A kind of copolyamide industrial yarn and preparation method thereof
Technical field
The present invention relates to a kind of co-polyamide materials, and in particular to a kind of copolyamide industrial yarn and preparation method thereof.
Background technique
Industrial yarn has the characteristics that intensity is high, elongation is low, good stability of the dimension, corrosion-resistant, endurance, ageing-resistant, because
This is widely used in tire cord, canvas, transmission belt, air bag, parachute, rope, safety belt, industrial filter cloth, tent
Equal fields.Currently, industrial yarn is mainly based on polyester, polyamide 6 and polyamide 66, however the fusing point of these materials generally exists
220-260℃。
The Chinese patent of Publication No. CN 105504240A discloses a kind of heat-resistance polyester industrial yarn and its preparation side
Method, the heat resistance high-strength polyester industrial silk are obtained by spinning after the solid-phase tack producing of polyester containing unsaturated double-bond and through ultraviolet light;
The above method introduces unsaturated double-bond in the polyester, and effectively and safely controls its crosslinking after the completion of polyester fiber preparation, hands over
The gel content of fiber greatly increases after connection, thus improve the mechanical property of polyester fiber, heat resistance, chemical-resistance and
Flame retardant property, the melting temperature of industrial yarn reach 275 DEG C or more.However, the above method needs ultraviolet light to make its crosslinking, it is raw
Production. art is relative complex, increases production cost, reduces yield;In addition, the wearability and chemically-resistant of above-mentioned polyester industrial fiber
Performance is lower, is generally lower than polyamide industrial yarn.
Therefore, especially expect a kind of heat-resisting quantity and thermal stability is good, fibre strength is high, wearability and chemical-resistance are good
Industrial yarn.
Summary of the invention
The present invention provides a kind of copolyamide industrial yarn and preparation method thereof, utilizes the copolyamide of preparation method preparation
Industrial yarn has the advantages such as heat-resisting quantity and thermal stability are good, intensity is high, elongation and percent thermal shrinkage are low.
The present invention provides a kind of copolyamide industrial yarn, and the copolyamide industrial yarn is by the polymerizable raw material including monomer
It obtains, the monomer includes 1,5- pentanediamine, the first binary acid and the second binary acid, and first binary acid is terephthaldehyde
Acid.
Copolyamide is the copolymer of two or more binary acid Yu more than one diamines;It is well known to those skilled in the art,
Copolyamide is mingled with since various structures are unordered, destroys the sequential structure regularity of strand, hinders the hydrogen of molecule interchain
Key joint, therefore physical property is different from the polyamide of original homopolymerization, often shows as crystallinity reduction, flexibility increases.This hair
Bright people has found through numerous studies: the polyamide being polymerized relative to 1,5- pentanediamine and other binary acid (the second binary acid),
The copolyamide that 1,5- pentanediamine, terephthalic acid (TPA) (the first binary acid) and other binary acid (the second binary acid) are polymerized
Fusing point significantly improves;The present invention is proposed based on this.
In the present invention, it is to be understood that the second binary acid is different binary acid from the first binary acid;Wherein,
Two binary acid can be aliphatic dicarboxylic acid.
Specifically, second binary acid can selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
Azelaic acid, decanedioic acid, eleven carbon diacids, dodecanedicarboxylic acid, tridecanyldicarboxylic acid, tetradecane diacid, pentadecane binary
In acid, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, maleic acid and Δ 9-1,18 octadecylene binary acid extremely
Few one kind, preferably at least one of adipic acid, decanedioic acid, eleven carbon diacids and dodecanedicarboxylic acid.
In the present invention, it is to be understood that the monomer be include 1,5- pentanediamine, the first binary acid and the second binary
The mix monomer of acid.Further, mass content of 1, the 5- pentanediamine in the monomer is 30-45%, preferably 35-
40%;Mass content of first binary acid in the monomer is 12-40%, preferably 25-40%;Second binary acid is described
Mass content in monomer is 20-45%, preferably 25-45%.
The present invention does not limit the preparation method of 1,5- pentanediamine strictly;Preferably, 1,5- pentanediamine can be by biology
Based raw material is prepared by fermentation method or enzyme transforming process, uses the material of non-petroleum base source (i.e. bio-based source), no
Larger pollution can be generated, is good for the environment.
Further, the monomer further includes ethylenediamine, hexamethylene diamine, cyclohexanediamine, benzene dimethylamine, 6-aminocaprolc acid, 11-
In amino undecanoic acid, 12 amino dodecanoic acid, p-aminomethylbenzoic acid, caprolactam and omega-lauric lactam at least
A kind of (i.e. other monomers).
In the present invention, the raw material can also include additive, and the additive is selected from delustering agent, fire retardant, antioxygen
Agent, heat stabilizer, ultraviolet absorbing agent, infrared absorbent, crystallization nucleating agent, fluorescent whitening agent, antistatic agent and pigment
At least one of;Preferably comprise antioxidant and/or heat stabilizer.Wherein, matter of the additive in the raw material
Measuring content can be 0.001-10wt%.
The present invention does not limit above-mentioned each additive strictly, can use additive commonly used in the art.For example,
Antioxidant can be sodium hypophosphite, antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant MB, antioxidant TPP, resist
At least one of oxygen agent TNP, antioxidant 164, antioxidant DNP and antioxidant 264 etc.;Heat stabilizer can be copper acetate, vinegar
At least one of sour manganese and potassium iodide etc.;Pigment can be at least one of organic pigment and/or inorganic pigment, in which:
Organic pigment can for phthalocyanine is red, phthalocyanine blue, phthalocyanine green, everbright fast red, macromolecular is red, macromolecular is yellow, permanent yellow, permanent violet and
At least one of azophloxine;Inorganic pigment can be in cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red and iron oxide yellow
It is at least one.
Copolyamide industrial yarn of the invention meets following conditions:
The fusing point of the copolyamide industrial yarn is 265-300 DEG C, preferably 269-296 DEG C, further preferably 273-
290 DEG C, be still more preferably 278-285 DEG C;
The dry-hot shrinkage of the copolyamide industrial yarn be 3.0-7.0%, preferably 3.5-6.5%, further preferably
For 4.0-6.0%;
The boiling water shrinkage of the copolyamide industrial yarn be 3.0-6.0%, preferably 3.4-5.6%, further preferably
For 3.8-5.2%.
Further, copolyamide industrial yarn of the invention also meets following conditions:
The fiber number of the copolyamide industrial yarn be 200-3500dtex, preferably 800-3200dtex, further preferably
For 1300-2500dtex;
The breaking strength of the copolyamide industrial yarn be 7.0-10.0cN/dtex, preferably 7.5-9.5cN/dtex, into
One step is preferably 8.0-9.0cN/dtex;
The elongation at break of the copolyamide industrial yarn is 6-24%, preferably 8-20%, further preferably 12-
16%;
The present invention also provides the preparation methods of above-mentioned copolyamide industrial yarn, include the following steps:
1) mixed solution is made in the raw material;
2) mixed solution is polymerize, pelletizing, solid-phase tack producing, thickening copolyamide resin is obtained, by the increasing
Viscous copolyamide resin heating melting obtains thickening copolyamide melt;
3) spinning is carried out to the thickening copolyamide melt, spun filament is made;
4) spun filament cool down, oil, stretched, coiling and molding, obtain the copolyamide industrial yarn.
In the present invention, step 1) can carry out in the following ways:
Mixed solution 1-1) is made in 1,5- pentanediamine, the first binary acid and the second binary acid in proportion;Or
The first solution 1-2) is made in 1,5- pentanediamine and the first binary acid, 1,5- pentanediamine and the second binary acid are made
First solution and the second solution are then mixed into mixed solution by the second solution in proportion.
Wherein, the quality proportioning in mixed solution between 1,5- pentanediamine, the first binary acid and the second binary acid is (30-
45): (12-40): (20-45);The pH of mixed solution is 6.5-9.0;Concentration (each monomer i.e. in mixed solution of mixed solution
Gross mass content) it is 40-80%.
Specifically, step 1-1) may include:
Under protective atmosphere, 1,5- pentanediamine, the first binary acid, the second binary acid and water are mixed in proportion, made
Obtain mixed solution;Wherein, protective atmosphere for example can be condition of nitrogen gas.
When raw material further includes additive, additive can be both added in step 1), can also be in step 2)
It is added.
In the present invention, step 2) can carry out in the following ways:
The mixed solution is polymerize, is dried, copolyamide resin is obtained;Then, copolyamide resin is carried out
It is sliced solid-phase tack producing, obtains thickening copolyamide resin;Copolyamide resin heating melting will be viscosified, thickening copolyamide is obtained
Melt.
Specifically, the polymerization process in step 2) may include:
The mixed solution is heated, the pressure in reaction system is risen into 0.35-6.0Mpa, is vented, pressure maintaining, then
Decompression makes the pressure in reaction system be down to gauge pressure 0-0.2MPa, and being evacuated to vacuum degree is -0.06~-0.01Mpa, is total to
Polyamide melt.
Wherein, the temperature of reaction system can be 240-300 DEG C at the end of the pressure maintaining;Reactant after the decompression
The temperature of system can be 260-320 DEG C;The temperature for vacuumizing rear reaction system can be 270-350 DEG C.
In step 2), the drying can carry out under protective atmosphere, and protective atmosphere for example can be condition of nitrogen gas;It is described
Dry temperature can be 100-140 DEG C;The time of the drying can be 15-30h.
In particular, it is described thickening copolyamide resin relative viscosity be 2.8-4.0, preferably 3.0-3.9, more preferably
3.6-3.8;Moisture content≤800ppm, preferably 200-700ppm, more preferably 300-600ppm, further preferably 400-
500ppm。
In the present invention, step 3) may include:
The thickening copolyamide melt is sprayed by the spinneret of spinning manifold, spun filament is formed, in spinning manifold
Spinneret below be arranged annealing device.
Wherein, the temperature of the spinning manifold is 270-350 DEG C, preferably 280-340 DEG C, further preferably 290-
310 DEG C, be still more preferably 295-305 DEG C;The pressure of the filament spinning component of the spinning manifold is 10-30MPa, preferably
15-25MPa, further preferably 17-23MPa;The slow cooling temperature of the annealing device is 150-240 DEG C, preferably 160-230
DEG C, further preferably 170-220 DEG C, be still more preferably 180-210 DEG C.
Further, the height of the annealing device can be 20-50mm, preferably 23-46mm, further preferably
26-42mm is still more preferably 30-38mm.In addition, the hole count to spinneret does not limit strictly, for example, can for 192f,
288f, 60f, 96f etc..
In the preparation process of copolyamide industrial yarn of the invention, annealing device is added below spinneret, is slowed down
The cooling rate of high-melting point polyamide spun filament, reduces freezing point position, improves subsequent drafting multiple, improve industry
The breaking strength of silk, while melt-blowing hole can be prevented to be quenched to form skin-core structure fiber, it is unfavorable for subsequent drawing-off.
In the present invention, in step 4):
The cooling can be carried out by cross air blasting;Wherein, the wind speed of the cross air blasting is 0.6-1.5m/s, preferably
0.8-1.3m/s;Wind-warm syndrome is 15-28 DEG C, preferably 18-26 DEG C, further preferably 22-24 DEG C;Humidity is 60-80%, preferably
For 65-75%.
The process of the stretching includes that level Four or more stretches, and progress heat is fixed when the third level stretches and the fourth stage stretches
Type, in which: total draw ratio is 3.5-7.0, and draft temperature is 60-150 DEG C, and heat setting temperature is 130-240 DEG C, preferably
180-220℃。
More specifically, the drawing process may include: that spun filament after oiling first passes around godet and feeds first pair
Hot-rolling carries out level-one stretching, then in second pair of hot-rolling and third to heat between first pair of hot-rolling and second pair of hot-rolling
Secondary drawing is carried out between roller, to progress three-level stretching between hot-rolling and the 4th pair of hot-rolling and carries out heat for the first time in the third
Sizing then carries out level Four stretching between the 4th pair of hot-rolling and the 5th pair of hot-rolling and carries out second of thermal finalization.
In addition, the speed of the coiling and molding be 2000-3500m/min, preferably 2200-3300m/min, further it is excellent
It is selected as 2400-3000m/min.
Implementation of the invention, at least has the advantage that
1, copolyamide industrial yarn of the invention has high intensity, low elongation, low thermal shrinkage performance, high temperature resistant and heat steady
The features such as qualitative good, can be widely applied for tire cord, canvas, transmission belt, air bag, parachute, rope, safety
The fields such as band, industrial filter cloth or tent.
2, one of raw materials for production of copolyamide industrial yarn of the invention pentanediamine is made of bioanalysis, for green material
Material, will not cause independent of petroleum resources and to environment serious pollution, therefore can reduce the discharge of carbon dioxide, subtract
The generation of few greenhouse effects.
3, preparation method of the invention adds annealing device below spinneret, and it is nascent to slow down high-melting point polyamide
The cooling rate of silk, reduces freezing point position, improves subsequent drafting multiple, improve the breaking strength of industrial yarn, simultaneously
Melt-blowing hole can be prevented to be quenched to form skin-core structure fiber, be unfavorable for subsequent drawing-off.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The detection method for the performance parameter that various embodiments of the present invention are related to is as follows:
1) relative viscosity:
Using Ubbelohde viscometer sulphate method: copolyamide 0.25 ± 0.0002g of resin sample after precise is dry,
The 50mL concentrated sulfuric acid (96%) is added to be dissolved, concentrated sulfuric acid flow time t0 is measured and recorded in 25 DEG C of constant temperature water baths and is total to
Polyamide sample solution flows through time t.
Relative viscosity calculates formula: relative viscosity=t/t0
T: copolyamide resin sample solution flow time;
T0: concentrated sulfuric acid flow time.
2) fiber number:
The copolyamide industrial yarn that certain length is batched with measuring reel, weighs its weight, and it is long fine to be converted into ten thousand metres
The weight of dimension to get arrive fiber number, unit dtex.
3) breaking strength, elongation at break:
It is measured according to GB/T 14344-2008 method.
4) dry-hot shrinkage:
It is measured according to the regulation of FZ/T 50004, wherein heat treatment temperature is 180 DEG C.
5) boiling water shrinkage:
It is measured with reference to GB/6505-2008 " chemical fiber long filament heat shrinkage test method ", specifically: take one section
Copolyamide industrial yarn, 0.05 ± 0.005cN/dtex of pre-tension use yarn after in-between both ends 50.00cm is marked
Cloth is wrapped, and is put into boiling in boiling water and is boiled 30min, then dries, measure the length between two mark points, be calculated using the following equation boiling water
Shrinking percentage:
Boiling water shrinkage=[(length after initial length-contraction)/initial length] × 100%.
Embodiment 1
The copolyamide industrial yarn of the present embodiment is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine, terephthalic acid (TPA) and adipic acid, the mass content of 1,5- pentanediamine is 40% in monomer, terephthaldehyde
The mass content of acid is 25%, and the mass content of adipic acid is 35%;Additive is antioxidant 1010.
The preparation method of the copolyamide industrial yarn of the present embodiment, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.32kg 1,5- pentanediamine, 0.817kg terephthalic acid (TPA), 1.16kg adipic acid, 3.3kg
Water and antioxidant 1010 are uniformly mixed in polymeric kettle, are used a small amount of pentanediamine to adjust pH value as 8.0, are obtained mixed solution;Its
In, the total concentration of monomer is 50wt% in mixed solution, and the content of antioxidant 1010 is 50ppm.
2, copolyamide melt is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 1.8Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.06Mpa, obtains copolyamide melt;Its
In, the temperature of reaction system is 265 DEG C at the end of pressure maintaining, and the temperature of reaction system is 295 DEG C after decompression, anti-after vacuumizing
The temperature for answering system is 300 DEG C.
Slice solid-phase tack producing is carried out to copolyamide resin made from pelletizing after above-mentioned polymerization, obtains thickening copolyamide tree
Rouge;It is detected, the relative viscosity of thickening copolyamide resin is 3.0, moisture content 380ppm.
By above-mentioned thickening copolyamide resin heating melting, thickening copolyamide melt is obtained.
3, spun filament is prepared
Above-mentioned thickening copolyamide melt is sprayed by the spinneret of spinning manifold, spun filament is formed, in spinning manifold
Spinneret below be arranged annealing device;Wherein, the hole count of spinneret is 192f, and the temperature of spinning manifold is 325 DEG C, spinning group
The pressure of part is 15MPa, and it is highly 35mm that the temperature of annealing device, which is 210 DEG C,.
4, copolyamide industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, copolyamide industrial yarn is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 0.7m/s, and the wind-warm syndrome of cross air blasting is 22 DEG C, and the humidity of cross air blasting is 62%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3000m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.4, draft temperature 90
DEG C, the temperature of thermal finalization is 200 DEG C.
The performance test results of the copolyamide industrial yarn of preparation are shown in Table 1.
Embodiment 2
The copolyamide industrial yarn of the present embodiment is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine, terephthalic acid (TPA) and adipic acid, the mass content of 1,5- pentanediamine is 40% in monomer, terephthaldehyde
The mass content of acid is 31%, and the mass content of adipic acid is 29%;Additive is copper acetate.
The preparation method of the copolyamide industrial yarn of the present embodiment, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.31kg 1,5- pentanediamine, 1.02kg terephthalic acid (TPA), 0.971kg adipic acid, 3.3kg
Water and copper acetate are uniformly mixed in polymeric kettle, are used a small amount of pentanediamine to adjust pH value as 8.0, are obtained mixed solution;Wherein, it mixes
The total concentration for closing monomer in solution is 50wt%, and the content of copper acetate is 0.5%.
2, copolyamide melt is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 2.0Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.08Mpa, obtains copolyamide melt;Its
In, the temperature of reaction system is 280 DEG C at the end of pressure maintaining, and the temperature of reaction system is 300 DEG C after decompression, anti-after vacuumizing
The temperature for answering system is 310 DEG C.
Slice solid-phase tack producing is carried out to copolyamide resin made from pelletizing after above-mentioned polymerization, obtains thickening copolyamide tree
Rouge;It is detected, the relative viscosity of thickening copolyamide resin is 3.1, moisture content 320ppm.
By above-mentioned thickening copolyamide resin heating melting, thickening copolyamide melt is obtained.
3, spun filament is prepared
Above-mentioned thickening copolyamide melt is sprayed by the spinneret of spinning manifold, spun filament is formed, in spinning manifold
Spinneret below be arranged annealing device;Wherein, the hole count of spinneret is 60f, and the temperature of spinning manifold is 340 DEG C, spinning group
The pressure of part is 14MPa, and it is highly 25mm that the temperature of annealing device, which is 190 DEG C,.
4, copolyamide industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, copolyamide industrial yarn is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 0.9m/s, and the wind-warm syndrome of cross air blasting is 26 DEG C, and the humidity of cross air blasting is 64%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3100m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.8, draft temperature 95
DEG C, the temperature of thermal finalization is 215 DEG C.
The performance test results of the copolyamide industrial yarn of preparation are shown in Table 1.
Embodiment 3
The copolyamide industrial yarn of the present embodiment is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine, terephthalic acid (TPA) and dodecanedicarboxylic acid, the mass content of 1,5- pentanediamine is 35% in monomer, right
The mass content of phthalic acid is 37%, and the mass content of dodecanedicarboxylic acid is 28%;Additive is sodium hypophosphite.
The preparation method of the copolyamide industrial yarn of the present embodiment, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.4kg1,5- pentanediamine, 1.47kg terephthalic acid (TPA), 1.09kg dodecanedicarboxylic acid,
2.64kg water and sodium hypophosphite are uniformly mixed in polymeric kettle, are used a small amount of pentanediamine to adjust pH value as 7.8, are obtained mixing molten
Liquid;Wherein, the total concentration of monomer is 60wt% in mixed solution, and the content of sodium hypophosphite is 80ppm.
2, copolyamide melt is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 2.0Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.08Mpa, obtains copolyamide melt;Its
In, the temperature of reaction system is 285 DEG C at the end of pressure maintaining, and the temperature of reaction system is 305 DEG C after decompression, anti-after vacuumizing
The temperature for answering system is 315 DEG C.
Slice solid-phase tack producing is carried out to copolyamide resin made from pelletizing after above-mentioned polymerization, obtains thickening copolyamide tree
Rouge;It is detected, the relative viscosity of thickening copolyamide resin is 3.3, moisture content 300ppm.
By above-mentioned thickening copolyamide resin heating melting, thickening copolyamide melt is obtained.
3, spun filament is prepared
Above-mentioned thickening copolyamide melt is sprayed by the spinneret of spinning manifold, spun filament is formed, in spinning manifold
Spinneret below be arranged annealing device;Wherein, the hole count of spinneret is 96f, and the temperature of spinning manifold is 330 DEG C, spinning group
The pressure of part is 18MPa, and it is highly 30mm that the temperature of annealing device, which is 180 DEG C,.
4, copolyamide industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, copolyamide industrial yarn is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 0.9m/s, and the wind-warm syndrome of cross air blasting is 25 DEG C, and the humidity of cross air blasting is 70%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3300m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.0, draft temperature 75
DEG C, the temperature of thermal finalization is 230 DEG C.
The performance test results of the copolyamide industrial yarn of preparation are shown in Table 1.
Embodiment 4
The copolyamide industrial yarn of the present embodiment is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine, terephthalic acid (TPA) and last of the ten Heavenly stems binary acid, the mass content of 1,5- pentanediamine is 36% in monomer, to benzene two
The mass content of formic acid is 38%, and the mass content of last of the ten Heavenly stems binary acid is 26%;Additive is sodium hypophosphite.
The preparation method of the copolyamide industrial yarn of the present embodiment, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.4kg1,5- pentanediamine, 1.47kg terephthalic acid (TPA), 0.983kg last of the ten Heavenly stems binary acid, 2.8kg
Water and antioxidant 1010 are uniformly mixed in polymeric kettle, are used pentanediamine to adjust pH value as 8.2, are obtained mixed solution;Wherein, it mixes
The total concentration for closing monomer in solution is 58wt%, and the content of sodium hypophosphite is 100ppm.
2, copolyamide melt is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 2.1Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.08Mpa, obtains copolyamide melt;Its
In, the temperature of reaction system is 288 DEG C at the end of pressure maintaining, and the temperature of reaction system is 305 DEG C after decompression, anti-after vacuumizing
The temperature for answering system is 320 DEG C.
Slice solid-phase tack producing is carried out to copolyamide resin made from pelletizing after above-mentioned polymerization, obtains thickening copolyamide tree
Rouge;It is detected, the relative viscosity of thickening copolyamide resin is 2.8, moisture content 400ppm.
By above-mentioned thickening copolyamide resin heating melting, thickening copolyamide melt is obtained.
3, spun filament is prepared
Above-mentioned thickening copolyamide melt is sprayed by the spinneret of spinning manifold, spun filament is formed, in spinning manifold
Spinneret below be arranged annealing device;Wherein, the hole count of spinneret is 96f, and the temperature of spinning manifold is 335 DEG C, spinning group
The pressure of part is 20MPa, and it is highly 50mm that the temperature of annealing device, which is 170 DEG C,.
4, copolyamide industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, copolyamide industrial yarn is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 1.1m/s, and the wind-warm syndrome of cross air blasting is 23 DEG C, and the humidity of cross air blasting is 68%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3400m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.5, draft temperature 85
DEG C, the temperature of thermal finalization is 220 DEG C.
The performance test results of the copolyamide industrial yarn of preparation are shown in Table 1.
Embodiment 5
The copolyamide industrial yarn of the present embodiment is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine, terephthalic acid (TPA) and adipic acid, the mass content of 1,5- pentanediamine is 40% in monomer, terephthaldehyde
The mass content of acid is 19%, and the mass content of adipic acid is 41%;Additive is sodium hypophosphite.
The preparation method of the copolyamide industrial yarn of the present embodiment, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.54kg 1,5- pentanediamine, 0.711kg terephthalic acid (TPA), 1.58kg adipic acid,
2.77kg water and sodium hypophosphite are uniformly mixed in polymeric kettle, are used pentanediamine to adjust pH value as 8.3, are obtained mixed solution;
Wherein, the total concentration of monomer is 58wt% in mixed solution, and the content of sodium hypophosphite is 100ppm.
2, copolyamide melt is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 1.7Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.06Mpa, obtains copolyamide melt;Its
In, the temperature of reaction system is 260 DEG C at the end of pressure maintaining, and the temperature of reaction system is 275 DEG C after decompression, anti-after vacuumizing
The temperature for answering system is 285 DEG C.
Slice solid-phase tack producing is carried out to copolyamide resin made from pelletizing after above-mentioned polymerization, obtains thickening copolyamide tree
Rouge;It is detected, the relative viscosity of thickening copolyamide resin is 3.2, moisture content 400ppm.
By above-mentioned thickening copolyamide resin heating melting, thickening copolyamide melt is obtained.
3, spun filament is prepared
Above-mentioned thickening copolyamide melt is sprayed by the spinneret of spinning manifold, spun filament is formed, in spinning manifold
Spinneret below be arranged annealing device;Wherein, the hole count of spinneret is 288f, and the temperature of spinning manifold is 320 DEG C, spinning group
The pressure of part is 20MPa, and it is highly 40mm that the temperature of annealing device, which is 230 DEG C,.
4, copolyamide industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, the copolyamide industrial yarn is obtained.Wherein,
It is cooled down using cross air blasting, the wind speed of cross air blasting is 0.8m/s, and the wind-warm syndrome of cross air blasting is 24 DEG C, and the humidity of cross air blasting is
67%;Drawing process is level Four stretching, and the speed of coiling and molding is 3400m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.5, draft temperature 70
DEG C, the temperature of thermal finalization is 220 DEG C.
The performance test results of the copolyamide industrial yarn of preparation are shown in Table 1.
Reference examples 1
Using polyamide 6 industrial yarn as control, preparation method includes the following steps: this reference examples
1, polyamide 6 melt is prepared
Polyamide 6 is dried in vacuum drum drying machine, drying temperature is 120 DEG C, and drying time is
20h;Then, dry polyamide 6 is heated to molten condition, obtains polyamide 6 melt, relative viscosity 3.0 contains
Water rate is 500ppm.
2, spun filament is prepared
Above-mentioned polyamide 6 melt is sprayed through the spinneret of spinning manifold, forms spun filament;Wherein, the hole count of spinneret
For 192f, the temperature of spinning manifold is 300 DEG C, and the pressure of filament spinning component is 12MPa.
3, polyamide 6 industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, polyamide 6 industrial yarn is obtained.Wherein, using side
Blowing is cooled down, and the wind speed of cross air blasting is 0.7m/s, and the wind-warm syndrome of cross air blasting is 22 DEG C, and the humidity of cross air blasting is 73%;It stretches
Process is level Four stretching, and the speed of coiling and molding is 3000m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.5, draft temperature 75
DEG C, the temperature of thermal finalization is 230 DEG C.
The performance test results of the polyamide 6 industrial yarn of preparation are shown in Table 1.
Reference examples 2
Using polyamide 66 industrial yarn as control, preparation method includes the following steps: this reference examples
1, polyamide 66 melt is prepared
Polyamide 66 resin is dried in vacuum drum drying machine, drying temperature is 120 DEG C, and drying time is
20h;Then, dry polyamide 66 resin is heated to molten condition, obtains polyamide 6 melt, relative viscosity 3.1,
Moisture content is 400ppm.
2, spun filament is prepared
Above-mentioned polyamide 66 melt is sprayed through the spinneret of spinning manifold, forms spun filament;Wherein, the hole count of spinneret
For 190f, the temperature of spinning manifold is 310 DEG C, and the pressure of filament spinning component is 14MPa.
3, polyamide 66 industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, polyamide 66 industrial yarn is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 0.8m/s, and the wind-warm syndrome of cross air blasting is 22 DEG C, and the humidity of cross air blasting is 75%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3200m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.0, draft temperature 70
DEG C, the temperature of thermal finalization is 200 DEG C.
The performance test results of the polyamide 66 industrial yarn of preparation are shown in Table 1.
Reference examples 3
56 industrial yarn of polyamide of this reference examples is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine and adipic acid, the mass content of 1,5- pentanediamine is 41.1% in monomer, the mass content of adipic acid
It is 58.9%;Additive is antioxidant 1010.
The preparation method of 56 industrial yarn of polyamide of this reference examples, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.48kg 1,5- pentanediamine, 2.12kg adipic acid, 2.4kg water and 0.18g antioxidant
1010 are uniformly mixed in polymeric kettle, use pentanediamine to adjust pH as 8.0, obtain mixed solution;Wherein, monomer in mixed solution
Total concentration be 60wt%, the content of antioxidant 1010 is 50ppm.
2,56 melt of polyamide is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 1.7Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.06Mpa, obtains 56 melt of polyamide;Its
In, the temperature of reaction system is 245 DEG C at the end of pressure maintaining, and the temperature of reaction system is 262 DEG C after decompression, anti-after vacuumizing
The temperature for answering system is 280 DEG C.
Slice solid-phase tack producing is carried out to above-mentioned 56 resin of polyamide, obtains thickening 56 resin of polyamide;It is detected, thickening is poly-
The relative viscosity of 56 resin of amide is 3.2, moisture content 300ppm.
By above-mentioned 56 resin heating melting of thickening polyamide, thickening 56 melt of polyamide is obtained.
3, spun filament is prepared
Above-mentioned 56 melt of thickening polyamide is sprayed through the spinneret of spinning manifold, forms spun filament;Wherein, spinneret
Hole count is 192f, and the temperature of spinning manifold is 325 DEG C, and the pressure of filament spinning component is 15MPa.
4,56 industrial yarn of polyamide is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, 56 industrial yarn of polyamide is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 0.7m/s, and the wind-warm syndrome of cross air blasting is 22 DEG C, and the humidity of cross air blasting is 62%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3000m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.4, draft temperature 90
DEG C, the temperature of thermal finalization is 200 DEG C.
The performance test results of 56 industrial yarn of polyamide of preparation are shown in Table 1.
Reference examples 4
The copolyamide industrial yarn of this reference examples is obtained by the polymerizable raw material including monomer and additive, wherein monomer
It is made of 1,5- pentanediamine, dodecanedicarboxylic acid and adipic acid, the mass content of 1,5- pentanediamine is 37.7%, 12 in monomer
The mass content of carbon dicarboxylic acid is 23.3%, and the mass content of adipic acid is 39%;Additive is antioxidant 1010.
The preparation method of the copolyamide industrial yarn of this reference examples, includes the following steps:
1, mixed solution is prepared
Under a nitrogen atmosphere, by 1.32kg 1,5- pentanediamine, 0.817kg dodecanedicarboxylic acid, 1.37kg adipic acid,
2.5kg water and antioxidant 1010 are uniformly mixed in polymeric kettle, are used pentanediamine to adjust pH value as 8.0, are obtained mixed solution;Its
In, the total concentration of monomer is 50wt% in mixed solution, and the content of antioxidant 1010 is 50ppm.
2, copolyamide melt is prepared
Above-mentioned mixed solution is heated, the pressure in reaction system is risen into 1.5Mpa, is vented, pressure maintaining, then be depressured
The pressure in reaction system is set to be down to gauge pressure 0MPa, being evacuated to vacuum degree is -0.6Mpa, obtains copolyamide melt;Wherein,
The temperature of reaction system is 220 DEG C at the end of pressure maintaining, and the temperature of reaction system is 245 DEG C after decompression, is reacted after vacuumizing
The temperature of system is 260 DEG C.
Slice solid-phase tack producing is carried out to copolyamide resin made from pelletizing after above-mentioned polymerization, obtains thickening copolyamide tree
Rouge;It is detected, the relative viscosity of thickening copolyamide resin is 3.1, moisture content 380ppm.
By above-mentioned thickening copolyamide resin heating melting, thickening copolyamide melt is obtained.
3, spun filament is prepared
Above-mentioned thickening copolyamide melt is sprayed through the spinneret of spinning manifold, forms spun filament;Wherein, spinneret
Hole count is 192f, and the temperature of spinning manifold is 260 DEG C, and the pressure of filament spinning component is 15MPa.
4, copolyamide industrial yarn is prepared
Above-mentioned spun filament cool down, oil, is stretched, coiling and molding, copolyamide industrial yarn is obtained.Wherein, it uses
Cross air blasting is cooled down, and the wind speed of cross air blasting is 0.7m/s, and the wind-warm syndrome of cross air blasting is 22 DEG C, and the humidity of cross air blasting is 62%;It draws
Journey is extended through as level Four stretching, the speed of coiling and molding is 3000m/min.
Drawing process are as follows: the spun filament after oiling first pass around godet feed first pair of hot-rolling, first pair of hot-rolling with
Level-one stretching is carried out between second pair of hot-rolling, then in second pair of hot-rolling and third to carrying out secondary drawing between hot-rolling, then
Third between hot-rolling and the 4th pair of hot-rolling to carrying out three-level stretching and carrying out first time thermal finalization, then in the 4th pair of hot-rolling and the
Level Four stretching is carried out between five pairs of hot-rollings and carries out second of thermal finalization;Wherein, total draw ratio is 4.4, draft temperature 90
DEG C, the temperature of thermal finalization is 200 DEG C.
The performance test results of the copolyamide industrial yarn of preparation are shown in Table 1.
The performance test results of the industrial yarn of each embodiment of table 1 and reference examples
As shown in Table 1:
1, the breaking strength of the copolyamide industrial yarn of various embodiments of the present invention is 8.4cN/dtex or more, elongation at break
For 16% hereinafter, dry-hot shrinkage is 7.0% hereinafter, boiling water shrinkage is 5.8% hereinafter, fusing point reaches 269 DEG C or more, copolymerization
Amide industrial yarn has the advantages such as high intensity, low elongation, low thermal shrinkage performance, high temperature resistant and good thermal stability.
2, the fusing point of traditional polyamide 6 and polyamide 66 industrial yarn be 260 DEG C hereinafter, breaking strength be 8.2cN/dtex with
Under, dry-hot shrinkage is 7.3% or more, and boiling water shrinkage is 7.5% or more, and intensity, heat-resisting quantity and thermal stability are not so good as
Copolyamide industrial yarn of the invention (referring to reference examples 1 and reference examples 2).
3, the fusing point of 56 industrial yarn of polyamide prepared using 1,5- pentanediamine and adipic acid is only 254 DEG C, breaking strength
For 8.0cN/dtex, dry-hot shrinkage 7.5%, boiling water shrinkage 8.0%, intensity, heat-resisting quantity and thermal stability are not
Such as copolyamide industrial yarn of the invention (referring to reference examples 3).
4, it is only using the fusing point of the copolyamide industrial yarn of 1,5- pentanediamine, dodecanedicarboxylic acid and adipic acid preparation
240 DEG C, breaking strength 8.3cN/dtex, dry-hot shrinkage 7.2%, boiling water shrinkage 7.6%, intensity, heat-resisting quantity
And thermal stability is not so good as copolyamide industrial yarn of the invention (referring to reference examples 4).
The above results explanation:
Other binary acid (such as adipic acid, dodecanedicarboxylic acid) with 1,5- pentanediamine and in addition to terephthalic acid (TPA) are poly-
That there are fusing points is low for polyamide or copolyamide made of conjunction, intensity, the defects of heat-resisting quantity and thermal stability are bad;However, with
The copolyamide industrial yarn that 1,5- pentanediamine, terephthalic acid (TPA) and other binary acid are polymerized can overcome drawbacks described above, from
And fusing point, mechanical property, high temperature resistance and the thermal stability of material are significantly improved, be conducive to the wide of copolyamide industrial yarn
General application.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations;To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement;And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.