CN104562279B - A kind of low-shrinkage anti-wicking polyester industrial fiber and manufacture method thereof - Google Patents

Abstract

The present invention relates to a kind of low-shrinkage anti-wicking polyester industrial fiber and manufacture method thereof.Cut into slices as raw material with the thickening of modified poly ester, process through melt spinning and anti-wicking and prepare；Described modified poly ester is made up of with amino ethylene glycol fatty acid polyester, described amino ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and the molecule interchain of described amino ethylene glycol fatty acid and described polyester has hydrogen bond action, described amino ethylene glycol fatty acid is made to fix with the relative position of the strand of described polyester；Containing perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group in anti-wicking agent.It is high that product had both had the intrinsic fracture strength of ultralow contraction terylene industry silk, the features such as dry shrinkage is little, possess again good hydrophobic performance and preferable resistance to UV aging, in fields such as high-grade lamp box advertisement cloth, waterproof cloth and swimming pool fabrics, there is application prospect widely.

Description

A kind of low-shrinkage anti-wicking polyester industrial fiber and manufacture method thereof

Technical field

The present invention relates to the production method of a kind of fibre modification, especially relate to a kind of anti-wicking and there is uvioresistant function The manufacture method of low-shrinkage anti-wicking polyester industrial fiber, belong to macromolecular fibre production technical field.

Background technology

In recent years, along with the development in the fields such as high-grade lamp box advertisement cloth, swimming pool cloth and puggaree, anti-core suction type terylene industrial The market demand and the application prospect of silk are more and more wide.Anti-core suction type polyester industrial yarn refers at fiber surface introducing-CF₂Base Group, drops low-fiber surface tension, makes fiber surface be difficult to infiltrate, thus the superior water proofing property of endowing terylene and grease proofness, make Fiber surface has good agent of low hygroscopicity energy.

The effective ingredient of anti-wicking agent is fluorocarbon.Fluorocarbon is a kind of surface activity with amphiphilic group Agent, contains hydrophobic fluoro-containing group and hydrophilic non-fluorin radical respectively.Fiber after heat treatment, along with moisture in anti-wicking agent Evaporation and high temperature action, the hydrophilic group originally stretching to outside is gradually retracted into intramolecule, forms film at fiber surface, hydrophobic The fluoroalkyl of property is distributed in fiber surface, makes fabric have excellent water repellent and oil repellent.

But, PET is partially crystalline polymer, and without active group in molecule, fiber surface molecule is difficult to be fluorinated with carbon There is effective chemical reaction in compound, therefore fluorocarbon simply forms membrane structure and is coated on fiber surface, fluorocarbon And firm chemical bonds between fiber surface, cannot be formed.In use, fluorocarbon is easily from fiber surface Run off and reduce anti-wicking capacity, the washability of anti-wicking industrial yarn and poor durability.

In a lot of fields, the fabric product of anti-wicking polyester industrial yarn must be in outdoor application.Such as, lamp box advertisement cloth And puggaree, need during use to stand long sun exposure.Ultraviolet and black light in daylight easily make polyester Molecular chain rupture, cause light degradation and photooxidative degradation, drop low-fiber intensity, affect the service life of polyester industrial yarn.

At present, the Chinese patent of Application No. 20121054270.X, disclose a kind of anti-core suction type lower shrinkage terylene industrial Silk and manufacture method thereof.This anti-core suction type lower shrinkage polyester industrial yarn glues PET with height and cuts into slices as raw material, through melt spinning, adds Carrying out drawing and heat-setting after appropriate spinning oil, after adding appropriate anti-wicking agent, winding is made, and the anti-measure wicking height of product≤ 2mm.In this invention, the position of upper anti-wicking agent is between drafting forming and winding, and tow is directly wound into after anti-wicking agent Type, not through the heat treatment of drawing-off hot-rolling, the anti-wicking agent uniformity on tow surface and tack are bad, the anti-core of product Suction effect is bad, and not through greenhouse heat treatment process after tow coiling and molding, anti-wick effect cannot obtain further Improve and consolidate.

The United States Patent (USP) of Publication No. US005116682A, discloses a kind of anti-core suction type polyester fiber and other anti-wickings The production method of the thermally-stabilised fiber of type.Anti-wicking agent described in this patent is aqueous fluorinated polymer emulsion, and described technique is special After point is fiber surface attachment anti-wicking agent, remove moisture removal with drying equipment, by infrared baking oven for heating to 200 DEG C～260 DEG C, Make fluoride and fiber surface combine, reach anti-wick effect.But the method described in this patent is after fiber coiling and molding The anti-wicking carried out processes, it is impossible in spinning technique, a step realizes, and without reference to the measure wicking height of anti-wicking fiber.

Within 2007, Shen Wei has delivered the paper of entitled " development of anti-wicking polyester industrial filament yarn ".This article describes one and exists The method that anti-wicking agent produces anti-wicking polyester industrial filament yarn is added before drafting forming.The method is by anti-wicking agent emulsion and spins Silk oiling agent mixing oils as oil preparation, and the anti-wicking producing the industrial yarn obtained in the case of improving heat treatment condition is high Degree is still above 2mm.Its shortcoming is anti-wicking agent and spinning oil to be mixed into compounding oil preparation once oil, anti-wicking agent Effective ingredient reduce, it is impossible to obtain optimal anti-wick effect.And, use the industrial yarn that this kind of method produces, fiber table Still cannot be carried out effective chemical reaction between face and anti-wicking agent composition, anti-wick effect cannot keep for a long time.

The Chinese patent of Application No. 201210321149.0, discloses the manufacture of a kind of superlow shrinkage type PET industrial yarn Method.This superlow shrinkage type PET industrial yarn production process uses common oil preparation to oil, does not add anti-wicking agent, obtain Product does not have anti-wick effect, it is impossible to for the high-grade field such as lamp box advertisement cloth and swimming pool fabric.

Summary of the invention

It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of low-shrinkage anti-wicking polyester industrial fiber Manufacture method.Produce anti-core suction type polyester industrial yarn it is crucial that one layer of fluorocarbon film can be formed at fiber surface, And form firm chemical bonds rather than simple physical bond between fluorocarbon and fiber surface.PET is portion Point crystalline polymer, without active group in strand, fiber surface can not and fluorocarbon between be difficult to occur effective Chemical reaction and form stable chemical bond, during use, fluorocarbon easily comes off loss at fiber surface, so The anti-wick effect of the anti-core suction type polyester industrial yarn that general enterprises produces is undesirable, and durability and washability are poor.

The present invention, before upper spinning oil, increases by one low temperature atomsphere plasma treatment process.Used jet flow type Atmosphere low-temperature plasma processor is mainly made up of plasma generator, gas delivery system and plasma spray first class sections.Deng Ion generator produces high voltagehigh frequency energy and is activated in nozzle steel pipe and creates low temperature etc. in controlled glow discharge Gas ions, sprays to fiber surface by compressed air by plasma.When this uncharged neutral plasma and fiber Time meeting in surface, create chemical action and physical change, the reactive group of some activity can be formed at fiber surface, as- C-O-,-C=N-,-CH₂OH etc., these hydroxyls, carboxyl isoreactivity group can be with anti-wickings Cross-linking agent (isocyanide ester) in agent and active group R (-COOH ,-OH ,-NH₂) there is chemical reaction, it is ensured that in anti-wicking agent Effective ingredient be permanently affixed to fiber surface, improve the anti-wicking capacity of fiber.

The present invention adds the block containing carbon fluorin radical and uvioresistant group of a kind of novel synthesis altogether in spinning oil Polymers, makes spinning oil become the anti-wicking agent of anti-ultraviolet ageing function.The synthon of this block copolymer is perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the Third monomer containing uvioresistant group.

The structural formula of described perfluoroalkyl (methyl) acrylate is:

Wherein X=H or CH₃, 2≤m≤8, n >=8；

The structural formula of described non-fluorinated alkylsilane (methyl) acrylate is:

Wherein X=H or CH₃, p >=16；

The described Third monomer containing uvioresistant group is O-hydroxyl-diphenyl ketone, salicylate and o-hydroxy triazole The monomer of group, its structural formula is respectively as follows:

Wherein 2≤q≤6；

Wherein 2≤q≤6；

Wherein 2≤q≤6；

Wherein, R can be-COOH ,-OH ,-NH₂Any one in isoreactivity group.

The reaction equation of the block copolymer of described novel synthesis is:

Wherein, 2≤m≤8, k >=8, p >=16, x=10～20, y=5～10, z=3～10, R ' is o-hydroxy benzophenone The uvioresistant group of ketone, salicylate and o-hydroxy triazole.

In this block copolymer, the effect of fluorination (methyl) acrylate is to reduce fiber surface energy, gives fiber and refuses Water oil repellent.The fluorocarbon chain section (n >=8) of whole-fluoroalkyl chain segment end is perpendicular to fiber surface close-packed arrays, can form more difficult moving That move, orderly layered crystal structure, makes the Oil repellent of fiber surface increase, and surface can reduce, and oil water contact angle increases, thus Give the water and oil repellant that fiber is certain.When 2, < during n≤6, fluorocarbon chain section does not have crystallinity, easily inclines at polymer surfaces Tiltedly, thus occurring surface molecular to reset in polar environment, polar group moves to surface, and fiber surface can generally increase, oil Water contact angle reduces.When n≤2, can not shield polar group completely owing to fluorocarbon chain section is the shortest, the exposure of surface carbonyl makes to gather Compound surface can significantly increase, and oil water contact angle is the least.Therefore, fluorocarbon chain section n >=8 that we select.In carbon fluorine chain section, close Suitable hydrocarbon interval is conducive to improving dissolubility and the heat stability of block copolymer, therefore select hydrocarbon be spaced apart 2≤m≤ 8。

In this block copolymer, the effect of nonfluorinated (methyl) acrylate segment is the dissolubility improving block copolymer And with the compatibility of other resins.This does not dissolves in general organic solvent mainly due to fluorination (methyl) acrylate homopolymer, The compatibility with other resins is poor.In order to solve this problem, fluorination (methyl) (methyl) acrylate monomer can be used with non- Fluorination (methyl) (methyl) acrylate monomer carries out copolymerization, can obtain the material with relatively low-surface-energy, also can have simultaneously Effect improves dissolubility and the compatibility of polymer.During p ＜ 16, the crystallinity of nonfluorinated (methyl) acrylate segment is poor, altogether Polymer surface can be higher；During p >=16, owing to nonfluorinated (methyl) acrylate segment is longer, copolymer is difficult in polar liquid To occur surface molecular to reset, the introducing of side chain nonfluorinated (methyl) acrylate segment forms crystallization to copolymer and has collaborative Effect, improves the hydrophobic stability of copolymer.

In this block copolymer, the effect of Third monomer segment is the water resistant grease resistance improving copolymer, promotes anti-wicking Agent and the combination of fiber surface, and give the function of resistant fiber ultraviolet ageing.Active group R in 3rd block (-COOH ,- OH ,-NH₂Deng) the active group generation chemical reaction that can produce at fiber surface with plasma, improve block copolymer with The binding ability of fiber surface, 2≤q≤6, hydrocarbon interval in the 3rd segment, it is ensured that entering smoothly of the polyreaction of reaction Row and the effecting reaction of R group.Due to R group and the chemical reaction of fiber surface activity group, Third monomer segment compares fluorine Change (methyl) (methyl) acrylate segment and nonfluorinated (methyl) acrylate segment, closer to fiber, make fluorination (methyl) Acrylate and nonfluorinated (methyl) acrylate segment migrate and ordered arrangement to fibrous outer surfaces.Additionally, Third monomer Uvioresistant group in segment contains sterically hindered bigger phenyl ring, can limit copolymer and surface molecular occurs in polar liquid Reset and migrate, the orderly close-packed arrays structure of established fluorocarbon chain section and nonfluorinated segment is had Stabilization, improve The water and oil repellant ability of fiber.Meanwhile, the phenyl ring that two volumes containing in the 3rd segment are bigger can cause block copolymer Be separated, improve surface roughness, beneficially fluorine element to surface migration, improve the water and oil repellant of copolymer, in synthesis During can also reduce the consumption of fluorine monomer.

In addition to above-mentioned ternary block polymer, another of fluorine-containing anti-wicking agent is mainly composed of cross-linking agent.Cross-linking agent master Tripolycyanamide to be, isocyanide ester carbamate or Biformyl.After fiber surface attachment anti-wicking agent, if without overheated place Reason, the caking property of fluorocarbon and fiber surface is relatively low, adheres to insecure, and durability and washability are the most poor, it is therefore desirable to The anti-wick effect of fiber is consolidated through suitable heat treatment.In heat treatment process, along with the steaming of moisture in anti-wicking agent Sending out and high temperature action, the hydrophilic group originally stretching to outside is gradually retracted into intramolecule, forms film, hydrophobicity at fiber surface Fluoroalkyl be distributed in fiber surface, make fabric have excellent water repellent and oil repellent.Meanwhile, the crosslinking in anti-wicking agent Agent can-COOH ,-OH ,-NH in the uvioresistant group (R ') of the 3rd block₂Isoreactivity group (R) reacts, at fiber table Face forms tridimensional network, prevents the loss of fluorocarbon, improves durability and the washability of resistant fiber wick effect.

Thermal processes act can affect the fluorocarbon binding ability at fiber surface, and then promotes the anti-wicking of industrial yarn Effect.On the one hand, before drafting forming, fiber not yet molding, the degree of orientation and degree of crystallinity are relatively low, there is more amorphous region, Due to anti-wicking agent molecular weight, molecular dimension is the least, is possible not only to be attached to fiber surface generation chemical reaction, also may be used The amorphous region bigger to penetrate into fibrous inside strand spacing；On the other hand, the high-temperature heating effect of hot-rolling can promote Fluorocarbon and the chemical reaction of fiber, improve durability and the washability of fiber.Therefore the present invention uses and determines in drawing-off heat Upper anti-wicking agent before type, it is ensured that fiber has optimal anti-wick effect.

In the present invention, the fiber after coiling and molding processes through special greenhouse, it is ensured that fluorocarbon and fiber The binding ability on surface, improves further and consolidates anti-wick effect.

The present invention is adjusted by the control of low temperature atomsphere plasma process, the improvement of anti-wicking oil preparation and Technology for Heating Processing Joint, it is provided that a kind of anti-wicking has the preparation method of the ultralow contraction terylene industry silk of uvioresistant function concurrently.

The present invention solves technical problem and is adopted the technical scheme that: the viscous section of height with modified poly ester is as raw material, through height Temperature melt spinning, low temperature atomsphere plasma processes, upper spinning oil, and upper anti-wicking agent carries out drawing and heat-setting, winding, warp Cross greenhouse process to make, it is characterised in that the height of described modified poly ester glues the viscous section of the height after viscosifying of cutting into slices, institute for solid phase Before the low temperature atomsphere plasma processing means stated is positioned at spin finishing, described spinning oil is for being specifically designed to production terylene The HM200 spinning oil of industrial yarn, described anti-wicking agent is washing containing smooth agent, emulsifying agent, antistatic additive and cross-linking agent Synthetic fibre filament yarn oil agent, and containing perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the base Han uvioresistant The ternary block polymer of group, has the function of water and oil repellant and anti-ultraviolet ageing.

Described a kind of low-shrinkage anti-wicking polyester industrial fiber, modified poly ester is by polyester and amino ethylene glycol fatty acid structure Becoming, described amino ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and described amino ethylene glycol fatty acid with The molecule interchain of described polyester has hydrogen bond action, makes described amino ethylene glycol fatty acid relative with the strand of described polyester Position is fixed；Described low-shrinkage anti-wicking polyester industrial fiber under the conditions of temperature is 70～80 DEG C, fibrous inside molecule interchain from 10～15v/v% are increased by volumetric spaces；

The molecular structural formula of described amino ethylene glycol fatty acid is:

H₂N(CH₂)_nOCOCH₂CH₂OCO(CH₂)_nNH₂

Wherein, n=10～50.

Described a kind of low-shrinkage anti-wicking polyester industrial fiber, it is characterised in that described amino ethylene glycol fatty acid accounts for institute The percentage by weight stating low-shrinkage anti-wicking polyester industrial fiber is 0.5～2.5%.

Described a kind of low-shrinkage anti-wicking polyester industrial fiber, it is characterised in that the height of described modified poly ester glues the system of section Standby step includes:

(1) preparation of amino ethylene glycol fatty acid:

1) binary of fatty acids is added in reactor with the amount of 1:1.5 mol ratio with methanol, under the catalysis of concentrated sulphuric acid, add Heat is to 80～110 DEG C, and refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；Described binary of fatty acids is 12 Alkane dicarboxylic acids is to the one in dopentacontane dicarboxylic acids；

2) described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene, under nitrogen atmosphere, 100 DEG C reaction, backflow, when no longer there being gas to produce, add a certain amount of dilute sulfuric acid reaction 2～3 hours, be washed out, purify and It is dried, obtains product bromo fatty acid；

3), by the ammonia of bromo fatty acid and 15～25wt% during 1:2 joins reactor in molar ratio, stirring, in room temperature Lower reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is less than 70 DEG C, until nothing Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, by product Vacuum drying obtains product amino fatty acid；

4) ethylene glycol and amino fatty acid are stirred for 1.1:2 in molar ratio, and press the hundred of amino fatty acid wt / mono-adds the sulphuric acid that concentration is 40～50wt%, carries out esterification, and esterification reaction temperature is 160～220 DEG C, esterification water It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；The separated purification of product obtains amino fatty acid second two Alcohol ester；

(2) preparation of modified PET, including esterification and polycondensation reaction:

Described esterification:

Use p-phthalic acid and ethylene glycol as raw material, after being made into uniform sizing material, carry out esterification, obtain esterification and produce Thing；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at normal pressure～0.3MPa, and temperature is at 250～260 DEG C, and esterification water evaporates It is esterification terminal that output reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

In the described polycondensation reaction coarse vacuum stage, esterification products adds catalyst and stabilizer, under conditions of negative pressure Starting polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, Response time is 30～50 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino ethylene glycol fatty acid, and stir；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275～280 DEG C, response time 50～90 minutes；

Prepare modified poly ester；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of modified PET height, intrinsic viscosity is 0.98dL/g.

The preparation method of described low-shrinkage anti-wicking polyester industrial fiber,

By the viscous section of the height of modified poly ester through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core The steps such as vapor, stretching, thermal finalization, winding and greenhouse process, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 290～320 DEG C；

The pathogenic wind-warm of described cooling is 20～25 DEG C；

Described low temperature atomsphere plasma processes: the distance between nozzle and fibre bundle is 5～8mm；

The described oil applying rate oiled is 0.4～0.6wt%；

The oil applying rate that described anti-core agent oils is 0.4～0.5wt%；

The speed of described winding is 2600～3400m/min；

The condition that described greenhouse processes is: temperature 70～80 DEG C, standing time is 20～30h；

Described anti-wicking agent contains smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) propylene Acid esters, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group, described anti-wicking agent quality Number is respectively as follows:

Described perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and containing uvioresistant group three The synthesis step of unit's block copolymer is:

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

(1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, it is sequentially added into catalyst CuBr or CuCl, monomer perfluoroalkyl (methyl) propylene Acid esters, solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: join Position agent: the mol ratio of monomer is 1:1:2:120, is warming up to 65～75 DEG C, isothermal reaction 6h；Reaction is molten with oxolane after terminating Solving, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is done through the vacuum that temperature is 40 DEG C Dry device is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

(2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) acrylate of bromination end-blocking divides greatly The preparation of sub-initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr or CuCl, solvent toluene, below 40 DEG C, treat perfluoroalkyl (methyl) acrylic acid that bromination blocks Ester large molecule initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, At 75～85 DEG C of more than isothermal reaction 24h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2: 10～60；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum crosses post separation mantoquita, and filtrate is precipitated poly-with dehydrated alcohol Compound, polymer is dried to constant weight through the vacuum desiccator that temperature is 40 DEG C, obtains the poly-perfluoroalkyl (methyl) of bromination end-blocking Acrylate poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent；

(3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr or CuCl, is then sequentially added into complexant Pentamethyldiethylenetriamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing anti-purple The olefinic monomer of outer group, more than isothermal reaction 10h in 105～115 DEG C, wherein macromole evocating agent: catalyst: coordination Agent: the mol ratio of monomer is 1:1:2:10～20；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum crosses post separation copper Salt, precipitates to obtain polymer with ethanol, and polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer Thing；

In the present invention, described anti-wicking agent is the polyester filament containing smooth agent, emulsifying agent, antistatic additive and cross-linking agent Oil preparation, is characterized in that containing perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the base Han uvioresistant The ternary block polymer of group, has the function of water and oil repellant and anti-ultraviolet ageing.

Use the INTELLIRAY 400 type large area ultraviolet curing equipment that UVITRON company of the U.S. produces, to terylene work Industry silk carries out ultra-vioket radiation, the anti-ultraviolet ageing ability of testing polyester industrial yarn.Experiment condition is as follows: by ordinary polyester industrial yarn Holding with the glass dish used for polyester industrial filament produced in the present invention and be placed in case, light intensity is arranged to 90% (1245 μ W/cm²), ripple A length of 325nm, altogether accumulative irradiation 12h.The most respectively by tension test test washing after 3h and 12h ultraviolet light irradiates The mechanical property of synthetic fibre industrial yarn.In the uvioresistant test result display present invention, the anti-ultraviolet ageing ability of polyester industrial yarn obtains bright Aobvious raising.

It is main that amino ethylene glycol fatty acid is mainly with C-C, C-O key, has certain molecular weight simultaneously, i.e. has certain The strand of length, strand flexibility is relatively big, linear big compared with benzene ring structure of the amount of crimp of amino ethylene glycol fatty acid Molecule is bigger, simultaneously strong compared with the linear macromolecule containing benzene ring structure to the sensitivity of temperature.When the temperature is changed, amino fatty acid Glycol ester moves prior to the linear macromolecule containing benzene ring structure, and the produced free volume of motion is far longer than containing phenyl ring Produced by the linear macromolecule of structure.

Added the free volume of polyester fiber by fatty acid ester, improve anti-wicking agent and enter within polyester fiber Degree.The present invention makes the space between polyester fiber fiber molecule at a certain temperature increase, and makes the anti-core of part in activation process Vapor molecule diffuses in fiber gap, improves the service efficiency of anti-wicking agent, and is formed on polyester industrial fiber surface Firm resinoid coating, it is ensured that the effective ingredient in anti-wicking agent is permanently affixed to fiber surface, improves the anti-of fiber Wicking capacity.

The low-shrinkage anti-wicking polyester industrial fiber prepared by preparation method of the present invention, its physical index is: line density Deviation ratio ± 1.5%, fracture strength 36.9cN/dtex, fracture strength CV value ￡ 3.0%, elongation at break is 22.5%, fracture Elongation CV value ￡ 8.0%, dry-hot shrinkage 2.2 ± 0.5%, measure wicking height ￡ 0.6mm.The polyester industrial yarn prepared by the present invention Possess the most hydrophobic and water resistance, reached preferable anti-wick effect, there is preferable anti-ultraviolet ageing ability simultaneously, Outdoor can be applicable on a large scale, before the fields such as high-grade lamp box advertisement cloth, waterproof cloth and swimming pool fabric have good market Scape.

Beneficial effect:

The low-shrinkage anti-wicking polyester industrial fiber of gained the most of the present invention, owing to amino ethylene glycol fatty acid is based on C-C, Having certain molecular weight simultaneously, i.e. have the strand of certain length, strand flexibility is relatively big, and amino adds and polyester The compatibility, thus make amino ethylene glycol fatty acid be improved with the compatibility of polyester industrial fiber.

2. the present invention makes the space between polyester fiber fiber molecule at a certain temperature increase, and makes part in activation process Anti-wicking agent molecule diffuses in fiber gap, improves the service efficiency of anti-wicking agent, and on polyester industrial fiber surface Form firm resinoid coating, it is ensured that the effective ingredient in anti-wicking agent is permanently affixed to fiber surface, improve fiber Anti-wicking capacity.

The low-shrinkage anti-wicking polyester industrial fiber of gained the most of the present invention, preferable anti-wick effect, have the most anti-simultaneously Ultraviolet ageing ability, has good market prospect.

Detailed description of the invention

Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited Fixed scope.

A kind of low-shrinkage anti-wicking polyester industrial fiber of the present invention, material is modified poly ester, and is processed prepared by anti-wicking, Described modified poly ester is made up of with amino ethylene glycol fatty acid polyester, and described amino ethylene glycol fatty acid is dispersed in described poly- The molecule interchain of ester, and the molecule interchain of described amino ethylene glycol fatty acid and described polyester has hydrogen bond action, makes described ammonia Base ethylene glycol fatty acid is fixed with the relative position of the strand of described polyester；Described low-shrinkage anti-wicking polyester industrial fiber is in temperature Under the conditions of degree is 70～80 DEG C, the free volume space of fibrous inside molecule interchain increases 10～15v/v%；

The molecular structure of described amino ethylene glycol fatty acid is:

H₂N(CH₂)_nCOOCH₂CH₂OOC(CH₂)_n NH₂；

Wherein, n=10-50.

Described a kind of low-shrinkage anti-wicking polyester industrial fiber: line density deviation ratio ± 1.5%, fracture strength CV value ￡ 2.5%, elongation at break is 14.0 ± 1.3%, extension at break CV value ￡ 7.0%, 177 DEG C, the test strip of 0.05cN/dtex Dry-hot shrinkage under part is 7.0 ± 0.5%.

Described a kind of low-shrinkage anti-wicking polyester industrial fiber, described amino ethylene glycol fatty acid accounts for the anti-wicking of described low-shrinkage The percentage by weight of polyester industrial fiber is 0.5～2.5%.

High viscous section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, heat The steps such as sizing, winding and greenhouse process, prepare low-shrinkage anti-wicking polyester industrial fiber.

Line density deviation ratio ± 1.5% of a kind of low-shrinkage as above anti-wicking polyester industrial fiber, fracture strength 37.5cN/dtex, fracture strength CV value ￡ 2.5%, elongation at break is 20.0 ± 1.5%, extension at break CV value ￡ 7.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be 2.5 ± 0.5%, measure wicking height ￡ 0.6mm.

Uvioresistant method of testing is:

Use the INTELLIRAY 400 type large area ultraviolet curing equipment that UVITRON company of the U.S. produces, to terylene work Industry silk carries out ultra-vioket radiation, the anti-ultraviolet ageing ability of testing polyester industrial yarn.Experiment condition is as follows: by ordinary polyester industrial yarn Holding with the glass dish used for polyester industrial filament produced in the present invention and be placed in case, light intensity is arranged to 90% (1245 μ W/cm²), ripple A length of 325nm, altogether accumulative irradiation 12h.Then washing after 3h and 12h ultraviolet light irradiates is tested respectively by tension test The mechanical property of synthetic fibre industrial yarn.

Performance anti wicking method of testing is:

Take a length of 30cm tow, hang up the weight of 0.05cN/dtex, put into and take out leaching after 150 DEG C of baking ovens dry 5min Enter in ink, measure the lifting height ￡ 0.6mm of ink after 30min, show that tow has possessed good hydrophobic performance.

Embodiment 1

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, it is sequentially added into catalyst CuBr, monomer perfluoroalkyl (methyl) acrylate, molten Agent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: single The mol ratio of body is 1:1:2:120, is warming up to 65 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized aluminum Crossing post separation mantoquita, filtrate precipitates to obtain polymer with dehydrated alcohol, polymer through the vacuum desiccator that temperature is 40 DEG C be dried to Constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 75 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:10；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 15h, wherein macromole evocating agent in 105 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:10；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 20；Emulsifying agent 3；Antistatic additive 5；Cross-linking agent 1；Ternary block polymer 30；

The effect composition of described anti-wicking agent is diluted with water to 15wt%, oils for anti-wicking agent；

(2) preparation of amino ethylene glycol fatty acid:

1) dodecanedicarboxylic acid is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, Being heated to 80 DEG C, refuxing esterification, cooling, separating-purifying obtains dodecanedicarboxylic acid mono-methyl；Described concentrated sulphuric acid refers to that quality is dense Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of dodecanedicarboxylic acid；

2) described dodecanedicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein Dodecanedicarboxylic acid mono-methyl concentration is 0.05mol/L, under nitrogen atmosphere, in 80 DEG C of reactions, backflow, produces when no longer there being gas Time raw, add a certain amount of dilute sulfuric acid and react 2 hours, be washed out, purify and be dried, obtain product bromoundecane carboxylic acid； Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is dodecanedicarboxylic acid mono-methyl 3wt%；

3), by the ammonia of bromoundecane carboxylic acid Yu 15wt% during 1:2 joins reactor in molar ratio, stirring, in room temperature Lower reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, uses silver nitrate Solution detects, and product vacuum drying is obtained product amino-undecanoic carboxylic acid；

4) ethylene glycol and amino-undecanoic carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino-undecanoic carboxylic acid 1% addition concentration of weight is the sulphuric acid of 40wt%, carries out esterification, and esterification reaction temperature is 160 DEG C, esterification water quantity of distillate Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino-undecanoic carboxylic acid ethylene glycol Ester；

(3) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

The p-phthalic acid using mol ratio to be 1:1.2 and ethylene glycol, as raw material, are esterified after being made into uniform sizing material Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is 250 DEG C, esterification It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, three oxidations of the 0.01% of addition p-phthalic acid weight in esterification products Two antimony and the triphenyl phosphate of p-phthalic acid weight 0.01%, start polycondensation reaction, this staged pressure under conditions of negative pressure Steadily be evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 DEG C, and the response time is 50 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino-undecanoic carboxylic acid glycol ester, and stir 15 points Clock；Described amino-undecanoic carboxylic acid glycol ester, addition is the 0.5wt% of modified poly ester；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 90 minutes response time；

Prepare modified poly ester.

(4) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.95dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 290 DEG C；The pathogenic wind-warm of described cooling is 20 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 5mm；Operating pressure is 0.5bar；The described oil applying rate oiled is 0.4wt%；Described anti- The oil applying rate that core agent oils is 0.4wt%；Heat setting temperature 100 DEG C；The speed of described winding is 3200m/min；

Described greenhouse processes and refers to place 30h under conditions of temperature 70 C；

Fracture strength 7.5cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.6mm, line density deviation Rate 1.5%, fracture strength CV value 2.5%, elongation at break is 21.5%, extension at break CV value 7.0%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 3.0%.Low-shrinkage anti-wicking polyester industrial fiber is 70 DEG C of bars in temperature Under part, the free volume space of fibrous inside molecule interchain increases 11v/v%.

Uvioresistant is tested

Embodiment 2

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 75 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuCl, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 85 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:60；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuCl, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 115 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:20；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 30；Emulsifying agent 5；Antistatic additive 10；Cross-linking agent 2；Ternary block polymer 50；

The effect composition of described anti-wicking agent is diluted with water to 10wt%, oils for anti-wicking agent；

(2) preparation of amino ethylene glycol fatty acid:

1) dopentacontane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, in the catalysis of concentrated sulphuric acid Under, it being heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains dopentacontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to Mass concentration is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of dopentacontane dicarboxylic acids；

2) described dopentacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), its Middle dopentacontane mono methyl dicarboxylate's concentration is 0.07mol/L, and under nitrogen atmosphere, 85 DEG C of reactions, backflow, when no longer there being gas When body produces, add a certain amount of dilute sulfuric acid and react 3 hours, be washed out, purify and be dried, obtain product bromo henpentacontane Carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is dopentacontane dicarboxylic acids The 3wt% of mono-methyl；

3), by the ammonia of bromo henpentacontane carboxylic acid Yu 25wt% during 1:2 joins reactor in molar ratio, stirring, in room The lower reaction of temperature, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 62 DEG C, until depletion of QI Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses nitric acid Silver solution detection, obtains product amino henpentacontane carboxylic acid by product vacuum drying；

4) ethylene glycol and amino henpentacontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino henpentacontane 2% addition concentration of carboxylic acid weight is the sulphuric acid of 45wt%, carries out esterification, and esterification reaction temperature is 220 DEG C, and esterification water evaporates It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino henpentacontane carboxylic acid Glycol ester；

(3) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification: the p-phthalic acid using mol ratio to be 1:2.0 and ethylene glycol, as raw material, are made into and are all homogenized Carry out esterification after material, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is in 0.2MPa, temperature At 260 DEG C, it is esterification terminal that esterification water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction: include polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, three oxidations of the 0.05% of addition p-phthalic acid weight in esterification products Two antimony and the triphenyl phosphate of p-phthalic acid weight 0.05%, start polycondensation reaction, this staged pressure under conditions of negative pressure Steadily be evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 270 DEG C, and the response time is 30 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino henpentacontane carboxylic acid glycol ester, and stir 20 points Clock；Described amino henpentacontane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 2.5%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 50 minutes response time；

(4) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.98dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 320 DEG C；The pathogenic wind-warm of described cooling is 23 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 8mm；Operating pressure is 0.7bar；The described oil applying rate oiled is 0.4wt%；Described anti- The oil applying rate that core agent oils is 0.4wt%；The speed of described winding is 3400m/min；Heat setting temperature 150 DEG C；

Described greenhouse processes and refers to place 30h under conditions of temperature 70 C；

Fracture strength 7.6cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, line density deviation ratio-1.5%, fracture Intensity CV value 2.3%, elongation at break is 21.4%, extension at break CV value 6.5%, 177 DEG C, the test of 0.05cN/dtex Under the conditions of dry-hot shrinkage be 2.5%, measure wicking height 0.6mm.Low-shrinkage anti-wicking polyester industrial fiber is 70 DEG C of conditions in temperature Under, the free volume space of fibrous inside molecule interchain increases 10v/v%.

Uvioresistant is tested

Embodiment 3

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 66 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 76 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:20；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 106 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:11；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 21；Emulsifying agent 3.2；Antistatic additive 6；Cross-linking agent 1.1；Ternary block polymer 32；

The effect composition of described anti-wicking agent is diluted with water to 11wt%, oils for anti-wicking agent；

(1) preparation of amino ethylene glycol fatty acid:

1) pentacosane dicarboxylic acid is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, Being heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains pentacosane dicarboxylic acid mono-methyl；Described concentrated sulphuric acid refers to that quality is dense Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of pentacosane dicarboxylic acid；

2) described pentacosane dicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein Pentacosane dicarboxylic acid mono-methyl concentration is 0.08mol/L, under nitrogen atmosphere, in 90 DEG C of reactions, backflow, produces when no longer there being gas Time raw, add a certain amount of dilute sulfuric acid and react 2.5 hours, be washed out, purify and be dried, obtain product bromotetradecane carboxylic Acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 50%, and dilute sulfuric acid addition is pentacosane dicarboxylic acid list first The 3wt% of ester；

3), by the ammonia of bromotetradecane carboxylic acid Yu 20wt% during 1:2 joins reactor in molar ratio, stirring, in room temperature Lower reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, uses silver nitrate Solution detects, and product vacuum drying is obtained product amino tetradecane carboxylic acid；

4) ethylene glycol and amino tetradecane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino tetradecane carboxylic acid 2% addition concentration of weight is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 190 DEG C, esterification water quantity of distillate Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino tetradecane carboxylic acid ethylene glycol Ester；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification: the p-phthalic acid using mol ratio to be 1:1.6 and ethylene glycol, as raw material, are made into and are all homogenized Carry out esterification after material, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is in 0.3MPa, temperature At 255 DEG C, it is esterification terminal that esterification water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction: include polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, three oxidations of the 0.03% of addition p-phthalic acid weight in esterification products Two antimony and the triphenyl phosphate of p-phthalic acid weight 0.03%, start polycondensation reaction, this staged pressure under conditions of negative pressure Steadily be evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 265 DEG C, and the response time is 40 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino tetradecane carboxylic acid glycol ester, and stir 16 points Clock；Described amino tetradecane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 1.0%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 276 DEG C, 70 minutes response time；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.98dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 295 DEG C；The pathogenic wind-warm of described cooling is 21 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 6mm；The described oil applying rate oiled is 0.42wt%；The oil applying rate that described anti-core agent oils For 0.41wt%；The speed of described winding is 3500m/min；Heat setting temperature 110 DEG C；

The condition that described greenhouse processes is: temperature 71 DEG C, standing time is 21h；

Fracture strength 7.8cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.6mm, line density deviation Rate-1.3%, fracture strength CV value 2.9%, elongation at break is 21.0%, extension at break CV value 6.8%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.0%.Low-shrinkage anti-wicking polyester industrial fiber is 71 DEG C of bars in temperature Under part, the free volume space of fibrous inside molecule interchain increases 11v/v%.

Uvioresistant is tested

Embodiment 4

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 67 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 77 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:30；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 112 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:12；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 22；Emulsifying agent 3.4；Antistatic additive 6；Cross-linking agent 1.2；Ternary block polymer 34；

The effect composition of described anti-wicking agent is diluted with water to 12wt%, oils for anti-wicking agent；

(1) preparation of amino ethylene glycol fatty acid:

1) eicosane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, Being heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains eicosane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to that quality is dense Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of eicosane dicarboxylic acids；

2) described eicosane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein Eicosane mono methyl dicarboxylate's concentration is 0.09mol/L, under nitrogen atmosphere, in 80 DEG C of reactions, backflow, produces when no longer there being gas Time raw, add a certain amount of dilute sulfuric acid and react 2.1 hours, be washed out, purify and be dried, obtain product bromo nonadecane carboxylic Acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 43%, and dilute sulfuric acid addition is eicosane dicarboxylic acids list first The 2wt% of ester；

3), by the ammonia of bromo nonadecane carboxylic acid Yu 16wt% during 1:2 joins reactor in molar ratio, stirring, in room temperature Lower reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until bubble-free Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, uses silver nitrate Solution detects, and product vacuum drying is obtained product amino nonadecane carboxylic acid；

4) ethylene glycol and amino nonadecane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino nonadecane carboxylic acid 2% addition concentration of weight is the sulphuric acid of 42wt%, carries out esterification, and esterification reaction temperature is 160 DEG C, esterification water quantity of distillate Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino nonadecane carboxylic acid ethylene glycol Ester；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

The p-phthalic acid using mol ratio to be 1:1.2 and ethylene glycol, as raw material, are esterified after being made into uniform sizing material Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.15MPa, and temperature, at 251 DEG C, is esterified It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, three oxidations of the 0.02% of addition p-phthalic acid weight in esterification products Two antimony and the triphenyl phosphate of p-phthalic acid weight 0.02%, start polycondensation reaction, this staged pressure under conditions of negative pressure Steadily be evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 262 DEG C, and the response time is 33 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino nonadecane carboxylic acid glycol ester, and stir 17 points Clock；Described amino nonadecane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 1.5%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 277 DEG C, 55 minutes response time；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.98dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 300 DEG C；The pathogenic wind-warm of described cooling is 22 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 7mm；The described oil applying rate oiled is 0.44wt%；The oil applying rate that described anti-core agent oils For 0.42wt%；The speed of described winding is 3600m/min；Heat setting temperature 100 DEG C；

The condition that described greenhouse processes is: temperature 72 DEG C, standing time is 22h；

Fracture strength 7.5cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.5mm, line density deviation Rate-0.5%, fracture strength CV value 2.8%, elongation at break is 20.0%, extension at break CV value 7.7%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.1%.Low-shrinkage anti-wicking polyester industrial fiber is 72 DEG C of bars in temperature Under part, the free volume space of fibrous inside molecule interchain increases 12v/v%.

Uvioresistant is tested

Embodiment 5

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 68 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuCl, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 78 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:30；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 108 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:13；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 24；Emulsifying agent 3.6；Antistatic additive 7；Cross-linking agent 1.6；Ternary block polymer 36；

The effect composition of described anti-wicking agent is diluted with water to 10wt%, oils for anti-wicking agent；

(1) preparation of amino ethylene glycol fatty acid:

1) melissane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, Being heated to 90 DEG C, refuxing esterification, cooling, separating-purifying obtains melissane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to that quality is dense Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of melissane dicarboxylic acids；

2) described melissane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein Melissane mono methyl dicarboxylate's concentration be 0.10mol/L under nitrogen atmosphere, 85 DEG C of reactions, backflow, produce when no longer there being gas Time raw, add a certain amount of dilute sulfuric acid and react 2.3 hours, be washed out, purify and be dried, obtain product bromo nonacosane carboxylic Acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is melissane dicarboxylic acids list first The 3wt% of ester；

3), by the ammonia of bromo nonacosane carboxylic acid Yu 18wt% during 1:2 joins reactor in molar ratio, stirring, in room The lower reaction of temperature, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 67 DEG C, until depletion of QI Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses nitric acid Silver solution detection, obtains product amino nonacosane carboxylic acid by product vacuum drying；

4) ethylene glycol and amino nonacosane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino nonacosane 2% addition concentration of carboxylic acid weight is the sulphuric acid of 48wt%, carries out esterification, and esterification reaction temperature is 170 DEG C, and esterification water evaporates It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino nonacosane carboxylic acid Glycol ester；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

The p-phthalic acid using mol ratio to be 1:1.5 and ethylene glycol, as raw material, are esterified after being made into uniform sizing material Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature, at 254 DEG C, is esterified It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, the ethylene glycol of the 0.01% of addition p-phthalic acid weight in esterification products Antimony and the trimethyl phosphate of p-phthalic acid weight 0.03%, under conditions of negative pressure start polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to below absolute pressure 500Pa, and temperature controls at 266 DEG C, and the response time is 39 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino nonacosane carboxylic acid glycol ester, and stir 18 points Clock；Described amino nonacosane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 2.5%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 278 DEG C, 60 minutes response time；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.95dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 305 DEG C；The pathogenic wind-warm of described cooling is 23 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 8mm；The described oil applying rate oiled is 0.46wt%；The oil applying rate that described anti-core agent oils For 0.43wt%；The speed of described winding is 3500m/min；Heat setting temperature 140 DEG C；

The condition that described greenhouse processes is: temperature 73 DEG C, standing time is 23h；

Fracture strength 7.8cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.5mm, line density deviation Rate 0.5%, fracture strength CV value 2.3%, elongation at break is 19.0%, extension at break CV value 6.7%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.1%.Low-shrinkage anti-wicking polyester industrial fiber is 73 DEG C of bars in temperature Under part, the free volume space of fibrous inside molecule interchain increases 12v/v%.

Uvioresistant is tested

Embodiment 6

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 70 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 80 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:35；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuCl, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 110 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:15；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 25；Emulsifying agent 4；Antistatic additive 7.5；Cross-linking agent 1.5；Ternary block polymer 40；

The effect composition of described anti-wicking agent is diluted with water to 13wt%, oils for anti-wicking agent；

(1) preparation of amino ethylene glycol fatty acid:

1) pentatriacontane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, in the catalysis of concentrated sulphuric acid Under, it being heated to 95 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatriacontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to matter Amount concentration is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 2wt% of pentatriacontane dicarboxylic acids；

2) described pentatriacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), its Middle pentatriacontane mono methyl dicarboxylate's concentration be 0.09mol/L under nitrogen atmosphere, 90 DEG C of reactions, backflow, when no longer there being gas When body produces, add a certain amount of dilute sulfuric acid and react 2.6 hours, be washed out, purify and be dried, obtain product bromo 34 Alkane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 45%, and dilute sulfuric acid addition is pentatriacontane dicarboxyl The 1wt% of acid mono-methyl

3), by the ammonia of bromo tetratriacontane carboxylic acid Yu 20wt% during 1:2 joins reactor in molar ratio, stirring, in room The lower reaction of temperature, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until depletion of QI Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses nitric acid Silver solution detection, obtains product amino tetratriacontane carboxylic acid by product vacuum drying；

4) ethylene glycol and amino tetratriacontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino tetratriacontane 1% addition concentration of carboxylic acid weight is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 180 DEG C, and esterification water evaporates It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino tetratriacontane carboxylic acid Glycol ester；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

The p-phthalic acid using mol ratio to be 1:1.6 and ethylene glycol, as raw material, are esterified after being made into uniform sizing material Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.4MPa, and temperature, at 256 DEG C, is esterified It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, the antimony acetate of the 0.04% of addition p-phthalic acid weight in esterification products With the NSC 6513 of p-phthalic acid weight 0.02%, under conditions of negative pressure start polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to below absolute pressure 500Pa, and temperature controls at 267 DEG C, and the response time is 40 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino tetratriacontane carboxylic acid glycol ester, and stir 18 points Clock；Described amino tetratriacontane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 2.0%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 70 minutes response time；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.96dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 315 DEG C；The pathogenic wind-warm of described cooling is 22 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 7mm；The described oil applying rate oiled is 0.50wt%；The oil applying rate that described anti-core agent oils For 0.45wt%；The speed of described winding is 3500m/min；Heat setting temperature 120 DEG C；

The condition that described greenhouse processes is: temperature 75 DEG C, standing time is 25h；

Fracture strength 7.7cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.4mm, line density deviation Rate 1.0%, fracture strength CV value 2.3%, elongation at break is 21.2%, extension at break CV value 6.5%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.2%.Low-shrinkage anti-wicking polyester industrial fiber is 75 DEG C of bars in temperature Under part, the free volume space of fibrous inside molecule interchain increases 13v/v%.

Uvioresistant is tested

Embodiment 7

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 72 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 82 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:35；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 112 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:16；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 23；Emulsifying agent 4；Antistatic additive 7；Cross-linking agent 2；Ternary block polymer 36；

The effect composition of described anti-wicking agent is diluted with water to 10wt%, oils for anti-wicking agent；

(1) preparation of amino ethylene glycol fatty acid:

1) tetracontane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, Being heated to 100 DEG C, refuxing esterification, cooling, separating-purifying obtains tetracontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to that quality is dense Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of tetracontane dicarboxylic acids；

2) described tetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein Tetracontane mono methyl dicarboxylate's concentration be 0.06mol/L under nitrogen atmosphere, 80 DEG C of reactions, backflow, produce when no longer there being gas Time raw, add a certain amount of dilute sulfuric acid and react 2.7 hours, be washed out, purify and be dried, obtain product bromo nonatriacontane carboxylic Acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 48%, and dilute sulfuric acid addition is tetracontane dicarboxylic acids list first The 2wt% of ester；

3), by the ammonia of bromo nonatriacontane carboxylic acid Yu 22wt% during 1:2 joins reactor in molar ratio, stirring, in room The lower reaction of temperature, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until depletion of QI Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses nitric acid Silver solution detection, obtains product amino nonatriacontane carboxylic acid by product vacuum drying；

4) ethylene glycol and amino nonatriacontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino nonatriacontane 2% addition concentration of carboxylic acid weight is the sulphuric acid of 46wt%, carries out esterification, and esterification reaction temperature is 190 DEG C, and esterification water evaporates It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino nonatriacontane carboxylic acid Glycol ester；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

The p-phthalic acid using mol ratio to be 1:1.8 and ethylene glycol, as raw material, are esterified after being made into uniform sizing material Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature, at 258 DEG C, is esterified It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, the antimony acetate of the 0.05% of addition p-phthalic acid weight in esterification products With the trimethyl phosphate of p-phthalic acid weight 0.03%, starting polycondensation reaction under conditions of negative pressure, this staged pressure is by often Flattening and be surely evacuated to below absolute pressure 500Pa, temperature controls at 268 DEG C, and the response time is 45 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino nonatriacontane carboxylic acid glycol ester, and stir 16 points Clock；Described amino nonatriacontane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 1.5%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 75 minutes response time；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.97dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 310 DEG C；The pathogenic wind-warm of described cooling is 22 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 7mm；The described oil applying rate oiled is 0.52wt%；The oil applying rate that described anti-core agent oils For 0.47wt%；The speed of described winding is 3500m/min；Heat setting temperature 130 DEG C；

The condition that described greenhouse processes is: temperature 76 DEG C, standing time is 27h；

Fracture strength 7.5cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.4mm, line density deviation Rate 1.2%, fracture strength CV value 2.2%, elongation at break is 21.1%, extension at break CV value 6.5%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.1%.

Uvioresistant is tested

Embodiment 8

The preparation method of a kind of low-shrinkage anti-wicking polyester industrial fiber, comprises the following steps:

(1) preparation of anti-wicking agent

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The synthesis step of section copolymer is:

1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr l, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 74 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, oxidized Aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is dried through the vacuum desiccator that temperature is 40 DEG C To constant weight, obtain poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking The preparation of initiator:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reaction In device, add catalyst CuBr, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) acrylate that bromination blocks divides greatly Sub-initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 84 DEG C Isothermal reaction 25h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:55；After reaction terminates Adding oxolane to dissolve, oxidized aluminum crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through temperature It is that the vacuum desiccator of 40 DEG C is dried to constant weight, obtains the poly-nonfluorinated of poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking Alkyl (methyl) acrylate macromole evocating agent；

3) preparation of fluorination triblock copolymer:

Under nitrogen protection, the poly-non-fluorinated alkylsilane of poly-perfluoroalkyl (methyl) acrylate (methyl) bromination blocked Acrylate macromole evocating agent joins in reactor, is initially charged catalyst CuBr, is then sequentially added into complexant pentamethyl Diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant group Olefinic monomer, isothermal reaction 13h, wherein macromole evocating agent in 114 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:18；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, precipitated to obtain polymer with ethanol, Polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；

4) effective ingredient is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) acrylic acid The mass fraction of ester, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group is respectively as follows:

Smooth agent 28；Emulsifying agent 4；Antistatic additive 8；Cross-linking agent 2；Ternary block polymer 46；

The effect composition of described anti-wicking agent is diluted with water to 14wt%, oils for anti-wicking agent；

(1) preparation of amino ethylene glycol fatty acid:

1) pentatetracontane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, in the catalysis of concentrated sulphuric acid Under, it being heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatetracontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to Mass concentration is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 2wt% of pentatetracontane dicarboxylic acids；

2) described pentatetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), its Middle pentatetracontane mono methyl dicarboxylate's concentration is 0.07mol/L, and under nitrogen atmosphere, 88 DEG C of reactions, backflow, when no longer there being gas When body produces, add a certain amount of dilute sulfuric acid and react 2.3 hours, be washed out, purify and be dried, obtain product bromo 44 Alkane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 45%, and dilute sulfuric acid addition is pentatetracontane dicarboxyl The 2wt% of acid mono-methyl；

3), by the ammonia of bromo tetratetracontane carboxylic acid Yu 25wt% during 1:2 joins reactor in molar ratio, stirring, in room The lower reaction of temperature, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is less than 70 DEG C, until Bubble-free produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses Silver nitrate solution detects, and product vacuum drying is obtained product amino tetratetracontane carboxylic acid；

4) ethylene glycol and amino tetratetracontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino tetratetracontane 1% addition concentration of carboxylic acid weight is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 210 DEG C, and esterification water evaporates It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino tetratetracontane carboxylic acid Glycol ester；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

The p-phthalic acid using mol ratio to be 1:2.0 and ethylene glycol, as raw material, are esterified after being made into uniform sizing material Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature, at 260 DEG C, is esterified It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

The described polycondensation reaction coarse vacuum stage, the ethylene glycol of the 0.02% of addition p-phthalic acid weight in esterification products Antimony and the trimethyl phosphate of p-phthalic acid weight 0.05%, under conditions of negative pressure start polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to below absolute pressure 500Pa, and temperature controls at 270 DEG C, and the response time is 50 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino tetratetracontane carboxylic acid glycol ester, and stir 20 points Clock；Described amino tetratetracontane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 2.0%；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 85 minutes response time；

(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.98dL/g.

By viscous for the height of modified poly ester section through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-core Vapor, stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 315 DEG C；The pathogenic wind-warm of described cooling is 23 DEG C；Described low temperature atomsphere plasma processes: Distance between nozzle and fibre bundle is 7mm；The described oil applying rate oiled is 0.56wt%；The oil applying rate that described anti-core agent oils For 0.49wt%；The speed of described winding is 3400m/min；Heat setting temperature 140 DEG C；

The condition that described greenhouse processes is: temperature 78 DEG C, standing time is 29h；

Fracture strength 7.8cN/dtex of gained low-shrinkage anti-wicking polyester industrial fiber, measure wicking height 0.4mm, line density deviation Rate 1.2%, fracture strength CV value 2.3%, elongation at break is 18.5%, extension at break CV value 6.8%, 177 DEG C, Dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.1%, and low-shrinkage anti-wicking polyester industrial fiber is 78 DEG C of bars in temperature Under part, the free volume space of fibrous inside molecule interchain increases 14v/v%.

Uvioresistant is tested

Claims (10)

1. a low-shrinkage anti-wicking polyester industrial fiber, is characterized in that: described low-shrinkage anti-wicking polyester industrial fiber is by modified poly ester Thickening slice spinning and anti-wicking process and prepare, and its surface adsorption has perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (first Base) acrylate and containing the ternary block polymer of uvioresistant group；Described modified poly ester is by polyester and amino fatty acid second two Alcohol ester is constituted, and described amino ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and described amino fatty acid second two Alcohol ester has hydrogen bond action with the molecule interchain of described polyester, makes the strand of described amino ethylene glycol fatty acid and described polyester Relative position fix；Described modified poly ester under the conditions of temperature is 70～80 DEG C, the free volume of polyester interior molecules interchain Space increases 10～15v/v%；

The molecular structural formula of described amino ethylene glycol fatty acid is:

H₂N(CH₂)nCOOCH₂CH₂OOC(CH₂)n NH₂；

Wherein, n=10～50；

Described perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary containing uvioresistant group are embedding The structural formula of section copolymer is:

Wherein, 2≤m≤8, k >=8, p >=16, x=10～20, y=5～10, z=3～10, R ' is O-hydroxyl-diphenyl ketone, water The uvioresistant group of poplar acid esters and o-hydroxy triazole；

Described low-shrinkage anti-wicking polyester industrial fiber 177 DEG C, under the test condition of 0.05cN/dtex dry-hot shrinkage be 2.5 ± 0.5%, measure wicking height≤0.6mm.

A kind of low-shrinkage anti-wicking polyester industrial fiber the most according to claim 1, it is characterised in that the anti-wicking of described low-shrinkage gathers The physical index of ester industrial yarn: line density deviation ratio ± 1.5%, fracture strength >=7.5cN/dtex, fracture strength CV value≤ 2.5%, elongation at break is 20.0 ± 1.5%, extension at break CV value≤7.0%.

A kind of low-shrinkage anti-wicking polyester industrial fiber the most according to claim 1, it is characterised in that described amino fatty acid second It is 0.5～2.5% that diol ester accounts for the percentage by weight of described modified poly ester, described perfluoroalkyl (methyl) acrylate, non-fluorine The adsorbance of change alkyl (methyl) acrylate and the ternary block polymer containing uvioresistant group accounts for the anti-wicking of described low-shrinkage and gathers The 0.3～2wt% of ester industrial yarn.

4. the method for the preparation a kind of low-shrinkage anti-wicking polyester industrial fiber as according to any one of claims 1 to 3, its feature Be: by the viscous section of the height of modified poly ester through measuring, extrude, cooling down, low temperature atomsphere plasma process, oil, upper anti-wicking agent, Stretching, thermal finalization, winding and greenhouse process step, prepare low-shrinkage anti-wicking polyester industrial fiber；

The temperature of described extrusion is 290～320 DEG C；

The pathogenic wind-warm of described cooling is 20～23 DEG C；

Described low temperature atomsphere plasma processes: the distance between nozzle and fibre bundle is 5～8mm；Operating pressure be 0.5～ 0.7bar；

The described oil applying rate oiled is 0.4～0.6wt%；

The oil applying rate that described anti-core agent oils is 0.4～0.5wt%；

Heat setting temperature 100～150 DEG C；

The speed of described winding is 3200～3600m/min；

Described greenhouse processes and refers to place under conditions of temperature 70～80 DEG C 20～30h；

The effective ingredient of described anti-wicking agent is smooth agent, emulsifying agent, antistatic additive and cross-linking agent, and perfluoroalkyl (methyl) Acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group, described anti-wicking agent Mass fraction is respectively as follows:

The effective ingredient of described anti-wicking agent is diluted with water to 10～15wt%, oils for anti-wicking agent；

Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the tri-block containing uvioresistant group are altogether The synthesis step of polymers is:

(1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:

In container under nitrogen protection, be sequentially added into catalyst CuBr or CuCl, monomer perfluoroalkyl (methyl) acrylate, Solvent toluene, complexant pentamethyldiethylenetriamine, initiator 2 bromopropionic acid ethyl ester, wherein initiator: catalyst: complexant: The mol ratio of monomer is 1:1:2:120, is warming up to 65～75 DEG C, isothermal reaction 6h；Reaction is dissolved with oxolane after terminating, warp Aluminium oxide crosses post separation mantoquita, and filtrate precipitates to obtain polymer with dehydrated alcohol, and polymer is through vacuum desiccator that temperature is 40 DEG C It is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking；

(2) poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole of bromination end-blocking draws Send out agent preparation:

Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent that bromination blocks is placed in reactor In, add catalyst CuBr or CuCl, solvent toluene, below 40 DEG C, treat perfluoroalkyl (methyl) acrylic acid that bromination blocks Ester large molecule initiator is completely dissolved, and adds non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, At 75～85 DEG C of more than isothermal reaction 24h, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2: 10～60；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum crosses post separation mantoquita, and filtrate is precipitated poly-with dehydrated alcohol Compound, polymer is dried to constant weight through the vacuum desiccator that temperature is 40 DEG C, obtains the poly-perfluoroalkyl (methyl) of bromination end-blocking Acrylate poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent；

(3) preparation of fluorination triblock copolymer:

Under nitrogen protection, poly-perfluoroalkyl (methyl) acrylate poly-non-fluorinated alkylsilane (methyl) propylene bromination blocked Acid esters macromole evocating agent joins in reactor, is initially charged catalyst CuBr or CuCl, is then sequentially added into complexant five first Base diethyl triamine and solvent benzotrifluoride, after at 40 DEG C, macromole evocating agent is completely dissolved, be eventually adding containing uvioresistant base The olefinic monomer of group, more than isothermal reaction 10h in 105～115 DEG C, wherein macromole evocating agent: catalyst: complexant: single The mol ratio of body is 1:1:2:10～20；Reaction adds oxolane after terminating and dissolves, and oxidized aluminum is crossed post separation mantoquita, used second Alcohol precipitates to obtain polymer, and polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains being fluorinated triblock copolymer；Described change Property polyester height viscous section preparation process as follows:

(1) preparation of amino ethylene glycol fatty acid:

1) binary of fatty acids is added in reactor with the amount of 1:1.5 mol ratio with methanol, under the catalysis of concentrated sulphuric acid, be heated to 80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；Described binary of fatty acids is dodecane two Carboxylic acid is to the one in dopentacontane dicarboxylic acids；

2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide during 1:1:1 is dissolved in benzene in molar ratio, wherein binary fat The concentration of fat acid mono-methyl is 0.05～0.1mol/L, and under nitrogen atmosphere, 80～90 DEG C of reactions, backflow, when no longer there being gas When body produces, add a certain amount of dilute sulfuric acid and react 2～3 hours, be washed out, purify and be dried, obtain product bromo fat Acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40～50%, and dilute sulfuric acid addition is binary of fatty acids list The 1～3wt% of methyl ester；

3) by the ammonia of bromo fatty acid and 15～25wt% during 1:2 joins reactor in molar ratio, stirring, the most instead Should, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is less than 70 DEG C, until bubble-free Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, by product vacuum It is dried to obtain product amino fatty acid；

4) ethylene glycol and amino fatty acid are stirred for 1.1:2 in molar ratio, and press the 1～3% of amino fatty acid wt Adding the sulphuric acid that concentration is 40～50wt%, carry out esterification, esterification reaction temperature is 160～220 DEG C, esterification water quantity of distillate Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino ethylene glycol fatty acid；

(2) preparation of modified poly ester, including esterification and polycondensation reaction:

Described esterification:

Use p-phthalic acid and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products；Ester Changing reaction to pressurize in nitrogen atmosphere, Stress control is at normal pressure～0.3MPa, and temperature is at 250～260 DEG C, and esterification water quantity of distillate reaches It is esterification terminal to more than the 90% of theoretical value；

Described polycondensation reaction:

Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:

In the described polycondensation reaction coarse vacuum stage, esterification products adds catalyst and stabilizer, starts under conditions of negative pressure Polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, reaction Time is 30～50 minutes；

After the described polycondensation reaction coarse vacuum stage terminates, add amino ethylene glycol fatty acid, and stir；

Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop To absolute pressure less than 100Pa, reaction temperature controls at 275～280 DEG C, response time 50～90 minutes；

Prepare modified poly ester；

(3) by modified poly ester solid-phase tack producing, making the viscous section of height of modified poly ester, intrinsic viscosity is 0.95～0.98dL/g.

The preparation method of a kind of low-shrinkage the most according to claim 4 anti-wicking polyester industrial fiber, it is characterised in that described second Glycol is 1.2～2.0:1 with the mol ratio of described p-phthalic acid.

The preparation method of a kind of low-shrinkage the most according to claim 4 anti-wicking polyester industrial fiber, it is characterised in that described in urge Agent one in antimony oxide, antimony glycol and antimony acetate, catalyst amount is described p-phthalic acid weight 0.01%～0.05%；Described stabilizer one in triphenyl phosphate, trimethyl phosphate and NSC 6513 is stable Agent consumption is the 0.01%～0.05% of described p-phthalic acid weight.

The preparation method of a kind of low-shrinkage the most according to claim 4 anti-wicking polyester industrial fiber, it is characterised in that add ammonia Stirring after base ethylene glycol fatty acid, the time is 15～20 minutes.

The preparation method of a kind of low-shrinkage the most according to claim 4 anti-wicking polyester industrial fiber, it is characterised in that spend from Son is washed to without using silver nitrate solution detection till bromide ion.

The preparation method of a kind of low-shrinkage the most according to claim 4 anti-wicking polyester industrial fiber, it is characterised in that described dense Sulphuric acid refers to the sulphuric acid that mass concentration is 70～80%, and concentrated sulphuric acid addition is the 1～3wt% of binary of fatty acids.

The preparation method of a kind of low-shrinkage the most according to claim 4 anti-wicking polyester industrial fiber, it is characterised in that described Smooth agent is in octyl polyoxyethylene ether, sorbitan stearate monoesters and DoJyoxyethylene xylitol stearate Kind；Described emulsifying agent is double dodecanoyl hydroxyl succinic acid dipotassiums；Described antistatic additive be alkyl phosphate triethanolamine, One in polyoxyethylene castor oil and potassium alkyl phosphate；Described cross-linking agent is tripolycyanamide, isocyanide ester amino first One in acid esters and Biformyl.