阅读说明：本技术 一种叠层片式聚合物静电抑制器 (Laminated sheet type polymer static suppressor ) 是由 张景松 梁汉钦 于 2020-05-26 设计创作，主要内容包括：本发明涉及静电抑制器领域,具体涉及一种叠层片式聚合物静电抑制器,包括形状呈长方体的静电抑制器基体,所述静电抑制器基体的每个侧面上至少设置有一个外电极,所述外电极与设置在所述静电抑制器基体内部的内电极相连,所述内电极沿其导电方向还设置有聚合物层。本发明解决了现有的聚合物层高分子材料耐热性及耐老化性不好,在重复施加静电情况下,会造成材料劣变而导致电性能的下降的问题。本发明的静电抑制器在结构上是叠层片式结构,这样结构的设计能够利于实现超低电容量,在传输信号较快时也不会造成信号的衰减及失真。(The invention relates to the field of static suppressors, in particular to a laminated sheet type polymer static suppressor, which comprises a static suppressor base body in a cuboid shape, wherein each side surface of the static suppressor base body is provided with at least one external electrode, the external electrode is connected with an internal electrode arranged in the static suppressor base body, and the internal electrode is also provided with a polymer layer along the conducting direction. The invention solves the problems that the heat resistance and the aging resistance of the polymer material of the existing polymer layer are poor, and the electrical property is reduced due to the deterioration of the material under the condition of repeatedly applying static electricity. The electrostatic suppressor is structurally of a laminated structure, so that the structural design is favorable for realizing ultra-low capacitance, and the signal attenuation and distortion can not be caused when the signal is transmitted quickly.)

1. The laminated sheet type polymer static suppressor is characterized by comprising a static suppressor substrate in a cuboid shape, wherein each side surface of the static suppressor substrate is provided with at least one external electrode, the external electrode is connected with an internal electrode arranged in the static suppressor substrate, and the internal electrode is also provided with a polymer layer along the conducting direction of the internal electrode; each of the internal electrodes and the polymer layer form a sheet unit, a plurality of the sheet units are arranged in a stacked sheet manner in a direction from an upper bottom surface to a lower bottom surface inside the static electricity suppressor base body, and the plurality of the sheet units form a stacked sheet type structure.

2. The multilayer sheet type polymer static suppressor according to claim 1, wherein the external electrodes on the opposite surfaces of the static suppressor substrate are arranged in a staggered manner.

3. The laminated sheet type polymer static suppressor according to claim 1, wherein the width of said inner electrode does not exceed the width of the outer electrode, and the thickness of said inner electrode is 1 to 10 μm; the thickness of the polymer layer is 5-20 μm.

4. The laminated sheet type polymer static electricity suppressor according to claim 1, wherein said polymer layer is composed of a heat-resistant type material and metal particles, and said metal particles are composed of conductive particles, semiconductor particles and insulating particles.

5. The laminated sheet type polymer static suppressor according to claim 1, wherein the distribution of the metal particles of the polymer layer is gradually decreased from the center of the laminated sheet type structure to the two bottom surfaces.

6. The laminated sheet type polymer static suppressor according to claim 4, wherein the heat-resistant material is composed of the following components in parts by weight:

50-100 parts of modified polyvinyl chloride resin, 2-15 parts of toughening agent and 3-10 parts of stabilizing agent.

7. The laminated sheet type polymer static suppressor according to claim 6, wherein the modified polyvinyl chloride resin is prepared by a method comprising:

s1, weighing lignans and m-bis (4-pyridyl) benzene, adding the lignans and the m-bis (4-pyridyl) benzene into N, N-dimethylformamide, vacuumizing, introducing rare gas serving as protective gas, stirring to be uniform, placing in an oil bath, stirring and reacting at 120-150 ℃ for 12-18 h, cooling to room temperature, filtering to obtain a solid, washing with chloroform for three times, and freeze-drying to obtain a product A;

wherein the mass ratio of the lignan to the m-bis (4-pyridyl) benzene to the N, N-dimethylformamide is 1: 2-3: 15-30;

s2, weighing the product A, adding the product A into acetone, stirring the mixture uniformly, adding ammonium perchlorate powder, stirring the mixture uniformly again, placing the mixture into an ice water bath, stirring the mixture for reaction for 10-15 hours, filtering the mixture to obtain a solid, washing the solid for three times by using chloroform, and freeze-drying the solid to obtain a product B;

wherein the solid-to-liquid ratio of the product A, the ammonium perchlorate powder and the acetone is 1: 0.05-0.1: 10-20;

s3, adding the product B into tetrahydrofuran, dispersing uniformly, slowly and dropwisely adding iron pentacarbonyl under a light-tight condition, stirring uniformly, placing in a water bath at 40-60 ℃ for light-tight reaction for 15-18 h by taking rare gas as protective gas, filtering by using a sand core funnel with silica gel as a layer, adding the filtered liquid into diethyl ether with the same volume as the filtered liquid, stirring for 1-2 h, filtering to obtain a solid, washing with diethyl ether for three times, freeze-drying, and crushing to obtain a nano particle, thus obtaining a product C;

wherein the mass ratio of the product B, the iron pentacarbonyl and the tetrahydrofuran is 1: 0.1-0.5: 10-20;

s4, adding polyvinyl chloride resin into a high-speed mixer, heating to 75-85 ℃, adding the product C, and mixing and stirring at a high speed until the mixture is uniform to obtain modified polyvinyl chloride resin;

wherein the mass ratio of the polyvinyl chloride resin to the product C is 1: 0.01-0.1.

8. The laminated sheet type polymer static suppressor according to claim 6, wherein the toughening agent is a modified liquid nitrile rubber;

the preparation method of the modified liquid nitrile rubber comprises the following steps:

s1, uniformly stirring N-methyl pyrrolidone and toluene in a volume ratio of 3:1 to form a mixed solvent; weighing liquid nitrile rubber, adding the weighed liquid nitrile rubber into the mixed solvent, stirring the mixture to be uniform, sequentially adding thiopropanoic acid and cumene hydroperoxide, taking rare gas as protective gas, placing the mixture in a water bath at the temperature of 80-90 ℃, stirring the mixture for reaction for 3-5 hours, and cooling the mixture to 30-40 ℃ to obtain liquid nitrile rubber modified mixed liquid;

wherein the mass ratio of the liquid nitrile rubber to the mixed solvent is 1: 5-10; the mass ratio of the liquid nitrile rubber, the thiopropionic acid and the cumene hydroperoxide is 1: 0.2-0.5: 0.01-0.1;

s2, adding N-methyl pyrrolidone into the liquid nitrile rubber modified mixed solution, stirring uniformly, adding ethanol for washing, removing an ethanol layer after layering, washing for three times, and performing vacuum drying to obtain a liquid nitrile rubber pre-modified substance;

wherein the volume ratio of the liquid nitrile rubber modified mixed solution to the N-methyl pyrrolidone is 1: 0.5 to 2;

s3, weighing the liquid nitrile rubber pre-modifier, adding the liquid nitrile rubber pre-modifier into N-methyl pyrrolidone, stirring until the mixture is uniform, dropwise adding glycidyl methacrylate, taking rare gas as protective gas, placing the mixture in a water bath at the temperature of 40-60 ℃, stirring and reacting for 1-4 hours, and performing vacuum drying to obtain modified liquid nitrile rubber;

wherein the mass ratio of the liquid nitrile rubber pre-modifier to the glycidyl methacrylate to the N-methyl pyrrolidone is 1: 0.02-0.1: 5-10.

9. The laminated sheet type polymer static suppressor according to claim 6, wherein the stabilizer is prepared by the following steps:

s1, weighing thiopropionic acid, adding the thiopropionic acid into chloroform, stirring the mixture uniformly, adding ferric chloride powder, stirring the mixture uniformly again, dropwise adding a potassium permanganate solution with the mass concentration of 0.05%, placing the mixture at room temperature, stirring the mixture for reaction for 3-5 hours, adding a saturated sodium carbonate solution with the same volume as that of the chloroform, shaking and washing the mixture, extracting an organic phase, adding deionized water with the same volume as that of the chloroform, shaking and washing the mixture, extracting the organic phase again, distilling the mixture under reduced pressure to dry the mixture, and grinding the mixture into powder to obtain a solid M;

wherein the mass ratio of the thiopropionic acid, the ferric chloride powder, the potassium permanganate solution and the chloroform is 1: 0.01-0.05: 0.05-0.1: 10-20;

s2, weighing the solid M, adding the solid M into diisopropyl ether, stirring the mixture uniformly, adding p-toluenesulfonic acid, placing the mixture at room temperature, stirring the mixture for reaction for 3-5 hours, adding deionized water with the same volume as the diisopropyl ether, shaking and washing the mixture, extracting an organic phase, distilling the organic phase under reduced pressure to be dry, and placing the dried organic phase in a grinder to grind the mixture to nano-particles to obtain a stabilizer;

wherein the mass ratio of the solid M, the p-toluenesulfonic acid and the diisopropyl ether is 1: 0.01-0.1: 10-20.

10. The laminated sheet type polymer static suppressor according to claim 4, wherein said conductive particles are nano-scale particles of nickel, nickel carbonyl, aluminum, silver, copper or carbon, said semiconductor particles are nano-scale particles of barium titanate, zinc oxide or silicon carbide, and said insulating particles are nano-scale particles of magnesium oxide, aluminum oxide or silicon dioxide.

Technical Field

The invention relates to the field of static suppressors, in particular to a laminated sheet type polymer static suppressor.

Background

Static electricity is typically generated by friction between two poor conductors, causing electrons to migrate from one poor conductor to the other, and can reach thousands of volts. For many electronic devices, the number of times of inserting and extracting the input and output interfaces of the electronic devices into and from the external electronic storage device is very large, so that static electricity is often applied to input and output connection electronic components, and when the generated static electricity discharges to voltage-sensitive electronic components, the electronic components can be damaged, so that the whole electronic circuit is damaged. The static electricity causes irreversible damage to electronic components and circuit systems, which makes the electronic products unable to work normally. Therefore, it is required to install a protection static suppressor in a general electronic circuit.

In the electrostatic suppressor, an electrostatic suppressing functional layer is used, and the electrostatic suppressing functional layer is generally formed by mixing metal particles and a polymer material, and then kneading them by means of grinding or the like. However, a polymer material for uniformly dispersing and isolating metal particles from each other is not good in heat resistance and aging resistance, and in the case of repeatedly applying static electricity, material deterioration is caused to cause a decrease in electrical properties.

Disclosure of Invention

In view of the above problems, the present invention provides a laminated sheet type polymer static suppressor, comprising a static suppressor substrate in a shape of a cuboid, wherein each side surface of the static suppressor substrate is provided with at least one external electrode, the external electrode is connected with an internal electrode arranged inside the static suppressor substrate, and the internal electrode is further provided with a polymer layer along a conductive direction thereof; each of the internal electrodes and the polymer layer form a sheet unit, a plurality of the sheet units are arranged in a stacked sheet manner in a direction from an upper bottom surface to a lower bottom surface inside the static electricity suppressor base body, and the plurality of the sheet units form a stacked sheet type structure.

Preferably, the external electrodes on the opposite faces of the static electricity suppressor base body are arranged in a staggered manner.

Preferably, the width of the inner electrode does not exceed the width of the outer electrode, and the thickness of the inner electrode is 1-10 μm; the thickness of the polymer layer is 5-20 μm.

Preferably, the polymer layer is composed of a heat-resistant type material and metal particles composed of conductive particles, semiconductor particles and insulating particles.

Preferably, the distribution of the metal particles of the polymer layer gradually decreases from the center of the laminated sheet structure to the two bottom surfaces.

Preferably, the heat-resistant material consists of the following components in parts by weight:

50-100 parts of modified polyvinyl chloride resin, 2-15 parts of toughening agent and 3-10 parts of stabilizing agent.

Preferably, the preparation method of the modified polyvinyl chloride comprises the following steps:

s1, weighing lignans and m-bis (4-pyridyl) benzene, adding the lignans and the m-bis (4-pyridyl) benzene into N, N-dimethylformamide, vacuumizing, introducing rare gas serving as protective gas, stirring to be uniform, placing in an oil bath, stirring and reacting at 120-150 ℃ for 12-18 h, cooling to room temperature, filtering to obtain a solid, washing with chloroform for three times, and freeze-drying to obtain a product A;

wherein the mass ratio of the lignan to the m-bis (4-pyridyl) benzene to the N, N-dimethylformamide is 1: 2-3: 15-30;

s2, weighing the product A, adding the product A into acetone, stirring the mixture uniformly, adding ammonium perchlorate powder, stirring the mixture uniformly again, placing the mixture into an ice water bath, stirring the mixture for reaction for 10-15 hours, filtering the mixture to obtain a solid, washing the solid for three times by using chloroform, and freeze-drying the solid to obtain a product B;

wherein the solid-to-liquid ratio of the product A, the ammonium perchlorate powder and the acetone is 1: 0.05-0.1: 10-20;

s3, adding the product B into tetrahydrofuran, dispersing uniformly, slowly and dropwisely adding iron pentacarbonyl under a light-tight condition, stirring uniformly, placing in a water bath at 40-60 ℃ for light-tight reaction for 15-18 h by taking rare gas as protective gas, filtering by using a sand core funnel with silica gel as a layer, adding the filtered liquid into diethyl ether with the same volume as the filtered liquid, stirring for 1-2 h, filtering to obtain a solid, washing with diethyl ether for three times, freeze-drying, and crushing to obtain a nano particle, thus obtaining a product C;

wherein the mass ratio of the product B, the iron pentacarbonyl and the tetrahydrofuran is 1: 0.1-0.5: 10-20;

s4, adding polyvinyl chloride resin into a high-speed mixer, heating to 75-85 ℃, adding the product C, and mixing and stirring at a high speed until the mixture is uniform to obtain modified polyvinyl chloride;

wherein the mass ratio of the polyvinyl chloride resin to the product C is 1: 0.01-0.1.

Preferably, the toughening agent is a modified liquid nitrile rubber.

Preferably, the preparation method of the modified liquid nitrile rubber comprises the following steps:

s1, uniformly stirring N-methyl pyrrolidone and toluene in a volume ratio of 3:1 to form a mixed solvent; weighing liquid nitrile rubber, adding the weighed liquid nitrile rubber into the mixed solvent, stirring the mixture to be uniform, sequentially adding thiopropanoic acid and cumene hydroperoxide, taking rare gas as protective gas, placing the mixture in a water bath at the temperature of 80-90 ℃, stirring the mixture for reaction for 3-5 hours, and cooling the mixture to 30-40 ℃ to obtain liquid nitrile rubber modified mixed liquid;

wherein the mass ratio of the liquid nitrile rubber to the mixed solvent is 1: 5-10; the mass ratio of the liquid nitrile rubber, the thiopropionic acid and the cumene hydroperoxide is 1: 0.2-0.5: 0.01-0.1;

s2, adding N-methyl pyrrolidone into the liquid nitrile rubber modified mixed solution, stirring uniformly, adding ethanol for washing, removing an ethanol layer after layering, washing for three times, and performing vacuum drying to obtain a liquid nitrile rubber pre-modified substance;

wherein the volume ratio of the liquid nitrile rubber modified mixed solution to the N-methyl pyrrolidone is 1: 0.5 to 2;

s3, weighing the liquid nitrile rubber pre-modifier, adding the liquid nitrile rubber pre-modifier into N-methyl pyrrolidone, stirring until the mixture is uniform, dropwise adding glycidyl methacrylate, taking rare gas as protective gas, placing the mixture in a water bath at the temperature of 40-60 ℃, stirring and reacting for 1-4 hours, and performing vacuum drying to obtain modified liquid nitrile rubber;

wherein the mass ratio of the liquid nitrile rubber pre-modifier to the glycidyl methacrylate to the N-methyl pyrrolidone is 1: 0.02-0.1: 5-10.

Preferably, the preparation method of the stabilizer comprises the following steps:

s1, weighing thiopropionic acid, adding the thiopropionic acid into chloroform, stirring the mixture uniformly, adding ferric chloride powder, stirring the mixture uniformly again, dropwise adding a potassium permanganate solution with the mass concentration of 0.05%, placing the mixture at room temperature, stirring the mixture for reaction for 3-5 hours, adding a saturated sodium carbonate solution with the same volume as that of the chloroform, shaking and washing the mixture, extracting an organic phase, adding deionized water with the same volume as that of the chloroform, shaking and washing the mixture, extracting the organic phase again, distilling the mixture under reduced pressure to dry the mixture, and grinding the mixture into powder to obtain a solid M;

wherein the mass ratio of the thiopropionic acid, the ferric chloride powder, the potassium permanganate solution and the chloroform is 1: 0.01-0.05: 0.05-0.1: 10-20;

s2, weighing the solid M, adding the solid M into diisopropyl ether, stirring the mixture uniformly, adding p-toluenesulfonic acid, placing the mixture at room temperature, stirring the mixture for reaction for 3-5 hours, adding deionized water with the same volume as the diisopropyl ether, shaking and washing the mixture, extracting an organic phase, distilling the organic phase under reduced pressure to be dry, and placing the dried organic phase in a grinder to grind the mixture to nano-particles to obtain a stabilizer;

wherein the mass ratio of the solid M, the p-toluenesulfonic acid and the diisopropyl ether is 1: 0.01-0.1: 10-20.

Preferably, the conductive particles are nanoscale particles of nickel, nickel carbonyl, aluminum, silver, copper or carbon, the semiconductor particles are nanoscale particles of barium titanate, zinc oxide or silicon carbide, and the insulating particles are nanoscale particles of magnesium oxide, aluminum oxide or silicon dioxide.

The invention has the beneficial effects that:

1. the invention discloses a laminated sheet type polymer static suppressor which is small in size, can remarkably reduce the occupied space of the static suppressor and provides more convenience for electronic circuit design and manufacture. Meanwhile, the electrostatic suppressor is structurally of a laminated sheet type structure, so that the structural design is favorable for realizing ultra-low capacitance, and the signal attenuation and distortion can not be caused when the signal is transmitted quickly. In addition, the polymer layer in the laminated sheet type design is prepared by mixing heat-resistant materials, metal ions and insulating particles, has good dispersity and excellent heat resistance and aging resistance, and does not cause the reduction of electric performance even under the condition of repeatedly applying static electricity.

2. The invention uses lignan and m-di (4-pyridyl) benzene to react to synthesize a lignin-bipyridyl carbene ligand, the ligand reacts with pentacarbonyl iron subsequently to generate lignin-iron carbene by combination, the product is a supermolecule compound containing a metal atom and a nonmetal atom heterocyclic organic framework, the heterocyclic organic framework is provided with a bipyridyl rigid ligand and a flexible ligand in a lignin structure, the ligand structures are expanded into a two-dimensional network structure through hydrogen bonds, and the ligand structures are further expanded into a three-dimensional supermolecule structure through stacking effect. The heterocyclic organic framework increases the compatibility of the polyvinyl chloride and other materials, and promotes the synthesized composite material to have better dispersibility, and the good dispersibility can directly influence the electrostatic protection performance of the composite material.

3. Although the liquid nitrile rubber can improve the cold resistance, heat resistance/light/aging resistance, oil resistance, migration resistance and the like of the polyvinyl chloride, the toughness of the polyvinyl chloride is improved to a certain extent at normal temperature, when the temperature of the polyvinyl chloride is increased, the toughening effect of the polyvinyl chloride is in a cliff type gliding mode. Therefore, the liquid nitrile rubber is modified to have stronger crosslinking property with polyvinyl chloride, and stronger toughening effect can be formed even at high temperature. Firstly, liquid nitrile rubber reacts with thiopropionic alcohol under the action of cumene hydroperoxide to carry out hydroxyl activation, and then gradually cross-linked to form a net structure under the action of glycidyl methacrylate, wherein the net structure is a sacrificial structure, and after being doped into polyvinyl chloride, the polyvinyl chloride is subjected to strong pulling deformation to break before a polyvinyl chloride main chain, so that chain segment orientation is promoted, and the strength, the modulus and the toughness of the polyvinyl chloride are improved.

4. The invention uses thiopropanoic acid to carry out auto-polymerization reaction under the action of ferric chloride and potassium permanganate to obtain a product solid M containing disulfide bonds, and the solid M is auto-polymerized into a ring-shaped substance, namely a stabilizer, under the catalytic action of methanesulfonic acid. The fracture toughness is mainly determined by the strength and plasticity of the resin, and the stabilizer has more flexible chains and can improve the plasticity of the polyvinyl chloride resin, so that the fracture toughness of the polyvinyl chloride resin is improved to a certain extent. In addition, the stabilizer can repair fine cracks, namely, the stabilizer can promote the fine cracks to complete self-repair in the use process of the static suppressor. As the polyvinyl chloride material belongs to a thermoplastic material, the temperature of the material can be raised to a higher temperature, the disulfide bonds in the stabilizer can be cracked to generate sulfur free radicals under the action of high temperature, and the generated sulfur free radicals can perform exchange reaction with other disulfide bonds, so that the material interface in the crack generates new cross-linking, and the crack repair is completed.

Drawings

The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.

FIG. 1 is a cross-sectional view of a laminated sheet polymer static suppressor of the present invention;

fig. 2 is a side view of a laminated sheet polymer static suppressor of the present invention.

Reference numerals: a static electricity suppressor base body 1; an outer electrode 2; an inner electrode 3; a polymer layer 4.

Detailed Description

The invention is further described with reference to the following examples.