CN109760396B - Polyester advertising cloth and preparation method thereof - Google Patents

Polyester advertising cloth and preparation method thereof Download PDF

Info

Publication number
CN109760396B
CN109760396B CN201811614147.4A CN201811614147A CN109760396B CN 109760396 B CN109760396 B CN 109760396B CN 201811614147 A CN201811614147 A CN 201811614147A CN 109760396 B CN109760396 B CN 109760396B
Authority
CN
China
Prior art keywords
polyester
reaction
acid
tert
modified polyester
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
CN201811614147.4A
Other languages
Chinese (zh)
Other versions
CN109760396A (en
Inventor
刘灯胜
李文刚
汤方明
张关健
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 CN201811614147.4A priority Critical patent/CN109760396B/en
Publication of CN109760396A publication Critical patent/CN109760396A/en
Application granted granted Critical
Publication of CN109760396B publication Critical patent/CN109760396B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Polyesters Or Polycarbonates (AREA)
  • Woven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a polyester advertising cloth and a preparation method thereof, wherein the preparation method comprises the following steps: warping, weaving, calendering and laminating the modified polyester industrial yarn with a PVC film to obtain the polyester advertising cloth; the modified polyester industrial yarn is prepared by solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of 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, dibasic acid with tertiary butyl lateral group and 2,5,6, 6-tetramethyl-2, 5-heptanediol, and then carrying out esterification reaction and polycondensation reaction in sequence. The warp direction tensile strength of the prepared product is more than or equal to 110N/cm, the weft direction tensile strength is more than or equal to 110N/cm, the tearing strength is more than or equal to 35N/cm, and the peeling strength is more than or equal to 10N/cm. The preparation method of the invention has simple process and low cost; the prepared product has high peel strength and good application prospect.

Description

Polyester advertising cloth and preparation method thereof
Technical Field
The invention belongs to the technical field of polyester fibers, and relates to a polyester advertising cloth and a preparation method thereof.
Background
With the continuous progress of society and the increasing abundance of commodities, the advertising industry develops rapidly, and higher requirements are put forward on advertising media. The flexible lamp box cloth which appears in recent years has gradually replaced the hard materials such as neon lamps, plastic films, organic glass and the like which are dominant in advertising media, and becomes the preferred material for manufacturing the advertising lamp box. The flexible lamp box cloth has the advantages that the manufactured lamp box is bright and attractive in color, long in service life, convenient to transport and safe to use, and the light-transmitting instant sticker can be pasted on the lamp box, and heat transfer printing, super heat printing, computer portrait and other treatment can be carried out; the shape and the size of the lamp box are convenient to customize; the lamp box is more striking at night than lamp boxes made of other materials. Due to this, although the development history of the lamp box cloth is short, the lamp box cloth has been rapidly developed in production and application. Warp-knitted biaxial fabrics processed by biaxial warp knitting machines have been used in large quantities as base fabric materials for flexible light boxes due to the characteristics of good mechanical properties, simple process, short flow, high speed, low cost and the like.
The terylene has the characteristics of high breaking strength, good breaking extensibility, small difference of dry and wet strength, difficult deformation, good wear resistance, strong light resistance, low thermal shrinkage, strong thermal stability, long service life and good durability, thereby becoming an ideal material of the advertisement cloth. However, the flame retardant property of terylene is poor, and although flame retardant terylene is available in the market, the cost is high, and the terylene is difficult to be used as lamp box cloth on a large scale.
Therefore, the performance of the lamp box cloth can be improved and the cost can be controlled by selecting a proper material to be attached to the polyester material. PVC is a common synthetic polymer material, has low price and wide source, and has excellent flame retardant property because the main chain contains halogen atoms. Meanwhile, PVC has high strength, insulativity, good weather resistance, excellent geometric stability and strong resistance to oxidizing agents, reducing agents and strong acids. PVC is one suitable composite material. The two materials can be effectively compounded through rolling. Because the synthetic fiber (polyester industrial yarn) has few ends, smooth surface and low chemical activity, and is difficult to establish an adhesive bond on an interface, a polyurethane adhesive is generally coated on the surface of the polyester fiber for enhancing the viscosity of the polyester fiber and PVC, and the polyurethane adhesive contains a compound which can be combined with fiber end groups, such as-NH2Active groups such as-OH, -COOH and the like can enhance the bonding fastness of the polyester fiber and PVC.
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 mutually parallel and mostly in a trans-conformation, an amorphous region is mostly in a cis-conformation, the molecular arrangement of the polyester fiber is quite tight, and active groups in the polyurethane adhesive are difficult to permeate into the fiber and then are combined with terminal groups in the fiber, so that the adhesion acting force between the polyester fiber and PVC is influenced to a great extent, and the peeling strength of the polyester lamp box cloth (polyester advertising cloth) is influenced.
Therefore, the research on the polyester advertising cloth with good peeling strength by enhancing the acting force between the polyester fiber and the PVC is of great practical significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a method for enhancing the acting force between polyester fibers and PVC, and further provides a polyester advertising cloth with good peel strength and a preparation method thereof. The invention modifies polyester by introducing 2,5,6, 6-tetramethyl-2, 5-heptanediol and dibasic acid with tertiary butyl side group into the polyester, so that the space free volume of the polyester is increased, and further, the molecular active group such as-NH in the adhesion promoter of PVC2OH, COOH 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 peel strength, the tear strength and the like are improved to a certain extent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the dacron advertising cloth, carry on warping, weave and mangle the laminated PVC membrane to make dacron advertising cloth of modified polyester industrial yarn, the preparation method of the dacron advertising cloth of the invention is basically the same as prior art, the most important difference lies in the material of the industrial yarn, the material of the prior art dacron advertising cloth is ordinary polyester, and the material of the dacron advertising cloth of the invention is modified polyester;
the modified polyester industrial yarn is prepared by performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting 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, dibasic acid with a tert-butyl side group and 2,5,6, 6-tetramethyl-2, 5-heptanediol, and then carrying out esterification reaction and polycondensation reaction in sequence;
the dibasic acid with tertiary butyl side group is 5-tertiary butyl-1, 3-phthalic acid, 2-tertiary butyl-1, 6-hexanedicarboxylic acid, 3-tertiary butyl-1, 6-hexanedicarboxylic acid or 2, 5-di-tertiary butyl-1, 6-hexanedicarboxylic acid, and the structural formula of 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:
Figure GDA0002551918970000021
according to the invention, 2,5,6, 6-tetramethyl-2, 5-heptanediol and dibasic acid with a tert-butyl side group are used for modifying polyester, the 2,5,6, 6-tetramethyl-2, 5-heptanediol and dibasic acid with a tert-butyl side group can obviously increase the space free volume of the modified polyester, and particularly, the existence of the tert-butyl group in the 2,5,6, 6-tetramethyl-2, 5-heptanediol and dibasic acid with a tert-butyl side group can cause the change of the activity of a main chain, so that the interaction force among chain units is changed, the distance among the chain units can be correspondingly changed, and the cavity free volume of the modified polyester is increased. The increase in free volume of the voids allows the molecular active groups such as-NH in the adhesion promoter of PVC2OH, COOH 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 peel strength, the tear strength and the like are improved to a certain extent.
As a preferred technical scheme:
in the preparation method of the polyester advertising cloth, the 2,5,6, 6-tetramethyl-2, 5-heptanediol is synthesized by the following steps:
(1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1-1.2: 1.2-1.3: 2.0-3.0, reacting for 2-4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(2) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2-3: 10: 0.01-0.03, reacting at the temperature of 40-50 ℃ for 50-60 min, continuously introducing hydrogen during the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol.
In the preparation method of the polyester advertising cloth, the synthesis method of the 2-tert-butyl-1, 6-hexanedicarboxylic acid, the 3-tert-butyl-1, 6-hexanedicarboxylic acid and the 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid comprises the following steps:
firstly, mixing tungstic acid and hydrogen peroxide, stirring for 10-15 min at room temperature, then adding raw material alcohol, reacting for 1-2 h at the temperature of 80-85 ℃, then heating to 90-95 ℃ and reacting for 2-3 h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining;
when the reaction starts, the molar ratio of the tungstic acid to the raw material alcohol to the hydrogen peroxide is 1: 30-40: 120-150;
the raw material alcohols corresponding to the 2-tert-butyl-1, 6-hexanedicarboxylic acid, the 3-tert-butyl-1, 6-hexanedicarboxylic acid and the 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid are respectively 2-tert-butylcyclohexanol, 4-tert-butylcyclohexanol and 2, 4-di-tert-butylcyclohexanol.
According to the preparation method of the polyester advertising cloth, the preparation steps of the modified polyester before solid-phase polycondensation and tackifying are as follows:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol, dibasic acid with a tert-butyl side group and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding a catalyst, a flatting agent and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction end point is determined when the water distillate in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, wherein the pressure in the stage is stably pumped from normal pressure to below 500Pa in 30-50 min, the reaction temperature is 250-260 ℃, the reaction time is 30-50 min, then continuously pumping vacuum to perform the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to below 100Pa, the reaction temperature is 270-282 ℃, and the reaction time is 50-90 min.
According to the preparation method of the polyester advertising cloth, the mole ratio of the terephthalic acid, the ethylene glycol, the dibasic acid with the tert-butyl side group and the 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1: 1.2-2.0: 0.01-0.02: 0.02-0.04, and the adding 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% of the adding amount of the terephthalic acid. The addition amount of the dibasic acid with the tertiary butyl side group and the 2,5,6, 6-tetramethyl-2, 5-heptanediol is preferably in the range, so that the modified fiber has good mechanical property and crystallinity, the peel strength of the polyester advertising cloth can be obviously improved, the production and the application of the fiber are facilitated, the addition amount of the dibasic acid with the tertiary butyl side group and the 2,5,6, 6-tetramethyl-2, 5-heptanediol can be properly adjusted according to actual needs, but the addition amount is not too large, the damage to the regularity of a polyester macromolecular structure is too large due to too high addition amount, 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 improvement of the peel strength is not obvious due to too low addition amount.
According to the preparation method of the polyester advertising cloth, 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.
According to the preparation method of the polyester advertising cloth, 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 polyester advertising cloth, the spinning process parameters of the modified polyester industrial yarn are as follows:
Figure GDA0002551918970000041
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000042
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 spinning process of the present invention is not limited thereto, and only one possible solution is exemplified here. The specific process parameters are not limited to the above and can be adjusted according to actual requirements.
The invention also provides the polyester advertising cloth prepared by the preparation method of the polyester advertising cloth, which has a composite layer structure and mainly comprises a modified polyester industrial yarn woven fabric layer and a PVC film layer;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment, a dibasic acid chain segment with a tert-butyl side group and a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment.
As a preferred technical scheme:
the modified polyester industrial yarn of the polyester advertising cloth has the advantages that the filament number of the modified polyester industrial yarn is 2-3 dtex, the filament number of the modified polyester industrial yarn is 300-500 dtex, the breaking strength is larger than or equal to 7.0cN/dtex, the linear density deviation rate is +/-1.5%, the breaking strength CV value is smaller than or equal to 3.0%, the breaking elongation is 13.0-16.5%, the breaking elongation CV value is smaller than or equal to 8.0%, the central value of the elongation of a 4.0cN/dtex load is 5.5-7.0%, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex is 5.8-9.2%, the network degree is (5-8) +/-2/m, and the oil content is 0.6 +/-0.2 wt%, the polyester industrial yarn is modified by introducing the dibasic acid with the tert-butyl side group and 2,5,6, 6-tetramethyl-2, 5-heptanediol, the mechanical properties of the prepared industrial yarn are not reduced and are equivalent to the prior art;
the PVC films are positioned on two sides of the modified polyester industrial yarn woven fabric, and the thickness of the PVC film on one side is 30-60 mu m;
the gram weight of the polyester advertising cloth is 150-200 g/m2The warp-direction tensile strength is more than or equal to 110N/cm, the weft-direction tensile strength is more than or equal to 110N/cm, the tear strength is more than or equal to 35N/cm, the peel strength is more than or equal to 10N/cm, the use temperature range is-30 ℃ to +60 ℃, the peel strength and the tear strength of the terylene advertisement cloth are higher than those of the prior art, mainly because the terylene advertisement cloth is improved in material, a dibasic acid chain segment with a tert-butyl side group and a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment are introduced into a polyester molecular chain, and the dibasic acid with the tert-butyl side group and the tert-butyl group in the 2,5,6, 6-tetramethyl-2, 5-heptanediol can be introducedThe change of the activity of the main chain changes the interaction force among the chain units, and the distance among the chain units is correspondingly changed, so that the free volume of the hollow cavity of the polymer is increased, and the increase of the free volume of the hollow cavity enables the molecular active group such as-NH in the adhesion promoter of PVC2OH, COOH 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 peel strength and the tear 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.
For ethylene glycol dihydric alcohol straight chain molecules, C on the main chainThe atoms are arranged in a zigzag form from top to bottom, when two H atoms on a methylene group on the main chain are substituted by methyl (-CH)3) When in substitution, the C atoms on the two side groups and the main chain C atoms are not in the same plane, so that four sp3 hybridized orbitals on the center C are respectively overlapped with empty orbitals on the four surrounding C atoms to form four completely same sigma bonds which are arranged in a regular tetrahedron, the four carbon atoms are respectively positioned at four vertexes of the regular tetrahedron, when three hydrogen of a methyl group is further substituted by a methyl group, the three hydrogen is equivalent to tert-butyl to form a larger tetrahedron structure, compared with molecular chains arranged in a zigzag manner, the molecular chains arranged in the regular tetrahedron manner have the empty free volume which is obviously increased by a large amount, and the permeability and diffusivity of small molecules can be obviously improved; when two H atoms on a certain methylene on the main chain are 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 small molecules is limited, and meanwhile, the long branched chain substituent has small rigidity, the molecular chains are easy to tangle, and the increase of the free volume is not facilitated.
For straight chain molecules such as isophthalic acid and adipic acid, when the H atom on the benzene ring of isophthalic acid or the H atom on the methylene group of adipic acid is replaced by a methyl group (-CH)3) When in substitution, the C atoms on the side groups and the main chain C atoms are not in the same plane, so that four sp3 hybridized orbitals on the center C are respectively overlapped with empty orbitals on the four surrounding C atoms to form four completely same sigma bonds which are arranged in a regular tetrahedron, the four carbon atoms are respectively positioned at four vertexes of the regular tetrahedron, when three hydrogen of a methyl group is further substituted by the methyl group, the three hydrogen is equivalent to tert-butyl to be substituted to form a larger tetrahedron structure, molecular chains arranged in the regular tetrahedron are relatively arranged in a zigzag manner, the free volume of the empty holes is obviously increased by a lot, and the permeability and diffusivity of small molecules can be obviously improved; when H atom on benzene ring of isophthalic acid or H atom on methylene of adipic acid is substituted by long-chain substituent, slit free volume is mainly increased, the increase amplitude is small, the improvement effect on permeability and diffusivity of small molecules is limited, and long-chain branch is takenThe substituent group has low rigidity, and molecular chains are easy to tangle, which is not beneficial to the increase of free volume.
According to the invention, 2,5,6, 6-tetramethyl-2, 5-heptanediol and dibasic acid with a tert-butyl side group are introduced into a polyester molecular chain, so that the peeling strength of the polyester advertising cloth is obviously improved, and the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:
Figure GDA0002551918970000061
the dibasic acid with the tertiary butyl side group is 5-tertiary butyl-1, 3-phthalic acid, 2-tertiary butyl-1, 6-adipic acid, 3-tertiary butyl-1, 6-adipic acid or 2, 5-di-tertiary butyl-1, 6-adipic acid, wherein the 2-tertiary butyl-1, 6-adipic acid, 3-tertiary butyl-1, 6-adipic acid and 2, 5-di-tertiary butyl-1, 6-adipic acid are adipic acid and are fatty acids, the rigidity of the fatty acids is less than that of the 5-tertiary butyl-1, 3-phthalic acid, and the softness of the polyester chain segment is favorably improved;
the existence of the tert-butyl group in the 2,5,6, 6-tetramethyl-2, 5-heptanediol and the dibasic acid with the tert-butyl side 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 the molecular chain units, so that the free volume of the cavity of the modified polyester is increased. Compared with short-chain substituent groups (such as methyl, ethyl and the like), the tertiary butyl group occupies a larger spatial position, and a larger free volume is obtained in the molecular chain arrangement mode; compared with the long-branched-chain substituent, on one hand, the tertiary butyl group has the increased free volume of a cavity, the long-branched-chain substituent has the increased free volume of a slit, and on the other hand, the rigidity of the tertiary butyl group is higher than that of the long-branched-chain substituent, so that entanglement among molecular chains is reduced, and the tertiary butyl group has more free volume than the long-branched-chain substituent in the arrangement mode of the molecular chains. The increase of free volume of the voids allows the molecular active groups such as-NH in the adhesion promoter of PVC2OH, COOH 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 peel strength and the tear strength are improved to a certain extent.
Has the advantages that:
(1) the preparation method of the polyester advertising cloth is simple in process and low in cost, the polyester is modified by introducing the dibasic acid with the 2,5,6, 6-tetramethyl-2, 5-heptanediol and the tertiary butyl side group into the polyester, the cavity free volume of the polyester is increased, and the peel strength of the polyester advertising cloth is obviously improved by matching with the adhesion promoter;
(2) the polyester advertising cloth disclosed by the invention is good in peel strength, good in mechanical property and wide in 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 GDA0002551918970000071
Example 1
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1:1:1.2:2.0, reacting for 2 hours under an ice bath condition, and cooling, crystallizing, centrifugally separating, washing, refining and drying after the reaction is finished to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2:10:0.01, reacting for 50min at the temperature of 40 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 5-tert-butyl-1, 3-phthalic acid into slurry, adding antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the temperature of the esterification reaction is 260 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 90% of the theoretical value, wherein the molar ratio of terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 5-tert-butyl-1, 3-phthalic acid is 1:1.2:0.01:0.025, and the addition amounts of antimony trioxide, titanium dioxide and triphenyl phosphate are 0.03 wt%, 0.22 wt% and 0.01 wt% of the addition amount of terephthalic acid, respectively;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 500 within 30min, the reaction temperature is 260 ℃, the reaction time is 30min, then continuously pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 60Pa, the reaction temperature is 280 ℃, and the reaction time is 50 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.1dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000081
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000082
the modified polyester industrial yarn has the filament number of 2dtex, the multifilament number of 450dtex, the breaking strength of 7.3cN/dtex, the deviation rate of linear density of-0.5 percent, the CV value of the breaking strength of 2.8 percent, the elongation at break of 16.5 percent, the CV value of the elongation at break of 7.9 percent, the central value of the elongation at 4.0cN/dtex load of 6.0 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 5.8 percent, the network degree of 8/m and the oil content of 0.8 percent by weight;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and calendered to attach a PVC film to obtain the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving is carried out by adopting a biaxial warp knitting machine, and primer coating is carried out before calendering and attaching, the primer coating refers to coating pasty PVC (a mixture of pasty PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanate of toluene diisocyanate with the weight ratio of 100:50:1:0.3 at 30 ℃, the pasty PVC is P440, the polymerization degree is 1500) containing an adhesive on polyester base cloth, then pre-curing is carried out for 35s at 140 ℃, and then calendering and attaching are carried out on the pre-cured base cloth, the calendering and attaching temperature is 165 ℃, the pressure is 5MPa, and the time is 80 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and PVC film layers, wherein the PVC films are positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 60 micrometers;
the gram weight of the terylene advertising cloth is 180g/m2The warp direction tensile strength is 110N/cm, the weft direction tensile strength is 130N/cm, the tearing strength is 38N/cm, the peeling strength is 11N/cm, and the use temperature range is-30 to +60 ℃.
Comparative example 1
A preparation method of terylene advertisement cloth, the preparation steps are basically the same as example 1, except that 2,5,6, 6-tetramethyl-2, 5-heptanediol and 5-tert-butyl-1, 3-phthalic acid are not added, namely polyester is not modified, the monofilament fineness of the prepared polyester industrial yarn is 2dtex, the multifilament fineness is 450dtex, the breaking strength is 7.5cN/dtex, the deviation rate of linear density is-0.5%, the CV value of breaking strength is 2.8%, the elongation at break is 15.5%, the CV value of breaking elongation is 7.9%, the central value of elongation at loading of 4.0cN/dtex is 6.0%, and the central value of elongation at loading of 177 ℃ is multiplied by 10min multiplied by 0.05cN is 6.0 ℃The dry heat shrinkage under dtex condition is 5.5 percent, the network degree is 8/m, and the oil content is 0.8 percent by weight; the gram weight of the finally prepared terylene advertisement cloth is 180g/m2The warp direction tensile strength is 110N/cm, the weft direction tensile strength is 132N/cm, the tearing strength is 7N/cm, the peeling strength is 7N/cm, and the use temperature range is-20 ℃ to +50 ℃.
Comparing example 1 with comparative example 1, the difference between this example and the terylene advertisement cloth of the invention is that the material is common polyester. Compared with the conventional polyester advertising cloth, the breaking strength and the tensile strength of the polyester advertising cloth prepared by the invention are obviously increased.
Comparative example 2
A preparation method of polyester advertising cloth, the preparation steps are basically the same as the example 1, except that 1, 2-dodecyl glycol is adopted to replace 2,5,6, 6-tetramethyl-2, 5-heptanediol and 5-tert-butyl-1, 3-phthalic acid in the step (1), the prepared polyester industrial yarn has a single filament fineness of 2dtex, a multifilament fineness of 450dtex, a breaking strength of 7.3cN/dtex, a linear density deviation rate of-0.5%, a breaking strength CV value of 2.8%, an elongation at break of 15.8%, an elongation at break CV value of 7.9%, a central value of elongation at a load of 4.0cN/dtex of 6.0%, a dry heat shrinkage rate under the conditions of 177 ℃ x 10min x 0.05cN/dtex of 5.5%, a network degree of 8/m, and an oil content of 0.8 wt%; the gram weight of the finally prepared terylene advertisement cloth is 180g/m2The warp direction tensile strength is 110N/cm, the weft direction tensile strength is 132N/cm, the tearing strength is 6.8N/cm, the peeling strength is 6.7N/cm, and the use temperature range is-20 ℃ to +50 ℃.
Compared with the example 1, it can be found that the 2,5,6, 6-tetramethyl-2, 5-heptanediol and the 5-tertiary butyl-1, 3-phthalic acid are more favorable for improving the mechanical properties such as breaking strength and tensile strength of the polyester advertising cloth compared with the 1, 2-dodecyl glycol containing long-branched-chain substituents, mainly because the tertiary butyl in the 2,5,6, 6-tetramethyl-2, 5-heptanediol and the 5-tertiary butyl-1, 3-phthalic acid increases the free volume more to be the cavity free volume on the one hand, and the long-branched-chain substituents in the 1, 2-dodecyl glycol increase the free volume more to be the slit free volume on the other hand, and the 2,5,6, 6-tetramethyl-2, 5-heptanediol and the 5-tertiary butyl-1, 3-BenzenedimethylThe rigidity of tertiary butyl in acid is larger than that of long-chain substituent in 1,2 dodecyl glycol, entanglement among molecular chains is reduced, so that 2,5,6, 6-tetramethyl-2, 5-heptanediol and 5-tertiary butyl-1, 3-phthalic acid have more free volume in the arrangement mode of polyester molecular chains than 1,2 dodecyl glycol, and molecular active groups such as-NH in diethyl phthalate2OH, COOH 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 peel strength and the tear strength are improved to a certain extent.
Example 2
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparation of 2-tert-butyl-1, 6-hexanedicarboxylic acid: firstly, mixing tungstic acid and hydrogen peroxide, stirring for 10min at room temperature, then adding 2-tert-butylcyclohexanol, reacting for 1h at the temperature of 80 ℃, heating to 94 ℃ for reaction for 2h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining, wherein the molar ratio of the tungstic acid to the 2-tert-butylcyclohexanol to the hydrogen peroxide is 1:35:120 at the beginning of the reaction;
(1.2) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1.1:1:1.2:2.3, reacting for 2 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2:10:0.01, reacting for 50min at the temperature of 45 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.3) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 2-tert-butyl-1, 6-hexanedioic acid into slurry, adding antimony trioxide, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the temperature of the esterification reaction is 250 ℃, the end point of the esterification reaction is when the distilled amount of water in the esterification reaction reaches 96% of a theoretical value, wherein the molar ratio of terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 2-tert-butyl-1, 6-hexanedioic acid is 1:1.2:0.02:0.02, and the addition amounts of antimony trioxide, titanium dioxide and trimethyl phosphate are 0.04 wt%, 0.20 wt% and 0.04 wt%, respectively, of the addition amount of terephthalic acid;
(1.4) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 450Pa within 35min, the reaction temperature is 255 ℃, the reaction time is 40min, then continuously pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 100Pa, the reaction temperature is 270 ℃, and the reaction time is 60 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.1dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000111
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000112
the modified polyester industrial yarn has the filament number of 3dtex, the multifilament number of 300dtex, the breaking strength of 7.2cN/dtex, the deviation rate of linear density of 0%, the CV value of the breaking strength of 3.0%, the elongation at break of 14.5%, the CV value of the elongation at break of 7.85%, the central value of the elongation at 4.0cN/dtex load of 6.0%, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 9.2%, the network degree of 3/m and the oil content of 0.6 wt%;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and laminated with a PVC film to prepare the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving is carried out by adopting a biaxial warp knitting machine, and primer coating is carried out before the calendering lamination, the primer coating refers to coating pasty PVC (a mixture of pasty PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanate of toluene diisocyanate with the weight ratio of 100:60:2: 2.0) containing an adhesive at 50 ℃, the pasty PVC is P440 with the polymerization degree of 1500) on polyester base cloth, then pre-curing is carried out for 45s at 160 ℃, and then the PVC calendering lamination is carried out on the pre-cured base cloth at the temperature of 165 ℃, the pressure of 5.5MPa and the time of 75 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and PVC film layers, wherein the PVC films are positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 45 microns;
the gram weight of the terylene advertising cloth is 170g/m2The warp direction tensile strength is 110N/cm, the weft direction tensile strength is 120N/cm, the tearing strength is 38N/cm, the peeling strength is 14N/cm, and the use temperature range is-25 to +60 ℃.
Example 3
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparation of 2-tert-butyl-1, 6-hexanedicarboxylic acid: firstly, mixing tungstic acid and hydrogen peroxide, stirring for 12min at room temperature, then adding 2-tert-butylcyclohexanol, reacting for 1.5h at 83 ℃, then heating to 90 ℃ for reacting for 2h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining, wherein the molar ratio of tungstic acid, 2-tert-butylcyclohexanol and hydrogen peroxide is 1:33:120 at the beginning of the reaction;
(1.2) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1.2:1:1.25:2.0, reacting for 3 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.03, reacting for 50min at the temperature of 40 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.3) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 2-tert-butyl-1, 6-hexanedioic acid into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphite, uniformly mixing them, pressurizing in nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 255 ℃, and the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 93 percent of the theoretical value, wherein the molar ratio of terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 2-tert-butyl-1, 6-hexanedioic acid is 1:1.5:0.01:0.02, and the addition amounts of ethylene glycol antimony, titanium dioxide and trimethyl phosphite are 0.05 wt%, 0.24 wt% and 0.03 wt% of the addition amount of terephthalic acid, respectively;
(1.4) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 460Pa within 40min, the reaction temperature is 256 ℃, the reaction time is 50min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 90Pa, the reaction temperature is 280 ℃, and the reaction time is 70 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.0dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000131
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000132
the modified polyester industrial yarn has the filament number of 2dtex, the multifilament number of 300dtex, the breaking strength of 7.1cN/dtex, the deviation rate of linear density of-1.5 percent, the CV value of the breaking strength of 2.92 percent, the elongation at break of 13.0 percent, the CV value of the elongation at break of 8.0 percent, the central value of the elongation at 4.0cN/dtex load of 7.0 percent, the dry heat shrinkage rate of 8.8 percent under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex, the network degree of 5/m and the oil content of 0.4wt percent;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and laminated with a PVC film to prepare the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving is carried out by adopting a biaxial warp knitting machine, and primer coating is carried out before the calendering lamination, and the primer coating refers to coating pasty PVC (a mixture of pasty PVC, diethyl phthalate, a zinc-tin stabilizer and polyisocyanate of toluene diisocyanate with the weight ratio of 100:55:1.5:1.2 at 40 ℃), the pasty PVC is P440, the polymerization degree is 1500) containing an adhesive on polyester base cloth, then precuring for 40s at 150 ℃, and then carrying out PVC calendering lamination on the precured base cloth at 167 ℃, the pressure is 5MPa and the time is 75 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and a PVC film layer, wherein the PVC film is positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 30 micrometers;
the gram weight of the terylene advertising cloth is 200g/m2Tensile strength in the warp direction of 110N/cm, tensile strength in the weft direction of 110N/cm, and tear strength of 40N/cm, the peel strength is 20N/cm, and the use temperature range is-30 to +55 ℃.
Example 4
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparation of 3-tert-butyl-1, 6-hexanedicarboxylic acid: firstly, mixing tungstic acid and hydrogen peroxide, stirring for 13min at room temperature, then adding 4-tert-butylcyclohexanol, reacting for 2h at the temperature of 85 ℃, heating to 90 ℃ and reacting for 3h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining, wherein the molar ratio of the tungstic acid to the 4-tert-butylcyclohexanol to the hydrogen peroxide is 1:30:130 at the beginning of the reaction;
(1.2) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1.2:1:1.3:2.5, reacting for 3 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2.5:10:0.02, reacting for 60min at the temperature of 45 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.3) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 3-tert-butyl-1, 6-hexanedioic acid into slurry, adding ethylene glycol antimony, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 250 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 91% of the theoretical value, wherein the molar ratio of terephthalic acid to ethylene glycol to 2,5,6, 6-tetramethyl-2, 5-heptanediol to 3-tert-butyl-1, 6-hexanedioic acid is 1:1.7:0.015:0.04, and the amounts of ethylene glycol antimony, titanium dioxide and triphenyl phosphate added are 0.05 wt%, 0.25 wt% and 0.05 wt%, respectively, of the amount of terephthalic acid added;
(1.4) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 470Pa within 45min, the reaction temperature is 250 ℃, the reaction time is 50min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 80Pa, the reaction temperature is 275 ℃, and the reaction time is 80 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.2dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000151
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000152
the modified polyester industrial yarn has the filament number of 2.2dtex, the multifilament number of 500dtex, the breaking strength of 7.0cN/dtex, the deviation rate of linear density of 1.0 percent, the CV value of the breaking strength of 2.7 percent, the elongation at break of 13.0 percent, the CV value of the elongation at break of 8.0 percent, the central value of the elongation of 4.0cN/dtex load of 5.5 percent, the dry heat shrinkage rate of 6.9 percent under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex, the network degree of 8 pieces/m and the oil content of 0.6 percent by weight;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and rolled and laminated with a PVC film to prepare the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving and priming process parameters are the same as those of example 1, the rolling and laminating temperature is 168 ℃, the pressure is 5.2MPa, and the time is 90 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and a PVC film layer, wherein the PVC film is positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 30 micrometers;
the gram weight of the terylene advertising cloth is 150g/m2The warp direction tensile strength is 130N/cm, the weft direction tensile strength is 140N/cm, the tearing strength is 40N/cm, the peeling strength is 10N/cm, and the use temperature range is-30 ℃ to +50 ℃.
Example 5
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparation of 3-tert-butyl-1, 6-hexanedicarboxylic acid: firstly, mixing tungstic acid and hydrogen peroxide, stirring for 14min at room temperature, then adding 4-tert-butylcyclohexanol, reacting for 2h at the temperature of 82 ℃, then heating to 92 ℃ for reacting for 3h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining, wherein the molar ratio of the tungstic acid to the 4-tert-butylcyclohexanol to the hydrogen peroxide is 1:40:130 at the beginning of the reaction;
(1.2) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1:1:1.3:3.0, reacting for 4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2.5:10:0.02, reacting for 55min at the temperature of 50 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.3) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 3-tert-butyl-1, 6-hexanedioic acid into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the temperature of the esterification reaction is 258 ℃, the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 95 percent of the theoretical value, wherein the molar ratio of terephthalic acid to ethylene glycol to 2,5,6, 6-tetramethyl-2, 5-heptanediol to 3-tert-butyl-1, 6-hexanedioic acid is 1:2.0:0.016:0.03, and the addition amounts of antimony acetate, titanium dioxide and trimethyl phosphate are 0.04 wt%, 0.23 wt% and 0.04 wt% of the addition amount of terephthalic acid, respectively;
(1.4) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 410Pa within 50min, the reaction temperature is 257 ℃, the reaction time is 38min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 85Pa, the reaction temperature is 282 ℃, and the reaction time is 90 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.0dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000161
Figure GDA0002551918970000171
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000172
the modified polyester industrial yarn has the filament number of 2.6dtex, the multifilament number of 400dtex, the breaking strength of 7.3cN/dtex, the deviation rate of linear density of 0.5 percent, the CV value of the breaking strength of 2.88 percent, the elongation at break of 16.5 percent, the CV value of the elongation at break of 7.8 percent, the central value of the elongation under the load of 4.0cN/dtex of 5.5 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 5.8 percent, the network degree of 8 pieces/m and the oil content of 0.8 percent by weight;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and rolled and laminated with a PVC film to prepare the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving and priming process parameters are the same as those of the example 2, the rolling and laminating temperature is 170 ℃, the pressure is 5.1MPa, and the time is 85 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and PVC film layers, wherein the PVC films are positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 60 micrometers;
the gram weight of the terylene advertising cloth is 150g/m2The warp direction tensile strength is 115N/cm, the weft direction tensile strength is 120N/cm, the tearing strength is 35N/cm, the peeling strength is 14N/cm, and the use temperature range is-25 ℃ to +60 ℃.
Example 6
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparation of 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid: firstly, mixing tungstic acid and hydrogen peroxide, stirring for 15min at room temperature, then adding 2, 4-di-tert-butylcyclohexanol, reacting for 1.5h at 83 ℃, then heating to 92 ℃ and reacting for 2.5h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining, wherein the molar ratio of the tungstic acid to the 2, 4-di-tert-butylcyclohexanol to the hydrogen peroxide is 1:40:120 when the reaction starts;
(1.2) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1.1:1:1.2:3.0, reacting for 4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.03, reacting for 60min at the temperature of 50 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.3) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 2, 5-di-tert-butyl-1, 6-hexanedioic acid 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 ℃, and the esterification reaction end point is determined when the distilled amount of water in the esterification reaction reaches 90% of a theoretical value, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the 2,5,6, 6-tetramethyl-2, 5-heptanediol to the 2, 5-di-tert-butyl-1, 6-hexanedioic acid is 1:2.0:0.02:0.04, the adding amount of the antimony acetate to the titanium dioxide to the trimethyl phosphite is 0.03 wt% of the adding amount of the terephthalic acid respectively, 0.25 wt% and 0.01 wt%;
(1.4) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 400Pa within 35min, the reaction temperature is 253 ℃, the reaction time is 30min, then continuously pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 100Pa, the reaction temperature is 274 ℃, and the reaction time is 65 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.0dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000181
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000182
Figure GDA0002551918970000191
the modified polyester industrial yarn has the filament number of 3dtex, the multifilament number of 500dtex, the breaking strength of 7.0cN/dtex, the deviation rate of linear density of 1.5 percent, the CV value of the breaking strength of 2.83 percent, the elongation at break of 15.5 percent, the CV value of the elongation at break of 7.9 percent, the central value of the elongation at 4.0cN/dtex load of 5.5 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 5.8 percent, the network degree of 10 pieces/m and the oil content of 0.4wt percent;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and rolled and laminated with a PVC film to prepare the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving and priming process parameters are the same as those of the example 3, the rolling and laminating temperature is 170 ℃, the pressure is 5.5MPa, and the time is 90 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and PVC film layers, wherein the PVC films are positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 50 micrometers;
the gram weight of the terylene advertising cloth is 150g/m2The warp direction tensile strength is 135N/cm, the weft direction tensile strength is 115N/cm, the tearing strength is 38N/cm, the peeling strength is 17N/cm, and the use temperature range is-30 ℃ to +40 ℃.
Example 7
The preparation method of the terylene advertisement cloth comprises the following steps:
(1) preparing modified polyester;
(1.1) preparation of 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid: firstly, mixing tungstic acid and hydrogen peroxide, stirring for 11min at room temperature, then adding 2, 4-di-tert-butylcyclohexanol, reacting for 1h at the temperature of 80 ℃, then heating to 95 ℃ and reacting for 2.2h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining, wherein the molar ratio of the tungstic acid to the 2, 4-di-tert-butylcyclohexanol to the hydrogen peroxide is 1:35:150 at the beginning of the reaction;
(1.2) preparing 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the synthesis method comprises the following steps:
(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1.2:1:1.2:3.0, reacting for 3 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(b) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.02, reacting for 55min at the temperature of 42 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);
(1.3) esterification reaction;
preparing terephthalic acid, ethylene glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid into slurry, adding antimony trioxide, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 258 ℃, the esterification reaction end point is determined when the water distillation amount in the esterification reaction reaches 95% of a theoretical value, the molar ratio of the terephthalic acid, the ethylene glycol, the 2,5,6, 6-tetramethyl-2, 5-heptanediol and the 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid is 1:1.9:0.01:0.03, the adding amount of the antimony trioxide, the titanium dioxide and the trimethyl phosphate is 0.04 wt% of the adding amount of the terephthalic acid respectively, 0.20 wt% and 0.04 wt%;
(1.4) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, wherein the pressure in the stage is stably pumped from normal pressure to the absolute pressure of 410Pa within 50min, the reaction temperature is 257 ℃, the reaction time is 38min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 85Pa, the reaction temperature is 277 ℃, and the reaction time is 90 min;
(2) preparing modified polyester industrial yarn;
the modified polyester industrial yarn is prepared by solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding of a modified polyester melt, the intrinsic viscosity of the modified polyester after solid-phase polycondensation tackifying is 1.1dL/g, and the spinning process parameters are as follows:
Figure GDA0002551918970000201
the technological parameters of stretching and heat setting are as follows:
Figure GDA0002551918970000202
the modified polyester industrial yarn has the filament number of 2dtex, the multifilament number of 370dtex, the breaking strength of 7.4cN/dtex, the deviation rate of linear density of-1.0 percent, the CV value of the breaking strength of 3.0 percent, the elongation at break of 16.5 percent, the CV value of the elongation at break of 8.0 percent, the central value of the elongation at load of 4.0cN/dtex of 7.0 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 9.2 percent, the network degree of 6/m and the oil content of 0.4wt percent;
(3) preparing polyester advertising cloth;
the modified polyester industrial yarn is warped, woven and rolled and laminated with a PVC film to prepare the polyester advertising cloth with a fabric structure of 1/1 plain weave, wherein the weaving and priming process parameters are the same as those of the example 1, the rolling and laminating temperature is 166 ℃, the pressure is 5MPa, and the time is 80 s.
The finally prepared polyester advertising cloth has a composite layer structure and mainly comprises a modified polyester industrial yarn woven cloth layer and PVC film layers, wherein the PVC films are positioned on two sides of the modified polyester industrial yarn woven cloth, and the thickness of the PVC film on one side is 60 micrometers;
the gram weight of the terylene advertising cloth is 200g/m2The warp direction tensile strength is 110N/cm, the weft direction tensile strength is 125N/cm, the tear strength is 39N/cm, the peel strength is 10N/cm, and the use temperature range is-20 ℃ to +55 ℃.

Claims (10)

1. The preparation method of the terylene advertisement cloth is characterized by comprising the following steps: warping, weaving, calendering and laminating the modified polyester industrial yarn with a PVC film to obtain the polyester advertising cloth;
the modified polyester industrial yarn is prepared by performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting 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, dibasic acid with a tert-butyl side group and 2,5,6, 6-tetramethyl-2, 5-heptanediol, and then carrying out esterification reaction and polycondensation reaction in sequence;
the dibasic acid with tertiary butyl side group is 5-tertiary butyl-1, 3-phthalic acid, 2-tertiary butyl-1, 6-hexanedicarboxylic acid, 3-tertiary butyl-1, 6-hexanedicarboxylic acid or 2, 5-di-tertiary butyl-1, 6-hexanedicarboxylic acid, and the structural formula of 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:
Figure FDA0002542637800000011
2. the method for preparing polyester advertisement cloth according to claim 1, wherein the 2,5,6, 6-tetramethyl-2, 5-heptanediol is synthesized by the following steps:
(1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1-1.2: 1.2-1.3: 2.0-3.0, reacting for 2-4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain heptynediol;
(2) mixing heptynediol, ethanol and a palladium catalyst according to the weight ratio of 2-3: 10: 0.01-0.03, reacting at the temperature of 40-50 ℃ for 50-60 min, continuously introducing hydrogen during the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol.
3. The method for preparing the polyester advertising cloth as claimed in claim 2, wherein the synthesis method of the 2-tert-butyl-1, 6-hexanedicarboxylic acid, the 3-tert-butyl-1, 6-hexanedicarboxylic acid and the 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid comprises the following steps:
firstly, mixing tungstic acid and hydrogen peroxide, stirring for 10-15 min at room temperature, then adding raw material alcohol, reacting for 1-2 h at the temperature of 80-85 ℃, then heating to 90-95 ℃ and reacting for 2-3 h, wherein reactants are always in a reflux state in the reaction process, and finally cooling, crystallizing, washing and refining;
when the reaction starts, the molar ratio of the tungstic acid to the raw material alcohol to the hydrogen peroxide is 1: 30-40: 120-150;
the raw material alcohols corresponding to the 2-tert-butyl-1, 6-hexanedicarboxylic acid, the 3-tert-butyl-1, 6-hexanedicarboxylic acid and the 2, 5-di-tert-butyl-1, 6-hexanedicarboxylic acid are respectively 2-tert-butylcyclohexanol, 4-tert-butylcyclohexanol and 2, 4-di-tert-butylcyclohexanol.
4. The preparation method of the polyester advertising cloth as claimed in claim 3, wherein the preparation steps of the modified polyester before solid phase polycondensation and tackifying are as follows:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol, dibasic acid with a tert-butyl side group and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding a catalyst, a flatting agent and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction end point is determined when the water distillate in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, wherein the pressure in the stage is stably pumped from normal pressure to below 500Pa in 30-50 min, the reaction temperature is 250-260 ℃, the reaction time is 30-50 min, then continuously pumping vacuum to perform the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to below 100Pa, the reaction temperature is 270-282 ℃, and the reaction time is 50-90 min.
5. The preparation method of the polyester advertising cloth as claimed in claim 4, wherein the molar ratio of the terephthalic acid, the ethylene glycol, the dibasic acid with the tertiary butyl side group and the 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1: 1.2-2.0: 0.01-0.02: 0.02-0.04, and the addition amounts of the catalyst, the delustrant 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.
6. The method for preparing the polyester advertising cloth as claimed in claim 5, wherein the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the matting agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
7. The preparation method of the polyester advertising cloth as claimed in claim 1, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and viscosity increase is 1.0-1.2 dL/g.
8. The preparation method of the polyester advertising cloth as claimed in claim 1, wherein the spinning process parameters of the modified polyester industrial yarn are as follows:
Figure FDA0002542637800000021
the technological parameters of stretching and heat setting are as follows:
Figure FDA0002542637800000022
Figure FDA0002542637800000031
the temperature of the rolling and bonding is 165-170 ℃, the pressure is 5-5.5 MPa, and the time is 75-90 s.
9. The polyester advertising cloth prepared by the preparation method of the polyester advertising cloth as claimed in any one of claims 1 to 8, which is characterized in that: the composite layer structure is 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, a dibasic acid chain segment with a tert-butyl side group and a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment.
10. The polyester advertising cloth as claimed in claim 9, wherein the modified polyester industrial yarn has a single filament fineness of 2 to 3dtex, a multifilament fineness of 300 to 500dtex, a breaking strength of 7.0cN/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 13.0 to 16.5%, an elongation at break CV value of 8.0% or less, a central value of elongation at a load of 4.0cN/dtex of 5.5 to 7.0%, a dry heat shrinkage ratio of 5.8 to 9.2% under 177 ℃ x 10min x 0.05cN/dtex, a network degree of (5 to 8) ± 2/m, and an oil content of 0.6 ± 0.2 wt%;
the PVC films are positioned on two sides of the modified polyester industrial yarn woven fabric, and the thickness of the PVC film on one side is 30-60 mu m;
the gram weight of the polyester advertising cloth is 150-200 g/m2The warp tensile strength is more than or equal to 110N/cm, the weft tensile strength is more than or equal to 110N/cm, the tear strength is more than or equal to 35N/cm, the peel strength is more than or equal to 10N/cm, and the service temperature range is-30 ℃ to +60 ℃.
CN201811614147.4A 2018-12-27 2018-12-27 Polyester advertising cloth and preparation method thereof Active CN109760396B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811614147.4A CN109760396B (en) 2018-12-27 2018-12-27 Polyester advertising cloth and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811614147.4A CN109760396B (en) 2018-12-27 2018-12-27 Polyester advertising cloth and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109760396A CN109760396A (en) 2019-05-17
CN109760396B true CN109760396B (en) 2020-11-06

Family

ID=66451054

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811614147.4A Active CN109760396B (en) 2018-12-27 2018-12-27 Polyester advertising cloth and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109760396B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381557B (en) * 2016-08-31 2018-07-27 江苏恒力化纤股份有限公司 A kind of high uniformity safety belt polyester industrial fiber and preparation method thereof
CN108385187B (en) * 2017-12-14 2020-05-05 江苏恒力化纤股份有限公司 High-strength airplane safety belt and preparation method thereof
CN108385194B (en) * 2017-12-14 2019-12-24 江苏恒力化纤股份有限公司 Dyeing polyester FDY fiber and preparation method thereof
CN108130611B (en) * 2017-12-14 2019-12-24 江苏恒力化纤股份有限公司 High-elongation low-shrinkage polyester industrial yarn and preparation method thereof
CN108130609B (en) * 2017-12-14 2020-02-21 江苏恒力化纤股份有限公司 Low-shrinkage polyester industrial yarn and preparation method thereof

Also Published As

Publication number Publication date
CN109760396A (en) 2019-05-17

Similar Documents

Publication Publication Date Title
CN108130611B (en) High-elongation low-shrinkage polyester industrial yarn and preparation method thereof
CN108130610B (en) Ultrahigh-strength polyester industrial yarn and preparation method thereof
JP7059446B2 (en) High modulus, low shrinkage, activated polyester industrial yarn and its manufacturing method
CN112339384B (en) Optical polyester film and preparation method thereof
KR20190140958A (en) Low shrinkage polyester industrial yarn and its manufacturing method
WO2019114277A1 (en) One-step spun elastic composite filament and preparation method therefor
CN109750380B (en) Preparation method of polyester lamp box advertisement cloth
CN109760396B (en) Polyester advertising cloth and preparation method thereof
CN109537091B (en) Cationic polyester fully drawn yarn and preparation method thereof
CN109750376B (en) Terylene heat-resistant canvas and preparation method thereof
CN109735944B (en) Terylene swimming pool fabric and preparation method thereof
CN111808273B (en) Polyester-polycarbonate copolymer, polyester product, preparation method and application thereof
CN109735928B (en) Teslin cloth and preparation method thereof
CN109719925B (en) Flame-retardant polyester canvas and preparation method thereof
CN109763194B (en) Preparation method of polyester industrial yarn for tire cord
CN112779809B (en) Papermaking forming net and preparation method thereof
CN108385187B (en) High-strength airplane safety belt and preparation method thereof
CN108385196B (en) High-strength colored polyester industrial yarn and preparation method thereof
CN109930232B (en) Preparation method of light tent cloth
CN109629017B (en) Super-bright polyester drawn yarn and preparation method thereof
CN109735931B (en) Preparation method of polyester industrial yarn for traction belt
CN109706543B (en) Terylene military tent and preparation method thereof
CN109722733B (en) Polyester industrial yarn for military bags and preparation method thereof
CN108914228A (en) Geotextile high mould flatness polyester industrial yarn and its production method
JP7067730B2 (en) Polyester resin and its manufacturing method

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