CN105504242B - A kind of low shrinkage polyester industrial filament and preparation method thereof - Google Patents
A kind of low shrinkage polyester industrial filament and preparation method thereof Download PDFInfo
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- CN105504242B CN105504242B CN201511017955.9A CN201511017955A CN105504242B CN 105504242 B CN105504242 B CN 105504242B CN 201511017955 A CN201511017955 A CN 201511017955A CN 105504242 B CN105504242 B CN 105504242B
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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
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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
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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Abstract
The present invention relates to a kind of low shrinkage polyester industrial filaments and preparation method thereof, the low shrinkage polyester industrial filament dissolves and washes away by polyester, after solid-phase tack producing spinning and obtain, dry-hot shrinkage of the low shrinkage polyester industrial filament in the case where temperature is the test condition of 190 DEG C × 15min × 0.01cN/dtex is 3.0 ± 0.5%；Fracture strength >=7.0cN/dtex；Using ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, its thermal degradation coefficient very little, oligomer is reduced in polymerization process, the reduction of thermal degradation in process, the impurity in polyester is greatly reduced, while also reduces the amount of nucleating agent in polyester, the probability of homogeneous nucleation is increased on the basis of heterogeneous nucleation is reduced, the content that further reduced oligomer is dissolved and washed away, is conducive to growing up and crystallizing integrity optimization for crystallite dimension in low shrinkage polyester industrial filament fiber.Low shrinkage polyester industrial filament has relatively low dry-hot shrinkage and preferable dimensional stability and is widely used in filter cloth, coated fabric, hose and conveyer belt weft etc..
Description
Technical field
The invention belongs to polyester industrial fiber preparing technical fields, are related to a kind of low shrinkage polyester industrial filament and preparation method thereof,
Particularly a kind of polycondensation catalyst is existed using the mixture and polyester slice of ethylene glycol magnesium and antimony glycol through water with dissolveing and washing away agent
120~130 DEG C, brew, the polyester of washing and low shrinkage polyester industrial filament and preparation method thereof under the conditions of 0.2~0.3MPa.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, PET with its modulus is high, intensity is high,
It is well-pressed, conformality is good, pure health, barrier property are good etc., be widely used in fiber, the fields such as bottle is packed, film and sheet material,
Yield cumulative year after year, position in industry are obviously improved.
Pet Industrial Fiber is primarily referred to as mostly being applied to industry, national defence, medical treatment, environmental protection and most advanced branches of science each side
Face is that have relatively special physicalchemical structure, performance and purposes or the chemical fibre with specific function, major embodiment
Be able to bear strong corrosion, low abrasion, high temperature resistant, radiation hardness, fire-retardant, fire-resistant, high voltage withstanding, high strength and modulus and plurality of medical work(
Energy.The PVC shelter cloths produced using high-strength low-shrinkage polyester industrial filament yarn as raw material have higher peel strength and tear by force
Degree makes shelter cloth be suitable for various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account
Paulin etc..It is that main textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack using high-strength low-shrinkage industrial yarn
To application.One kind as earth working material has many advantages, such as light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make
It is used time safe ready, efficient, and lifting object will not be damaged.The application field of Pet Industrial Fiber, which is expanded, drives application
The whole competitiveness in field is promoted, and no matter in the weight for mitigating composite material, cost is raised in the durability used and reduction repair
Etc. all various aspects, polyesters high-performance fiber has increasingly given play to its synthetic competitive advantages.Following many decades, high-performance polyester
The development of fiber not only has a considerable progress in quantity, more carrying in the expansion of application field and industrial chain whole competitiveness
It goes up and obtains substantive effect.
The Main way that high intensity, high-modulus, lower shrinkage, dimensional stability, functionalization develop Pet Industrial Fiber,
And influence fiber quality be polyester macromolecule collection state structure, the active force being mainly concerned between polyester molecule, the shape of crystallization
State and structure, orientation structure etc., and the form and structure that crystallize are emphasis therein.Polyester industrial yarn is widely used in not
Same field for lower shrinkage type polyester industrial yarn, has relatively low dry-hot shrinkage and preferable dimensional stability etc.
Feature and be widely used in filter cloth, coated fabric, hose and conveyer belt weft etc..
End carboxyl, oligomer, diethylene glycol (DEG) (DEG) content are the important quality index of polyester slice, wherein oligomer, two sweet
Alcohol is all oligomer, they not only reflect the quality of production status, also affects the product quality of spinning processing.Therefore,
Reducing the end carboxyl in polyester slice, oligomer, diethylene glycol content just becomes the critically important link of raising polyester product quality.End
Influence of the carboxyl to polymer performance is not allowed not regard, and only control polyester content of carboxyl end group is stablized in production, could stablize
Control the homogeneity of its relative molecular mass distribution.Content of the diethylene glycol (DEG) in polyester slice be in production of polyester one it is critically important
Quality index.Because it directly influences the fusing point of polyester slice, the fusing point of polyester slice can be with the increasing of the wherein content of DEG
Urgent acute decline, so it not only reflects the quality of production status, directly influences the matter of post-processing-spinning technique and silk
Amount.Oligomer in polyester refers to the oligomer that the degree of polymerization is less than 10, is divided into linear oligomerization object and cyclic oligomer, wherein with ring
Shape aggressiveness particularly cyclic trimer is in the majority, and oligomer is mainly concerned with heterogeneous nucleation, spinning processing etc., performance to polyester and
Road processing afterwards causes certain harmful effect.It is particularly significant in polyester production process to control content of the three in polyester slice
Subject.
Invention content
The object of the present invention is to provide a kind of low shrinkage polyester industrial filaments and preparation method thereof, are that a kind of polycondensation catalyst is adopted
Polyester and low shrinkage polyester industrial filament of the mixture of spent glycol magnesium and antimony glycol and preparation method thereof.The present invention uses
The mixture of ethylene glycol magnesium and antimony glycol be polycondensation catalyst, by thermal degradation be reduced to minimum and polyester slice through water with
Agent is dissolved and washed away at 130 DEG C, brew, washing under the conditions of 0.3MPa；End carboxyl, oligomer, diethylene glycol content is reduced to add Direct-spinning of PET Fiber
The influence of work.
A kind of low shrinkage polyester industrial filament of the present invention, the low shrinkage polyester industrial filament are increased by polyester through dissolveing and washing away with solid phase
It glues rear spinning and obtains, the low shrinkage polyester industrial filament is in the test condition that temperature is 190 DEG C × 15min × 0.01cN/dtex
Under dry-hot shrinkage be 3.0 ± 0.5%；Fracture strength >=7.0cN/dtex；The polyester is terephthalic acid (TPA) and ethylene glycol
Through esterification and the mixture through catalytic of ethylene glycol magnesium and antimony glycol effect under polycondensation and after granulation be made；
In the slice of the polyester, content of carboxyl end group is less than 15mol/t, and oligomer mass percentage content is less than 0.5%,
The mass percentage content of diethylene glycol (DEG) is less than 0.5%；
The molecular formula of the ethylene glycol magnesium is Mg (OCH2CH2OH)2；
Described dissolve and wash away refers to that the slice after being granulated is boiled with dissolveing and washing away agent under the conditions of 120~130 DEG C with 0.2~0.3MPa through water
Bubble and washing.
The Main way that high intensity, high-modulus, lower shrinkage, dimensional stability, functionalization develop Pet Industrial Fiber,
And influence fiber quality be polyester macromolecule collection state structure, the active force being mainly concerned between polyester molecule, the shape of crystallization
State and structure, orientation structure etc., and the form and structure that crystallize are emphasis therein.
Lower shrinkage, dimensional stability are to influence the principal element of high-quality polyester, and the macroscopic view of polyester fiber is heat-shrinked phenomenon
It is the Entropy Changes trend because of local elongation macromolecular chain, the internal stress and spinning process generated to rolled state development is freezed
Axial internal stress in the sample, this local internal stress can be relayed to entire material by molecule web frame, when the external world provides foot
During enough thermal energy, the phenomenon that generation.
Polyester fiber belongs to orientation hypocrystalline high molecular material, is made of the different structural unit of orientation stability：(1)
The crystalline portion of high stable and high integrity degree；(2) the not perfect crystalline portion of relatively low stability；(3) knot of low stability
Transition zone between brilliant and amorphous；(4) unstable orientation amorphous phase.When polyester fiber is heated, it may occur however that following situation：
Retraction and crystallization occur for the amorphous phase of orientation；The destruction of not perfect crystalline portion be recrystallized with possible：The thickening of crystal grain or
Crystal grain melts completely.Illustrate that crystallite dimension and crystallization degree of perfection are an important factor for ensureing fiber high temperature dimensional stability.177
DEG C percent thermal shrinkage it is low be the splendid fiber of thermal dimensional stability, there are two design features for tool：Crystallite dimension is greatly and crystallization is perfect
Property is good.Therefore the crystallite dimension of fiber is greatly and crystallization integrity is good, is the guarantee of low shrinkage fibre quality.
The factor for influencing crystallizing polyester mainly has：(1) structure of strand in itself.(2) selection of crystallization temperature.(3) divide
The influence of son amount.(4) application of nucleating agent.(5) be exactly finally process conditions influence.Wherein nucleation is that crystallization process is main
A critically important ring nucleating agent is the progress that can accelerate crystallization to a certain extent in link, while to low-shrinkage polyester industrial
Silk more importantly influences the size of crystallization and crystallization integrity.
Determining terminal carboxy group in PET is high, and the thermal stability of polyester resin is poor, while polyester gathers with what carboxylic acid reactant salt generated
The carboxylate of ester large molecule chain, consists of nucleus, and polyester is made to accelerate heterogeneous nucleation.The oligomer containing 3-4%, more in polyester
Exist in the form of low molecular ether and ester, mainly based on cyclic trimer oligomer, diethylene glycol (DEG), oligomer is to the product of polyester
Matter is affected, and the crystallization nucleation mechanism of polyester, crystallinity, crystal habit and crystallization are mainly influenced in a manner of nucleating agent
The percent thermal shrinkage of integrality etc. and then the quality, particularly polyester industrial fiber of influence polyester fiber.Pure polyester without diethylene glycol (DEG),
No matter how crystallization condition changes, and is all not in the form of abnormal spherocrystal；And when containing diethylene glycol (DEG) in sample, meeting in crystalline region
There is the form normally coexisted with abnormal spherocrystal, and with the increase of diethylene glycol content, abnormal spherocrystal is in entire form
Ratio rises, thus influences the integrality of crystallization, makes the crystallization integrity of its polyester reduce.Cyclic trimer polyester mostly with
The mode of nucleation occurs, and nucleating agent is more, and crystallization rate is fast, and crystal grain quantity is big, but crystallite dimension is smaller, and then influences crystallization
Integrity.The increase of heterogeneous nucleation so that high stable and the crystalline portion of high integrity degree are reduced, relatively low stability it is endless
Transition zone between the crystallization of kind crystalline portion and low stability and amorphous increases, and bad shadow is generated to the thermal contraction of polyester fiber
It rings.
A kind of low shrinkage polyester industrial filament as described above, line density deviation ratio≤1.5% of the lower shrinkage industrial yarn,
Fracture strength CV value≤2.5%, extension at break are 20.0 ± 1.5%, extension at break CV value≤7.0%, network 6 ± 2.
In the mixture of a kind of low shrinkage polyester industrial filament as described above, the ethylene glycol magnesium and antimony glycol, second two
Magnesium alkoxide is 2~3 with antimony glycol mass ratio:1.
It is terephthalic acid (TPA) and ethylene glycol through ester the present invention also provides a kind of preparation method of low shrinkage polyester industrial filament
Change and polyester be made, then obtains polyester slice through pelletizing in polycondensation under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol,
Then by dissolveing and washing away, solid phase polycondensation thickening；Again through measuring, squeezing out, cooling down, oiling, stretching, thermal finalization, winding, heat resistance is made
Polyester industrial fiber.
A kind of preparation method of low shrinkage polyester industrial filament as described above, main technique are：
(1) preparation of catalyst glycol magnesium：
In single-cell for electrolyzation plus ethylene glycol, supporting electrolyte are magnesium chloride, and metal MAG block is anode, and cathode is graphite；
Logical direct current, 6~10VV of starting voltage, cathode-current density are 150~200mA, and 50~60 DEG C of whens are electrolysed 10~12 hours, electricity
Electrode is taken out after solution, obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and second two is obtained after dry
Magnesium alkoxide；
(2) preparation of polyester, including esterification and polycondensation reaction：
The esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, anti-ether agent is added in, esterification is carried out after being made into uniform sizing material,
Obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled in normal pressure~0.3MPa, and temperature is 250~260
DEG C, esterification water quantity of distillate reaches more than the 90% of theoretical value for esterification terminal；
The polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst and stabilizer, under conditions of negative pressure in esterification products
Start polycondensation reaction, which by normal pressure is steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is at 260~270 DEG C,
Reaction time is 30~50 minutes；The catalyst is ethylene glycol magnesium and the mixture of antimony glycol；
The polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure less than 100Pa, and reaction temperature control is at 275~280 DEG C, 50~90 minutes reaction time；
Polyester is made, polyester slice is obtained through pelletizing；
(3) it dissolves and washes away
The polyester slice is through water and dissolves and washes away agent brew 3-5 hours under the conditions of 120~130 DEG C with 0.2~0.3MPa, after
It is washed；
(4) solid phase polycondensation：
Acquired polyester slice is viscosified by solid phase polycondensation, and the inherent viscosity of polyester slice is made to be increased to 1.0~1.2dL/
G, as high viscous slice；
(5) spinning main technologic parameters：
The temperature of the extrusion is 290~320 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process：
500~600m/min of GR-1 speed；Temperature is room temperature；
520~1000m/min of GR-2 speed；80~100 DEG C of temperature；
1800~2500m/min of GR-3 speed；100~150 DEG C of temperature；
2800~3500m/min of GR-4 speed；200~250 DEG C of temperature；
2800~3500m/min of GR-5 speed；200~250 DEG C of temperature；
2600~3400m/min of GR-6 speed；150~220 DEG C of temperature；
The speed of the winding is 2600~3400m/min.
A kind of preparation method of low shrinkage polyester industrial filament as described above, the ethylene glycol and the terephthalic acid (TPA)
Molar ratio is 1.2~2.0:1.
A kind of preparation method of low shrinkage polyester industrial filament as described above, the mixing of the ethylene glycol magnesium and antimony glycol
In object, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is the terephthalic acid (TPA) quality
0.01%~0.05%.
Using ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to comparatively gentle one
Class, thermal degradation coefficient very little, the side reaction caused during the reaction is less, reduces end carboxyl in process and low
The generation of polymers.The principal element for causing thermal degradation is high mild catalyst, and high temperature is that response intensity is excessively high, and degradation is caused to add
Speed produces end carboxyl, while also increases cyclic oligomer；Catalyst is then related to the degradation reaction constant of catalyst,
In polycondensation process, the effect of catalyst, which is not only in that, can be catalyzed generation main reaction, so as to influence the rate and yield of reaction, simultaneously
Thermal degradation and ehter bond generation can also be catalyzed, increases the content of diethylene glycol (DEG), so as to increase the content of end carboxyl.
A kind of preparation method of low shrinkage polyester industrial filament as described above, the stabilizer are selected from triphenyl phosphate, phosphorus
One kind in sour trimethyl and Trimethyl phosphite, stabilizing agent dosage for the terephthalic acid (TPA) weight 0.01%~
0.05%.For stabilizer mainly based on phosphate, main function is the free radical that catching reaction generates in the course of the polymerization process, is reduced
Side reaction.
A kind of preparation method of low shrinkage polyester industrial filament as described above, the water are with the mass ratio for dissolveing and washing away agent
100:3~4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio is 1:5-10；It is described to dissolve and wash away agent as one second of ethylene glycol
One kind in ether, propyl cellosolve and ethylene glycol monobutyl ether (EGMBE), what addition was a small amount of in water dissolves and washes away agent, dissolves and washes away agent and is dissolved in water, together
When also can dissolve most of low molecular ethers and ester, be conducive to improve washing effect and oligomer reduction.
A kind of preparation method of low shrinkage polyester industrial filament as described above, polyester slice is used after the washing refers to brew
70~80 DEG C of 10~15min of hot water wash, are then cleaned, Drying and cooling is spare with cold water.
A kind of preparation method of low shrinkage polyester industrial filament as described above, the anti-ether agent are in sodium acetate and calcium acetate
One kind, anti-ether agent dosage be the terephthalic acid (TPA) weight 0.01%~0.05%.Anti- ether agent is by adding in a small amount of NaAc
The generation of ether in acid condition is reduced, so as to reduce the activity of glycol reaction generation diethylene glycol (DEG).
The object of the present invention is to provide a kind of low shrinkage polyester industrial filament, using relatively mild a kind of polycondensation catalyst second two
Magnesium alkoxide, the less side reaction caused during the reaction is less and process in less thermal degradation, reduce and processing
The generation of oligomer in the process.Polyester slice is through water and dissolves and washes away agent at 130 DEG C, and brew is conducive to improve washing under the conditions of 0.3MPa
Effect and oligomer reduction.Oligomer is reduced in polymerization process, and the reduction of thermal degradation, greatly reduces in process
Impurity in polyester, while the amount of nucleating agent in polyester is also reduced, it increases on the basis of heterogeneous nucleation is reduced and coordinates
The probability of core, be conducive to the crystallite dimension in low shrinkage polyester industrial filament fiber grow up and crystallize integrity optimization.
Advantageous effect：
● using ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to comparatively gentle one
Class, thermal degradation coefficient very little, the side reaction caused during the reaction is less, reduces end carboxyl in process and low
The generation of polymers.
● the content of carboxyl end group of polyester slice is less than 15mol/t, and oligomer mass percentage content is less than 0.5%, and two is sweet
The mass percentage content of alcohol is less than 0.5%, is conducive to further improve the quality of fiber.
● polyester slice through water with dissolve and wash away agent brew under the conditions of 120~130 DEG C with 0.2~0.3MPa be conducive to improve wash
The effect washed and the reduction of oligomer.
● anti-ether agent reduces the generation of ether in acid condition by adding in a small amount of NaAc, so as to reduce glycol reaction
Generate the activity of diethylene glycol (DEG).
● oligomer is reduced in polymerization process, and the reduction of thermal degradation, greatly reduces miscellaneous in polyester in process
Matter, while the amount of nucleating agent in polyester is also reduced, the probability of homogeneous nucleation is increased on the basis of heterogeneous nucleation is reduced, is had
Conducive in low shrinkage polyester industrial filament fiber crystallite dimension grow up and crystallize integrity optimization.
● lower shrinkage type polyester industrial yarn has the characteristics that relatively low dry-hot shrinkage and preferable dimensional stability and wide
It is general to apply in filter cloth, coated fabric, hose and conveyer belt weft etc..
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
A kind of preparation method of low shrinkage polyester industrial filament of the present invention, terephthalic acid (TPA) and ethylene glycol are through esterification and in second
Polyester is made, then obtains polyester slice through pelletizing in the lower polycondensation of the mixture through catalytic of two magnesium alkoxides and antimony glycol effect；Then pass through
It dissolves and washes away and is viscosified with solid phase polycondensation；Again through measuring, squeezing out, cooling down, oiling, stretching, thermal finalization and winding, low shrinkage polyester work is made
Industry silk.
Embodiment 1
A kind of preparation method of low shrinkage polyester industrial filament, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 6V, cathode-current density 150mA, 50 DEG C of whens, are electrolysed 10 hours, and electricity is taken out after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1.2:1, it adds in
Anti- ether agent sodium acetate, sodium acetate dosage are the 0.01% of terephthalic acid (TPA) weight, carry out esterification after being made into uniform sizing material, obtain
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled in normal pressure, and at 250 DEG C, esterification water quantity of distillate reaches temperature
It is esterification terminal to the 91% of theoretical value；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst and stabilizer triphenyl phosphate ester, triphenyl phosphate in esterification products
Ester dosage is the 0.01% of terephthalic acid (TPA) weight, and catalyst amount is the 0.01% of terephthalic acid (TPA) quality, in the item of negative pressure
Start polycondensation reaction under part, which is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature is controlled at 260 DEG C, reaction
Between be 30 minutes；Catalyst is ethylene glycol magnesium and the mixture of antimony glycol, and ethylene glycol magnesium is 2 with antimony glycol mass ratio:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
To absolute pressure 98Pa, reaction temperature control is at 275 DEG C, 50 minutes reaction time；Polyester is made, obtains polyester through pelletizing and cuts
Piece；
(3) it dissolves and washes away
Polyester slice is through water and dissolves and washes away agent ethylene glycol monoethyl ether brew 3 hours under the conditions of 120 DEG C with 0.2MPa, by washing
It washs, i.e., 70 DEG C of hot water wash 10min of polyester slice, are then cleaned with cold water after brew, and Drying and cooling is spare, and water is with dissolveing and washing away agent
Mass ratio is 100:3, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio is 1:5；
(4) solid phase polycondensation：
Acquired polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.0dL/g, as
The viscous slice of height；
(5) spinning main technologic parameters：
The temperature of extrusion is 290 DEG C；
The wind-warm syndrome of cooling is 20 DEG C；
It stretches, heat setting process：
GR-1 speed 500m/min；Temperature is room temperature；
GR-2 speed 520m/min；80 DEG C of temperature；
GR-3 speed 1800m/min；100 DEG C of temperature；
GR-4 speed 2800m/min；200 DEG C of temperature；
GR-5 speed 2800m/min；200 DEG C of temperature；
GR-6 speed 2600m/min；150 DEG C of temperature；
The speed of winding is 2600m/min.
Low shrinkage polyester industrial filament obtained is in the case where temperature is the test condition of 190 DEG C × 15min × 0.01cN/dtex
Dry-hot shrinkage is 3.5%；Fracture strength 7.1cN/dtex；Line density deviation ratio 1.3%, fracture strength CV values 2.4%, fracture
It is 21.5% to extend, extension at break CV values 6.9%, network 6.
Embodiment 2
A kind of preparation method of low shrinkage polyester industrial filament, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 10V, cathode-current density 200mA, 60 DEG C of whens, are electrolysed 12 hours, and electricity is taken out after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 2.0:1, it adds in
Anti- ether agent calcium acetate, calcium acetate dosage are the 0.05% of terephthalic acid (TPA) weight, carry out esterification after being made into uniform sizing material, obtain
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is in 0.3MPa, and temperature is at 260 DEG C, esterification water quantity of distillate
It is esterification terminal to reach the 92% of theoretical value；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst and stabilizer trimethyl phosphate, tripotassium phosphate in esterification products
Ester dosage is the 0.02% of the terephthalic acid (TPA) weight, and catalyst amount is the 0.02% of terephthalic acid (TPA) quality, in negative pressure
Under conditions of start polycondensation reaction, which is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature is controlled at 265 DEG C, instead
It is 40 minutes between seasonable；Catalyst is ethylene glycol magnesium and the mixture of antimony glycol, and ethylene glycol magnesium is with antimony glycol mass ratio
3:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, reaction pressure is made to be down to absolutely
To pressure 98Pa, reaction temperature control is at 278 DEG C, 80 minutes reaction time；Polyester is made, polyester slice is obtained through pelletizing；
(3) it dissolves and washes away
Polyester slice is through water and dissolves and washes away agent propyl cellosolve brew 4 hours under the conditions of 125 DEG C with 0.25MPa, by
Washing, i.e., 78 DEG C of hot water wash 12min of polyester slice, are then cleaned with cold water after brew, and Drying and cooling is spare, and water is with dissolveing and washing away agent
Mass ratio be 100:4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio is 1:9；
(4) solid phase polycondensation：
Acquired polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.1dL/g, as
The viscous slice of height；
(5) spinning main technologic parameters：
The temperature of extrusion is 320 DEG C；
The wind-warm syndrome of cooling is 30 DEG C；
It stretches, heat setting process：
GR-1 speed 600m/min；Temperature is room temperature；
GR-2 speed 1000m/min；100 DEG C of temperature；
GR-3 speed 2500m/min；150 DEG C of temperature；
GR-4 speed 2800m/min；250 DEG C of temperature；
GR-5 speed 3500m/min；250 DEG C of temperature；
GR-6 speed 3400m/min；220 DEG C of temperature；
The speed of winding is 3400m/min
Low shrinkage polyester industrial filament obtained is in the case where temperature is the test condition of 190 DEG C × 15min × 0.01cN/dtex
Dry-hot shrinkage is 2.5%；Fracture strength 7.6cN/dtex；Line density deviation ratio 1.1%, fracture strength CV values 2.1%, fracture
It is 18.5% to extend, extension at break CV values 6.7%, network 4.
Embodiment 3
A kind of preparation method of low shrinkage polyester industrial filament, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 8V, cathode-current density 160mA, 56 DEG C of whens, are electrolysed 11 hours, and electricity is taken out after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1.8:1, it adds in
Anti- ether agent sodium acetate, sodium acetate dosage are the 0.03% of terephthalic acid (TPA) weight, carry out esterification after being made into uniform sizing material, obtain
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is in 0.2MPa, and temperature is at 255 DEG C, esterification water quantity of distillate
It is esterification terminal to reach the 95% of theoretical value；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst and stabilizer Trimethyl phosphite, phosphorous acid in esterification products
Trimethyl dosage is the 0.03% of terephthalic acid (TPA) weight, and catalyst amount is the 0.04% of terephthalic acid (TPA) quality, in negative pressure
Under conditions of start polycondensation reaction, which is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature is controlled at 266 DEG C, instead
It is 38 minutes between seasonable；Catalyst is ethylene glycol magnesium and the mixture of antimony glycol, and ethylene glycol magnesium is with antimony glycol mass ratio
3:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, reaction pressure is made to be down to absolutely
To pressure 99Pa, reaction temperature control is at 277 DEG C, 70 minutes reaction time；Polyester is made, polyester slice is obtained through pelletizing；
(3) it dissolves and washes away
Polyester slice is through water and dissolves and washes away agent ethylene glycol monobutyl ether (EGMBE) brew 3 hours under the conditions of 128 DEG C with 0.25MPa, by
Washing, i.e., 75 DEG C of hot water wash 12min of polyester slice, are then cleaned with cold water after brew, and Drying and cooling is spare, and water is with dissolveing and washing away agent
Mass ratio be 100:4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio is 1:8；
(4) solid phase polycondensation：
Acquired polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.2dL/g, as
The viscous slice of height；
(5) spinning main technologic parameters：
The temperature of extrusion is 320 DEG C；
The wind-warm syndrome of cooling is 20 DEG C；
It stretches, heat setting process：
GR-1 speed 500m/min；Temperature is room temperature；
GR-2 speed 600m/min；90 DEG C of temperature；
GR-3 speed 1900m/min；120 DEG C of temperature；
GR-4 speed 2900m/min；220 DEG C of temperature；
GR-5 speed 3000m/min；220 DEG C of temperature；
GR-6 speed 3200m/min；180 DEG C of temperature；
The speed of winding is 2800m/min.
Low shrinkage polyester industrial filament obtained is in the case where temperature is the test condition of 190 DEG C × 15min × 0.01cN/dtex
Dry-hot shrinkage is 3.0%；Fracture strength 7.8cN/dtex；Line density deviation ratio 1.3%, fracture strength CV values 2.4%, fracture
It is 20.5% to extend, extension at break CV values 6.6%, network 7.
Embodiment 4
A kind of preparation method of low shrinkage polyester industrial filament, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 10V, cathode-current density 150mA, 50 DEG C of whens, are electrolysed 12 hours, and electricity is taken out after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 19:1, it adds in
Anti- ether agent sodium acetate, sodium acetate dosage are the 0.04% of terephthalic acid (TPA) weight, carry out esterification after being made into uniform sizing material, obtain
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is in 0.2MPa, and temperature is at 258 DEG C, esterification water quantity of distillate
It is esterification terminal to reach the 96% of theoretical value；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, catalyst and stabilizer triphenyl phosphate ester are added in esterification products, triphenyl phosphate ester is used
0.03% for terephthalic acid (TPA) weight is measured, catalyst amount is the 0.04% of terephthalic acid (TPA) quality, under conditions of negative pressure
Start polycondensation reaction, which is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature control is in 265 DEG C, reaction time
30 minutes；Catalyst is ethylene glycol magnesium and the mixture of antimony glycol, and ethylene glycol magnesium is 3 with antimony glycol mass ratio:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, reaction pressure is made to be down to absolutely
To pressure 98Pa, reaction temperature control is at 277 DEG C, 70 minutes reaction time；Polyester is made, polyester slice is obtained through pelletizing；
(3) it dissolves and washes away
Polyester slice is through water and dissolves and washes away agent ethylene glycol monoethyl ether brew 5 hours under the conditions of 120 DEG C with 0.3MPa, by washing
It washs, i.e., 72 DEG C of hot water wash 12min of polyester slice, are then cleaned with cold water after brew, and Drying and cooling is spare, and water is with dissolveing and washing away agent
Mass ratio is 100:4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio is 1:8；
(4) solid phase polycondensation：
Acquired polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.2dL/g, as
The viscous slice of height；
(5) spinning main technologic parameters：
The temperature of extrusion is 300 DEG C；
The wind-warm syndrome of cooling is 25 DEG C；
It stretches, heat setting process：
GR-1 speed 550m/min；Temperature is room temperature；
GR-2 speed 600m/min；90 DEG C of temperature；
GR-3 speed 1900m/min；120 DEG C of temperature；
GR-4 speed 3200m/min；220 DEG C of temperature；
GR-5 speed 2900m/min；220 DEG C of temperature；
GR-6 speed 3300m/min；160 DEG C of temperature；
The speed of winding is 2800m/m
Low shrinkage polyester industrial filament obtained is in the case where temperature is the test condition of 190 DEG C × 15min × 0.01cN/dtex
Dry-hot shrinkage is 2.5%；Fracture strength 8.0cN/dtex；Line density deviation ratio 1.5%, fracture strength CV values 1.9%, fracture
It is 19.5% to extend, extension at break CV values 6.8%, network 6.
Claims (9)
1. a kind of low shrinkage polyester industrial filament, it is characterized in that：The low shrinkage polyester industrial filament is increased by polyester through dissolveing and washing away with solid phase
It glues rear spinning and obtains, the low shrinkage polyester industrial filament is in the test condition that temperature is 190 DEG C × 15min × 0.01cN/dtex
Under dry-hot shrinkage be 3.0 ± 0.5%；Fracture strength >=7.0cN/dtex；The polyester is terephthalic acid (TPA) and ethylene glycol
Through esterification and the mixture through catalytic of ethylene glycol magnesium and antimony glycol effect under polycondensation and after granulation be made；
In the slice of the polyester, content of carboxyl end group is less than 15mol/t, and oligomer mass percentage content is less than 0.5%, and two is sweet
The mass percentage content of alcohol is less than 0.5%；
The molecular formula of the ethylene glycol magnesium is Mg (OCH2CH2OH)2；
In the mixture of the ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；
Described dissolve and wash away refers to the slice after being granulated through water and dissolves and washes away agent under the conditions of 120~130 DEG C with 0.2~0.3MPa after brew
Washing.
A kind of 2. low shrinkage polyester industrial filament according to claim 1, which is characterized in that the line of the lower shrinkage industrial yarn
Density variation rate≤1.5%, fracture strength CV value≤2.5%, elongation at break are 20.0 ± 1.5%, elongation at break CV values
≤ 7.0%, internet pricing 6 ± 2.
3. such as a kind of preparation method of low shrinkage polyester industrial filament according to any one of claims 1 to 2, it is characterized in that：It is right
Polyester is made in polycondensation through esterification and under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol for phthalic acid and ethylene glycol, then
Polyester slice is obtained through pelletizing；Then it is viscosified by dissolveing and washing away with solid phase polycondensation；Again through measuring, squeezing out, cooling down, oiling, stretching, heat
Sizing and winding, are made low shrinkage polyester industrial filament.
4. a kind of preparation method of low shrinkage polyester industrial filament according to claim 3, it is characterised in that：Main technique
For：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is graphite；It is logical
Direct current, 6~10V of starting voltage, cathode-current density are 150~200mA, are electrolysed 10~12 hours at 50~60 DEG C, electrolysis
After take out electrode, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol is obtained after dry
Magnesium；
(2) preparation of polyester, including esterification and polycondensation reaction：
The esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, anti-ether agent is added in, esterification is carried out after being made into uniform sizing material, obtains
Esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is in normal pressure~0.3MPa, and temperature is at 250~260 DEG C, ester
It is esterification terminal to change water quantity of distillate to reach more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst and stabilizer in esterification products, starts under conditions of negative pressure
Polycondensation reaction, the staged pressure are steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is reacted at 260~270 DEG C by normal pressure
Time is 30~50 minutes；The catalyst is ethylene glycol magnesium and the mixture of antimony glycol；
The polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
It is less than 100Pa to absolute pressure, reaction temperature control is at 275~280 DEG C, 50~90 minutes reaction time；
Polyester is made, polyester slice is obtained through pelletizing；
(3) it dissolves and washes away
The polyester slice is through water and dissolves and washes away agent brew 3-5 hours under the conditions of 120~130 DEG C with 0.2~0.3MPa, by washing
It washs；
(4) solid phase polycondensation：
Acquired polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.0~1.2dL/g, i.e.,
For the viscous slice of height；
(5) spinning main technologic parameters：
The temperature of the extrusion is 290~320 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process：
500~600m/min of GR-1 speed；Temperature is room temperature；
520~1000m/min of GR-2 speed；80~100 DEG C of temperature；
1800~2500m/min of GR-3 speed；100~150 DEG C of temperature；
2800~3500m/min of GR-4 speed；200~250 DEG C of temperature；
2800~3500m/min of GR-5 speed；200~250 DEG C of temperature；
2600~3400m/min of GR-6 speed；150~220 DEG C of temperature；
The speed of the winding is 2600~3400m/min.
A kind of 5. preparation method of low shrinkage polyester industrial filament according to claim 3 or 4, which is characterized in that the second
The molar ratio of glycol and the terephthalic acid (TPA) is 1.2~2.0:1.
A kind of 6. preparation method of low shrinkage polyester industrial filament according to claim 4, which is characterized in that the ethylene glycol
In the mixture of magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is described
The 0.01%~0.05% of terephthalic acid (TPA) quality；The stabilizer is selected from triphenyl phosphate, trimethyl phosphate and phosphorous acid three
One kind in methyl esters, stabilizing agent dosage are the 0.01%~0.05% of the terephthalic acid (TPA) weight.
7. a kind of preparation method of low shrinkage polyester industrial filament according to claim 4, which is characterized in that the water with it is molten
The mass ratio of lotion is 100:3~4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio is 1:5~10；It is described molten
Lotion is one kind in ethylene glycol monoethyl ether, propyl cellosolve and ethylene glycol monobutyl ether (EGMBE).
8. the preparation method of a kind of low shrinkage polyester industrial filament according to claim 4, which is characterized in that the washing is
70~80 DEG C of 10~15min of hot water wash of polyester slice after finger brew, are then cleaned, Drying and cooling is spare with cold water.
A kind of 9. preparation method of low shrinkage polyester industrial filament according to claim 4, which is characterized in that the anti-ether agent
For one kind in sodium acetate and calcium acetate, anti-ether agent dosage is the 0.01%~0.05% of the terephthalic acid (TPA) weight.
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| CN105646858B (en) | 2015-12-29 | 2018-07-27 | 江苏恒力化纤股份有限公司 | A kind of ultralow contractive polyester industrial yarn and preparation method thereof |
| CN105504241B (en) * | 2015-12-29 | 2018-06-12 | 江苏恒力化纤股份有限公司 | A kind of high mode and low mode polyester industrial fiber and preparation method thereof |
| CN108130609B (en) * | 2017-12-14 | 2020-02-21 | 江苏恒力化纤股份有限公司 | Low-shrinkage polyester industrial yarn and preparation method thereof |
| CN107937997B (en) * | 2017-12-14 | 2020-08-14 | 江苏恒力化纤股份有限公司 | Preparation method of high-strength low-elongation polyester industrial yarn |
| CN108385189B (en) * | 2017-12-14 | 2020-05-05 | 江苏恒力化纤股份有限公司 | Low-shrinkage high-strength polyester industrial yarn and preparation method thereof |
| CN108385188B (en) * | 2017-12-14 | 2020-07-07 | 江苏恒力化纤股份有限公司 | Low-shrinkage activated polyester industrial yarn and preparation method thereof |
| JP2020033677A (en) * | 2018-08-31 | 2020-03-05 | 株式会社ブリヂストン | Belt-like fabric for hose, and hose using the same |
| CN115322349A (en) * | 2022-09-13 | 2022-11-11 | 安徽皖维高新材料股份有限公司 | Polyester chip deeply dyed by disperse dye at normal temperature and normal pressure and low in shrinkage and preparation method thereof |
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| CN102797057B (en) * | 2012-09-03 | 2015-04-01 | 江苏恒力化纤股份有限公司 | Manufacturing method for high-modulus low-shrinkage PET industrial yarn |
| CN102797056B (en) * | 2012-09-03 | 2014-10-01 | 江苏恒力化纤股份有限公司 | Manufacturing method for superlow shrinkage type PET industrial yarn |
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