CN111944279A - Neck-hanging line sizing material based on polyester elastomer and preparation method and application thereof - Google Patents
Neck-hanging line sizing material based on polyester elastomer and preparation method and application thereof Download PDFInfo
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- CN111944279A CN111944279A CN202010847557.4A CN202010847557A CN111944279A CN 111944279 A CN111944279 A CN 111944279A CN 202010847557 A CN202010847557 A CN 202010847557A CN 111944279 A CN111944279 A CN 111944279A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R1/00—Details of transducers, loudspeakers or microphones
- H04R1/10—Earpieces; Attachments therefor ; Earphones; Monophonic headphones
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention relates to the field of polymer materials, in particular to a neck hanging line sizing material based on a polyester elastomer, and a preparation method and application thereof. The neck hanging line sizing material is prepared from the following raw materials in parts by weight: 50-70 parts of polyester elastomer, 15-25 parts of TPU, 10-25 parts of polyolefin elastomer, 3-5 parts of compatilizer, 1-3 parts of lubricant and 3-4 parts of auxiliary agent. The sizing material provided by the invention polymerizes a polyester elastomer by introducing TPU and a polyolefin elastomer, and improves the compatibility among materials under the action of a compatilizer, wherein the introduction of TPU improves the flexibility and toughness of the neck line sizing material, and the rebound resilience and impact resistance of the sizing material are improved by combining the polyolefin elastomer; and the neck-hanging line shaping material prepared after polymerization can be prepared and molded in a lower-temperature environment, so that the preparation difficulty and the energy consumption cost are reduced, the product has good rebound resilience and is not easy to deform, and the fracture strength and the impact strength are high and not easy to fracture.
Description
Technical Field
The invention relates to the field of polymer materials, in particular to a neck hanging line sizing material based on a polyester elastomer, and a preparation method and application thereof.
Background
The existing earphones are divided into wired earphones and wireless earphones, and the wired earphones are connected with each other through a cable; two built-in bluetooth units of earphone of wireless formula, mutual wireless communication between two bluetooth units, and all be connected with signal source transmitting equipment, this makes the earphone of two separations all need be equipped with bluetooth unit and independent battery, but the technical degree of difficulty is big, and use cost is high, and the dropping that appears single earphone easily leads to whole double earphone can't become double use. In order to achieve a good wearing effect, the conventional wireless Bluetooth headset generally adopts a neck hanging type structure, so that a stable connection structure of the wireless Bluetooth headset is improved, and the phenomenon of falling is avoided; however, in the actual use process, the connection between the neck line and the earphone is easy to break, which affects the service life of the earphone, and on the other hand, the deformed elastic resilience is weak, so that the neck line is easy to deform under pressure, and the wearing effect is reduced.
Disclosure of Invention
Aiming at the problems of easy breakage and low resilience of a neck hanging wire in the prior art, the first object of the invention is to provide a neck hanging wire setting material of a polyester elastomer, which has the advantages of good resilience, difficult deformation, high breaking strength, high impact strength and difficult breakage.
The second purpose of the invention is to provide a preparation method of the neck-hanging wire sizing material of the polyester elastomer, the preparation method is simple and convenient to operate, easy to control and high in production efficiency, and the prepared neck-hanging wire sizing material has good rebound elasticity, breaking strength and impact strength, is not easy to deform, has long service life and can be produced in a large scale.
The third purpose of the invention is to provide the application of the neck hanging line shaping material of the polyester elastomer, the application preparation method is simple to operate, easy to control and short in forming period, and the prepared neck hanging line is high in strength, stable in performance, good in rebound resilience and long in service life.
In order to achieve the first object, the invention provides the following technical scheme: a neck hanging line sizing material based on a polyester elastomer is prepared from the following raw materials in parts by weight:
50-70 parts of polyester elastomer
15-25 parts of TPU
10-25 parts of polyolefin elastomer
3-5 parts of compatilizer
1-3 parts of lubricant
3-4 parts of an auxiliary agent.
In the prior art, the preparation temperature is 180-240 ℃ in the process of producing the neck hanging wire, the temperature is higher, the requirement on equipment is higher, and large-scale mass production is difficult to achieve; the polyester elastomer has elasticity like rubber and strength like engineering plastics, but has better processing performance and longer service life than the rubber and the engineering plastics, and is widely applied to producing and preparing the neck hanging wire. However, the elasticity of the polyester elastomer is not enough to form the excellent resilience of the neck line, and the soft segment of the polyester elastomer enables the neck line to have low weather resistance and aging resistance and to be easily aged in long-term use, so that the joint of the neck line and the earphone is easily aged, hardened and broken.
In contrast, the technology introduces TPU and polyolefin elastomer to polymerize the polyester elastomer, and improves the compatibility among materials under the action of a compatilizer, wherein the introduction of the TPU improves the flexibility and toughness of the neck line sizing material, and the rebound resilience and impact resistance of the sizing material are improved by combining the polyolefin elastomer; and the neck-hanging line shaping material prepared after polymerization can be prepared and molded in a lower-temperature environment, so that the preparation difficulty and the energy consumption cost are reduced. The lubricating agent is adopted to improve the lubricating property of the molding material, so that the molding material is easy to demould, and the demoulded product has stable performance and good subsequent processing performance.
Further, the compatilizer is one or a combination of SEBS-g-MAH, GMA-g-PE, GMA-g-PP, PP-g-MAH, POE-g-MAH and PE-g-MAH.
The compatilizer adopted by the technology can effectively improve the sensitivity of the polyester elastomer to notch strength, promote the chemical bonding between materials and a polymer matrix and increase the compatibility between the materials, wherein epoxy groups contained in Glycidyl Methacrylate (GMA) molecules can react with the tail end of a high polymer, so that the compatibility between the materials is realized, and the compatibility between the high polymer and the materials is improved.
The SEBS-g-MAH is adopted to modify the polyester elastomer and the TPU, so that the toughness and the elongation at break of the sizing material are improved and tend to be stable, and the prepared material for hanging the neck has stable performance, good resilience and difficult fracture.
Further, the lubricant is one or a combination of several of methyl silicone oil, benzyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl vinyl silicone oil and methyl hydroxyl silicone oil.
The lubricant adopted by the technology can improve the lubricity of the molding material, so that the molding material is easy to demould, and the adhesion force on the surface of the molding material is reduced, so that the mechanical shearing force is reduced, and the processing performance is improved; wherein, the methyl silicone and the benzyl silicone oil have good high temperature resistance and low temperature resistance, good weather resistance and good chemical stability; the ethyl silicone oil has small surface tension, is waterproof and has good chemical corrosion resistance, and the prepared sizing material has stable performance.
Further, each part of the auxiliary agent comprises 2-3 parts of antioxidant and 1-2 parts of anti-UV agent.
Further, the antioxidant is one or a combination of more of 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanate, pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite and N, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide).
The technology can improve the oxidation resistance and the aging resistance of the setting material by adopting the antioxidant, is not easy to oxidize, age and yellow, has good weather resistance, and prolongs the service life of the setting material.
Further, the anti-UV agent is one or a combination of more of a light stabilizer 770, a light stabilizer 622, an ultraviolet light absorber UV-327 and an ultraviolet light absorber UV-531.
By adopting the UV resistant agent, the UV absorption and stabilization effects of the sizing material on UV can be improved, and the yellowing phenomenon can be improved; the ultraviolet absorbent is used as an ultraviolet absorption component in a high polymer system, has good compatibility, can obstruct and absorb ultraviolet rays, can effectively absorb ultraviolet rays with the wavelength of 270-380nm, greatly reduces the radiation intensity born by the polymer, slows down the aging speed, maintains the long-acting performance and stability of the product, can improve the light aging resistance under the synergistic action with a light stabilizer, and the light stabilizer can capture free radicals in the material, block the chain reaction of light and oxygen aging, so that the free radicals can not continuously damage molecular chains, effectively protects the polymer, avoids the problems of yellowing, gloss reduction, yellowing and the like, effectively improves the phenomena of deterioration, generation of gloss reduction, embrittlement, cracking and the like of the molding material due to the action of Ultraviolet (UV) and the like, and improves the weather resistance of the product.
The adopted anti-UV agent improves the light aging resistance of the molding material, effectively inhibits light aging degradation and is not easy to yellow.
Further, the neck line sizing material also comprises 1-3 parts of wear-resistant filler, and the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
Further, the wollastonite/silicon dioxide composite microspheres are prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
Further, in the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.1-0.3MPa, the crushing pressure is 0.4-0.7MPa, the magnetic vibration feeding current is 30-40mA, and the wollastonite is crushed to have the length-diameter ratio of 12-18:1 and the diameter value of 0.2-0.6 μm.
Further, in the step A, the weight of stearic acid is 1-4% of wollastonite; after mixing, the temperature is raised to 65-90 ℃, and the mixture is stirred for 18-30min under the condition of the rotation speed of 800-1200 rpm.
Further, in the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2-3:0.5-1.5: 10; the mesh number of the silicon dioxide is 4000-5000 meshes; the dispersing agent is one or a combination of polyethylene glycol sodium fatty acid, sodium dodecyl sulfate and sodium polymethacrylate.
Further, in the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 1-4; the grafted modified wollastonite is mixed with the dispersing material and heated to 80-100 ℃ and stirred for 15-20min under the condition of the rotation speed of 600-1000 rpm.
Further, in the step D, cooling the coated microsphere precursor to 45-60 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 1-3% of the weight of the coated microsphere precursor, the stirring speed is 600-; the coupling agent is a titanate coupling agent, and further is one or a combination of more of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, isopropyl dioleate acyloxy (dioctyl phosphato) titanate and bis (dioctyl oxide pyrophosphate) ethylene titanate.
According to the technology, wollastonite is used as a wear-resistant scraping filler, so that the wear resistance and the scraping resistance of the neck-hanging shaped material can be effectively improved, the prepared neck-hanging shaped material has a matte effect and fine hand feeling, the weather resistance of the neck-hanging shaped material can be improved, and the extrusion stability of the neck-hanging shaped material in the extrusion process can be improved.
It is well known in the art that the addition of wollastonite increases the compression set of the material, but the technology is faced with the problem of insufficient resilience of the polyester elastomer, the introduction of wollastonite increases the compression set of the polyester elastomer, and the phenomenon of insufficient resilience is difficult to improve, and the conventional technical personnel generally cannot think about the introduction of wollastonite in the technology. The technology introduces TPU and polyolefin elastomer to polymerize the polyester elastomer, the TPU improves the flexibility and toughness of the neck line shaping material, the polyolefin elastomer improves the resilience and impact resistance of the shaping material, and the problem of resilience of wollastonite to the polyester elastomer is solved; meanwhile, the amount of wollastonite is strictly controlled and modified, so that the wollastonite is used as a filler, and the material dispersibility, wear resistance, scratch resistance, tensile strength, bending strength and matte effect of a system are improved.
Wherein, the length-diameter ratio of the wollastonite subjected to supersonic airflow pulverization treatment is 12-18:1, the diameter value is 0.2-0.6 μm, the wollastonite with the specific length-diameter ratio and the specific diameter value has a better specific surface area, a larger contact area with a matrix and larger interaction, the bonding strength with the matrix is increased, and the properties of the polymer matrix such as tensile strength, elongation and the like are improved; if the diameter value of the wollastonite is too large, the specific surface area is small, the contact area with the substrate is small, and the reinforcing effect is low. When the molding material introduced with the wollastonite is stressed, the load is generally directly loaded on the substrate, and then the stress is transmitted to the wollastonite through the top end of the wollastonite and the interface connecting the wollastonite and the substrate, so that if the length-diameter ratio of the wollastonite is too small, the length of the load transmission is reduced, the wollastonite can bear the stress transmitted from the substrate, and the mechanical property of the molding material is further reduced.
And then, the introduced wollastonite is modified in a supersonic airflow pulverizing phase by stearic acid, and the airflow moves at a high speed to cause collision, splitting, mutual friction and shearing among particles so as to achieve good crushing effect, so that the surface energy of the wollastonite is reduced, the interfacial tension is small, the dispersibility of wollastonite powder in a matrix is improved, the total contact area between two phases is favorably improved, the surface of the wollastonite is grafted and coated and modified by the stearic acid, the stearic acid is firstly dissociated to form carboxylate radical particles under the action of mechanical force, the carboxylate radical particles generate chemical adsorption and chemical bonding action at active points on the surface of the wollastonite, fine grafts are formed on the surface, the hydrophilicity of the surface of the wollastonite is reduced, the lipophilicity is improved, the hydrophilicity is changed into hydrophobicity, and the surface energy and the interfacial tension of the wollastonite are further reduced, improve the dispersibility and the filling property, lead the composite material to have longer length-diameter ratio and keep better mechanical property. However, the reduction of the interfacial tension is accompanied by the reduction of the adhesion work, so that the bonding strength between the two phases is reduced, and the bonding strength between the wollastonite and the polyester elastomer and the mechanical properties of the setting material product are further influenced.
Therefore, the silicon dioxide is adopted to coat the wollastonite subjected to stearic acid grafting modification to form a core-shell microsphere structure with a wollastonite core, a stearic acid graft in the middle layer and a silicon dioxide shell to form composite microspheres, so that the uniform dispersion in a matrix is improved, a good bonding interface is formed between the two phases, the nucleation activity is improved, the crystallinity and the grain size of the matrix are reduced, and the toughness and the resilience of the molding material are improved. Meanwhile, the silicon dioxide has a large specific surface area, and the porous structure of the silicon dioxide permeates into the elastomer branches to form a three-dimensional net-shaped connecting system, so that under the impact of large stress, the porous structure of the silicon dioxide is used as one of the stress action points, the stress is buffered, the stress is reduced, the pressure of the stress on the base body is deformed, the elasticity of the molding material is buffered and recovered, and the molding material has excellent resilience.
The composite microspheres are further modified by a coupling agent, so that the interface bonding performance of the silica on the outer shell layer of the composite microspheres and the matrix is improved, and the impact strength and the wear resistance of the sizing material are improved. The adopted coupling agent can improve the compatibility of the composite microsphere and the matrix directly, improve the filling property in the system matrix, reduce the displacement and stress relaxation between the composite microsphere and the matrix, improve the toughness of the molding material, keep higher recovery capability and reduce the compression permanent deformation.
In conclusion, the technology adopts wollastonite with higher length-diameter ratio, stearic acid is subjected to mechanochemical modification in supersonic airflow pulverization, silicon dioxide is coated on the surface of the wollastonite subjected to grafting modification to form a composite microsphere structure, the nucleation activity is improved, the crystallinity and the grain size of a matrix are reduced, finally, the surface treatment is carried out by using a coupling agent, the condition parameters of each step are strictly controlled, and the impact strength, the wear resistance, the tensile strength and the rebound resilience of the molding material are improved.
In order to achieve the second object, the invention provides the following technical scheme: a preparation method of a neck hanging line sizing material based on a polyester elastomer comprises the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 120-150 ℃; the extrusion time is 10-40 min.
The preparation steps of the neck hanging line sizing material are simple and convenient to operate, easy to control and high in production efficiency, so that the prepared neck hanging line sizing material has good rebound resilience, breaking strength and impact strength, is not easy to deform and long in service life, and can be produced in a large scale.
In order to achieve the third object, the invention provides the following technical solutions: the application of the neck-hanging line sizing material based on the polyester elastomer comprises the following steps: heating the polyester elastomer-based neck-hanging wire sizing material to 160-180 ℃, melting, adding into a neck-hanging wire mold, and cooling and molding to obtain the polyester elastomer neck-hanging wire.
The neck line shaping material has wide application, and if the neck line shaping material is applied to preparing a neck line, the steps are simple to operate and easy to control, and the prepared neck line has high strength, stable performance, good resilience and long service life.
In conclusion, the invention has the following beneficial effects:
firstly, the TPU and the polyolefin elastomer are introduced into the fixing material for the hanging neck line to polymerize the polyester elastomer, and the compatibility among the materials is improved under the action of the compatilizer, wherein the introduction of the TPU improves the flexibility and toughness of the fixing material for the hanging neck line, and the rebound resilience and impact resistance of the fixing material are improved by combining the polyolefin elastomer; and the neck-hanging line shaping material prepared after polymerization can be prepared and molded in a lower-temperature environment, so that the preparation difficulty and the energy consumption cost are reduced. The lubricating agent is adopted to improve the lubricating property of the molding material, so that the molding material is easy to demould, and the demoulded product has stable performance and good subsequent processing performance.
Secondly, the preparation method of the dirty-resistant and wear-resistant fixing material for the hanging neck line is simple and convenient to operate, easy to control and high in production efficiency, so that the prepared fixing material for the hanging neck line has good rebound resilience, breaking strength and impact strength, is not easy to deform and long in service life, and can be produced in a large scale.
Thirdly, the neck line hanging setting material has wide application range, and the application means is simple to operate and easy to control, so that the prepared product has high strength, stable performance, good resilience and long service life.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A neck hanging line sizing material based on a polyester elastomer is prepared from the following raw materials in parts by weight:
50 parts of polyester elastomer
TPU15 parts
10 parts of polyolefin elastomer
Compatilizer 3 parts
1 part of lubricant
And 3 parts of an auxiliary agent.
The polyester elastomer is selected from thermoplastic polyester elastomers of U.S. Dupont 4069.
The polyolefin elastomer is selected from polyolefin elastomers of U.S. Dupont 8200 brand.
The compatilizer is GMA-g-PE.
The lubricant is methyl ethoxy silicone oil.
Each part of the auxiliary agent comprises 2 parts of antioxidant and 1 part of anti-UV agent; the antioxidant is 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanate; the anti-UV agent is a light stabilizer 770.
A preparation method of a neck hanging line sizing material based on a polyester elastomer comprises the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 120 ℃; the extrusion time was 40 min.
The application of the neck-hanging line sizing material based on the polyester elastomer comprises the following steps: heating the polyester elastomer-based neck-hanging thread setting material to 160 ℃, melting, adding into a neck-hanging thread mold, and cooling and molding to obtain the polyester elastomer neck-hanging thread.
Example 2
A neck hanging line sizing material based on a polyester elastomer is prepared from the following raw materials in parts by weight:
55 parts of polyester elastomer
TPU 18 parts
14 parts of polyolefin elastomer
Compatilizer 3.5 parts
1.5 parts of lubricant
And 3.2 parts of an auxiliary agent.
The polyester elastomer is selected from thermoplastic polyester elastomers of U.S. Dupont 4069.
The polyolefin elastomer is selected from polyolefin elastomers of U.S. Dupont 8200 brand.
The compatilizer is GMA-g-PP.
The lubricant is ethyl silicone oil.
Each part of the auxiliary agent comprises 2.2 parts of antioxidant and 1.2 parts of anti-UV agent; the antioxidant is pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite; the anti-UV agent is a light stabilizer 622.
A preparation method of a neck hanging line sizing material based on a polyester elastomer comprises the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 130 ℃; the extrusion time was 30 min.
The application of the neck-hanging line sizing material based on the polyester elastomer comprises the following steps: heating the polyester elastomer-based neck-hanging wire shaping material to 165 ℃, melting, adding into a neck-hanging wire mold, and cooling and molding to obtain the polyester elastomer neck-hanging wire.
Example 3
A neck hanging line sizing material based on a polyester elastomer is prepared from the following raw materials in parts by weight:
60 parts of polyester elastomer
TPU 20 parts
Polyolefin elastomer 18 parts
4 portions of compatilizer
2 portions of lubricant
And 3.5 parts of an auxiliary agent.
The polyester elastomer is selected from thermoplastic polyester elastomers of U.S. Dupont 4069.
The polyolefin elastomer is selected from polyolefin elastomers of U.S. Dupont 8200 brand.
The compatilizer is SEBS-g-MAH.
The lubricant is benzyl silicone oil.
Each part of the auxiliary agent comprises 2.5 parts of antioxidant and 1.5 parts of anti-UV agent; the antioxidant is N, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide); the anti-UV agent is an ultraviolet absorbent UV-327.
A preparation method of a neck hanging line sizing material based on a polyester elastomer comprises the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 135 ℃; the extrusion time was 25 min.
The application of the neck-hanging line sizing material based on the polyester elastomer comprises the following steps: heating the polyester elastomer-based neck-hanging wire shaping material to 170 ℃, melting, adding into a neck-hanging wire mold, and cooling and molding to obtain the polyester elastomer neck-hanging wire.
Example 4
A neck hanging line sizing material based on a polyester elastomer is prepared from the following raw materials in parts by weight:
65 parts of polyester elastomer
TPU 23 parts
Polyolefin elastomer 23 parts
1.5 parts of compatilizer
2.5 portions of lubricant
And 3.8 parts of an auxiliary agent.
The polyester elastomer is selected from thermoplastic polyester elastomers of U.S. Dupont 4069.
The polyolefin elastomer is selected from polyolefin elastomers of U.S. Dupont 8200 brand.
The compatilizer is PP-g-MAH.
The lubricant is methyl chlorphenyl silicone oil.
Each part of the auxiliary agent comprises 2.8 parts of antioxidant and 1.8 parts of anti-UV agent; the antioxidant is 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanate; the anti-UV agent is an ultraviolet absorbent UV-531.
A preparation method of a neck hanging line sizing material based on a polyester elastomer comprises the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 140 ℃; the extrusion time was 20 min.
The application of the neck-hanging line sizing material based on the polyester elastomer comprises the following steps: heating the polyester elastomer-based neck-hanging wire sizing material to 175 ℃, melting, adding into a neck-hanging wire mold, and cooling and molding to obtain the polyester elastomer neck-hanging wire.
Example 5
A neck hanging line sizing material based on a polyester elastomer is prepared from the following raw materials in parts by weight:
70 portions of polyester elastomer
TPU 25 parts
Polyolefin elastomer 25 parts
5 portions of compatilizer
3 portions of lubricant
And 4 parts of an auxiliary agent.
The polyester elastomer is selected from thermoplastic polyester elastomers of U.S. Dupont 4069.
The polyolefin elastomer is selected from polyolefin elastomers of U.S. Dupont 8200 brand.
The compatilizer is POE-g-MAH.
The lubricant is methyl vinyl silicone oil.
Each part of the auxiliary agent comprises 3 parts of antioxidant and 2 parts of anti-UV agent; the antioxidant is pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite; the anti-UV agent is an ultraviolet absorbent UV-327.
A preparation method of a neck hanging line sizing material based on a polyester elastomer comprises the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 150 ℃; the extrusion time was 10 min.
The application of the neck-hanging line sizing material based on the polyester elastomer comprises the following steps: heating the polyester elastomer-based neck-hanging thread setting material to 180 ℃, melting, adding into a neck-hanging thread mold, and cooling and molding to obtain the polyester elastomer neck-hanging thread.
Example 6
This embodiment differs from embodiment 1 described above in that:
the neck-hanging line shaping material also comprises 1 part of wear-resistant filler, and the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.1MPa, the crushing pressure is 0.4MPa, the magnetic vibration feeding current is 30mA, and the wollastonite is crushed to have the length-diameter ratio of 12: 1, diameter value of 0.2 μm.
In the step A, the weight of stearic acid is 1 percent of that of wollastonite; after mixing, the temperature is raised to 65 ℃, and the mixture is stirred for 30min under the condition that the rotating speed is 800 rpm.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2:0.5: 10; the mesh number of the silicon dioxide is 4000 meshes; the dispersing agent is polyethylene glycol sodium aliphatate.
In the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 1; the grafted modified wollastonite is mixed with the dispersing material, heated to 80 ℃, and stirred for 20min at the rotating speed of 600 rpm.
In the step D, cooling the coated microsphere precursor to 45 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 1% of the weight of the coated microsphere precursor, the stirring speed is 600rpm, and the stirring time is 25 min; the coupling agent is isopropyl dioleic acid acyloxy (dioctyl phosphate acyloxy) titanate.
Example 7
This embodiment differs from embodiment 1 described above in that:
the neck-hanging line shaping material also comprises 1.5 parts of wear-resistant filler, and the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.15MPa, the crushing pressure is 0.5MPa, the magnetic vibration feeding current is 32mA, and the wollastonite is crushed to have the length-diameter ratio of 13: 1, diameter value of 0.3 μm.
In the step A, the weight of stearic acid is 2 percent of that of wollastonite; after mixing, the temperature is raised to 70 ℃, and the mixture is stirred for 28min under the condition that the rotating speed is 900 rpm.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.2:0.8: 10; the mesh number of the silicon dioxide is 4200 meshes; the dispersing agent is sodium polymethacrylate.
In the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 2; the grafted modified wollastonite is mixed with the dispersing material, heated to 85 ℃, and stirred for 19min at the rotating speed of 700 rpm.
In the step D, cooling the coated microsphere precursor to 48 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 1.5% of the weight of the coated microsphere precursor, the stirring speed is 800rpm, and the stirring time is 23 min; the coupling agent is bis (dioctyloxy pyrophosphate) ethylene titanate.
Example 8
This embodiment differs from embodiment 1 described above in that:
the neck-hanging line shaping material also comprises 2 parts of wear-resistant filler, wherein the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.2MPa, the crushing pressure is 0.5MPa, the magnetic vibration feeding current is 35mA, and the wollastonite is crushed to have the length-diameter ratio of 15: 1, diameter value of 0.4 μm.
In the step A, the weight of stearic acid is 2.5 percent of that of wollastonite; after mixing, the temperature was raised to 750 ℃ and the mixture was stirred at 1000rpm for 25 min.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.5:1.0: 10; the mesh number of the silicon dioxide is 4500 meshes; the dispersing agent is sodium polymethacrylate.
In the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 2.5; the grafted modified wollastonite is mixed with the dispersing material, heated to 90 ℃, and stirred for 18min at the rotating speed of 800 rpm.
In the step D, cooling the coated microsphere precursor to 52 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 2% of the weight of the coated microsphere precursor, the stirring speed is 900rpm, and the stirring time is 22 min; the coupling agent is isopropyl dioleic acid acyloxy (dioctyl phosphate acyloxy) titanate.
Example 9
This embodiment differs from embodiment 1 described above in that:
the neck-hanging line shaping material also comprises 2.5 parts of wear-resistant filler, and the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.25MPa, the crushing pressure is 0.6MPa, the magnetic vibration feeding current is 38mA, and the wollastonite is crushed to have the length-diameter ratio of 17: 1, diameter value of 0.5 μm.
In the step A, the weight of stearic acid is 3 percent of that of wollastonite; after mixing, the temperature was raised to 80 ℃ and stirred for 22min at a rotation speed of 1100 rpm.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.8:1.3: 10; the mesh number of the silicon dioxide is 4800 meshes; the dispersing agent is polyethylene glycol sodium aliphatate.
In the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 3; the grafted modified wollastonite is mixed with the dispersing material, heated to 95 ℃, and stirred for 16min at the rotation speed of 900 rpm.
In the step D, cooling the coated microsphere precursor to 55 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 2.5% of the weight of the coated microsphere precursor, the stirring speed is 1000rpm, and the stirring time is 21 min; the coupling agent is bis (dioctyloxy pyrophosphate) ethylene titanate.
Example 10
This embodiment differs from embodiment 1 described above in that:
the neck-hanging line shaping material also comprises 3 parts of wear-resistant filler, wherein the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.3MPa, the crushing pressure is 0.7MPa, the magnetic vibration feeding current is 40mA, and the wollastonite is crushed to have the length-diameter ratio of 18:1 and the diameter value of 0.6 μm.
In the step A, the weight of stearic acid is 4 percent of that of wollastonite; after mixing, the temperature is raised to 90 ℃, and the mixture is stirred for 18min under the condition that the rotating speed is 1200 rpm.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 3:1.5: 10; the mesh number of the silicon dioxide is 5000 meshes; the dispersant is sodium dodecyl sulfate.
In the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 4; the grafted modified wollastonite is mixed with the dispersing material, heated to 100 ℃, and stirred for 15min at the rotation speed of 1000 rpm.
In the step D, cooling the coated microsphere precursor to 60 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 3% of the weight of the coated microsphere precursor, the stirring speed is 1200rpm, and the stirring time is 20 min; the coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
Comparative example 1
This comparative example differs from example 8 above in that:
the neck hanging line shaping material also comprises 2 parts of wear-resistant filler, and the wear-resistant filler is modified wollastonite.
The modified wollastonite is prepared by the following steps: and (2) crushing wollastonite through supersonic airflow, mixing the wollastonite with stearic acid, heating and stirring to obtain the modified wollastonite.
Wherein the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.2MPa, the crushing pressure is 0.5MPa, the magnetic vibration feeding current is 35mA, and the crushed wollastonite has the length-diameter ratio of 15: 1, diameter value of 0.4 μm.
Wherein, the weight of the stearic acid is 2.5 percent of that of the wollastonite; after mixing, the temperature was raised to 750 ℃ and the mixture was stirred at 1000rpm for 25 min.
Comparative example 2
This comparative example differs from example 8 above in that:
the neck-hanging line shaping material also comprises 2 parts of wear-resistant filler, wherein the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and B: adding wollastonite into the dispersing material prepared in the step A, heating and stirring to prepare a coated microsphere precursor;
and C: and D, cooling the coated microsphere precursor prepared in the step B, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to obtain the wollastonite/silicon dioxide composite microsphere.
In the step A, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.5:1.0: 10; the mesh number of the silicon dioxide is 4500 meshes; the dispersing agent is sodium polymethacrylate.
In the step B, the length-diameter ratio of the wollastonite is 15: 1, the diameter value is 0.4 mu m; the mixing weight ratio of the wollastonite to the dispersing material is 10: 2.5; mixing wollastonite with the dispersion material, heating to 90 ℃, and stirring for 18min at the rotation speed of 800 rpm.
In the step C, cooling the coated microsphere precursor to 52 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 2% of the weight of the coated microsphere precursor, the stirring speed is 900rpm, and the stirring time is 22 min; the coupling agent is isopropyl dioleic acid acyloxy (dioctyl phosphate acyloxy) titanate.
Comparative example 3
This comparative example differs from example 8 above in that:
the neck-hanging line shaping material also comprises 2 parts of wear-resistant filler, wherein the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and B: and D, adding wollastonite into the dispersing material prepared in the step A, heating and stirring, cooling to room temperature, and drying to obtain the wollastonite/silicon dioxide composite microspheres.
In the step A, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.5:1.0: 10; the mesh number of the silicon dioxide is 4500 meshes; the dispersing agent is sodium polymethacrylate.
In the step B, the length-diameter ratio of the wollastonite is 15: 1, the diameter value is 0.4 mu m; the mixing weight ratio of the wollastonite to the dispersing material is 10: 2.5; mixing wollastonite with the dispersion material, heating to 90 ℃, and stirring for 18min at the rotation speed of 800 rpm.
Comparative example 4
This comparative example differs from example 8 above in that:
the neck-hanging line shaping material also comprises 2 parts of wear-resistant filler, wherein the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding a coupling agent into the dispersed material prepared in the step B, and heating and stirring to prepare modified silicon dioxide;
step D: and D, cooling the modified silicon dioxide prepared in the step C, adding the modified silicon dioxide into the grafted modified wollastonite prepared in the step A, heating and stirring, cooling to normal temperature, and drying to obtain the wollastonite/silicon dioxide composite microsphere.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.2MPa, the crushing pressure is 0.5MPa, the magnetic vibration feeding current is 35mA, and the wollastonite is crushed to have the length-diameter ratio of 15: 1, diameter value of 0.4 μm.
In the step A, the weight of stearic acid is 2.5 percent of that of wollastonite; after mixing, the temperature was raised to 750 ℃ and the mixture was stirred at 1000rpm for 25 min.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.5:1.0: 10; the mesh number of the silicon dioxide is 4500 meshes; the dispersing agent is sodium polymethacrylate.
In the step C, the addition amount of the coupling agent is 2% of the weight of the dispersed material, the stirring speed is 900rpm, and the stirring time is 22 min; the coupling agent is isopropyl dioleic acid acyloxy (dioctyl phosphate acyloxy) titanate.
In the step D, the modified silicon dioxide is cooled to 52 ℃, and then is added into the grafted modified wollastonite; the mixing weight ratio of the grafted modified wollastonite to the modified silicon dioxide is 10: 2.5; the grafted modified wollastonite and the modified silicon dioxide are mixed and heated to 90 ℃, and stirred for 18min at the rotating speed of 800 rpm.
Comparative example 5
This comparative example differs from example 8 above in that:
the neck-hanging line shaping material also comprises 2 parts of wear-resistant filler, wherein the wear-resistant filler is wollastonite/silicon dioxide composite microspheres.
The wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor; finally, cooling to normal temperature and drying to prepare the wollastonite/silicon dioxide composite microspheres.
In the step A, the crushing conditions of the supersonic airflow crushing treatment are that the feeding pressure is 0.2MPa, the crushing pressure is 0.5MPa, the magnetic vibration feeding current is 35mA, and the wollastonite is crushed to have the length-diameter ratio of 15: 1, diameter value of 0.4 μm.
In the step A, the weight of stearic acid is 2.5 percent of that of wollastonite; after mixing, the temperature was raised to 750 ℃ and the mixture was stirred at 1000rpm for 25 min.
In the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2.5:1.0: 10; the mesh number of the silicon dioxide is 4500 meshes; the dispersing agent is sodium polymethacrylate.
In the step C, the mixing weight ratio of the grafted modified wollastonite to the dispersing material is 10: 2.5; the grafted modified wollastonite is mixed with the dispersing material, heated to 90 ℃, and stirred for 18min at the rotating speed of 800 rpm.
Comparative example 6
This comparative example differs from example 8 above in that:
in the step D, the coupling agent is a silane coupling agent KH-560.
Comparative example 7
This comparative example differs from example 8 above in that:
the neck hanging line molding material further comprises 2 parts of wear-resistant filler, and the wear-resistant filler is white carbon black.
Comparative example 8
This comparative example differs from example 8 above in that:
the neck-hanging line shaping material further comprises 2 parts of wear-resistant filler, and the wear-resistant filler is calcium carbonate.
The neck hanging line setting materials prepared in the above examples 3 and 8 and comparative examples 1 to 8 are made into sheets with the length of 15cm, the width of 15cm and the thickness of 1cm, and the sheets are subjected to performance tests such as tensile strength, flexural modulus, compression deformation rate, wear resistance, scratch resistance, matte effect and the like, and the test results are as follows:
table 1 table of performance test data
Wherein the tensile strength is tested according to the GB/T1040-1992 plastic tensile test method, the flexural modulus is tested according to the GB/T9341-2000 plastic flexural performance test method, and the compression deformation rate is tested according to the GB/T14483-1993 plastic load deformation test method; the abrasion scratch resistance test is carried out according to the standard GB/T3960-1983 Plastic sliding friction abrasion test method.
According to the experimental results, wollastonite with a high length-diameter ratio is subjected to mechanochemical modification in supersonic airflow pulverization by stearic acid, the surface of the wollastonite subjected to grafting modification is coated with silicon dioxide to form a composite microsphere structure, the nucleation activity is improved, the crystallinity and the grain size of a matrix are reduced, and finally the surface of the wollastonite is treated by a coupling agent, the condition parameters of each step are strictly controlled, and the wear resistance, the tensile strength and the rebound resilience of the molding material are improved.
In the comparative example 1, the wollastonite is subjected to surface grafting treatment only by stearic acid, compared with the scheme of the embodiment 3 without adding the wollastonite, the mechanical strength, the rebound resilience and the compression set property of the wollastonite are improved, but compared with the embodiment 8, the wollastonite has reduced tensile strength, rebound resilience and compression set property, slight scratches appear on the surface and lower wear resistance effect, and the wollastonite subjected to grafting modification by stearic acid is improved in dispersibility and filling property in a matrix, but is insufficient in bonding strength, so that the mechanical strength, the rebound resilience and the compression set property of the wollastonite are lower than those of the embodiment 8.
Compared with the embodiment 8, the wollastonite modified by the coupling agent has the advantages that the wollastonite is not grafted by stearic acid, is directly coated by silicon dioxide to form a composite material, and is modified by the coupling agent, so that the wollastonite modified by the coupling agent has reduced tensile strength, rebound resilience and compression deformation, has slight abrasion and scratch on the surface, and has lower abrasion resistance; comparative example 3 does not use stearic acid for grafting treatment of wollastonite, directly uses silicon dioxide for coating to form a composite material, and does not use coupling modification treatment, compared with example 8, the wollastonite modified composite material has the advantages that the tensile strength, the rebound resilience and the compression deformation performance are also reduced, the surface is slightly abraded and slightly scratched, and the wear-resisting effect is lower. Comparative example 2 and comparative example 3 reflect that in the technology, wollastonite is grafted by stearic acid, then coated by silicon dioxide and subsequently coupled and modified, stearic acid is dissociated to form carboxylate radical particles, chemical adsorption and chemical bonding are generated at active points on the surface of the wollastonite, fine grafts are formed on the surface, the coating associativity of the silicon dioxide is improved, the abrasion phenomenon caused by the fact that the silicon dioxide falls off due to abrasion is reduced, the associativity of the wollastonite and the silicon dioxide is improved, the mechanical strength and the rebound resilience of the sizing material are improved, and the sizing material is not easy to deform. Meanwhile, the scheme of the comparative example 5 is combined (the coating microsphere is not treated by a coupling agent after being coated by the silicon dioxide), which reflects that the composite microsphere is modified by the coupling agent, the interface bonding performance of the silicon dioxide of the outer shell layer of the composite microsphere and the matrix is improved, and the mechanical strength and the wear resistance of the sizing material are improved.
Comparative example 4 for the preparation of wollastonite/silica composite microspheres, silica is subjected to surface coupling modification and then is compounded with wollastonite, compared with example 8, the tensile strength, resilience and compression deformation performance of the silica composite microspheres are reduced as well, and the surface of the silica composite microspheres is slightly abraded and slightly scratched, so that the abrasion resistance effect is low; the reaction of silica after coupling treatment with the graft modified wollastonite is reflected, the coating effect is not ideal, and the improvement effect on the mechanical property and the compression resilience of the matrix is not as obvious as that of the embodiment 8, which shows that the silica is coated on the surface of the graft modified wollastonite to form a composite microsphere structure, so that the nucleation activity is improved, the crystallinity and the grain size of the matrix are reduced, and finally, the mechanical strength, the wear resistance and the resilience of the molding material can be improved through the surface treatment of the coupling agent.
Comparative example 6 for the preparation of wollastonite/silica composite microspheres, silane coupling agent is used for coupling treatment, compared with example 8, the tensile strength, resilience and compression set property of the microspheres are reduced, slight scratches appear on the surface, and the wear-resistant effect is low; the titanate coupling agent is adopted to modify the coated microspheres, so that the interface bonding performance of the silicon dioxide of the shell layer of the composite microspheres and the matrix can be effectively improved, the mechanical strength and the wear resistance of the molding material are improved, and the effect is better than that of a silane coupling agent.
In contrast, in comparative example 7, white carbon black is used as a filler, and in comparative example 8, calcium carbonate is used as a filler, compared with example 8, the tensile strength, resilience and compression set performance of the composite material are obviously reduced, the surface of the composite material is slightly abraded and scratched, and the surface matte effect is not obvious, so that the impact strength, wear resistance, tensile strength and resilience of the molding material can be improved by adopting the wollastonite/silicon dioxide composite microspheres prepared by the technology.
The neck line product prepared by the technical scheme has better mechanical strength, rebound resilience, wear resistance, scratch resistance, matte effect and other performances, and the neck line is linearly changed into 15 degrees after being pressed by 3000 degrees, so that the rebound resilience is good, and the compressibility variability is low.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. The neck hanging line sizing material based on the polyester elastomer is characterized by being prepared from the following raw materials in parts by weight:
50-70 parts of polyester elastomer
15-25 parts of TPU
10-25 parts of polyolefin elastomer
3-5 parts of compatilizer
1-3 parts of lubricant
3-4 parts of an auxiliary agent.
2. The neck wire sizing material based on the polyester elastomer as claimed in claim 1, wherein the compatilizer is one or a combination of SEBS-g-MAH, GMA-g-PE, GMA-g-PP, PP-g-MAH, POE-g-MAH and PE-g-MAH; the lubricant is one or a combination of methyl silicone oil, benzyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl vinyl silicone oil and methyl hydroxyl silicone oil.
3. The neck line molding compound based on polyester elastomer as claimed in claim 1, wherein each part of the auxiliary agent comprises 2-3 parts of antioxidant and 1-2 parts of anti-UV agent; the antioxidant is one or a combination of more of 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanate, pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite and N, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide); the anti-UV agent is one or a combination of more of a light stabilizer 770, a light stabilizer 622, an ultraviolet absorbent UV-327 and an ultraviolet absorbent UV-531.
4. The neckline molding compound based on the polyester elastomer as claimed in claim 1, further comprising 1-3 parts of a wear-resistant filler, wherein the wear-resistant filler is wollastonite/silica composite microspheres.
5. The neck wire molding compound based on polyester elastomer as claimed in claim 4, wherein the wollastonite/silicon dioxide composite microsphere is prepared by the following steps:
step A: carrying out supersonic airflow crushing treatment on wollastonite, then mixing the wollastonite with stearic acid, heating and stirring to prepare graft modified wollastonite;
and B: adding silicon dioxide and a dispersing agent into deionized water, and mixing and dispersing to prepare a bulk material;
and C: adding the grafted modified wollastonite prepared in the step A into the dispersing material prepared in the step B, and heating and stirring to prepare a coated microsphere precursor;
step D: and D, cooling the coated microsphere precursor prepared in the step C, adding a coupling agent, stirring and dispersing, cooling to normal temperature, and drying to prepare the wollastonite/silicon dioxide composite microsphere.
6. The neck wire molding compound based on polyester elastomer as claimed in claim 5, wherein in step A, the supersonic jet milling treatment is carried out under the conditions of feeding pressure of 0.1-0.3MPa, crushing pressure of 0.4-0.7MPa, magnetic vibration feeding current of 30-40mA, and milling to wollastonite with length-diameter ratio of 12-18:1 and diameter value of 0.2-0.6 μm.
7. The neck wire molding compound based on polyester elastomer as claimed in claim 5, wherein in the step A, the weight of stearic acid is 1-4% of wollastonite; heating to 65-90 ℃ after mixing, and stirring for 18-30min at the rotation speed of 800-; in the step B, the mixing weight ratio of the silicon dioxide, the dispersing agent and the water is 2-3:0.5-1.5: 10; the mesh number of the silicon dioxide is 4000-5000 meshes.
8. The neck wire molding compound based on polyester elastomer as claimed in claim 5, wherein in the step C, the mixing weight ratio of the graft modified wollastonite to the dispersing material is 10: 1-4; mixing the grafted modified wollastonite with the dispersing material, heating to 80-100 ℃, and stirring for 15-20min at the rotation speed of 600-1000 rpm; in the step D, cooling the coated microsphere precursor to 45-60 ℃, and then adding a coupling agent, wherein the addition amount of the coupling agent is 1-3% of the weight of the coated microsphere precursor, the stirring speed is 600-1200rpm, and the stirring time is 20-25 min; the coupling agent is a titanate coupling agent.
9. The preparation method of the neck hanging setting material based on the polyester elastomer as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps: mixing and dispersing the raw materials according to the parts by weight, and extruding and granulating to obtain a neck-hanging line sizing material based on the polyester elastomer; the extrusion temperature of the extrusion granulation is 120-150 ℃; the extrusion time is 10-40 min.
10. The application of the neck-hanging setting compound based on the polyester elastomer as claimed in any one of claims 1 to 8, is characterized by comprising the following steps: and heating and melting the polyester elastomer-based neck-hanging line sizing material, then adding the material into a neck-hanging line mold, and cooling and molding to obtain the polyester elastomer neck-hanging line.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112831157A (en) * | 2020-12-08 | 2021-05-25 | 江苏鑫易达新材料科技有限公司 | TPEE base film of automobile protection film |
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| CN115304904A (en) * | 2022-09-08 | 2022-11-08 | 东莞市兴晟达智能科技有限公司 | Anti-aging high-resilience earphone neck hanging wire and preparation method thereof |
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| CN112831157A (en) * | 2020-12-08 | 2021-05-25 | 江苏鑫易达新材料科技有限公司 | TPEE base film of automobile protection film |
| CN113061324A (en) * | 2021-03-26 | 2021-07-02 | 东莞易昌塑胶布业有限公司 | High-strength shape memory composite material, preparation method thereof and high-tensile-strength mesh cloth |
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| CN115011086B (en) * | 2022-07-18 | 2023-09-15 | 会通新材料(上海)有限公司 | Wear-resistant low-voltage-change composite material and preparation method and application thereof |
| CN115304904A (en) * | 2022-09-08 | 2022-11-08 | 东莞市兴晟达智能科技有限公司 | Anti-aging high-resilience earphone neck hanging wire and preparation method thereof |
| CN115304904B (en) * | 2022-09-08 | 2024-02-20 | 东莞市兴晟达智能科技有限公司 | Aging-resistant high-resilience earphone neck hanging wire and preparation method thereof |
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