CN109750381A - The preparation method of polyester industrial yarn for TGXG - Google Patents

Abstract

The present invention relates to a kind of preparation method of polyester industrial yarn for TGXG, detailed processes are as follows: by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, thermal finalization, heat treatment without tension and winding are made and are used for the polyester industrial yarn of TGXG；Modified poly ester the preparation method comprises the following steps: terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol successively to be carried out to esterification and polycondensation reaction after mixing before solid phase polycondensation viscosifies；Heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；Relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；Certain temperature refers to 200~240 DEG C.The thermal shrinkage of preparation method simple process of the invention, final polyester industrial yarn obtained can be excellent, and acid-proof alkaline is excellent, long service life.

Description

The preparation method of polyester industrial yarn for TGXG

Technical field

The invention belongs to modified polyester fiber technical fields, are related to a kind of preparation of polyester industrial yarn for TGXG Method.

Background technique

TGXG be by polymer materials such as polypropylene, high density polyethylene (HDPE), polyester fiber, glass fibres to stretch, What the techniques such as braiding or welding were formed after being processed has regular net holes and the higher geosynthetics of intensity, it is as one Kind New Building Materials have the advantages such as tensile capacity strong, deformation is small, corrosion-resistant, the service life is long, construction is convenient, low cost, It is widely used in railway and highway subgrade, harbour, harbour, flood control dam, barricade, tunnel, side slope protection and mine working Etc. Reinforced Material with Clay Engineering.With the continuous enhancing of national comprehensive strength, country also constantly adds the investment of infrastructure construction Greatly, types of functionality, fining, high performance TGXG are appeared on the market in succession to meet the market demand.

Polyester (terylene) TGXG have ultraviolet-resistant aging, corrosion-resistant, wear-resistant, tensile strength is high, elongation percentage is small, The features such as with soil and rubble interlocking power strong, at low cost, while having stronger bite force with base-material, also there is drainage.It is existing Be mainly used in the reinforcement of railway and the road surfaces enhancing such as highway soft soil ground enhancing, airport and town road, dykes and dams and river with And the fields such as side slope of embankment and retaining wall reinforcement.

There are symmetrical benzene ring structure, functional group's marshalling and unbranched presence, molecule chain rigiditys in polyester molecule chain By force, intermolecular force is strong.Polyester intensity with higher and transparency, rub resistance and creep resistant, have good resistance to consumption, Corrosion resistance, fatigue durability and dimensional stability.

The strength of the main strength and coating material including enhancing base materials of the tension failure strength of composite material, generally Say, synthetic polyester fibers due to end is rare, surface is smooth and chemical activity it is low it is more difficult establish adhesive bond at interface, by closing Need to carry out water repellent finish when making TGXG at fiber process using water repellent finishing agent, however water repellent finishing agent and polyester are fine The binding strength of the synthetic fibers such as dimension is limited, and the civil grille being made by synthetic fibers is in the environment of acid or alkalinity for a long time In, the bonding force of water repellent finishing agent and synthetic fibers therein can be gradually reduced, and the mechanical property of civil grille is caused to reduce, special It is not that tensile strength reduction becomes apparent.In addition, tending to occur irreversible thermal contraction after synthetic fibers are heated, washed in hot water When with ironing, contraction shows to become apparent, the civil grille being made by synthetic fibers at high temperature using easily deforming, It is used for having an adverse effect.

Therefore, the polyester industrial yarn of TGXG is modified to improve the heat resistance and resistance to acid and alkali of TGXG It can be of great significance.

Summary of the invention

It is of the existing technology the purpose of the present invention is overcoming the problems, such as, the polyester industrial yarn for TGXG is changed Into the heat resistance and acid-proof alkaline to improve TGXG, the improved thinking of the present invention are as follows: one, to polyester industrial yarn Material improves, and enhances the binding force of itself and water repellent finishing agent, and then improve the acid-proof alkaline of TGXG；Two, right Polyester industrial yarn carries out thermal finalization, to reduce its dry-hot shrinkage, and then improves the heat resistance of TGXG.

In order to achieve the above objectives, The technical solution adopted by the invention is as follows:

Modified poly ester melt is carried out solid phase polycondensation thickening, melted by the preparation method of the polyester industrial yarn for TGXG Melt, measure, squeezing out, cooling down, oiling, stretching, terylene industrial for TGXG is made in thermal finalization, heat treatment without tension and winding Silk；

Before the solid phase polycondensation viscosifies modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol and 2,2,3,4, 5,5- hexamethyl -3,4- hexylene glycol successively carries out esterification and polycondensation reaction after mixing；

The structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol is as follows:

After the present invention introduces 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols in polyester molecule chain, 2,2,3,4,5,5- The presence of tert-butyl can cause the variation of main chain activity in hexamethyl -3,4- hexylene glycol, thus the phase between changing chain element Interreaction force, the distance between molecule chain element can also occur to change accordingly, and the empty free volume of polyester is caused to increase, cavity The reactive group that free volume increase is conducive in water repellent finishing agent diffuses into fiber gap during heat treatment, obtains Good interface combines, thus the adhesive effect between fiber and water repellent finishing agent is improved, so that TGXG is acidproof, alkaline-resisting obtains Biggish raising is obtained, service life increases；

Compared with short-chain branch substituent group (such as methyl, ethyl group), tert-butyl occupies biggish spatial position, is dividing Bigger free volume will be obtained in the mode of subchain arrangement；Compared with chain substituent of drawing money on credit, what one side tert-butyl increased is Empty free volume, and draw money on credit chain substituent increase is slit free volume, the rigidity of another aspect tert-butyl, which is greater than, draws money on credit Chain substituent, reduces the entanglement between strand, thus tert-butyl is compared with drawing money on credit chain substituent in the mode that strand arranges With more free volumes, simultaneously because empty free volume has bigger useful space size compared with slit free volume, Reactive group more conducively in water repellent finishing agent penetrates into fibrous inside, and then mentions to civil grille acid resistance and alkaline resistance properties Ascending effect becomes apparent from；

The heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；

The relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；

The certain temperature refers to 200~240 DEG C；

The present invention reduces the shrinking percentage of polyester industrial fiber, polyester work by the mutual cooperation of heat treatment temperature and over feed rate(OFR) The shrinking percentage of industry silk reduces so that the heat resistance of TGXG as made from it is promoted, and fiber is in heat treatment, amorphous area Interior macromolecular chain folded chain easy to form, is conducive to the further growth of crystal grain, and crystallinity increases at this time, along with crystallinity Raising, fiber can generate a certain amount of contraction, on the one hand the present invention eliminates high elastic deformation to winding by improving over feed rate(OFR) Influence, on the other hand eliminate crystallinity improve during fiber contraction influence.

As a preferred option:

The preparation method of polyester industrial yarn as described above for TGXG, the polyester industrial yarn for TGXG Filament number be 3.0~5.0dtex, breaking strength >=8.5cN/dtex, line density deviation ratio be ± 1.5%, breaking strength CV value≤3.0%, elongation at break are 18.0~20.0%, extension at break CV value≤8.0%, initial modulus >=120.0cN/ Dtex, dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex are 2.0~2.8%, same size it is common Dry-hot shrinkage of industrial yarn under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.8.~3.8%；

The TGXG as made from the polyester industrial yarn for TGXG is 70~80 DEG C and volumetric concentration in temperature After impregnating 200~300h in 20% hydrochloric acid solution, stretching strength retentivity >=95.0% is 23~26 DEG C and pH in temperature After impregnating 6 weeks in the lye that value is 10, stretching strength retentivity >=98.0%；Common TGXG temperature be 23~26 DEG C and After impregnating 6 weeks in the lye that pH value is 10, stretching strength retentivity >=94.0%.The soil as made from polyester industrial yarn of the invention The acid resistance and alkali resistance of work grid are much higher than the prior art, are primarily due to the present invention and carry out to the material of polyester industrial yarn It improves, 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol segments, 2,2,3,4,5,5- pregnancy is introduced in the strand of polyester The presence of tert-butyl can cause the variation of main chain activity in base -3,4- hexylene glycol, thus the phase interaction between changing chain element Firmly, the distance between molecule chain element can also occur to change accordingly, as a result lead to the increase of polymer cavity free volume, empty Free volume increase in hole is conducive to molecule reactive group such as-NH in fluorine-containing water repellent finishing agent₂,-OH etc. during heat treatment It diffuses into fiber gap, obtains good interface and combine, thus improve the bonding between fiber and fluorine-containing water repellent finishing agent Effect so that TGXG it is acidproof, it is alkaline-resisting obtain biggish raising, service life increases.

The preparation method of polyester industrial yarn as described above for TGXG, described 2,2,3,4,5,5- hexamethyls- The synthetic method of 3,4- hexylene glycols are as follows: after mixing by palladium acetate and dimethyl di-t-butyl ethylene, mass concentration, which is added, is 10~15% hydrogen peroxide solution reacts 3~4h under conditions of temperature is 70~75 DEG C, through cooling, crystallizes and be refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, the quality of the dimethyl di-t-butyl ethylene, hydrogen peroxide solution and palladium acetate Than for 1:1.5~2.0:0.015.

The preparation method of polyester industrial yarn as described above for TGXG, the solid phase polycondensation thickening are preceding modified poly- The preparation step of ester is as follows:

(1) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols are made into slurry, and catalysis is added Agent, delustering agent and stabilizer after mixing, in nitrogen atmosphere pressurization carry out esterification, moulding pressure be normal pressure~ 0.3MPa, the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches 90% or more of theoretical value When be esterification terminal；

(2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 250~260 DEG C, the reaction time is 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 270~282 DEG C, the reaction time is 50~90min.

The preparation method of the polyester industrial yarn for TGXG as described above, the terephthalic acid (TPA), ethylene glycol and The molar ratio of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is 1:1.2~2.0:0.03~0.04, the catalyst, delustring The additional amount of agent and stabilizer is respectively 0.03~0.05wt%, the 0.20~0.25wt% and 0.01 of terephthalic acid (TPA) additional amount ~0.05wt% (mass percent).The additive amount of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol can according to the actual situation into Row adjustment, but adjust amplitude and should not be too large, additive amount is excessive, and it is too big to the regularity destruction of polyester molecule structure, to polyester fibre The crystallinity and Effect on Mechanical Properties of dimension are excessive, are unfavorable for the production and application of fiber；Additive amount is very few, to empty free body Long-pending increase is unobvious, little to the effect for the binding force for promoting fiber and water repellent finishing agent, to civil grille acid-proof alkaline Promotion effect it is unobvious.

The preparation method of the polyester industrial yarn for TGXG as described above, the catalyst be antimony oxide, Antimony glycol or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or phosphorous Sour trimethyl.

The preparation method of polyester industrial yarn as described above for TGXG, the solid phase polycondensation are modified poly- after viscosifying The inherent viscosity of ester is 1.0~1.2dL/g, and inherent viscosity can be adjusted in the appropriate range, but be should not be too large or too small, Excessive to cause melt viscosity excessive, spinnability decline, thermal degradation increases；It is too small, illustrate that molecular weight is relatively low, is not able to satisfy industrial yarn Performance indicator.

The preparation method of polyester industrial yarn as described above for TGXG, the space of the certain temperature refers to one To the space between arranged in parallel and non-coplanar hot plate, hot plate is located at last group of setting roller and take-up roll in FDY equipment Between；Along the traffic direction of modified poly ester tow, the length of two hot plates is 3.0~4.0m, and the both ends of two hot plates flush；It is modified poly- When ester tow passes through among two hot plates, the distance between two hot plates are 5~10mm.The present invention passes through control hot plate temperature (the i.e. described certain temperature) guarantees that macromolecular rearrangement can obtain energy, controls the length of hot plate to guarantee enough crystallization times, Control tow guarantees that the efficiency of heat treatment, the mutual coordinated of three improve the integrality of fiber crystallization at a distance from hot plate, And then reduce the thermal contraction during fiber applications, wherein hot plate temperature is too low, it is difficult to guarantee that macromolecular rearrangement can obtain foot Enough energy；Hot plate temperature is excessively high to destroy former established structure；Hot plate length is too short, and crystallization time is too short, influences fiber The integrality of crystallization influences fiber percent thermal shrinkage；The too long efficiency decline manufacturing apparatus waste of hot plate length；Tow is at a distance from hot plate Too small be easy to cause contacts with the direct of tow；Tow excessive thermal efficiency at a distance from hot plate reduces.

The preparation method of polyester industrial yarn as described above for TGXG, last group of setting roller and take-up roll Between spacing be 300~400mm；Spacing between two hot plates and last group of setting roller is 200~300mm.

The preparation method of polyester industrial yarn as described above for TGXG, the terylene work for TGXG The spinning technology parameter of industry silk is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

Invention mechanism:

It needs to carry out water repellent finish to polyester industrial yarn when making civil grille by polyester industrial yarn, to overcome terylene industrial Silk end is rare, surface is smooth and the low more difficult defect that adhesive bond is established at interface of chemical activity, and good mechanical performance is made Civil grille.Material of the present invention to polyester industrial yarn --- polyester is improved, and 2,2,3 are introduced in its strand, 4,5,5- hexamethyl -3,4- hexylene glycol segments, and then improve the empty free volume of polyester, empty free volume increase so that When carrying out water repellent finish, the reactive group in water repellent finishing agent can diffuse into polyester industrial yarn during heat treatment In fiber gap, the binding force of water repellent finishing agent and polyester industrial yarn is higher, for a long time both in acid or alkaline environment It still is able to be firmly combined, maintains the excellent mechanical property of civil grille, improve the acid-proof alkaline of civil grille.Simultaneously The present invention also carries out heat treatment without tension to polyester industrial yarn, to reduce its dry-hot shrinkage, the thermal stability of polyester industrial yarn It is promoted, so that the heat resistance of civil grille as made from it is promoted.Specific mechanism is explained as follows:

(1) present invention promotes the mechanism of polyester cavity free volume

Macromolecular chain in polymer is not closely to pile up completely, always with the presence of gap between macromolecular chain, this Portion void volume is free volume.It penetrates into small molecule inside macromolecule, to have foot in macromolecule or between macromolecule Enough big gaps, so pore size (the i.e. ruler of free volume in the permeability and diffusivity of small molecule and macromolecular structure It is very little) it is related, in a certain range, the size of free volume is bigger, and the permeability of small molecule is higher, and diffusivity is better.Free body Product is divided into empty free volume and slit free volume again, and empty free body has bigger bulk compared with slit free volume, Promotion for the permeability of small molecule, empty free volume are more obvious compared with slit free volume effect.

The size and type of free volume depend primarily on the structure of polymer, and the principal element for influencing polymer architecture is Steric hindrance, side group size, side group structure etc..When position a certain on main polymer chain is replaced by side group, necessarily cause main chain The variation of activity, to change the interaction force of chain and interchain, chain can also occur to change accordingly at a distance from interchain, As a result lead to the variation of cohesive energy and free volume, polarity, size and length of the substituent group on polymer side chain etc. are to molecule The fractional free volume of chain rigidity, intermolecular interaction or even polymer architecture all has a certain impact, and therefore, replaces The effect that base difference generates is different, and the permeability and separation performance for often leading to polymer is also different.

For the dihydric alcohols straight chain molecule such as ethylene glycol, butanediol, the C atom on main chain is arranged in indention one on the other Column, when the H atom on main chain on some methylene is by methyl (- CH₃) when replacing, C atom and main chain C atom in side group do not exist In same plane, then, four sp3 hybridized orbits on the C of center are Chong Die with the unoccupied orbital on four C atoms around respectively, shape It at four identical σ keys, is arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, works as first When three hydrogen of base is further replaced by methyl, it is at this moment equivalent to tert-butyl substitution, forms a bigger tetrahedral structure, The strand that this strand in the arrangement of positive tetrahedron shape is arranged relative to indention, empty free volume significantly increase Very much, the permeability and diffusivity of small molecule can be significantly improved；And when the H atom on main chain on some methylene is by long-chain branch When substituent group replaces, what is mainly increased is slit free volume, and it is smaller to increase amplitude, permeability to small molecule and diffusible Promotion effect is limited, simultaneously because the rigidity for chain substituent of drawing money on credit is smaller, entanglement is easy to happen between strand, is unfavorable for freedom The increase of volume.

The present invention introduces 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols in polyester molecule chain, and 2,2,3,4,5,5- The structural formula of hexamethyl -3,4- hexylene glycol is as follows:

The presence of tert-butyl can cause the variation of main chain activity in 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, from And the interaction force between chain element is changed, the distance between molecule chain element can also occur to change accordingly, cause polyester empty The increase of hole free volume.Compared with short-chain branch substituent group (such as methyl, ethyl group), tert-butyl occupies biggish space Position will obtain bigger free volume in the mode of strand arrangement；Compared with chain substituent of drawing money on credit, one side tert-butyl What is increased is empty free volume, and draw money on credit chain substituent increase is slit free volume, the rigidity of another aspect tert-butyl Greater than chain substituent of drawing money on credit, reduce the entanglement between strand, thus tert-butyl relatively draws money on credit chain substituent in strand arrangement Mode on there are more free volumes, simultaneously because empty free volume has bigger effective sky compared with slit free volume Between size, the more conducively active group of water repellent finishing agent penetrates into fibrous inside, thus empty free volume is to promoting terylene industrial The water repellent effect contribution of silk is bigger, becomes apparent to the promotion effect of civil grille acid-proof alkaline.

(2) present invention reduces the mechanism of polyester industrial yarn dry-hot shrinkage

Fiber is in post-processing stretching process, and due to the effect of mechanical stress, fiber orientation degree is significantly increased and has Certain crystallinity, to make elongate fiber and total deformation work reduce, during stretching, although the big portion of fibrogenic deformation Dividing is expendable plastic deformation under room temperature, and often because crystallization is fixed, however some can be in room temperature It is lower to restore because of the relaxation of tensile stress, or reply can be shunk in subsequent heat-treated, in the application process of fiber In this shrink that reply be that the shrinking percentage of fiber will be largely affected by performance (such as security performance, endurance quality of fiber Deng), it is assumed that the fiber is used as tire cord, and in use, cord fabric thread is stretched repeatedly, compressed, is bent tire, causes Tire is heated, leads to curtain linear shrinkage creep, but when curtain linear shrinkage is excessive may knife cord fabric delamination, and then lead to tire Disintegrate, this carrys out greatly hidden danger to using of seat belts for tire.

It is the shrinking percentage for reducing polyester industrial fiber as much as possible at present during the spin-drawing of polyester industrial fiber, It generally requires to carry out nervous thermal finalization (carrying out shaping fiber under some tension using setting roller) after carrying out multiple tracks stretching, To overfeeding of the over feed rate(OFR) for 1~2% is wound with after nervous thermal finalization, by carrying out nervous thermal finalization to fiber, in certain temperature Under conditions of degree and some tension, the mobility of molecule segment is improved, so that intermolecular combination obtains even closer, raising fiber Average grain size and crystallinity, to drop low-fiber shrinking percentage, but since fiber has certain height during stretching Deformation is played, elastic recovery can be generated in the case where tension reduces, therefore, it is fixed that the speed of winding head has to be lower than last group heat The speed of type roller needs certain over feed rate(OFR), is shunk, is expired with guaranteeing that the silk after stretching obtains a degree of low-tension The final product quality of meaning and package prevent package from causing turned-down edge because of overtension, over feed rate(OFR) need to control in a certain range (1~ 2%) it, crosses conference and adverse effect is generated to final product quality and package.Although can be to a certain extent by nervous thermal finalization+overfeeding Reduce shrinking percentage, but in nervous heat-setting process, due to the length of fiber be fixed it is immutable, it is suppressed that macromolecular chain Folding, thus the rate of grain growth is restricted, and causes to crystallize existing defects (crystallinity increases less), and only pass through Control overfeeding can not reduce crystal defect, when this will lead to fiber obtained and is heat-treated in application process, fiber it is big Strand and segment have higher activity, are easy to produce deorientation, cause fiber that a certain amount of shrink occurs and (shrink Rate is larger).

In fact, the thermal finalization mode of fiber is not only nervous thermal finalization, further includes relaxation heat setting.Relaxation heat setting is again Referred to as free shrink thermal finalization is fiber under complete no-station pole canopy or the lesser situation of tension, by certain temperature to fiber Be heat-treated, under the conditions of relaxation heat setting, fiber can free shrink, the macromolecular chain folding easy to form in amorphous area Chain is conducive to the further growth of crystal grain, in addition more abundant heat treatment time, therefore after heat treatment without tension, the knot of fiber Brilliant degree increases more (compared to nervous thermal finalization), to make that fibrous inside high elastic deformation is restored while internal stress is filled Divide relaxation, so that fibrogenic contraction reply is smaller when being heat-treated in application process.Current relaxation heat is fixed Type be mainly used for polyester staple fiber carry out thermal finalization processing, heat treatment temperature is lower (130 DEG C or so), heat treatment time compared with It is long, it is difficult to be suitable for long filament and produce.

The present invention by the way that the over feed rate(OFR) that polyester tow is wound is promoted to 3~5% in the process of polyester industrial fiber, Hot plate arranged in parallel above and below a pair of is set between last one of setting roller and take-up roll simultaneously, polyester tow is warm from two It is passed through among plate, improves the crystallinity of polyester tow, restored the high elastic deformation inside polyester tow, so that in polyester tow Stress obtains a certain amount of relaxation, and then reduces and shunk back in application process by polyester industrial fiber when being heat-treated It is multiple.The present invention reduces the shrinking percentage of polyester industrial fiber, fiber by the mutual cooperation of heat treatment temperature and higher over feed rate(OFR) In heat treatment, macromolecular chain folded chain easy to form in amorphous area is conducive to the further growth of crystal grain, crystallizes at this time Degree increases, and along with the raising of crystallinity, fiber can generate a certain amount of contraction, and the present invention is by improving over feed rate(OFR), on the one hand Influence of the high elastic deformation to winding is eliminated, the influence of the contraction of fiber during crystallinity improves on the other hand is eliminated.This Outside, on the one hand the present invention is overcome existing by the mutual cooperation of heat treatment temperature, hot plate length and tow and hot plate apart from three There is technology heat treatment without tension not to be suitable for the defect of long filament production, on the other hand, improves the integrality of fiber crystallization, improve The stability of fiber size reduces the thermal contraction in its application process.

The utility model has the advantages that

(1) preparation method of the polyester industrial yarn for TGXG of the invention, by heat treatment temperature with it is higher The mutual cooperation of over feed rate(OFR) improves the integrality of fiber crystallization, reduces the thermal contraction in its application process, and then improve The heat resistance of civil grille as made from it；

(2) preparation method of the polyester industrial yarn for TGXG of the invention, by increasing the cavity of polyester freely Volume, improves the binding force of fiber and water repellent finishing agent, and then improves the acid-proof alkaline of civil grille as made from it；

(3) preparation method of the polyester industrial yarn for TGXG of the invention, simple process and low cost are great Application prospect.

Specific embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.

Embodiment 1

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 10%, reacts 3h under conditions of temperature is 72 DEG C, pass through Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen Aqueous solution and the mass ratio of palladium acetate are 1:2.0:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols (I) shown in；

(1.2) esterification；

By molar ratio be 1:1.2:0.03 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, pressurizes and carries out in nitrogen atmosphere Esterification, moulding pressure are normal pressure, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 95% when be esterification terminal, the additional amount of antimony oxide, titanium dioxide and triphenyl phosphate is respectively to benzene two 0.03wt%, 0.20wt% and 0.01wt% of formic acid additional amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min The interior absolute pressure that is steadily evacuated to by normal pressure is 480Pa, and reaction temperature is 250 DEG C, reaction time 30min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 80Pa, reaction temperature 270 DEG C, reaction time 50min, the number-average molecular weight of modified poly ester obtained is 24000, molecular weight distributing index 1.9；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.0dL/g, the polyester tow that it is 3% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar same The space between hot plate that Shi Wendu is 200 DEG C, hot plate are located in FDY equipment between last group of setting roller and take-up roll, Along the traffic direction of polyester tow, the length of two hot plates is 3.0m, and the both ends of two hot plates flush, and polyester tow is among two hot plates Across when, the distance between two hot plates are 5mm, and spacing between last group of setting roller and take-up roll is 300mm, two Spacing between hot plate and last group of setting roller is 200mm；The spinning technique of polyester industrial yarn for TGXG is joined Number is as follows: each area's temperature of screw rod is 290 DEG C；Spin manifold temperature is 295 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C； Side-blown wind moisture is 75%；Cross air blasting wind speed is 0.5m/s；Winding speed is 5305m/min；It stretches, the technological parameter of thermal finalization Are as follows: a roller speed is 3000m/min；One roll temperature is 75 DEG C；Two roller speeds are 4000m/min；Two roll temperatures are 90 DEG C；Three rollers Speed is 5500m/min；Three roll temperatures are 250 DEG C；Four roller speeds are 5470m/min；Four roll temperatures are 250 DEG C；Five roller speeds For 5470m/min；Five roll temperatures are 250 DEG C.

The filament number of polyester industrial yarn for TGXG is 3.0dtex, breaking strength 9.3cN/dtex, and line is close Spending deviation ratio is 1.3%, and breaking strength CV value is 2.4%, elongation at break 20.0%, and extension at break CV value is 7.2%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.0%, initial modulus 130.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 70 DEG C in temperature and volumetric concentration is After impregnating 200h in 20% hydrochloric acid solution, stretching strength retentivity 95.0%, in the alkali that temperature is 23 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.0%.

Comparative example 1

The preparation method of polyester industrial yarn, preparation method and embodiment 1 are almost the same, the difference is that in step (1.2) not Add 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol.The filament number of polyester industrial yarn is 3.0dtex, and breaking strength is 9.3cN/dtex, line density deviation ratio are 1.3%, and breaking strength CV value is 2.4%, and elongation at break 2,1.0%, fracture is stretched Long CV value is 7.5%, and dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.0%, and initial modulus is 132.0cN/dtex；

Under preparation condition same as Example 1, the TGXG as made from the polyester industrial yarn is 70 DEG C in temperature And after volumetric concentration is impregnates 200h in 20% hydrochloric acid solution, stretching strength retentivity 94% is 23 DEG C and pH in temperature After impregnating 6 weeks in the lye that value is 10, stretching strength retentivity 94%.It compares with embodiment 1 it can be found that due to the present invention 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols can increase the empty free volume of polyester, empty free volume increase has Conducive to the molecule reactive group such as-NH in fluorine-containing water repellent finishing agent₂,-OH etc. diffuse into fiber sky during heat treatment It in gap, obtains good interface and combines, thus improve the adhesive effect between fiber and fluorine-containing water repellent finishing agent, so that TGXG Acidproof, alkaline-resisting to obtain biggish raising, service life increases, at the same the mechanical property of modified polyester industrial fiber itself not by It influences.

Comparative example 2

The preparation method of polyester industrial yarn, preparation method and embodiment 1 are almost the same, the difference is that adopting in step (1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols are replaced with 1,2 dodecanediol, under preparation condition same as Example 1, The TGXG as made from the polyester industrial yarn is impregnated in the hydrochloric acid solution that temperature is 70 DEG C and volumetric concentration is 20% After 200h, stretching strength retentivity 94%, after 6 weeks are impregnated in the lye that temperature is 23 DEG C and pH value is 10, tensile strength Conservation rate is 94%.It compares with embodiment 1 it can be found that compared to slit free volume, due to of the invention 2,2,3,4,5, The empty free volume that 5- hexamethyl -3,4- hexylene glycol increases is more advantageous to the molecule reactive group made in fluorine-containing water repellent finishing agent Such as-NH₂,-OH etc. diffuse into fiber gap during heat treatment, obtain good interface and combine, thus improve fiber With the adhesive effect between fluorine-containing water repellent finishing agent so that TGXG is acidproof, alkaline-resisting obtains biggish raising.

Embodiment 2

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 11%, reacts 4h under conditions of temperature is 70 DEG C, pass through Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen Aqueous solution and the mass ratio of palladium acetate are 1:1.8:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols (I) shown in；

(1.2) esterification；

By molar ratio be 1:1.5:0.032 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony oxide, titanium dioxide and trimethyl phosphate is added after mixing, pressurizes and carries out in nitrogen atmosphere Esterification, moulding pressure 0.25MPa, the temperature of esterification is 252 DEG C, when the water quantity of distillate in esterification reaches reason By value 95% when be esterification terminal, the additional amount of antimony oxide, titanium dioxide and trimethyl phosphate is respectively to benzene 0.02wt%, 0.22wt% and 0.03wt% of dioctyl phthalate additional amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 44min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 252 DEG C, reaction time 32min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 90, and reaction temperature is 270 DEG C, Reaction time is 55min, and the number-average molecular weight of modified poly ester obtained is 24800, molecular weight distributing index 1.9；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.0dL/g, the polyester tow that it is 3.1% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 207 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.2m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 6mm, and the spacing between last group of setting roller and take-up roll is 311mm, the spacing between two hot plates and last group of setting roller are 220mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 290 DEG C；Cabinet temperature Degree is 295 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 75%；Cross air blasting wind speed is 0.5m/s；Winding speed is 5300m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3000m/min；One roller temperature Degree is 75 DEG C；Two roller speeds are 4000m/min；Two roll temperatures are 90 DEG C；Three roller speeds are 5500m/min；Three roll temperatures are 250 ℃；Four roller speeds are 5470m/min；Four roll temperatures are 250 DEG C；Five roller speeds are 5470m/min；Five roll temperatures are 250 DEG C.

The filament number of polyester industrial yarn for TGXG is 3.0dtex, breaking strength 9.2cN/dtex, and line is close Spending deviation ratio is -1.3%, and breaking strength CV value is 2.4%, elongation at break 19.0%, and extension at break CV value is 7.4%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.2%, initial modulus 130.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 70 DEG C in temperature and volumetric concentration is After impregnating 200h in 20% hydrochloric acid solution, stretching strength retentivity 95.2%, in the alkali that temperature is 23 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.2%.

Embodiment 3

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 12%, reacts 4h under conditions of temperature is 74 DEG C, pass through Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen Aqueous solution and the mass ratio of palladium acetate are 1:1.6:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols (I) shown in；

(1.2) esterification；

By molar ratio be 1:1.5:0.034 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing, pressurizes and carries out in nitrogen atmosphere Esterification, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches reason By value 95% when be esterification terminal, the additional amount of antimony glycol, titanium dioxide and Trimethyl phosphite is respectively to benzene 0.03wt%, 0.25wt% and 0.05wt% of dioctyl phthalate additional amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 38min The interior absolute pressure that is steadily evacuated to by normal pressure is 440Pa, and reaction temperature is 251 DEG C, reaction time 33min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 272 DEG C, reaction time 60min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 2.0；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.1dL/g, the polyester tow that it is 3.77% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-total Temperature is space between 215 DEG C of hot plate simultaneously in face, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.3m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 7mm, and the spacing between last group of setting roller and take-up roll is 335mm, the spacing between two hot plates and last group of setting roller are 235mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 300 DEG C；Cabinet temperature Degree is 297 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 5350m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3050m/min；One roller temperature Degree is 80 DEG C；Two roller speeds are 4100m/min；Two roll temperatures are 95 DEG C；Three roller speeds are 5600m/min；Three roll temperatures are 252 ℃；Four roller speeds are 5560m/min；Four roll temperatures are 255 DEG C；Five roller speeds are 5560m/min；Five roll temperatures are 255 DEG C.

The filament number of polyester industrial yarn for TGXG is 3.5dtex, breaking strength 9.0cN/dtex, and line is close Spending deviation ratio is -1.4%, and breaking strength CV value is 2.5%, elongation at break 19.0%, and extension at break CV value is 7.4%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.2%, initial modulus 129.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 75 DEG C in temperature and volumetric concentration is After impregnating 220h in 20% hydrochloric acid solution, stretching strength retentivity 95.5%, in the alkali that temperature is 25 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.5%.

Embodiment 4

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 13%, reacts 3.5h under conditions of temperature is 74 DEG C, It through cooling, crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, double Oxygen aqueous solution and the mass ratio of palladium acetate are 1:1.5:0.015, and the structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is such as Shown in formula (I)；

(1.2) esterification；

By molar ratio be 1:1.5:0.036 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony glycol, titanium dioxide and triphenyl phosphate is added after mixing, and pressurization carries out ester in nitrogen atmosphere Change reaction, moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 95% when be esterification terminal, the additional amount of antimony glycol, titanium dioxide and triphenyl phosphate is respectively terephthaldehyde 0.05wt%, 0.25wt% and 0.03wt% of sour additional amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 460Pa, and reaction temperature is 253 DEG C, reaction time 35min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 88Pa, reaction temperature 274 DEG C, reaction time 65min, the number-average molecular weight of modified poly ester obtained is 25500, molecular weight distributing index 2.2；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.1dL/g, the polyester tow that it is 3.77% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-total Temperature is space between 222 DEG C of hot plate simultaneously in face, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.4m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 8mm, and the spacing between last group of setting roller and take-up roll is 346mm, the spacing between two hot plates and last group of setting roller are 250mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 300 DEG C；Cabinet temperature Degree is 297 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 5350m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3050m/min；One roller temperature Degree is 80 DEG C；Two roller speeds are 4100m/min；Two roll temperatures are 95 DEG C；Three roller speeds are 5600m/min；Three roll temperatures are 252 ℃；Four roller speeds are 5560m/min；Four roll temperatures are 255 DEG C；Five roller speeds are 5560m/min；Five roll temperatures are 255 DEG C.

The filament number of polyester industrial yarn for TGXG is 3.5dtex, breaking strength 8.8cN/dtex, and line is close Spending deviation ratio is -1.4%, and breaking strength CV value is 2.5%, elongation at break 19.0%, and extension at break CV value is 7.4%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.5%, initial modulus 128.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 75 DEG C in temperature and volumetric concentration is After impregnating 220h in 20% hydrochloric acid solution, stretching strength retentivity 95.7%, in the alkali that temperature is 25 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.8%.

Embodiment 5

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1)) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 14%, reacts 3.5h under conditions of temperature is 71 DEG C, It through cooling, crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, double Oxygen aqueous solution and the mass ratio of palladium acetate are 1:1.7:0.015, and the structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is such as Shown in formula (I)；

(1.2) esterification；

By molar ratio be 1:1.5:0.07 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony acetate, titanium dioxide and triphenyl phosphate is added after mixing, pressurizes and is esterified in nitrogen atmosphere Reaction, moulding pressure are normal pressure, and the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 95%, the additional amount of antimony acetate, titanium dioxide and triphenyl phosphate is respectively that terephthalic acid (TPA) is added 0.03wt%, 0.20wt% and 0.02wt% of amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 42min The interior absolute pressure that is steadily evacuated to by normal pressure is 470Pa, and reaction temperature is 255 DEG C, reaction time 36min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 92Pa, reaction temperature 274 DEG C, reaction time 70min, the number-average molecular weight of modified poly ester obtained is 26300, molecular weight distributing index 2.4；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 3.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 232 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.6m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 8.5mm, and the spacing between last group of setting roller and take-up roll is 368mm, the spacing between two hot plates and last group of setting roller are 260mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 310 DEG C；Cabinet temperature Degree is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 5490m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3100m/min；One roller temperature Degree is 80 DEG C；Two roller speeds are 4000m/min；Two roll temperatures are 95 DEG C；Three roller speeds are 5600m/min；Three roll temperatures are 255 ℃；Four roller speeds are 5660m/min；Four roll temperatures are 250 DEG C；Five roller speeds are 5660m/min；Five roll temperatures are 250 DEG C.

The filament number of polyester industrial yarn for TGXG is 4.5dtex, breaking strength 8.7cN/dtex, and line is close Spending deviation ratio is -1.4%, and breaking strength CV value is 2.7%, elongation at break 19.0%, and extension at break CV value is 7.7%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.5%, initial modulus 128.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 75 DEG C in temperature and volumetric concentration is After impregnating 250h in 20% hydrochloric acid solution, stretching strength retentivity 95.7%, in the alkali that temperature is 25 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.8%.

Embodiment 6

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and 2,2,3,4,5,5- are synthesized After mixing, the hydrogen peroxide solution that mass concentration is 15% is added in hexamethyl -3,4- hexylene glycol dimethyl di-t-butyl ethylene, Temperature be 75 DEG C under conditions of react 3h, through cooling, crystallize and be refining to obtain 2,2,3,4,5,5- hexamethyls -3,4- oneself two Alcohol, wherein the mass ratio of dimethyl di-t-butyl ethylene, hydrogen peroxide solution and palladium acetate be 1:1.9:0.015,2,2,3,4,5, Shown in the structural formula such as formula (I) of 5- hexamethyl -3,4- hexylene glycol；

(1.2) esterification；

By molar ratio be 1:2.0:0.038 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, and pressurization carries out ester in nitrogen atmosphere Change reaction, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 95% when be esterification terminal, the additional amount of antimony acetate, titanium dioxide and Trimethyl phosphite is respectively terephthaldehyde 0.05wt%, 0.20wt% and 0.01wt% of sour additional amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 46min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 258 DEG C, reaction time 38min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 95Pa, reaction temperature 275 DEG C, reaction time 80min, the number-average molecular weight of modified poly ester obtained is 26700, molecular weight distributing index 2.1；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 3.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 235 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.8m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 9mm, and the spacing between last group of setting roller and take-up roll is 384mm, the spacing between two hot plates and last group of setting roller are 280mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 310 DEG C；Cabinet temperature Degree is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 5490m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3100m/min；One roller temperature Degree is 80 DEG C；Two roller speeds are 4200m/min；Two roll temperatures are 95 DEG C；Three roller speeds are 5600m/min；Three roll temperatures are 255 ℃；Four roller speeds are 5660m/min；Four roll temperatures are 250 DEG C；Five roller speeds are 5660m/min；Five roll temperatures are 250 DEG C.

The filament number of polyester industrial yarn for TGXG is 4.0dtex, breaking strength 8.6cN/dtex, and line is close Spending deviation ratio is -1.5%, and breaking strength CV value is 2.8%, elongation at break 18.0%, and extension at break CV value is 7.7%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.7%, initial modulus 124.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 75 DEG C in temperature and volumetric concentration is After impregnating 250h in 20% hydrochloric acid solution, stretching strength retentivity 96.7%, in the alkali that temperature is 25 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.5%.

Embodiment 7

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 13.5%, reacts under conditions of temperature is 73 DEG C 3.4h through cooling, is crystallized and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl second The mass ratio of alkene, hydrogen peroxide solution and palladium acetate is 1:1.8:0.015, the knot of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols Shown in structure formula such as formula (I)；

(1.2) esterification；

By molar ratio be 1:1.8:0.038 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two Alcohol is made into slurry, and antimony acetate, titanium dioxide and triphenyl phosphate is added after mixing, pressurizes and is esterified in nitrogen atmosphere Reaction, moulding pressure 0.25MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical value 95% when be esterification terminal, the additional amount of antimony acetate, titanium dioxide and triphenyl phosphate is respectively that terephthalic acid (TPA) adds Enter 0.02wt%, 0.20wt% and 0.05wt% of amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min The interior absolute pressure that is steadily evacuated to by normal pressure is 490Pa, and reaction temperature is 259 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 83Pa, reaction temperature 282 DEG C, reaction time 85min, the number-average molecular weight of modified poly ester obtained is 27000, molecular weight distributing index 1.9；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed The polyester industrial yarn for TGXG is made in type, heat treatment without tension and winding, wherein modified poly ester after solid phase polycondensation thickening Inherent viscosity is 1.2dL/g, and the polyester tow that it is 5.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of of parallel Column and non-co-planar while temperature are the space between 240 DEG C of hot plate, hot plate be located in FDY equipment last group of setting roller and Between take-up roll, along the traffic direction of polyester tow, the length of two hot plates is 4.0m, and the both ends of two hot plates flush, polyester tow When passing through among from two hot plates, the distance between two hot plates are 10mm, between last group of setting roller and take-up roll Spacing is 400mm, and the spacing between two hot plates and last group of setting roller is 300mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 320 DEG C；Cabinet temperature Degree is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 85%；Cross air blasting wind speed is 0.7m/s；Winding speed is 5375m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3100m/min；One roller temperature Degree is 85 DEG C；Two roller speeds are 4200m/min；Two roll temperatures are 100 DEG C；Three roller speeds are 5700m/min；Three roll temperatures are 255℃；Four roller speeds are 5660m/min；Four roll temperatures are 255 DEG C；Five roller speeds are 5660m/min；Five roll temperatures are 255 ℃。

The filament number of polyester industrial yarn for TGXG is 4.5dtex, breaking strength 8.7cN/dtex, and line is close Spending deviation ratio is 1.5%, and breaking strength CV value is 2.9%, elongation at break 18.0%, and extension at break CV value is 7.7%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.8%, initial modulus 122.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 75 DEG C in temperature and volumetric concentration is After impregnating 300h in 20% hydrochloric acid solution, stretching strength retentivity 96.9%, in the alkali that temperature is 25 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 98.8%.

Embodiment 8

The preparation method of polyester industrial yarn for TGXG, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 13.5%, reacts under conditions of temperature is 73 DEG C 3.4h through cooling, is crystallized and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl second The mass ratio of alkene, hydrogen peroxide solution and palladium acetate is 1:1.8:0.015, the knot of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols Shown in structure formula such as formula (I)；

(1.2) esterification；

Terephthalic acid (TPA), ethylene glycol and the 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol for being 1:2:0.04 by molar ratio It is made into slurry, antimony acetate, titanium dioxide and triphenyl phosphate is added after mixing, pressurization be esterified anti-in nitrogen atmosphere It answers, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 95%, the additional amount of antimony acetate, titanium dioxide and triphenyl phosphate is respectively that terephthalic acid (TPA) is added 0.03wt%, 0.25wt% and 0.05wt% of amount；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min The interior absolute pressure that is steadily evacuated to by normal pressure is 400Pa, and reaction temperature is 260 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 96Pa, reaction temperature 274 DEG C, reaction time 90min, the number-average molecular weight of modified poly ester obtained is 28000, molecular weight distributing index 2.4；

(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 5.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 240 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 4.0m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 10mm, and the spacing between last group of setting roller and take-up roll is 400mm, the spacing between two hot plates and last group of setting roller are 300mm；

The spinning technology parameter of polyester industrial yarn for TGXG is as follows: each area's temperature of screw rod is 320 DEG C；Cabinet temperature Degree is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 85%；Cross air blasting wind speed is 0.7m/s；Winding speed is 5375m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 3100m/min；One roller temperature Degree is 85 DEG C；Two roller speeds are 4200m/min；Two roll temperatures are 100 DEG C；Three roller speeds are 5700m/min；Three roll temperatures are 255℃；Four roller speeds are 5660m/min；Four roll temperatures are 255 DEG C；Five roller speeds are 5660m/min；Five roll temperatures are 255 ℃。

The filament number of polyester industrial yarn for TGXG is 5.0dtex, breaking strength 8.5cN/dtex, and line is close Spending deviation ratio is -1.5%, and breaking strength CV value is 3.0%, elongation at break 18.0%, and extension at break CV value is 8.0%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 3.0%, initial modulus 120.0cN/dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 80 DEG C in temperature and volumetric concentration is After impregnating 300h in 20% hydrochloric acid solution, stretching strength retentivity 97.9%, in the alkali that temperature is 26 DEG C and pH value is 10 After impregnating 6 weeks in liquid, stretching strength retentivity 99%.

Claims (10)

1. the preparation method of the polyester industrial yarn for TGXG, it is characterized in that: modified poly ester melt is carried out solid phase polycondensation It viscosifies, melts, measure, squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding are made for TGXG Polyester industrial yarn；

Modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- before the solid phase polycondensation viscosifies Hexamethyl -3,4- hexylene glycol successively carries out esterification and polycondensation reaction after mixing；

The structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol is as follows:

The heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；

The relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；

The certain temperature refers to 200~240 DEG C.

2. the preparation method of the polyester industrial yarn according to claim 1 for TGXG, which is characterized in that for soil The filament number of the polyester industrial yarn of work grid is 3.0~5.0dtex, breaking strength >=8.5cN/dtex, line density deviation ratio It is ± 1.5%, breaking strength CV value≤3.0%, elongation at break is 18.0~20.0%, extension at break CV value≤8.0%, Dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.0~2.8%, initial modulus >=120.0cN/ dtex；

The TGXG as made from the polyester industrial yarn for TGXG be 70~80 DEG C in temperature and volumetric concentration is After impregnating 200~300h in 20% hydrochloric acid solution, stretching strength retentivity >=95.0% is 23~26 DEG C and pH value in temperature After impregnating 6 weeks in 10 lye, stretching strength retentivity >=98.0%.

3. the preparation method of the polyester industrial yarn according to claim 1 for TGXG, which is characterized in that described 2, The synthetic method of 2,3,4,5,5- hexamethyl -3,4- hexylene glycol are as follows: be uniformly mixed palladium acetate and dimethyl di-t-butyl ethylene Afterwards, the hydrogen peroxide solution that mass concentration is 10~15% is added, 3~4h is reacted under conditions of temperature is 70~75 DEG C, through cold But, crystallize and be refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, the dimethyl di-t-butyl ethylene, hydrogen peroxide Solution and the mass ratio of palladium acetate are 1:1.5~2.0:0.015.

4. the preparation method of the polyester industrial yarn according to claim 3 for TGXG, which is characterized in that described solid The preparation step of modified poly ester is as follows before phase condensation viscosity enhancing:

(1) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols are made into slurry, and catalyst is added, disappears After mixing, pressurization carries out esterification in nitrogen atmosphere for photo etching and stabilizer, and moulding pressure is normal pressure~0.3MPa, ester The temperature for changing reaction is 250~260 DEG C, anti-for esterification when the water quantity of distillate in esterification reaches 90% or more of theoretical value Answer terminal；

(2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 250~260 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 270~282 DEG C, and the reaction time is 50~90min.

5. the preparation method of the polyester industrial yarn according to claim 4 for TGXG, which is characterized in that described right The molar ratio of phthalic acid, ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol be 1:1.2~2.0:0.03~ 0.04, the additional amount of the catalyst, delustering agent and stabilizer be respectively terephthalic acid (TPA) additional amount 0.03~0.05wt%, 0.20~0.25wt% and 0.01~0.05wt%.

6. the preparation method of the polyester industrial yarn according to claim 5 for TGXG, which is characterized in that described to urge Agent is antimony oxide, antimony glycol or antimony acetate, and the delustering agent is titanium dioxide, and the stabilizer is phosphoric acid triphen Ester, trimethyl phosphate or Trimethyl phosphite.

7. the preparation method of the polyester industrial yarn according to claim 6 for TGXG, which is characterized in that described solid The inherent viscosity of modified poly ester is 1.0~1.2dL/g after phase condensation viscosity enhancing.

8. the preparation method of the polyester industrial yarn according to claim 1 for TGXG, which is characterized in that described one The space for determining temperature refers to space between a pair of arranged in parallel and non-coplanar hot plate, and hot plate is located at last in FDY equipment Between group setting roller and take-up roll；Along the traffic direction of modified poly ester tow, the length of two hot plates is 3.0~4.0m, two heat The both ends of plate flush；When modified poly ester tow passes through among two hot plates, the distance between two hot plates are 5~10mm.

9. the preparation method of the polyester industrial yarn according to claim 8 for TGXG, which is characterized in that last Spacing between group setting roller and take-up roll is 300~400mm；Spacing between two hot plates and last group of setting roller is 200~300mm.

10. the preparation method of the polyester industrial yarn according to claim 1 for TGXG, which is characterized in that

The spinning technology parameter of the polyester industrial yarn for TGXG is as follows:

It stretches, the technological parameter of thermal finalization are as follows: