CN109735935B

CN109735935B - Preparation method of marine polyester cable rope

Info

Publication number: CN109735935B
Application number: CN201811614081.9A
Authority: CN
Inventors: 邵义伟; 赵艳丽; 张元华
Original assignee: Jiangsu Hengli Chemical Fiber Co Ltd
Current assignee: Jiangsu Hengli Chemical Fiber Co Ltd
Priority date: 2018-12-27
Filing date: 2018-12-27
Publication date: 2020-08-14
Anticipated expiration: 2038-12-27
Also published as: CN109735935A

Abstract

The invention relates to a marine polyester cable and a preparation method thereof, which comprises the steps of carrying out gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns to prepare the marine polyester cable; the modified polyester industrial yarn is prepared by performing solid phase polycondensation tackifying on a modified polyester melt and then performing a spinning process; the preparation method of the modified polyester before solid phase polycondensation tackifying comprises the following steps: terephthalic acid, ethylene glycol, dihydric alcohol with silicon-containing main chain, 2,5,6, 6-tetramethyl-2, 5-heptanediol and Sb modified by doping metal oxide₂O₃Uniformly mixing the powder, and then carrying out esterification reaction and polycondensation reaction in sequence; the dihydric alcohol with the silicon-containing main chain is dimethyl silicon glycol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol, the linear density of the prepared marine terylene cable is 1200 +/-3 ktex, and the breaking strength is more than or equal to 480 kN. The method has simple process, and the prepared marine terylene cable has high breaking strength and good quality.

Description

Preparation method of marine polyester cable rope

Technical Field

The invention belongs to the technical field of modified polyester fibers, and relates to a marine polyester cable and a preparation method thereof.

Background

Terylene is the commodity name of polyester fiber in China. In the initial development stage of polyester fiber, the varieties mainly comprise cotton type, wool type short fiber and common filament, and are mainly applied to the fields of clothing and decoration. At present, the catalyst commonly used for polyester synthesis is antimony catalyst, and the common antimony catalyst in the market is Sb₂O₃The addition amount of the antimony catalyst in the polyester synthesis process is large, the influence of the large addition amount of the antimony catalyst on the environment is large, the polyester environment-friendly production is not facilitated, meanwhile, the antimony catalyst can be converted into an antimony simple substance in a polycondensation reaction, the gray brightness of the polyester color is reduced, the larger the addition amount of the antimony catalyst is, the larger the influence on the color, the quality and the like of the polyester is, but the antimony catalyst with the small addition amount cannot catalyze the reaction of all raw materials participating in the polyester synthesis, and the requirement of the polyester production cannot be met.

The rope is a kind of special textile, it is a soft and slender object made up by using fibre (natural fibre, chemical fibre) or metal wire and adopting the mode of twisting or braiding, etc. to make reinforcement, and has a certain tensile strength, and can be used as connecting and drawing tool. The types of the ropes can be divided into plant fiber ropes, synthetic fiber ropes, steel wire ropes and mixed ropes according to the raw materials of the ropes; the rope can be divided into a rope (the diameter is 1-4 mm), a cable (the diameter is 4-40 mm) and a cable (40-120 mm) according to the thickness of the rope; the main components of the yarn are three, four, six, eight and fancy strands according to the cross section; can be divided into twisted rope, braided rope and braided twisted rope according to the structure.

The annual demand of the current marine mooring rope in China is high, and with the improvement of the economic development level of China, the marine mooring rope made of high-performance fibers gradually replaces the existing mooring rope. In order to further expand the application range of the polyester industrial yarns in the marine mooring rope and further develop the marine mooring rope, it is very necessary to research and develop the polyester industrial yarns with different properties and increase the varieties of the polyester industrial yarns. The mooring rope made of the high-strength polyester industrial yarn has the characteristics of light weight, high strength, long service cycle, wear resistance, moisture resistance, large breaking elongation and the like, is widely applied to ocean engineering such as oil tankers, asphalt ships and the like, and has an extremely rapid development speed. However, in the process of manufacturing the marine mooring rope, the polyester industrial yarn is often subjected to post-treatment such as impregnation treatment in the prior art to achieve the effects of prolonging the service life and improving the mechanical properties of the marine mooring rope, and then, because the finished polyester fiber product is of a partially crystallized supermolecular structure, molecular chains of the crystallized parts of the polyester fiber product are parallel to each other and mostly in a trans-conformation, and an amorphous region is mostly in a cis-conformation, the molecular arrangement of the polyester fiber product is quite tight, and the structure of the polyester molecule is relatively regular, the treatment effect of the impregnation solution on the polyester fiber is poor in the impregnation treatment process, and the breaking strength of the manufactured marine polyester mooring rope is difficult to further improve.

Therefore, the research of the preparation method of the high-performance marine polyester cable with high breaking strength has practical significance.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provide a preparation method of a marine polyester cable with high breaking strength.

In order to achieve the purpose, the invention adopts the technical scheme that:

the preparation method of the marine polyester mooring rope, carry on the gumming treatment to the rope that is got by twisting and weaving of modified polyester industrial yarn and make the marine polyester mooring rope, the preparation method of the marine polyester mooring rope of the invention is basically the same as preparation method of the ordinary marine polyester mooring rope, the main difference lies in the material of the industrial yarn, the invention has improved the material of the industrial yarn, introduced the diatomic alcohol chain segment that the main chain contains silicon and 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment in the molecular chain of polyester, and then improved the gumming effect of the industrial yarn, lengthened the service life of the mooring rope;

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: terephthalic acid, ethylene glycol, dihydric alcohol with silicon-containing main chain, 2,5,6, 6-tetramethyl-2, 5-heptanediol and doped modified Sb₂O₃Uniformly mixing the powder, and then carrying out esterification reaction and polycondensation reaction in sequence;

the dihydric alcohol with silicon-containing main chain is dimethyl silicon glycol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol, and the structural formula of 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:

according to the invention, 2,5,6, 6-tetramethyl-2, 5-heptanediol and the dihydric alcohol with a silicon-containing main chain are adopted as reactants in the polyester synthesis process, so that the gum dipping effect of the marine polyester cable is improved, and the breaking strength of the marine polyester cable is further obviously improved.

The existence of tert-butyl in a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment can cause the change of the activity of a main chain, thereby changing the interaction force among chain units, and correspondingly changing the distance among the chain units to increase the free volume of the hollow of the modified polyester; compared with short-chain substituent groups (such as methyl, ethyl and the like), the tertiary butyl group occupies a larger spatial position, and a larger free volume is obtained in the molecular chain arrangement mode; compared with the long-branched-chain substituent, on one hand, the tertiary butyl group has the increased cavity free volume, the long-branched-chain substituent has the increased slit free volume, and on the other hand, the rigidity of the tertiary butyl group is higher than that of the long-branched-chain substituent, so that the entanglement among molecular chains is reduced, and the tertiary butyl group has more free volume than the long-branched-chain substituent in the arrangement mode of the molecular chains;

further, the Si atom and-CH in the main chain of the polymer in the main chain silicon-containing glycol segment₃Is connected to-CH₃Perpendicular to the plane of the Si-O-Si atom, the-CH results from the Si-C bond being longer than the C-C bond₃Three of H are in a spread state, -CH₃Three propped H atoms in the polyester can rotate freely to increase the distance between adjacent Si-O molecular chain segments, and in addition, the inert methyl of the side chain blocks the approach of macromolecules, so that the polymer material is very flexible, the free volume of a cavity is obviously increased compared with the polymer material without introducing the diol with silicon in the main chain, and the free volume of the cavity of the polyester is also obviously increased by the diol chain segment with silicon in the main chain. The increase of the free volume of the cavity can enable active groups such as amino groups on molecules of the dipping solution to be better bonded with polyester molecules in the process of cable dipping treatment, thereby achieving better dipping effect, further improving the breaking strength of the rope and prolonging the service life;

Sb₂O₃the doping modification process comprises the following steps: firstly, containing metal ions M^x+With Sb-containing solution³⁺Uniformly mixing the solution, then dropwise adding a precipitator until the pH value of the mixed solution is 9-10, and finally calcining and crushing a precipitation product; metal ion M^x+Is Mg²⁺、Ca²⁺、Ba²⁺And Zn²⁺One or more of (1);

the invention is realized by adding metal ions M^x+With Sb-containing solution³⁺The solution is firstly mixed uniformly, then precipitated and finally calcined, thereby realizing the metal oxide with certain catalytic activity and the metal oxideAfter the metal oxide is doped with the antimony trioxide, the metal oxide enters the lattice site of the antimony by inhibiting the crystallization of the antimony trioxide, the growth of cubic antimony trioxide crystal grains and isomorphous substitution of the antimony, so that the antimony trioxide crystal generates defects, the crystal form is changed, the crystal grain size is reduced, and the specific surface area S of the antimony trioxide catalyst is improved_gMeanwhile, the metal is also enriched on the surface of part of the antimony trioxide crystal, so that the activity r on the unit surface area of the antimony trioxide_sIncrease of specific surface area S_gAnd activity per unit surface area r_sThe larger the catalyst, the higher the catalytic activity of the catalyst, and therefore the invention is able to operate at low Sb₂O₃The catalytic synthesis of the polyester is realized under the addition amount, which is beneficial to the environmental-friendly production and ensures the quality of the synthesized polyester, thereby ensuring the quality of the final product.

As a preferred technical scheme:

according to the preparation method of the marine polyester mooring rope, the filament number of the modified polyester industrial yarn is 5-10 dtex, the multifilament number is 1100-3300 dtex, the breaking strength is more than or equal to 8.1cN/dtex, the linear density deviation rate is +/-1.5%, the breaking strength CV value is less than or equal to 3.0%, the elongation at break is 13.0-16.5%, the elongation at break CV value is less than or equal to 8.0%, the central value of the elongation at 4.0cN/dtex load is 5.5-6.0%, the dry heat shrinkage rate under the condition of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex is 5.5-9.0%, the network degree is (5-8) +/-2/m, and the oil content is 0.6 +/-0.2 wt%; the mechanical property of the modified polyester industrial yarn is equivalent to that of the prior art, and the mechanical property of the modified polyester industrial yarn is not reduced due to modification;

the linear density of the marine polyester cable is 1200 +/-3 ktex, the breaking strength is more than or equal to 480kN, and the breaking strength of the marine polyester cable is far higher than that of the marine polyester cable in the prior art with the same specification, mainly because a 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment and a dihydric alcohol chain segment with a silicon-containing main chain are introduced into a polyester molecular chain, the free volume of a cavity of the polyester is increased, and the active groups such as amino groups on molecules of a dipping solution can be better bonded with the polyester molecules in the dipping treatment process of the cable due to the increase of the free volume of the cavity, so that the better dipping effect is achieved, the breaking strength of the cable is further improved, and the service life of the cable is prolonged.

According to the preparation method of the marine polyester cable, the 2,5,6, 6-tetramethyl-2, 5-heptanediol is synthesized by the following steps:

(1) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to a molar ratio of 1-1.2: 1.2-1.3: 2.0-3.0, reacting for 2-4 hours under an ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;

(2) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2-3: 10: 0.01-0.03, reacting at the temperature of 40-50 ℃ for 50-60 min, continuously introducing hydrogen during the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol.

The preparation method of the marine terylene cable containing the metal ions M^x+The concentration of the solution is 0.5-1.0 mol%, the solvent is water, and the anion in the solution is NO₃ ^-(ii) a The Sb-containing compound³⁺The solution of (a) is Sb with the concentration of 5-10 mol%₂O₃The solvent of (1) is oxalic acid; the precipitator is ammonia water with the concentration of 2 mol/L; at the beginning of the precipitation, the metal ions M in the mixed solution^x+And Sb³⁺The molar ratio of (A) to (B) is 1-3: 100; sb₂O₃Is the polyester catalyst with highest cost performance at present, and is prepared by permeating metal oxide (namely M)₂O_X) Inhibiting antimony trioxide (Sb)₂O₃) Crystallization of (b) and growth of cubic antimony trioxide grains, with metal ion M^x+Can replace antimony to enter the lattice site of antimony, so that the antimony trioxide crystal generates defects to improve the catalytic activity of antimony trioxide; if the amount of the doped metal oxide is too small (the molar ratio is too low), the influence on the crystal grains of the antimony trioxide is low, and if the amount of the doped metal oxide is too large (the molar ratio is too high), the Sb in the main body of the catalyst is enabled to be too much³⁺The large reduction range is not favorable for improving the catalytic activity of the antimony trioxide;

washing and drying the precipitate product before calcining, wherein the drying temperature is 105-110 ℃, and the drying time is 2-3 h; the calcining process comprises the following steps: firstly, heating to 400 ℃, then preserving heat for 2-3 h, then heating to 900 ℃, preserving heat for 1-2 h, and finally cooling in the air;

Sb₂O₃after doping modification, crushing to obtain powder with average grain size less than 0.5 micron.

According to the preparation method of the marine polyester cable, 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, dihydric alcohol with silicon-containing main chain and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, and adding doped modified Sb₂O₃Uniformly mixing the powder, the flatting agent and the stabilizing agent, and 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 endpoint is determined when the distilled amount of water 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 marine polyester mooring rope, the molar ratio of the terephthalic acid, the ethylene glycol, the dihydric alcohol with a silicon-containing main chain and the 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1: 1.2-2.0: 0.01-0.015;

in the invention, the addition amount of 2,5,6, 6-tetramethyl-2, 5-heptanediol is too much, which greatly damages the regularity of the macromolecular structure of the polyester and greatly affects the crystallinity and the mechanical property (rigidity) of the modified polyester, thus being not beneficial to the production and the application of the fiber; the addition amount is too small, the increase of the free volume of the polyester cavity is not obvious, and the gum dipping effect of the marine polyester cable is difficult to obviously improve;

the addition amount of the dihydric alcohol with the silicon-containing main chain is preferably in the range, so that the modified fiber has good mechanical property and crystallinity, the gum dipping effect of the terylene can be obviously improved, the production and the application of the fiber are facilitated, the addition amount of the dihydric alcohol with the silicon-containing main chain can be properly adjusted according to actual needs, but the addition amount is not too high, the regularity of a polyester macromolecular structure is greatly damaged 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 gum dipping effect is not obviously improved due to too low addition amount;

the doped and modified Sb₂O₃The addition amounts of the powder, the delustering agent and the stabilizer are respectively 0.012-0.015 wt%, 0.20-0.25 wt% and 0.01-0.05 wt% of the addition amount of the terephthalic acid; sb in polyester synthesis process in prior art₂O₃The amount of (A) is usually 0.02 to 0.04 wt% of the amount of terephthalic acid, and the amount of antimony-based catalyst is high, mainly due to undoped Sb₂O₃Activity per unit surface area r_sLow and specific surface area S_gSmall, therefore Sb₂O₃The overall catalytic activity is lower, and the invention is realized by the p-Sb₂O₃Doping modification is carried out to improve Sb₂O₃Thus significantly reducing Sb in the polyester synthesis process₂O₃The amount of (c) added.

According to the preparation method of the marine polyester cable, the flatting agent is titanium dioxide, and the stabilizing agent is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.

According to the preparation method of the marine polyester mooring rope, 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 marine polyester cable, the spinning process parameters of the modified polyester industrial yarns are as follows:

the technological parameters of stretching and heat setting are as follows:

according to the preparation method of the marine polyester cable rope, the gum dipping treatment adopts the water-based polyurethane glue, and the mass ratio of polyurethane to water in the water-based polyurethane glue is l: 5-10; the time of the gum dipping treatment is 50-60 s; and drying for 10-15 min at the temperature of 80-100 ℃ after the gum dipping treatment.

The invention mechanism is as follows:

in the invention, 2,5,6, 6-tetramethyl-2, 5-heptanediol and dihydric alcohol with a silicon-containing main chain are adopted as reactants in the polyester synthesis process, and doped modified Sb is adopted₂O₃The powder is used as a catalyst, and a rope obtained by twisting and weaving modified polyester industrial yarns is subjected to impregnation treatment to prepare the marine polyester cable rope, so that the impregnation effect of the marine polyester cable rope is improved, the breaking strength of the marine polyester cable rope is further remarkably improved, and the quality of the prepared marine polyester cable rope is also ensured, specifically the following steps:

(one) for 2,5,6, 6-tetramethyl-2, 5-heptanediol:

the macromolecular chains in the polymer are not completely tightly packed, and voids always exist among the macromolecular chains, and the void volume is the free volume. Since small molecules are allowed to penetrate into the polymer, voids are sufficiently large in the polymer or between the polymers, the permeability and diffusivity of the small molecules are related to the size of the voids (i.e., the size of free volume) in the polymer structure, and within a certain range, the larger the size of the free volume, the higher the permeability of the small molecules, and the better the diffusivity. The free volume is divided into a cavity free volume and a slit free volume, the cavity free volume has larger space size than the slit free volume, and the effect of the cavity free volume is more obvious than the effect of the slit free volume for improving the permeability of small molecules.

The size and type of free volume depends primarily on the structure of the polymer, and the primary factors affecting the polymer structure are steric hindrance, pendant group size, pendant group structure, and the like. When a certain position on the main chain of the polymer is substituted by a side group, the activity of the main chain is inevitably changed, so that the interaction force between chains is changed, the distance between the chains is also correspondingly changed, and consequently, the cohesive energy and the free volume are changed, and the polarity, the size, the length and the like of the substituent on the side chain of the polymer have certain influences on the rigidity of the molecular chain, the interaction between molecules and the free volume fraction of the polymer structure, so that the effects generated by different substituents are different, and the osmotic separation performance of the polymer is often different.

For glycol straight chain molecules such as ethylene glycol, butanediol and the like, C atoms on a main chain are arranged in a zigzag manner from top to bottom, and when two H atoms on a certain methylene on the main chain are replaced 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.

The structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is as follows:

the existence of the tert-butyl group in the 2,5,6, 6-tetramethyl-2, 5-heptanediol 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 cavity free volume 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.

(II) for the dihydric alcohol containing silicon in the main chain:

the dihydric alcohol with the silicon-containing main chain is dimethyl silicon glycol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol, and the structural formulas are respectively as follows:

the rigidity of the high molecular chain is determined by the size of a rotation potential barrier in the molecular chain, the main chain structures are different, wherein the bond angles and bond lengths are different or the bonding modes are different, the rigidity is also different, after the diatomic alcohol with silicon in the main chain is introduced, the high molecular main chain contains-Si-O-Si-bonds, the silicon-oxygen bond gaps are larger, the internal rotation activation energy is lower, the free rotation of atoms is facilitated, and meanwhile, the Si atoms and-CH on the high molecular main chain₃Is connected to-CH₃Perpendicular to the plane of the Si-O-Si atom, the-CH results from the Si-C bond being longer than the C-C bond₃Three of H are in a spread state, -CH₃Three propped H atoms in the polymer material can freely rotate to increase the distance between adjacent Si-O molecular chain segments, and in addition, the inert methyl of the side chain blocks the approach of the high polymer, so that the high polymer material is very flexible, and the free volume of the cavity is obviously increased compared with the high polymer material without introducing the dihydric alcohol containing silicon in the main chain; when the Si atom on the main chain of the polymer is linked to the substituent of the long branched chain, the slit free body is mainly enlargedThe product and the increase range are small, the improvement effect on the permeability and diffusivity of small molecules is limited, meanwhile, the long branched chain substituent has low rigidity, the molecular chains are easy to tangle and are not beneficial to the increase of free volume, and the introduction of the diatomic alcohol with silicon in the main chain also increases the cavity free volume of the modified polyester.

In conclusion, the 2,5,6, 6-tetramethyl-2, 5-heptanediol chain segment and the diol chain segment with the silicon-containing main chain can both increase the cavity free volume of the polyester, and meanwhile, compared with the increase of the slit free volume, the increase of the cavity free volume to the total free volume of the polyester is larger, and the increase of the cavity free volume enables active groups such as amino groups on molecules of the dipping solution to be better bonded with the polyester molecules, so that a better dipping effect is achieved, the breaking strength of the rope is further improved, and the service life of the rope is prolonged.

(III) for doping-modified Sb₂O₃Powder:

doped modified Sb used in polyester synthesis process₂O₃The powder is mainly used as a catalyst, the prior polyester catalyst mainly takes antimony compounds such as antimony trioxide, ethylene glycol antimony and antimony acetate as main components, the addition amount of antimony in industrial polyester synthesis is more than 200ppm, the antimony is heavy metal, the era progress has more and more strict restriction on the antimony catalyst, and although titanium catalysis is applied, the antimony cannot be replaced in a short time due to various reasons such as color and activity control.

Catalytic activity of the catalyst and specific surface area S of the catalyst_gInternal surface utilization factor f and activity per surface area r_sProportional ratio, and for a certain component of the catalyst, the catalytic activity of the catalyst depends on the specific surface area S of the catalyst_gAnd the internal surface utilization factor f, the activity per unit surface area of the catalyst r_sAt a certain time, the larger the specific surface area, the higher the catalytic activity.

The invention realizes the doping and blending of the metal oxide and the antimony trioxide with certain catalytic polycondensation reaction activity by solution blending, coprecipitation and calcination, wherein the metal oxide is more than one of MgO, CaO, BaO and ZnO, the valence and the valence of the antimony are different, the ionic radius and the antimony are different, and the differences can change the crystal face structure of the antimony trioxide, thereby influencing the related performance. In addition, MgO, CaO, BaO and ZnO are all white crystals, and do not cause color change when used as a polyester catalyst.

The influence of the metal oxide on the antimony trioxide is mainly reflected in that: on the one hand, the metal oxide can inhibit crystallization of the antimony trioxide and growth of cubic antimony trioxide crystal grains, so that the specific surface area S of the antimony trioxide catalyst_gThe catalytic activity of the antimony trioxide is improved; on the other hand, the metal can isomorphously replace the antimony and enter the lattice site of the antimony, so that the antimony trioxide crystal generates defects, the crystal form is changed, the crystal grain size is reduced, and the specific surface area S is increased_gIncreasing the activity r per unit surface area of the crystal by enriching the metal on part of the crystal surface_sThe catalytic activity of the antimony trioxide is improved. If only the metal oxide with certain catalytic polycondensation reaction activity is simply and physically blended with the antimony trioxide, the catalytic activity of the antimony trioxide cannot be obviously improved, because the simple physical blending does not generate crystal defects, the crystal form does not change, the grain size remains unchanged, the total surface area of the crystal does not change, and the catalytic activity cannot be influenced.

According to the invention, the antimony trioxide is doped, so that the catalytic activity of the antimony trioxide is improved to a certain extent, the improvement of the catalytic activity of the antimony trioxide is beneficial to reducing the using amount of the antimony trioxide, and in the polyester synthesis process, under the condition that the polycondensation process conditions are unchanged and the polyester achieves the same index, the using amount of the antimony trioxide can be reduced by more than 30% after the antimony trioxide is doped by adopting the metal oxide, so that the problem of large adding amount of the existing antimony trioxide is effectively solved, meanwhile, the requirement of polyester production can be met, the quality of the produced PET is ensured, and further, the quality of the marine polyester mooring rope can be ensured.

Has the advantages that:

(1) according to the preparation method of the marine polyester cable rope, 2,5,6, 6-tetramethyl-2, 5-heptanediol and the dihydric alcohol with the silicon-containing main chain are introduced into the polyester to modify the polyester, so that the dipping effect of the polyester cable rope is improved, the dipping solution can be better bonded with polyester molecules, and the breaking strength of the marine polyester cable rope is further remarkably improved;

(2) according to the preparation method of the marine polyester cable rope, the antimony trioxide is doped and modified by the metal oxide with certain catalytic activity, so that the specific surface area S of the antimony trioxide is increased_gAnd activity per unit surface area r_sThereby improving the catalytic activity of the antimony trioxide and improving the polymerization efficiency; the addition amount of the antimony catalyst during polyester synthesis can be reduced while the production requirement of polyester is met, the antimony emission of the subsequently prepared fiber is effectively reduced, and the environment-friendly production is favorably realized;

(3) the marine polyester cable rope prepared by the preparation method of the marine polyester cable rope has the advantages of high breaking strength, good quality 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.

Example 1

The preparation method of the marine polyester cable rope comprises the following steps:

(1) preparing modified polyester;

(1.1) the synthesis steps of 2,5,6, 6-tetramethyl-2, 5-heptanediol are as follows:

(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1:1:1.2:2.0, reacting for 2 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;

(b) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2:10:0.01, reacting for 50min at the temperature of 40 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Mg (NO) at a concentration of 0.8 mol%₃)₂Aqueous solution with Sb concentration of 8 mol%₂O₃The solution of (A) is mixed uniformly, Sb₂O₃The solvent of the solution is oxalic acid, and Mg in the mixed solution²⁺And Sb³⁺In a molar ratio of 2: 100;

(1.2.2) dropwise adding ammonia water with the concentration of 2mol/L until the pH value of the mixed solution is 9 to obtain a precipitate, and then washing and drying the precipitate at the temperature of 105 ℃ for 2.5 hours;

(1.2.3) heating the dried product to 400 ℃ firstly, then preserving heat for 2.5h, then heating to 900 ℃ and preserving heat for 1.5h, finally cooling in air and crushing to obtain the doped modified Sb with the average grain diameter of 0.4 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, dimethyl silicon glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, and adding doped modified Sb₂O₃Uniformly mixing the powder, titanium dioxide and trimethyl phosphite, 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 endpoint is when the distilled amount of water in the esterification reaction reaches 92% of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol, dimethyl silicon glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1:1.5:0.01:0.01, and the modified Sb is doped₂O₃The adding amount of the powder, the titanium dioxide and the trimethyl phosphite is respectively 0.015 wt%, 0.20 wt% and 0.04 wt% of the adding amount of the 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 400Pa within 40min, the reaction temperature is 250 ℃, 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 80Pa, the reaction temperature is 272 ℃, and the reaction time is 65 min;

(2) preparing modified polyester industrial yarn;

carrying out solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding on the modified polyester melt to obtain the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.0dL/g, and the spinning process parameters are as follows:

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 5dtex, the multifilament number of 1100dtex, the breaking strength of 8.3cN/dtex, the deviation rate of linear density of-1.0 percent, the CV value of the breaking strength of 2.8 percent, the elongation at break of 14.5 percent, the CV value of the elongation at break of 8.0 percent, the central value of the elongation under the load of 4.0cN/dtex of 6.0 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 6.5 percent, the network degree of 3/m and the oil content of 0.6 weight percent;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by performing gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twist degree of twisting is 30 twists/10 cm, the weft density of weaving is 1.5/10cm, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:5, the gum dipping treatment time is 50s, and the rope is dried for 15min at the temperature of 85 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1201ktex, and the breaking strength is 550 kN.

Comparative example 1

The preparation method of the marine polyester cable rope comprises the same preparation steps as those in example 1, except that dimethyl silicon glycol, 2,5,6, 6-tetramethyl-2, 5-heptanediol and doped modified Sb are not added₂O₃The powder, namely polyester is not modified, the filament number of the prepared polyester industrial yarn is 5dtex, the multifilament number is 1100dtex, the breaking strength is 8.2cN/dtex, the deviation rate of linear density is-1.0%, the breaking strength CV value is 2.8%, the breaking elongation is 14.7%, the breaking elongation CV value is 8.1%, the central value of the elongation under the load of 4.0cN/dtex is 6.0%, the dry heat shrinkage rate under the condition of × 10min × 0.05.05 cN/dtex at 177 ℃ is 6.6%, the network degree is 3/m, and the oil content is 0.6 wt%, and the finally prepared marine polyester cable has the linear density of 1201ktex and the breaking strength of 472 kN.

Comparing the example 1 with the comparative example 1, it can be seen that the invention modifies polyester through dimethyl silicon glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol, increases the cavity free volume of polyester fiber, enables the aqueous polyurethane adhesive to better adhere with polyester molecules in the process of gum dipping treatment, improves the bonding fastness between the two, further remarkably improves the breaking strength of the marine polyester cable, and remarkably reduces the addition amount of antimony catalysts in the process of synthesizing polyester, thereby realizing environmental protection production and ensuring the quality of products.

Comparative example 2

A preparation method of a marine polyester cable is basically the same as that of example 1, except that 1, 2-dodecyl glycol is adopted to replace dimethyl silicon glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol in the preparation process of modified polyester, the prepared modified polyester industrial yarn has the filament number of 5dtex, the multifilament number of 1100dtex, the breaking strength of 8.3cN/dtex, the deviation rate of linear density of-1.0%, the CV value of breaking strength of 2.8%, the elongation at break of 13.7%, the CV value of breaking elongation of 8.1%, the central value of elongation of 4.0cN/dtex load is 6.0%, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex is 6.6%, the network degree is 3/m, and the oil content is 0.6 wt%. The linear density of the finally prepared marine polyester cable is 1201ktex, and the breaking strength is 465 kN.

Compared with the example 1, the dimethyl silicon glycol and the 2,5,6, 6-tetramethyl-2, 5-heptanediol are more favorable for improving the mechanical properties such as breaking strength, tensile strength and the like of the marine polyester cable compared with the 1, 2-dodecyl glycol containing long-branched-chain substituents, mainly because on one hand, the tert-butyl group in the 2,5,6, 6-tetramethyl-2, 5-heptanediol has more increased free volume and is hollow free volume, the long-branched-chain substituents in the 1, 2-dodecyl glycol has more increased free volume and is slit free volume, and on the other hand, the tert-butyl group in the 2,5,6, 6-tetramethyl-2, 5-heptanediol has more rigidity than the long-branched-chain substituents in the 1, 2-dodecyl glycol, the entanglement among molecular chains is reduced, and the dimethyl silicon glycol is introduced to ensure that the polyester main chain contains-Si-O-Si- The silicon-oxygen bond gap is larger, the internal rotation activation energy is lower, the free rotation of atoms is facilitated, the free volume of cavities is further increased, and therefore the dimethyl silicon glycol and the 2,5,6, 6-tetramethyl-2, 5-heptanediol have more free volumes in the polyester molecular chain arrangement mode than the 1, 2-dodecyl glycol, active groups such as amino groups on water-based polyurethane glue molecules can be further facilitated to diffuse into fiber gaps, good interface combination is obtained, the adhesion effect between fibers and water-based polyurethane glue is improved, the gum dipping effect is ensured, and the breaking strength of the marine polyester cable is greatly improved.

Example 2

(1) preparing modified polyester;

(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1.1:1:1.2:2.3, reacting for 2 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;

(b) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2:10:0.01, reacting for 50min at the temperature of 45 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Ca (NO) was added at a concentration of 0.5 mol%₃)₂Aqueous solution with Sb concentration of 5 mol%₂O₃The solution of (A) is mixed uniformly, Sb₂O₃The solvent of the solution (A) is oxalic acid, and Ca is contained in the mixed solution²⁺And Sb³⁺In a molar ratio of 1: 100;

(1.2.2) dropwise adding ammonia water with the concentration of 2mol/L until the pH value of the mixed solution is 10 to obtain a precipitate product, and then washing and drying the precipitate product at the drying temperature of 110 ℃ for 2 hours;

(1.2.3) heating the dried product to 400 ℃ firstly, then preserving heat for 2h, heating to 900 ℃ and then preserving heat for 1h, cooling in air and crushing to obtain the doped modified Sb with the average grain diameter of 0.4 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, dimethyl diphenyl disiloxane diol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, and adding doped modified Sb₂O₃Uniformly mixing the powder, titanium dioxide and trimethyl phosphite, 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 endpoint is when the water distillate in the esterification reaction reaches 92% of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol, dimethyl diphenyl disiloxane glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1:1.5:0.01:0.015, and the modified Sb is doped₂O₃The adding amount of the powder, the titanium dioxide and the trimethyl phosphite is 0.0135 wt%, 0.25 wt% and 0.01 wt% of the adding amount of the 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 400Pa within 40min, the reaction temperature is 250 ℃, the reaction time is 40min, 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 270 ℃, and the reaction time is 50 min;

(2) preparing modified polyester industrial yarn;

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 5dtex, the multifilament number of 3300dtex, the breaking strength of 8.1cN/dtex, the linear density deviation rate of 1.5 percent, the breaking strength CV value of 2.8 percent, the elongation at break of 13.0 percent, the elongation at break CV value of 7.9 percent, the central value of the elongation at 4.0cN/dtex load of 5.8 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 8.0 percent, the network degree of 5/m and the oil content of 0.4wt percent;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by performing gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twist degree of twisting is 20 twists/10 cm, the weft density of weaving is 1.8/10cm, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:5, the gum dipping treatment time is 60s, and the rope is dried for 11min at the temperature of 80 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1198ktex, and the breaking strength is 500 kN.

Example 3

(1) preparing modified polyester;

(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 octynediol;

(b) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.03, reacting for 50min at the temperature of 40 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Ba (NO) was added at a concentration of 1.0 mol%₃)₂Aqueous solution with 10 mol% Sb₂O₃The solution of (A) is mixed uniformly, Sb₂O₃The solvent of the solution (A) is oxalic acid, and Ba in the mixed solution²⁺And Sb³⁺In a molar ratio of 3: 100;

(1.2.2) dropwise adding ammonia water with the concentration of 2mol/L until the pH value of the mixed solution is 9.5 to obtain a precipitate, and then washing and drying the precipitate at the temperature of 105 ℃ for 3 hours;

(1.2.3) heating the dried product to 400 ℃ firstly, then preserving heat for 3h, heating to 900 ℃ and then preserving heat for 2h, cooling in air and crushing to obtain the doped modified Sb with the average grain diameter of 0.5 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, tetramethyl disiloxane diol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding doped modified Sb₂O₃Powder, titanium dioxide andafter triphenyl phosphate is uniformly mixed, the mixture is pressurized in a nitrogen atmosphere to carry out esterification reaction, the pressurization pressure is 0.2MPa, the temperature of the esterification reaction is 255 ℃, the end point of the esterification reaction is when the distilled amount of water in the esterification reaction reaches 90 percent of the theoretical value, wherein the molar ratio of terephthalic acid, ethylene glycol, tetramethyl disiloxane diol to 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1:2.0:0.012:0.01, and the doped modified Sb is Sb₂O₃The addition amounts of the powder, the titanium dioxide and the triphenyl phosphate are respectively 0.012 wt%, 0.21 wt% and 0.03 wt% of the addition amount of the 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 45min, 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 100Pa, the reaction temperature is 275 ℃, 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 the 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:

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 6dtex, the multifilament number of 1100dtex, the breaking strength of 8.5cN/dtex, the deviation rate of linear density of-1.5 percent, the CV value of the breaking strength of 3.0 percent, the elongation at break of 13.0 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 9.0 percent, the network degree of 10 pieces/m and the oil content of 0.4 percent by weight;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by performing gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twist degree of twisting is 25 twists/10 cm, the weft density of weaving is 1.6/10cm, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:8, the gum dipping treatment time is 50s, and the rope is dried for 10min at the temperature of 80 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1203ktex, and the breaking strength is 480 kN.

Example 4

(1) preparing modified polyester;

(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 octynediol;

(b) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 2.5:10:0.02, reacting for 60min at the temperature of 45 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Zn (NO) at a concentration of 0.6 mol%₃)₂Aqueous solution with Sb concentration of 6 mol%₂O₃The solution of (A) is mixed uniformly, Sb₂O₃Of the solution ofThe solvent is oxalic acid, and Zn is contained in the mixed solution²⁺And Sb³⁺In a molar ratio of 1.2: 100;

(1.2.2) dropwise adding ammonia water with the concentration of 2mol/L until the pH value of the mixed solution is 10 to obtain a precipitate product, and then washing and drying the precipitate product at the drying temperature of 110 ℃ for 2.5 hours;

(1.2.3) heating the dried product to 400 ℃, then preserving heat for 2.5h, then heating to 900 ℃, then preserving heat for 1h, finally cooling in air and crushing to obtain the doped modified Sb with the average grain diameter of 0.4 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, dimethyl silicon glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, and adding doped modified Sb₂O₃Uniformly mixing the powder, titanium dioxide and trimethyl phosphite, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the esterification reaction temperature is 250 ℃, the esterification reaction endpoint is when the water distillation amount in the esterification reaction reaches 90% of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol, dimethyl silicon glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1:1.5:0.013:0.011, and the modified Sb is doped₂O₃The addition amounts of the powder, the titanium dioxide and the trimethyl phosphite are respectively 0.012 wt%, 0.20 wt% and 0.02 wt% of the addition amount of the 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 420Pa within 50min, the reaction temperature is 260 ℃, the reaction time is 35min, 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 85Pa, the reaction temperature is 270 ℃, and the reaction time is 90 min;

(2) preparing modified polyester industrial yarn;

carrying out solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding on the modified polyester melt to obtain the modified polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.2dL/g, and the spinning process parameters are as follows:

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 8dtex, the multifilament number of 2300dtex, the breaking strength of 8.3cN/dtex, the deviation rate of linear density of-1.0 percent, the CV value of the breaking strength of 2.83 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 5.5 percent, the network degree of 5/m and the oil content of 0.5wt percent;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by carrying out gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twisting and weaving process parameters are the same as those of the example 1, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:8, the gum dipping treatment time is 55s, and the rope is dried for 10min at the temperature of 100 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1197ktex, and the breaking strength is 520 kN.

Example 5

(1) preparing modified polyester;

(a) mixing KOH powder, 3-methyl-3-hydroxybutyne, 3-dimethyl-2-butanone and isopropyl ether according to the molar ratio of 1:1:1.3:3.0, reacting for 4 hours under the ice bath condition, and after the reaction is finished, cooling, crystallizing, centrifugally separating, washing, refining and drying to obtain octynediol;

(b) mixing octynediol, 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);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Mg (NO) at a concentration of 0.7 mol%₃)₂Aqueous solution with Sb concentration of 8 mol%₂O₃The solution of (A) is mixed uniformly, Sb₂O₃The solvent of the solution is oxalic acid, and Mg in the mixed solution²⁺And Sb³⁺In a molar ratio of 2: 100;

(1.2.3) heating the dried product to 400 ℃ firstly, then preserving heat for 2.5h, heating to 900 ℃ and preserving heat for 2h, cooling in air and crushing to obtain the doped modified Sb with the average grain diameter of 0.5 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, dimethyl diphenyl disiloxane diol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, and adding doped modified Sb₂O₃Uniformly mixing the powder, titanium dioxide and trimethyl phosphate, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 252 ℃, the esterification reaction endpoint is when the distilled amount of water in the esterification reaction reaches 90% of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol, dimethyl diphenyl disiloxane glycol and 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1:1.6:0.015:0.014, and the modified Sb is doped₂O₃Powder, titanium dioxide and phosphoric acidThe addition amount of trimethyl ester is 0.015 wt%, 0.24 wt% and 0.01 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 500Pa within 30min, the reaction temperature is 256 ℃, the reaction time is 45min, 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 88Pa, the reaction temperature is 280 ℃, and the reaction time is 75 min;

(2) preparing modified polyester industrial yarn;

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 10dtex, the multifilament number of 3100dtex, the breaking strength of 8.2cN/dtex, the deviation rate of linear density of-1.5 percent, the CV value of the breaking strength of 3.0 percent, the elongation at break of 14.5 percent, the CV value of the elongation at break of 7.6 percent, the central value of the elongation under the load of 4.0cN/dtex of 6.0 percent, the dry heat shrinkage rate under the conditions of 177 ℃ multiplied by 10min multiplied by 0.05cN/dtex of 5.5 percent, the network degree of 6/m and the oil content of 0.8 percent by weight;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by carrying out gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twisting and weaving process parameters are the same as those of the example 1, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:10, the gum dipping treatment time is 56s, and the rope is dried for 15min at the temperature of 95 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1200ktex, and the breaking strength is 530 kN.

Example 6

(1) preparing modified polyester;

(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 octynediol;

(b) mixing octynediol, ethanol and a palladium catalyst according to the weight ratio of 3:10:0.03, reacting for 60min at the temperature of 50 ℃, continuously introducing hydrogen in the reaction process, and separating and purifying after the reaction is finished to obtain 2,5,6, 6-tetramethyl-2, 5-heptanediol, wherein the structural formula of the 2,5,6, 6-tetramethyl-2, 5-heptanediol is shown as a formula (I);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Mg (NO) was added in a concentration of 0.8 mol% in each case₃)₂Mixing the aqueous solution with Ca (NO)₃)₂Mixing the aqueous solution according to the volume ratio of 1:1 to obtain M containing metal ions^x+Aqueous solution of (2), containing metal ions M^x+With 8 mol% Sb₂O₃The solution of (A) is mixed uniformly, Sb₂O₃The solvent of the solution is oxalic acid, and M in the mixed solution^x+And Sb³⁺In a molar ratio of 2.5: 100;

(1.2.2) dropwise adding ammonia water with the concentration of 2mol/L until the pH value of the mixed solution is 10 to obtain a precipitate product, and then washing and drying the precipitate product at the drying temperature of 105 ℃ for 3 hours;

(1.2.3) heating the dried product to 400 ℃ firstly, then preserving heat for 3h, then heating to 900 ℃ and preserving heat for 1.5h, and finally cooling in the airPost-crushing to obtain doped modified Sb with average grain size of 0.4 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, tetramethyl disiloxane diol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding doped modified Sb₂O₃Uniformly mixing the powder, titanium dioxide and triphenyl phosphate, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 260 ℃, the esterification reaction endpoint is when the water distillation amount in the esterification reaction reaches 95 percent of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol, tetramethyldisiloxane glycol and 2,2,3,4,5, 5-hexamethyl-3, 4-hexanediol is 1:1.8:0.015:0.013, and the modified Sb is doped₂O₃The adding amount of the powder, the titanium dioxide and the triphenyl phosphate is respectively 0.014 wt%, 0.21 wt% and 0.05 wt% of the adding amount of the 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 absolute pressure of 490Pa, the reaction temperature is 260 ℃ and the reaction time is 50min within 30min, then continuously pumping vacuum to carry out the polycondensation reaction in the high vacuum stage, and further reducing the reaction pressure to absolute pressure of 90Pa, the reaction temperature is 275 ℃ and the reaction time is 50 min;

(2) preparing modified polyester industrial yarn;

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 10dtex, the multifilament number of 3300dtex, the breaking strength of 8.4cN/dtex, the deviation rate of linear density of-1.5 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 8.0 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 5.5 percent, the network degree of 6/m and the oil content of 0.6wt percent;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by carrying out gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twisting and weaving process parameters are the same as those of the example 2, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:10, the gum dipping treatment time is 60s, and the rope is dried for 13min at the temperature of 100 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1197ktex, and the breaking strength is 480 kN.

Example 7

(1) preparing modified polyester;

(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 octynediol;

(b) mixing octynediol, 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);

(1.2) preparation of doped modified Sb₂O₃；

(1.2.1) Mg (NO) was added in a concentration of 0.5 mol% in each case₃)₂Aqueous solution, Ba (NO)₃)₂Mixing the aqueous solution with Ca (NO)₃)₂Mixing the aqueous solution according to the volume ratio of 1:1:1 to obtain M containing metal ions^x+Aqueous solution of (2), containing metal ions M^x+With 10 mol% Sb₂O₃The solution of (A) is mixed uniformly, Sb₂O₃The solvent of the solution is oxalic acid, and the metal ions M in the mixed solution^x+And Sb³⁺In a molar ratio of 2: 100;

(1.2.2) dropwise adding ammonia water with the concentration of 2mol/L until the pH value of the mixed solution is 9 to obtain a precipitate, and then washing and drying the precipitate at the temperature of 108 ℃ for 2.5 hours;

(1.2.3) heating the dried product to 400 ℃, then preserving heat for 2.5h, then heating to 900 ℃, then preserving heat for 2h, finally cooling in air and crushing to obtain the doped modified Sb with the average grain diameter of 0.4 micron₂O₃Powder;

(1.3) esterification reaction;

preparing terephthalic acid, ethylene glycol, tetramethyl disiloxane diol and 2,5,6, 6-tetramethyl-2, 5-heptanediol into slurry, adding doped modified Sb₂O₃Uniformly mixing the powder, titanium dioxide and trimethyl phosphite, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the esterification reaction temperature is 250 ℃, the esterification reaction endpoint is when the water distillation amount in the esterification reaction reaches 92% of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol, tetramethyldisiloxane glycol and 2,2,3,4,5, 5-hexamethyl-3, 4-hexanediol is 1:1.2:0.015:0.015, and the modified Sb is doped₂O₃The adding amount of the powder, the titanium dioxide and the trimethyl phosphite is 0.015 wt%, 0.25 wt% and 0.03 wt% of the adding amount of the 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 absolute pressure of 440Pa within 40min, the reaction temperature is 260 ℃, the reaction time is 40min, 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 absolute pressure of 95Pa, the reaction temperature is 282 ℃, and the reaction time is 70 min;

(2) preparing modified polyester industrial yarn;

the technological parameters of stretching and heat setting are as follows:

the prepared modified polyester industrial yarn has the filament number of 7dtex, the multifilament number of 1100dtex, the breaking strength of 8.1cN/dtex, the linear density deviation rate of 1.3 percent, the breaking strength CV value of 2.9 percent, the elongation at break of 14.0 percent, the elongation at break CV value of 7.5 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 9.0 percent, the network degree of 7 pieces/m and the oil content of 0.4 percent by weight;

(3) preparing a polyester cable rope for a ship;

the marine polyester cable rope is prepared by carrying out gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns, wherein the twisting and weaving process parameters are the same as those of the example 3, the gum dipping treatment adopts water-based polyurethane glue, the mass ratio of polyurethane to water in the water-based polyurethane glue is l:9, the gum dipping treatment time is 50s, and the rope is dried for 15min at the temperature of 90 ℃ after the gum dipping treatment.

The linear density of the finally prepared marine polyester cable is 1203ktex, and the breaking strength is 510 kN.

Claims

1. The preparation method of the marine polyester mooring rope is characterized by comprising the following steps: carrying out gum dipping treatment on a rope obtained by twisting and weaving modified polyester industrial yarns to obtain a marine polyester cable rope;

at the beginning of the precipitation, the metal ions M in the mixed solution^x+And Sb³⁺The molar ratio of (A) to (B) is 1-3: 100;

the doped and modified Sb₂O₃The addition amount of the powder is 0.012-0.015 wt% of the addition amount of the terephthalic acid.

2. The preparation method of the marine polyester mooring rope as claimed in claim 1, wherein the modified polyester industrial yarn has a single fiber fineness of 5-10 dtex, a multifilament fineness of 1100-3300 dtex, a breaking strength of not less than 8.1cN/dtex, a linear density deviation ratio of +/-1.5%, a breaking strength CV value of not more than 3.0%, an elongation at break of 13.0-16.5%, an elongation at break CV value of not more than 8.0%, a central value of elongation at 4.0cN/dtex load of 5.5-6.0%, a dry heat shrinkage rate of 5.5-9.0% under 177 ℃ x 10min x 0.05cN/dtex condition, a network degree of (5-8) ± 2/m, and an oil content of 0.6 ± 0.2 wt%; the linear density of the marine polyester cable is 1200 +/-3 ktex, and the breaking strength is more than or equal to 480 kN.

3. The method for preparing the marine polyester cable as claimed in 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.

4. The method for preparing marine polyester cable rope according to claim 3, wherein the metal ion M is contained^x+The concentration of the solution is 0.5-1.0 mol%, the solvent is water, and the anion in the solution is NO₃ ^-(ii) a The Sb-containing compound³⁺The solution of (a) is Sb with the concentration of 5-10 mol%₂O₃The solvent of (1) is oxalic acid; the precipitator is ammonia water with the concentration of 2 mol/L;

5. The method for preparing the marine polyester cable rope as claimed in claim 4, wherein the steps of preparing the modified polyester before solid-phase polycondensation and tackifying are as follows:

(1) performing esterification reaction;

(2) performing polycondensation reaction;

6. The preparation method of the marine polyester cable rope as claimed in claim 5, wherein the molar ratio of the terephthalic acid, the ethylene glycol, the diol with silicon-containing main chain and the 2,5,6, 6-tetramethyl-2, 5-heptanediol is 1: 1.2-2.0: 0.01-0.015, and the addition amount of the delustrant and the stabilizer is 0.20-0.25 wt% and 0.01-0.05 wt% of the addition amount of the terephthalic acid, respectively.

7. The method for preparing the marine polyester cable as claimed in claim 6, wherein the matting agent is titanium dioxide and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.

8. The preparation method of the marine polyester cable rope as claimed in claim 1, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation and tackifying is 1.0-1.2 dL/g.

9. The preparation method of the marine polyester cable rope as claimed in claim 1, wherein the spinning process parameters of the modified polyester industrial yarn are as follows:

the technological parameters of stretching and heat setting are as follows:

10. the preparation method of the marine polyester cable rope as claimed in claim 1, wherein the gum dipping treatment adopts water-based polyurethane glue, and the mass ratio of polyurethane to water in the water-based polyurethane glue is l: 5-10; the time of the gum dipping treatment is 50-60 s; and drying for 10-15 min at the temperature of 80-100 ℃ after the gum dipping treatment.