CN111074370B - Low-melting-point chinlon thermal fuse and preparation method thereof - Google Patents
Low-melting-point chinlon thermal fuse and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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Abstract
The invention discloses a low-melting-point chinlon thermal fuse and a preparation method thereof, which are characterized in that polybasic acid and polyamine are used as reactants to carry out polymerization reaction, and additives such as a modifier, a palladium catalyst, a defoaming agent and the like are added at the same time, wherein the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine; the modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether; a palladium catalyst bis (dibenzylideneacetone) palladium or tris (dibenzylideneacetone) dipalladium; the defoaming agent is polydimethylsiloxane or ethylene glycol siloxane; the thermal fuse prepared by the invention not only has a lower melting point, but also has higher strength and elongation, and even after long-time ultraviolet irradiation, the thermal fuse still has higher strength and elongation, and can meet the requirements of actual production and life.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a low-melting-point chinlon thermal fuse and a preparation method thereof.
Background
Thermal fuses, also known as low-melting fibers, are one of the most rapidly developing functional fibers in recent years. The thermal fuse is divided into a polyester thermal fuse and a nylon thermal fuse, and the melting point can be controlled between 85 ℃ and 180 ℃ by adjusting the characteristics of the raw materials. The thermal fuse is woven with other fibers into a fabric at normal temperature, then pressure is applied to the fabric in a dry or wet hot state, and the thermal fuse is gradually melted when the temperature is higher than the melting point of the thermal fuse. At this temperature, conventional other fibers remain unchanged and are thus bonded together by the thermal fuse.
The hot melt is used for replacing chemical adhesives such as glue and the like, so that the pollution of volatile matters and dust is avoided, the environment is protected, the toxicity is avoided, and the process flow is saved; in addition, the thermal fuse can also improve the lightness of the material, improve the wear resistance and the like; therefore, the thermal fuse is concerned by various large enterprises in China. Most of the existing thermal fuses on the market have high strength and elongation, but after long-time irradiation of ultraviolet rays, the strength and elongation of the thermal fuses are greatly reduced, so that the application range of the thermal fuses is greatly limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a low-melting-point nylon thermal fuse and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a low-melting-point chinlon hot melt yarn comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
10-20 parts of a modifier;
1-3 parts of a palladium catalyst;
2-4 parts of a dispersing agent;
1-3 parts of an anti-aging agent;
1-2 parts of a defoaming agent;
the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the mass ratio of the polybasic acid to the dodecanedioic acid is 1:4: 2;
the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine in a mass ratio of 3:1: 1.
As a further improvement of the invention, the modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4 '-diaminodiphenyl ether, and the mass ratio of the N-benzyl-4-trifluoromethyl phenyl methylamine to the 4,4' -diaminodiphenyl ether is 1: 1;
the structural formula of the N-benzyl-4-trifluoromethyl phenyl methylamine is shown in the specification
The structural formula of the 4,4' -diaminodiphenyl ether is shown in the specification
As a further improvement of the invention, the preparation method of the N-benzyl-4-trifluoromethyl phenyl methylamine comprises the following steps: under the protection of nitrogen, pouring N-benzyl-4-trifluoromethyl benzamide, pinacol borane and a rare earth catalyst bis (trimethylsilyl) amino yttrium into a reaction vessel filled with a solvent xylene, and stirring and mixing; after being uniformly mixed, the mixture reacts for 24 hours at the temperature of 110 ℃ to prepare N-benzyl-4-trifluoromethyl phenyl methylamine; the reaction formula is as follows:
as a further development of the invention, the palladium catalyst is bis (dibenzylideneacetone) palladium or tris (dibenzylideneacetone) dipalladium.
As a further improvement of the invention, the dispersant is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the two is 1:1: 1.
As a further improvement of the invention, the anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-dione, and the mass ratio of the anti-aging agent to the anti-aging agent is 3:2: 1.
As a further improvement of the invention, the defoaming agent is polydimethylsiloxane or ethylene glycol siloxane.
As a further improvement of the invention, the preparation method of the low-melting-point chinlon thermal fuse comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight part, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 180-210 ℃, the reaction pressure is 0.15-0.25MPa, and a mixture is obtained after the reaction is finished;
step two: adding the mixture and a modifier into a first polymerization kettle, and carrying out polymerization reaction at normal pressure at the reaction temperature of 240 ℃ and 250 ℃ to obtain a polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, wherein the reaction temperature is 270-280 ℃, the reaction pressure is 0.25-0.35MPa, and obtaining a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 50-70 ℃ at a heating speed of 3 ℃/min to dry so that the water content of the low-melting-point polyamide particles is reduced to be below 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting the granules, and drying the granules at 50-70 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0.
As a further improvement of the invention, the temperature of each section of the screw extruder in the fifth step is 130-.
As a further improvement of the invention, the temperature of each section of the screw extruder in the sixth step is 150 ℃ in the first zone 140-.
The invention has the beneficial effects that: the speed and the quality of the polymerization reaction are further improved by taking polybasic acid and polyamine as reactants to carry out the polymerization reaction and adding a modifier, a palladium catalyst, a defoaming agent and other auxiliaries; finally obtaining the thermal fuse with excellent performance. The polybasic acid is selected from the mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the polyamine is selected from the mixture of decanediamine, 12-lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propanediamine; through the polymerization reaction between the three polybasic acid acids and the three polyamines, the polymerization degree and quality can be greatly improved, so that the finally prepared thermal fuse has higher strength and elongation; in addition, the polymerization reaction time of the polybasic acid and the polybasic amine is longer, the polymerization rate is very low under the condition of not adding a catalyst, even if a common catalyst is used, the polymerization rate is still very low, and the requirement of actual production cannot be met.
In addition, in order to further improve the mechanical property of the thermal fuse, the invention adds a modifier which is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether, wherein the N-benzyl-4-trifluoromethyl phenyl methylamine is prepared by the reaction of N-benzyl-4-trifluoromethyl benzamide and pinacol borane; the preparation method has the advantages of easily obtained reactant raw materials, wide sources, low cost, stable property, easiness in storage, simplicity and convenience in operation and strong reaction selectivity, can directly synthesize a target product, does not need to separate an intermediate product, and can obtain the target product only by reacting under normal pressure. N-benzyl-4-trifluoromethyl phenyl methylamine contains imino, phenyl and fluoro groups, 4' -diamino diphenyl ether contains amino and phenyl, and the modifier can further produce polymerization reaction with polybasic acid, so as to further raise the rigidity of chain segment and make the polymer possess relatively high mechanical performance, and the finally-made hot-melt wire possesses relatively high strength and elongation.
In addition, a defoaming agent is added, because the problem of bubbles can occur in the later stage of polymerizing polyamine and polybasic acid into amide, the invention uses the silicone defoaming agent polydimethylsiloxane or ethylene glycol siloxane, and the problem of bubbles can be better solved under the action of the defoaming agent, so that the polymerization rate and the quality are improved; in addition, a dispersing agent and an anti-aging agent are added, wherein the dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and under the combined action of the materials, on one hand, the anti-aging agent can be dispersed more uniformly, the compatibility is improved, and on the other hand, the mechanical property of the hot melt wire can be further improved; the anti-aging agent is a mixture of- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octyloxy benzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the anti-aging agent can greatly improve the ultraviolet resistance of the thermal fuse.
The thermal fuse prepared by the invention has lower melting point, higher strength and elongation, and higher strength and elongation even after long-time ultraviolet irradiation, and can meet the requirements of actual production and life.
Detailed Description
Example 1
Preparation of N-benzyl-4-trifluoromethylphenylmethylamine:
under the protection of nitrogen, sequentially adding N-benzyl-4-trifluoromethyl benzamide (0.5mmol), pinacol borane (4.0mmol) and a rare earth catalyst bis (trimethylsilyl) amino yttrium (0.05mmol) into a reaction vessel filled with 3ml of solvent xylene, and stirring and mixing; after being uniformly mixed, the mixture reacts for 23 hours at the temperature of 120 ℃ to prepare N-benzyl-4-trifluoromethyl phenyl methylamine;
characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.60(d,J＝8.0Hz,2H),7.47(d,J＝8.0Hz,2H),7.38-7.33(m,4H),7.31-7.26(m,1H),3.86(s,2H),3.82(s,2H),1.76(brs,1H).13C NMR(CDCl3125MHz, ppm) delta 144.6,140.1,129.3(q, J-32.3 Hz),128.5,128.3,128.2,127.0,125.2(q, J-3.8 Hz),124.4(q, J-271.9 Hz),53.2,52.6, the structural formula of the N-benzyl-4-trifluoromethylphenyl methylamine is shown in the specification
The reaction formula is as follows:
example 2
A low-melting-point chinlon hot melt yarn comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
15 parts of a modifier;
2 parts of a palladium catalyst;
3 parts of a dispersing agent;
2 parts of an anti-aging agent;
1 part of a defoaming agent;
the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the mass ratio of the polybasic acid to the dodecanedioic acid is 1:4: 2;
the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine in a mass ratio of 3:1: 1.
The modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether, and the mass ratio of the modifier to the modifier is 1: 1;
the structural formula of the 4,4' -diaminodiphenyl ether is shown in the specification
The N-benzyl-4-trifluoromethylphenylmethylamine was prepared as in example 1.
The palladium catalyst is bis (dibenzylidene acetone) palladium;
the dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the dispersing agent to the sodium sulfonate is 1:1: 1.
The anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the mass ratio of the anti-aging agent to the anti-aging agent is 3:2: 1.
The defoaming agent is polydimethylsiloxane.
A preparation method of a low-melting-point chinlon thermal fuse comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 200 ℃, the reaction pressure is 0.20MPa, the reaction time is 5h, and obtaining a mixture after the reaction is finished;
step two: adding the mixture and a modifier into a first polymerization kettle, carrying out polymerization reaction at the normal pressure, wherein the reaction temperature is 245 ℃, the reaction time is 4 hours, and obtaining polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, reacting at 275 ℃, under 0.30MPa for 4h to obtain a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 60 ℃ at a heating speed of 3 ℃/min for drying to reduce the water content of the low-melting-point polyamide particles to be less than 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting the granules, and drying the granules at 60 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0. Wherein the temperature of each section of the screw extruder in the fifth step is 130-.
Wherein the temperature of each section of the screw extruder in the sixth step is 150 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 200 ℃ in the fifth zone and 210 ℃ in the sixth zone.
Example 3
A low-melting-point chinlon hot melt yarn comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
12 parts of a modifier;
1 part of palladium catalyst;
2 parts of a dispersing agent;
1 part of an anti-aging agent;
1 part of a defoaming agent;
the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the mass ratio of the polybasic acid to the dodecanedioic acid is 1:4: 2;
the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine in a mass ratio of 3:1: 1.
The modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether, and the mass ratio of the modifier to the modifier is 1: 1;
the structural formula of the 4,4' -diaminodiphenyl ether is shown in the specification
The N-benzyl-4-trifluoromethylphenylmethylamine was prepared as in example 1.
The palladium catalyst is tris (dibenzylideneacetone) dipalladium.
The dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the dispersing agent to the sodium sulfonate is 1:1: 1.
The anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the mass ratio of the anti-aging agent to the anti-aging agent is 3:2: 1.
The defoaming agent is ethylene glycol siloxane.
A preparation method of a low-melting-point chinlon thermal fuse comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 200 ℃, the reaction pressure is 0.20MPa, the reaction time is 5h, and obtaining a mixture after the reaction is finished;
step two: adding the mixture and a modifier into a first polymerization kettle, carrying out polymerization reaction at the normal pressure, wherein the reaction temperature is 245 ℃, the reaction time is 4 hours, and obtaining polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, reacting at 275 ℃, under 0.30MPa for 4h to obtain a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 60 ℃ at a heating speed of 3 ℃/min for drying to reduce the water content of the low-melting-point polyamide particles to be less than 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting the granules, and drying the granules at 60 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0. Wherein the temperature of each section of the screw extruder in the fifth step is 130-.
Wherein the temperature of each section of the screw extruder in the sixth step is 150 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 200 ℃ in the fifth zone and 210 ℃ in the sixth zone.
Example 4
A low-melting-point chinlon hot melt is characterized in that: the composition comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
18 parts of a modifier;
3 parts of a palladium catalyst;
3 parts of a dispersing agent;
2 parts of an anti-aging agent;
2 parts of a defoaming agent;
the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the mass ratio of the polybasic acid to the dodecanedioic acid is 1:4: 2;
the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine in a mass ratio of 3:1: 1.
The modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether, and the mass ratio of the modifier to the modifier is 1: 1;
the structural formula of the 4,4' -diaminodiphenyl ether is shown in the specification
The N-benzyl-4-trifluoromethylphenylmethylamine was prepared as in example 1.
The palladium catalyst is bis (dibenzylidene acetone) palladium.
The dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the dispersing agent to the sodium sulfonate is 1:1: 1.
The anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the mass ratio of the anti-aging agent to the anti-aging agent is 3:2: 1.
The defoaming agent is ethylene glycol siloxane.
A preparation method of a low-melting-point chinlon thermal fuse comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 200 ℃, the reaction pressure is 0.20MPa, the reaction time is 5h, and obtaining a mixture after the reaction is finished;
step two: adding the mixture and a modifier into a first polymerization kettle, carrying out polymerization reaction at the normal pressure, wherein the reaction temperature is 245 ℃, the reaction time is 4h, and obtaining polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, reacting at 275 ℃, under 0.30MPa for 4h to obtain a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 60 ℃ at a heating speed of 3 ℃/min for drying to reduce the water content of the low-melting-point polyamide particles to be less than 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting the granules, and drying the granules at 60 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0. Wherein the temperature of each section of the screw extruder in the fifth step is 130-.
Wherein the temperature of each section of the screw extruder in the sixth step is 150 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 200 ℃ in the fifth zone and 210 ℃ in the sixth zone.
Comparative example 1
A low-melting-point chinlon hot melt yarn comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
15 parts of a modifier;
2 parts of a palladium catalyst;
3 parts of a dispersing agent;
2 parts of an anti-aging agent;
1 part of a defoaming agent;
the polybasic acid is sebacic acid;
the polyamine is decamethylenediamine.
The modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether, and the mass ratio of the modifier to the modifier is 1: 1;
the structural formula of the 4,4' -diaminodiphenyl ether is shown in the specification
The N-benzyl-4-trifluoromethylphenylmethylamine was prepared as in example 1.
The palladium catalyst is bis (dibenzylidene acetone) palladium;
the dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the dispersing agent to the sodium sulfonate is 1:1: 1.
The anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the mass ratio of the anti-aging agent to the anti-aging agent is 3:2: 1.
The defoaming agent is polydimethylsiloxane.
A preparation method of a low-melting-point chinlon thermal fuse comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 200 ℃, the reaction pressure is 0.20MPa, the reaction time is 5h, and obtaining a mixture after the reaction is finished;
step two: adding the mixture and a modifier into a first polymerization kettle, carrying out polymerization reaction at the normal pressure, wherein the reaction temperature is 245 ℃, the reaction time is 4 hours, and obtaining polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, reacting at 275 ℃, under 0.30MPa for 4h to obtain a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 60 ℃ at a heating speed of 3 ℃/min for drying to reduce the water content of the low-melting-point polyamide particles to be less than 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting into granules, and drying at 60 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0. Wherein the temperature of each section of the screw extruder in the fifth step is 130-140 ℃ in the first zone, 150 ℃ in the second zone, 150-160 ℃ in the third zone, 180 ℃ in the fourth zone, 190 ℃ in the fifth zone and 200 ℃ in the sixth zone.
Wherein the temperature of each section of the screw extruder in the sixth step is 150 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 200 ℃ in the fifth zone and 210 ℃ in the sixth zone.
Comparative example 2
A low-melting-point chinlon hot melt yarn comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
2 parts of a palladium catalyst;
3 parts of a dispersing agent;
2 parts of an anti-aging agent;
1 part of a defoaming agent;
the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the mass ratio of the polybasic acid to the dodecanedioic acid is 1:4: 2;
the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine in a mass ratio of 3:1: 1.
The palladium catalyst is bis (dibenzylidene acetone) palladium;
the dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the dispersing agent to the sodium sulfonate is 1:1: 1.
The anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the mass ratio of the two is 3:2: 1.
The defoaming agent is polydimethylsiloxane.
A preparation method of a low-melting-point chinlon thermal fuse comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 200 ℃, the reaction pressure is 0.20MPa, the reaction time is 5h, and obtaining a mixture after the reaction is finished;
step two: adding the mixture into a first polymerization kettle, carrying out polymerization reaction at the normal pressure, wherein the reaction temperature is 245 ℃, the reaction time is 4 hours, and obtaining polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, reacting at 275 ℃, under 0.30MPa for 4h to obtain a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 60 ℃ at a heating speed of 3 ℃/min for drying to reduce the water content of the low-melting-point polyamide particles to be less than 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting the granules, and drying the granules at 60 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0. Wherein the temperature of each section of the screw extruder in the fifth step is 130-.
Wherein the temperature of each section of the screw extruder in the sixth step is 150 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 200 ℃ in the fifth zone and 210 ℃ in the sixth zone.
Performance testing the samples prepared in examples 2-4 were subjected to melting point testing:
the sample was dried in a vacuum oven at 70 ℃ for 12h and then placed in an aluminum crucible of DSC with N2As a shielding gas, a scan test was performed according to the following procedure: (1) keeping the temperature at 25 ℃ for 1 min; (2) the temperature rise rate is 5 ℃/min at 25-250 ℃; (3) keeping the temperature at 250 ℃ for 2 min; (4) the temperature is 250-25 ℃, and the cooling rate is 5 ℃/min; (5) keeping the temperature at 25 ℃ for 1 min; (6) 25-250 ℃ and the heating rate is 5 ℃/min.
| Test specimen | Melting Point/. degree.C |
| Example 2 | 105 |
| Example 3 | 101 |
| Example 4 | 113 |
As can be seen from the above table, the melting points of the thermal fuses of the present invention are all below 120 ℃, and compared with the melting point of 130-160 ℃ in the market, the nylon thermal fuse prepared by the present invention has a wider application range.
The mechanical properties of the samples obtained in examples 2 to 4 and comparative examples 1 to 2 were measured:
hanging the bottom end of the monofilament with a total clamp to ensure that the T/D of the fiber is approximately equal to 0.15, measuring the fiber number of the monofilament by a vibrating fiber number instrument, taking out the fiber, placing the fiber on a fiber strength and elongation instrument, clamping by an upper clamp and a lower clamp, and then testing various mechanical properties.
| Test specimen | Fineness (dtex) | Maximum intensity (cN) | Elongation (%) |
| Example 2 | 4.31 | 18.6 | 91.26 |
| Example 3 | 4.28 | 17.8 | 90.56 |
| Example 4 | 4.35 | 18.7 | 87.76 |
| Comparative example 1 | 3.59 | 10.4 | 42.13 |
| Comparative example 2 | 3.73 | 12.5 | 58.72 |
As can be seen from the table above, the thermal fuse prepared by the invention has higher strength and elongation, can meet the requirements of actual production and has good application value;
the samples prepared in examples 2-4 and comparative examples 1-2 were irradiated under an ultraviolet lamp for 96 hours, and then subjected to various mechanical property tests.
| Test specimen | Maximum intensity (cN) | Elongation (%) |
| Example 2 | 18.2 | 89.14 |
| Example 3 | 17.5 | 88.75 |
| Example 4 | 18.3 | 85.96 |
| Comparative example 1 | 10.1 | 40.05 |
| Comparative example 2 | 12.0 | 56,37 |
From the above table, after the long-time irradiation of ultraviolet rays, the thermal fuse prepared by the invention still has higher strength and elongation, so that the thermal fuse prepared by the invention has stronger ultraviolet resistance and wider application range.
The samples obtained in examples 2 to 4 were FDY-spun on the same spinning machine at a high speed to obtain the full lap of each sample over a period of 5 days, wherein the spinning speed was 4500 m/min, and the higher the full lap, the less yarn breakage.
| Test specimen | Full-roll rate/%) |
| Example 2 | 95 |
| Example 3 | 94 |
| Example 4 | 94 |
The table shows that the full-package rate of the hot melt wire prepared by the invention is more than 90%, the wire breakage is not easy to occur in the spinning process, the requirements of actual production can be well met, the hot melt wire has strong application value and wider application range;
the samples prepared in examples 2-4 were placed under an ultraviolet lamp for 96 hours and then subjected to a full-curl test, the results of which are shown in the following table:
FDY is rapidly produced on the same spinning machine to obtain the full-package rate of each sample in 5 days, wherein the spinning speed is 4500 m/min,
| test specimen | Full-roll rate/%) |
| Example 2 | 92 |
| Example 3 | 90 |
| Example 4 | 91 |
From the above table, after the long-time irradiation of ultraviolet rays, the thermal fuse prepared by the invention still has low possibility of filament breakage, and the full-package rate of the thermal fuse reaches more than 90 percent, which also shows that the thermal fuse prepared by the invention has stronger ultraviolet resistance and wider application range.
According to the low-melting-point chinlon thermal fuse, polyacid and polyamine are used as reactants to carry out polymerization reaction, and meanwhile, additives such as a modifier, a palladium catalyst and a defoaming agent are added to further improve the speed and quality of the polymerization reaction; finally obtaining the thermal fuse with excellent performance. The polybasic acid is selected from the mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the polyamine is selected from the mixture of decanediamine, 12-lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propanediamine; the polymerization reaction between the three polybasic acid acids and the three polybasic amine is adopted, so that the polymerization degree and the quality can be greatly improved, and the finally prepared hot melt wire has higher strength and elongation; in addition, the polymerization reaction time of the polybasic acid and the polybasic amine is longer, the polymerization rate is very low under the condition of not adding a catalyst, even if a common catalyst is used, the polymerization rate is still very low, and the requirement of actual production cannot be met.
In addition, in order to further improve the mechanical property of the hot melt, the invention adds a modifier which is a mixture of N-benzyl-4-trifluoromethylphenyl methylamine and 4,4 '-diaminodiphenyl ether, wherein the N-benzyl-4-trifluoromethylphenyl methylamine is prepared by reacting N-benzyl-4-trifluoromethylbenzamide with pinacol borane, the N-benzyl-4-trifluoromethylphenyl methylamine contains groups such as imino, phenyl and fluoro, the 4,4' -diaminodiphenyl ether contains amino and phenyl, the modifier can further carry out polymerization reaction with polybasic acid, thereby further improving the rigidity of chain segments, leading the polymer to have larger mechanical property, and finally preparing the hot melt with larger strength and elongation, and the yarn is not easy to break, and the full-package rate is higher.
In addition, a defoaming agent is added, because the problem of bubbles can occur in the later period of polymerizing polyamine and polybasic acid into amide, the invention uses the silicone defoaming agent polydimethylsiloxane or ethylene glycol siloxane, and the problem of foaming can be better solved under the action of the defoaming agent, and the polymerization rate and the quality are improved; in addition, a dispersing agent and an anti-aging agent are added, wherein the dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and under the combined action of the materials, on one hand, the anti-aging agent can be dispersed more uniformly, the compatibility is improved, and on the other hand, the mechanical property of the hot melt wire can be further improved; the anti-aging agent is a mixture of- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octyloxy benzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the anti-aging agent can greatly improve the ultraviolet resistance of the thermal fuse.
The hot melt prepared by the invention has lower melting point, higher strength and elongation and difficult occurrence of filament breakage; even after long-time ultraviolet irradiation, the film still has high strength and elongation, the full-roll rate still reaches more than 90, the requirements of actual production and life can be met, and the application range is wide.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A low-melting-point chinlon hot melt is characterized in that: the composition comprises the following substances in parts by weight:
100 parts of polybasic acid;
80 parts of polyamine;
10-20 parts of a modifier;
1-3 parts of a palladium catalyst;
2-4 parts of a dispersing agent;
1-3 parts of an anti-aging agent;
1-2 parts of a defoaming agent;
the polybasic acid is a mixture of oxalic acid, sebacic acid and dodecanedioic acid, and the mass ratio of the polybasic acid to the dodecanedioic acid is 1:4: 2;
the polyamine is a mixture of decamethylene diamine, 12 lactam and N- (3-aminopropyl) -N-dodecyl-1, 3-propane diamine in a mass ratio of 3:1: 1;
the modifier is a mixture of N-benzyl-4-trifluoromethyl phenyl methylamine and 4,4' -diaminodiphenyl ether, and the mass ratio of the modifier to the modifier is 1: 1;
the structural formula of the N-benzyl-4-trifluoromethyl phenyl methylamine is shown in the specification
；
The structural formula of the 4,4' -diaminodiphenyl ether is shown in the specification
；
The palladium catalyst is bis (dibenzylidene acetone) palladium or tris (dibenzylidene acetone) dipalladium.
2. The low melting point chinlon thermal fuse of claim 1, wherein: the preparation method of the N-benzyl-4-trifluoromethyl phenyl methylamine comprises the following steps: under the protection of nitrogen, pouring N-benzyl-4-trifluoromethyl benzamide, pinacol borane and a rare earth catalyst bis (trimethylsilyl) amino yttrium into a reaction vessel filled with a solvent xylene, and stirring and mixing; after being uniformly mixed, the mixture reacts for 24 hours at the temperature of 110 ℃ to prepare N-benzyl-4-trifluoromethyl phenyl methylamine;
the reaction formula is as follows:
3. the low melting point chinlon thermal fuse of claim 2, wherein: the dispersing agent is a mixture of polyacrylamide, 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate and 7-benzamido-4-hydroxynaphthalene-2-sodium sulfonate, and the mass ratio of the dispersing agent to the sodium sulfonate is 1:1: 1.
4. A low melting point chinlon thermal fuse according to claim 3, characterized in that: the anti-aging agent is a mixture of 2- (2-hydroxy-5-benzyl) benzotriazole, 2-hydroxy-4-N-octoxybenzophenone and 5, 5-dimethyl-1, 3-di (ethylene oxide methyl) imidazolidine-2, 4-diketone, and the mass ratio of the anti-aging agent to the anti-aging agent is 3:2: 1.
5. The low melting point chinlon thermal fuse of claim 4, wherein: the defoaming agent is polydimethylsiloxane or ethylene glycol siloxane.
6. The preparation method of the low-melting-point chinlon thermal fuse as claimed in claim 5, wherein the preparation method comprises the following steps: the method comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight part, adding polybasic acid, polyamine and a palladium catalyst into a mixing kettle, carrying out mixing reaction under the protection of nitrogen, wherein the reaction temperature is 180-;
step two: adding the mixture and a modifier into a first polymerization kettle, carrying out polymerization reaction at normal pressure, wherein the reaction temperature is 240 ℃ and 250 ℃, the reaction time is 3-5h, and obtaining a polyamide oligomer after the reaction is finished;
step three: adding polyamide oligomer and a defoaming agent into a second polymerization kettle, reacting at the temperature of 270-280 ℃, under the pressure of 0.25-0.35MPa for 3-5h to obtain a low-melting-point polyamide melt after the reaction is finished;
step four: discharging the prepared low-melting-point polyamide melt, cooling and dicing to obtain low-melting-point polyamide particles, and heating to 50-70 ℃ at a heating speed of 3 ℃/min to dry so that the water content of the low-melting-point polyamide particles is reduced to be below 0.05 wt%;
step five: uniformly mixing a dispersing agent, an anti-aging agent and low-melting-point polyamide particles in a kneader, putting the mixture into a screw extruder for melt extrusion granulation, cutting the granules, and drying the granules at 50-70 ℃ to reduce the water content to below 0.05 wt% to obtain low-melting-point modified polyamide master batch;
step six: putting the low-melting-point modified polyamide master batch into a screw extruder for melt extrusion, and preparing the polyamide hot melt filament through spinning, cooling and drafting setting, wherein the spinning speed is 1000 m/min; the draft magnification was 4.0.
7. The method for preparing a low-melting-point chinlon thermal fuse according to claim 6, characterized in that: the temperature of each section of the screw extruder in the step five is 140 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 180 ℃ in the fourth zone, 190 ℃ in the fifth zone and 200 ℃ in the sixth zone.
8. The method for preparing a low-melting-point chinlon thermal fuse according to claim 7, characterized in that: in the sixth step, the temperature of each section of the screw extruder is 150 ℃ in the first zone, 150 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 200 ℃ in the fifth zone and 210 ℃ in the sixth zone.
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