CN109719925B - Flame-retardant polyester canvas and preparation method thereof - Google Patents

Flame-retardant polyester canvas and preparation method thereof Download PDF

Info

Publication number
CN109719925B
CN109719925B CN201811614100.8A CN201811614100A CN109719925B CN 109719925 B CN109719925 B CN 109719925B CN 201811614100 A CN201811614100 A CN 201811614100A CN 109719925 B CN109719925 B CN 109719925B
Authority
CN
China
Prior art keywords
modified polyester
reaction
temperature
trimethylsilyl
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811614100.8A
Other languages
Chinese (zh)
Other versions
CN109719925A (en
Inventor
杨超明
王山水
汤方明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hengli Chemical Fiber Co Ltd
Original Assignee
Jiangsu Hengli Chemical Fiber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Hengli Chemical Fiber Co Ltd filed Critical Jiangsu Hengli Chemical Fiber Co Ltd
Priority to CN201811614100.8A priority Critical patent/CN109719925B/en
Publication of CN109719925A publication Critical patent/CN109719925A/en
Application granted granted Critical
Publication of CN109719925B publication Critical patent/CN109719925B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a terylene flame retardant canvas and a preparation method thereof, wherein the preparation method comprises the following steps: calendering the surface of the modified polyester industrial yarn woven fabric and attaching a PVC film to the surface of the modified polyester industrial yarn woven fabric to obtain the polyester flame-retardant canvas; the modified polyester industrial yarn is prepared by solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding of 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, dihydric alcohol with trimethylsilyl lateral group and 2-carboxyethyl phenyl hypophosphorous acid, and then carrying out esterification reaction and polycondensation reaction in sequence; the relaxation heat treatment means that the modified polyester filament bundle passes through a space of 200-240 ℃ in a state that the overfeed rate of winding is 3.0-5.0%. The preparation method disclosed by the invention is simple in process and low in cost, and the prepared product is excellent in mechanical property, the adhesive strength is 50-60N/cm, and the peel strength is more than or equal to 8.5N/cm.

Description

Flame-retardant polyester canvas and preparation method thereof
Technical Field
The invention belongs to the technical field of modified polyester fibers, and relates to a terylene flame retardant canvas and a preparation method thereof.
Background
Since the advent of polyethylene terephthalate (PET) fibers, the production of which has become the world's synthetic fibers, has been rapidly developed due to its excellent properties. Because the polyester fiber has a series of excellent performances such as high breaking strength, high elastic modulus, moderate rebound resilience, excellent heat setting performance, good heat and light resistance, good acid, alkali and corrosion resistance and the like, and the fabric prepared from the polyester fiber has the advantages of good crease resistance, good stiffness and smoothness and the like, the polyester fiber is widely applied to various fields. In China, polyester with the content of polyethylene terephthalate exceeding 85 percent is called terylene. The polyester filament yarn has excellent performance, is one of the fastest-developing products with the highest yield in synthetic fibers, and has wide application in decoration, industry and textile and clothing industry.
With the development and progress of society, industries such as steel, mining and cement are developed vigorously, and the requirement of the industries on a conveying belt is huge, particularly the requirement on a flame-retardant conveying belt. At present, the flame-retardant conveying belt mainly uses common polyester yarns or nylon yarns as a canvas framework, the flame retardant property of the canvas is improved by rubberizing on the surface of the canvas, but the rubberizing cannot completely soak the canvas layer, and even if the canvas is completely wrapped by the rubberizing, the canvas is a combustible material, so that an ideal flame retardant material cannot be obtained.
The current flame-retardant conveyor belt generally mainly comprises a belt core (formed by one or more layers of canvas covered with rubber through calendering), an upper covering layer, a lower covering layer and edge rubber. The upper covering layer and the lower covering layer are generally PVC films, molten PVC can easily enter the gaps of the fabric under the action of pressure through calendering, so that the PVC is well combined, meanwhile, a firmer bonding layer can be formed between the molten PVC and the yarns, the interface bonding of the molten PVC and the yarns is enhanced, and the tensile strength is further improved. Meanwhile, because the synthetic fiber (polyester industrial yarn) has few end heads, smooth surface and low chemical activity, an adhesive bond is difficult to establish on an interface, in order to improve the viscosity of the PVC film and the fiber, impregnation is generally needed before calendering, and impregnation liquid generally contains the components such as-NH capable of being combined with fiber end groups2Polar groups such as-OH and-COOH. The most common impregnation liquid at present is RFL (resorcinol-formaldehyde resin) impregnation liquid which is suitable for treating cotton, rayon, nylon, polyester or glass fiber fabrics, because the RF resin contains active hydrogen atoms, which can generate crosslinking action with PVC and can generate-NH in fibers2-OH bonding.
However, the finished product of the polyester fiber is a partially crystallized supermolecular structure, molecular chains of the crystallized parts of the polyester fiber are parallel to each other and mostly in a trans-conformation, while an amorphous region is mostly in a cis-conformation, the molecular arrangement of the polyester fiber is quite tight, and an active group in an impregnation liquid is difficult to permeate into the fiber and then is combined with a terminal group in the polyester fiber, so that the adhesion force between the polyester fiber and a PVC (polyvinyl chloride) film is influenced to a great extent, and the peeling strength of the flame-retardant conveyor belt (polyester flame-retardant canvas) is influenced.
In addition, the shrinkage rate is an important performance index of the polyester industrial yarn, and is different from the reversible expansion and contraction phenomena of general solid substances, the chemical fiber is heated and then is subjected to irreversible thermal shrinkage, and the shrinkage is more obvious when the chemical fiber is washed and ironed by hot water. Industrial yarns (such as cords, conveyor belts and conveyor belts) are used at high temperature for a long time, the shrinkage rate performance becomes an important evaluation index, and the industrial yarns in the prior art have high thermal shrinkage rate, so that the thermal stability of fabrics prepared from the industrial yarns is poor.
Therefore, the research on the method for enhancing the interaction force between the fibers and the PVC and reducing the thermal shrinkage rate of the polyester industrial yarns so as to prepare the polyester flame-retardant canvas with high peeling strength and low thermal shrinkage rate has practical significance.
Disclosure of Invention
The invention aims to overcome the defects of low peel strength and high thermal shrinkage rate of polyester flame-retardant canvas in the prior art, and provides the polyester flame-retardant canvas with high peel strength and low thermal shrinkage rate and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the terylene flame retardant canvas comprises the steps of preparing the terylene flame retardant canvas by calendaring and attaching a PVC film on the surface of modified polyester industrial yarn woven cloth, wherein the terylene flame retardant canvas is a fabric with flame retardant property, after the flame retardant industrial yarn is warped and woven into the woven cloth by a weaving mode, the preparation method of the terylene flame retardant canvas is basically the same as the preparation method of the terylene flame retardant canvas in the prior art, except for the material of industrial yarn and the processing process of the industrial yarn, the industrial yarn material of the terylene flame retardant canvas in the prior art is common flame retardant polyester, the industrial yarn material of the terylene flame retardant canvas is modified flame retardant polyester, the heat setting procedure is followed by the winding procedure in the processing procedure of the industrial yarn of the terylene flame retardant canvas in the prior art, in the processing process of the industrial yarn of the terylene flame retardant canvas, a relaxation heat treatment process is additionally arranged between a heat setting process and a winding 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, dihydric alcohol with trimethylsilyl lateral group and 2-carboxyethyl phenyl hypophosphorous acid, and then carrying out esterification reaction and polycondensation reaction in sequence;
the structural formula of the dihydric alcohol with the trimethylsilyl lateral group is as follows:
Figure BDA0001925458770000031
in the formula, R is-CH2-、-CH(CH3) -or-C ((CH)3)2)-；
The relaxation heat treatment refers to that the modified polyester tows pass 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 ℃.
In the process of preparing the polyester flame-retardant canvas by the polyester industrial yarns, RFL impregnation liquid is generally needed to be soaked, the RFL impregnation liquid has the function of improving the binding force between the fabric and the PVC membrane, the invention uses the dihydric alcohol with the trimethylsilyl group (3-trimethylsilyl-1, 2-propylene glycol, 3-trimethylsilyl-3-methyl-1, 2-propylene glycol or 3-trimethylsilyl-3, 3-dimethyl-1, 2-propylene glycol) to modify the polyester, and the dihydric alcohol with the trimethylsilyl group can obviously increase the space free volume of the modified polyester, particularly the dihydric alcohol with the trimethylsilyl groupThe existence of trimethylsilyl in the radical diol can cause the change of the activity of the main chain, thereby changing the interaction force among chain units, correspondingly changing the distance among the molecular chain units, increasing the free volume of the hollow of the modified polyester, and leading the active groups of molecules in the RFL dipping solution, such as-NH2OH and COOH can be easily diffused 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, the bonding strength is greatly improved, the peel strength of the terylene flame retardant canvas is further improved, and the peel strength of the terylene flame retardant canvas can also be improved by increasing the free volume of cavities if other impregnation liquids are adopted.
The invention also reduces the shrinkage rate of the polyester industrial yarn by the mutual matching of the heat treatment temperature and the overfeed rate so as to ensure the performance of the polyester industrial yarn product, when the fiber is subjected to heat treatment, macromolecular chains in an amorphous region of the fiber are easy to form folding chains, which is beneficial to the further growth of crystal grains, the crystallinity is increased, 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 flame retardant canvas, the synthesis steps of the dihydric alcohol with the trimethylsilyl lateral group are as follows:
(1) mixing raw materials of alkene, peracetic acid and dichloromethane according to a molar ratio of 1: 5-10: 10-15, reacting for 5-8 hours at the temperature of 35-40 ℃, stirring during the reaction, removing a solvent after the reaction is finished, and purifying and refining to obtain the trimethylsilyl propylene epoxide;
(2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating the mixture to 80-85 ℃ in a water bath under the stirring condition, carrying out heat preservation reaction for l 0-15 min, cooling the mixture to room temperature after the reaction is finished, and carrying out neutralization, distillation, separation and purification to obtain dihydric alcohol with a trimethylsilyl lateral group, wherein the concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to the water is 1: 20-40 at the beginning of the reaction, and the mass of the concentrated sulfuric acid accounts for 0.1-0.15% of the total mass of the mixture;
the structural formula of the dihydric alcohol with the trimethylsilyl lateral group is shown in the specification, wherein R is-CH (CH)3) -and-C ((CH)3)2) When said starting alkenes correspond to 3-trimethylsilyl-3-methylpropene and 3-trimethylsilyl-3, 3-dimethylpropene.
According to the preparation method of the terylene flame retardant canvas, 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, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with trimethylsilyl lateral groups 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 distillation amount in the esterification reaction reaches more than 90% of the 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 flame retardant canvas, the molar ratio of the terephthalic acid to the glycol with the side trimethylsilyl group to the ethylene glycol to the 2-carboxyethylphenylphosphinic acid to the glycol with the side trimethylsilyl group is 1: 1.2-2.0: 0.03-0.05: 0.02-0.03, and the addition amounts of the catalyst, the delustering agent and the stabilizer are respectively 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. The addition amount of the diol with the trimethylsilyl group side group is not limited to the above, and a person skilled in the art can adjust the actual condition, but the adjustment range is not too large, the excessive addition amount has too large damage to the regularity of the macromolecular structure of the polyester, the influence on the crystallinity and the mechanical property of the fiber is too large, the production and the application of the fiber are not facilitated, and the effect (the effect of improving the bonding strength) is not obvious if the addition amount is too low.
According to the preparation method of the terylene flame retardant canvas, 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 dacron flame-retardant canvas, the intrinsic viscosity of the modified polyester after solid-phase polycondensation and tackifying is 1.0-1.2 dL/g.
According to the preparation method of the terylene flame retardant canvas, 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 tows, and the two ends of the two hot plates are flush; when the modified polyester tows pass through the middle of the two hot plates, the distance between the modified polyester tows and the two hot plates is 5-10 mm; the heat treatment method has the advantages that the energy can be obtained through macromolecular rearrangement by controlling the temperature of the hot plate (namely the certain temperature), the length of the hot plate is controlled to ensure enough crystallization time, the distance between a tow and the hot plate is controlled to ensure the heat treatment efficiency, the three are mutually cooperated, the integrity of fiber crystallization is improved, and further the thermal shrinkage in the fiber application process is reduced, wherein the temperature of the hot plate is too low, and the sufficient energy can be hardly obtained through macromolecular rearrangement; the structure formed originally can be damaged when the temperature of the hot plate is too high; the length of the hot plate is too short, the crystallization time is too short, the integrity of fiber crystallization is influenced, and the thermal shrinkage rate of the fiber is influenced; the length of the hot plate is too long, the efficiency is reduced, and equipment waste is caused; the direct contact between the tows and the hot plate is easily caused when the distance between the tows and the hot plate is too small; the thermal efficiency is reduced due to the overlarge distance between the tows and the hot plate;
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 flame retardant canvas, the spinning process parameters of the modified polyester industrial yarn are as follows:
Figure BDA0001925458770000051
the technological parameters of stretching and heat setting are as follows:
Figure BDA0001925458770000061
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 the two sides of the modified polyester industrial yarn woven fabric, and the thickness of the PVC film on one side is 0.40-0.75 mm.
The preparation process of the present invention is not limited thereto, and only one possible technical solution is exemplified herein. The specific process parameters are not limited to the above and can be adjusted according to actual requirements.
The invention also provides the polyester flame-retardant canvas prepared by the preparation method of the polyester flame-retardant canvas, which has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment, 2-carboxyethyl phenyl hypophosphorous acid and a dihydric alcohol chain segment with a trimethylsilyl lateral group.
As a preferred technical scheme:
according to the polyester flame-retardant canvas, the filament number of the modified polyester industrial yarn is 3.0-5.0 dtex, the breaking strength is more than or equal to 7.5cN/dtex, the linear density deviation rate is +/-1.5%, the breaking strength CV value is less than or equal to 3.0%, the breaking elongation is 18.0-20.0%, and the breaking elongation CV value is less than or equal to 8.0%, the mechanical properties of the prepared fiber are not reduced by introducing the dihydric alcohol with the trimethylsilyl group side group, compared with the prior art, the dry heat shrinkage rate of the modified polyester industrial yarn under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.5-3.3%, the network degree is (5-8) +/-2/m, the LOI is 30-34, the dry heat shrinkage rate of the low-shrinkage type polyester industrial yarn in the prior art under the test condition is 3.5-4.3%, and the comparison shows that the invention obviously reduces the heat shrinkage rate of the polyester industrial yarn;
the gram weight of the terylene flame retardant canvas is 500-800 g/m2The flame burning time is less than or equal to 1.5s, the flameless burning time is less than or equal to 2.5s, the bonding strength is 50-60N/cm, the peeling strength is more than or equal to 8.5N/cm, the longitudinal tensile strength is more than or equal to 281N/cm, the transverse tensile strength is more than or equal to 285N/cm, the longitudinal elongation at break is 6.3-6.5%, the transverse elongation at break is 5.6-6.0%, the use temperature range is-30 ℃ to +60 ℃, the hydrostatic pressure resistance value is more than or equal to 90KPa, the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure, the numerical value of the friction resistance value is more than or equal to 3000 times, the numerical value of the friction resistance value is the friction times when the fabric just starts to change under the action of continuous friction, the bonding strength, the peeling strength and the tensile strength of the dacron flame retardant canvas are far higher than those of the dacron flame retardant canvas in the prior art, mainly because the, the diol chain segment with trimethylsilyl lateral group is introduced into the polyester molecular chain, the existence of trimethylsilyl in the diol with trimethylsilyl lateral group can cause the change of the activity of the main chain, thereby changing the interaction force among chain units, and correspondingly changing the distance among molecular chain units, consequently causing the increase of the free volume of polymer cavities, and the increase of the free volume of the cavities can lead the active groups of molecules in the RFL dipping solution, such as-NH2and-OH and the like are diffused 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 bonding strength, the peeling strength and the tensile strength are improved to a certain extent.
The invention mechanism is as follows:
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.
The invention obviously improves the bonding strength of the polyester flame-retardant canvas by introducing the dihydric alcohol with the trimethylsilyl lateral group into a polyester molecular chain, and the structural formula of the dihydric alcohol with the trimethylsilyl lateral group is as follows:
Figure BDA0001925458770000081
in the formula, R is-CH2- (diols with trimethylsilyl side group being 3-trimethylsilyl-1, 2-propanediol), -CH (CH)3) - (diols with trimethylsilyl side groups being 3-trimethylsilyl-3-methyl-1, 2-propanediol) or-C ((CH)3)2) - (the diol having trimethylsilyl side groups is 3-trimethylsilyl-3, 3-dimethyl-1, 2-propanediol);
for ethylene glycol straight chain molecules, the C atoms on the main chain are arranged in a zigzag arrangement 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 substituted, the C atoms of the substituents are not in the same plane as the main chain C atoms, so that the center C isThe four sp3 hybridized orbitals are respectively overlapped with empty orbitals on four surrounding C atoms to form four completely same sigma bonds which are arranged in a regular tetrahedron, four carbon atoms are respectively positioned at four vertexes of the regular tetrahedron, when three hydrogen of a methyl group is further replaced by a methyl group or a trimethylsilyl group, a larger tetrahedron structure can be formed, compared with molecular chains arranged in a zigzag manner, the molecular chains arranged in the regular tetrahedron shape have the advantages that the free volume of the empty hole is greatly increased, the permeability and the diffusivity of small molecules can be obviously improved, in addition, the bond length of the carbon-silicon bond in the trimethylsilyl group is larger than that of the carbon-carbon bond, the atoms can rotate freely, and the free volume of the empty hole can be further increased; when the H atom on a certain methylene on the main chain is replaced 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 the 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.
The existence of trimethylsilyl in the diol with trimethylsilyl lateral groups 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 molecular chain units, so that the free volume of the hollow cavity of the polyester is increased. Compared with short-branched-chain substituent groups (such as methyl groups, ethyl groups and the like), the trimethylsilyl 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 increased rigidity of the trimethylsilyl group is greater than that of the long-branched-chain substituent, so that the entanglement among molecular chains is reduced, and therefore, the longer-branched-chain substituent of the trimethylsilyl group has more free volume in the arrangement mode of the molecular chains. The increase of the free volume of the cavity enables the molecule active group such as-NH in the RFL dipping solution2OH and COOH can be diffused 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 bonding strength, the peeling strength and the tensile strength are improved to a certain extent.
In addition, the invention also adjusts the processing technology of the polyester industrial yarn to reduce the heat shrinkage rate of the polyester industrial yarn;
in the post-processing and stretching process of the fiber, due to the action of mechanical stress, the fiber orientation degree is greatly increased and has certain crystallinity, so that the fiber elongation and the total deformation work are reduced, but in the stretching process, although most of the deformation generated by the fiber is plastic deformation which can not be recovered at normal temperature, the deformation is often fixed due to crystallization, but part of the deformation is recovered due to the relaxation of tensile stress at room temperature or is subjected to shrinkage recovery in subsequent heat treatment, 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 and the like) of the fiber, if the fiber is used as a tire cord, the tire cord is repeatedly stretched, compressed and bent in the use process of the tire, so that the tire is heated, the tire cord is shrunk and creeps, but the cutter cord is likely to delaminate when the tire 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) the preparation method of the terylene flame retardant canvas has simple process and low cost, improves the cavity free volume of the polyester by introducing the dihydric alcohol with the trimethylsilyl lateral group into the polyester, and obviously improves the bonding strength of the canvas by matching with the subsequent RFL dipping process;
(2) according to the preparation method of the terylene flame retardant canvas, the heat treatment temperature is matched with the higher overfeed rate, so that the integrity of fiber crystallization is improved, and the thermal shrinkage in the application process is reduced;
(3) the terylene flame retardant canvas has the advantages of good bonding strength, good mechanical property and wide application prospect.
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.
Figure BDA0001925458770000111
Example 1
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and 3-trimethylsilyl-1, 2-propanediol with the molar ratio of 1:1.2:0.03:0.02 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 normal pressure, the esterification reaction temperature is 250 ℃, the esterification reaction endpoint is determined when the distilled water amount in the esterification reaction reaches 95% 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 0.01 wt% of the adding amount of the terephthalic acid;
(1.2) 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 absolute pressure of 480Pa within 40min, controlling the reaction temperature to be 250 ℃ 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 absolute pressure of 80Pa, control the reaction temperature to be 270 ℃ and control the reaction time to be 50min, wherein the number average molecular weight of the prepared modified polyester is 24000 and the molecular weight distribution index is 1.9;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.0dL/g, the relaxation heat treatment means that the polyester filament bundle with 5 percent 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, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the heat setting roller and the two hot plates is 5mm, the distance between the last group of heat setting rollers and the winding roller 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 temperature of each zone of the screw is 290 ℃; the temperature of the box body is 295 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 75 percent; the air speed of the cross air blow is 0.5 m/s; the winding speed is 3268 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 480 m/min; the temperature of one roller is 23 ℃; the two-roll speed is 500 m/min; the temperature of the two rollers is 80 ℃; the three-roller speed is 1800 m/min; the temperature of the three rollers is 100 ℃; the four-roll speed is 2800 m/min; the temperature of the four rollers is 200 ℃; the speed of the five rollers is 2800 m/min; the temperature of the five rollers is 200 ℃; the speed of the six rollers is 3440 m/min; the temperature of the six rollers is 150 ℃;
the filament number of the modified polyester industrial yarn is 3.0dtex, the breaking strength is 8.4cN/dtex, the deviation rate of linear density is-1.3%, the CV value of the breaking strength is 2.5%, the elongation at break is 18.0%, the CV value of the elongation at break is 7.2%, the dry heat shrinkage rate under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.5%, the network degree is 3/m, and the LOI is 30;
(3) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving is carried out by adopting a biaxial warp knitting machine, the longitudinal density of the modified polyester industrial yarn woven cloth is 3.8 coils/cm, the transverse density is 7.3 coils/cm, and the surface density is 42.0g/m2Performing primary coating before calendering and attaching, wherein the primary coating refers to coating pasty PVC (a mixture of pasty PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanurate of toluene diisocyanate in a weight ratio of 100:50:1:0.3 at 30 ℃) containing an adhesive on modified polyester industrial yarn woven fabric, pre-curing the mixture at 140 ℃ for 35s, and performing PVC calendering and attaching on the pre-cured modified polyester industrial yarn woven fabric at 165 ℃ under 5.0MPa for 75 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.4 mm.
The flame-retardant polyester canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layerThe gram weight of the flame-retardant canvas is 500g/m2The flame burning time is 1.2s, the flameless burning time is 2.0s, the adhesive strength is 50N/cm, the peel strength is 8.5N/cm, the longitudinal tensile strength is 281N/cm, the transverse tensile strength is 287N/cm, the longitudinal elongation at break is 6.3%, the transverse elongation at break is 5.8%, the use temperature range is-30 ℃ to +60 ℃, the hydrostatic resistance value is 90KPa, the hydrostatic resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the number of times of friction resistance is 3000 times, and the number of times of friction resistance is the number of times of the fabric just beginning to change under the action of continuous friction.
Comparative example 1
The preparation method of the terylene flame retardant canvas is basically consistent with the preparation method of the terylene flame retardant canvas in the embodiment 1, except that 3-trimethylsilyl-1, 2-propylene glycol is not added in the step 1.1, the monofilament titer of the prepared terylene industrial yarn is 3.0dtex, the breaking strength is 8.5cN/dtex, the linear density deviation rate is-1.3%, the breaking strength CV value is 2.5%, the breaking elongation is 18.0%, the breaking elongation CV value is 7.5%, the dry heat shrinkage rate under the conditions of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex is 2.5%, the network degree is 3/m, and the LOI is 30;
under the same preparation conditions as example 1, the gram weight of the polyester flame retardant canvas prepared from the polyester industrial yarn is 500g/m2The flame burning time is 1.2s, the flameless burning time is 2.0s, the adhesive strength is 32N/cm, the peel strength is 6.1N/cm, the longitudinal tensile strength is 262N/cm, the transverse tensile strength is 265N/cm, the longitudinal elongation at break is 6.5%, the transverse elongation at break is 5.7%, the use temperature range is-20 ℃ to +50 ℃, the hydrostatic resistance value is 64KPa, the hydrostatic resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the numerical value of the friction resistance is 2000 times, and the numerical value of the friction resistance is the friction times of the fabric just beginning to change under the action of continuous friction. As can be seen by comparison with example 1, the 3-trimethylsilyl-1, 2-propanediol of the present invention increases the void free volume of the polyester, which increases the molecular active groups such as-NH-in diethyl phthalate during subsequent processing2OH and COOH in the heat treatment processThe PVC film can diffuse into fiber gaps to obtain good interface bonding, so that the bonding effect between the fibers and the PVC film is improved, and the bonding strength, the peeling strength and the tensile strength are improved to a certain extent.
Comparative example 2
The preparation method of the terylene flame retardant canvas is basically consistent with the example 1, except that 1, 2-dodecyl glycol is adopted to replace 3-trimethylsilyl-1, 2-propanediol in the step (1.3), and the gram weight of the terylene flame retardant canvas prepared from the terylene industrial yarn is 500g/m under the same preparation condition as the example 12The flame burning time is 1.2s, the flameless burning time is 2.0s, the adhesive strength is 34N/cm, the peel strength is 6.2N/cm, the longitudinal tensile strength is 240N/cm, the transverse tensile strength is 241N/cm, the longitudinal elongation at break is 6.3%, the transverse elongation at break is 5.8%, the use temperature range is-20 ℃ to +50 ℃, the hydrostatic resistance value is 57KPa, the hydrostatic resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the numerical value of the friction resistance is 2000 times, and the numerical value of the friction resistance is the friction times of the fabric just beginning to change under the action of continuous friction. In comparison with example 1, it can be seen that the increased void free volume of 3-trimethylsilyl-1, 2-propanediol of the present invention is more favorable for molecular active groups such as-NH in diethyl phthalate during subsequent processing than for slit free volume2OH and COOH can be diffused 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 bonding strength, the peeling strength and the tensile strength are improved to a certain extent.
Example 2
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and 3-trimethylsilyl-1, 2-propylene glycol with a molar ratio of 1:1.4:0.032:0.022 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 0.2MPa, the esterification reaction temperature is 255 ℃, the esterification reaction end point is the end point when the distilled amount of water in the esterification reaction reaches 95% of a theoretical value, and the adding amounts of the ethylene glycol antimony, the titanium dioxide and the triphenyl phosphate are respectively 0.035 wt%, 0.22 wt% and 0.02 wt% of the adding amount of the terephthalic acid;
(1.2) 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 500Pa within 44min, controlling the reaction temperature to be 252 ℃ and the reaction time to be 32min, then continuing to pump the vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to the absolute pressure of 90, control the reaction temperature to be 270 ℃ and control the reaction time to be 55min, wherein the number average molecular weight of the prepared modified polyester is 24800 and the molecular weight distribution index is 1.9;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.0dL/g, the relaxation heat treatment means that the polyester filament bundle with 5 percent 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 hot plate and the hot plate is 6mm, the distance between the last group of heat setting rollers and the winding roller 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 temperature of each zone of the screw is 290 ℃; the temperature of the box body is 295 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 75 percent; the air speed of the cross air blow is 0.5 m/s; the winding speed is 3268 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 480 m/min; the temperature of one roller is 23 ℃; the two-roll speed is 500 m/min; the temperature of the two rollers is 80 ℃; the three-roller speed is 1800 m/min; the temperature of the three rollers is 100 ℃; the four-roll speed is 2800 m/min; the temperature of the four rollers is 200 ℃; the speed of the five rollers is 2800 m/min; the temperature of the five rollers is 200 ℃; the speed of the six rollers is 3440 m/min; the temperature of the six rollers is 150 ℃;
the filament number of the modified polyester industrial yarn is 3.0dtex, the breaking strength is 8.2cN/dtex, the linear density deviation rate is 1.3%, the breaking strength CV value is 2.6%, the elongation at break is 18.0%, 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 2.6%, the network degree is 3/m, and the LOI is 31;
(3) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving is carried out by adopting a biaxial warp knitting machine, the longitudinal density of the modified polyester industrial yarn woven cloth is 3.6 coils/cm, the transverse density is 7.1 coils/cm, and the surface density is 38.0g/m2Performing primary coating before calendering and attaching, wherein the primary coating refers to coating pasty PVC (a mixture of pasty PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanurate of toluene diisocyanate with the weight ratio of 100:60:2:2.0 at 50 ℃, the type of the pasty PVC is P440, and the polymerization degree is 1500) containing an adhesive on modified polyester industrial yarn woven fabric, pre-curing the mixture at 160 ℃ for 45s, and performing PVC calendering and attaching on the pre-cured modified polyester industrial yarn woven fabric at 165 ℃ under 5.2MPa for 75 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.4 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 500g/m2The flame combustion time is 1.3s, the flameless combustion time is 2.0s, the adhesive strength is 52N/cm, the peel strength is 8.6N/cm, the longitudinal tensile strength is 282N/cm, the transverse tensile strength is 285N/cm, the longitudinal elongation at break is 6.3%, the transverse elongation at break is 5.6%, the use temperature range is-30 ℃ to +60 ℃, the hydrostatic pressure resistance value is 90KPa, the hydrostatic pressure resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, and the friction resistance value is 3000 timesThe number of times of abrasion resistance is the number of times of abrasion when the fabric begins to change under the action of continuous abrasion.
Example 3
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing dihydric alcohol with trimethylsilyl lateral groups;
(1.1.1) mixing 3-trimethylsilyl-3-methylpropene, peracetic acid and dichloromethane according to the molar ratio of 1:5:10, reacting for 5 hours at the temperature of 35 ℃, stirring during the reaction, removing the solvent after the reaction is finished, and purifying and refining to obtain trimethylsilyl propylene epoxide;
(1.1.2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating the mixture in water bath to 80 ℃ under the condition of stirring, preserving the heat for reaction for 10min, cooling the mixture to room temperature after the reaction is finished, and neutralizing, distilling, separating and purifying the mixture to obtain the dihydric alcohol with the trimethylsilyl lateral group shown in the formula (I), wherein R in the formula (I) is-CH (CH)3) The concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to water is 1:20 when the reaction starts, and the mass of the concentrated sulfuric acid accounts for 0.1% of the mass sum of the mixture;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethylphenylhypophosphorous acid and dihydric alcohol with trimethylsilyl lateral groups in a molar ratio of 1:1.5:0.035:0.023 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 0.3MPa, the temperature of the esterification reaction is 255 ℃, 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 ethylene glycol antimony, the titanium dioxide and the trimethyl phosphate 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 a low vacuum stage under the condition of negative pressure, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 440Pa within 38min, the reaction temperature is 251 ℃ and the reaction time is 33min, then continuously pumping vacuum to carry out the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 100Pa, the reaction temperature is 272 ℃ and the reaction time is 60min, and the number average molecular weight of the prepared modified polyester is 25000 and the molecular weight distribution index is 2.0;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.1dL/g, the relaxation heat treatment means that the polyester filament bundle with 3.5 percent 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, when the polyester filament bundle passes through the middle of the two hot plates, the distance between the hot plate and the hot plate is 7mm, the distance between the last group of heat setting rollers and the winding roller is 335mm, and the distance between the hot plates and the last group of heat setting rollers is 235 mm;
the spinning process parameters are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 297 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 80%; the air speed of the cross air blow is 0.6 m/s; the winding speed is 3300 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 500 m/min; the first roller temperature is 25 ℃; the two-roll speed is 700 m/min; the temperature of the two rollers is 90 ℃; the three-roller speed is 2000 m/min; the temperature of the three rollers is 120 ℃; the four-roller speed is 3200 m/min; the temperature of the four rollers is 220 ℃; the speed of the five rollers is 3000 m/min; the temperature of the five rollers is 220 ℃; the speed of the six rollers is 3420 m/min; the temperature of the six rollers is 170 ℃;
the modified polyester industrial yarn has the filament number of 3.5dtex, the breaking strength of 8.2cN/dtex, the linear density deviation rate of 1.3 percent, the breaking strength CV value of 2.7 percent, the elongation at break of 19.0 percent, the elongation at break CV value of 7.4 percent, the dry heat shrinkage rate of 2.7 percent under the condition of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex, the network degree of 3/m and the LOI of 32;
(3) weaving modified polyester industrial yarn into cloth and then modifyingThe surface of the modified polyester industrial yarn woven fabric is calendered and attached with a PVC film to prepare the polyester flame-retardant canvas with a 1/1 plain weave structure, wherein the weaving is carried out by adopting a biaxial warp knitting machine, the longitudinal density of the modified polyester industrial yarn woven fabric is 3.8 coils/cm, the transverse density is 7.3 coils/cm, and the surface density is 42.0g/m2Performing primary coating before calendering and attaching, wherein the primary coating refers to coating pasty PVC (a mixture of pasty PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanurate of toluene diisocyanate in a weight ratio of 100:55:1.5:1.2 at 40 ℃, the type of the pasty PVC is P440, and the polymerization degree is 1500) containing an adhesive on modified polyester industrial yarn woven fabric, pre-curing the mixture at 150 ℃ for 40s, and performing PVC calendering and attaching on the modified polyester industrial yarn woven fabric subjected to the pre-curing treatment, wherein the calendering and attaching temperature is 165 ℃, the pressure is 5.5MPa, and the time is 75 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.6 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 600g/m2The flame burning time is 1.3s, the flameless burning time is 2.2s, the adhesive strength is 52N/cm, the peel strength is 8.2N/cm, the longitudinal tensile strength is 286N/cm, the transverse tensile strength is 290N/cm, the longitudinal elongation at break is 6.3%, the transverse elongation at break is 5.6%, the use temperature range is-20 ℃ to +60 ℃, the hydrostatic resistance value is 92KPa, the hydrostatic resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the number of the friction resistance value is 3100 times, and the number of the friction resistance value is the number of times of the fabric just beginning to change under the action of continuous friction.
Example 4
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing dihydric alcohol with trimethylsilyl lateral groups;
(1.1.1) mixing 3-trimethylsilyl-3-methylpropene, peracetic acid and dichloromethane according to the molar ratio of 1:10:15, reacting for 8 hours at the temperature of 40 ℃, stirring during the reaction, removing the solvent after the reaction is finished, and purifying and refining to obtain trimethylsilyl propylene epoxide;
(1.1.2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating the mixture in water bath to 85 ℃ under the condition of stirring, preserving the heat for reaction for 15min, cooling the mixture to room temperature after the reaction is finished, and neutralizing, distilling, separating and purifying the mixture to obtain the dihydric alcohol with the trimethylsilyl lateral group shown in the formula (I), wherein R in the formula (I) is-CH (CH)3) The concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to water is 1:40 when the reaction starts, and the mass of the concentrated sulfuric acid accounts for 0.15% of the mass sum of the mixture;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with a trimethylsilyl lateral group in a molar ratio of 1:1.5:0.04:0.024 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 255 ℃, the esterification reaction end point 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 acetate, the titanium dioxide and the trimethyl phosphite are respectively 0.04 wt%, 0.25 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 a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to absolute pressure of 460Pa within 30min, controlling the reaction temperature to be 253 ℃, controlling the reaction time to be 35min, then continuously pumping vacuum, and carrying out the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to absolute pressure of 88Pa, the reaction temperature is 274 ℃, the reaction time is 65min, the number average molecular weight of the prepared modified polyester is 25500, and the molecular weight distribution index is 2.2;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.1dL/g, the relaxation heat treatment means that the polyester filament bundle with the winding overfeed rate of 3.3 percent 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 hot plate and the hot plate is 8mm, the distance between the last group of heat setting rollers and the winding roller is 346mm, and the distance between the hot plates and the last group of heat setting rollers is 250 mm;
the spinning process parameters are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 297 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 80%; the air speed of the cross air blow is 0.6 m/s; the winding speed is 2650 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 500 m/min; the first roller temperature is 25 ℃; the two-roll speed is 700 m/min; the temperature of the two rollers is 90 ℃; the three-roller speed is 2000 m/min; the temperature of the three rollers is 120 ℃; the four-roller speed is 3200 m/min; the temperature of the four rollers is 220 ℃; the speed of the five rollers is 3000 m/min; the temperature of the five rollers is 220 ℃; the speed of the six rollers is 2740 m/min; the temperature of the six rollers is 170 ℃;
the modified polyester industrial yarn has the filament number of 3.5dtex, the breaking strength of 8.0cN/dtex, the linear density deviation rate of 1.3 percent, the breaking strength CV value of 2.8 percent, the elongation at break of 19.0 percent, the elongation at break CV value of 7.4 percent, the dry heat shrinkage rate of 2.7 percent under the conditions of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex, the network degree of 5/m and the LOI of 32;
(3) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving and priming process parameters are the same as those of the example 1, the calendering and attaching temperature is 165 ℃, the pressure is 5.5MPa, and the time is 75 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.6 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 600g/m2The flaming combustion time is 1.3s, the flameless combustion time is 2.3s, and the viscosity is highThe combined strength is 53N/cm, the peel strength is 8.3N/cm, the longitudinal tensile strength is 287N/cm, the transverse tensile strength is 290N/cm, the longitudinal elongation at break is 6.3%, the transverse elongation at break is 5.6%, the use temperature range is-20 ℃ to +60 ℃, the hydrostatic pressure resistance value is 93KPa, the hydrostatic pressure resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the friction resistance value is 3100 times, and the friction resistance value is the friction times of the fabric just beginning to change under the action of continuous friction.
Example 5
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing dihydric alcohol with trimethylsilyl lateral groups;
(1.1.1) mixing 3-trimethylsilyl-3-methylpropene, peracetic acid and dichloromethane according to the molar ratio of 1:10:10, reacting for 6 hours at the temperature of 36 ℃, stirring during the reaction, removing the solvent after the reaction is finished, and purifying and refining to obtain trimethylsilyl propylene epoxide;
(1.1.2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating the mixture in water bath to 84 ℃ under the condition of stirring, preserving the heat for reaction for 12min, cooling the mixture to room temperature after the reaction is finished, and neutralizing, distilling, separating and purifying the mixture to obtain the dihydric alcohol with the trimethylsilyl lateral group shown in the formula (I), wherein R in the formula (I) is-CH (CH)3) The concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to water is 1:30 when the reaction starts, and the mass of the concentrated sulfuric acid accounts for 0.14% of the mass sum of the mixture;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with a trimethylsilyl lateral group in a molar ratio of 1:1.5:0.04:0.026 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 260 ℃, the esterification reaction end point 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 acetate, the titanium dioxide and the trimethyl phosphite are respectively 0.05 wt%, 0.20 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 a low vacuum stage under the negative pressure condition, smoothly pumping the pressure in the stage from normal pressure to absolute pressure of 470Pa within 42min, at the reaction temperature of 255 ℃ for reaction time of 36min, then continuing to pump vacuum, and carrying out the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to absolute pressure of 92Pa, the reaction temperature is 274 ℃, the reaction time is 70min, the number average molecular weight of the prepared modified polyester is 26300, and the molecular weight distribution index is 2.4;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.2dL/g, the relaxation heat treatment means that the polyester filament bundle with the winding overfeed rate of 3.3 percent 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 heat setting roller and the two hot plates is 8.5mm, the distance between the last group of heat setting rollers and the winding roller 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 temperature of each area of the screw is 310 ℃; the temperature of the box body is 300 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 80%; the air speed of the cross air blow is 0.6 m/s; the winding speed is 2650 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 500 m/min; the temperature of one roller is 26 ℃; the two-roll speed is 800 m/min; the temperature of the two rollers is 90 ℃; the three-roller speed is 2200 m/min; the temperature of the three rollers is 120 ℃; the four-roller speed is 3200 m/min; the temperature of the four rollers is 220 ℃; the speed of the five rollers is 3200 m/min; the temperature of the five rollers is 230 ℃; the speed of the six rollers is 2740 m/min; the temperature of the six rollers is 200 ℃;
the modified polyester industrial yarn has the filament number of 4.0dtex, the breaking strength of 7.9cN/dtex, the linear density deviation rate of 1.4 percent, the breaking strength CV value of 2.8 percent, the elongation at break of 19.0 percent, the elongation at break CV value of 7.4 percent, the dry heat shrinkage rate of 2.8 percent under the conditions of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex, the network degree of 5/m and the LOI of 32;
(3) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving and priming process parameters are the same as those of the example 2, the calendering and attaching temperature is 170 ℃, the pressure is 5.2MPa, and the time is 80 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.65 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 700g/m2The flame burning time is 1.5s, the flameless burning time is 2.3s, the adhesive strength is 55N/cm, the peel strength is 8.3N/cm, the longitudinal tensile strength is 287N/cm, the transverse tensile strength is 290N/cm, the longitudinal elongation at break is 6.3%, the transverse elongation at break is 5.6%, the use temperature range is-30 ℃ to +50 ℃, the hydrostatic resistance value is 95KPa, the hydrostatic resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the number of the friction resistance value is 3200 times, and the number of the friction resistance value is the number of times of the fabric just beginning to change under the action of continuous friction.
Example 6
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing dihydric alcohol with trimethylsilyl lateral groups;
(1.1.2) mixing 3-trimethylsilyl-3, 3-dimethylpropene, peracetic acid and dichloromethane according to the molar ratio of 1:8:12, reacting for 5 hours at the temperature of 40 ℃, stirring during the reaction, removing the solvent after the reaction is finished, and purifying and refining to obtain trimethylsilyl propylene epoxide;
(1.1.2) epoxidation of Water, concentrated sulfuric acid and Trisilyl propeneMixing the materials, heating to 85 deg.C with water bath under stirring, keeping the temperature for reaction for 10min, cooling to room temperature after reaction, neutralizing, distilling, separating and purifying to obtain diol with trimethylsilyl side group shown in formula (I), wherein R in formula (I) is-C ((CH)3)2) The concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to water is 1:25 when the reaction starts, and the mass of the concentrated sulfuric acid accounts for 0.12% of the mass sum of the mixture;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with a trimethylsilyl lateral group in a molar ratio of 1:1.6:0.042:0.027 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 255 ℃, the esterification reaction endpoint is determined when the distilled water amount in the esterification reaction reaches 95% of a theoretical value, and the adding amounts of the antimony acetate, the titanium dioxide and the trimethyl phosphate are respectively 0.03-wt%, 0.20 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 46min, the reaction temperature of 258 ℃ and the reaction time of 38min, 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 95Pa, the reaction temperature of 275 ℃ and the reaction time of 80min, wherein the number average molecular weight of the prepared modified polyester is 26700 and the molecular weight distribution index is 2.1;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.2dL/g, the relaxation heat treatment means that the polyester filament bundle with 3.2 percent 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 hot plate and the two hot plates is 9mm, the distance between the last group of heat setting rollers and the winding roller 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 temperature of each area of the screw is 310 ℃; the temperature of the box body is 300 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 80%; the air speed of the cross air blow is 0.6 m/s; the winding speed is 3330 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 500 m/min; the temperature of one roller is 26 ℃; the two-roll speed is 800 m/min; the temperature of the two rollers is 90 ℃; the three-roller speed is 2200 m/min; the temperature of the three rollers is 120 ℃; the four-roller speed is 3200 m/min; the temperature of the four rollers is 220 ℃; the speed of the five rollers is 3200 m/min; the temperature of the five rollers is 230 ℃; the speed of the six rollers is 3440 m/min; the temperature of the six rollers is 200 ℃;
the modified polyester industrial yarn has the filament number of 4.0dtex, the breaking strength of 7.8cN/dtex, the linear density deviation rate of 1.4 percent, the breaking strength CV value of 2.8 percent, the elongation at break of 20.0 percent, the elongation at break CV value of 7.4 percent, the dry heat shrinkage rate of 2.9 percent under the conditions of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex, the network degree of 5/m and the LOI of 33;
(3) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving and priming process parameters are the same as those of the example 1, the calendering and attaching temperature is 170 ℃, the pressure is 5.2MPa, and the time is 80 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.65 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 700g/m2The flaming combustion time was 1.5s, the flameless combustion time was 2.3s, the adhesive strength was 56N/cm, the peel strength was 8.5N/cm, the longitudinal tensile strength was 287N/cm, the transverse tensile strength was 295N/cm, the longitudinal elongation at break was 6.3%, the transverse elongation at break was 5.6%,the service temperature range is-30 ℃ to +50 ℃, the hydrostatic pressure resistance value is 96KPa, the hydrostatic pressure resistance value is the pressure value when the fabric starts to permeate under the action of continuously rising water pressure, the friction resistance number value is 3200 times, and the friction resistance number value is the friction number when the fabric starts to change under the action of continuous friction.
Example 7
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing dihydric alcohol with trimethylsilyl lateral groups;
(1.1.1) mixing 3-trimethylsilyl-3, 3-dimethylpropene, peracetic acid and dichloromethane according to the molar ratio of 1:10:10, reacting for 6 hours at the temperature of 35 ℃, stirring during the reaction, removing the solvent after the reaction is finished, and purifying and refining to obtain trimethylsilyl propylene epoxide;
(1.1.2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating the mixture in water bath to 80 ℃ under the condition of stirring, preserving the heat for reaction for 15min, cooling the mixture to room temperature after the reaction is finished, and neutralizing, distilling, separating and purifying the mixture to obtain the dihydric alcohol with the trimethylsilyl lateral group shown in the formula (I), wherein R in the formula (I) is-C ((CH)3)2) The concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to water is 1:35 when the reaction starts, and the mass of the concentrated sulfuric acid accounts for 0.14% of the mass sum of the mixture;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with a trimethylsilyl lateral group in a molar ratio of 1:1.7:0.043:0.028 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 0.3MPa, the esterification reaction temperature is 260 ℃, the esterification reaction end point is determined when the distilled water amount in the esterification reaction reaches 95% of a theoretical value, and the adding amounts of the ethylene glycol antimony, the titanium dioxide and the trimethyl phosphate are respectively 0.05 wt%, 0.25 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, smoothly pumping the pressure in the stage from normal pressure to absolute pressure of 490Pa within 35min, controlling the reaction temperature to 259 ℃ and the reaction time to 50min, then continuing to pump vacuum, and carrying out the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to absolute pressure of 83Pa, the reaction temperature is 282 ℃, the reaction time is 85min, the number average molecular weight of the prepared modified polyester is 27000, and the molecular weight distribution index is 1.9;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.2dL/g, the relaxation heat treatment means that the polyester filament bundle with the winding overfeed rate of 3.0 percent 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 hot plate and the two hot plates is 10mm, the distance between the last group of heat setting rollers and the winding roller 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 temperature of each area of the screw is 320 ℃; the temperature of the box body is 300 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 85%; the air speed of the cross air blow is 0.7 m/s; the winding speed is 2658 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 600 m/min; the temperature of one roller is 26 ℃; the two-roll speed is 1000 m/min; the temperature of the two rollers is 100 ℃; the three-roller speed is 2500 m/min; the temperature of the three rollers is 150 ℃; the four-roller speed is 3500 m/min; the temperature of the four rollers is 250 ℃; the speed of the five rollers is 3500 m/min; the temperature of the five rollers is 250 ℃; the speed of the six rollers is 2740 m/min; the temperature of the six rollers is 220 ℃;
the modified polyester industrial yarn has the filament number of 5.0dtex, the breaking strength of 7.7cN/dtex, the linear density deviation rate of 1.5 percent, the breaking strength CV value of 2.9 percent, the elongation at break of 20.0 percent, the elongation at break CV value of 7.4 percent, the dry heat shrinkage rate of 3.1 percent under the conditions of 190 ℃ multiplied by 15min multiplied by 0.01cN/dtex, the network degree of 8/m and the LOI of 33;
(2) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving and priming process parameters are the same as those of the example 3, the calendering and attaching temperature is 170 ℃, the pressure is 5.5MPa, and the time is 90 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.75 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 800g/m2The flame burning time is 1.5s, the flameless burning time is 2.5s, the adhesive strength is 58N/cm, the peel strength is 8.7N/cm, the longitudinal tensile strength is 290N/cm, the transverse tensile strength is 300N/cm, the longitudinal elongation at break is 6.4%, the transverse elongation at break is 5.6%, the use temperature range is-30 ℃ to +60 ℃, the hydrostatic resistance value is 96KPa, the hydrostatic resistance value is the pressure value of the fabric just beginning to permeate under the action of continuously rising water pressure, the number of times of friction resistance is 3300, and the number of times of friction resistance is the number of times of friction of the fabric just beginning to change under the action of continuous friction.
Example 8
The preparation method of the terylene flame retardant canvas comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing dihydric alcohol with trimethylsilyl lateral groups;
(1.1.1) mixing 3-trimethylsilyl-3, 3-dimethylpropene, peracetic acid and dichloromethane according to the molar ratio of 1:5:15, reacting for 7 hours at the temperature of 37 ℃, stirring during the reaction, removing the solvent after the reaction is finished, and purifying and refining to obtain trimethylsilyl propylene epoxide;
(1.1.2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating to 82 ℃ in water bath under stirring, keeping the temperature for reaction for 12min, cooling to room temperature after the reaction is finished, and neutralizing, distilling, separating and purifying to obtain the productA diol having trimethylsilyl side groups represented by the formula (I), wherein R in the formula (I) is-C ((CH)3)2) The concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to water is 1:29 when the reaction starts, and the mass of the concentrated sulfuric acid accounts for 0.13% of the mass sum of the mixture;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with trimethylsilyl lateral groups in a molar ratio of 1:1.7:0.05:0.03 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 esterification reaction temperature is 260 ℃, the esterification reaction end point is determined when the distilled water amount in the esterification reaction reaches 95% 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 a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to 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 a high vacuum stage to further reduce the reaction pressure to absolute pressure of 96Pa, control the reaction temperature to be 274 ℃ and control the reaction time to be 90min, wherein the number average molecular weight of the prepared modified polyester is 28000 and the molecular weight distribution index is 2.4;
(2) solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment and winding are carried out on the modified polyester melt to prepare the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.2dL/g, the relaxation heat treatment means that the polyester filament bundle with the winding overfeed rate of 3.0 percent 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 hot plate and the two hot plates is 10mm, the distance between the last group of heat setting rollers and the winding roller 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 temperature of each area of the screw is 320 ℃; the temperature of the box body is 300 ℃; the head pressure is 140 bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 85%; the air speed of the cross air blow is 0.7 m/s; the winding speed is 2658 m/min; the technological parameters of stretching and heat setting are as follows: the speed of one roller is 600 m/min; the temperature of one roller is 26 ℃; the two-roll speed is 1000 m/min; the temperature of the two rollers is 100 ℃; the three-roller speed is 2500 m/min; the temperature of the three rollers is 150 ℃; the four-roller speed is 3500 m/min; the temperature of the four rollers is 250 ℃; the speed of the five rollers is 3500 m/min; the temperature of the five rollers is 250 ℃; the speed of the six rollers is 2740 m/min; the temperature of the six rollers is 220 ℃;
the filament number of the modified polyester industrial yarn is 5.0dtex, the breaking strength is 7.5cN/dtex, the deviation rate of linear density is-1.5%, the CV value of the breaking strength is 3.0%, the elongation at break is 18.0%, the CV value of the elongation at break 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 3.3%, the network degree is 10/m, and the LOI is 34;
(2) weaving the modified polyester industrial yarns into cloth, and then calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven cloth to prepare the polyester flame-retardant canvas with a 1/1 plain weave fabric structure, wherein the weaving and priming process parameters are the same as those of the example 1, the calendering and attaching temperature is 170 ℃, the pressure is 5.5MPa, and the time is 90 s; the PVC film is positioned on the surfaces of both sides of the modified polyester industrial silk woven fabric, and the thickness of the single-side PVC film is 0.75 mm.
The terylene flame-retardant canvas has a composite layer structure and mainly comprises a modified polyester industrial yarn weaving layer and a PVC film layer, and the gram weight of the terylene flame-retardant canvas is 800g/m2The flame burning time is 1.5s, the flameless burning time is 2.5s, the bonding strength is 60N/cm, the peeling strength is 8.8N/cm, the longitudinal tensile strength is 290N/cm, the transverse tensile strength is 300N/cm, the longitudinal elongation at break is 6.5 percent, the transverse elongation at break is 6.0 percent, the use temperature range is-30 ℃ to +60 ℃, the hydrostatic pressure resistance value is 97KPa, and the hydrostatic pressure resistance value is that the fabric just starts to generate water pressure under the action of continuously rising water pressureThe pressure value during permeation is 3300 times, and the abrasion resistance value is the initial change of the fabric under continuous friction.

Claims (10)

1. The preparation method of the terylene flame retardant canvas is characterized in that: calendering and attaching a PVC film on the surface of the modified polyester industrial yarn woven fabric to obtain the polyester flame-retardant canvas;
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, dihydric alcohol with trimethylsilyl lateral group and 2-carboxyethyl phenyl hypophosphorous acid, and then carrying out esterification reaction and polycondensation reaction in sequence;
the structural formula of the dihydric alcohol with the trimethylsilyl lateral group is as follows:
Figure FDA0001925458760000011
in the formula, R is-CH2-、-CH(CH3) -or-C ((CH)3)2)-；
The relaxation heat treatment refers to that the modified polyester tows pass 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 ℃.
2. The method for preparing the dacron flame retardant canvas as recited in claim 1, wherein the diol with trimethylsilyl group side group is synthesized by the following steps:
(1) mixing raw materials of alkene, peracetic acid and dichloromethane according to a molar ratio of 1: 5-10: 10-15, reacting for 5-8 hours at the temperature of 35-40 ℃, stirring during the reaction, removing a solvent after the reaction is finished, and purifying and refining to obtain the trimethylsilyl propylene epoxide;
(2) mixing water, concentrated sulfuric acid and trimethylsilyl propylene epoxide, heating the mixture to 80-85 ℃ in a water bath under the stirring condition, carrying out heat preservation reaction for l 0-15 min, cooling the mixture to room temperature after the reaction is finished, and carrying out neutralization, distillation, separation and purification to obtain dihydric alcohol with a trimethylsilyl lateral group, wherein the concentrated sulfuric acid is sulfuric acid with the mass concentration of 70%, the molar ratio of the trimethylsilyl propylene epoxide to the water is 1: 20-40 at the beginning of the reaction, and the mass of the concentrated sulfuric acid accounts for 0.1-0.15% of the total mass of the mixture;
the structural formula of the dihydric alcohol with the trimethylsilyl lateral group is shown in the specification, wherein R is-CH (CH)3) -and-C ((CH)3)2) When said starting alkenes correspond to 3-trimethylsilyl-3-methylpropene and 3-trimethylsilyl-3, 3-dimethylpropene.
3. The method for preparing the dacron flame retardant canvas as claimed in claim 2, wherein the modified polyester before solid phase polycondensation and tackifying is prepared by the following steps:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with trimethylsilyl lateral groups 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 distillation amount in the esterification reaction reaches more than 90% of the 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.
4. The preparation method of the terylene flame retardant canvas according to claim 3, wherein the molar ratio of the terephthalic acid, the ethylene glycol, the 2-carboxyethylphenylphosphinic acid and the diol with trimethylsilyl lateral group is 1: 1.2-2.0: 0.03-0.05: 0.02-0.03, 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% of the addition amount of the terephthalic acid respectively.
5. The method for preparing the dacron flame retardant canvas as claimed in claim 4, 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.
6. The preparation method of the dacron flame retardant canvas as claimed in claim 5, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.0-1.2 dL/g.
7. The method for preparing flame retardant polyester canvas as claimed in claim 1, wherein the space of a certain temperature is a space between a pair of parallel arranged and non-coplanar hot plates, and the hot plates are located between the last group of heat setting rollers and the winding roller 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 tows, and the two ends of the two hot plates are flush; when the modified polyester tows pass through the middle of the two hot plates, the distance between the modified polyester tows and the two hot plates is 5-10 mm;
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.
8. The preparation method of the polyester flame retardant canvas as claimed in claim 1, wherein the spinning process parameters of the modified polyester industrial yarn are as follows:
Figure FDA0001925458760000031
the technological parameters of stretching and heat setting are as follows:
Figure FDA0001925458760000032
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 the two sides of the modified polyester industrial yarn woven fabric, and the thickness of the PVC film on one side is 0.40-0.75 mm.
9. The polyester flame retardant canvas manufactured by the method for manufacturing polyester flame retardant canvas as claimed in any one of claims 1 to 8, which is characterized in that: the composite layer structure is mainly composed of a modified polyester industrial yarn weaving layer and a PVC film layer;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment, 2-carboxyethyl phenyl hypophosphorous acid and a dihydric alcohol chain segment with a trimethylsilyl lateral group.
10. The flame-retardant polyester canvas as claimed in claim 9, wherein the modified polyester industrial yarn has a single filament number of 3.0-5.0 dtex, a breaking strength of 7.5cN/dtex or more, a linear density deviation ratio of ± 1.5%, a breaking strength CV value of 3.0% or less, an elongation at break of 18.0-20.0%, an elongation at break CV value of 8.0% or less, a dry heat shrinkage rate of 2.5-3.3% under 190 ℃ x 15min x 0.01cN/dtex conditions, a network degree of (5-8) ± 2/m, and an LOI of 30-34;
the gram weight of the terylene flame retardant canvas is 500-800 g/m2The flame burning time is less than or equal to 1.5s, the flameless burning time is less than or equal to 2.5s, the adhesive strength is 50-60N/cm, the peel strength is more than or equal to 8.5N/cm, the longitudinal tensile strength is more than or equal to 281N/cm, the transverse tensile strength is more than or equal to 285N/cm, the longitudinal elongation at break is 6.3-6.5%, the transverse elongation at break is 5.6-6.0%, the service temperature range is-30 ℃ to +60 ℃, the hydrostatic pressure resistance value is more than or equal to 90KPa, the hydrostatic pressure resistance value is the pressure value when the fabric just starts to permeate under the action of continuously rising water pressure, the friction resistance value is more than or equal to 3000 times, and the friction resistance value is more than or equalThe rubbing times are the initial changes of the fabric under the continuous rubbing action.
CN201811614100.8A 2018-12-27 2018-12-27 Flame-retardant polyester canvas and preparation method thereof Active CN109719925B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811614100.8A CN109719925B (en) 2018-12-27 2018-12-27 Flame-retardant polyester canvas and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811614100.8A CN109719925B (en) 2018-12-27 2018-12-27 Flame-retardant polyester canvas and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109719925A CN109719925A (en) 2019-05-07
CN109719925B true CN109719925B (en) 2021-01-05

Family

ID=66296459

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811614100.8A Active CN109719925B (en) 2018-12-27 2018-12-27 Flame-retardant polyester canvas and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109719925B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111058106B (en) * 2019-12-31 2020-10-23 深圳市宏翔新材料发展有限公司 Preparation method of flame-retardant canvas

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101139435A (en) * 2006-09-08 2008-03-12 东丽纤维研究所（中国）有限公司 Polyester having excellent fire-retardancy and preparation method thereof
CN105463610A (en) * 2015-12-29 2016-04-06 江苏恒力化纤股份有限公司 Flame-resistant polyester fiber and preparation method thereof
CN106245149A (en) * 2016-08-31 2016-12-21 江苏恒力化纤股份有限公司 A kind of high uniformity car mould polyester industrial fiber and preparation method thereof
CN106283251A (en) * 2016-08-31 2017-01-04 江苏恒力化纤股份有限公司 A kind of porous ptt fiber HOY silk and preparation method thereof
CN106381557A (en) * 2016-08-31 2017-02-08 江苏恒力化纤股份有限公司 High-uniformity polyester industrial yarn used for safety belt and production method thereof
CN106739354A (en) * 2017-01-21 2017-05-31 浙江飞虎新材料有限公司 Anti-aging PVC coating paulin capping material and its manufacturing process
CN108071009A (en) * 2017-12-14 2018-05-25 江苏恒力化纤股份有限公司 A kind of method for reducing spun polyester thread filoplume
CN108130611A (en) * 2017-12-14 2018-06-08 江苏恒力化纤股份有限公司 It is a kind of high to stretch low-shrinkage type polyester industrial fiber and preparation method thereof
CN108130624A (en) * 2017-12-14 2018-06-08 江苏恒力化纤股份有限公司 A kind of polyester imitates linen look abnormal contraction composite filament and preparation method thereof
CN108385186A (en) * 2017-12-14 2018-08-10 江苏恒力化纤股份有限公司 A kind of polyester POY fibers and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101139435A (en) * 2006-09-08 2008-03-12 东丽纤维研究所（中国）有限公司 Polyester having excellent fire-retardancy and preparation method thereof
CN105463610A (en) * 2015-12-29 2016-04-06 江苏恒力化纤股份有限公司 Flame-resistant polyester fiber and preparation method thereof
CN106245149A (en) * 2016-08-31 2016-12-21 江苏恒力化纤股份有限公司 A kind of high uniformity car mould polyester industrial fiber and preparation method thereof
CN106283251A (en) * 2016-08-31 2017-01-04 江苏恒力化纤股份有限公司 A kind of porous ptt fiber HOY silk and preparation method thereof
CN106381557A (en) * 2016-08-31 2017-02-08 江苏恒力化纤股份有限公司 High-uniformity polyester industrial yarn used for safety belt and production method thereof
CN106739354A (en) * 2017-01-21 2017-05-31 浙江飞虎新材料有限公司 Anti-aging PVC coating paulin capping material and its manufacturing process
CN108071009A (en) * 2017-12-14 2018-05-25 江苏恒力化纤股份有限公司 A kind of method for reducing spun polyester thread filoplume
CN108130611A (en) * 2017-12-14 2018-06-08 江苏恒力化纤股份有限公司 It is a kind of high to stretch low-shrinkage type polyester industrial fiber and preparation method thereof
CN108130624A (en) * 2017-12-14 2018-06-08 江苏恒力化纤股份有限公司 A kind of polyester imitates linen look abnormal contraction composite filament and preparation method thereof
CN108385186A (en) * 2017-12-14 2018-08-10 江苏恒力化纤股份有限公司 A kind of polyester POY fibers and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ASYMMETRIC DIHYDROXYLATION OF VINYL AND ALLYLSILANES;John A. Soderquist等;《Tetrahedron Letters》;19931231;第34卷(第12期);第1893-1896页 *

Also Published As

Publication number Publication date
CN109719925A (en) 2019-05-07

Similar Documents

Publication Publication Date Title
CN109972228B (en) Preparation method of polyamide and nylon fiber prepared by preparation method
CN108130611B (en) High-elongation low-shrinkage polyester industrial yarn and preparation method thereof
JP7059446B2 (en) High modulus, low shrinkage, activated polyester industrial yarn and its manufacturing method
WO2018040690A1 (en) Different-shrinkage composite yarn and preparation method therefor
CN108130610B (en) Ultrahigh-strength polyester industrial yarn and preparation method thereof
CN109735955B (en) Double-component orange-peel composite fiber and preparation method thereof
CN106811821A (en) It is a kind of leafy special-shaped polyester fiber FDY and preparation method thereof
CN109719925B (en) Flame-retardant polyester canvas and preparation method thereof
CN109750376B (en) Terylene heat-resistant canvas and preparation method thereof
CN109750380B (en) Preparation method of polyester lamp box advertisement cloth
CN109763194B (en) Preparation method of polyester industrial yarn for tire cord
CN109735928B (en) Teslin cloth and preparation method thereof
CN109930232B (en) Preparation method of light tent cloth
CN109735931B (en) Preparation method of polyester industrial yarn for traction belt
CN109518298B (en) Flat polyester filament yarn and preparation method thereof
CN109735944B (en) Terylene swimming pool fabric and preparation method thereof
KR102030360B1 (en) Manufacturing Method For Tire Cord Fabric By Displaying Slit Site
CN108385187B (en) High-strength airplane safety belt and preparation method thereof
CN109735946B (en) Colored polyester hoisting belt and preparation method thereof
CN109680359B (en) Preparation method of fluffy chenille yarn for low boiling water
CN112779809B (en) Papermaking forming net and preparation method thereof
CN109722733B (en) Polyester industrial yarn for military bags and preparation method thereof
CN109930231B (en) Preparation method of polyester sun-shading cloth
CN109735947B (en) Water-repellent canvas and preparation method thereof
US5693275A (en) Method of making an improved pre-adherized polyester filament yarn

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant