CN105463619A - Low-chromatic-aberration polyester POY and preparation method thereof - Google Patents
Low-chromatic-aberration polyester POY and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D7/00—Collecting the newly-spun products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to a low-chromatic-aberration polyester POY and a preparation method thereof. The low-chromatic-aberration polyester POY is obtained through polyester spinning; the breaking strength of the high-dye-uptake polyester fiber POY is larger than or equal to 2.6 cN/dtex, the elongation at break is 100.0+/-10.0%, and the chromatic aberration delta E is smaller than 0.200. According to the low-chromatic-aberration polyester POY and the preparation method thereof, ethylene glycol magnesium is milder, the thermal degradation coefficient is very small, side reactions caused in the reaction process are few, and generation of oligomers in the processing process is reduced; the mass percentage content of the oligomers is smaller than 0.5%, and the mass percentage content of diethylene glycol is smaller than 0.5%; the oligomers are decreased in the polymerizing process and are further decreased in the soluble washing process, and therefore in the polyester fiber dyeing and post processing heat setting processes, the quantity of the oligomers which migrate from the interior of the fiber to the exterior of the fiber is reduced, occurrence of color spots and strip patterns is reduced, and the fiber levelling property and crockfastness are guaranteed.
Description
Technical field
The invention belongs to polyester preparing technical field, relate to a kind of low aberration polyester POY silk and preparation method thereof, particularly a kind of polycondensation catalyst adopts the mixture of ethylene glycol magnesium and antimony glycol and polyester slice through water and dissolves and washes away agent at 120 ~ 130 DEG C, low aberration polyester POY silk of brew, washing under 0.2 ~ 0.3MPa condition and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, PET is high with its modulus, intensity is high, well-pressed, conformality good, pure health, barrier property are good, be widely used in the fields such as fiber, bottle packaging, film and sheet material, output cumulative year after year, position in industry significantly promotes.
PET belongs to symmetric straight chain macromolecular, and strand is not containing side-chain radical, and regularity is very good, and the glass transition temperature of this structure is higher, needs to dye at very high temperatures, promotes that dye molecule is to the diffusion of fibrous inside.In addition, the strand of PET is regular, good crystallinity, and strand arrangement is tight, and the polar group that strand is not had an effect with dye molecule, make the colouring of polyester fiber more difficult.Owing to not having hydrophilic radical in its molecule, hygroscopicity is very poor, and this causes the dyeing of terylene more difficult.The main high-temperature and high pressure dyeing process method of terylene disperse dyeing
Oligomer in polyester fiber is a kind of low-molecular-weight ester or ether, mainly refers to oligomer, diethylene glycol (DEG) that the degree of polymerization is less than 10, is produce as a by-product.Wherein oligomer is divided into linear oligomerization thing and cyclic oligomer, and wherein with ring-type aggressiveness, particularly cyclic trimer is in the majority, and oligomer is mainly concerned with heterogeneous nucleation, spinning process, dyeing etc., causes certain harmful effect to the performance of polyester and the processing of rear road.Ethylene glycol terephthalate polymer (PET) approximately contains oligomer 3-4%, when fiber surface occurs that oligomer will make troubles to dyeing and aft-loaded airfoil.The temperature control diffused out when the most easily occurring in dyeing of oligomer heats up and holding stage.When lowering the temperature, equally with dyestuff sharply to reduce because the solubility with temperature of oligomer in water reduces, therefore can crystallization, the dyestuff of separating out and oligomer are attached to fiber surface pole and are not easy to wash away, thus bring a lot of trouble to dyeing and aft-loaded airfoil, in dyeing course, dyestuff and the oligomer of gathering stick to fiber surface, occur the phenomenons such as dyestuff color dot, spot, look flower.In the pipeline being deposited on dyeing machine and valve, hinder stream recirculates, cause dyeing difficulty.Eliminating oligomer key to be to eliminate oligomer cyclic trimer and diethylene glycol (DEG), is the generation reducing oligomer in the course of the polymerization process on the one hand, is remove before dyeing or in dyeing on the other hand.
Summary of the invention
The object of this invention is to provide a kind of low aberration polyester POY silk and preparation method thereof, is polyester and low aberration polyester POY silk and preparation method thereof that a kind of polycondensation catalyst adopts the mixture of ethylene glycol magnesium and antimony glycol.The present invention adopts the mixture of ethylene glycol magnesium and antimony glycol to be polycondensation catalyst, and thermal degradation is reduced to minimum, and polyester slice through water with dissolve and wash away agent at 130 DEG C, brew, washing under 0.3MPa condition; Reduce oligomer, diethylene glycol content on polyester POY silk dye impact.
One of the present invention low aberration polyester POY silk, for the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol that is terephthalic acid (TPA) and ethylene glycol of described polyester, granulation and after dissolveing and washing away spinning obtain;
In the section of described industry polyester, oligomer mass percentage content is less than 0.5%, and the mass percentage content of diethylene glycol (DEG) is less than 0.5%;
The molecular formula of described ethylene glycol magnesium is Mg (OCH
2cH
2oH)
2;
Described dissolve and wash away the section after referring to granulation through water with dissolve and wash away agent 120 ~ 130 DEG C with 0.2 ~ 0.3MPa condition under brew and washing.
Described low aberration polyester POY silk dissolves and washes away rear spinning by polyester and obtains, the fracture strength >=2.6cN/dtex of described low aberration polyester POY silk, and elongation at break is 100.0 ± 10.0%, and aberration Δ E is less than 0.200,
In dyeing polyester fibers and aft-loaded airfoil, the factor affecting surface oligomers precipitation is a lot, mainly contains the factors such as temperature and time.Improve dyeing temperature by the migration of aggravation oligomer, particularly when having some auxiliary agent or dyestuff to exist, migration velocity improves faster.The time of dye liquor circulation continuous is longer, and oligomer increases from fiber to the amount of external migration, the existence of frequent cold cycling and some auxiliary agents, dyestuff can greatly aggravate oligomer shift out and deposition.The temperature and time of heat setting simultaneously has a significant impact oligomer migration speed and migration amount.Be an extremely important operation concerning heat setting synthetic fiber dyeing and finishing processing, its main purpose eliminates existing fine wrinkle on fabric and improves the DIMENSIONAL STABILITY of fabric and improve the performances such as the brute force of fabric, feel, pilling and surfacing.But, often such phenomenon is there is in yarn-dyed fabric shaping process, easily there is color spot and barriness in the fabric face namely after heat setting, level-dyeing property and crock fastness also significantly decline, especially for Polyester Fabric of Ultra-fine Fibre under Alkali Condition, impact is particularly serious, and oligomer migration from inside to outside under heat effect is one of the main reasons.Existing technology all concentrates on dyeing link and solves the impact of oligomer on dyeing, and this is that one controls calibration method, only solves from source and is only effect a permanent cure basic.
Adopt ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to a comparatively gentle class, and its thermal degradation coefficient is very little, and the side reaction caused in course of reaction is less, decreases the generation of oligomer in process.Cause the principal element of thermal degradation to be high temperature and catalyst, high temperature is that response intensity is too high, causes degraded to be accelerated, creates end carboxyl, also make cyclic oligomer increase simultaneously; Catalyst is then relevant to the degradation reaction constant of catalyst, in polycondensation process, the effect of catalyst is not only catalysis to generate main reaction, thus the velocity ratio and output of impact reaction, can also degrade and ehter bond generation by catalytic thermal simultaneously, increase the content of cyclic oligomer and diethylene glycol (DEG).
Line density deviation ratio≤0.2% of a kind of low aberration polyester POY silk as above, fracture strength CV value≤3.0%, extension at break CV value≤6.0%.
One as above low aberration polyester POY silk, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1.
Present invention also offers a kind of preparation method of low aberration polyester POY silk, a kind of preparation method of low aberration polyester POY silk, for the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol of terephthalic acid (TPA) and ethylene glycol obtains polyester, obtain polyester slice through pelletizing again, after then being dissolved and washed away by polyester slice, namely obtain polyester; Again through measuring, extrude, cool, oil and reeling, obtained low aberration polyester fiber POY silk; Main technique is:
(1) preparation of catalyst glycol magnesium:
In single-cell for electrolyzation, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 6 ~ 10VV, cathode-current density is 150 ~ 200mA, electrolysis 10 ~ 12 hours when 50 ~ 60 DEG C, and electrolysis terminates rear taking-up electrode, obtains white turbid liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, add anti-ether agent, 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; Described catalyst is the mixture of ethylene glycol magnesium and antimony glycol;
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 polyester, obtains polyester slice through pelletizing;
(3) dissolve and wash away
Described polyester slice is through water and dissolve and wash away agent brew 3-5 hour under 120 ~ 130 DEG C with 0.2 ~ 0.3MPa condition, by washing; Obtain polyester.
(4) spinning main technologic parameters:
The described temperature extruded is 280 ~ 290 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 25 DEG C;
The speed of described winding is 2500 ~ 3000m/min;
Filament number is 0.3 ~ 2.0dtex;
The preparation method of a kind of low aberration polyester POY silk as above, the mol ratio of described ethylene glycol and described terephthalic acid (TPA) is 1.2 ~ 2.0:1.
The preparation method of a kind of low aberration polyester POY silk as above, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1; Described catalyst amount is 0.01% ~ 0.05% of described terephthalic acid (TPA) quality.
The preparation method of a kind of low aberration polyester POY silk as above, 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.Stabilizing agent is mainly based on phosphate, and Main Function is the free radical of catching reaction generation in the course of the polymerization process, reduces side reaction.
The preparation method of a kind of low aberration polyester POY silk as above, described water is 100:3 ~ 4 with the mass ratio dissolveing and washing away agent, polyester slice and water and the ratio dissolveing and washing away agent, and namely solid-to-liquid ratio is 1:5-10; It is described that to dissolve and wash away agent be one in ethylene glycol monoethyl ether, propyl cellosolve and ethylene glycol monobutyl ether (EGMBE), add in water and a small amount of dissolve and wash away agent, dissolve and wash away agent water-soluble, simultaneously also the most ofs low molecular ether of solubilized and ester, be conducive to the minimizing improving effect and the oligomer washed.
The preparation method of a kind of low aberration polyester POY silk as above, described washing refers to polyester slice 70 ~ 80 DEG C of hot water wash 10 ~ 15min after brew, and then clean with cold water, Drying and cooling is for subsequent use.
The preparation method of a kind of low aberration polyester POY silk as above, described anti-ether agent is the one in sodium acetate and calcium acetate, and anti-ether agent consumption is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight.Anti-ether agent reduces the generation of ether in acid condition by adding a small amount of NaAc, thus reduces the activity that glycol reaction generates diethylene glycol (DEG).
The object of this invention is to provide a kind of low aberration polyester POY silk, adopt a relatively mild class polycondensation catalyst ethylene glycol magnesium, less thermal degradation in the less and process of the less side reaction caused in course of reaction, decreases the generation of oligomer in process.Polyester slice is through water and dissolve and wash away agent at 130 DEG C, and under 0.3MPa condition, brew is conducive to improving the effect of washing and the minimizing of oligomer.The minimizing of oligomer, make in dyeing polyester fibers and aft-loaded airfoil heat setting, oligomer reduces from fiber to the amount of external migration, decreases color spot and barriness appearance, ensure that fiber level-dyeing property and crock fastness.
Beneficial effect:
● adopt ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to a comparatively gentle class, and its thermal degradation coefficient is very little, and the side reaction caused in course of reaction is less, decreases the generation of end carboxyl and oligomer in process.
● the oligomer mass percentage content of polyester slice is less than 0.5%, and the mass percentage content of diethylene glycol (DEG) is less than 0.5%, is conducive to the quality improving fiber further.
● polyester slice through water with dissolve and wash away agent brew under 120 ~ 130 DEG C with 0.2 ~ 0.3MPa condition and be conducive to improving the minimizing of effect and the oligomer washed.
● anti-ether agent reduces the generation of ether in acid condition by adding a small amount of NaAc, thus reduces the activity that glycol reaction generates diethylene glycol (DEG).
● the minimizing of oligomer in polymerization process, dissolve and wash away oligomer in process to reduce further, make in dyeing polyester fibers and aft-loaded airfoil heat setting, oligomer reduces from fiber to the amount of external migration, decrease color spot and barriness appearance, ensure that fiber level-dyeing property and crock fastness.
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.
One of the present invention low aberration polyester POY silk, low aberration polyester POY silk is by polyester spinning and obtaining after dissolveing and washing away, fracture strength>=the 2.6cN/dtex of low aberration polyester POY silk, elongation at break is 100.0 ± 10.0%, aberration Δ E is less than 0.200, the polyester polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol that is terephthalic acid (TPA) and ethylene glycol, then obtain polyester slice through pelletizing; In the section of industry polyester, oligomer mass percentage content is less than 0.5%, and the mass percentage content of diethylene glycol (DEG) is less than 0.5%; The molecular formula of ethylene glycol magnesium is Mg (OCH
2cH
2oH)
2; Dissolve and wash away the section after referring to granulation through water with dissolve and wash away agent 120 ~ 130 DEG C with 0.2 ~ 0.3MPa condition under brew and washing.
Wherein, line density deviation ratio≤0.2% of low aberration polyester POY silk, fracture strength CV value≤3.0%, extension at break CV value≤6.0%.
Wherein, in the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1.
1, dyestuff:
Disperse brilliant blue 2BLN, 5% (o.w.f)
2, dyeing:
Fiber enters to contaminate insulation 10 ~ 15min at 70 ~ 80 DEG C, heating rate 1.0 ~ 2.0 DEG C/min, 120 ~ 130 DEG C of insulation 40 ~ 60min, cooling, 70 ~ 80 DEG C of reduction cleaning 20 ~ 30min.
3, the mensuration of dye uptake
Dye by above-mentioned technique, and liquid before drawing dye respectively, each 2ml of Liquid Residue, in 10ml volumetric flask, adds acetone 4ml, and dyestuff is fully dissolved.With distilled water diluting to scale, then measure λ with spectrophotometric
max, time dyeing before and after the absorbance A 0 of dyestuff, A1 then:
Dye uptake (%)=(l mono-A1/A0) × 100%
In formula: the absorbance of liquid before A0---dye
The absorbance of A1---Liquid Residue
4, the mensuration of dyefastness
Test by GB3920-83, GB251-64, GB3921-83
5, the mensuration of tinctorial yield and aberration
Adopt the test of color measurement and color match instrument.
6, the mensuration of the apparent colour degree of depth (K/S)
Storehouse Bel's card-Munch (kubelka-munk) function is utilized to calculate: in K/S=(1-R) 2//2R. formula, K is the absorption coefficient of testee; S is the scattering coefficient of testee; Reflectivity when R is testee infinite thickness.The test of application SF600XDatacolor color measurement and color match instrument, every sample tests 5 times in zones of different, gets its mathematical mean.
Embodiment 1
A preparation method for low aberration polyester POY silk, main technique comprises:
(1) preparation of catalyst glycol magnesium:
In single-cell for electrolyzation, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 6V, cathode-current density is 150mA, electrolysis 10 hours when 50 DEG C, and electrolysis terminates rear taking-up electrode, obtains white turbid liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation reaction:
Esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 1.2:1, and add anti-ether agent sodium acetate, sodium acetate consumption is 0.01% of terephthalic acid (TPA) weight, carries out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at normal pressure, and temperature is at 250 DEG C, and esterification water quantity of distillate reaches 91% of theoretical value for esterification terminal;
Polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The polycondensation reaction low vacuum stage, catalyst and stabilizing agent triphenyl phosphate is added in esterification products, catalyst amount is 0.01% of terephthalic acid (TPA) quality, triphenyl phosphate consumption is 0.01% of terephthalic acid (TPA) weight, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature controls at 260 DEG C, and the reaction time is 30 minutes; Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 2:1;
Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 96Pa, and reaction temperature controls at 275 DEG C, 50 minutes reaction time; Obtained polyester, obtains polyester slice through pelletizing;
(3) dissolve and wash away
Polyester slice through water with dissolve and wash away agent ethylene glycol monoethyl ether brew 3 hours under 120 DEG C with 0.2MPa condition, by washing, i.e. polyester slice 70 DEG C of hot water wash 10min after brew, then clean with cold water, Drying and cooling is for subsequent use; Obtain polyester, water is 100:3 with the mass ratio dissolveing and washing away agent, and polyester slice and water and the ratio dissolveing and washing away agent, namely solid-to-liquid ratio is 1:5.
(4) spinning main technologic parameters:
The temperature extruded is 280 DEG C;
The wind-warm syndrome of cooling is 20 DEG C;
The speed of winding is 2500m/min;
Filament number is 0.3dtex; The fracture strength of obtained low aberration polyester POY silk is 2.6cN/dtex, and elongation at break is 110.0%; The line density deviation ratio of low aberration polyester POY silk is 0.2%, fracture strength CV value is 3.0%, and extension at break CV value is 6.0%.
(5) dye
Embodiment 2
A preparation method for low aberration polyester POY silk, main technique comprises:
(1) preparation of catalyst glycol magnesium:
In single-cell for electrolyzation, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 10V, cathode-current density is 200mA, electrolysis 12 hours when 60 DEG C, and electrolysis terminates rear taking-up electrode, obtains white turbid liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation reaction:
Esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 2.0:1, and add anti-ether agent calcium acetate, calcium acetate consumption is 0.05% of terephthalic acid (TPA) weight, carries out esterification, obtain esterification products after being made into uniform sizing material; 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 92% of theoretical value for esterification terminal;
Polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The polycondensation reaction low vacuum stage, catalyst and stabilizing agent trimethyl phosphate is added in esterification products, catalyst amount is 0.05% of terephthalic acid (TPA) quality, trimethyl phosphate consumption is 0.05% of terephthalic acid (TPA) weight, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 270 DEG C, and the reaction time is 50 minutes; Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 3:1;
Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 95Pa, and reaction temperature controls at 280 DEG C, 90 minutes reaction time; Obtained polyester, obtains polyester slice through pelletizing;
(3) dissolve and wash away
Polyester slice through water with dissolve and wash away agent propyl cellosolve brew 5 hours under 130 DEG C with 0.3MPa condition, by washing, i.e. polyester slice 80 DEG C of hot water wash 15min after brew, then clean with cold water, Drying and cooling is for subsequent use; Obtain polyester, water is 100:4 with the mass ratio dissolveing and washing away agent, and polyester slice and water and the ratio dissolveing and washing away agent, namely solid-to-liquid ratio is 1:10.
(4) spinning main technologic parameters:
The temperature extruded is 290 DEG C;
The wind-warm syndrome of cooling is 25 DEG C;
The speed of winding is 3000m/min;
Filament number is 2.0dtex; The fracture strength of obtained low aberration polyester POY silk is 2.7cN/dtex, and elongation at break is 90%; The line density deviation ratio of low aberration polyester POY silk is 0.15%, fracture strength CV value is 2.5%, and extension at break CV value is 5.5%.
(5) dye
Embodiment 3
A preparation method for low aberration polyester POY silk, main technique comprises:
(1) preparation of catalyst glycol magnesium:
In single-cell for electrolyzation, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 7V, cathode-current density is 160mA, electrolysis 11 hours when 55 DEG C, and electrolysis terminates rear taking-up electrode, obtains white turbid liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation reaction:
Esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 1.5:1, and add anti-ether agent sodium acetate, sodium acetate consumption is 0.02% of terephthalic acid (TPA) weight, carries out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches 92% of theoretical value for esterification terminal;
Polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The polycondensation reaction low vacuum stage, catalyst and stabilizing agent Trimethyl phosphite is added in esterification products, catalyst amount is 0.02% of terephthalic acid (TPA) quality, Trimethyl phosphite consumption is 0.02% of terephthalic acid (TPA) weight, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 265 DEG C, and the reaction time is 35 minutes; Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 3:1;
Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 98Pa, and reaction temperature controls at 277 DEG C, 60 minutes reaction time; Obtained polyester, obtains polyester slice through pelletizing;
(3) dissolve and wash away
Polyester slice through water with dissolve and wash away agent ethylene glycol monobutyl ether (EGMBE) brew 3 hours under 125 DEG C with 0.2MPa condition, by washing, i.e. polyester slice 70 DEG C of hot water wash 15min after brew, then clean with cold water, Drying and cooling is for subsequent use; Obtain polyester, water is 100:4 with the mass ratio dissolveing and washing away agent, and polyester slice and water and the ratio dissolveing and washing away agent, namely solid-to-liquid ratio is 1:10.
(4) spinning main technologic parameters:
The temperature extruded is 285 DEG C;
The wind-warm syndrome of described cooling is 24 DEG C;
The speed of described winding is 2700m/min;
Filament number is 1.3dtex; The fracture strength 2.6cN/dtex of obtained low aberration polyester POY silk, elongation at break is 100.0%; Line density deviation ratio 0.2%, the fracture strength CV value 3.0% of low aberration polyester POY silk, extension at break CV value 6.0%.
(5) dye
Embodiment 4
A preparation method for low aberration polyester POY silk, main technique comprises:
(1) preparation of catalyst glycol magnesium:
In single-cell for electrolyzation, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 7V, cathode-current density is 170mA, electrolysis 11 hours when 58 DEG C, and electrolysis terminates rear taking-up electrode, obtains white turbid liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation reaction:
Esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and described terephthalic acid (TPA) is 1.8:1, and add anti-ether agent sodium acetate, sodium acetate consumption is 0.02% of terephthalic acid (TPA) weight, 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 250 DEG C, and esterification water quantity of distillate reaches 98% of theoretical value for esterification terminal;
Polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The polycondensation reaction low vacuum stage, catalyst and stabilizing agent triphenyl phosphate is added in esterification products, catalyst amount is 0.02% of described terephthalic acid (TPA) quality, triphenyl phosphate consumption is 0.02% of terephthalic acid (TPA) weight, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 264 DEG C, and the reaction time is 38 minutes; Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 3:1;
Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 99Pa, and reaction temperature controls at 280 DEG C, 90 minutes reaction time; Obtained polyester, obtains polyester slice through pelletizing;
(3) dissolve and wash away
Polyester slice through water with dissolve and wash away agent ethylene glycol monoethyl ether brew 3 hours under 120 DEG C with 0.3MPa condition, by washing, i.e. polyester slice 70 DEG C of hot water wash 15min after brew, then clean with cold water, Drying and cooling is for subsequent use; Obtain polyester, water is 100:4 with the mass ratio dissolveing and washing away agent, and polyester slice and water and the ratio dissolveing and washing away agent, namely solid-to-liquid ratio is 1:8.
(4) spinning main technologic parameters:
The temperature extruded is 285 DEG C;
The wind-warm syndrome of cooling is 25 DEG C;
The speed of winding is 3000m/min;
Filament number is 2.0dtex; The fracture strength of obtained low aberration polyester POY silk is 2.8cN/dtex, and elongation at break is 105%; The line density deviation ratio of low aberration polyester POY silk is 0.18%, fracture strength CV value is 2.8%, and extension at break CV value is 5.6%.
(5) dye
Claims (10)
1. one kind low aberration polyester POY silk, it is characterized in that: described low aberration polyester POY silk is by polyester spinning and obtaining after dissolveing and washing away, fracture strength >=the 2.6cN/dtex of described low aberration polyester POY silk, elongation at break is 100.0 ± 10.0%, aberration Δ E is less than 0.200, the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol that is terephthalic acid (TPA) and ethylene glycol of described polyester, then obtain polyester slice through pelletizing;
In the section of described industry polyester, oligomer mass percentage content is less than 0.5%, and the mass percentage content of diethylene glycol (DEG) is less than 0.5%;
The molecular formula of described ethylene glycol magnesium is Mg (OCH
2cH
2oH)
2;
Described dissolve and wash away the section after referring to granulation through water with dissolve and wash away agent 120 ~ 130 DEG C with 0.2 ~ 0.3MPa condition under brew and washing.
2. one according to claim 1 low aberration polyester POY silk, is characterized in that, line density deviation ratio≤0.2% of described low aberration polyester POY silk, fracture strength CV value≤3.0%, extension at break CV value≤6.0%.
3. one according to claim 1 low aberration polyester POY silk, is characterized in that, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1.
4. the preparation method of a kind of low aberration polyester POY silk according to any one of claims 1 to 3, it is characterized in that: the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol of terephthalic acid (TPA) and ethylene glycol obtains polyester, obtain polyester slice through pelletizing again, after then being dissolved and washed away by polyester slice, namely obtain polyester; Again through measuring, extrude, cool, oil and reeling, obtained low aberration polyester fiber POY silk.
5. the preparation method of a kind of low aberration polyester POY silk according to claim 4, it is characterized in that, main technique comprises:
(1) preparation of catalyst glycol magnesium:
In single-cell for electrolyzation, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 6 ~ 10V, cathode-current density is 150 ~ 200mA, electrolysis 10 ~ 12 hours when 50 ~ 60 DEG C, and electrolysis terminates rear taking-up electrode, obtains white turbid liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt terephthalic acid (TPA) and ethylene glycol as raw material, add anti-ether agent, 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; Described catalyst is the mixture of ethylene glycol magnesium and antimony glycol;
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 polyester, obtains polyester slice through pelletizing;
(3) dissolve and wash away
Described polyester slice is through water and dissolve and wash away agent brew 3-5 hour under 120 ~ 130 DEG C with 0.2 ~ 0.3MPa condition, by washing; Obtain polyester.
(4) spinning main technologic parameters:
The described temperature extruded is 280 ~ 290 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 25 DEG C;
The speed of described winding is 2500 ~ 3000m/min;
Filament number is 0.3 ~ 2.0dtex.
6. the preparation method of a kind of low aberration polyester POY silk according to claim 4 or 5, it is characterized in that, the mol ratio of described ethylene glycol and described terephthalic acid (TPA) is 1.2 ~ 2.0:1.
7. the preparation method of a kind of low aberration polyester POY silk according to claim 5, it is characterized in that, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1; Described catalyst amount is 0.01% ~ 0.05% of described terephthalic acid (TPA) quality; 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.
8. the preparation method of a kind of low aberration polyester POY silk according to claim 5, is characterized in that, described water is 100:3 ~ 4 with the mass ratio dissolveing and washing away agent, polyester slice and water and the ratio dissolveing and washing away agent, and namely solid-to-liquid ratio is 1:5 ~ 10; It is described that to dissolve and wash away agent be one in ethylene glycol monoethyl ether, propyl cellosolve and ethylene glycol monobutyl ether (EGMBE).
9. the preparation method of a kind of low aberration polyester POY silk according to claim 5, is characterized in that, described washing refers to polyester slice 70 ~ 80 DEG C of hot water wash 10 ~ 15min after brew, and then clean with cold water, Drying and cooling is for subsequent use.
10. the preparation method of a kind of low aberration polyester POY silk according to claim 5, is characterized in that, described anti-ether agent is the one in sodium acetate and calcium acetate, and anti-ether agent consumption is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight.
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| CN107557902A (en) * | 2017-09-07 | 2018-01-09 | 江苏恒科新材料有限公司 | A kind of preparation method of cation dyeable polyester POY silks |
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