrinkage;
wherein the polyethylene terephthalate after in-situ polymerization modification contains an in-situ polymerization modifier, and the in-situ polymerization modifier comprises polymeric carbon and barium sulfate.
As a further improved technical scheme of the invention, the preparation method of the polyethylene glycol terephthalate after in-situ polymerization modification comprises the following steps:
step 1: blending polymeric carbon and barium sulfate with ethylene glycol in the presence of a dispersant to form a suspension, the concentration of the suspension being 30-40% by weight, the suspension being stored in a stirred, jacketed, insulated storage tank, the temperature of the suspension in the storage tank being 70 + -5 ℃;
step 2: metering and injecting suspension into mixed slurry containing terephthalic acid and ethylene glycol, then sending the mixed slurry into an esterification kettle for esterification, and sending the esterification product into a polycondensation kettle for polycondensation through an oligomer pipeline; or sending mixed slurry containing terephthalic acid and ethylene glycol into an esterification kettle for esterification reaction, sending the esterification product into a polycondensation kettle for polycondensation reaction through an oligomer pipeline, and simultaneously metering and injecting the suspension into the oligomer pipeline;
and step 3: the melt obtained after polycondensation is the melt of the polyethylene glycol terephthalate after in-situ polymerization modification.
As a further improved technical scheme of the invention, the polymeric carbon is ultrafine powder nano-particles, the average particle diameter of the polymeric carbon is 400-1200 nm, and the addition amount of the polymeric carbon is 0.3-3.5 percent of the weight of the polyethylene terephthalate.
As a further improved technical scheme of the invention, the barium sulfate is ultrafine powder nano-particles, the average particle diameter of the barium sulfate is 500-1500 nm, and the addition amount is 0.2-3.0 percent by weight of the polyethylene terephthalate.
As a further improvement of the present invention, the dispersant is phosphate, and the amount added is 1 to 3% by weight based on the total amount of the polymeric carbon and the barium sulfate.
As a further improved technical scheme of the invention, the phosphate adopts potassium tripolyphosphate.
The invention has the beneficial effects that:
the in-situ polymerization modifier does not participate in the high-molecular synthesis reaction of esterification and polycondensation, does not influence the catalytic effect of the catalysts of esterification, polycondensation titanium and antimony of polyethylene glycol terephthalate, and can be stably and uniformly distributed in a high polymer melt.
The flow property of the modified melt is not changed, the use condition of the melt filter is not influenced, and the condition of the melt conveying process does not need to be specially adjusted.
The polyester nascent fiber after spinning and high-speed drawing has the characteristic of anisotropy, and macromolecules along the fiber axis direction have partial orientation, which can cause instability in the redrawing process after bundling and cause uneven shrinkage rate of the final fiber, so that the polyester nascent fiber needs to be balanced for at least 24 hours under the conditions of basically stable environment, relative humidity of 60 +/-10 RH% and temperature of 24-28 ℃, so that the orientation degree of the macromolecules of the fiber is reduced from 20% to less than 5%.
Compared with the common polyester nascent fiber, the nascent fiber containing the in-situ polymerization modifier has the characteristics of better heat conductivity and easy crystallinity, can be suitable for 3-4 times of mechanical drawing, greatly improves the drawing orientation degree of the fiber, enables macromolecules to be more easily laid into crystal lattices in the subsequent heat setting process to form crystals, and has the same result no matter whether the traditional titanium dioxide matting agent is added or not.
When the macromolecules in the drawn fiber have high orientation and are induced to form partial crystallization, the further application of heat to eliminate the internal stress of the macromolecules outside a crystal area due to the high orientation is an important step for reducing the thermal shrinkage rate in the axial direction of the final fiber. Because the heat conduction capacity of the polyethylene terephthalate is low, the heat transfer speed of the metal hot roller or hot air is hindered by the filament layer, so that the heat quantity and time obtained by the fiber in different filament sheets are different, and the unevenness is caused, therefore, the traditional post-treatment process, namely the heat setting of the filament bundle under the tension condition or the tension-free condition to improve the conduction speed, cannot meet the result that the shrinkage rate of the fiber is less than 2 percent. The in-situ polymerization modifier in the fiber has good heat conduction performance, and greatly improves the heat conduction efficiency between fibers, so that the difference of the thermal shrinkage rate of the fiber can be reduced on the conventional polyester fiber post-treatment device. Indirectly, it can also be confirmed from the uniformity of the tensile strength of the fiber.
The adoption of far infrared heating filament bundles is a means for making up for further increasing the heating temperature under the condition of the existing heat setting equipment, the maximum light emission of a quartz infrared lamp appears in the range of about 1100-1200nm wave band, but the polyethylene glycol terephthalate has poorer energy absorption in the range of 500-2000nm, so the in-situ polymerization modifier, especially the existence of polymeric carbon, of the invention greatly improves the acceptance range of the energy emitted by the quartz far infrared lamp. Therefore, in the existing production line, the filament bundle can be heated by further infrared radiation after being curled by adopting the hot roller type Zhang Re shaping process; far infrared radiation heating can also be added behind hot air setting equipment adopting a relaxation heat setting process so as to further heat the silk slices.
The invention is suitable for polyethylene glycol terephthalate single fiber with linear density of 0.88-9.99 detx, and the dry heat shrinkage rate measured at 180 + -1 deg.C and 0.075 + -0.0075 cN/dtex for 30 minutes can be controlled within the range of 0.1-1.0%, which is smaller than the heat shrinkage rate of the fiber prepared by the existing method for reducing the heat shrinkage rate of the fiber. The rest of the crimping performance and the physical and mechanical properties all meet the technical requirements of superior products such as corresponding national standards (GB/T14464 polyester staple fibers) of various polyester staple fibers and the group (industry) standards (FZ/T52005 polyester staple fibers for sewing threads).
Detailed Description
The following further illustrates embodiments of the invention:
example 1:
the preparation method of the polyester staple fiber with ultralow heat shrinkage rate comprises the following steps:
conveying the melt of the polyethylene glycol terephthalate subjected to in-situ polymerization modification to a spinning manifold, metering, extruding, quenching to form filaments, spinning the filaments at the speed of 1000m/min, balancing for more than 24 hours under the environmental conditions that the relative humidity is 55RH% and the temperature is 20 ℃, drawing and curling the filaments after bundling, treating the filaments by adopting a metal hot roller and additionally arranging a far infrared heat radiation device under the conditions of high temperature of 190 ℃ and long time of 60 minutes, and then cutting the filaments into short fibers, wherein the short fibers are polyester short fibers with ultralow heat shrinkage.
The polyethylene glycol terephthalate after in-situ polymerization modification contains in-situ polymerization modifiers, wherein the in-situ polymerization modifiers comprise two types, one type is nano-scale polymeric carbon, and the other type is an amorphous carbon structural material which is prepared by high-temperature pyrolysis and carbonization of furan resin. Also called glassy carbon, which is structurally different from graphite and although it contains a microcrystalline layered structure, it is not aligned and is amorphous carbon as a whole, but forms a nodular structure of the polymer. The ultrafine powder particles used in this example had an average particle diameter of 400nm and were added in an amount of 3.5% by weight based on the polyethylene terephthalate. The second is ultrafine powder barium sulfate having an average particle diameter of 500nm, and the amount added is 3.0% by weight based on ethylene terephthalate.
The preparation method of the polyethylene glycol terephthalate after in-situ polymerization modification comprises the following steps:
step 1: the in-situ polymerization modifier is pretreated by in-situ polymerization, the polymeric carbon and barium sulfate are mixed with glycol to prepare suspension with the concentration of 30 percent by weight in the presence of dispersant potassium tripolyphosphate, the suspension is stored in a stirred and jacketed storage tank, and the temperature of the suspension in the storage tank is 65 ℃.
Step 2: according to the main industrial process routes of PET synthesis and direct spinning, suspension can be metered and injected into mixed slurry containing terephthalic acid and ethylene glycol, then the mixed slurry is sent into an esterification kettle for esterification reaction, and an esterification product is sent into a polycondensation kettle for polycondensation reaction through an oligomer pipeline; the esterification and polycondensation processes are basically the same as those before modification, namely the esterification and polycondensation processes are suitable for different processes and scales of the existing production device.
And step 3: the melt obtained after polycondensation is the melt of the polyethylene glycol terephthalate after in-situ polymerization modification.
The dispersant of this example was a phosphate, specifically potassium tripolyphosphate, and the amount added was 1% by weight of the total amount of the polymeric carbon and barium sulfate. The mass ratio of terephthalic acid to ethylene glycol in the mixed slurry of step 2 was 1.12, the mixed slurry further contained a catalyst and 0.4% by weight of a matting agent, the catalyst was 0.18% by weight of an antimony-based catalyst or 0.0005% by weight of a titanium-based catalyst.
Example 2:
the preparation method of the polyester staple fiber with ultralow heat shrinkage comprises the following steps:
the melt of the polyethylene glycol terephthalate modified by in-situ polymerization is conveyed to a spinning manifold, metering and extrusion are carried out, the melt is quenched into filament yarns, the filament yarns are spun at the speed of 1350m/min, the balance is carried out for more than 24 hours under the environmental conditions that the relative humidity is 60RH% and the temperature is 28 ℃, the filament yarns are stretched and curled after bundling, the filament yarns are treated by hot air and a far infrared heat radiation device under the conditions of high temperature of 240 ℃ and long time of 20 minutes, and then the filament yarns are cut into short fibers, wherein the short fibers are polyester short fibers with ultra-low heat shrinkage.
The polyethylene glycol terephthalate after in-situ polymerization modification contains in-situ polymerization modifiers, wherein the in-situ polymerization modifiers comprise two types, one type is nano-scale polymeric carbon, and the other type is an amorphous carbon structural material which is prepared by high-temperature pyrolysis and carbonization of furan resin. Also called glassy carbon, which is structurally different from graphite and although it contains a microcrystalline layered structure, it is not aligned and is amorphous carbon as a whole, but forms a nodular structure of the polymer. In this example, ultrafine powder microparticles having an average particle diameter of 1200nm were used in an amount of 0.3% by weight based on polyethylene terephthalate. The second is ultrafine powder barium sulfate having an average particle diameter of 1500nm, and the amount added is 0.2% by weight based on the amount of ethylene terephthalate.
The preparation method of the polyethylene glycol terephthalate after in-situ polymerization modification comprises the following steps:
step 1: the in situ polymerization modifier was pretreated by in situ polymerization, and the polymeric carbon and barium sulfate were blended with ethylene glycol in the presence of the dispersant potassium tripolyphosphate to make a suspension with a concentration of 40% by weight, which was stored in a stirred, jacketed, insulated storage tank where the suspension temperature was 75 ℃.
Step 2: according to the main industrial process routes of PET synthesis and direct spinning, suspension can be metered and injected into mixed slurry containing terephthalic acid and ethylene glycol, then the mixed slurry is sent into an esterification kettle for esterification reaction, and an esterification product is sent into a polycondensation kettle for polycondensation reaction through an oligomer pipeline; the esterification and polycondensation processes are basically the same as those before modification, namely the esterification and polycondensation processes are suitable for different processes and scales of the existing production device.
And step 3: the melt obtained after polycondensation is the melt of the polyethylene glycol terephthalate after in-situ polymerization modification.
The dispersant of this example was a phosphate, specifically potassium tripolyphosphate, and the amount added was 3% by weight of the total amount of polymeric carbon and barium sulfate. The mass ratio of terephthalic acid to ethylene glycol in the mixed slurry in step 2 was 1.17, and the mixed slurry further contained a catalyst, which was 0.28% by weight of an antimony-based catalyst or 0.001% by weight of a titanium-based catalyst.
Example 3:
the preparation method of the polyester staple fiber with ultralow heat shrinkage comprises the following steps:
conveying the melt of the polyethylene glycol terephthalate subjected to in-situ polymerization modification to a spinning manifold, metering and extruding, quenching to form filaments, spinning the filaments at a speed of 1200m/min, balancing for more than 24 hours under the environmental conditions that the relative humidity is 65RH% and the temperature is 24 ℃, bundling, stretching and curling the filaments, treating the filaments by adopting a metal hot roller and additionally arranging a far infrared heat radiation device under the conditions of high temperature of 215 ℃ and long time of 40 minutes, and then cutting the filaments into short fibers, wherein the short fibers are polyester short fibers with ultralow heat shrinkage.
The polyethylene glycol terephthalate after in-situ polymerization modification contains in-situ polymerization modifiers, wherein the in-situ polymerization modifiers comprise two types, one type is nano-scale polymeric carbon, and the non-crystalline carbon structural material is prepared by high-temperature pyrolysis and carbonization of furan resin. Also called glassy carbon, which is structurally different from graphite and although it contains a microcrystalline layered structure, it is not aligned and is amorphous carbon as a whole, but forms a nodular structure of the polymer. In this example, ultrafine powder microparticles having an average particle size of 800nm were used in an amount of 2% by weight of polyethylene terephthalate. The second is ultrafine powder barium sulfate having an average particle diameter of 1000nm, added in an amount of 1.6% by weight based on the amount of ethylene terephthalate.
The preparation method of the polyethylene glycol terephthalate after in-situ polymerization modification comprises the following steps:
step 1: the in-situ polymerization modifier is pretreated by in-situ polymerization, the polymeric carbon and barium sulfate are mixed with glycol to prepare suspension in the presence of dispersant potassium tripolyphosphate, the concentration of the suspension is 35 percent by weight, the suspension is stored in a stirred and jacketed storage tank, and the temperature of the suspension in the storage tank is 70 ℃.
Step 2: sending mixed slurry containing terephthalic acid and ethylene glycol into an esterification kettle for esterification reaction, sending an esterification product into a polycondensation kettle through an oligomer pipeline for polycondensation reaction, and simultaneously, metering and injecting suspension into the oligomer pipeline; the esterification and polycondensation processes are basically consistent with those before modification, namely the method is suitable for different processes and scales of the existing production device.
And step 3: the melt obtained after polycondensation is the melt of the polyethylene glycol terephthalate after in-situ polymerization modification.
The dispersant of this example was a phosphate, specifically potassium tripolyphosphate, and the amount added was 2% by weight of the total amount of the polymeric carbon and barium sulfate. The mass ratio of terephthalic acid to ethylene glycol in the mixed slurry of step 2 was 1.15, the mixed slurry further contained a catalyst and 0.4% by weight of a matting agent, the catalyst was 0.23% by weight of an antimony-based catalyst or 0.0008% by weight of a titanium-based catalyst.
The above examples all have the following characteristics:
the in-situ polymerization modifier does not participate in the high-molecular synthesis reaction of esterification and polycondensation, does not influence the catalytic effect of catalysts of polyethylene glycol terephthalate esterification, titanium polycondensation and antimony, and can be stably and uniformly distributed in a high polymer melt.
The flow property of the modified melt is not changed, the use condition of the melt filter is not influenced, and the condition of the melt conveying process does not need to be specially adjusted.
The polyester nascent fiber after spinning and high-speed drawing has the characteristic of anisotropy, and macromolecules along the fiber axis direction have partial orientation, which can cause instability in the redrawing process after bundling and cause uneven shrinkage rate of the final fiber, so that the polyester nascent fiber needs to be balanced for at least 24 hours under the conditions of basically stable environment, relative humidity of 60 +/-10 RH% and temperature of 24-28 ℃, so that the orientation degree of the macromolecules of the fiber is reduced from 20% to less than 5%.
Compared with the common polyester nascent fiber, the nascent fiber containing the in-situ polymerization modifier has the characteristics of better heat conductivity and easy crystallinity, can be suitable for 3-4 times of mechanical drawing, greatly improves the drawing orientation degree of the fiber, enables macromolecules to be more easily laid into crystal lattices in the subsequent heat setting process to form crystals, and has the same result no matter whether the traditional titanium dioxide matting agent is added or not.
When the macromolecules in the drawn fiber have high orientation and are induced to form partial crystallization, the further application of heat to eliminate the internal stress of the macromolecules outside a crystal area due to the high orientation is an important step for reducing the thermal shrinkage rate in the axial direction of the final fiber. Because the heat conduction capacity of the polyethylene terephthalate is low, the heat transfer speed of the metal hot roller or hot air is hindered by the filament layer, so that the heat quantity and time obtained by the fiber in different filament sheets are different, and the unevenness is caused, therefore, the traditional post-treatment process, namely the heat setting of the filament bundle under the tension condition or the tension-free condition to improve the conduction speed, cannot meet the result that the shrinkage rate of the fiber is less than 2 percent. The in-situ polymerization modifier in the fiber has good heat conduction performance, and greatly improves the heat conduction efficiency between fibers, so that the difference of the thermal shrinkage rate of the fiber can be reduced on the conventional polyester fiber post-treatment device. Indirectly, it can also be confirmed from the uniformity of the tensile strength of the fibers.
The adoption of far infrared heating filament bundles is a means for making up for further increasing the heating temperature under the condition of the existing heat setting equipment, the maximum light emission of a quartz infrared lamp appears in the range of about 1100-1200nm wave band, but the polyethylene glycol terephthalate has poorer energy absorption in the range of 500-2000nm, so the in-situ polymerization modifier, especially the existence of polymeric carbon, in the embodiment greatly improves the acceptance range of the energy emitted by the quartz far infrared lamp. Therefore, in the existing production line, the filament bundle can be heated by further infrared radiation after being curled by adopting the hot roller type Zhang Re shaping process; far infrared radiation heating can also be added behind hot air setting equipment adopting a relaxation heat setting process so as to further heat the silk slices. The surface temperature of the silk slice reaches 190-240 ℃, and the heating time is 30-20 minutes according to the surface temperature of the silk slice.
Table 1 shows the main processes of examples 4 to 7 and comparative examples 1 to 2. Table 2 shows the results of the quality of the fibers prepared in examples 4 to 7 and comparative examples 1 to 2. Examples 4-7 were prepared in the same manner as the ultra low heat shrinkage polyester staple fibers of examples 1-3, except that the major process parameters were different, and the different process parameters are listed in table 1.
The fiber of comparative example 1 was prepared mainly by the following procedure: the barium sulfate and the dispersing agent are metered and injected into mixed slurry containing terephthalic acid, ethylene glycol and a catalyst, then the mixed slurry is sent into an esterification kettle for esterification reaction, and an esterification product is sent into a polycondensation kettle through an oligomer pipeline for polycondensation reaction; the melt of the polyethylene terephthalate obtained after polycondensation is formed by spinning, balancing, stretching, heat setting and the like. Wherein the amount of barium sulfate added was 0.2% by weight of polyethylene terephthalate, the amount of dispersant added was 2% by weight of polyethylene terephthalate, and the catalyst in the mixed slurry was an antimony-based catalyst, accounting for 0.025% by weight. The remaining main process parameters are seen in table 1.
The fiber of comparative example 2 was prepared mainly by the following procedure: sending mixed slurry containing terephthalic acid, ethylene glycol, a catalyst and a flatting agent into an esterification kettle for esterification reaction, and sending an esterification product into a polycondensation kettle through an oligomer pipeline for polycondensation reaction; the melt of the polyethylene terephthalate obtained after polycondensation is formed by spinning, balancing, stretching, heat setting and the like. The content of the matting agent in the mixed slurry was 0.4% by weight, and the content of the catalyst was 0.001% by weight, which was a titanium-based catalyst. The remaining main process parameters are seen in table 1.
Table 1 shows the main processes of examples 4 to 7 and comparative examples 1 to 2:
table 2 shows the results of the quality of the fibers prepared in examples 4 to 7 and comparative examples 1 to 2:
as is clear from the above table, the linear density of the polyethylene terephthalate single fiber to which the present invention is applied is 0.88 to 9.99detx, and the dry heat shrinkage rate at 180. + -. 1 ℃ for 30 minutes is controlled to be 0.1 to 1.0%. The rest of the crimping performance and the physical and mechanical performance all meet the technical requirements of superior products such as corresponding national standards (GB/T14464 polyester staple fiber) of various polyester staple fibers and group (industry) standards (FZ/T52005 polyester staple fiber for sewing threads).
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that may occur to those skilled in the art are all within the scope of the present invention.
Claims (6)
1. A preparation method of polyester staple fiber with ultralow heat shrinkage rate is characterized by comprising the following steps:
conveying the melt of the polyethylene glycol terephthalate subjected to in-situ polymerization modification to a spinning manifold, metering, extruding, quenching to form filaments, spinning the filaments at the speed of 1000-1350 m/min, balancing for more than 24 hours under the environmental conditions that the relative humidity is 60 +/-5 RH% and the temperature is 20-28 ℃, drawing and curling the filaments after bundling, treating the filaments by adopting a metal hot roller or hot air and additionally arranging a far infrared heat radiation device under the conditions of high temperature of 190-240 ℃ and long time of 20-60 minutes, and then cutting the filaments into short fibers, wherein the short fibers are polyester short fibers with ultralow heat shrinkage;
wherein the polyethylene terephthalate after in-situ polymerization modification contains an in-situ polymerization modifier, and the in-situ polymerization modifier comprises polymeric carbon and barium sulfate.
2. The method for preparing the polyester staple fiber with ultralow heat shrinkage according to claim 1, wherein the method for preparing the polyethylene terephthalate after in-situ polymerization modification comprises the following steps:
step 1: blending polymeric carbon and barium sulfate with ethylene glycol to prepare suspension liquid in the presence of a dispersing agent, wherein the concentration of the suspension liquid is 30-40 wt%, the suspension liquid is stored in a storage tank which is stirred and is insulated by a jacket, and the temperature of the suspension liquid in the storage tank is 70 +/-5 ℃;
step 2: metering and injecting suspension into mixed slurry containing terephthalic acid and ethylene glycol, then sending the mixed slurry into an esterification kettle for esterification, and sending an esterification product into a polycondensation kettle through an oligomer pipeline for polycondensation; or sending mixed slurry containing terephthalic acid and ethylene glycol into an esterification kettle for esterification reaction, sending the esterification product into a polycondensation kettle for polycondensation reaction through an oligomer pipeline, and simultaneously metering and injecting the suspension into the oligomer pipeline;
and 3, step 3: the melt obtained after polycondensation is the melt of the polyethylene glycol terephthalate after in-situ polymerization modification.
3. The method for preparing polyester staple fiber with ultra-low thermal shrinkage according to claim 2, wherein the polymeric carbon is ultrafine powder nanoparticles having an average particle size of 400 to 1200nm and added in an amount of 0.3 to 3.5wt% of polyethylene terephthalate.
4. The method for preparing polyester staple fiber with ultra-low thermal shrinkage according to claim 2, wherein the barium sulfate is ultrafine powder nanoparticles having an average particle size of 500 to 1500nm and added in an amount of 0.2 to 3.0wt% of polyethylene terephthalate.
5. The method for preparing polyester staple fiber with ultra-low thermal shrinkage as claimed in claim 2, wherein the dispersant is phosphate, and the amount of the dispersant added is 1-3 wt% of the total amount of the polymeric carbon and the barium sulfate.
6. The method for preparing the ultra-low heat shrinkage polyester staple fiber according to claim 5, wherein the phosphate is potassium tripolyphosphate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1544733A (en) * | 2003-11-27 | 2004-11-10 | 济南正昊化纤新材料有限公司 | Bright sewing thread type polyester staple fiber and process for making same |
| CN104963024A (en) * | 2015-06-18 | 2015-10-07 | 江苏江南高纤股份有限公司 | Polyester directly-spun short fiber for hydrolysis-resistant and photoaging-resistant industry and preparation method thereof |
| CN110747531A (en) * | 2018-07-23 | 2020-02-04 | 慈溪市佳吉化纤有限公司 | Polyester staple fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544733A (en) * | 2003-11-27 | 2004-11-10 | 济南正昊化纤新材料有限公司 | Bright sewing thread type polyester staple fiber and process for making same |
| CN104963024A (en) * | 2015-06-18 | 2015-10-07 | 江苏江南高纤股份有限公司 | Polyester directly-spun short fiber for hydrolysis-resistant and photoaging-resistant industry and preparation method thereof |
| CN110747531A (en) * | 2018-07-23 | 2020-02-04 | 慈溪市佳吉化纤有限公司 | Polyester staple fiber and preparation method thereof |
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