CN109750380B - Preparation method of polyester lamp box advertisement cloth - Google Patents
Preparation method of polyester lamp box advertisement cloth Download PDFInfo
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- CN109750380B CN109750380B CN201811615794.7A CN201811615794A CN109750380B CN 109750380 B CN109750380 B CN 109750380B CN 201811615794 A CN201811615794 A CN 201811615794A CN 109750380 B CN109750380 B CN 109750380B
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Abstract
The invention relates to a preparation method of a polyester lamp box advertising cloth, which is characterized in that modified polyester industrial yarns are warped, woven, rolled and laminated with a PVC film to prepare the polyester lamp box advertising cloth, the modified polyester industrial yarns are prepared by performing solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding on modified polyester melt, and the preparation method of the modified polyester before the solid-phase polycondensation tackifying comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol, and then carrying out esterification reaction and polycondensation reaction in sequence, wherein the relaxation heat treatment is to pass the modified polyester industrial yarn through a space with a certain temperature in a proper relaxation state, the proper relaxation state is to wind the modified polyester industrial yarn with an overfeed rate of 3.0-5.0%, and the certain temperature is 200-240 ℃. The preparation method is simple, the cost is low, and the prepared polyester light box advertising cloth has the advantages of good tensile strength, high peeling strength and low thermal shrinkage.
Description
Technical Field
The invention belongs to the technical field of modified polyester fibers, and relates to a preparation method of polyester lamp box advertising cloth.
Background
With the continuous progress of society and the increasing abundance of commodities, the advertising industry develops rapidly, and higher requirements are put forward on advertising media. The flexible lamp box cloth which appears in recent years has gradually replaced the hard materials such as neon lamps, plastic films, organic glass and the like which are dominant in advertising media, and becomes the preferred material for manufacturing the advertising lamp box. The flexible lamp box cloth has the advantages that the manufactured lamp box is bright in color, attractive, long in service life, convenient to transport and safe to use, the light-transmitting instant sticker can be pasted on the lamp box, heat transfer printing, super heat printing, computer portrait and the like can be carried out, the lamp box can be made into a large or super-large lamp box, the plane and the curved surface can be shaped randomly, and the lamp box is more striking than the lamp box made of other materials at night. Due to the fact that the development history of the lamp box cloth is short, the lamp box cloth is rapidly developed in production and application. Warp-knitted biaxial fabrics processed by biaxial warp knitting machines have been used in large quantities as base fabric materials for flexible light boxes due to the characteristics of good mechanical properties, simple process, short flow, high speed, low cost and the like.
The terylene has higher breaking strength and better breaking extensibility, and the fiber is not easy to deform under the action of small load, and has good wear resistance, strong light resistance, low thermal shrinkage and strong thermal stability. Although the price of the terylene is slightly higher than that of the polypropylene, the vinylon and the like, the polypropylene is easy to age and poor in light resistance, the vinylon is low in strength, and the service life of a finished product is short, so that the two materials are not suitable for being used as materials for manufacturing the lamp box cloth, and the price defect can be made up by the advantages of low consumption of the terylene, long service life of the finished product and the like. Other materials such as aramid, carbon fiber, glass fiber, etc. are either expensive or unsuitable in properties, such as glass fiber, which is brittle and can cause hydrolysis, cracking and creep after prolonged exposure to humid air. Therefore, the terylene is still the preferred raw material of the base cloth of the lamp box cloth.
As a common synthetic polymer material, PVC has excellent flame retardant property due to the fact that a main chain contains halogen atoms. Meanwhile, PVC has the characteristics of high strength, insulativity, good weather resistance, excellent geometric stability and the like, has strong resistance to an oxidant, a reducing agent and strong acid, and is low in price and wide in source, so that the PVC is widely applied. In the prior art, the polyester industrial yarn and the polyester industrial yarn are rolled to prepare the lamp box advertising cloth with good light transmission performance. The tensile breaking strength of the composite material mainly comprises the strength of reinforcing base cloth and the strength of a coating material, molten resin can easily enter gaps of a fabric under the action of pressure through calendering, the resin is well combined, a firmer bonding layer can be formed between the molten resin and yarns, the interface bonding of the molten resin and the yarns is enhanced, and the tensile strength is greatly improved. However, when the composite material is subjected to a large tearing force, the bonding effect between the layers is still poor, so that the tensile strength and the peel strength of the prepared lamp box advertising cloth cannot meet the actual use requirements.
In addition, the shrinkage rate is an important performance index of the industrial yarn, and is different from the reversible expansion and contraction phenomena of general solid substances, the chemical fiber is usually subjected to irreversible thermal shrinkage after being heated, and the shrinkage is more obvious when the chemical fiber is washed and ironed by hot water. Because the light box advertising cloth generally needs to be used at a high temperature for a long time, the expression of the shrinkage rate of the light box advertising cloth becomes an important evaluation index, and the heat shrinkage rate of the light box advertising cloth in the prior art is often higher.
Therefore, the development of the preparation method of the polyester lamp box advertising cloth with good tensile strength, high peeling strength and low thermal shrinkage rate has practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of the polyester lamp box advertising cloth with good tensile strength, high peel strength and low thermal shrinkage. According to the invention, the polyester is modified by 2,5,6, 6-tetramethyl-2, 5-heptanediol, so that the cavity free volume of the polyester molecules is increased, and the active groups of the urethane bonding layer molecules are diffused into fiber gaps in the heat treatment process by the increase of the cavity free volume to obtain good interface bonding, thereby improving the bonding effect between the fibers and the PVC film and greatly improving the tensile strength and the peeling strength.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of terylene lamp box advertisement cloth, which is characterized in that modified polyester industrial yarns are warped, woven and rolled and adhered with a PVC film to obtain the terylene lamp box advertisement cloth, the terylene lamp box advertisement cloth is a light-transmitting fabric, the industrial yarns are warped and then woven in a weaving mode, and the surface of the woven cloth is rolled and adhered with a thinner and more transparent PVC film A relaxation heat treatment process;
the modified polyester industrial yarn is prepared by performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding on a modified polyester melt;
the preparation method of the modified polyester before solid-phase polycondensation tackifying comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol, and then carrying out esterification reaction and polycondensation reaction in sequence;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment; the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:
according to the invention, polyester is modified by 2,5,6, 6-tetramethyl-2, 5-heptanediol, so that the tensile strength and peel strength of the prepared polyester lamp box advertising cloth are far higher than those of the polyester lamp box advertising cloth in the prior art, and the existence of tert-butyl in 2,5,6, 6-tetramethyl-2, 5-heptanediol can cause the change of the activity of a main chain, thereby changing the interaction force among chain units, and correspondingly changing the distance among the chain units to increase the free volume of a modified polyester cavity; compared with short-chain substituent groups (such as methyl, ethyl and the like), the tertiary butyl group occupies a larger spatial position, and a larger free volume is obtained in the molecular chain arrangement mode; compared with the long-branched-chain substituent, on one hand, the tertiary butyl group has the increased cavity free volume, the long-branched-chain substituent has the increased slit free volume, and on the other hand, the rigidity of the tertiary butyl group is higher than that of the long-branched-chain substituent, so that the entanglement among molecular chains is reduced, and the tertiary butyl group has more free volume than the long-branched-chain substituent in the arrangement mode of the molecular chains; meanwhile, the free volume of the cavity is larger than that of the slit, so that active groups in molecules of the polyurethane bonding layer can penetrate into the fiber and can be well combined with the interior of the polyester molecule, the bonding effect between the fiber and the PVC film is improved, and the tensile strength is greatly improved;
the relaxation heat treatment refers to that the modified polyester industrial yarn passes through a space with a certain temperature in a proper relaxation state;
the proper relaxation state means that the overfeed rate of winding is 3.0-5.0%;
the certain temperature is 200-240 ℃.
The shrinkage rate of the polyester industrial yarn is reduced by the mutual matching of the heat treatment temperature and the overfeed rate, when the fiber is subjected to heat treatment, macromolecular chains in an amorphous area of the fiber are easy to form folding chains, the further growth of crystal grains is facilitated, the crystallinity is increased at the moment, and the fiber can shrink a certain amount along with the increase of the crystallinity.
As a preferred technical scheme:
according to the preparation method of the polyester lamp box advertising cloth, the filament number of the modified polyester industrial yarn is 1.0-2.0 dtex, the breaking strength is more than or equal to 8.2cN/dtex, the linear density deviation rate is +/-1.5%, the breaking strength CV value is less than or equal to 3.0%, the elongation at break is 18.0-20.0%, the elongation at break CV value is less than or equal to 8.0%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.0-2.8%, and the network degree is (5-8) +/-2/m; the processing and mechanical properties of the modified polyester industrial yarn are equivalent to those of the polyester industrial yarn in the prior art;
the gram weight of the polyester light box advertising cloth is 300-400 g/m2The polyester lamp box advertising cloth has a certain light transmittance, light rays can be emitted from the inside to the outside of the lamp box, the longitudinal tensile strength is more than or equal to 160N/cm, the transverse tensile strength is more than or equal to 160N/cm, the peel strength is more than or equal to 10N/cm, and the using temperature range is within the range of 25-35 percentThe circumference is-30 to +60 ℃, the hydrostatic pressure resistance value is more than or equal to 50KPa, the hydrostatic pressure resistance value is the pressure value when the fabric begins to permeate under the action of continuously rising water pressure, the tensile strength and the peel strength of the polyester lamp box advertising cloth are far higher than those of the polyester lamp box advertising cloth in the prior art, mainly because the polyester lamp box advertising cloth is improved in material, 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment is introduced into the polyester molecular chain, the existence of tert-butyl in 2,5,6, 6-tetramethyl-2, 5-heptanediol can cause the change of the main chain mobility, therefore, the interaction force among the chain units is changed, the distance among the chain units is also correspondingly changed, and consequently, the free volume of the polymer cavity is increased, and the free volume of the cavity is increased, so that the molecular active groups such as-NH in the adhesion promoter of PVC can be realized.2OH and the like are easy to diffuse into fiber gaps in the heat treatment process to obtain good interface bonding, so that the bonding effect between the fibers and the PVC film is improved, and the tensile strength and the peel strength are improved to a certain extent.
In the preparation method of the polyester light box advertisement cloth, the 2,5,6, 6-tetramethyl-2, 5-heptanediol is synthesized by the following steps:
(1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1-1.2: 1.2-1.3: 2.0-3.0, reacting for 2-4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2-3: 10: 0.01-0.03, reacting at the temperature of 40-50 ℃ for 50-60 min, continuously introducing hydrogen during the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol.
According to the preparation method of the terylene lamp box advertisement cloth, the preparation steps of the modified polyester before solid phase polycondensation and tackifying are as follows:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding a catalyst, a delustering agent and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction end point is determined when the water distillate in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, wherein the pressure in the stage is stably pumped from normal pressure to below 500Pa in 30-50 min, the reaction temperature is 250-260 ℃, the reaction time is 30-50 min, then continuously pumping vacuum to perform the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to below 100Pa, the reaction temperature is 270-282 ℃, and the reaction time is 50-90 min.
According to the preparation method of the terylene lamp box advertisement cloth, the molar ratio of the terephthalic acid to the ethylene glycol to the 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1: 1.2-2.0: 0.03-0.05, and the addition amounts of the catalyst, the delustering agent and the stabilizer are 0.03-0.05 wt%, 0.20-0.25 wt% and 0.01-0.05 wt% (mass percentage) of the addition amount of the terephthalic acid respectively; the addition amount of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is not limited to the above, and a person skilled in the art can adjust the actual conditions, but the adjustment range is not too large, the excessive addition amount has too much damage to the regularity of the polyester macromolecular structure, has too much influence on the crystallinity and the mechanical property of the fiber, and is not beneficial to the production and application of the fiber, and the effect is not obvious if the addition amount is too low.
According to the preparation method of the terylene lamp box advertisement cloth, the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the flatting agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
According to the preparation method of the terylene lamp box advertisement cloth, the intrinsic viscosity of the modified polyester after solid-phase polycondensation and tackifying is 1.0-1.2 dL/g; the intrinsic viscosity can be adjusted within a proper range, but is not too high or too low, the spinnability is reduced when the intrinsic viscosity is too high, and the molecular weight of the polyester is too low when the intrinsic viscosity is too low, so that the requirement of industrial yarns cannot be met.
According to the preparation method of the polyester lamp box advertising cloth, the space with a certain temperature is a space between a pair of hot plates which are arranged in parallel and are not coplanar, and the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment; the length of the two hot plates is 3.0-4.0 m along the running direction of the modified polyester industrial yarn, and the two ends of the two hot plates are flush; when the modified polyester industrial yarn passes through the middle of the two hot plates, the distance between the modified polyester industrial yarn and the two hot plates is 5-10 mm.
According to the preparation method of the polyester lamp box advertising cloth, the distance between the last group of heat setting rollers and the winding roller is 300-400 mm; the distance between the two hot plates and the last group of heat setting rollers is 200-300 mm.
According to the preparation method of the polyester lamp box advertising cloth, the spinning process parameters of the modified polyester industrial yarns are as follows:
the technological parameters of stretching and heat setting are as follows:
the temperature of the rolling and bonding is 165-170 ℃, the pressure is 5-5.5 MPa, and the time is 75-90 s; the PVC film is located on the surfaces of two sides of the modified polyester industrial yarn woven fabric, and the thickness of the PVC film on one side is 0.10-0.12 mm.
The invention mechanism is as follows:
the invention improves the material of the polyester lamp box advertising cloth, introduces the 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment into the polyester molecular chain, improves the bonding effect between the fiber and the PVC film, and ensures that the tensile strength and the peeling strength are improved to a certain extent.
The macromolecular chains in the polymer are not completely tightly packed, and voids always exist among the macromolecular chains, and the void volume is the free volume. Since small molecules are allowed to penetrate into the polymer, voids are sufficiently large in the polymer or between the polymers, the permeability and diffusivity of the small molecules are related to the size of the voids (i.e., the size of free volume) in the polymer structure, and within a certain range, the larger the size of the free volume, the higher the permeability of the small molecules, and the better the diffusivity. The free volume is divided into a cavity free volume and a slit free volume, the cavity free volume has larger space size than the slit free volume, and the effect of the cavity free volume is more obvious than the effect of the slit free volume for improving the permeability of small molecules.
The size and type of free volume depends primarily on the structure of the polymer, and the primary factors affecting the polymer structure are steric hindrance, pendant group size, pendant group structure, and the like. When a certain position on the main chain of the polymer is substituted by a side group, the activity of the main chain is inevitably changed, so that the interaction force between chains is changed, the distance between the chains is also correspondingly changed, and consequently, the cohesive energy and the free volume are changed, and the polarity, the size, the length and the like of the substituent on the side chain of the polymer have certain influences on the rigidity of the molecular chain, the interaction between molecules and the free volume fraction of the polymer structure, so that the effects generated by different substituents are different, and the osmotic separation performance of the polymer is often different.
For glycol straight chain molecules such as ethylene glycol and butanediol, the C atoms on the main chain are arranged in a zigzag manner from top to bottom, and when the H atom on a certain methylene on the main chain is replaced by a methyl group (-CH)3) When in substitution, the C atoms on the side groups and the main chain C atoms are not in the same plane, so that four sp3 hybridized orbitals on the center C are respectively overlapped with empty orbitals on the four surrounding C atoms to form four completely same sigma bonds which are arranged in a regular tetrahedron, the four carbon atoms are respectively positioned at four vertexes of the regular tetrahedron, when three hydrogen of a methyl group is further substituted by the methyl group, the three hydrogen is equivalent to tert-butyl to form a larger tetrahedron structure, and compared with the molecular chain which is arranged in a zigzag manner, the molecular chain which is arranged in the regular tetrahedron manner has the advantages that the free volume of the empty hole is obviously increased, and the permeability and the diffusivity of small molecules can be obviously improved; while in the main chainWhen the H atom on a certain methylene is substituted by the long branched chain substituent, the slit free volume is mainly increased, the increase amplitude is small, the improvement effect on the permeability and diffusivity of the micromolecule is limited, and meanwhile, the long branched chain substituent has low rigidity, the molecular chains are easy to tangle, and the increase of the free volume is not facilitated.
According to the invention, 2,5,6, 6-tetramethyl-2, 5-heptanediol is introduced into the polyester molecular chain, so that the bonding effect between the fiber and the PVC film is obviously improved, the tensile strength and the peel strength of the prepared polyester light box advertising cloth are improved to a certain extent, and the activity of the main chain is changed due to the existence of tert-butyl in the 2,5,6, 6-tetramethyl-2, 5-heptanediol, so that the interaction force among chain units is changed, and the distance among the molecular chain units is correspondingly changed, thereby increasing the free volume of the modified polyester cavity. Compared with short-chain substituent groups (such as methyl, ethyl and the like), the tertiary butyl group occupies a larger spatial position, and a larger free volume is obtained in the molecular chain arrangement mode; compared with the long-branched-chain substituent, on one hand, the tertiary butyl group has the increased free volume of a cavity, the long-branched-chain substituent has the increased free volume of a slit, and on the other hand, the rigidity of the tertiary butyl group is higher than that of the long-branched-chain substituent, so that entanglement among molecular chains is reduced, and the tertiary butyl group has more free volume than the long-branched-chain substituent in the arrangement mode of the molecular chains. Meanwhile, the free volume of the cavity is larger than that of the slit, so that the free volume of the cavity is increased, and the active groups of molecules in the adhesion promoter of the PVC, such as-NH2OH and the like are easy to diffuse into fiber gaps in the heat treatment process to obtain good interface bonding, so that the bonding effect between the fibers and the PVC film is improved, and the tensile strength and the peel strength are improved to a certain extent.
In addition, in the post-processing and stretching process of the fiber, the fiber orientation degree is greatly increased and has a certain degree of crystallinity due to the effect of mechanical stress, so that the fiber elongation and the total deformation work are reduced, but in the stretching process, although the deformation of the fiber is mostly plastic deformation which can not be recovered at normal temperature, and is often fixed due to crystallization, a part of the fiber is recovered due to relaxation of tensile stress at room temperature, or is subjected to shrinkage recovery in subsequent heat treatment, and the shrinkage recovery, namely the shrinkage rate of the fiber in the application process of the fiber greatly influences the performance (such as safety performance, durability performance and the like) of the fiber, if the fiber is used as a tire cord, the tire is repeatedly stretched, compressed and bent during the use process of the tire, so that the tire is heated, and the tire cord is subjected to shrinkage creep deformation, but the cutter cord may delaminate when the cord is excessively shrunk, further, the tire is disassembled, which brings great danger to the safety of the tire. At present, in the spinning and stretching process of the polyester industrial yarn, in order to reduce the shrinkage rate of the polyester industrial yarn as much as possible, after a plurality of stretching processes, tension heat setting (the heat setting roller is adopted to set the fiber under certain tension) is often needed, after tension heat setting, overfeeding with the overfeeding rate of 1-2% is wound, through tension heat setting of the fiber, under the conditions of certain temperature and certain tension, the activity capability of a polymer chain segment is improved, the intermolecular combination is tighter, the average size and the crystallinity of crystal grains of the fiber are improved, so as to reduce the shrinkage rate of the fiber, but because the fiber has certain high elastic deformation in the stretching process, the elastic recovery can be generated under the condition that the tension is reduced, therefore, the speed of a winding head must be lower than the speed of the last group of heat setting rollers, namely, a certain overfeeding rate is needed, so as to ensure that the stretched yarn obtains low tension shrinkage to a certain degree, obtaining satisfactory finished product quality and package, preventing package edge collapse caused by overlarge tension, controlling the overfeeding rate within a certain range (1-2%), and having adverse effect on the finished product quality and the package when the overfeeding rate is overlarge. Although the shrinkage can be reduced to a certain extent by tension heat setting and overfeeding, in the tension heat setting process, the length of the fiber is fixed and can not be changed, so that the folding of macromolecular chains is inhibited, the growth rate of crystal grains is limited, the crystallization defect (the crystallinity is increased less) is caused, and the crystallization defect can not be reduced by controlling the overfeeding alone, so that when the prepared fiber is subjected to heat treatment in the application process, the macromolecular chains and chain segments of the fiber have higher mobility, the de-orientation effect is easy to generate, and the fiber is subjected to a certain amount of shrinkage (the shrinkage is larger).
In fact, the heat setting of the fibers is not only tension heat setting but also relaxation heat setting. The relaxation heat setting is also called as free shrinkage heat setting, namely, the fiber is subjected to heat treatment at a certain temperature under the condition of no tension or small tension, the fiber can be freely shrunk under the condition of the relaxation heat setting, macromolecular chains in an amorphous region easily form folding chains, and further growth of crystal grains is facilitated. At present, the relaxation heat setting is mainly used for carrying out heat setting treatment on polyester short fibers, the heat treatment temperature is low (about 130 ℃), the heat treatment time is long, and the relaxation heat setting is difficult to be suitable for filament production. According to the invention, the overfeed rate of polyester filament bundle winding is increased to 3-5% in the processing process of the polyester industrial yarn, and meanwhile, a pair of hot plates which are arranged in parallel up and down are arranged between the last heat setting roller and the winding roller in the FDY equipment, so that the polyester filament bundle passes through the two hot plates, the crystallinity of the polyester filament bundle is improved, the high elastic deformation in the polyester filament bundle is recovered, the internal stress of the polyester filament bundle is relaxed by a certain amount, and the shrinkage recovery of the polyester industrial yarn when the polyester industrial yarn is subjected to heat treatment in the application process is reduced. The heat treatment temperature and the higher overfeed rate are matched with each other to reduce the shrinkage rate of the polyester industrial yarn, when the fiber is subjected to heat treatment, macromolecular chains in an amorphous region of the fiber are easy to form folding chains, further growth of crystal grains is facilitated, the crystallinity is increased at the moment, and the fiber can shrink a certain amount along with the increase of the crystallinity. In addition, the heat treatment temperature, the length of the hot plate and the distance between the tows and the hot plate are matched, so that the defect that the relaxation heat treatment in the prior art is not suitable for filament production is overcome, the completeness of fiber crystallization is improved, the stability of fiber size is improved, and the thermal shrinkage in the application process is reduced.
Has the advantages that:
(1) according to the preparation method of the polyester lamp box advertising cloth, the modified component 2,5,6, 6-tetramethyl-2, 5-heptanediol is introduced into the polyester, so that the adhesion between the fibers and the PVC film is remarkably improved, and the tensile strength and the peel strength of the prepared polyester lamp box advertising cloth are improved to a certain extent;
(2) according to the preparation method of the polyester lamp box advertising cloth, the heat treatment temperature is matched with the high overfeeding rate, so that the integrity of fiber crystallization is improved, and the thermal shrinkage in the application process is reduced;
(3) the preparation method of the polyester lamp box advertising cloth has the advantages of simple process, low cost and great application prospect;
(4) the polyester lamp box advertising cloth prepared by the invention has good light transmission, excellent mechanical property and wide application range.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1:1:1.2:2.0, reacting for 2 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2:10:0.01, reacting for 50min at the temperature of 40 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as the formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol with a molar ratio of 1:1.2:0.03 into slurry, adding antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the esterification reaction temperature is 250 ℃, the esterification reaction end point is determined when the distilled amount of water in the esterification reaction reaches 93% of a theoretical value, and the adding amounts of the antimony trioxide, the titanium dioxide and the triphenyl phosphate are respectively 0.03 wt%, 0.20 wt% and 0.02 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 480Pa within 30min, controlling the reaction temperature to be 250 ℃ and the reaction time to be 31min, then continuing pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 100Pa, control the reaction temperature to be 270 ℃ and control the reaction time to be 50min, thus obtaining the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.0 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 4.9% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 200 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 3.0m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, the distance between the polyester filament bundle and the two hot plates is 5mm when the polyester filament bundle passes through the middle of the two hot plates, the distance between the last group of heat setting rollers and the winding rollers is 300mm, and the distance between the two hot plates and the last group of heat setting rollers is 200 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the filament number of the prepared modified polyester industrial yarn is 2.0dtex, the breaking strength is 9.0cN/dtex, the linear density deviation rate is 0.2%, the breaking strength CV value is 2.4%, the elongation at break is 20.0%, the elongation at break CV value is 6.4%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.7%, and the network degree is 10/m;
(3) warping and weaving the modified polyester industrial yarns to obtain modified polyester industrial yarn woven cloth, and calendering and attaching PVC films to the surfaces of the two sides of the modified polyester industrial yarn woven cloth to obtain the polyester lamp box advertisement cloth; wherein the weaving is completed by a biaxial warp knitting machine, the fabric of the modified polyester industrial yarn woven fabric has the longitudinal density of 3.6 coils/cm, the transverse density of 7.1 coils/cm and the surface density of 38.0g/m2Before rolling and attaching, the base coat is also carried out, wherein the base coat is formed by coating pasty PVC (mixture of pasty PVC, diethyl phthalate, zinc tin stabilizer and polyisocyanurate of toluene diisocyanate in a weight ratio of 100:50:1:0.3 at 30 ℃, the type of the pasty PVC is P440, and the degree of polymerization is 1500) containing adhesive on modified polyester industrial yarn woven fabric, pre-curing the mixture at 140 ℃ for 35s, carrying out PVC rolling and attaching on the modified polyester industrial yarn woven fabric after pre-curing treatment, wherein the temperature of rolling and attaching is 165 ℃, the pressure is 5MPa, the time is 75s, and the thickness of a single-side PVC film is equal to that of a single-side PVC filmIs 0.10 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 300g/m2The transmittance is 25 percent, the longitudinal tensile strength is 160N/cm, the transverse tensile strength is 160N/cm, the peel strength is 10N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is 50KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Comparative example 1
A preparation method of polyester advertising cloth is basically the same as that of example 1, except that 2,5,6, 6-tetramethyl-2, 5-heptanediol is not added in the step (1), the step (2) does not undergo a relaxation heat treatment process, the winding speed is 2680m/min, the winding overfeed rate is 1.47%, the filament number of the prepared polyester industrial yarn is 2.0dtex, the breaking strength is 8.3cN/dtex, the linear density deviation rate is 0.2%, the breaking strength CV value is 2.4%, the breaking elongation is 26.0%, the breaking elongation CV value is 6.4%, the dry heat shrinkage rate under the conditions of × 0.01.01 cN/dtex at 190 ℃ of × 15min is 3.7%, the network degree is 10/m, and the gram weight of the prepared polyester advertising cloth is 300g/m2The transmittance is 23 percent, the longitudinal tensile strength is 136N/cm, the transverse tensile strength is 148N/cm, the peel strength is 7N/cm, the use temperature range is-30 to +60 ℃, and the hydrostatic pressure resistance value is 42 KPa.
Comparative example 2
The preparation method of the polyester advertising cloth is basically the same as that of the example 1, except that 2,5,6, 6-tetramethyl-2, 5-heptanediol is not added in the step (1), the prepared polyester industrial yarn has the filament number of 2.0dtex, the breaking strength of 8.6cN/dtex, the linear density deviation rate of 0.2 percent, the breaking strength CV value of 2.4 percent, the elongation at break of 26.0 percent, the elongation at break CV value of 6.4 percent, the dry heat shrinkage rate under the condition of 350.01 cN/dtex at 190 ℃ of × 15min of × 0.01.15 min of 2.7 percent and the network degree of 10 counts/m, and the gram weight of the prepared polyester advertising cloth is 300g/m2The transmittance is 23 percent, the longitudinal tensile strength is 132N/cm, the transverse tensile strength is 145N/cm, the peel strength is 7N/cm, the use temperature range is-30 to +60 ℃, and the hydrostatic pressure resistance value is 43 KPa.
Comparative example 3
A kind ofThe preparation method of the polyester advertising cloth is basically the same as that of the embodiment 1, and is different from the step (2) in that the relaxation heat treatment process is not carried out, the winding speed is 2680m/min, the winding overfeed rate is 1.47%, the filament number of the prepared polyester industrial yarn is 2.0dtex, the breaking strength is 8.2cN/dtex, the linear density deviation rate is 0.2%, the breaking strength CV value is 2.4%, the breaking elongation is 26.0%, the breaking elongation CV value is 6.4%, the dry heat shrinkage rate under the condition of × 15min × 0.01.01 cN/dtex at 190 ℃ is 4.1%, the network degree is 10/m, and the gram weight of the prepared polyester advertising cloth is 300g/m2The transmittance is 23 percent, the longitudinal tensile strength is 145N/cm, the transverse tensile strength is 149N/cm, the peel strength is 10N/cm, the use temperature range is-30 to +60 ℃, and the hydrostatic pressure resistance value is 50 KPa.
By comprehensively analyzing the example 1 and the comparative examples 1 to 3, the peeling strength of the polyester advertising cloth is remarkably improved by adding the 2,5,6, 6-tetramethyl-2, 5-heptanediol. 2,5,6, 6-tetramethyl-2, 5-heptanediol by increasing the void free volume of the polyester to make the molecular active group such as-NH in diethyl phthalate2OH and the like are easy to diffuse into fiber gaps in the heat treatment process, so that the adhesion between the fibers and the PVC film is improved, and the tensile strength and the peel strength are improved to a certain extent. The invention also improves the integrity of fiber crystallization and reduces the thermal shrinkage in the application process of the industrial yarn by the mutual matching of the heat treatment temperature and the higher overfeed rate. In addition, the addition of 2,5,6, 6-tetramethyl-2, 5-heptanediol and the relaxation heat treatment have little influence on other properties of the fiber and do not influence the processability and mechanical properties thereof.
Comparative example 4
The preparation method of the terylene advertisement cloth comprises the steps which are basically the same as the steps in the embodiment 1, and the difference is that the 1,2 dodecyl glycol is adopted to replace the 2,5,6, 6-tetramethyl-2, 5-heptanediol in the step (1), the filament number of the prepared polyester industrial yarn is 2.0dtex, the breaking strength is 8.3cN/dtex, the linear density deviation rate is 0.2%, the CV value of the breaking strength is 2.4%, the elongation at break is 26.0%, the CV value of the elongation at break is 6.4%, the dry heat shrinkage rate under the condition of ×.01cN/dtex at the temperature of 190 ℃ of × 15min is 4.1%, and the network degree is 10 & lt & gtm; the gram weight of the prepared terylene advertising cloth is 300g/m2The transmittance is 23 percent, the longitudinal tensile strength is 145N/cm, the transverse tensile strength is 142N/cm, the peel strength is 7N/cm, the use temperature range is-30 to +60 ℃, and the hydrostatic pressure resistance value is 38 KPa.
Compared with example 1, it can be seen that 2,5,6, 6-tetramethyl-2, 5-heptanediol is more favorable for improving the performance of the fiber than 1, 2-dodecyl diol containing long-branched substituents, mainly because the free volume increase of the tertiary butyl group in 2,5,6, 6-tetramethyl-2, 5-heptanediol is more void free volume on the one hand, and the free volume increase of the long-branched substituents in 1, 2-dodecyl diol is more slit free volume on the other hand, the rigidity of the tertiary butyl group in 2,5,6, 6-tetramethyl-2, 5-heptanediol is more rigid than the long-branched substituents in 1, 2-dodecyl diol, which reduces the entanglement between molecular chains, so that 2,5,6, 6-tetramethyl-2, 5-heptanediol is more rigid than 1, the 2-dodecyl glycol has more free volume in the arrangement mode of the polyester molecular chain, which is beneficial to leading the molecular active group such as-NH in the diethyl phthalate2OH and the like are diffused into fiber gaps in the heat treatment process, so that the adhesion between the fibers and the PVC film is improved, and the tensile strength and the peel strength of the polyester advertising cloth are improved to a certain extent.
Example 2
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1.1:1:1.2:2.3, reacting for 2 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2:10:0.01, reacting for 50min at the temperature of 45 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as the formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol with a molar ratio of 1:1.5:0.04 into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the temperature of the esterification reaction is 251 ℃, the end point of the esterification reaction is determined when the water distillation amount in the esterification reaction reaches 92% of a theoretical value, and the adding amounts of the ethylene glycol antimony, the titanium dioxide and the trimethyl phosphate are respectively 0.04 wt%, 0.22 wt% and 0.01 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to the absolute pressure of 500Pa within 30min, controlling the reaction temperature to be 252 ℃ and the reaction time to be 30min, then continuing to pump vacuum, and carrying out the polycondensation reaction in a high vacuum stage to further reduce the reaction pressure to the absolute pressure of 100Pa, control the reaction temperature to be 271 ℃ and control the reaction time to be 55min, thus obtaining the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.0 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 4.2% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 207 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 3.2m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the polyester filament bundle and the two hot plates is 6mm, the distance between the last group of heat setting rollers and the winding rollers is 311mm, and the distance between the two hot plates and the last group of heat setting rollers is 220 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the filament number of the prepared modified polyester industrial yarn is 1.5dtex, the breaking strength is 8.6cN/dtex, the linear density deviation rate is 0.8%, the breaking strength CV value is 2.7%, the elongation at break is 19.0%, the elongation at break CV value is 7.2%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.4%, and the network degree is 7/m;
(3) warping and weaving the modified polyester industrial yarns to obtain modified polyester industrial yarn woven cloth, and calendering and attaching PVC films to the surfaces of the two sides of the modified polyester industrial yarn woven cloth to obtain the polyester lamp box advertisement cloth; wherein the weaving is completed by a biaxial warp knitting machine, the fabric of the modified polyester industrial yarn woven fabric has the longitudinal density of 3.8 coils/cm, the transverse density of 7.3 coils/cm and the surface density of 42.0g/m2And performing primary coating before calendering and attaching, wherein the primary coating is to coat paste PVC (a mixture of paste PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanurate of toluene diisocyanate in a weight ratio of 100:60:2:2.0 at 50 ℃, the type of the paste PVC is P440, and the polymerization degree is 1500) containing an adhesive on the modified polyester industrial yarn woven fabric, perform pre-curing at 160 ℃ for 45s, perform PVC calendering and attaching on the modified polyester industrial yarn woven fabric after the pre-curing treatment, wherein the calendering and attaching temperature is 170 ℃, the pressure is 5.5MPa, the time is 90s, and the thickness of a single-side PVC film is 0.11 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 350g/m2Transmittance of 30%, longitudinal tensile strength of 168N/cm, transverse tensile strength of 168N/cm, peel strength of 10.5N/cm, and service temperatureThe degree range is-30 to +60 ℃, the hydrostatic pressure resistance value is 52KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Example 3
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1.2:1:1.25:2.0, reacting for 3 hours under the ice-bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.03, reacting for 50min at the temperature of 40 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as the formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry with the molar ratio of 1:1.8:0.035, adding antimony acetate, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 252 ℃, the esterification reaction end point is when the water distillation amount in the esterification reaction reaches 90% of a theoretical value, and the adding amounts of the antimony acetate, the titanium dioxide and the trimethyl phosphite are respectively 0.04 wt%, 0.23 wt% and 0.03 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, smoothly pumping the pressure in the low vacuum stage from normal pressure to the absolute pressure of 450Pa within 35min, controlling the reaction temperature to 253 ℃ and controlling the reaction time to 35min, then continuously pumping the vacuum to perform the polycondensation reaction in the high vacuum stage, further reducing the reaction pressure to the absolute pressure of 90Pa, controlling the reaction temperature to 274 ℃ and controlling the reaction time to 60min, and preparing the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.1 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 3.3% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 215 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 3.3m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, the distance between the polyester filament bundle and the two hot plates is 7mm when the polyester filament bundle passes through the middle of the two hot plates, the distance between the last group of heat setting rollers and the winding rollers is 335mm, and the distance between the two hot plates and the last group of heat setting rollers is 235 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the single filament number of the prepared modified polyester industrial yarn is 1.6dtex, the breaking strength is 8.7cN/dtex, the linear density deviation rate is 1.5%, the breaking strength CV value is 2.6%, the elongation at break is 18.8%, the elongation at break CV value is 6.8%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.2%, and the network degree is 8/m;
(3) warping and weaving the modified polyester industrial yarn to obtain modified polyester industrial yarn woven fabricCalendering and attaching PVC films on the surfaces of both sides of the industrial yarn woven fabric to obtain polyester lamp box advertising cloth; wherein the weaving is completed by a biaxial warp knitting machine, the fabric of the modified polyester industrial yarn woven fabric has the longitudinal density of 3.7 coils/cm, the transverse density of 7.2 coils/cm and the surface density of 40.0g/m2And performing primary coating before rolling and attaching, wherein the primary coating is to coat paste PVC (a mixture of paste PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanurate of toluene diisocyanate in a weight ratio of 100:55:1.5:1.2 at 30-50 ℃, the type of the paste PVC is P440, and the polymerization degree is 1500) containing an adhesive on the modified polyester industrial yarn woven fabric, pre-cure the mixture at 150 ℃ for 40s, and then perform PVC rolling and attaching on the pre-cured modified polyester industrial yarn woven fabric, wherein the rolling and attaching temperature is 168 ℃, the pressure is 5.2MPa, the time is 80s, and the thickness of the single-side PVC film is 0.11 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 380g/m2The transmittance is 28 percent, the longitudinal tensile strength is 170N/cm, the transverse tensile strength is 175N/cm, the peel strength is 11N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is 54KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Example 4
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1.2:1:1.3:2.5, reacting for 3 hours under the ice-bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2.5:10:0.02, reacting for 60min at the temperature of 45 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol with a molar ratio of 1:1.9:0.04 into slurry, adding antimony acetate, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 254 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 96% of a theoretical value, and the adding amounts of the antimony acetate, the titanium dioxide and the triphenyl phosphate are respectively 0.03 wt%, 0.25 wt% and 0.05 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to the absolute pressure of 410Pa within 40min, controlling the reaction temperature to be 255 ℃ and the reaction time to be 32min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to the absolute pressure of 95Pa, control the reaction temperature to be 275 ℃ and control the reaction time to be 70min, thus obtaining the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.2 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 4.8% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 222 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 3.4m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the polyester filament bundle and the two hot plates is 8mm, the distance between the last group of heat setting rollers and the winding rollers is 346mm, and the distance between the two hot plates and the last group of heat setting rollers is 250 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the filament number of the prepared modified polyester industrial yarn is 1.2dtex, the breaking strength is 8.7cN/dtex, the deviation rate of linear density is-1.5%, the CV value of the breaking strength is 2.7%, the elongation at break is 18.9%, the CV value of the elongation at break is 7.5%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.6%, and the network degree is 6/m;
(3) warping and weaving the modified polyester industrial yarns to obtain modified polyester industrial yarn woven cloth, and calendering and attaching PVC films to the surfaces of the two sides of the modified polyester industrial yarn woven cloth to obtain the polyester lamp box advertisement cloth; the weaving and priming coating process parameters are the same as example 1, the calendering and laminating temperature is 165 ℃, the pressure is 5.5MPa, the time is 90s, and the thickness of the single-side PVC film is 0.12 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 400g/m2The transmittance is 25 percent, the longitudinal tensile strength is 176N/cm, the transverse tensile strength is 176N/cm, the peel strength is 10.6N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is 54KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Example 5
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1:1:1.3:3.0, reacting for 4 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2.5:10:0.02, reacting at the temperature of 50 ℃ for 55min, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol with the molar ratio of 1:2.0:0.042 into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 256 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 99% of a theoretical value, and the adding amounts of the ethylene glycol antimony, the titanium dioxide and the trimethyl phosphite are respectively 0.03 wt%, 0.20 wt% and 0.04 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 490Pa within 45min, controlling the reaction temperature to 257 ℃ and the reaction time to 40min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 90Pa, control the reaction temperature to 277 ℃ and control the reaction time to 75min, thus obtaining the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.05 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 4.0% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 232 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 3.6m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the polyester filament bundle and the two hot plates is 8.5mm, the distance between the last group of heat setting rollers and the winding rollers is 368mm, and the distance between the two hot plates and the last group of heat setting rollers is 260 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the single filament number of the prepared modified polyester industrial yarn is 1.5dtex, the breaking strength is 8.5cN/dtex, the linear density deviation rate is 1.0%, the breaking strength CV value is 2.6%, the elongation at break is 18.8%, the elongation at break CV value is 6.8%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.5%, and the network degree is 7/m;
(3) warping and weaving the modified polyester industrial yarns to obtain modified polyester industrial yarn woven cloth, and calendering and attaching PVC films to the surfaces of the two sides of the modified polyester industrial yarn woven cloth to obtain the polyester lamp box advertisement cloth; the weaving and priming coating process parameters are the same as example 2, the calendering and laminating temperature is 168 ℃, the pressure is 5.2MPa, the time is 75s, and the thickness of the single-side PVC film is 0.11 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 320g/m2The transmittance is 30 percent, the longitudinal tensile strength is 168N/cm, the transverse tensile strength is 165N/cm, the peel strength is 10.5N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is 52KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Example 6
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1.1:1:1.2:3.0, reacting for 4 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.03, reacting for 60min at the temperature of 50 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as the formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol with the molar ratio of 1:1.2:0.05 into slurry, adding antimony trioxide, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 258 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 95% of a theoretical value, and the adding amounts of the antimony trioxide, the titanium dioxide and the trimethyl phosphate are respectively 0.04 wt%, 0.23 wt% and 0.01 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 430Pa within 35min, the reaction temperature of 258 ℃ and the reaction time of 40min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 94Pa, the reaction temperature of 280 ℃ and the reaction time of 80min to obtain the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.1 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 3.0% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 235 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 3.8m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the polyester filament bundle and the two hot plates is 9mm, the distance between the last group of heat setting rollers and the winding rollers is 384mm, and the distance between the two hot plates and the last group of heat setting rollers is 280 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the single filament number of the prepared modified polyester industrial yarn is 1.0dtex, the breaking strength is 8.2cN/dtex, the linear density deviation rate is 0.4%, the breaking strength CV value is 3.0%, the elongation at break is 18.0%, the elongation at break CV value is 8.0%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.0%, and the network degree is 3/m;
(3) warping and weaving the modified polyester industrial yarns to obtain modified polyester industrial yarn woven cloth, and calendering and attaching PVC films to the surfaces of the two sides of the modified polyester industrial yarn woven cloth to obtain the polyester lamp box advertisement cloth; the weaving and priming coating process parameters are the same as example 3, the calendering and laminating temperature is 165 ℃, the pressure is 5.5MPa, the time is 75s, and the thickness of the single-side PVC film is 0.12 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 400g/m2The transmittance is 35 percent, the longitudinal tensile strength is 176N/cm, the transverse tensile strength is 176N/cm, the peel strength is 11N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is 55KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Example 7
A preparation method of polyester lamp box advertisement cloth comprises the following specific steps:
(1) preparing modified polyester;
(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1.1.1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1.2:1:1.2:3.0, reacting for 3 hours under the ice-bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;
(1.1.2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.02, reacting at 42 ℃ for 55min, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as the formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol with a molar ratio of 1:2.0:0.05 into slurry, adding ethylene glycol antimony, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 260 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 91% of a theoretical value, and the adding amounts of the ethylene glycol antimony, the titanium dioxide and the triphenyl phosphate are respectively 0.05 wt%, 0.25 wt% and 0.05 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, smoothly pumping the pressure in the stage from normal pressure to the absolute pressure of 400Pa within 50min, controlling the reaction temperature to be 260 ℃ and the reaction time to be 50min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to the absolute pressure of 88Pa, control the reaction temperature to be 282 ℃ and control the reaction time to be 90min, thus obtaining the modified polyester;
(1.4) carrying out solid phase polycondensation tackifying on the modified polyester to obtain a modified polyester melt with the intrinsic viscosity of 1.15 dL/g;
(2) melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding the modified polyester melt to prepare modified polyester industrial yarns;
the relaxation heat treatment is that the polyester filament bundle with 5.0% of winding overfeed rate passes through a space between a pair of hot plates which are arranged in parallel and are not coplanar and have the temperature of 240 ℃, the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment, the length of the two hot plates is 4.0m along the running direction of the polyester filament bundle, the two ends of the two hot plates are flush, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the polyester filament bundle and the two hot plates is 10mm, the distance between the last group of heat setting rollers and the winding rollers is 400mm, and the distance between the two hot plates and the last group of heat setting rollers is 300 mm;
the spinning process parameters are as follows:
the technological parameters of stretching and heat setting are as follows:
the filament number of the prepared modified polyester industrial yarn is 1.2dtex, the breaking strength is 8.3cN/dtex, the deviation rate of linear density is-0.5%, the CV value of the breaking strength is 2.9%, the elongation at break is 18.1%, the CV value of the elongation at break is 8.0%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.8%, and the network degree is 4/m;
(3) warping and weaving the modified polyester industrial yarns to obtain modified polyester industrial yarn woven cloth, and calendering and attaching PVC films to the surfaces of the two sides of the modified polyester industrial yarn woven cloth to obtain the polyester lamp box advertisement cloth; the weaving and priming coating process parameters are the same as example 1, the calendering and laminating temperature is 165 ℃, the pressure is 5.5MPa, the time is 90s, and the thickness of the single-side PVC film is 0.10 mm.
The gram weight of the finally prepared terylene lamp box advertisement cloth is 330g/m2Transmittance of 28%The longitudinal tensile strength is 169N/cm, the transverse tensile strength is 168N/cm, the peel strength is 10.8N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is 52KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
Claims (10)
1. The preparation method of the terylene lamp box advertisement cloth is characterized by comprising the following steps: warping, weaving, calendering and laminating the modified polyester industrial yarn with a PVC film to obtain the polyester lamp box advertising cloth;
the modified polyester industrial yarn is prepared by performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding on a modified polyester melt;
the preparation method of the modified polyester before solid-phase polycondensation tackifying comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol, and then carrying out esterification reaction and polycondensation reaction in sequence;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment; the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:
the relaxation heat treatment refers to that the modified polyester industrial yarn passes through a space with a certain temperature in a proper relaxation state;
the proper relaxation state means that the overfeed rate of winding is 3.0-5.0%;
the space with a certain temperature is a space between a pair of hot plates which are arranged in parallel and are not coplanar, and the hot plates are positioned between the last group of heat setting rollers and the winding rollers in the FDY equipment;
the certain temperature is 200-240 ℃.
2. The preparation method of the terylene lamp box advertisement cloth according to claim 1, characterized in that the modified polyester industrial yarn has a filament number of 1.0-2.0 dtex, a breaking strength of not less than 8.2cN/dtex, a linear density deviation rate of +/-1.5%, a breaking strength CV value of not more than 3.0%, an elongation at break of 18.0-20.0%, an elongation at break CV value of not more than 8.0%, a dry heat shrinkage rate of 2.0-2.8% under the conditions of 190 ℃ x 15min x 0.01cN/dtex, and a network degree of (5-8) ± 2/m;
the gram weight of the polyester light box advertising cloth is 300-400 g/m2The light transmittance is 25-35%, the longitudinal tensile strength is more than or equal to 160N/cm, the transverse tensile strength is more than or equal to 160N/cm, the peel strength is more than or equal to 10N/cm, the use temperature range is-30 to +60 ℃, the hydrostatic pressure resistance value is more than or equal to 50KPa, and the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure.
3. The method for preparing terylene lamp box advertisement cloth according to claim 1, wherein the synthesis steps of the 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:
(1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1-1.2: 1.2-1.3: 2.0-3.0, reacting for 2-4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(2) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2-3: 10: 0.01-0.03, reacting at the temperature of 40-50 ℃ for 50-60 min, continuously introducing hydrogen during the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol.
4. The preparation method of the terylene lamp box advertisement cloth according to claim 3, wherein the preparation steps of the modified polyester before solid phase polycondensation and tackifying are as follows:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding a catalyst, a delustering agent and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction end point is determined when the water distillate in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, wherein the pressure in the stage is stably pumped from normal pressure to below 500Pa in 30-50 min, the reaction temperature is 250-260 ℃, the reaction time is 30-50 min, then continuously pumping vacuum to perform the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to below 100Pa, the reaction temperature is 270-282 ℃, and the reaction time is 50-90 min.
5. The preparation method of the terylene lamp box advertisement cloth according to claim 4, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1:1.2 to 2.0:0.03 to 0.05, and the addition amounts of the catalyst, the matting agent and the stabilizer are 0.03 to 0.05 wt%, 0.20 to 0.25 wt% and 0.01 to 0.05 wt% of the addition amount of the terephthalic acid, respectively.
6. The method for preparing the terylene lamp box advertisement cloth according to claim 5, wherein the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the delustering agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
7. The preparation method of the polyester light box advertisement cloth as claimed in claim 6, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.0-1.2 dL/g.
8. The preparation method of the terylene lamp box advertisement cloth according to claim 1, wherein the length of the two hot plates is 3.0-4.0 m along the running direction of the modified polyester industrial yarn, and the two ends of the two hot plates are flush; when the modified polyester industrial yarn passes through the middle of the two hot plates, the distance between the modified polyester industrial yarn and the two hot plates is 5-10 mm.
9. The preparation method of the terylene lamp box advertisement cloth according to claim 8, wherein the distance between the last group of heat setting rollers and the winding roller is 300-400 mm; the distance between the two hot plates and the last group of heat setting rollers is 200-300 mm.
10. The method for preparing the terylene lamp box advertisement cloth according to claim 1, wherein the spinning process parameters of the modified polyester industrial yarn are as follows:
the technological parameters of stretching and heat setting are as follows:
the temperature of the rolling and bonding is 165-170 ℃, the pressure is 5-5.5 MPa, and the time is 75-90 s; the PVC film is located on the surfaces of two sides of the modified polyester industrial yarn woven fabric, and the thickness of the PVC film on one side is 0.10-0.12 mm.
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