CN104562279A - Low-shrinkage anti-wicking industrial polyester filament and manufacturing method thereof - Google Patents

Low-shrinkage anti-wicking industrial polyester filament and manufacturing method thereof Download PDF

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CN104562279A
CN104562279A CN201410851757.1A CN201410851757A CN104562279A CN 104562279 A CN104562279 A CN 104562279A CN 201410851757 A CN201410851757 A CN 201410851757A CN 104562279 A CN104562279 A CN 104562279A
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methyl
acrylate
wicking
agent
low
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CN104562279B (en
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杨大矛
赵慧荣
张耀鹏
宋光坤
范晓兵
蔡明建
刘亚涛
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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Abstract

The invention relates to a low-shrinkage anti-wicking industrial polyester filament and a manufacturing method thereof. Viscosity-enhancing slices of modified polyester are taken as raw materials and subjected to melt spinning and anti-wicking treatment to prepare the low-shrinkage anti-wicking industrial polyester filament; the modified polyester consists of polyester and aminoadipic acid glycol ester; aminoadipic acid glycol ester is dispersed among molecular chains of polyester, and a hydrogen-bond interaction exists between aminoadipic acid glycol ester and the molecular chains of polyester, so that the relative position of aminoadipic acid glycol ester and the molecular chains of polyester are set; an anti-wicking agent contains perfluoroalkyl (methyl) acrylate, non-fluorinated alkyl (methyl) acrylate and a ternary segmented copolymer containing an anti-ultraviolet group. The low-shrinkage anti-wicking industrial polyester filament has not only the characteristics of inherent high fracture strength, small dry thermal shrinkage and the like of superlow-shrinkage industrial terylene filaments but also excellent hydrophobicity and relatively good anti-ultraviolet ageing performance and has an extremely wide application prospect in the field of high-end lamp box poster cloth, waterproof cloth, swimming pond fabrics and the like.

Description

A kind of anti-wicking polyester industrial fiber of low-shrinkage and manufacture method thereof
Technical field
The present invention relates to a kind of production method of fibre modification, especially relate to a kind of anti-wicking and there is the manufacture method of the anti-wicking polyester industrial fiber of low-shrinkage of uvioresistant function, belonging 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, the market demand and the application prospect of anti-core suction type polyester industrial yarn are more and more wide.Anti-core suction type polyester industrial yarn refers at fiber surface introducing-CF 2low-fiber surface tension, falls in group, makes fiber surface be difficult to infiltrate, thus the superior water proofing property of endowing terylene and grease proofness, make fiber surface have good agent of low hygroscopicity energy.
The active ingredient of anti-wicking agent is fluorocarbon.Fluorocarbon is a kind of surfactant with amphiphilic group, respectively containing hydrophobic fluoro-containing group and hydrophilic non-fluorin radical.Fiber after heat treatment, along with evaporation and the high temperature action of moisture in anti-wicking agent, originally stretch to outside hydrophilic group and be retracted into intramolecule gradually, form film at fiber surface, hydrophobic fluoroalkyl is distributed in fiber surface, fabric is had and excellent refuses water and oil repellent.
But, PET is partially crystalline polymer, not containing active group in molecule, fiber surface molecule is difficult to, with fluorocarbon, effective chemical reaction occurs, therefore fluorocarbon just forms membrane structure and is coated on fiber surface, cannot form firmly chemical bonds between fluorocarbon and fiber surface.In use, fluorocarbon easily runs off from fiber surface and reduces anti-wicking capacity, the washability of anti-wicking industrial yarn and poor durability.
In a lot of field, the fabric product of anti-wicking polyester industrial yarn must in outdoor application.Such as, lamp box advertisement cloth and puggaree, need in use procedure to stand long solar radiation.Ultraviolet in daylight and black light easily make the molecular chain rupture of polyester, cause light degradation and photooxidative degradation, fall low-fiber intensity, affect the service life of polyester industrial yarn.
At present, application number is the Chinese patent of 20121054270.X, discloses a kind of anti-core suction type lower shrinkage polyester industrial yarn and manufacture method thereof.This anti-core suction type lower shrinkage polyester industrial yarn glues PET section for raw material with height, and through melt spinning, carry out drawing and heat-setting after adding appropriate spinning oil, after adding appropriate anti-wicking agent, winding is made, the anti-measure wicking height≤2mm of product.In this invention, the position of upper anti-wicking agent is between drafting forming and winding, direct coiling and molding after anti-wicking agent on tow, not through the heat treatment of drawing-off hot-rolling, the uniformity of anti-wicking agent on tow surface and tack bad, the anti-wick effect of product is bad, and not through greenhouse heat treatment process after tow coiling and molding, anti-wick effect cannot be further improved and consolidate.
Publication number is the United States Patent (USP) of US005116682A, discloses the production method of a kind of anti-core suction type polyester fiber and the thermally-stabilised fiber of other anti-core suction types.Anti-wicking agent described in this patent is moisture fluorinated polymer emulsion, described process characteristic is after fiber surface attachment anti-wicking agent, removes moisture, be heated to 200 DEG C ~ 260 DEG C by IR bake with drying equipment, fluoride and fiber surface are combined, reaches anti-wick effect.But the method described in this patent is the anti-wicking process carried out after fiber roll winding forming, a step cannot realizes in spinning technique, and not relate to the measure wicking height of anti-wicking fiber.
Within 2007, Shen Wei has delivered the paper being entitled as " development of anti-wicking polyester industrial filament yarn ".This article describes a kind of anti-wicking agent of adding before drafting forming to produce the method for anti-wicking polyester industrial filament yarn.Anti-wicking agent emulsion and spinning oil mixing oil as finish by the method, and the anti-measure wicking height producing the industrial yarn obtained when improving heat-treat condition is still greater than 2mm.Its shortcoming anti-wicking agent and spinning oil is mixed into composite finish once oil, and the active ingredient of anti-wicking agent reduces, and cannot obtain best anti-wick effect.And adopt the industrial yarn that this kind of method is produced, still cannot carry out effective chemical reaction between fiber surface and anti-wicking agent composition, anti-wick effect cannot keep for a long time.
Application number is the Chinese patent of 201210321149.0, discloses a kind of manufacture method of superlow shrinkage type PET industrial yarn.Adopt common finish to oil in this superlow shrinkage type PET industrial yarn production process, do not add anti-wicking agent, the product obtained does not have anti-wick effect, cannot be used for the fields such as high-grade lamp box advertisement cloth and swimming pool fabric.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the manufacture method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage is provided.The key of producing anti-core suction type polyester industrial yarn can form one deck fluorocarbon film at fiber surface, and form firmly chemical bonds between fluorocarbon and fiber surface, instead of simple physical bond.PET is partially crystalline polymer, not containing active group in strand, fiber surface can not and fluorocarbon between be difficult to there is effective chemical reaction and form stable chemical bond, in use procedure, fluorocarbon easily to come off loss at fiber surface, so the anti-wick effect of anti-core suction type polyester industrial yarn that general enterprises is produced is undesirable, durability and washability poor.
The present invention, before upper spinning oil, increases by one low temperature atomsphere plasma treatment process.Use jet flow type atmosphere low-temperature plasma processor to form primarily of plasma generator, gas delivery system and plasma spray first class sections.Plasma generator produces high voltagehigh frequency energy and is activated in nozzle steel pipe and creates low temperature plasma in controlled glow discharge, by compressed air, plasma is sprayed to fiber surface.When this uncharged neutral plasma and fiber surface meet, create chemical action and physical change, the reactive group of some activity can be formed at fiber surface, as-C-O-,-C=N-, -CH 2oH etc., these hydroxyls, carboxyl isoreactivity group can with the crosslinking agent (isocyanide ester) in anti-wicking agent and active group R (-COOH ,-OH ,-NH 2) there is chemical reaction, ensure that the active ingredient in anti-wicking agent is for good and all attached to fiber surface, improve the anti-wicking capacity of fiber.
The present invention adds a kind of block copolymer containing carbon fluorin radical and uvioresistant group of novel synthesis in spinning oil, 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 CH 3, 2≤m≤8, n>=8;
The structural formula of described non-fluorinated alkylsilane (methyl) acrylate is:
wherein X=H or CH 3, p>=16;
The described Third monomer containing uvioresistant group is O-hydroxyl-diphenyl ketone, salicylate and o-hydroxy and the monomer of triazole group, and its structural formula is respectively:
wherein 2≤q≤6;
wherein 2≤q≤6;
wherein 2≤q≤6;
Wherein, R can be-COOH ,-OH ,-NH 2any 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-hydroxyl-diphenyl ketone, salicylate and o-hydroxy the uvioresistant group of triazole.
In this block copolymer, the effect of fluoridizing (methyl) acrylate reduces fiber surface energy, gives fiber water and oil repellant.The fluorocarbon chain section (n >=8) of whole-fluoroalkyl chain segment end is perpendicular to fiber surface close-packed arrays, that can form more difficult migration, orderly layered crystal structure, the Oil repellent of fiber surface is increased, surface energy reduces, oil water contact angle increases, thus gives fiber certain water and oil repellant.When 2<n≤6, fluorocarbon chain section does not have crystallinity, and easily in polymer surfaces run-off the straight, thus surface molecular rearrangement occurs in polarity environment, polar group moves to surface, and fiber surface can totally increase, and oil water contact angle reduces.When n≤2, can not shield polar group completely because fluorocarbon chain section is too short, the exposure of surperficial carbonyl makes surface energy polymer obviously increase, and oil water contact angle is all less.Therefore, our fluorocarbon chain section n >=8 of selecting.In carbon fluorine segment, suitable hydrocarbon interval is conducive to improving the dissolubility of block copolymer and heat endurance, and that therefore selects is hydrocarbonly spaced apart 2≤m≤8.
In this block copolymer, the effect of nonfluorinated (methyl) acrylate segment improves the dissolubility of block copolymer and the compatibility with other resins.This is mainly insoluble to general organic solvent owing to fluoridizing (methyl) acrylate homopolymer, poor with the compatibility of other resins.In order to head it off, can adopt and fluoridize (methyl) (methyl) acrylate monomer and nonfluorinated (methyl) (methyl) acrylate monomer carries out copolymerization, can obtain that there is the material compared with low-surface-energy, also can effectively improve structure adaptability and compatibility simultaneously.During p < 16, the crystallinity of nonfluorinated (methyl) acrylate segment is poor, and copolymer surface energy is higher; During p >=16, because nonfluorinated (methyl) acrylate segment is longer, copolymer is difficult to that in polar liquid surface molecular occurs and resets, the introducing of side chain nonfluorinated (methyl) acrylate segment forms crystallization to copolymer and has synergy, 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 the combination of anti-wicking agent and fiber surface, and gives the function of resistant fiber ultraviolet ageing.Active group R (-COOH ,-OH ,-NH in 3rd block 2deng) the active group generation chemical reaction that can produce at fiber surface with plasma, improve the binding ability of block copolymer and fiber surface, 2≤q≤6, hydrocarbon interval in 3rd segment, what can ensure the polymerisation of reacting carries out the effecting reaction with R group smoothly.Due to the chemical reaction of R group and fiber surface activity group, Third monomer segment is compared and is fluoridized (methyl) (methyl) acrylate segment and nonfluorinated (methyl) acrylate segment closer to fiber, makes to fluoridize (methyl) acrylate and nonfluorinated (methyl) acrylate segment to fibrous outer surfaces migration and ordered arrangement.In addition, uvioresistant group in Third monomer segment contains sterically hindered larger phenyl ring, copolymer can be limited surface molecular rearrangement and migration occur in polar liquid, to the orderly close-packed arrays structure of established fluorocarbon chain section and nonfluorinated segment, there is stabilization, improve the water and oil repellant ability of fiber.Simultaneously, the phenyl ring that two volumes contained in 3rd segment are larger can cause being separated of block copolymer, improves surface roughness, is conducive to fluorine element to surface migration, improve the water and oil repellant of copolymer, the consumption of fluorine monomer can also be reduced in building-up process.
Except above-mentioned ternary block polymer, another main component of fluorine-containing anti-wicking agent is crosslinking agent.Crosslinking agent is mainly melamine, isocyanide ester carbamate or glyoxal.After fiber surface attachment anti-wicking agent, if without heat treatment, the caking property of fluorocarbon and fiber surface is lower, adheres to insecure, and durability and washability are all poor, therefore needs through suitable heat treatment to consolidate the anti-wick effect of fiber.In heat treatment process, along with evaporation and the high temperature action of moisture in anti-wicking agent, originally stretch to outside hydrophilic radical and be retracted into intramolecule gradually, form film at fiber surface, hydrophobic fluoroalkyl is distributed in fiber surface, fabric is had and excellent refuses water and oil repellent.Meanwhile, crosslinking agent in anti-wicking agent can-COOH in the uvioresistant group (R ') of the 3rd block ,-OH ,-NH 2isoreactivity group (R) reacts, and forms tridimensional network, prevent the loss of fluorocarbon at fiber surface, improves durability and the washability of resistant fiber wick effect.
Thermal processes act can affect the binding ability of fluorocarbon at fiber surface, and then promotes the anti-wick effect of industrial yarn.On the one hand, before drafting forming, fiber is not yet shaping, the degree of orientation and degree of crystallinity lower, there is more amorphous region, due to anti-wicking agent molecular weight, molecular dimension is also less, not only can be attached to fiber surface generation chemical reaction, the amorphous region that fibrous inside strand spacing is larger can also be penetrated into; On the other hand, the high-temperature heating effect of hot-rolling can promote the chemical reaction of fluorocarbon and fiber, improves durability and the washability of fiber.Therefore the present invention adopts the front upper anti-wicking agent in drawing and heat-setting, ensures that fiber has best anti-wick effect.
In the present invention, the fiber after coiling and molding, through special greenhouse process, can ensure the binding ability of fluorocarbon and fiber surface, improves and consolidate anti-wick effect further.
The present invention, by low temperature atomsphere plasma process, the anti-improvement of wicking finish and the control and regulation of Technology for Heating Processing, provides a kind of anti-wicking to have the preparation method of the ultralow contraction terylene industry silk of uvioresistant function concurrently.
The technical scheme that technical solution problem of the present invention is taked is: with the sticky section of the height of modified poly ester for raw material, through high-temperature fusion spinning, low temperature atomsphere plasma process, upper spinning oil, upper anti-wicking agent, carry out drawing and heat-setting, winding, make through greenhouse process, it is characterized in that, the height of described modified poly ester glues section for the sticky section of the height after solid phase thickening, before described low temperature atomsphere plasma treating apparatus is positioned at spin finishing, described spinning oil is be specifically designed to the HM200 spinning oil producing polyester industrial yarn, described anti-wicking agent is for containing smooth agent, emulsifying agent, the polyester filament oil agent of antistatic additive and crosslinking agent, and containing perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group, there is the function of water and oil repellant and anti-ultraviolet ageing.
The anti-wicking polyester industrial fiber of described a kind of low-shrinkage, modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described amino ethylene glycol fatty acid is dispersed between the strand of described polyester, and have hydrogen bond action between the strand of described amino ethylene glycol fatty acid and described polyester, the relative position of the strand of described amino ethylene glycol fatty acid and described polyester is fixed; The anti-wicking polyester industrial fiber of described low-shrinkage is under temperature is 70 ~ 80 DEG C of conditions, and the free volume space between fibrous inside strand increases 10 ~ 15v/v%;
The molecular structural formula of described amino ethylene glycol fatty acid is:
H 2N(CH 2) nOCOCH 2CH 2OCO(CH 2) nNH 2
Wherein, n=10 ~ 50.
The anti-wicking polyester industrial fiber of described a kind of low-shrinkage, is characterized in that, the percentage by weight that described amino ethylene glycol fatty acid accounts for the anti-wicking polyester industrial fiber of described low-shrinkage is 0.5 ~ 2.5%.
The anti-wicking polyester industrial fiber of described a kind of low-shrinkage, is characterized in that, the preparation process that the height of described modified poly ester glues section comprises:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by binary of fatty acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric 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 that dodecanedicarboxylic acid 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 of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid reaction 2 ~ 3 hours, then wash, purify and drying, obtain product bromo aliphatic acid;
3) by the ammoniacal liquor of bromo aliphatic acid and 15 ~ 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is no more than 70 DEG C, until bubble-free produces, namely stop distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, product vacuumize is obtained the amino aliphatic acid of product;
4) by ethylene glycol and amino aliphatic acid in molar ratio for 1.1:2 stirs, and add by one of the percentage of amino fatty acid wt the sulfuric acid that concentration is 40 ~ 50wt%, carry out esterification, esterification reaction temperature is 160 ~ 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino ethylene glycol fatty acid through separating-purifying;
(2) preparation of modified PET, comprises esterification and polycondensation reaction:
Described esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; 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 quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, in esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction time is 30 ~ 50 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino ethylene glycol fatty acid, and stir;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 ~ 280 DEG C, 50 ~ 90 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of modified PET height, inherent viscosity is 0.98dL/g.
The preparation method of the anti-wicking polyester industrial fiber of described low-shrinkage,
By the sticky section of the height of modified poly ester through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, the step such as winding and greenhouse process, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 290 ~ 320 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 25 DEG C;
Described low temperature atomsphere plasma process: 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 of described greenhouse process is: temperature 70 ~ 80 DEG C, and standing time is 20 ~ 30h;
Described anti-wicking agent contains smooth agent, emulsifying agent, antistatic additive and crosslinking 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:
Described perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
(1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br or CuCl, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 65 ~ 75 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
(2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br or CuCl, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add 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; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
(3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br or CuCl, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, more than isothermal reaction 10h in 105 ~ 115 DEG C, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:10 ~ 20; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
In the present invention, described anti-wicking agent is the polyester filament oil agent containing smooth agent, emulsifying agent, antistatic additive and crosslinking agent, it is characterized in that, containing perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group, there is the function of water and oil repellant and anti-ultraviolet ageing.
The INTELLIRAY 400 type large area ultraviolet curing equipment using UVITRON company of the U.S. to produce, carries out ultraviolet irradiation to polyester industrial yarn, the anti-ultraviolet ageing ability of testing polyester industrial yarn.Experiment condition is as follows: held by the glass dish used for polyester industrial filament produced in ordinary polyester industrial yarn and the present invention and be placed in case, and light intensity is arranged to 90% (1245 μ W/cm 2), wavelength is 325nm, altogether accumulative irradiation 12h.Then respectively by the mechanical property of the polyester industrial yarn of tension test test after 3h and 12h UV-irradiation.The anti-ultraviolet ageing ability that uvioresistant test result shows polyester industrial yarn in the present invention is improved significantly.
Amino ethylene glycol fatty acid is mainly with C-C, C-O key is main, there is certain molecular weight simultaneously, namely there is the strand of certain length, strand flexibility is larger, the amount of crimp of amino ethylene glycol fatty acid is larger compared with the linear macromolecule of benzene ring structure, simultaneously strong to the linear macromolecule of sensitivity comparatively containing benzene ring structure of temperature.When the temperature is changed, amino ethylene glycol fatty acid moves prior to the linear macromolecule containing benzene ring structure, and the free volume linear macromolecule be far longer than containing benzene ring structure that motion produces produces.
Added the free volume of polyester fiber by fatty acid ester, improve the degree that anti-wicking agent enters polyester fiber inside.The present invention makes the space of polyester fiber at a certain temperature between fiber molecule increase, in activation process, make part anti-wicking agent molecular diffusion enter into fiber gap, improve the service efficiency of anti-wicking agent, and form firmly resinoid coating on polyester industrial fiber surface, ensure that the active ingredient in anti-wicking agent is for good and all attached to fiber surface, improve the anti-wicking capacity of fiber.
The anti-wicking polyester industrial fiber of the low-shrinkage 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%, extension at break 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 possesses well hydrophobic and water resistance, reach good anti-wick effect, there is good anti-ultraviolet ageing ability simultaneously, outdoor can be applicable on a large scale, in fields such as high-grade lamp box advertisement cloth, WATERPROOF FABRIC and swimming pool fabrics, there are good market prospects.
Beneficial effect:
1. the anti-wicking polyester industrial fiber of the low-shrinkage of gained of the present invention, because amino ethylene glycol fatty acid is based on C-C, there is certain molecular weight simultaneously, namely there is the strand of certain length, strand flexibility is larger, amino adds the compatibility with polyester, thus makes the compatibility of amino ethylene glycol fatty acid and polyester industrial fiber be improved.
2. the present invention makes the space of polyester fiber at a certain temperature between fiber molecule increase, in activation process, make part anti-wicking agent molecular diffusion enter into fiber gap, improve the service efficiency of anti-wicking agent, and form firmly resinoid coating on polyester industrial fiber surface, ensure that the active ingredient in anti-wicking agent is for good and all attached to fiber surface, improve the anti-wicking capacity of fiber.
3. the anti-wicking polyester industrial fiber of the low-shrinkage of gained of the present invention, good anti-wick effect, has good anti-ultraviolet ageing ability simultaneously, has good market prospects.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The anti-wicking polyester industrial fiber of a kind of low-shrinkage of the present invention, material is modified poly ester, and obtained by anti-wicking process, described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described amino ethylene glycol fatty acid is dispersed between the strand of described polyester, and have hydrogen bond action between the strand of described amino ethylene glycol fatty acid and described polyester, the relative position of the strand of described amino ethylene glycol fatty acid and described polyester is fixed; The anti-wicking polyester industrial fiber of described low-shrinkage is under temperature is 70 ~ 80 DEG C of conditions, and the free volume space between fibrous inside strand increases 10 ~ 15v/v%;
The molecular structure of described amino ethylene glycol fatty acid is:
H 2N(CH 2) nCOOCH 2CH 2OOC(CH 2) nNH 2；
Wherein, n=10-50.
The anti-wicking polyester industrial fiber of described a kind of low-shrinkage: 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, dry-hot shrinkage under the test condition of 0.05cN/dtex is 7.0 ± 0.5%.
The anti-wicking polyester industrial fiber of described a kind of low-shrinkage, the percentage by weight that described amino ethylene glycol fatty acid accounts for the anti-wicking polyester industrial fiber of described low-shrinkage is 0.5 ~ 2.5%.
High sticky section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, the step such as winding and greenhouse process, obtain the anti-wicking polyester industrial fiber of low-shrinkage.
Line density deviation ratio ± 1.5% of the anti-wicking polyester industrial fiber of a kind of low-shrinkage as above, 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 is 2.5 ± 0.5%, measure wicking height ￡ 0.6mm.
Uvioresistant method of testing is:
The INTELLIRAY 400 type large area ultraviolet curing equipment using UVITRON company of the U.S. to produce, carries out ultraviolet irradiation to polyester industrial yarn, the anti-ultraviolet ageing ability of testing polyester industrial yarn.Experiment condition is as follows: held by the glass dish used for polyester industrial filament produced in ordinary polyester industrial yarn and the present invention and be placed in case, and light intensity is arranged to 90% (1245 μ W/cm 2), wavelength is 325nm, altogether accumulative irradiation 12h.Then the mechanical property of the polyester industrial yarn after 3h and 12h UV-irradiation is tested respectively by tension test.
Performance anti wicking method of testing is:
Getting length is 30cm tow, hangs up the weight of 0.05cN/dtex, puts into after 150 DEG C of baking ovens dry 5min and takes out immersion ink, measure the lifting height ￡ 0.6mm of ink, show that tow has possessed good hydrophobic performance after 30min.
Embodiment 1
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 65 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 75 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:10; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 15h, wherein macromole evocating agent in 105 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:10; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 20; Emulsifying agent 3; Antistatic additive 5; Crosslinking 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) add in reactor by dodecanedicarboxylic acid and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 80 DEG C, refuxing esterification, cooling, separating-purifying obtains dodecanedicarboxylic acid mono-methyl; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of dodecanedicarboxylic acid;
2) described dodecanedicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein dodecanedicarboxylic acid mono-methyl concentration is 0.05mol/L, under nitrogen atmosphere, 80 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2 hours, then wash, purify and drying, obtain product bromoundecane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40%, and dilute sulfuric acid addition is the 3wt% of dodecanedicarboxylic acid mono-methyl;
3) by the ammoniacal liquor of bromoundecane carboxylic acid and 15wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, product vacuumize is obtained product amino-undecanoic carboxylic acid;
4) by ethylene glycol and amino-undecanoic carboxylic acid in molar ratio for 1.1:2 stirs, and add by 1% of amino-undecanoic carboxylic acid weight the sulfuric acid that concentration is 40wt%, carry out esterification, esterification reaction temperature is 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino-undecanoic carboxylic acid glycol ester through separating-purifying;
(3) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.2 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.01% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.01% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 DEG C, and the reaction time is 50 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino-undecanoic carboxylic acid glycol ester, and stir 15 minutes; 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 low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 90 minutes reaction time;
Obtained modified poly ester.
(4) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.95dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 290 DEG C; The wind-warm syndrome of described cooling is 20 DEG C; Described low temperature atomsphere plasma process: the distance between nozzle and fibre bundle is 5mm; Operating pressure is 0.5bar; The described oil applying rate oiled is 0.4wt%; The oil applying rate that described anti-core agent oils is 0.4wt%; Heat setting temperature 100 DEG C; The speed of described winding is 3200m/min;
Described greenhouse process refers to places 30h under the condition of temperature 70 C;
The fracture strength 7.5cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.6mm, line density deviation ratio 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%.The anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 70 DEG C of conditions, and the free volume space between fibrous inside strand increases 11v/v%.
Uvioresistant is tested
Embodiment 2
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 75 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Cl, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 85 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:60; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Cl, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 115 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:20; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 30; Emulsifying agent 5; Antistatic additive 10; Crosslinking 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) add in reactor by dopentacontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains dopentacontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of dopentacontane dicarboxylic acids;
2) described dopentacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein dopentacontane mono methyl dicarboxylate concentration is 0.07mol/L, under nitrogen atmosphere, 85 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 3 hours, then wash, purify and drying, obtain product bromo henpentacontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40%, and dilute sulfuric acid addition is the 3wt% of dopentacontane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo henpentacontane carboxylic acid and 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 62 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino henpentacontane carboxylic acid of product;
4) by ethylene glycol and amino henpentacontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino henpentacontane carboxylic acid weight the sulfuric acid that concentration is 45wt%, carry out esterification, esterification reaction temperature is 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino henpentacontane carboxylic acid glycol ester through separating-purifying;
(3) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification: adopt mol ratio be the terephthalic acid (TPA) of 1:2.0 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature is at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction: comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.05% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.05% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 270 DEG C, and the reaction time is 30 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino henpentacontane carboxylic acid glycol ester, and stir 20 minutes; Described amino henpentacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 50 minutes reaction time;
(4) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.98dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 320 DEG C; The wind-warm syndrome of described cooling is 23 DEG C; Described low temperature atomsphere plasma process: the distance between nozzle and fibre bundle is 8mm; Operating pressure is 0.7bar; The described oil applying rate oiled is 0.4wt%; The oil applying rate that described anti-core agent oils is 0.4wt%; The speed of described winding is 3400m/min; Heat setting temperature 150 DEG C;
Described greenhouse process refers to places 30h under the condition of temperature 70 C;
The fracture strength 7.6cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, line density deviation ratio-1.5%, fracture strength CV value 2.3%, elongation at break is 21.4%, extension at break CV value 6.5%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.5%, measure wicking height 0.6mm.The anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 70 DEG C of conditions, and the free volume space between fibrous inside strand increases 10v/v%.
Uvioresistant is tested
Embodiment 3
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 66 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 76 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:20; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 106 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:11; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 21; Emulsifying agent 3.2; Antistatic additive 6; Crosslinking 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) add in reactor by pentacosane dicarboxylic acid and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains pentacosane dicarboxylic acid mono-methyl; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of pentacosane dicarboxylic acid;
2) described pentacosane dicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein pentacosane dicarboxylic acid mono-methyl concentration is 0.08mol/L, under nitrogen atmosphere, 90 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2.5 hours, then wash, purify and drying, obtain product bromotetradecane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 50%, and dilute sulfuric acid addition is the 3wt% of pentacosane dicarboxylic acid mono-methyl;
3) by the ammoniacal liquor of bromotetradecane carboxylic acid and 20wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino tetradecane carboxylic acid of product;
4) by ethylene glycol and amino tetradecane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of the amino tetradecane carboxylic acid weight sulfuric acid that concentration is 50wt%, carry out esterification, esterification reaction temperature is 190 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino tetradecane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification: adopt mol ratio be the terephthalic acid (TPA) of 1:1.6 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction: comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.03% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.03% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 265 DEG C, and the reaction time is 40 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino tetradecane carboxylic acid glycol ester, and stir 16 minutes; Described amino tetradecane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.0%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 276 DEG C, 70 minutes reaction time;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.98dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 295 DEG C; The wind-warm syndrome of described cooling is 21 DEG C; Described low temperature atomsphere plasma process: the 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 is 0.41wt%; The speed of described winding is 3500m/min; Heat setting temperature 110 DEG C;
The condition of described greenhouse process is: temperature 71 DEG C, and standing time is 21h;
The fracture strength 7.8cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.6mm, line density deviation ratio-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%.The anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 71 DEG C of conditions, and the free volume space between fibrous inside strand increases 11v/v%.
Uvioresistant is tested
Embodiment 4
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 67 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 77 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:30; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 112 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:12; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 22; Emulsifying agent 3.4; Antistatic additive 6; Crosslinking 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) add in reactor by eicosane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains eicosane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of eicosane dicarboxylic acids;
2) described eicosane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein eicosane mono methyl dicarboxylate concentration is 0.09mol/L, under nitrogen atmosphere, 80 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2.1 hours, then wash, purify and drying, obtain product bromo nonadecane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 43%, and dilute sulfuric acid addition is the 2wt% of eicosane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo nonadecane carboxylic acid and 16wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino nonadecane carboxylic acid of product;
4) by ethylene glycol and amino nonadecane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino nonadecane carboxylic acid weight the sulfuric acid that concentration is 42wt%, carry out esterification, esterification reaction temperature is 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino nonadecane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.2 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.15MPa, and temperature is at 251 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.02% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.02% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 262 DEG C, and the reaction time is 33 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino nonadecane carboxylic acid glycol ester, and stir 17 minutes; Described amino nonadecane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 277 DEG C, 55 minutes reaction time;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.98dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 300 DEG C; The wind-warm syndrome of described cooling is 22 DEG C; Described low temperature atomsphere plasma process: the 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 is 0.42wt%; The speed of described winding is 3600m/min; Heat setting temperature 100 DEG C;
The condition of described greenhouse process is: temperature 72 DEG C, and standing time is 22h;
The fracture strength 7.5cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.5mm, line density deviation ratio-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%.The anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 72 DEG C of conditions, and the free volume space between fibrous inside strand increases 12v/v%.
Uvioresistant is tested
Embodiment 5
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 68 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Cl, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 78 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:30; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 108 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:13; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 24; Emulsifying agent 3.6; Antistatic additive 7; Crosslinking 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) add in reactor by melissane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 90 DEG C, refuxing esterification, cooling, separating-purifying obtains melissane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of melissane dicarboxylic acids;
2) described melissane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein melissane mono methyl dicarboxylate concentration be 0.10mol/L under nitrogen atmosphere, 85 DEG C of reactions, backflow, when no longer including gas and producing, add a certain amount of dilute sulfuric acid and react 2.3 hours, then wash, purify and drying, obtain product bromo nonacosane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40%, and dilute sulfuric acid addition is the 3wt% of melissane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo nonacosane carboxylic acid and 18wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 67 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino nonacosane carboxylic acid of product;
4) by ethylene glycol and amino nonacosane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino nonacosane carboxylic acid weight the sulfuric acid that concentration is 48wt%, carry out esterification, esterification reaction temperature is 170 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino nonacosane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.5 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is at 254 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony glycol of 0.01% of terephthalic acid (TPA) weight and the trimethyl phosphate of terephthalic acid (TPA) weight 0.03% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 266 DEG C, and the reaction time is 39 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino nonacosane carboxylic acid glycol ester, and stir 18 minutes; Described amino nonacosane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 278 DEG C, 60 minutes reaction time;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.95dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 305 DEG C; The wind-warm syndrome of described cooling is 23 DEG C; Described low temperature atomsphere plasma process: the 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 is 0.43wt%; The speed of described winding is 3500m/min; Heat setting temperature 140 DEG C;
The condition of described greenhouse process is: temperature 73 DEG C, and standing time is 23h;
The fracture strength 7.8cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.5mm, line density deviation ratio 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%.The anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 73 DEG C of conditions, and the free volume space between fibrous inside strand increases 12v/v%.
Uvioresistant is tested
Embodiment 6
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 70 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 80 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:35; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Cl, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 110 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:15; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 25; Emulsifying agent 4; Antistatic additive 7.5; Crosslinking 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) add in reactor by pentatriacontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 95 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatriacontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 2wt% of pentatriacontane dicarboxylic acids;
2) described pentatriacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein pentatriacontane mono methyl dicarboxylate concentration be 0.09mol/L under nitrogen atmosphere, 90 DEG C of reactions, backflow, when no longer including gas and producing, add a certain amount of dilute sulfuric acid and react 2.6 hours, then wash, purify and drying, obtain product bromo tetratriacontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 45%, and dilute sulfuric acid addition is the 1wt% of pentatriacontane mono methyl dicarboxylate
3) by the ammoniacal liquor of bromo tetratriacontane carboxylic acid and 20wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino tetratriacontane carboxylic acid of product;
4) by ethylene glycol and amino tetratriacontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 1% of amino tetratriacontane carboxylic acid weight the sulfuric acid that concentration is 50wt%, carry out esterification, esterification reaction temperature is 180 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino tetratriacontane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.6 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.4MPa, and temperature is at 256 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony acetate of 0.04% of terephthalic acid (TPA) weight and the Trimethyl phosphite of terephthalic acid (TPA) weight 0.02% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 267 DEG C, and the reaction time is 40 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino tetratriacontane carboxylic acid glycol ester, and stir 18 minutes; Described amino tetratriacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.0%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 70 minutes reaction time;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.96dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 315 DEG C; The wind-warm syndrome of described cooling is 22 DEG C; Described low temperature atomsphere plasma process: the 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 is 0.45wt%; The speed of described winding is 3500m/min; Heat setting temperature 120 DEG C;
The condition of described greenhouse process is: temperature 75 DEG C, and standing time is 25h;
The fracture strength 7.7cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.4mm, line density deviation ratio 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%.The anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 75 DEG C of conditions, and the free volume space between fibrous inside strand increases 13v/v%.
Uvioresistant is tested
Embodiment 7
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 72 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 82 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:35; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 112 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:16; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 23; Emulsifying agent 4; Antistatic additive 7; Crosslinking 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) add in reactor by tetracontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 100 DEG C, refuxing esterification, cooling, separating-purifying obtains tetracontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of tetracontane dicarboxylic acids;
2) described tetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein tetracontane mono methyl dicarboxylate concentration be 0.06mol/L under nitrogen atmosphere, 80 DEG C of reactions, backflow, when no longer including gas and producing, add a certain amount of dilute sulfuric acid and react 2.7 hours, then wash, purify and drying, obtain product bromo nonatriacontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 48%, and dilute sulfuric acid addition is the 2wt% of tetracontane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo nonatriacontane carboxylic acid and 22wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino nonatriacontane carboxylic acid of product;
4) by ethylene glycol and amino nonatriacontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino nonatriacontane carboxylic acid weight the sulfuric acid that concentration is 46wt%, carry out esterification, esterification reaction temperature is 190 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino nonatriacontane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.8 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature is at 258 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony acetate of 0.05% of terephthalic acid (TPA) weight and the trimethyl phosphate of terephthalic acid (TPA) weight 0.03% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 268 DEG C, and the reaction time is 45 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino nonatriacontane carboxylic acid glycol ester, and stir 16 minutes; Described amino nonatriacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 75 minutes reaction time;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.97dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 310 DEG C; The wind-warm syndrome of described cooling is 22 DEG C; Described low temperature atomsphere plasma process: the 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 is 0.47wt%; The speed of described winding is 3500m/min; Heat setting temperature 130 DEG C;
The condition of described greenhouse process is: temperature 76 DEG C, and standing time is 27h;
The fracture strength 7.5cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.4mm, line density deviation ratio 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
A preparation method for the anti-wicking polyester industrial fiber of low-shrinkage, comprises the following steps:
(1) preparation of anti-wicking agent
Perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the synthesis step containing the ternary block polymer of uvioresistant group are:
1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br l, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 74 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add non-fluorinated alkylsilane (methyl) acrylate and complexant pentamethyldiethylenetriamine, at 84 DEG C of isothermal reaction 25h, wherein macromole evocating agents: catalyst: complexant: the mol ratio of monomer is 1:1:2:55; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, isothermal reaction 13h, wherein macromole evocating agent in 114 DEG C: catalyst: complexant: the mol ratio of monomer is 1:1:2:18; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer;
4) active ingredient is smooth agent, emulsifying agent, antistatic additive and crosslinking agent, and perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the mass fraction containing the ternary block polymer of uvioresistant group are respectively:
Smooth agent 28; Emulsifying agent 4; Antistatic additive 8; Crosslinking 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) add in reactor by pentatetracontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatetracontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 2wt% of pentatetracontane dicarboxylic acids;
2) described pentatetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein pentatetracontane mono methyl dicarboxylate concentration is 0.07mol/L, under nitrogen atmosphere, 88 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2.3 hours, then wash, purify and drying, obtain product bromo tetratetracontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 45%, and dilute sulfuric acid addition is the 2wt% of pentatetracontane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo tetratetracontane carboxylic acid and 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is no more than 70 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino tetratetracontane carboxylic acid of product;
4) by ethylene glycol and amino tetratetracontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 1% of amino tetratetracontane carboxylic acid weight the sulfuric acid that concentration is 50wt%, carry out esterification, esterification reaction temperature is 210 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino tetratetracontane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:2.0 and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony glycol of 0.02% of terephthalic acid (TPA) weight and the trimethyl phosphate of terephthalic acid (TPA) weight 0.05% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 270 DEG C, and the reaction time is 50 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino tetratetracontane carboxylic acid glycol ester, and stir 20 minutes; Described amino tetratetracontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.0%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 85 minutes reaction time;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.98dL/g.
By sticky for the height of modified poly ester section through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 315 DEG C; The wind-warm syndrome of described cooling is 23 DEG C; Described low temperature atomsphere plasma process: the 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 is 0.49wt%; The speed of described winding is 3400m/min; Heat setting temperature 140 DEG C;
The condition of described greenhouse process is: temperature 78 DEG C, and standing time is 29h;
The fracture strength 7.8cN/dtex of the anti-wicking polyester industrial fiber of gained low-shrinkage, measure wicking height 0.4mm, line density deviation ratio 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%, the anti-wicking polyester industrial fiber of low-shrinkage is under temperature is 78 DEG C of conditions, and the free volume space between fibrous inside strand increases 14v/v%.
Uvioresistant is tested

Claims (10)

1. the anti-wicking polyester industrial fiber of low-shrinkage, it is characterized in that: described low-shrinkage anti-wicking polyester industrial fiber is obtained by the thickening slice spinning of modified poly ester and anti-wicking process, its adsorption has perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the ternary block polymer containing uvioresistant group; Described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described amino ethylene glycol fatty acid is dispersed between the strand of described polyester, and have hydrogen bond action between the strand of described amino ethylene glycol fatty acid and described polyester, the relative position of the strand of described amino ethylene glycol fatty acid and described polyester is fixed; Described modified poly ester is under temperature is 70 ~ 80 DEG C of conditions, and the free volume space of polyester interior molecules interchain increases 10 ~ 15v/v%;
The molecular structural formula of described amino ethylene glycol fatty acid is:
H 2N(CH2)nCOOCH 2CH 2OOC(CH 2)n NH 2；
Wherein, n=10 ~ 50;
Described perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the structural formula containing the ternary block polymer of uvioresistant group are:
Wherein, 2≤m≤8, k >=8, p >=16, x=10 ~ 20, y=5 ~ 10, z=3 ~ 10, R ' is O-hydroxyl-diphenyl ketone, salicylate and o-hydroxy the uvioresistant group of triazole.
The anti-wicking polyester industrial fiber of described low-shrinkage 177 DEG C, dry-hot shrinkage is 2.5 ± 0.5% under the test condition of 0.05cN/dtex, measure wicking height≤0.6mm.
2. the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 1, it is characterized in that, the physical index of the anti-wicking polyester industrial fiber of described low-shrinkage: 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%.
3. the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 1, it is characterized in that, the percentage by weight that described amino ethylene glycol fatty acid accounts for described modified poly ester is 0.5 ~ 2.5%, and described perfluoroalkyl (methyl) acrylate, non-fluorinated alkylsilane (methyl) acrylate and the adsorbance containing the ternary block polymer of uvioresistant group account for 0.3 ~ 2wt% of the anti-wicking polyester industrial fiber of described low-shrinkage.
4. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to any one of claims 1 to 3, it is characterized in that: by the sticky section of the height of modified poly ester through measure, extruding, cool, low temperature atomsphere plasma process, oil, upper anti-wicking agent, stretching, HEAT SETTING, winding and greenhouse treatment step, obtain the anti-wicking polyester industrial fiber of low-shrinkage;
The described temperature extruded is 290 ~ 320 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 23 DEG C;
Described low temperature atomsphere plasma process: the distance between nozzle and fibre bundle is 5 ~ 8mm; Operating pressure is 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 process refers to placement 20 ~ 30h under the condition of temperature 70 ~ 80 DEG C;
The active ingredient of described anti-wicking agent is smooth agent, emulsifying agent, antistatic additive and crosslinking 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:
The effect composition 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 synthesis step containing the ternary block polymer of uvioresistant group are:
(1) preparation of poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking:
In container under nitrogen protection, add Catalysts Cu Br or CuCl, monomer perfluoroalkyl (methyl) acrylate, solvent toluene, complexant pentamethyldiethylenetriamine, initator 2 bromopropionic acid ethyl ester successively, wherein initator: catalyst: complexant: the mol ratio of monomer is 1:1:2:120, be warming up to 65 ~ 75 DEG C, isothermal reaction 6h; Reaction terminates rear oxolane and dissolves, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, and the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking;
(2) preparation of poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking:
Under nitrogen protection, poly-perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking is placed in reactor, add Catalysts Cu Br or CuCl, solvent toluene, below 40 DEG C, treat that perfluoroalkyl (methyl) the acrylate macromole evocating agent of bromination end-blocking dissolves completely, add 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; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, filtrate precipitates to obtain polymer with absolute ethyl alcohol, the vacuum desiccator that polymer is 40 DEG C through temperature is dried to constant weight, obtains poly-perfluoroalkyl (methyl) acrylate-poly-non-fluorinated alkylsilane (methyl) the acrylate macromole evocating agent of bromination end-blocking;
(3) preparation of triblock copolymer is fluoridized:
Under nitrogen protection, by poly-perfluoroalkyl (methyl) acrylate of bromination end-blocking-poly-non-fluorinated alkylsilane (methyl) acrylate macromole evocating agent joins in reactor, first add Catalysts Cu Br or CuCl, then complexant pentamethyldiethylenetriamine and solvent benzotrifluoride is added successively, after at 40 DEG C, macromole evocating agent dissolves completely, finally add the olefinic monomer containing uvioresistant group, more than isothermal reaction 10h in 105 ~ 115 DEG C, wherein macromole evocating agent: catalyst: complexant: the mol ratio of monomer is 1:1:2:10 ~ 20; Add oxolane after reaction terminates to dissolve, cross post through aluminium oxide and be separated mantoquita, obtain polymer with alcohol settling, polymer is dried to constant weight through the vacuum desiccator of 40 DEG C, obtains fluoridizing triblock copolymer; The height sticky section preparation process of described modified poly ester is as follows:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by binary of fatty acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric 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 that dodecanedicarboxylic acid is to the one in dopentacontane dicarboxylic acids;
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 be dissolved in benzene, wherein the concentration of binary of fatty acids mono-methyl is 0.05 ~ 0.1mol/L, under nitrogen atmosphere, 80 ~ 90 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid reaction 2 ~ 3 hours, then wash, purify and drying, obtain product bromo aliphatic acid;
3) by the ammoniacal liquor of bromo aliphatic acid and 15 ~ 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is no more than 70 DEG C, until bubble-free produces, namely stop distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, product vacuumize is obtained the amino aliphatic acid of product;
4) by ethylene glycol and amino aliphatic acid in molar ratio for 1.1:2 stirs, and add by 1 ~ 3% of amino fatty acid wt the sulfuric acid that concentration is 40 ~ 50wt%, carry out esterification, esterification reaction temperature is 160 ~ 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino ethylene glycol fatty acid through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; 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 quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, in esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction time is 30 ~ 50 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino ethylene glycol fatty acid, and stir;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 ~ 280 DEG C, 50 ~ 90 minutes reaction time;
Obtained modified poly ester;
(3) by modified poly ester solid-phase tack producing, make the sticky section of height of modified poly ester, inherent viscosity is 0.95 ~ 0.98dL/g.
5. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 4, is characterized in that, the mol ratio of described ethylene glycol and described terephthalic acid (TPA) is 1.2 ~ 2.0:1.
6. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 4, it is characterized in that, described catalyst is selected from the one in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight; Described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of described terephthalic acid (TPA) // weight.
7. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 4, is characterized in that, add the stirring after amino ethylene glycol fatty acid, and the time is 15 ~ 20 minutes.
8. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 4, is characterized in that, is washed till without adopting liquor argenti nitratis ophthalmicus to detect till bromide ion with deionized water.
9. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 4, is characterized in that, the described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70 ~ 80%, and concentrated sulfuric acid addition is 1 ~ 3wt% of binary of fatty acids; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40 ~ 50%, and dilute sulfuric acid addition is 1 ~ 3wt% of binary of fatty acids mono-methyl.
10. the preparation method of the anti-wicking polyester industrial fiber of a kind of low-shrinkage according to claim 4, is characterized in that, described smooth agent is the one in octyl polyoxyethylene ether, sorbitan stearate monoesters and DoJyoxyethylene xylitol stearate; Described emulsifying agent is two dodecanoyl hydroxysuccinic acid dipotassiums; Described antistatic additive is the one in alkyl phosphate triethanolamine, Emulsifier EL-60 and potassium alkyl phosphate; Described crosslinking agent is the one in melamine, isocyanide ester carbamate and glyoxal.
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