CN114031931A - Nylon coated thermoplastic elastomer - Google Patents
Nylon coated thermoplastic elastomer Download PDFInfo
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- CN114031931A CN114031931A CN202111315665.8A CN202111315665A CN114031931A CN 114031931 A CN114031931 A CN 114031931A CN 202111315665 A CN202111315665 A CN 202111315665A CN 114031931 A CN114031931 A CN 114031931A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L2201/12—Shape memory
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- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention relates to a nylon coated thermoplastic elastomer, which comprises the following raw materials in parts by weight: the feed comprises the following raw materials in parts by weight: 10-20 parts of styrene-ethylene/butylene/styrene-styrene copolymer, 5-10 parts of plasticizer, 10-15 parts of nylon elastomer, 12-18 parts of maleic anhydride graft, 3-10 parts of calcium carbonate and 10-15 parts of composite adhesion reinforcing agent; the composite adhesion reinforcing agent is formed by mixing a main agent and a synergistic additive according to the weight ratio of 1: 5; as a thermoplastic elastomer, the styrene-ethylene/butylene/styrene-styrene copolymer has good toughness and hand feeling, and the styrene-ethylene/butylene/styrene-styrene copolymer has better shock absorption performance and fluidity than common SEBS materials, has better compatibility with polar materials, has better infiltration performance to nylon plastics, is added with the nylon elastomer as a filler, can meet the infiltration performance of materials, and improves the coating capacity.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a nylon-coated thermoplastic elastomer.
Background
Nylon has been used as a high molecular material with good properties in various products and electric tools. The thermoplastic elastomer is used as a rubber product, and has good shock absorption effect and skin contact feeling. Can effectively reduce external acting force. Maleic anhydride can react with nylon at high temperature, a large amount of maleic anhydride graft copolymer is generally added into materials to achieve the purpose of coating for many products in the market, the odor of the maleic anhydride graft copolymer is large, and the odor of the product is large due to excessive addition; and maleic anhydride and nylon amino need to produce the rapid reaction under the condition of high temperature of more than 230 ℃ without catalyst, the processing temperature is high, the hot melt material in the flowing process of the mould, the heat is lost greatly, in the injection moulding process, the position close to the sprue is encapsulated well, the position far away is encapsulated generally or the coating force is insufficient, and the product is sticky. At present, polyurethane-coated nylon products are available in the market, but the polyurethane-coated nylon products have the advantages of common coating performance, poor demolding performance and common damping effect.
Disclosure of Invention
In order to solve the above-mentioned technical problems, the present invention provides a nylon-coated thermoplastic elastomer.
The purpose of the invention can be realized by the following technical scheme:
the nylon-coated thermoplastic elastomer comprises the following raw materials in parts by weight: 10-20 parts of styrene-ethylene/butylene/styrene-styrene copolymer, 5-10 parts of plasticizer, 10-15 parts of nylon elastomer, 12-18 parts of maleic anhydride graft, 3-10 parts of calcium carbonate and 10-15 parts of composite adhesion reinforcing agent;
the composite adhesion reinforcing agent is formed by mixing a main agent and a synergistic agent according to the weight ratio of 1: 5, wherein the main agent comprises the following steps:
step S1, adding 1, 5-pentanediamine into absolute ethyl alcohol, stirring at a constant speed for 15min, adding sebacic acid, continuing stirring and reacting for 36h, slowly crystallizing in the reaction process, performing suction filtration, washing, collecting crystals, and performing vacuum drying at 65 ℃ to obtain an intermediate, wherein the molar ratio of the 1, 5-pentanediamine to the sebacic acid is controlled to be 1: 1;
step S2, adding hexamethylene diamine adipate and the intermediate into a reaction kettle filled with deionized water, stirring at a constant speed, adding caprolactam, introducing nitrogen to discharge air, heating to 240 ℃, maintaining the pressure in the reaction kettle at 1.6MPa, preserving heat and reacting for 2 hours to prepare a main agent, controlling the molar ratio of the hexamethylene diamine adipate to the caprolactam to be 1: 2.5-2.8, and controlling the using amount of the intermediate to be 10% of the sum of the weight of the hexamethylene diamine adipate and the weight of the caprolactam.
In the step S1, absolute ethyl alcohol is used as a solvent, and 1, 5-pentanediamine and sebacic acid react to generate an intermediate; in step S2, adipic acid hexamethylene diamine salt, an intermediate and caprolactam are used as raw materials, and melt polymerization is carried out at high temperature and high pressure to prepare a main agent, wherein the main agent is a copolyamide hot melt adhesive;
further: the maleic anhydride graft is maleic anhydride grafted polyethylene or its copolymer, the functionality is 0.5-1.5%, the melt index is not lower than 5(190 ℃/2.16KG), and its copolymer is selected from any one of polyethylene and its copolymer, POE, ethylene propylene diene monomer copolymer.
Further: the synergistic additive is prepared by the following steps:
step S11, adding polyethylene glycol into 3% by mass of a billows chloride aqueous solution, stirring at a constant speed for 10min to obtain a mixed solution, and carrying out ultrasonic treatment for 30min for later use; then slowly dropwise adding an ammonium bicarbonate aqueous solution with the mass fraction of 10% into the mixed solution, keeping the system temperature at 0-5 ℃ in the dropwise adding process, continuing to perform ultrasonic treatment for 30min after the dropwise adding is finished, filtering, washing a filter cake with absolute ethyl alcohol and deionized water, then placing the filter cake into an evaporation dish, drying the filter cake at the temperature of 100 ℃ and 110 ℃ for 2h, and then calcining the filter cake at the temperature of 500 ℃ for 4h to prepare modified particles, wherein the molar ratio of the billows chloride to the ammonium bicarbonate is controlled to be 1: 3, and the dosage of the polyethylene glycol is half of the weight of the billows chloride;
and step S11, adding polyethylene glycol as a surfactant, reacting the water solution of the billows chloride with the water solution of the ammonium bicarbonate under ultrasound, and then drying and calcining to prepare modified particles.
Step S12, respectively heating and melting polyester dihydric alcohol, 1, 4-butanediol and diisocyanate into liquid for later use; mixing the heated polyester diol and modified particles, heating to 120 ℃ while stirring, carrying out vacuum dehydration for 1h, transferring to a closed reaction kettle, carrying out ultrasonic dispersion for 15min, sequentially adding the heated 1, 4-butanediol and diisocyanate, stirring at a high speed for 30min, pouring into a die preheated to 125 ℃, standing, curing and forming, transferring to a drying oven, heating to 120 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation and drying for 4h to obtain the synergistic additive, controlling the weight ratio of the polyester diol to the 1, 4-butanediol to the diisocyanate to be 3: 0.5: 1, and controlling the using amount of the modified particles to be 2.5-3% of the weight of the polyester diol.
In step S12, in order to prevent the polyester diol and the modified particles from absorbing moisture in the air and causing the prepared synergistic additive to generate bubbles, vacuum dehydration is performed first, then 1, 4-butanediol is added as a chain extender, diisocyanate and 1, 4-butanediol are used as hard segments, the polyester diol is used as a soft segment, the modified particles are added, under the action of high-speed stirring and ultrasound, van der waals force between the agglomerated modified particles is destroyed, and further dispersed in the polyester polyol in the form of particles, and finally the synergistic additive is prepared, which is a modified polyurethane elastomer, the modified particles are rare earth lan element particles, the special unfilled electronic structure of the modified particles can form coordination bonds with polar groups in the molecular structure of the elastomer to play a role in chemical crosslinking, so as to significantly improve the mechanical properties of the modified particles, and the modified particles are rigid particles, the Shore hardness of the prepared elastomer can be improved.
Further: the elastomer is prepared by the following steps:
firstly, adding styrene-ethylene/butylene/styrene-styrene copolymer into a mixer, adding a plasticizer into the mixer through a spraying device, and mixing while spraying to prepare a primary material;
and secondly, sequentially adding the nylon elastomer, the maleic anhydride graft, the calcium carbonate and the composite adhesion reinforcing agent into the primary material, uniformly mixing, adding the mixture into a double-screw extruder, extruding and granulating to obtain the nylon-coated thermoplastic elastomer, wherein the extrusion temperature is 200-230 ℃, and the feeding frequency is 20-30 Hz.
The invention has the beneficial effects that:
the thermoplastic elastomer is a shape memory thermoplastic elastomer, and the product has good shape recovery capability; as a thermoplastic elastomer, the thermoplastic elastomer has good toughness and hand feeling, and the copolymer is used as a base material, the styrene-ethylene/butylene/styrene-styrene copolymer has damping performance and flowing performance compared with the common SEBS material, has better compatibility with polar materials and better infiltration performance to nylon plastics, the nylon elastomer is added, the nylon elastomer is a low-hardness nylon elastomer with the hardness of 28-30D, and can meet the infiltration performance of the material as a filler, the coating capacity is improved, the melt material can not be rapidly cooled in the injection molding process, and the hand feeling and the damping performance of the material can be improved due to the addition of the nylon elastomer.
The main agent is a copolyamide hot melt adhesive, belongs to nylon substances, can endow the elastomer and a nylon base material with good adhesiveness when the main agent and the synergistic additive are used as the adhesion enhancer, but the strong polarity of the adhesion enhancer causes poor compatibility with other components, so the synergistic additive prepared by the invention is a block polymer, can improve the uniformity of the base body after being blended and used, ensures that the main agent can exert good adhesion performance, is used as a high-elasticity body, and is blended and extruded after being added into the base body as the synergistic additive, thereby further improving the mechanical property of the thermoplastic elastomer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The composite adhesion reinforcing agent is formed by mixing a main agent and a synergistic agent according to the weight ratio of 1: 5, wherein the main agent comprises the following steps:
step S1, adding 1, 5-pentanediamine into absolute ethyl alcohol, stirring at a constant speed for 15min, adding sebacic acid, continuing stirring and reacting for 36h, slowly crystallizing in the reaction process, performing suction filtration, washing, collecting crystals, and performing vacuum drying at 65 ℃ to obtain an intermediate, wherein the molar ratio of the 1, 5-pentanediamine to the sebacic acid is controlled to be 1: 1;
step S2, adding hexamethylene diamine adipate and the intermediate into a reaction kettle filled with deionized water, stirring at a constant speed, adding caprolactam, introducing nitrogen to discharge air, heating to 240 ℃, maintaining the pressure in the reaction kettle at 1.6MPa, preserving heat and reacting for 2 hours to prepare a main agent, controlling the molar ratio of the hexamethylene diamine adipate to the caprolactam to be 1: 2.5, and controlling the using amount of the intermediate to be 10% of the sum of the weight of the hexamethylene diamine adipate and the weight of the caprolactam.
The synergistic additive is prepared by the following steps:
step S11, adding polyethylene glycol into 3% by mass of a billows chloride aqueous solution, stirring at a constant speed for 10min to obtain a mixed solution, and carrying out ultrasonic treatment for 30min for later use; then slowly dropwise adding an ammonium bicarbonate aqueous solution with the mass fraction of 10% into the mixed solution, keeping the system temperature at 0 ℃ in the dropwise adding process, continuing to perform ultrasonic treatment for 30min after the dropwise adding is finished, filtering, washing a filter cake with absolute ethyl alcohol and deionized water, then placing the filter cake into an evaporating dish, drying the filter cake at 100 ℃ for 2h, and then calcining the filter cake at 500 ℃ for 4h to prepare modified particles, wherein the molar ratio of the ammonium bicarbonate to the ammonium chloride is controlled to be 1: 3, and the dosage of the polyethylene glycol is half of the weight of the ammonium chloride;
step S12, respectively heating and melting polyester dihydric alcohol, 1, 4-butanediol and diisocyanate into liquid for later use; mixing the heated polyester diol and the modified particles, heating to 120 ℃ while stirring, carrying out vacuum dehydration for 1h, then transferring to a closed reaction kettle, carrying out ultrasonic dispersion for 15min, sequentially adding the heated 1, 4-butanediol and diisocyanate, stirring at a high speed for 30min, then pouring into a die preheated to 125 ℃, standing, curing and forming, then transferring to a drying oven, heating to 120 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation and drying for 4h to obtain the synergistic additive, controlling the weight ratio of the polyester diol, the 1, 4-butanediol and the diisocyanate to be 3: 0.5: 1, and controlling the using amount of the modified particles to be 2.5% of the weight of the polyester diol.
Example 2
The composite adhesion reinforcing agent is formed by mixing a main agent and a synergistic agent according to the weight ratio of 1: 5, wherein the main agent comprises the following steps:
step S1, adding 1, 5-pentanediamine into absolute ethyl alcohol, stirring at a constant speed for 15min, adding sebacic acid, continuing stirring and reacting for 36h, slowly crystallizing in the reaction process, performing suction filtration, washing, collecting crystals, and performing vacuum drying at 65 ℃ to obtain an intermediate, wherein the molar ratio of the 1, 5-pentanediamine to the sebacic acid is controlled to be 1: 1;
step S2, adding hexamethylene diamine adipate and the intermediate into a reaction kettle filled with deionized water, stirring at a constant speed, adding caprolactam, introducing nitrogen to discharge air, heating to 240 ℃, maintaining the pressure in the reaction kettle at 1.6MPa, preserving heat and reacting for 2 hours to prepare a main agent, controlling the molar ratio of the hexamethylene diamine adipate to the caprolactam to be 1: 2.7, and controlling the using amount of the intermediate to be 10% of the sum of the weight of the hexamethylene diamine adipate and the weight of the caprolactam.
The synergistic additive is prepared by the following steps:
step S11, adding polyethylene glycol into 3% by mass of a billows chloride aqueous solution, stirring at a constant speed for 10min to obtain a mixed solution, and carrying out ultrasonic treatment for 30min for later use; then slowly dropwise adding an ammonium bicarbonate aqueous solution with the mass fraction of 10% into the mixed solution, keeping the system temperature at 3 ℃ in the dropwise adding process, continuing to perform ultrasonic treatment for 30min after the dropwise adding is finished, filtering, washing a filter cake with absolute ethyl alcohol and deionized water, then placing the filter cake into an evaporating dish, drying the filter cake at 105 ℃ for 2h, and then calcining the filter cake at 500 ℃ for 4h to prepare modified particles, wherein the molar ratio of the ammonium chloride to the ammonium bicarbonate is controlled to be 1: 3, and the dosage of the polyethylene glycol is half of the weight of the ammonium chloride;
step S12, respectively heating and melting polyester dihydric alcohol, 1, 4-butanediol and diisocyanate into liquid for later use; mixing the heated polyester diol and the modified particles, heating to 120 ℃ while stirring, carrying out vacuum dehydration for 1h, then transferring to a closed reaction kettle, carrying out ultrasonic dispersion for 15min, sequentially adding the heated 1, 4-butanediol and diisocyanate, stirring at a high speed for 30min, then pouring into a die preheated to 125 ℃, standing, curing and forming, then transferring to a drying oven, heating to 120 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation and drying for 4h to obtain the synergistic additive, controlling the weight ratio of the polyester diol, the 1, 4-butanediol and the diisocyanate to be 3: 0.5: 1, and controlling the using amount of the modified particles to be 2.8% of the weight of the polyester diol.
Example 3
The composite adhesion reinforcing agent is formed by mixing a main agent and a synergistic agent according to the weight ratio of 1: 5, wherein the main agent comprises the following steps:
step S1, adding 1, 5-pentanediamine into absolute ethyl alcohol, stirring at a constant speed for 15min, adding sebacic acid, continuing stirring and reacting for 36h, slowly crystallizing in the reaction process, performing suction filtration, washing, collecting crystals, and performing vacuum drying at 65 ℃ to obtain an intermediate, wherein the molar ratio of the 1, 5-pentanediamine to the sebacic acid is controlled to be 1: 1;
step S2, adding hexamethylene diamine adipate and the intermediate into a reaction kettle filled with deionized water, stirring at a constant speed, adding caprolactam, introducing nitrogen to discharge air, heating to 240 ℃, maintaining the pressure in the reaction kettle at 1.6MPa, preserving heat and reacting for 2 hours to prepare a main agent, controlling the molar ratio of the hexamethylene diamine adipate to the caprolactam to be 1: 2.8, and controlling the using amount of the intermediate to be 10% of the sum of the weight of the hexamethylene diamine adipate and the weight of the caprolactam.
The synergistic additive is prepared by the following steps:
step S11, adding polyethylene glycol into 3% by mass of a billows chloride aqueous solution, stirring at a constant speed for 10min to obtain a mixed solution, and carrying out ultrasonic treatment for 30min for later use; then slowly dropwise adding an ammonium bicarbonate aqueous solution with the mass fraction of 10% into the mixed solution, keeping the system temperature at 5 ℃ in the dropwise adding process, continuing to perform ultrasonic treatment for 30min after the dropwise adding is finished, filtering, washing a filter cake with absolute ethyl alcohol and deionized water, then placing the filter cake into an evaporating dish, drying the filter cake at 110 ℃ for 2h, and then calcining the filter cake at 500 ℃ for 4h to prepare modified particles, wherein the molar ratio of the ammonium bicarbonate to the ammonium chloride is controlled to be 1: 3, and the dosage of the polyethylene glycol is half of the weight of the ammonium chloride;
step S12, respectively heating and melting polyester dihydric alcohol, 1, 4-butanediol and diisocyanate into liquid for later use; mixing the heated polyester diol and modified particles, heating to 120 ℃ while stirring, carrying out vacuum dehydration for 1h, transferring to a closed reaction kettle, carrying out ultrasonic dispersion for 15min, sequentially adding the heated 1, 4-butanediol and diisocyanate, stirring at a high speed for 30min, pouring into a die preheated to 125 ℃, standing, curing and forming, transferring to a drying oven, heating to 120 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation and drying for 4h to obtain the synergistic additive, controlling the weight ratio of the polyester diol to the 1, 4-butanediol to the diisocyanate to be 3: 0.5: 1, and controlling the using amount of the modified particles to be 3% of the weight of the polyester diol.
Example 4
The nylon-coated thermoplastic elastomer comprises the following raw materials in parts by weight: 10 parts of styrene-ethylene/butylene/styrene-styrene copolymer, 5 parts of straight-chain alkane oil, 15 parts of nylon elastomer, 12 parts of maleic anhydride graft, 10 parts of calcium carbonate and 10 parts of the composite adhesion enhancer prepared in example 1;
the elastomer is prepared by the following steps:
firstly, adding styrene-ethylene/butylene/styrene-styrene copolymer into a mixer, adding straight-chain alkane oil into the mixer through a spraying device, and mixing while spraying to prepare a primary material;
and secondly, sequentially adding the nylon elastomer, the maleic anhydride graft, the calcium carbonate and the composite adhesion reinforcing agent into the primary material, uniformly mixing, adding the mixture into a double-screw extruder, extruding and granulating to obtain the nylon-coated thermoplastic elastomer, wherein the extrusion temperature is 200 ℃, and the feeding frequency is 20 Hz.
The maleic anhydride graft is maleic anhydride grafted polyethylene.
Example 5
The nylon-coated thermoplastic elastomer comprises the following raw materials in parts by weight: 15 parts of styrene-ethylene/butylene/styrene-styrene copolymer, 8 parts of linear alkane oil, 12 parts of nylon elastomer, 15 parts of maleic anhydride graft, 8 parts of calcium carbonate and 12 parts of the composite adhesion enhancer prepared in example 1;
the elastomer is prepared by the following steps:
firstly, adding styrene-ethylene/butylene/styrene-styrene copolymer into a mixer, adding straight-chain alkane oil into the mixer through a spraying device, and mixing while spraying to prepare a primary material;
and secondly, sequentially adding the nylon elastomer, the maleic anhydride graft, the calcium carbonate and the composite adhesion reinforcing agent into the primary material, uniformly mixing, adding the mixture into a double-screw extruder, extruding and granulating to obtain the nylon-coated thermoplastic elastomer, wherein the extrusion temperature is 210 ℃, and the feeding frequency is 25 Hz.
The maleic anhydride graft is maleic anhydride grafted polyethylene.
Example 6
The nylon-coated thermoplastic elastomer comprises the following raw materials in parts by weight: 20 parts of styrene-ethylene/butylene/styrene-styrene copolymer, 10 parts of straight-chain alkane oil, 10 parts of nylon elastomer, 18 parts of maleic anhydride graft, 3 parts of calcium carbonate and 15 parts of the composite adhesion enhancer prepared in example 1;
the elastomer is prepared by the following steps:
firstly, adding styrene-ethylene/butylene/styrene-styrene copolymer into a mixer, adding straight-chain alkane oil into the mixer through a spraying device, and mixing while spraying to prepare a primary material;
and secondly, sequentially adding the nylon elastomer, the maleic anhydride graft, the calcium carbonate and the composite adhesion reinforcing agent into the primary material, uniformly mixing, adding the mixture into a double-screw extruder, extruding and granulating to obtain the nylon-coated thermoplastic elastomer, wherein the extrusion temperature is 230 ℃, and the feeding frequency is 30 Hz.
The maleic anhydride graft is maleic anhydride grafted polyethylene.
Comparative example 1
This comparative example compares to example 4 without the addition of a composite adhesion enhancer.
Comparative example 2
This comparative example is a thermoplastic elastomer from a commercial company.
Examples 4 to 6 and comparative examples 1 to 2 were subjected to secondary molding by an injection molding machine, and the encapsulating temperature: 190 ℃ and 250 ℃, preparing a material coated with nylon as a matrix, testing the bonding coating force according to the GB/T2790-1995 standard, testing the hardness according to the ISO868 standard, and testing the tensile strength and the elongation according to the ISO37 standard, wherein the results are shown in the following table:
the following states are characteristic for the bonding effect: the magnitude of the peel strength is expressed in terms of data, wherein the peel strength is less than 0-0.5kN/m, which means that the adhesion is small; the peel strength is 0.5-1.0kN/m, which indicates that the adhesive has certain adhesive force, but the adhesive property is general; the peel strength is 1.0-1.5kN/m, which shows that the adhesive has better adhesive property; the peel strength is 1.5-1.8kN/m, which shows that the adhesive property is good; the peel strength was 1.8kN/m or more, indicating excellent adhesion.
As can be seen from the above table, examples 4 to 6 of the present invention have high hardness and excellent mechanical properties, and have a good coating effect on a nylon substrate.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The nylon-coated thermoplastic elastomer is characterized in that: the feed comprises the following raw materials in parts by weight: 10-20 parts of styrene-ethylene/butylene/styrene-styrene copolymer, 5-10 parts of plasticizer, 10-15 parts of nylon elastomer, 12-18 parts of maleic anhydride graft, 3-10 parts of calcium carbonate and 10-15 parts of composite adhesion reinforcing agent;
the composite adhesion reinforcing agent is formed by mixing a main agent and a synergistic agent according to the weight ratio of 1: 5, wherein the main agent comprises the following steps:
step S1, adding 1, 5-pentanediamine into absolute ethyl alcohol, stirring at a constant speed for 15min, adding sebacic acid, continuing stirring and reacting for 36h, slowly crystallizing in the reaction process, performing suction filtration and washing, collecting crystals, and performing vacuum drying at 65 ℃ to obtain an intermediate;
step S2, adding hexamethylene diamine adipate and the intermediate into a reaction kettle filled with deionized water, stirring at a constant speed, adding caprolactam, introducing nitrogen to discharge air, heating to 240 ℃, maintaining the pressure in the reaction kettle at 1.6MPa, preserving heat and reacting for 2 hours to obtain the main agent.
2. The nylon-coated thermoplastic elastomer according to claim 1, wherein: the maleic anhydride graft is maleic anhydride grafted polyethylene or its copolymer with functionality of 0.5-1.5%, and the copolymer is selected from any one of polyethylene and its copolymer, POE, and ethylene propylene diene monomer copolymer.
3. The nylon-coated thermoplastic elastomer according to claim 1, wherein: in step S1, the molar ratio of 1, 5-pentanediamine to sebacic acid is controlled to be 1: 1, in step S2, the molar ratio of adipic acid hexamethylene diamine salt to caprolactam is controlled to be 1: 2.5-2.8, and the using amount of the intermediate is 10% of the sum of the weight of adipic acid hexamethylene diamine salt and caprolactam.
4. The nylon-coated thermoplastic elastomer according to claim 1, wherein: the synergistic additive is prepared by the following steps:
step S11, adding polyethylene glycol into 3% by mass of a billows chloride aqueous solution, stirring at a constant speed for 10min to obtain a mixed solution, and carrying out ultrasonic treatment for 30min for later use; then slowly dropwise adding an ammonium bicarbonate aqueous solution with the mass fraction of 10% into the mixed solution, keeping the temperature of the system at 0-5 ℃ in the dropwise adding process, continuing to perform ultrasonic treatment for 30min after the dropwise adding is finished, filtering, washing a filter cake by using absolute ethyl alcohol and deionized water, drying for 2h at the temperature of 100 ℃ and 110 ℃, and then calcining for 4h at the temperature of 500 ℃ to prepare modified particles;
step S12, respectively heating and melting polyester dihydric alcohol, 1, 4-butanediol and diisocyanate into liquid for later use; mixing the heated polyester diol and the modified particles, heating to 120 ℃ while stirring, carrying out vacuum dehydration for 1h, then transferring to a closed reaction kettle, carrying out ultrasonic dispersion for 15min, sequentially adding the heated 1, 4-butanediol and diisocyanate, carrying out high-speed stirring for 30min, then pouring into a die preheated to 125 ℃, standing, curing and forming, then transferring to a drying oven, heating to 120 ℃ at the heating rate of 1 ℃/min, and carrying out heat preservation and drying for 4h to obtain the synergistic additive.
5. The nylon-coated thermoplastic elastomer according to claim 4, wherein: in the step S11, the molar ratio of the chloride to the ammonium bicarbonate is controlled to be 1: 3, the dosage of the polyethylene glycol is half of the weight of the chloride, in the step S12, the weight ratio of the polyester diol, the 1, 4-butanediol and the diisocyanate is controlled to be 3: 0.5: 1, and the dosage of the modified particles is 2.5-3% of the weight of the polyester diol.
6. The nylon-coated thermoplastic elastomer according to claim 1, wherein: the elastomer is prepared by the following steps:
firstly, adding styrene-ethylene/butylene/styrene-styrene copolymer into a mixer, adding a plasticizer into the mixer through a spraying device, and mixing while spraying to prepare a primary material;
and secondly, sequentially adding the nylon elastomer, the maleic anhydride graft, the calcium carbonate and the composite adhesion reinforcing agent into the initial material, uniformly mixing, adding the mixture into a double-screw extruder, extruding and granulating to obtain the nylon-coated thermoplastic elastomer.
7. The nylon-coated thermoplastic elastomer according to claim 6, wherein: in the second step, the extrusion temperature is 200-230 ℃, and the feeding frequency is 20-30 Hz.
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