CN111378220B - Thermoplastic elastomer composite material replacing shielding magnetic ring and preparation method thereof - Google Patents
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Abstract
The invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring and a preparation method thereof, wherein the composite material comprises the following components in parts by mass: 15 to 35 parts of nano iron oxide, 5 to 15 parts of nano zinc oxide, 15 to 35 parts of nano manganic oxide, 0.05 to 0.2 part of functional auxiliary component, 10 to 30 parts of polypropylene resin, 10 to 30 parts of ethylene acrylate copolymer, 1 to 5 parts of POE grafted maleic anhydride, 0.1 to 1 part of silane coupling agent and 0.1 to 3 parts of processing aid.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a thermoplastic elastomer composite material for replacing a shielding magnetic ring and a preparation method thereof.
Background
With the continuous development of electronic technology, especially the rapid development of digital technology, countries around the world put great demands on anti-electromagnetic interference (EMI) technology for high-speed signal transmission, which requires that signal transmission cables, especially high-frequency signal transmission lines, have high EMI resistance. The soft magnetic ferrite is used as an important component material, a shielding magnetic ring prepared from the soft magnetic ferrite material is generally applied to various signal transmission cables, is a common anti-interference element in an electronic circuit, has a good inhibition effect on high-frequency noise, and is generally applied to power cables of precise electronic components in order to prevent interference caused by current impact during wire plugging and unplugging of various precise electronic devices, so that the impact of instantaneous surge current on the precise components during wire plugging and unplugging is prevented.
For a traditional process for preparing the magnetic ring, a series of procedures such as ball milling, drying, molding and sintering are usually carried out, the process is relatively complex, the sintering process is high in temperature and needs to consume large energy, meanwhile, the ball milling is carried out in an air atmosphere, so that a certain amount of air is adsorbed in powder, and in the sintering process, due to the high-temperature effect, the oxygen reacts with the powder, so that the magnetic property of the product is unstable, and the qualification rate of the product is increased. In the process of cable processing, the shielding magnetic ring is usually fixed by manually or mechanically threading and winding and finally injecting a layer of plastic on the shielding magnetic ring, so that the time and cost of the cable preparation process are increased by the whole process.
In recent years, nanotechnology has become more and more important in the polymer material modification industry, and a patent with application number 201610697635.0 discloses a preparation method of manganese-zinc ferrite nano-powder, wherein an active manganese-zinc ferrite nano-powder material is prepared by a chemical method, has the diameter of about 30nm, and has very high magnetic induction intensity. The patent with application number 201310294605.1 discloses a method for preparing a nano manganese zinc ferrite material by utilizing spray pyrolysis, and the prepared nano manganese zinc ferrite material has the characteristics of moderate particle size, good dispersion uniformity and excellent magnetic performance. The relatively mature preparation technology of the nano manganese zinc ferrite provides a raw material guarantee for preparing the thermoplastic elastomer composite material for replacing the shielding magnetic ring.
Disclosure of Invention
The invention aims to provide a thermoplastic elastomer composite material for replacing a shielding magnetic ring and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the coating comprises the following components in parts by mass:
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the particle size of the nano ferric oxide, the nano zinc oxide and the nano mangano-manganic oxide is within the range of 10nm to 100nm, and the purity of the nano ferric oxide, the nano zinc oxide and the nano mangano-manganic oxide is more than 99.5 percent;
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the functional auxiliary component is one or a mixture of several of nano titanium oxide, nano cobalt oxide, nano nickel oxide, nano calcium oxide and nano tin oxide;
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the polypropylene resin is one or the mixture of homopolymerized polypropylene resin and copolymerized polypropylene resin, the melt index range is 50-200 g/10min, the melt index test condition is 230 ℃, and 2.16 kg;
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the ethylene acrylate copolymer is one or a mixture of ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer and ethylene butyl acrylate copolymer, the content of acrylate in the copolymer molecule is 10-40%, the melt index range of the ethylene acrylate copolymer is 10-100 g/10min, and the melt index test condition is 190 ℃ and 2.16 kg;
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the POE grafted maleic anhydride is maleic anhydride grafted ethylene-propylene copolymer, maleic anhydride grafted ethylene-butylene copolymer or maleic anhydride grafted ethylene-octene copolymer, the grafting rate of the maleic anhydride is 0.8-1.5%, and the ratio of ethylene to a second monomer (propylene, butylene or octene) in the copolymer is 1: 1-3: 1;
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the silane coupling agent is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane and propenyl trimethoxy silane;
the invention relates to a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following components in percentage by weight: the processing aid comprises: an antioxidant and a lubricant, wherein: the antioxidant is one or a mixture of more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite, dilauryl thiodipropionate and octyl beta (3, 5-di-tert-butyl-4-hydroxy-propene) propionate; the lubricant is one or a mixture of more of oleamide, erucamide, PE wax and siloxane polymer;
the invention relates to a preparation method of a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following steps: comprises the following steps:
(1) accurately weighing nano iron oxide, nano zinc oxide, nano manganic manganous oxide, functional auxiliary components and a silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic manganous oxide and functional auxiliary components into an internal mixer, adjusting the temperature of the internal mixer to be 50-100 ℃, mixing for 8-15 minutes, adding the silane coupling agent while mixing by a liquid spraying device on the internal mixer, and continuously mixing for 5-10 minutes;
(2) after the temperature of the internal mixer is raised to 150 to 200 ℃, adding the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid in the proportion, and continuously mixing for 10 to 15 minutes;
(3) the banburying mixed material is put into a cone double-forced feeding machine through an automatic elevator, the temperature of the cone double-forced feeding machine is maintained at 150-200 ℃, the cone double-forced feeding machine feeds materials to a double-screw extruder, the double-screw extruder performs granulation, and the materials are granulated and dried to obtain the thermoplastic elastomer composite material replacing the shielding magnetic ring;
the invention relates to a preparation method of a thermoplastic elastomer composite material for replacing a shielding magnetic ring, which comprises the following steps: the double-screw extruder is composed of a feeding section, a conveying section, a melting section and a machine head in sequence, wherein the temperature of each section is set as follows: the material feeding section is 130 ℃ to 160 ℃, the conveying section is 150 ℃ to 190 ℃, the melting section is 170 ℃ to 230 ℃, and the machine head is 180 ℃ to 220 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ethylene-acrylate copolymer is added into the thermoplastic elastomer composite material for replacing the shielding magnetic ring, the copolymer and the polypropylene have good compatibility and a good coating effect on the inorganic nano-powder, and the addition of the ethylene-acrylate copolymer can obviously improve the filling amount of the material on the inorganic powder.
(2) According to the invention, the POE grafted maleic anhydride with high fluidity is added in the preparation of the thermoplastic elastomer composite material for replacing the shielding magnetic ring, and in the processing process, the POE grafted maleic anhydride with high fluidity can rapidly infiltrate the nano inorganic powder, so that the binding force of the resin to the nano inorganic powder is improved, and the impact strength of the material can be obviously improved.
(3) When the thermoplastic elastomer composite material replacing the shielding magnetic ring is prepared, a whole set of processing procedures of banburying by an internal mixer, feeding by a conical double-forced feeder and double-screw extrusion granulation are adopted, so that the dispersion of the nano inorganic powder in the resin is greatly improved, and the nano inorganic powder forms a stable magnetic conductive network in a polymer.
(4) The thermoplastic elastomer composite material replacing the shielding magnetic ring provided by the invention omits a series of processes such as ball milling, drying, forming, sintering and the like in the traditional magnetic ring preparation, can be directly fixed on the wire outer cover by injection molding in an injection molding machine injection molding mode, and saves the energy consumption and the production time in the production process.
Detailed Description
In order to better understand the invention, the invention will be further illustrated by the following examples, which are only used to explain the invention and should not be construed as limiting the invention in any way.
Example 1
A thermoplastic elastomer composite material for replacing a shielding magnetic ring comprises the following components in parts by mass:
25 parts of nano ferric oxide, 10 parts of nano zinc oxide, 21 parts of nano manganic oxide,
0.1 part of functional auxiliary component, 18 parts of polypropylene resin, 20 parts of ethylene acrylate copolymer,
4 parts of POE grafted maleic anhydride, 0.5 part of silane coupling agent and 1.4 parts of processing aid;
the preparation method of the composite material comprises the following steps:
(1) accurately weighing the nano iron oxide, the nano zinc oxide, the nano manganic oxide, the functional auxiliary component and the silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic oxide and the functional auxiliary component into an internal mixer, adjusting the temperature of the internal mixer to 80 ℃, mixing for 10 minutes, adding the silane coupling agent while mixing through a liquid spraying device on the internal mixer, and then continuously mixing for 10 minutes.
(2) Raising the temperature of the internal mixer to 170 ℃, adding the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid which are weighed according to the proportion, and continuously mixing for 12 minutes.
(3) The banburying mixed material is put into a cone double-forced feeding machine through an automatic elevator, the temperature of the cone double-forced feeding machine is maintained at 180 ℃, the cone double-forced feeding machine feeds the material to a double-screw extruder, and the temperature of each section in the double-screw extruder is set as follows: the feeding section is 150 ℃, the conveying section is 170 ℃, the melting section is 190 ℃ and the head is 210 ℃. Granulating by a double-screw extruder, granulating and drying to obtain the thermoplastic elastomer composite material for replacing the shielding magnetic ring.
Example 2
A thermoplastic elastomer composite material for replacing a shielding magnetic ring comprises the following components in parts by mass:
22 parts of nano ferric oxide, 9 parts of nano zinc oxide, 24 parts of nano manganic oxide,
0.08 part of functional auxiliary component, 14 parts of polypropylene resin, 25 parts of ethylene acrylate copolymer,
3.5 parts of POE grafted maleic anhydride, 0.4 part of silane coupling agent and 2.02 parts of processing aid;
the preparation method of the composite material comprises the following steps:
(1) accurately weighing the nano iron oxide, the nano zinc oxide, the nano manganic manganous oxide, the functional auxiliary component and the silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic manganous oxide and functional auxiliary component into an internal mixer, adjusting the temperature of the internal mixer to 90 ℃, mixing for 12 minutes, adding the silane coupling agent while mixing by a liquid spraying device on the internal mixer, and then continuously mixing for 8 minutes;
(2) after the temperature of the internal mixer is raised to 190 ℃, the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid which are weighed according to the proportion are added, and the mixture is continuously mixed for 10 minutes;
(3) the banburying mixed material is put into a cone double-forced feeding machine through an automatic elevator, the temperature of the cone double-forced feeding machine is maintained at 170 ℃, the cone double-forced feeding machine feeds the material to a double-screw extruder, and the temperature of each section in the double-screw extruder is set as follows: and the thermoplastic elastomer composite material replacing the shielding magnetic ring is obtained by granulating, granulating and drying through a double-screw extruder at the charging section of 160 ℃, the conveying section of 180 ℃, the melting section of 195 ℃ and the machine head of 205 ℃.
Example 3
A thermoplastic elastomer composite material for replacing a shielding magnetic ring comprises the following components in parts by mass:
23 parts of nano ferric oxide, 8 parts of nano zinc oxide, 22 parts of nano manganic manganous oxide,
0.12 part of functional auxiliary component, 22 parts of polypropylene resin, 18 parts of ethylene acrylate copolymer,
4.5 parts of POE grafted maleic anhydride, 0.6 part of silane coupling agent and 1.78 parts of processing aid;
the preparation method of the composite material comprises the following steps:
(1) accurately weighing the nano iron oxide, the nano zinc oxide, the nano manganic oxide, the functional auxiliary component and the silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic oxide and the functional auxiliary component into an internal mixer, adjusting the temperature of the internal mixer to 85 ℃, mixing for 14 minutes, adding the silane coupling agent while mixing by a liquid spraying device on the internal mixer, and then continuously mixing for 9 minutes;
(2) raising the temperature of the internal mixer to 175 ℃, adding the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid which are weighed according to the proportion, and continuously mixing for 13 minutes;
(3) the banburying mixed material is put into a conical double-forced feeding machine through an automatic elevator, the temperature of the conical double-forced feeding machine is maintained at 165 ℃, the conical double-forced feeding machine feeds the material to a double-screw extruder, and the temperature of each section in the double-screw extruder is set as follows: and the feeding section is 140 ℃, the conveying section is 175 ℃, the melting section is 220 ℃, the head is 200 ℃, a double-screw extruder is used for granulating, pelletizing and drying to obtain the thermoplastic elastomer composite material replacing the shielding magnetic ring.
Example 4
A thermoplastic elastomer composite material for replacing a shielding magnetic ring comprises the following components in parts by mass:
24 parts of nano iron oxide, 9 parts of nano zinc oxide, 23 parts of nano manganic manganous oxide,
0.09 part of functional auxiliary component, 20 parts of polypropylene resin, 18 parts of ethylene acrylate copolymer,
4 parts of POE grafted maleic anhydride, 0.45 part of silane coupling agent and 1.46 parts of processing aid;
the preparation method of the composite material comprises the following steps:
(1) accurately weighing the nano iron oxide, the nano zinc oxide, the nano manganic oxide, the functional auxiliary component and the silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic oxide and the functional auxiliary component into an internal mixer, adjusting the temperature of the internal mixer to 60 ℃, mixing for 11 minutes, adding the silane coupling agent while mixing through a liquid spraying device on the internal mixer, and then continuously mixing for 7 minutes;
(2) raising the temperature of the internal mixer to 185 ℃, adding the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid which are weighed according to the proportion, and continuously mixing for 10 minutes;
(3) the banburying mixed material is put into a cone double-forced feeding machine through an automatic elevator, the temperature of the cone double-forced feeding machine is maintained at 170 ℃, the cone double-forced feeding machine feeds the material to a double-screw extruder, and the temperature of each section in the double-screw extruder is set as follows: and the feeding section is 150 ℃, the conveying section is 180 ℃, the melting section is 210 ℃, the head is 210 ℃, granulation is carried out by a double-screw extruder, and the composite material replacing the shielding magnetic ring thermoplastic elastomer is obtained after granulation and drying.
Example 5
A thermoplastic elastomer composite material for replacing a shielding magnetic ring comprises the following components in parts by mass:
22 parts of nano ferric oxide, 7 parts of nano zinc oxide, 26 parts of nano manganic oxide,
0.11 part of functional auxiliary component, 20 parts of polypropylene resin, 19 parts of ethylene acrylate copolymer,
3.7 parts of POE grafted maleic anhydride, 0.55 part of silane coupling agent and 1.64 parts of processing aid;
the preparation method of the composite material comprises the following steps:
(1) accurately weighing the nano iron oxide, the nano zinc oxide, the nano manganic oxide, the functional auxiliary component and the silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic oxide and the functional auxiliary component into an internal mixer, adjusting the temperature of the internal mixer to 90 ℃, mixing for 10 minutes, adding the silane coupling agent while mixing by a liquid spraying device on the internal mixer, and continuing mixing for 8 minutes;
(2) after the temperature of the internal mixer is raised to 190 ℃, the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid which are weighed according to the proportion are added, and the mixture is continuously mixed for 10 minutes.
(3) The banburying mixed material is put into a conical double-forced feeding machine through an automatic elevator, the temperature of the conical double-forced feeding machine is maintained at 165 ℃, the conical double-forced feeding machine feeds the material to a double-screw extruder, and the temperature of each section in the double-screw extruder is set as follows: and the feeding section is 155 ℃, the conveying section is 175 ℃, the melting section is 205 ℃, the head is 210 ℃, granulation is carried out by a double-screw extruder, and the composite material for replacing the shielding magnetic ring thermoplastic elastomer is obtained after granulation and drying.
The test results are shown in table 1.
TABLE 1
From table 1, the thermoplastic elastomer prepared by the invention has high magnetic conductivity and saturation magnetic induction intensity, has excellent mechanical properties, and can replace a shielding magnetic ring.
The foregoing is considered as illustrative of the embodiments of the present invention and is not to be construed as limiting thereof. The scope of the invention should be determined from the following claims.
Claims (10)
1. A thermoplastic elastomer composite material for replacing a shielding magnetic ring is characterized in that: the coating comprises the following components in parts by mass:
2. the substitute shielding magnetic ring thermoplastic elastomer composite material as claimed in claim 1, wherein: the particle size of the nano ferric oxide, the nano zinc oxide and the nano mangano-manganic oxide is within the range of 10nm to 100nm, and the purity of the nano ferric oxide, the nano zinc oxide and the nano mangano-manganic oxide is more than 99.5 percent.
3. The substitute shielding magnetic ring thermoplastic elastomer composite material as claimed in claim 2, wherein: the functional auxiliary component is one or a mixture of several of nano titanium oxide, nano cobalt oxide, nano nickel oxide, nano calcium oxide and nano tin oxide.
4. The alternative shielding magnet ring thermoplastic elastomer composite material as set forth in claim 3, wherein: the polypropylene resin is one or the mixture of homopolymerized polypropylene resin and copolymerized polypropylene resin, the melt index range is 50-200 g/10min, and the melt index test condition is 230 ℃ and 2.16 kg.
5. The substitute shielding magnetic ring thermoplastic elastomer composite material as claimed in claim 4, wherein: the ethylene acrylate copolymer is one or a mixture of ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer and ethylene butyl acrylate copolymer, the content of acrylate in the copolymer molecule is 10-40%, the melt index range of the ethylene acrylate copolymer is 10-100 g/10min, and the melt index test condition is 190 ℃ and 2.16 kg.
6. The composite material as claimed in claim 5, wherein the thermoplastic elastomer is selected from the group consisting of: the POE grafted maleic anhydride is maleic anhydride grafted ethylene-propylene copolymer, maleic anhydride grafted ethylene-butylene copolymer or maleic anhydride grafted ethylene-octene copolymer, the grafting rate of the maleic anhydride is 0.8-1.5%, and the ratio of ethylene to propylene, butylene or octene in the copolymer is 1: 1-3: 1.
7. The substitute shielding magnetic ring thermoplastic elastomer composite material as claimed in claim 6, wherein: the silane coupling agent is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane and propenyl trimethoxy silane.
8. The composite material as claimed in claim 7, wherein the thermoplastic elastomer is selected from the group consisting of: the processing aid comprises: an antioxidant and a lubricant, wherein: the antioxidant is one or a mixture of more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite, dilauryl thiodipropionate and octyl beta (3, 5-di-tert-butyl-4-hydroxy-propene) propionate; the lubricant is one or a mixture of more of oleamide, erucamide, PE wax and siloxane polymer.
9. The method for preparing the thermoplastic elastomer composite material for the substitute shielding magnetic ring as claimed in claim 8, wherein the method comprises the following steps: comprises the following steps:
(1) accurately weighing nano iron oxide, nano zinc oxide, nano manganic manganous oxide, functional auxiliary components and a silane coupling agent according to the proportion, putting the weighed nano iron oxide, nano zinc oxide, nano manganic manganous oxide and functional auxiliary components into an internal mixer, adjusting the temperature of the internal mixer to be 50-100 ℃, mixing for 8-15 minutes, adding the silane coupling agent while mixing by a liquid spraying device on the internal mixer, and continuously mixing for 5-10 minutes;
(2) after the temperature of the internal mixer is raised to 150 to 200 ℃, adding the polypropylene resin, the ethylene acrylate copolymer, the POE grafted maleic anhydride and the processing aid in the proportion, and continuously mixing for 10 to 15 minutes;
(3) and (3) putting the internally mixed material into a conical double-forced feeding machine through an automatic elevator, maintaining the temperature of the conical double-forced feeding machine at 150-200 ℃, feeding the material into a double-screw extruder through the conical double-forced feeding machine, granulating by the double-screw extruder, and granulating and drying to obtain the thermoplastic elastomer composite material for replacing the shielding magnetic ring.
10. The method for preparing the composite material of the thermoplastic elastomer for the substitute shielding magnetic ring as claimed in claim 9, wherein: the double-screw extruder is composed of a feeding section, a conveying section, a melting section and a machine head in sequence, wherein the temperature of each section is set as follows: the feeding section is 130-.
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