CN115725180B - Strong magnetic silicone rubber wristband core material and preparation method thereof - Google Patents
Strong magnetic silicone rubber wristband core material and preparation method thereof Download PDFInfo
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- CN115725180B CN115725180B CN202110989006.6A CN202110989006A CN115725180B CN 115725180 B CN115725180 B CN 115725180B CN 202110989006 A CN202110989006 A CN 202110989006A CN 115725180 B CN115725180 B CN 115725180B
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 86
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 77
- 239000011162 core material Substances 0.000 title claims abstract description 61
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006247 magnetic powder Substances 0.000 claims abstract description 71
- 239000007822 coupling agent Substances 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 230000005294 ferromagnetic effect Effects 0.000 claims abstract description 22
- 229910001172 neodymium magnet Inorganic materials 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 210000000707 wrist Anatomy 0.000 claims abstract description 17
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 15
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000004381 surface treatment Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 21
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- -1 phenyl vinyl Chemical group 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000005389 magnetism Effects 0.000 abstract description 8
- 239000010985 leather Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000001054 cortical effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a ferromagnetic silicone rubber wristband core material, which comprises the following steps: carrying out surface treatment on the NdFeB magnetic powder by adopting an ethanol solution of a composite coupling agent to obtain modified magnetic powder, wherein the composite coupling agent is formed by mixing vinyl triethoxysilane and methacryloxypropyl trimethoxysilane; mixing the modified magnetic powder, the solid silicone rubber raw rubber and the vulcanizing agent, and performing mould pressing to obtain the wrist strap core material. The preparation method can greatly improve the addition amount of the magnetic powder in the silicone rubber system, remarkably improves the magnetism of the silicone rubber, has large magnetic attraction, is comfortable to wear when being used as a wrist strap of the intelligent watch, has good quality feel, has more motion feel and smooth hand feel compared with a leather magnetic attraction wrist strap, and has better wear resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a ferromagnetic silicone rubber wristband core material, and a preparation method of the ferromagnetic silicone rubber wristband core material.
Background
In the intelligent watch industry, the wrist strap plays a role in fixing the watch head on the wrist, and the common practice is to design a cavity at the side of a long watchband, and the cavity is connected through a buckle to adjust the tightness. Some manufacturers use convenient buckles, elastic designs or embedded magnets, and holes are not designed on the watchband, so that the watchband has good overall sense. The magnetic watchband is convenient to use and is favored by consumers. However, the existing magnetic watchband has the problems of insufficient magnetic attraction, easy abrasion of leather watchband, no motion feeling and the like.
Therefore, there is an urgent need to develop a material having strong magnetism for a wristband of a smart watch.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: in the current intelligent watch magnetic attraction watchband, 1, for the scheme of embedding a metal net in a short watchband or embedding a magnetic block at the tail end of a long watchband, the problems of small magnetic attraction, easy tripping and poor appearance consistency exist; 2. for the scheme of embedding the magnet in the cortical material in sections, the problems of insufficient magnetic attraction, easiness in abrasion of the cortical watchband, no motion feeling and the like exist. In addition, there are also technical solutions to add magnetic powder to thermoplastic elastomers at present, but thermoplastic elastomers have high cost, the price of thermoplastic elastomers used in the wearing industry is 80-150 yuan/kg, and a wristband solution with low cost and strong magnetism needs to be found.
The present invention aims to solve at least one of the technical problems in the related art to some extent.
Therefore, the embodiment of the first aspect of the invention provides a preparation method of a ferromagnetic silicone rubber wristband core material, which can greatly improve the addition amount of magnetic powder in a silicone rubber system, remarkably improve the magnetism of silicone rubber, has large magnetic attraction, is comfortable to wear when used as a smart watch wristband, has good quality feel, has more motion feel and smooth hand feel and has better wear resistance compared with a leather magnetic attraction wristband.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, which is an embodiment of the first aspect of the present invention, the preparation method comprises the following steps:
Carrying out surface treatment on the NdFeB magnetic powder by adopting an ethanol solution of a composite coupling agent to obtain modified magnetic powder, wherein the composite coupling agent is formed by mixing vinyl triethoxysilane and methacryloxypropyl trimethoxysilane;
Mixing the modified magnetic powder, the solid silicone rubber raw rubber and the vulcanizing agent, and performing mould pressing to obtain the wrist strap core material.
According to the method provided by the embodiment of the invention, the compound coupling agent is adopted to modify the NdFeB magnetic powder, so that the dispersibility and compatibility of the magnetic powder in the silicone rubber are improved, the magnetic powder can be uniformly dispersed in the silicone rubber, and the addition amount of the magnetic powder in the silicone rubber is obviously improved; 2. in the method provided by the embodiment of the invention, the prepared core material has excellent performance, high magnetism and can meet the mechanical performance requirement of the wrist strap of the smart watch, and can be used as the core material of the wrist strap of the smart watch; 3. the method provided by the embodiment of the invention is simple, the cost of raw materials is low, the price of each kilogram of silicon rubber is 30-60 yuan, the price of the silicon rubber is far lower than that of the thermoplastic elastomer, and the method has a good application prospect and can be applied to various wearing equipment.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, which is provided by the embodiment of the first aspect of the invention, the mass ratio of vinyltriethoxysilane to methacryloxypropyl trimethoxysilane in the composite coupling agent is 0.5:1-1.5:1.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, the mass ratio of vinyl triethoxysilane to methacryloxypropyl trimethoxysilane in the composite coupling agent is 1:1.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, which is an embodiment of the first aspect of the invention, the surface treatment of the neodymium iron boron magnetic powder by adopting the ethanol solution of the composite coupling agent comprises the following steps:
Mixing neodymium iron boron magnetic powder with an ethanol solution of a composite coupling agent, wherein the volume ratio of the composite coupling agent to the ethanol is 1:8-1:10, the particle size of the neodymium iron boron magnetic powder is 70-100 mu m, and the solid content of the neodymium iron boron magnetic powder after being mixed with the ethanol solution of the composite coupling agent is 40-60%;
Stirring and refluxing for 3-5 hours at 50-90 ℃;
filtering, and drying at 110-160deg.C for 2-6 hr.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, according to the first aspect of the embodiment of the present invention, the solid silicone rubber raw rubber is at least one selected from vinyl silicone rubber raw rubber, methyl silicone rubber raw rubber or phenyl vinyl silicone rubber raw rubber; and/or, the vulcanizing agent is bis-25 or benzoyl peroxide; and/or the hardness of the vulcanized solid silicone rubber raw rubber is Shore A50-70.
According to the method for preparing the ferromagnetic silicone rubber wristband core material of the first aspect of the embodiment of the present invention, wherein,
Mixing 80-92 parts by weight of modified magnetic powder, 9-20 parts by weight of solid silicone rubber raw rubber and 0.1-0.4 part by weight of vulcanizing agent at 40-50 ℃ and a roller ratio of 1.2-1.4;
And (3) molding the mixed rubber obtained by mixing at the mold temperature of 160-180 ℃ for 160-190s to obtain the wristband core material.
Embodiments of the second aspect of the present invention also provide a ferromagnetic silicone rubber wristband core prepared by the method of the embodiments of the first aspect of the present invention.
According to the ferromagnetic silicone rubber wristband core material of the second aspect of the embodiment of the invention, the magnetic powder is high in addition amount, can be uniformly dispersed in silicone rubber, can meet the mechanical performance requirement of the wrist strap of the watch while having high magnetism, and can be used as the core material of the wrist strap of the smart watch.
Embodiments of the third aspect of the present invention also provide a magnetic wristband comprising the wristband core of the embodiment of the second aspect of the present invention.
The magnetic wristband according to the embodiment of the third aspect of the invention has strong magnetic attraction, excellent mechanical properties, comfortable wear, good quality, better motion feeling, smooth hand feeling and better wear resistance compared with the leather magnetic attraction wristband.
The embodiment of the fourth aspect of the invention also provides a preparation method of the magnetic wristband, and the wristband core material of the embodiment of the second aspect of the invention is coated and magnetized to obtain the magnetic wristband.
The preparation method of the magnetic wristband according to the embodiment of the fourth aspect of the invention has the advantages of simple preparation method, low raw material cost, strong magnetic attraction force of the prepared wristband, excellent mechanical property and good wear resistance.
According to the preparation method of the magnetic wristband, according to the fourth aspect of the embodiment of the invention, the wristband core material is coated by thermosetting silicone rubber, and the hardness of the thermosetting silicone rubber is Shore A50-70.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, which is an embodiment of the first aspect of the present invention, the preparation method comprises the following steps:
Carrying out surface treatment on the NdFeB magnetic powder by adopting an ethanol solution of a composite coupling agent to obtain modified magnetic powder, wherein the composite coupling agent is formed by mixing vinyl triethoxysilane and methacryloxypropyl trimethoxysilane;
Mixing the modified magnetic powder, the solid silicone rubber raw rubber and the vulcanizing agent, and performing mould pressing to obtain the wrist strap core material.
According to the preparation method of the ferromagnetic silicone rubber wristband core material, disclosed by the embodiment of the first aspect of the invention, the neodymium-iron-boron magnetic powder is modified by adopting the composite coupling agent, so that the dispersibility and compatibility of the magnetic powder in silicone rubber are improved, the magnetic powder can be uniformly dispersed in the silicone rubber, and the addition amount of the magnetic powder in the silicone rubber is obviously increased; the core material prepared by the method provided by the embodiment of the invention has excellent performance, high magnetism and can meet the mechanical performance requirement of the wrist strap of the watch, and can be used as the core material of the wrist strap of the intelligent watch; the method provided by the embodiment of the invention is simple, the cost of raw materials is low, the price of each kilogram of silicon rubber is 30-60 yuan, the price of the silicon rubber is far lower than that of the thermoplastic elastomer, and the method has a good application prospect and can be applied to various wearing equipment.
In some embodiments, the mass ratio of vinyltriethoxysilane to methacryloxypropyl trimethoxysilane in the composite coupling agent is 0.5:1 to 1.5:1, e.g., 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc., preferably 1:1. In the method of the embodiment of the invention, a double-component silane coupling agent is adopted for compounding, vinyl triethoxysilane (CAS: 78-08-0) is hydrolyzed and then dehydrated and condensed into a polymer, the polymer is hydrated with hydroxyl on the surface of magnetic powder, the surface of the magnetic powder is dehydrated and reacted through heating and drying, and finally covered by the silane coupling agent, double bonds are modified on the surface of the magnetic powder, so that the chemical bonds between the magnetic powder and a silicon rubber chain segment are increased, and the dispersion of the magnetic powder in the silicon rubber is improved; after methacryloxypropyl trimethoxy silane (CAS: 2530-85-0) reacts with magnetic powder, two adjacent groups are condensed to generate siloxane, so that the compatibility of the magnetic powder in the silicon rubber is improved; the two silane coupling agents are compounded for use, and the two silane coupling agents are synergistic, so that chemical bonds and compatibility between the magnetic powder and the silicon rubber are increased, the high-content magnetic powder can be uniformly dispersed, the magnetic performance of the wrist strap core material is remarkably improved, the magnetic force can be improved by more than 14% compared with the magnetic force of the single coupling agent, and meanwhile, the mechanical performance of the core material is also improved.
In some embodiments, the surface treatment of the neodymium iron boron magnetic powder with the ethanol solution of the composite coupling agent comprises: mixing the neodymium iron boron magnetic powder with an ethanol solution of the composite coupling agent, carrying out reflux treatment on the mixture, and filtering and drying to obtain the modified magnetic powder.
In some embodiments, the volume ratio of the complex coupling agent to ethanol is 1:8-1:10, e.g., 1:8, 1:8.2, 1:8.4, 1:8.6, 1:8.8, 1:9, 1:9.2, 1:9.4, 1:9.6, 1:9.8, 1:10, etc.
In some embodiments, the neodymium iron boron magnetic powder has a particle size of 70-100 μm, such as 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, etc.
In some embodiments, the NdFeB magnetic powder has a solid content of 40-60% after being mixed with the ethanol solution of the composite coupling agent; for example, 42%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, etc., preferably 50%.
In some embodiments, the reflux conditions are: reflux is stirred at 50-90℃for 3-5 hours, for example, at 50℃55℃60℃65℃70℃75℃80℃85℃90℃and the like, for 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours and the like, preferably at 70℃for 4 hours.
In some embodiments, the drying temperature is 110-160 ℃, e.g., 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, etc., preferably 120 ℃, the drying time is 2-6 hours, e.g., 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, etc., preferably 4 hours.
In the method of the embodiment of the invention, the magnetic powder is mixed with the composite coupling agent, the temperature is raised, stirring and reflux treatment are carried out, the magnetic powder is fully contacted with the composite coupling agent, the magnetic powder after being filtered and dried, and the modified magnetic powder is obtained, and the magnetic powder after being subjected to surface modification by the composite coupling agent in the method of the embodiment of the invention has excellent dispersion performance in silicon rubber.
In some embodiments, after the magnetic powder is subjected to surface treatment by the composite coupling agent to obtain modified magnetic powder, mixing the modified magnetic powder, the solid silicone rubber raw rubber and the vulcanizing agent, and molding the mixed rubber obtained by mixing to obtain the wristband core material.
In some embodiments, the modified magnetic powder in the mixing is added in an amount of 80 to 92 parts by weight, for example 80 parts by weight, 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, etc.; the solid silicone rubber raw rubber is added in an amount of 9 to 20 parts by weight, for example, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 20 parts by weight, etc.; the vulcanizing agent is added in an amount of 0.1 to 0.4 parts by weight, for example, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, and the like. In the method of the embodiment of the invention, up to 92% of modified magnetic powder can be added into the silicone rubber, so that the prepared wristband core material has excellent magnetic performance.
In some embodiments, the solid silicone rubber raw rubber is selected from at least one of vinyl silicone rubber raw rubber, methyl silicone rubber raw rubber, or phenyl vinyl silicone rubber raw rubber, preferably vinyl silicone rubber raw rubber; the vulcanizing agent is bis-25 or benzoyl peroxide; the hardness of the vulcanized solid silicone rubber is between 50 and 70 Shore A, such as 50 Shore A, 55 Shore A, 60 Shore A, 65 Shore A, 70 Shore A and the like.
In some embodiments, the mixing temperature is 40-50 ℃, e.g., 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃,50 ℃, etc., and the roll ratio is 1.2-1.4, e.g., 1.2, 1.22, 1.24, 1.26, 1.28, 1.3, 1.32, 1.34, 1.36, 1.38, 1.4, etc.
In some embodiments, the mold temperature is 160-180 ℃, e.g., 160 ℃, 162 ℃, 164 ℃, 166 ℃, 168 ℃, 170 ℃, 172 ℃, 174 ℃, 176 ℃, 178 ℃, 180 ℃, etc., and the time is 160-190s, e.g., 160s, 164s, 168s, 172s, 176s, 180s, 184s, 188s, 190s, etc. In the method provided by the embodiment of the invention, the process conditions of mixing and mould pressing are optimized, and the wristband core material with excellent performance is prepared.
Embodiments of the second aspect of the present invention also provide a ferromagnetic silicone rubber wristband core prepared by the method of the embodiments of the first aspect of the present invention. The ferromagnetic silicone rubber wristband core material of the second aspect of the embodiment of the invention has high magnetic powder addition amount, can be uniformly dispersed in silicone rubber, can meet the mechanical performance requirement of the wrist strap of the watch while having high magnetism, and can be used as the core material of the wrist strap of the smart watch.
Embodiments of the third aspect of the present invention also provide a magnetic wristband comprising the wristband core of the embodiment of the second aspect of the present invention. The magnetic wristband of the third aspect of the embodiment of the invention has strong magnetic attraction, excellent mechanical property, comfortable wearing and good quality sense, and has more motion sense, smooth hand feeling and better wear resistance compared with the leather magnetic attraction wristband.
The embodiment of the fourth aspect of the invention also provides a preparation method of the magnetic wristband, and the wristband core material of the embodiment of the second aspect of the invention is coated and magnetized to obtain the magnetic wristband. The magnetic wristband disclosed by the embodiment of the fourth aspect of the invention is simple in preparation method, low in raw material cost, strong in magnetic attraction force, excellent in mechanical property and good in wear resistance, and the wristband after magnetizing can be effectively magnetically attracted together.
In some embodiments, the wristband core is preferably coated with a thermoset silicone rubber having a hardness of shore a50-70, such as shore a50, shore a55, shore a60, shore a65, shore a70, and the like.
The present invention will be described in detail with reference to examples.
Example 1
(1) Modification of magnetic powder
Mixing vinyl triethoxysilane and methacryloxypropyl trimethoxy silane with a mass ratio of 1:1 to form a composite coupling agent, mixing the composite coupling agent with ethanol according to a volume ratio of 1:9, adding neodymium iron boron magnetic powder with a particle size of 70 mu m, stirring and refluxing for 4 hours at 70 ℃, filtering, and drying for 4 hours at 120 ℃ to obtain modified magnetic powder;
(2) Mixing
Mixing 80 parts by weight of modified magnetic powder, 20 parts by weight of vinyl silicone rubber raw rubber (the hardness after vulcanization without adding the magnetic powder is Shore A50) and 0.1 part by weight of vulcanizing agent double-25 by adopting a double-roll open mill, wherein the specific process of mixing is to add the modified magnetic powder into the vinyl silicone rubber raw rubber for three times, then adding the vulcanizing agent, mixing uniformly, wherein the mixing temperature is 40 ℃, and the roller ratio is 1.2;
(3) Mould pressing
And (3) molding the rubber compound obtained in the step (2) at 180 ℃ for 180 seconds to obtain the wristband core material containing magnetic powder, wherein the thickness of the wristband core material is 1.1 mm.
The properties of the silicone rubber wristband core material prepared in this example are shown in table 1.
Examples 2 to 18 and comparative examples 1 to 24
The same procedure as in example 1 was repeated except that the amount of the modified magnetic powder added, the compound coupling agent, and the hardness Shore A of the solid silicone rubber green after vulcanization were different, as shown in tables 1 to 3.
The wristband core materials prepared in examples 1 to 18 and comparative examples 1 to 24 were subjected to performance test, the test results are shown in tables 1 to 3, the density test standard is ISO 1183-1, the magnetic performance test is performed after magnetizing the wristband core material, the magnetic force test standard is GB11209-1989, the tensile strength test standard is ISO 37, and the tear strength test standard is ISO 34-1.
In tables 1 to 3, the magnetic powder addition amount=w Modified magnetic powder /(W Modified magnetic powder +W Raw silicone rubber ), W being the weight of each substance;
The coupling agent A refers to vinyl triethoxysilane, the coupling agent B refers to methacryloxypropyl trimethoxysilane, and the coupling agent A and the coupling agent B refer to the mass ratio of the two coupling agents;
the hardness (Shore A) of the silicone rubber refers to the hardness of the solid silicone rubber after vulcanization without adding magnetic powder.
TABLE 1
Note that: in comparative examples 1 to 4, only vinyltriethoxysilane was used as a coupling agent, and in comparative examples 5 to 8, only methacryloxypropyl trimethoxysilane was used as a coupling agent.
TABLE 2
Note that: in comparative examples 9 to 12, only vinyltriethoxysilane was used as a coupling agent, and in comparative examples 13 to 16, only methacryloxypropyl trimethoxysilane was used as a coupling agent.
TABLE 3 Table 3
Note that: in comparative examples 17 to 20, only vinyltriethoxysilane was used as a coupling agent, and in comparative examples 21 to 24, only methacryloxypropyl trimethoxysilane was used as a coupling agent.
The wristband core materials prepared in the embodiments 1-18 are coated with thermosetting silicone rubber, preformed, the wristband core materials are coated in the thermosetting silicone rubber to form a thermosetting silicone rubber-wristband core material-thermosetting silicone rubber three-layer structure, the wristband is obtained through compression molding, the wristband is placed in a magnetic field to be magnetized to obtain a strong magnetic silicone rubber wristband, the magnetic force of the wristband coated with the thermosetting silicone rubber after testing is not reduced compared with that of the wristband core materials in the corresponding embodiments 1-18, the wristband core materials in the embodiments of the invention have strong magnetic attraction, the original magnetic force level can still be kept after the thermosetting silicone rubber is coated on the outer surface of the wristband core materials, and the wristband can be applied to various wearing equipment and has good application prospects.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., 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, schematic representations of the above terms are not necessarily directed 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. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. The preparation method of the ferromagnetic silicone rubber wristband core material is characterized by comprising the following steps of:
Carrying out surface treatment on the neodymium iron boron magnetic powder by adopting an ethanol solution of a composite coupling agent to obtain modified magnetic powder, wherein the composite coupling agent is formed by mixing vinyl triethoxysilane and methacryloxypropyl trimethoxysilane in a mass ratio of 0.5:1-1.5:1;
Mixing the modified magnetic powder, the solid silicone rubber raw rubber and the vulcanizing agent, and performing mould pressing to obtain the wrist strap core material.
2. The method for preparing a ferromagnetic silicone rubber wristband core material according to claim 1, wherein the mass ratio of vinyltriethoxysilane to methacryloxypropyl trimethoxysilane in the composite coupling agent is 1:1.
3. The method for preparing a ferromagnetic silicone rubber wristband core material according to claim 1 or 2, wherein the surface treatment of the neodymium iron boron magnetic powder with the ethanol solution of the composite coupling agent comprises:
Mixing neodymium iron boron magnetic powder with an ethanol solution of a composite coupling agent, wherein the volume ratio of the composite coupling agent to the ethanol is 1:8-1:10, the particle size of the neodymium iron boron magnetic powder is 70-100 mu m, and the solid content of the neodymium iron boron magnetic powder after being mixed with the ethanol solution of the composite coupling agent is 40-60%;
Stirring and refluxing for 3-5 hours at 50-90 ℃;
filtering, and drying at 110-160deg.C for 2-6 hr.
4. The method for producing a ferromagnetic silicone wristband core according to claim 1 or 2, wherein the solid silicone rubber raw rubber is at least one selected from vinyl silicone rubber raw rubber, methyl silicone rubber raw rubber, or phenyl vinyl silicone rubber raw rubber; and/or, the vulcanizing agent is bis-25 or benzoyl peroxide; and/or the hardness of the vulcanized solid silicone rubber raw rubber is Shore A50-70.
5. The method for producing a ferromagnetic silicone rubber wristband core material according to claim 1 or 2, wherein,
Mixing 80-92 parts by weight of modified magnetic powder, 9-20 parts by weight of solid silicone rubber raw rubber and 0.1-0.4 part by weight of vulcanizing agent at 40-50 ℃ and a roller ratio of 1.2-1.4;
And (3) molding the mixed rubber obtained by mixing at the mold temperature of 160-180 ℃ for 160-190s to obtain the wristband core material.
6. A ferromagnetic silicone rubber wristband core material, characterized in that it is produced by the method according to any one of claims 1 to 5.
7. A magnetic wristband comprising the wristband core of claim 6.
8. A method for producing a magnetic wristband, comprising coating and magnetizing the wristband core material according to claim 6, thereby obtaining a magnetic wristband.
9. The method of manufacturing a magnetic wristband according to claim 8, wherein the wristband core is coated with a thermosetting silicone rubber having a hardness of shore a50-70.
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