Heat stabilizer, industrial yarn heat-resistant agent master batch, preparation method of industrial yarn heat-resistant agent master batch and spinning method

Abstract

The invention discloses a heat stabilizer, an industrial yarn heat-resistant agent master batch and a preparation method thereof, and a spinning method for modifying polyamide by using the master batch. The heat stabilizer comprises the following components in parts by mass: 10-20 parts of an organic hybrid copper compound containing an amido bond or an amido group or / and 5-15 parts of an inorganic copper compound, and 25-50 parts of a hindered amine light stabilizer containing an amido bond or an amido group, the thermal decomposition temperature of the phosphite ester antioxidant is higher than the spinning processing temperature; the hindered phenol antioxidant is 10-20 parts by mass; the components are compounded in proportion. The heat stability of the polyamide fiber can be improved, the heat resistance and breaking strength retention rate of the fiber are improved, the fiber strength is improved, the spinning performance is improved by improving the stability of the polyamide melt, the end breakage rate in the spinning process is reduced, and the melt pressure is more stable.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical materials and relates to a heat resistant agent masterbatch, in particular to a heat stabilizer, an industrial yarn heat resistant agent masterbatch and a preparation method and a spinning method thereof. Background Art

[0002] The thermal stability modification of polyamide is very common in the field of engineering plastics, and is mainly used in the fields of automobiles, aerospace, chemicals, machinery, electronics and electrical appliances. The modification method is mainly to add heat stabilizers and glass fibers during the melt processing to improve the thermal stability of the product, and additives are usually added during the modification process for granulation. In the existing process, the heat stabilizer used is usually an organic antioxidant (such as hindered phenol, hindered amine, etc.) compounded with inorganic filler (such as glass fiber, minerals, metal salts, etc.); although the heat stabilizer additive used has a significant effect on engineering plastics, it cannot be used for spinning due to poor dispersibility. There is also the addition of phase volume to improve the compatibility of the heat stabilizer with the modified matrix. This method can basically meet the needs for plastics, but for spinning, due to the long melt residence time, the inorganic heat resistant agent is easily precipitated, resulting in instability of the melt and processing equipment, greatly reducing the fiber performance; in addition, there is also the addition of trace amounts of water-soluble inorganic copper salts during the nylon polymerization process to maintain relatively good dispersibility while improving thermal stability, but the stabilizer added in the polymerization process is greatly reduced during the long high-temperature polymerization process and the long residence time of the melt in the subsequent spinning. Industrial yarns have very high requirements for the efficiency of heat resistant agents, the uniformity of raw materials and the melt stability, otherwise they will not be produced normally due to the high breakage and hairy yarn rate during the spinning process.

[0003] With the increasing requirements of polyamide industrial yarns in recent years, whether it is automobile tire cord yarn or industrial rope, etc., higher requirements have been put forward for the heat resistance of polyamide industrial yarns. At present, the polyamide thermal stability modification method in the field of engineering plastics cannot meet the requirements of spinning performance and heat resistance of polyamide industrial yarns. The commonly used method in the field of industrial yarns is to add a small amount of inorganic copper salt complex (Cu I / KI or Cu / KBr or CuSO4 / KI, etc.) during the polymerization stage of polyamide to achieve excellent dispersibility; but only trace amounts can be added to balance the spinnability of the polymer and the heat resistance of the fiber; in addition, the effect of the heat stabilizer added in the polymerization is greatly reduced after a long period of high temperature polymerization, so the heat resistance of the final obtained fiber is poor.

[0004] In view of this, the present invention designs a new heat-resistant agent masterbatch to overcome at least part of the above-mentioned defects of the existing heat-resistant agent masterbatch. Summary of the invention

[0005] The invention provides a heat stabilizer, an industrial yarn heat resistant agent masterbatch and a preparation method and a spinning method thereof, which can improve the thermal stability of polyamide fibers, improve the heat resistant strength and breaking strength retention rate of the fibers, improve the fiber strength and spinning performance, and reduce the breakage rate in the spinning process.

[0006] To solve the above technical problem, according to one aspect of the present invention, the following technical solution is adopted:

[0007] A heat stabilizer comprises: 10-20 parts by weight of a copper compound or / and 5-15 parts by weight of an inorganic copper compound, 25-50 parts by weight of a hindered amine light stabilizer, 10-25 parts by weight of a phosphite antioxidant and 10-20 parts by weight of a hindered phenol antioxidant; the above components are compounded according to proportion.

[0008] As an embodiment of the present invention, the copper compound is an organic hybrid copper compound containing an amide bond or an amine group; the hindered amine light stabilizer is a hindered amine light stabilizer containing an amide bond or an amine group; the phosphite antioxidant is a phosphite antioxidant having a thermal decomposition temperature greater than the spinning temperature of the modified matrix;

[0009] That is, the heat stabilizer comprises: 10-20 parts by weight of an organic hybrid copper compound containing an amide bond or an amine group or / and 5-15 parts by weight of an inorganic copper compound, 25-50 parts by weight of a hindered amine light stabilizer containing an amide bond or an amine group, 10-25 parts by weight of a phosphite antioxidant whose thermal decomposition temperature is greater than the spinning temperature of the modified matrix, and 10-20 parts by weight of a hindered phenol antioxidant; the above components are compounded according to proportion.

[0010] The above organic copper contains amide bonds or amine groups, which can not only melt the cuprous ions and make the charge state of the cuprous ions more stable, but also the organic part of the amide bonds or amine groups is very compatible with the polyamide matrix, so that the heat stabilizer is completely compatible with the polyamide and well dispersed, and the melt remains uniform and stable during the spinning process. The above-mentioned phosphite has a thermal decomposition temperature greater than the spinning temperature of the polyamide matrix, so that the antioxidant effect of the phosphite can play a role not only in the processing process, but also in the subsequent long-term use, so the heat resistance effect is better.

[0011] As an embodiment of the present invention, the heat stabilizer further comprises 20-30 parts by mass of potassium halide or sodium halide.

[0012] As an embodiment of the present invention, the hindered amine light stabilizer containing an amide bond or an amine group is at least one of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxylate, poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]1,3,5,-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexanediyl-[(2,2,6,6-tetramethylpiperidinyl)-imino]}, 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reactants;

[0013] The chemical formula of the reactants of 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine is as follows:

[0014]

[0015] As an embodiment of the present invention, the phosphite antioxidant is at least one of 3,5-di-tert-butyl-4-hydroxybenzoic acid octyl ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol-diphosphite.

[0016] As an embodiment of the present invention, the hindered phenol antioxidant is at least one of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzoamide) and bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane.

[0017] According to another aspect of the present invention, the following technical solution is adopted: an industrial yarn heat resistant agent masterbatch, the industrial yarn heat resistant agent masterbatch comprising:

[0018] 30-80 parts by weight of polyamide resin;

[0019] 10-40 parts by weight of the above-mentioned heat stabilizer;

[0020] 2-4 parts by weight of processing aid.

[0021] According to another aspect of the present invention, the following technical solution is adopted: a method for preparing the above-mentioned industrial yarn heat-resistant agent masterbatch, the preparation method comprising:

[0022] Step S1, grinding the polyamide resin into a powder of 20-200 mesh;

[0023] Step S2, drying all the composition raw materials used to prepare the industrial silk heat-resistant agent masterbatch;

[0024] Step S3: uniformly mix all the composition raw materials according to the proportion, and extrude and granulate them using an extruder.

[0025] As an embodiment of the present invention, in step S1, the polyamide resin has a high molecular weight polyamide resin with a relative viscosity of 3.0-4.0;

[0026] The polyamide resin includes at least one of conventional polyamide, bio-based polyamide, special polyamide resin, copolymerized polyamide resin, and blended polyamide resin;

[0027] In step S2, after the composition raw material is dried, the moisture content is 200-2000 ppm.

[0028] As an embodiment of the present invention, in step S3, extrusion granulation is performed using a twin-screw extruder;

[0029] The melt viscosity will increase significantly during the blending and granulation process of the composition, resulting in unsmooth strand cutting and pelletizing. It is necessary to appropriately improve the existing twin-screw and change it to an underwater pelletizing method for pelletizing.

[0030] According to another aspect of the present invention, the following technical solution is adopted: a spinning method using the above-mentioned industrial yarn heat-resistant agent masterbatch, the spinning method comprising:

[0031] The industrial yarn heat resistant agent masterbatch is first dried at 80-120°C, with a vacuum degree of less than 20Pa, and continuous drying for a set time;

[0032] The masterbatch is quantitatively and evenly mixed with the main material above the spinning machine screw by a high-precision mass mixer and then enters the buffer hopper, and then fed into the screw. The mixed raw materials are melted and extruded through a single screw;

[0033] The mixer and buffer hopper are protected by nitrogen flow;

[0034] The addition amount of the heat-resistant agent masterbatch does not exceed 5%, and the polyamide resin in the masterbatch is selected to be the same as the main spinning material for modification;

[0035] The melt melted in the screw is quantitatively transported to the spinneret by a metering pump. After post-heating, side-blowing cooling, and oiling of the nozzle, it enters the drafting rollers. After being drafted and heat-set by multiple pairs of rollers, it is continuously wound into the finished yarn.

[0036] The beneficial effects of the present invention are as follows: the heat stabilizer, industrial yarn heat resistant agent masterbatch, preparation method thereof, and spinning method proposed in the present invention can improve the thermal stability of polyamide fibers, improve the heat resistance strength and breaking strength retention rate of fibers (such as nylon 6, nylon 66 or nylon 56 fibers, etc.) (from the conventional 90-92% to more than 95%), improve the fiber strength (the strength is slightly improved) and spinning performance, reduce the breakage rate in the spinning process (can be reduced by 5%), and make the melt pressure more stable.

[0037] Improving the thermal stability of polyamide fibers can increase the heat resistance and breaking strength retention of nylon 6, nylon 66 or nylon 56 fibers, as well as other nylon fibers, from the conventional 90-92% to more than 95%, and slightly increase the strength. At the same time, it can effectively improve the spinning performance, reduce the breakage rate in the spinning process by 5%, and make the melt pressure more stable. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The present invention is a flow chart of a method for preparing a heat-resistant masterbatch of industrial yarns in one embodiment of the present invention. DETAILED DESCRIPTION

[0039] The preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0040] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0041] The description in this section is only for several typical embodiments, and the present invention is not limited to the scope of the embodiments. The same or similar prior art means and some technical features in the embodiments are mutually replaced within the scope of the present invention.

[0042] The description of the steps in each embodiment in the specification is only for the convenience of explanation, and the implementation method of the present application is not limited by the order of implementation of the steps.

[0043] The invention discloses a heat stabilizer, which comprises: 10-20 parts by weight of a copper compound or / and 5-15 parts by weight of an inorganic copper compound, 25-50 parts by weight of a hindered amine light stabilizer, 10-25 parts by weight of a phosphite antioxidant and 10-20 parts by weight of a hindered phenol antioxidant; the above components are compounded according to proportion.

[0044] In one embodiment of the present invention, the heat stabilizer comprises: 10-20 parts by weight of an organic hybrid copper compound containing an amide bond or an amine group or / and 5-15 parts by weight of an inorganic copper compound, 25-50 parts by weight of a hindered amine light stabilizer containing an amide bond or an amine group, 10-25 parts by weight of a phosphite antioxidant having a thermal decomposition temperature greater than the spinning temperature of the modified matrix, and 10-20 parts by weight of a hindered phenol antioxidant; the above ingredients are compounded in proportion. The heat stabilizer may further comprise 20-30 parts by weight of a potassium halide or a sodium halide.

[0045] The above organic copper contains amide bonds or amine groups, which can not only melt the cuprous ions and make the charge state of the cuprous ions more stable, but also the organic part of the amide bonds or amine groups is very compatible with the polyamide matrix, so that the heat stabilizer is completely compatible with the polyamide and well dispersed, and the melt remains uniform and stable during the spinning process. The above-mentioned phosphite has a thermal decomposition temperature greater than the spinning temperature of the polyamide matrix, so that the antioxidant effect of the phosphite can play a role not only in the processing process, but also in the subsequent long-term use, so the heat resistance effect is better.

[0046] In one embodiment of the present invention, the hindered amine light stabilizer containing an amide bond or an amine group is at least one of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxylate, poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]1,3,5,-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexanediyl-[(2,2,6,6-tetramethylpiperidinyl)-imino]}, 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reactants;

[0047] The chemical formula of the reactants of 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine is as follows:

[0048]

[0049] The phosphite antioxidant may be at least one of 3,5-di-tert-butyl-4-hydroxybenzoic acid octyl ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol-diphosphite.

[0050] The hindered phenol antioxidant may be at least one of N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzoamide) and bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane.

[0051] The present invention discloses an industrial yarn heat resistant agent masterbatch, and the industrial yarn heat resistant agent masterbatch comprises:

[0052] 30-80 parts by weight of polyamide resin;

[0053] 10-40 parts by weight of the above-mentioned heat stabilizer;

[0054] 2-4 parts by weight of processing aid.

[0055] The present invention discloses a method for preparing the above-mentioned industrial yarn heat-resistant agent masterbatch, and the preparation method comprises:

[0056] [Step S1] Grinding the polyamide resin into a powder of 20-200 mesh;

[0057] In one embodiment of the present invention, the polyamide resin may be a high molecular weight polyamide resin with a relative viscosity of 3.0-4.0.

[0058] The polyamide resin includes conventional polyamide (such as PA6, PA66), bio-based polyamide (such as PA56, PA46, PA510, PA512, etc.), special polyamide resin (such as PA610, PA612, PA410, PA11, PA12, PA1212, PA5T, PA6T, etc.), and copolymerized polyamide resin or blended polyamide resin.

[0059] [Step S2] Drying all the composition raw materials used to prepare the industrial yarn heat-resistant agent masterbatch;

[0060] The moisture content of the composition raw material after drying can be 200-2000 ppm. In one embodiment, the moisture content of the composition raw material after drying is 300-600 ppm.

[0061] [Step S3] All the raw materials of the composition are mixed uniformly according to a proportion, and extruded into granules by an extruder, such as a twin-screw extruder.

[0062] When PA6 is used as the resin, the twin-screw extrusion temperature can be 230-260°C (such as 240-250°C, specifically 240°C, 245°C, 250°C); when PA56 or PA66 is used as the resin, the twin-screw extrusion temperature can be 260-290°C (such as 265-280°C, specifically 265°C, 280°C, 290°C). For other types of polyamide resins, the extrusion temperature can be appropriately adjusted according to the melting point.

[0063] The melt viscosity of the composition will increase significantly during the blending and granulation process, resulting in unsmooth strand cutting and pelletizing. It is necessary to appropriately improve the existing twin screw and change it to an underwater pelletizing method for pelletizing.

[0064] The present invention further discloses a spinning method using the above-mentioned industrial yarn heat-resistant agent masterbatch, the spinning method comprising:

[0065] The industrial yarn heat resistant agent masterbatch is first dried under the conditions of 80-120°C, vacuum degree below 20Pa, and continuous drying for a set time (such as more than 8 hours). The moisture content of the masterbatch after drying can be below 600ppm.

[0066] The masterbatch is quantitatively and evenly mixed with the main material above the spinning machine screw by a high-precision mass mixer and then enters the buffer hopper, and then fed into the screw. The mixed raw materials are melted and extruded through a single screw;

[0067] The mixer and buffer hopper are protected by nitrogen flow;

[0068] The addition amount of the heat-resistant agent masterbatch does not exceed 5%, and the polyamide resin in the masterbatch is selected to be the same as the main spinning material for modification;

[0069] The melt melted in the screw is quantitatively transported to the spinneret by a metering pump. After post-heating, side-blowing cooling, and oiling of the nozzle, it enters the drafting rollers. After being drafted and heat-set by multiple pairs of rollers, it is continuously wound into the finished yarn.

[0070] Example 1 Preparation of polyamide 6 heat-resistant masterbatch

[0071] Raw materials: polyamide 6 chips (pure material, relative viscosity 3.2-3.6), heat stabilizer (cuprous iodide, potassium iodide, cuprous phosphate, potassium bromide, antioxidant hindered phenol antioxidant is N, N'-hexamethylene bis (3, 5-di-tert-butyl-4-hydroxybenzoic acid amide), antioxidant bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propane, phosphite 3, 5-di-tert-butyl-4-hydroxybenzoic acid octyl ester, phosphite bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarbamide, etc.), dispersant (polyethylene wax, oxidized polyethylene wax, trimethylolethane), etc. The formula is as follows:

[0072] Polyamide 6 resin 60 parts

[0073] 38 parts of compound heat stabilizer

[0074] Dispersant 2 parts

[0075] 2. Preparation process:

[0076] (1) Resin treatment: Polyamide 6 with a relative viscosity of 3.20-3.60 was crushed into 30-50 mesh powder and then dried in a vacuum oven at 90°C to a moisture content of 300-600 ppm.

[0077] (2) Mix all the raw materials in the formula evenly;

[0078] (3) Blending and granulation in a twin-screw extruder to prepare masterbatch; the twin-screw temperature range is 230°C-260°C; the temperature of each section increases sequentially, and the melt temperature range is 250-270°C (for example: 230°C, 240°C, 250°C, 260°C, 260°C, 255°C).

[0079]

[0080] Example 2 Preparation of High Heat Resistant Polyamide 6 Industrial Yarn

[0081] Raw materials: polyamide 6 chips (relative viscosity 3.2-3.6), polyamide 6 heat resistant agent masterbatch prepared above.

[0082] Polyamide 6 industrial yarn spinning process and spinning conditions:

[0083] In one-step melt spinning, the prepared heat-resistant agent masterbatch is quantitatively fed into the screw inlet through a metering feeder, the mixed raw materials are melted and extruded through a single screw, and then quantitatively transported to the spinneret by a metering pump. After slow cooling, side blowing cooling, and oiling device, it enters the drawing roller, and after two to three stages of drawing and heat setting, it is wound into silk.

[0084] Fiber fineness: 20D-3000D. Single fiber fineness is 1 denier or more.

[0085] High heat resistant polyamide 6 fiber performance and spinning conditions:

[0086] (1) 150D / 24F spinning process:

[0087]

[0088] (2) 150D / 24F fiber physical properties:

[0089]

[0090] (3) Spinning conditions of 150D / 24F fiber

[0091]

[0092]

[0093] (4) Physical properties and spinning conditions of coarse denier fibers

[0094]

[0095] Example 3 Preparation of polyamide 66 heat resistant agent masterbatch

[0096] 1. Raw materials: polyamide 66 chips (relative viscosity 2.4-3.6), heat stabilizers (cuprous iodide, potassium iodide, cuprous phosphate, potassium bromide, antioxidant 1098, antioxidant 1076, phosphite 168, phosphite 626, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarbamide, etc.), dispersants (polyethylene wax, oxidized polyethylene wax, trimethylolethane), etc. The formula is as follows:

[0097] Polyamide 66 resin 60 parts

[0098] Compound heat stabilizer (same formula as PA6 masterbatch MB5# heat stabilizer) 38 parts

[0099] Dispersant 2 parts

[0100] 2. Preparation process of polyamide 66 heat resistant agent masterbatch:

[0101] (1) Base resin treatment: The relative viscosity of polyamide 66 industrial yarn-grade chips is 2.4-2.8, and the relative viscosity is increased to 3.2-3.6 by solid phase thickening; the chips are then crushed into 30-50 mesh powders, and then dried in a vacuum oven at 90°C to a moisture content of 300-600 ppm.

[0102] (2) Mix all the raw materials in the formula evenly;

[0103] (3) Blending and granulation in a twin-screw extruder to prepare masterbatch. The twin-screw temperature range is 250°C-280°C. The temperature of each section increases successively, and the melt temperature range is 270-280°C (for example: 250°C, 260°C, 270°C, 275°C, 275°C, 270°C).

[0104] Example 4 Preparation of highly heat-resistant modified polyamide 66 industrial yarn

[0105] Raw materials: polyamide 66 industrial yarn-grade chips (relative viscosity may be 2.4-2.8), polyamide 66 heat-resistant agent masterbatch prepared above.

[0106] Solid phase viscosity enhancement of polyamide 66 spinning chips: rotary drum vacuum viscosity enhancement or nitrogen flow solid phase viscosity enhancement tower viscosity enhancement, viscosity enhancement temperature 160℃-180℃, viscosity enhancement time 25-35 hours.

[0107] High heat resistant polyamide 66 industrial yarn spinning process, spinning conditions and fiber properties:

[0108] In one-step melt spinning, the prepared heat-resistant agent masterbatch is quantitatively fed into the screw inlet through a metering feeder, the mixed raw materials are melted and extruded through a single screw, and then quantitatively transported to the spinneret by a metering pump. After slow cooling and side blowing cooling, it enters the drawing roller, goes through two to three stages of drawing and heat setting, and is wound into filaments.

[0109] Fiber fineness: 20D-3000D fiber. Single fiber fineness is above 1dpf.

[0110] Polyamide 66 fiber properties:

[0111]

[0112]

[0113] In summary, the heat stabilizer, industrial yarn heat resistant agent masterbatch, preparation method and spinning method thereof proposed in the present invention can improve the thermal stability of polyamide fibers, improve the heat resistance and breaking strength retention rate of fibers (such as nylon 6, nylon 66 or nylon 56 fibers, etc.) (from the conventional 90-92% to more than 95%), improve fiber strength (strength is slightly improved) and spinning performance, reduce the breakage rate in the spinning process (can be reduced by 5%), and make the melt pressure more stable.

[0114] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0115] The description and application of the present invention here are illustrative, and it is not intended to limit the scope of the present invention to the above-mentioned embodiments. The effects or advantages involved in the embodiments may not be embodied in the embodiments due to interference from various factors, and the description of the effects or advantages is not used to limit the embodiments. The deformation and change of the embodiments disclosed here are possible, and the replacement of the embodiments and the various equivalent parts are well known to those of ordinary skill in the art. It should be clear to those skilled in the art that the present invention can be implemented in other forms, structures, arrangements, proportions, and with other components, materials and parts without departing from the spirit or essential features of the present invention. Other deformations and changes can be made to the embodiments disclosed here without departing from the scope and spirit of the present invention.

Claims

1. A heat stabilizer, It is characterized in that The heat stabilizer comprises: 10-20 parts by weight of a copper compound or / and 5-15 parts by weight of an inorganic copper compound, 25-50 parts by weight of a hindered amine light stabilizer, 10-25 parts by weight of a phosphite antioxidant and 10-20 parts by weight of a hindered phenol antioxidant; the above components are compounded according to proportion.

2. The heat stabilizer according to claim 1, Features: The copper compound is an organic hybrid copper compound containing an amide bond or an amine group; the hindered amine light stabilizer is a hindered amine light stabilizer containing an amide bond or an amine group; the phosphite antioxidant is a phosphite antioxidant having a thermal decomposition temperature greater than the spinning temperature of the modified matrix; The organic copper contains an amide bond or an amine group, which makes the cuprous ions melt and the charge state of the cuprous ions more stable. In addition, the organic part of the amide bond or the amine group has good compatibility with the polyamide matrix, so that the heat stabilizer is completely compatible with the polyamide and well dispersed, and the melt remains uniform and stable during the spinning process. The phosphite has a thermal decomposition temperature greater than the spinning temperature of the polyamide matrix, so that the anti-oxidation effect of the phosphite can play a role not only in the processing process but also in the subsequent long-term use, and the heat resistance effect is better.

3. The heat stabilizer according to claim 2, Features: The hindered amine light stabilizer containing an amide bond or an amine group is at least one of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxylate, poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]1,3,5,-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexanediyl-[(2,2,6,6-tetramethylpiperidinyl)-imino]}, 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reactants; The chemical formula of the reactants of 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine is as follows:

4. The heat stabilizer according to claim 1, Features: The heat stabilizer further comprises 20-30 parts by weight of potassium halide or sodium halide.

5. The heat stabilizer according to claim 1, Features: The phosphite antioxidant is at least one of 3,5-di-tert-butyl-4-hydroxybenzoic acid octyl ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and bis(2,4-dicumylphenyl)pentaerythritol-diphosphite.

6. The heat stabilizer according to claim 1, Features: The hindered phenol antioxidant is at least one of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzoamide) and bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane.

7. A heat-resistant masterbatch for industrial yarn, It is characterized in that The industrial silk heat resistant agent masterbatch comprises: 30-80 parts by weight of polyamide resin; 10-40 parts by weight of the heat stabilizer according to any one of claims 1 to 6; 2-4 parts by weight of processing aid.

8. A method for preparing the heat-resistant masterbatch of industrial yarn according to claim 7, It is characterized in that The preparation method comprises: Step S1, grinding the polyamide resin into a powder of 20-200 mesh; Step S2, drying all the composition raw materials used to prepare the industrial silk heat-resistant agent masterbatch; Step S3: uniformly mix all the composition raw materials according to the proportion, and extrude and granulate them using an extruder.

9. The preparation method according to claim 8, Features: In step S1, the polyamide resin is a high molecular weight polyamide resin with a relative viscosity of 3.0-4.0; The polyamide resin includes at least one of conventional polyamide, bio-based polyamide, special polyamide resin, copolymerized polyamide resin, and blended polyamide resin; In step S2, after the composition raw material is dried, the moisture content is 200-2000 ppm; In step S3, extrusion granulation is performed by using a twin-screw extruder in an underwater pelletizing manner.

10. A spinning method using the industrial yarn heat-resistant agent masterbatch according to claim 7, It is characterized in that The spinning method comprises: The industrial yarn heat resistant agent masterbatch is dried at 80-120°C, with a vacuum degree of less than 20Pa, and the drying is continued for a set time; The masterbatch is quantitatively and evenly mixed with the main material above the spinning machine screw by a high-precision mass mixer and then enters the buffer hopper, and then fed into the screw. The mixed raw materials are melted and extruded through a single screw; The mixer and buffer hopper are protected by nitrogen flow; The addition amount of the heat-resistant agent masterbatch does not exceed 5%, and the polyamide resin in the masterbatch is selected to be the same as the main spinning material for modification; The melt melted in the screw is quantitatively transported to the spinneret by a metering pump. After post-heating, side-blowing cooling, and oiling of the nozzle, it enters the drafting rollers. After being drafted and heat-set by multiple pairs of rollers, it is continuously wound into the finished yarn.

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