CN105463608B - A kind of high-strength safety belt polyester industrial fiber and preparation method thereof - Google Patents
A kind of high-strength safety belt polyester industrial fiber and preparation method thereof Download PDFInfo
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- CN105463608B CN105463608B CN201511017954.4A CN201511017954A CN105463608B CN 105463608 B CN105463608 B CN 105463608B CN 201511017954 A CN201511017954 A CN 201511017954A CN 105463608 B CN105463608 B CN 105463608B
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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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- 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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- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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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
- D01D5/12—Stretch-spinning methods
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Abstract
The present invention relates to a kind of high-strength safety belt polyester industrial fiber and preparation method thereof, the high-strength safety belt polyester industrial fiber dissolves and washes away by polyester, after solid-phase tack producing spinning and obtain, the high-strength safety belt polyester industrial fiber fracture strength >=8.1cN/dtex, extension at break is the elongation 5.5 ± 0.5% of 14.0 ± 1.5%, 4.0cN/dtex loads；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 nucleator in polyester, the probability of homogeneous nucleation is added on the basis of heterogeneous nucleation is reduced, the content that reduce further oligomer is dissolved and washed away, is advantageous to growing up and crystallizing integrity optimization for crystallite dimension in high-strength safety belt polyester industrial silk fiber.
Description
Technical field
The invention belongs to polyester industrial fiber preparing technical field, is related to a kind of high-strength safety belt polyester industrial fiber and its preparation side
Method, particularly a kind of polycondensation catalyst through water and dissolve and wash away agent using the mixture and polyester slice of ethylene glycol magnesium and antimony glycol
At 120~130 DEG C, brew, the polyester of washing and high-strength safety belt polyester industrial fiber and its preparation under the conditions of 0.2~0.3MPa
Method.
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 field 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, it is that there is 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 strong
Degree, makes shelter cloth be applied to 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 the advantages that light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make
Used time safe ready, efficiency high, and lifting object will not be damaged.The application field of Pet Industrial Fiber, which is expanded, drives application
The whole competitiveness lifting in field, no matter mitigating the weight of composite, the durability used and reduction maintenance, raising cost
Etc. all many-sides, 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 considerable progress in quantity, more in the expansion of application field and carrying for industrial chain whole competitiveness
Go up and obtain substantial 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.
End carboxyl, oligomer, diethylene glycol (DEG) (DEG) content are the important quality index of polyester slice, wherein oligomer, two sweet
Alcohol is all oligomer, and 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 turns into 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 stable 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 wherein DEG content
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 thing 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
Problem.
The content of the invention
It is an object of the invention to provide a kind of high-strength safety belt polyester industrial fiber and preparation method thereof, is a kind of polycondensation catalysis
Agent is using polyester and high-strength safety belt polyester industrial fiber of ethylene glycol magnesium and the mixture of antimony glycol and preparation method thereof.Institute
High-strength safety belt polyester industrial fiber fracture strength >=8.1cN/dtex is stated, extension at break is that 14.0 ± 1.5%, 4.0cN/dtex is born
The elongation 5.5 ± 0.5% of lotus.The present invention uses the mixture of ethylene glycol magnesium and antimony glycol as polycondensation catalyst, by heat drop
Solution is reduced to minimum, and polyester slice is through water and dissolveing and washing away agent at 130 DEG C, brew, washing under the conditions of 0.3MPa；Reduce end carboxylic
The influence that base, oligomer, diethylene glycol content are processed to Direct-spinning of PET Fiber.
A kind of high-strength safety belt polyester industrial fiber of the present invention, it is terephthalic acid (TPA) and ethylene glycol through esterification for the polyester
With the mixture through catalytic of ethylene glycol magnesium and antimony glycol effect under polycondensation, be granulated and dissolve and wash away, after solid-phase tack producing spinning and obtain；
In the section of the industry 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 section after being granulated is boiled under the conditions of 120~130 DEG C with 0.2~0.3MPa through water with dissolveing and washing away agent
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.
Fracture strength is one of very important performance of industrial yarn, and there is high strength industrial filament highest amorphous area to be orientated and break
Resistance to spalling.There is preferable corresponding relation, amorphous area between amorphous area orientation and fracture strength to be orientated higher, the fracture of fiber
Intensity is higher, and the main influence for being stretched multiple of the orientation of amorphous area, and high strength industrial filament passes through the low speed, high stretching, low spun
Heat setting temperature technique is realized.High strength industrial filament has that crystallinity is low, crystal grain is small and more, amorphous area orientation highest, lamella incline
The features such as rake angle is maximum, long period is big.The elongation at break of fiber is mainly determined by molecular chain orientation.Molecular chain orientation journey
Degree it is lower, strand by be crimped onto stretch caused by deformation it is bigger, the elongation of fiber is bigger.On the contrary, molecular chain orientation degree
Height, the degree that the strand stretched can strain reduce, and the elongation of fiber also reduces therewith.
Determining terminal carboxy group in PET is high, and the heat endurance 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, polyester is accelerated 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), product of the oligomer to polyester
Matter is had a great influence, and the crystallization nucleation mechanism of polyester, crystallinity, crystal habit and crystallization are mainly influenceed in a manner of nucleator
Integrality etc. and then the percent thermal shrinkage for influenceing the quality, particularly polyester industrial fiber of polyester fiber.Pure polyester without diethylene glycol (DEG),
No matter how crystallization condition changes, all without the form for abnormal spherocrystal occur；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 whole form
Ratio rises, thus has influence on the integrality of crystallization, makes the crystallization integrity of its polyester reduce.Cyclic trimer more than the polyester with
The mode of nucleation occurs, and nucleator is more, and crystallization rate is fast, and crystal grain quantity is big, but crystallite dimension is smaller, and then has influence on 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
Kind transition zone between crystalline portion and the crystallization of low stability and amorphous increases, and the thermal contraction to polyester fiber produces bad shadow
Ring.
Linear or cyclic dimer of the oligomer of part low melting point such as containing ehter bond, as polyester fondant is in HTHP
During extrusion, due to the significantly decline of temperature and pressure, the oligomer just left because the change of temperature and pressure can evaporate,
Volatile formation bubble, causes melt quality to decline.Dystectic cyclic oligomer mainly influences to be heterogeneous nucleation, in finished product shape
Into fisheye, stretching is impacted, the raising of draw ratio is limited, further has influence on the mechanical property of industrial yarn.
A kind of high-strength safety belt polyester industrial fiber as described above, the line density deviation ratio of the high-strength safety belt industrial yarn
≤ 1.5%, fracture strength CV value≤2.5%, extension at break CV value≤7.0%, network 6 ± 2, it is 177 DEG C × 10min in temperature
Under × 0.05cN/dtex test condition, the dry-hot shrinkage of fiber is 8.0 ± 1.5%.
A kind of high-strength safety belt polyester industrial fiber as described above, in the mixture of the ethylene glycol magnesium and antimony glycol,
Ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1.
Present invention also offers a kind of preparation method of high-strength safety belt polyester industrial fiber, is terephthalic acid (TPA) and ethylene glycol
Through esterification and the obtained polyester of polycondensation under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol, then obtain polyester through pelletizing and cut
Piece, then by dissolveing and washing away, solid phase polycondensation thickening；Again through measuring, extruding, cooling down, oiling, stretching, thermal finalization, winding, be made resistance to
Hot polyester industrial fiber.
A kind of preparation method of high-strength safety belt polyester industrial fiber as described above, main technique are：
(1) preparation of catalyst glycol magnesium：
Add ethylene glycol in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite；
Logical direct current, 6~10VV of starting voltage, cathode-current density be 150~200mA, are electrolysed 10~12 hours at 50~60 DEG C, electric
Solution takes out electrode after terminating, and obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and second two is obtained after drying
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, esterification is carried out after being made into uniform sizing material,
Obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is in normal pressure~0.3MPa, and temperature is 250~260
DEG C, what esterification water quantity of distillate reached theoretical value more than 90% is 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, catalyst and stabilizer are added in esterification products, under conditions of negative pressure
Start polycondensation reaction, the staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control at 260~270 DEG C,
Reaction time is 30~50 minutes；The catalyst is the mixture of ethylene glycol magnesium and antimony glycol；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to vacuumize, make reaction pressure
Power is down to absolute pressure and is 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) dissolve and wash 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 scrubbed；
(4) solid phase polycondensation：
Resulting polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is brought up to 1.0~1.2dL/
G, it is high viscous section；
(5) spinning main technologic parameters：
The temperature of the extrusion is 290~310 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
Described stretching, heat setting process：
440~650m/min of GR-1 speed；75~85 DEG C of temperature；
460~680m/min of GR-2 speed；90~100 DEG C of temperature；
1900~2400m/min of GR-3 speed；125~140 DEG C of temperature；
2700~3600m/min of GR-4 speed；220~250 DEG C of temperature；
2500~3600m/min of GR-5 speed；150~170 DEG C of temperature；
The speed of the winding is 2500~3600m/min.
A kind of preparation method of high-strength safety belt polyester industrial fiber as described above, the ethylene glycol and the terephthaldehyde
The mol ratio of acid is 1.2~2.0:1.
A kind of preparation method of high-strength safety belt polyester industrial fiber as described above, the ethylene glycol magnesium and antimony glycol
In mixture, 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%.
Belong to comparatively gentle one as polycondensation catalyst, ethylene glycol magnesium using ethylene glycol magnesium and antimony glycol mixture
Class, its thermal degradation coefficient very little, the side reaction triggered during the course of the reaction is less, reduces end carboxyl in process and low
The generation of polymers.The principal element for causing thermal degradation is high temperature and catalyst, and high temperature is that response intensity is too high, causes degraded to add
Speed, end carboxyl is generated, while also increase 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 speed 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 high-strength safety belt polyester industrial fiber as described above, the stabilizer are selected from phosphoric acid triphen
One kind in ester, trimethyl phosphate 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 free radical caused by catching reaction in the course of the polymerization process, is reduced
Side reaction.
A kind of preparation method of high-strength safety belt polyester industrial fiber as described above, the water and the mass ratio for dissolveing and washing away agent
For 100:3~4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio are 1:5-10；It is described that to dissolve and wash away agent be the second of ethylene glycol one
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 advantageous to improve washing effect and oligomer reduction.
A kind of preparation method of high-strength safety belt polyester industrial fiber as described above, polyester is cut after the washing refers to brew
70~80 DEG C of 10~15min of hot water wash of piece, are then cleaned, Drying and cooling is standby with cold water.
A kind of preparation method of high-strength safety belt polyester industrial fiber as described above, the anti-ether agent is sodium acetate and acetic acid
One kind in calcium, anti-ether agent dosage are the 0.01%~0.05% of the terephthalic acid (TPA) weight.Anti- ether agent is a small amount of by adding
NaAc reduces the generation of ether in acid condition, so as to reduce the activity of glycol reaction generation diethylene glycol (DEG).
It is an object of the invention to provide a kind of high-strength safety belt polyester industrial fiber, using relatively mild a kind of polycondensation catalyst
Ethylene glycol magnesium, the less side reaction triggered during the course of the reaction is less and process in less thermal degradation, reduce
The generation of oligomer in process.Polyester slice is through water and dissolves and washes away agent at 130 DEG C, and brew is advantageous to improve under the conditions of 0.3MPa
The effect of washing and the reduction of oligomer.Oligomer is reduced in polymerization process, and the reduction of thermal degradation, greatly subtracts in process
The impurity in polyester is lacked, while has also reduced the amount of nucleator in polyester, added on the basis of heterogeneous nucleation is reduced
The mutually probability of nucleation, be advantageous to the crystallite dimension in high-strength safety belt polyester industrial silk fiber grow up and to crystallize integrity excellent
Change.
Beneficial effect：
● belong to comparatively gentle one as polycondensation catalyst, ethylene glycol magnesium using ethylene glycol magnesium and antimony glycol mixture
Class, its thermal degradation coefficient very little, the side reaction triggered during the course of 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 advantageous to further improve the quality of fiber.
● polyester slice is advantageous to raising with dissolveing and washing away agent brew under the conditions of 120~130 DEG C with 0.2~0.3MPa through water and washed
The effect washed and the reduction of oligomer.
● anti-ether agent reduces the generation of ether in acid condition by adding 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, is greatly reduced miscellaneous in polyester in process
Matter, while the amount of nucleator in polyester is also reduced, the probability of homogeneous nucleation is added on the basis of heterogeneous nucleation is reduced, is had
Beneficial in high-strength safety belt polyester industrial silk fiber crystallite dimension grow up and crystallize integrity optimization.
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
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
A kind of preparation method of high-strength safety belt polyester industrial fiber of the present invention, terephthalic acid (TPA) and ethylene glycol through esterification and
Polyester is made in polycondensation under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol, then obtains polyester slice through pelletizing；Then
Viscosified by dissolveing and washing away with solid phase polycondensation；Again through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding, high-strength safety is made
Band polyester industrial fiber.
Embodiment 1
A kind of preparation method of high-strength safety belt polyester industrial fiber, 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 negative electrode is stone
Ink；Logical direct current, starting voltage 6V, cathode-current density 150mA, it is electrolysed 10 hours at 50 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 1.2:1, add
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 Stress control is 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, catalyst and stabilizer triphenyl phosphate ester, triphenyl phosphate are added 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 bar of negative pressure
Start polycondensation reaction under part, the staged pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature control is at 260 DEG C, reaction
Between be 30 minutes；Catalyst is the mixture of ethylene glycol magnesium and 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, continue to vacuumize, drop 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) dissolve and wash 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
Wash, 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 standby, 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 are 1:5；
(4) solid phase polycondensation：
Resulting polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is brought up to 1.0dL/g, is
The viscous section 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；
Stretching, heat setting process：
GR-1 speed 440m/min；75 DEG C of temperature；
GR-2 speed 460m/min；90 DEG C of temperature；
GR-3 speed 1900m/min；125 DEG C of temperature；
GR-4 speed 2700m/min；220 DEG C of temperature；
GR-5 speed 2500m/min；150 DEG C of temperature；
The speed of the winding is 2500m/min.
Obtained high-strength safety belt polyester industrial fiber fracture strength 8.1cN/dtex, extension at break 15.5%, 4.0cN/
The elongation 6.0% of dtex loads；Line density deviation ratio 1.5%, fracture strength CV values 2.5%, extension at break CV values 7.0%,
Network 8, in the case where temperature is 177 DEG C × 10min × 0.05cN/dtex test condition, the dry-hot shrinkage of fiber is 9.5%.
Embodiment 2
A kind of preparation method of high-strength safety belt polyester industrial fiber, 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 negative electrode is stone
Ink；Logical direct current, starting voltage 10V, cathode-current density 200mA, it is electrolysed 12 hours at 60 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 2.0:1, add
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 Stress 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：
In the polycondensation reaction low vacuum stage, catalyst and stabilizer trimethyl phosphate, tripotassium phosphate are added 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, the staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature control is at 265 DEG C, instead
It is 40 minutes between seasonable；Catalyst is the mixture of ethylene glycol magnesium and 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, continue to vacuumize, reaction pressure is 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) dissolve and wash 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 standby, 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 are 1:9；
(4) solid phase polycondensation：
Resulting polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is brought up to 1.1dL/g, is
The viscous section of height；
(5) spinning main technologic parameters：
The temperature of extrusion is 310 DEG C；
The wind-warm syndrome of cooling is 30 DEG C；
Stretching, heat setting process：
GR-1 speed 650m/min；85 DEG C of temperature；
GR-2 speed 680m/min；100 DEG C of temperature；
GR-3 speed 2400m/min；140 DEG C of temperature；
GR-4 speed 3600m/min；250 DEG C of temperature；
GR-5 speed 3600m/min；170 DEG C of temperature；
The speed of winding is 3600m/min.
Obtained high-strength safety belt polyester industrial fiber fracture strength 8.2cN/dtex, extension at break 12.5%, 4.0cN/
The elongation 5.0% of dtex loads；Line density deviation ratio 1.3%, fracture strength CV values 2.3%, extension at break CV values 6.8%,
Network 4, in the case where temperature is 177 DEG C × 10min × 0.05cN/dtex test condition, the dry-hot shrinkage of fiber is 6.5%.
Embodiment 3
A kind of preparation method of high-strength safety belt polyester industrial fiber, 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 negative electrode is stone
Ink；Logical direct current, starting voltage 8V, cathode-current density 160mA, it is electrolysed 11 hours at 56 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 1.8:1, add
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 Stress 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：
In the polycondensation reaction low vacuum stage, catalyst and stabilizer Trimethyl phosphite, phosphorous acid are added 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, the staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature control is at 266 DEG C, instead
It is 38 minutes between seasonable；Catalyst is the mixture of ethylene glycol magnesium and 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, continue to vacuumize, reaction pressure is 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) dissolve and wash 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 standby, 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 are 1:8；
(4) solid phase polycondensation：
Resulting polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is brought up to 1.2dL/g, is
The viscous section 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；
Stretching, heat setting process：
GR-1 speed 500m/min；80 DEG C of temperature；
GR-2 speed 500m/min；95 DEG C of temperature；
GR-3 speed 2000m/min；130 DEG C of temperature；
GR-4 speed 3200m/min；230 DEG C of temperature；
GR-5 speed 3500m/min；160 DEG C of temperature；
The speed of winding is 3200m/min.
Obtained high-strength safety belt polyester industrial fiber fracture strength 8.5cN/dtex, extension at break 14.0%, 4.0cN/
The elongation 5.0% of dtex loads；Line density deviation ratio 1.2%, fracture strength CV values 2.3%, extension at break CV values 7.0%,
Network 4, in the case where temperature is 177 DEG C × 10min × 0.05cN/dtex test condition, the dry-hot shrinkage of fiber is 9.5%.
Embodiment 4
A kind of preparation method of high-strength safety belt polyester industrial fiber, 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 negative electrode is stone
Ink；Logical direct current, starting voltage 10V, cathode-current density 150mA, it is electrolysed 12 hours at 50 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid (TPA) is 19:1, add
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 Stress 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
Measure as the 0.03% of terephthalic acid (TPA) weight, catalyst amount is the 0.04% of terephthalic acid (TPA) quality, under conditions of negative pressure
Start polycondensation reaction, the staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature control is in 265 DEG C, reaction time
30 minutes；Catalyst is the mixture of ethylene glycol magnesium and 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, continue to vacuumize, reaction pressure is 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) dissolve and wash 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
Wash, 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 standby, 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 are 1:8；
(4) solid phase polycondensation：
Resulting polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is brought up to 1.2dL/g, is
The viscous section of height；
(5) spinning main technologic parameters：
The temperature of extrusion is 300 DEG C；
The wind-warm syndrome of cooling is 20 DEG C；
Stretching, heat setting process：
GR-1 speed 650m/min；85 DEG C of temperature；
GR-2 speed 460m/min；100 DEG C of temperature；
GR-3 speed 1900m/min；140 DEG C of temperature；
GR-4 speed 3600m/min；220 DEG C of temperature；
GR-5 speed 3600m/min；150 DEG C of temperature；
The speed of winding is 2500m/min.
Obtained high-strength safety belt polyester industrial fiber fracture strength 8.6cN/dtex, extension at break 12.5%, 4.0cN/
The elongation 5.5% of dtex loads；Line density deviation ratio 1.4%, fracture strength CV values 2.3%, extension at break CV values 6.7%,
Network 4, in the case where temperature is 177 DEG C × 10min × 0.05cN/dtex test condition, the dry-hot shrinkage of fiber is 8.0%.
Claims (9)
1. a kind of high-strength safety belt polyester industrial fiber, it is characterized in that：The high-strength safety belt polyester industrial fiber is by polyester through dissolveing and washing away
Obtained, the high-strength safety belt polyester industrial fiber fracture strength >=8.1cN/dtex with spinning after solid-phase tack producing, extension at break is
The elongation 5.5 ± 0.5% of 14.0 ± 1.5%, 4.0cN/dtex load；The polyester is terephthalic acid (TPA) and ethylene glycol through ester
Change and the mixture through catalytic of ethylene glycol magnesium and antimony glycol effect under polycondensation and after granulation be made；
In the section 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；
It is described dissolve and wash away refer to be granulated after section through water and dissolve and wash away agent 120~130 DEG C with 0.2~0.3MPa under the conditions of brew and
Washing.
A kind of 2. high-strength safety belt polyester industrial fiber according to claim 1, it is characterised in that the high-strength safety belt work
Line density deviation ratio≤1.5% of industry silk, fracture strength CV value≤2.5%, extension at break CV value≤7.0%, network 6 ± 2,
Temperature is under 177 DEG C × 10min × 0.05cN/dtex test condition, and the dry-hot shrinkage of fiber is 8.0 ± 1.5%.
3. such as a kind of preparation method of high-strength safety belt polyester industrial fiber according to any one of claims 1 to 2, its feature
It is：Polycondensation is made poly- through esterification and under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol for terephthalic acid (TPA) and ethylene glycol
Ester, then obtain polyester slice through pelletizing；Then viscosified by dissolveing and washing away with solid phase polycondensation；Again through measuring, extruding, cooling down, oiling, drawing
Stretch, thermal finalization and winding, high-strength safety belt polyester industrial fiber is made.
A kind of 4. preparation method of high-strength safety belt polyester industrial fiber according to claim 3, it is characterised in that：
Main technique is：
(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 negative electrode 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
Electrode is taken out after end, obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol is obtained after drying
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, esterification is carried out after being made into uniform sizing material, obtains
Esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress 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, catalyst and stabilizer are added in esterification products, is started under conditions of negative pressure
Polycondensation reaction, the staged pressure are steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature control is at 260~270 DEG C, reaction
Time is 30~50 minutes；The catalyst is the mixture of ethylene glycol magnesium and antimony glycol；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to vacuumize, drop 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) dissolve and wash 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
Wash；
(4) solid phase polycondensation：
Resulting polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is brought up to 1.0~1.2dL/g, i.e.,
For the viscous section of height；
(5) spinning main technologic parameters：
The temperature of the extrusion is 290~310 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
Described stretching, heat setting process：
440~650m/min of GR-1 speed；75~85 DEG C of temperature；
460~680m/min of GR-2 speed；90~100 DEG C of temperature；
1900~2400m/min of GR-3 speed；125~140 DEG C of temperature；
2700~3600m/min of GR-4 speed；220~250 DEG C of temperature；
2500~3600m/min of GR-5 speed；150~170 DEG C of temperature；
The speed of the winding is 2500~3600m/min.
A kind of 5. preparation method of high-strength safety belt polyester industrial fiber according to claim 3 or 4, it is characterised in that institute
The mol ratio for stating ethylene glycol and the terephthalic acid (TPA) is 1.2~2.0:1.
A kind of 6. preparation method of high-strength safety belt polyester industrial fiber according to claim 4, it is characterised in that the second
In the mixture of two magnesium alkoxides and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is
The 0.01%~0.05% of the terephthalic acid (TPA) quality；The stabilizer is selected from triphenyl phosphate, trimethyl phosphate and phosphorous
One kind in sour trimethyl, stabilizing agent dosage are the 0.01%~0.05% of the terephthalic acid (TPA) weight.
A kind of 7. preparation method of high-strength safety belt polyester industrial fiber according to claim 4, it is characterised in that the water
Mass ratio with dissolveing and washing away agent is 100:3~4, polyester slice and water and the ratio for dissolveing and washing away agent, i.e. solid-to-liquid ratio are 1:5~10；Institute
State and dissolve and wash away agent as one kind in ethylene glycol monoethyl ether, propyl cellosolve and ethylene glycol monobutyl ether (EGMBE).
8. the preparation method of a kind of high-strength safety belt polyester industrial fiber according to claim 4, it is characterised in that described to wash
Wash and refer to 70~80 DEG C of 10~15min of hot water wash of polyester slice after brew, then cleaned with cold water, Drying and cooling is standby.
9. the preparation method of a kind of high-strength safety belt polyester industrial fiber according to claim 4, it is characterised in that described anti-
Ether agent is one kind in sodium acetate and calcium acetate, and 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 |
| CN108385187B (en) * | 2017-12-14 | 2020-05-05 | 江苏恒力化纤股份有限公司 | High-strength airplane safety belt and preparation method thereof |
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