CN1267893A - Magnetic polymer base material and shapes of the material - Google Patents
Magnetic polymer base material and shapes of the material Download PDFInfo
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- CN1267893A CN1267893A CN99114711A CN99114711A CN1267893A CN 1267893 A CN1267893 A CN 1267893A CN 99114711 A CN99114711 A CN 99114711A CN 99114711 A CN99114711 A CN 99114711A CN 1267893 A CN1267893 A CN 1267893A
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Abstract
The magnetic polymer base material consists of one kind of magnetic polymer metal material containing ferrocene component with amino or amido group or metal compound of low-molecular weight magnetic material as component A and metal compound of small-molecular glycol and diaminodihydrazine or dioxime as component B and conventional thermoplastic resin material and is prepared through mixing and modification. The said metal may be one of Fe, Co, Ni, Cu, Zn, Ca, Mg, Ga, Yb and Gd. The total amount of component A and component B is 10-70% of the base material, and the rest is the modifying thermoplastic resin material. The base material is produced into sheet, rod or ring through extrusion, injection or hot pressing.
Description
What the present invention relates to is that a kind of macromolecule magnetic polymer base material material reaches by its macromolecule magnetic polymer base material of making.
In modern science and technology, microwave communication and microstrip circuit are just little towards lightweight, miniaturization and plane, and promptly light, little, thin direction develops.Though traditional inorganic soft magnetic material such as ferrite, metal and alloy material is widely used at the everyway of producing and live already, but it can sharply increase with the increase of frequency of utilization than great and magnetic loss, therefore these traditional inorganic soft magnetic materials and dielectric material have been difficult to adapt to the requirement of microwave communication, can not directly be made into the magnetic substrate and are used for charged road of little electricity and microstrip antenna.
For making microwave device light, little, thin, a kind of dielectric material substrate of normal at present use.As realizing industrialized ceramic substrate, titanium dioxide-barium titanate (strontium titanates), polytetrafluoroethylene and glass fibre composite dielectric substrate, and different materials substrates such as polytetrafluoroethylene or polystyrene substrate.Wherein, ceramic substrate be with purity be 99.99% pottery behind high temperature sintering, in surface evaporation crome metal is arranged, copper facing becomes substrate again.Be characterized in the dielectric constant height, loss is low, but complex process is crisp firmly, and processing difficulties costs an arm and a leg.Titanium dioxide, barium titanate (strontium titanates) and polytetrafluoroethylene composite dielectric substrate be with its three after fully mixing, through hot-forming and be laminated with copper sheet and form.Be characterized in certain dielectric constant, processing is relatively easy, but property is crisp firmly, high price.Directly with polytetrafluoroethylene or polystyrene as dielectric substrate, though easy to process, dielectric constant only is 2～3, the physical dimension of electronic device is too big, thereby only can be applicable to some ground communications facility.
The objective of the invention is at above-mentioned situation, a kind of macromolecule magnetic polymer base material material is provided and,, satisfies light, little, the thin needs on the manufacturing microwave device to address the above problem by its macromolecule magnetic polymer base material of making.
Usually, when electromagnetic wave by relative dielectric constant ε
rWith relative permeability μ
rMaterial the time, wavelength decreases
Doubly.Because physical dimension is relevant with the wavelength in the magnetic material, thus with non-magnetic dielectric material relatively, the magnetic wave antenna that contracts obviously can have littler size.With above-mentioned dielectric material substrate (sheet) relatively, use suitable magnetic material after, can make it both have certain magnetic permeability μ
r, have certain DIELECTRIC CONSTANT again
rAnd these two have the combination of the factor of the wave energy that contracts that the physical dimension of microwave communication device is reduced, and can also improve the function as others such as directivity.
The macromolecule magnetic polymer base material material that the present invention is alleged, become through blending and modifying by at least a with the conventional thermoplastic resin material in following component A and the B component, wherein total consumption of component A and B component is 10%～70% of a macromolecule magnetic polymer base material material total weight, the plastics resin material that all the other are used for modification.Wherein said component A can be for any contains the organometallic polymer magnetic material of the ferrocene composition of amido, amino or carbonyl in ferrocene phenylenediamine, ferrocene ethylenediamine, ferrocene benzidine, ferrocene diketone, ferrocene dialdehyde, ferrocene aminobenzene phenylate and the ferrocene MDA, or the metal complex of the metal organic low molecular magnetic material of said ferrocene composition.Here said organometallic polymer or the low molecular magnetic materials division boundary aspect molecular weight is very not strict, and is very unimportant yet, for example, and can be roughly approximately with molecular weight 3000 boundary.Said B component can be the metal complex of any micromolecule glycol, diamines (ammonia), two hydrazines or dioxime in ethylene glycol, hexylene glycol, benzene dimethanol, ethylenediamine, hexamethylene diamine, benzidine, MDA, chrysoidine, the diaminourea phenylate, and what wherein related metal all can be in iron, cobalt, nickel, copper, zinc, calcium, magnesium, gallium, yttrium, the gadolinium is any.The thermoplastic resin material of said routine can be in powdery, granular or bar-shaped polyethylene, polypropylene, polystyrene, Merlon, polyurethane, polysulfones, polyethers, polyphenylene sulfide, polymethyl methacrylate, polyphenylene oxide, polyester terephthalate, epoxy resin, unsaturated-resin, the polytetrafluoroethylene any in the component.
For component A and B component, according to the difference of use field and/or purposes, can only use wherein a kind of separately, also can the different mixture ratio example use A and two kinds of components of B simultaneously.Generally can select for use by employed different frequency range.Because the ferrocene high score subclass organo-metallic material among the component A has low magnetic loss, low permeability, therefore when the frequency of utilization scope is frequency range more than 1000 megahertzes, can preferentially select this type of material for use; When the frequency range of frequency of utilization in 300～1000 megahertz range, suggestion can be selected low molecular material or the category-B component in the A component for use; Frequency of utilization is when the frequency range of 20～300 megahertz range, can use the mixture of forming by two kinds of components of A, B, and can be according to the relative height that uses frequency range, suitably adjust the ratio of component A and B component, reach the demand that can adapt to special frequency channel best, though can satisfy the needs on the performance that the higher permeability of magnetic loss also can be higher again.
Selecting for use of the B component that constitutes for above-mentioned metal complex by micromolecule glycol, diamines (ammonia), two hydrazines or dioxime, can select according to the difference of use field and/or purposes equally, general also can the employed frequency range of product as the guideline of selecting for use.As, frequency of utilization when the frequency range of 300～1000 megahertz range, the metal complex of glycol that optional usefulness is above-mentioned or two hydrazine classes; Frequency of utilization can be selected the metal complex of dioxime or two amines for use when the frequency range of 20～300 megahertz range.Test also shows, and is if the metal complex of glycol, two hydrazine classes is mixed use mutually with dioxime or diamines metal complexes, then except that the dielectric constant that slightly increases material, generally little to the influence that its magnetic permeability changes.
The thermoplastic resin material of above-mentioned component A and/or B component and routine is carried out blending and modifying, can be at SK type or SKL type mixing roll commonly used, or X (S) M type banbury, or in the GH type high speed kneader, compounding process routinely, as, can be in 100 ℃～400 ℃ normal ranges mixingly carry out modification more than 30 minutes, this process and operation be there is no other specific (special) requirements.
On the basis of above-mentioned composition, use the needs in field according to difference, can also be incorporated as 0～20% conventional pulverous carbonyl iron of raw material total weight in case of necessity, carbonyl nickel, permalloy, soft magnetic ferrite, the dilval of crystalline state, amorphous alloy, titanium oxide, silica, barium titanate, strontium titanates, the aluminium oxide sapphire, tantalum oxide, muscovite, quartzy, pottery, any inorganic constituents in the glass, wherein said soft magnetic ferrite can be nickel-zinc ferrite, manganese-zinc ferrite, tri-iron tetroxide, α-di-iron trioxide, in γ-di-iron trioxide any; Amorphous alloy can be in the cobalt ferronickel silicon boron alloy of the Ni-based iron nickel molybdenum boron alloy of iron-cobalt-silicon boron alloy, the iron of iron-based, cobalt-based any.Because these inorganic constituentss generally have lower-cost remarkable advantage, but can increase magnetic loss to a certain extent, therefore when the frequency range of frequency of utilization below 1000 megahertzes, generally not high because of requirement to magnetic loss, can in said scope, suitably add above-mentioned inorganic constituents material.But if during the frequency range of frequency of utilization more than 1000 megahertzes, because of generally magnetic loss all there being the requirement of strictness, so not use above-mentioned inorganic constituents material to be advisable.
For improving the effect of carrying out blending and modifying with said thermoplastic resin material, in the thermoplastic resin material of used routine, also can be incorporated as 2～10% titanate ester of total weight, in the silane coupling agent any in case of necessity, as three isostearoyl oxygen base titanate esters isopropyl alcohols commonly used, three (DBSA acyloxy) isopropyl titanate, vinyltriethoxysilane, trivinyl trichlorosilane etc.
Right, above-mentioned methods such as material modified extrusion molding through routine, injection moulding or hot pressing can be made the section bar of forms such as operational en plaque, bar-shaped or ring-type according to the instructions for use of different field with the above-mentioned corresponding macromolecule magnetic of macromolecule magnetic polymer base material made polymer base material.In addition, according to the special requirement in the difference use field, also can further adopt electric conducting material rete or the lamellas such as surface-coated layer of copper, gold or silver of conventional methods such as vacuum sputtering, plastic electroplating method or pressure sintering at these section bars that become.
What below introduce is specific embodiment as foregoing of the present invention, and can be further described foregoing of the present invention thus.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.
Example 1
(be weight portion with 5 parts, as follows) ferrocene diaminourea phenylate macromolecule magnetic material (number-average molecular weight is 2500～4000) fully mixes with 1 part of barium titanate, 0.5 part of silicon dioxide, 0.2 part of silica flour, again with 3.7 parts of polyethylene in 120 ℃～160 ℃ in conventional mixing roll mixing about 40 minutes, carry out chemistry and physical modification.Make the magnetic polymer base material section bar product of plate, rod or ring-type then according to the use needs with extrusion molding, injection moulding or pressure sintering.The suitable frequency range of this product is about 1000 megahertzes.
Example 2
(chemical composition is (NiZn) Fe to the nickel-zinc ferrite magnetic that is 1-10 μ with 6 parts of ferrocene diketone macromolecule magnetic materials (number-average molecular weight 3000～5000) and 1 part of commercially available fineness
2O
4), 2 parts of tri-iron tetroxides (chemical pure), 0.1 part of alundum (Al and 0.2 part of molybdenum sesquioxide and polyethylene, in 120 ℃～180 ℃ in mixing roll, carried out blending and modifying in mixing 1 hour after, use extrusion molding, injection moulding or hot-forming again, and be laminated with one deck copper film or copper sheet at product surface according to a conventional method.The suitable frequency range of this product is 300～1000 megahertzes.
Example 3
With the gallium complex of 4 parts low molecule ferrocene dialdehyde, 1 part of chemical pure tri-iron tetroxide and 1 part of titanium dioxide and barium titanate, 0.2 part of silicon dioxide, 0.2 part of ceramic powder and 3.6 parts of Merlon in kneader, after 250 ℃～300 ℃ abundant down kneading modifications, be extruded into the section bar of appropriate format, be laminated with copper sheet on the surface again.The suitable frequency range of this product is 300～1000 megahertzes.
Example 4
With the complex of 4 parts of polytetrafluoroethylene and 2 parts of ethylenediamine copper and 1 part of barium titanate, 2 parts of inorganic soft magnetic materials (Ni-Zn) Fe
2O
4, 0.2 part of chemical pure tri-iron tetroxide and 1 part of nitrided iron, under 320 ℃～350 ℃ temperature, in kneader, fully mediated 40 minutes, hot-formingly then be laminated with copper sheet on the surface again.The suitable frequency range of this product is 20～300 megahertzes.
Example 5
With 4 parts of ferrocene benzidine macromolecule magnetic materials (number-average molecular weight is 3000～50000), 1 part of polytetrafluoroethylene, 2 parts of titanium dioxide, 0.5 part of alundum (Al, 0.5 part of alundum (Al, 0.2 part of silicon dioxide and 0.8 part of Merlon, fully mediated 40 minutes in kneader in 250 ℃～300 ℃ temperature are following, extrusion modling then is laminated with copper sheet on the surface again.The suitable frequency range of this product is more than 1000 megahertzes.
Example 6
With 3 parts of ferrocene diamines nickel complexes, 4 parts of polystyrene and 2 parts of chemical pure tri-iron tetroxides, 1 part of titanium dioxide, 0.5 part of alundum (Al and 1 part of silicon dioxide, under 120 ℃～180 ℃ temperature, blend is 40 minutes in mixing roll, injection moulding or hot-forming then, and be laminated with copper sheet on the surface.The suitable band limits of this product is 300～1000 megahertzes.
Example 7
Complex, 3 parts of ferrocene diketone macromolecule magnetic materials (number-average molecular weight is 3000～5000), 0.5 part of titanium dioxide, 0.5 part of γ-di-iron trioxide and 3 parts of polystyrene with 3 parts of MDA cobalts, after 120 ℃～180 ℃ temperature ShiShimonoseki are mixed 1 hour, be squeezed into magnetic sheet, bar magnet or magnet ring again.The suitable frequency range of this product is 300～1000 megahertzes.
Example 8
With the complex of 4 parts of benzidine nickel, 2 parts of carbonyl irons, 1 part of tri-iron tetroxide and 3 parts of polyphenylene sulfides, blend was hot pressed into magnetic sheet, and is laminated with copper sheet on the surface after 40 minutes under 250 ℃～300 ℃ temperature.The suitable frequency range of this product is 300～1000 megahertzes.
Example 9
With the complex of 3 parts of ethylene glycol copper, 2 parts of diaminourea phenylates, 2 parts of ferrocene dialdehyde macromolecule magnetic materials (number-average molecular weight 3000～4000), 3 parts of polypropylene, blend was hot pressed into magnetic sheet, bar magnet or magnet ring after 40 minutes under 120 ℃～180 ℃ temperature.The suitable band limits of this product is 300～1000 megahertzes.
Example 10
With 3 parts of ferrocene ethylenediamine macromolecule magnetic materials (number-average molecular weight is 3000～4000), 2 parts of copper complexes, 4 parts of polyester terephthalates, 0.5 part of silica flour and 0.5 part of barium titanate to benzene two hydrazines, blend is after 40 minutes under 180 ℃～220 ℃ temperature, be hot pressed into magnetic sheet, and through conventional vacuum sputtering at surface-coated copper film.The suitable band limits of this product is more than 1000 megahertzes.
Example 11
With the complex of 5 parts of p-phenylenediamine (PPD) zinc, 1 part of tri-iron tetroxide, 0.5 part of alundum (Al, 0.5 part of titanium dioxide and 3 parts of polysulfones, blend is after 40 minutes, through being hot pressed into magnetic sheet, bar magnet or magnet ring under 250 ℃～300 ℃ temperature.The suitable band limits of this product is 20～3000 megahertzes.
Example 12
With the amino phenylate macromolecule magnetic material (number-average molecular weight is 3000～4000) of 3 parts of ferrocene, the complex of 2 parts of benzene dimethanol yttriums, 1 part of barium titanate and 4 parts of polyethylene, blend was injection molded into bar magnet or magnet ring after 40 minutes under 120 ℃～180 ℃ temperature.The suitable band limits of this product is more than 1000 megahertzes.
Example 13
With the amino phenylate macromolecule magnetic material (number-average molecular weight is 3000～5000) of 5 parts of ferrocene, 1 part of tri-iron tetroxide and 4 parts of Merlon, blend was hot pressed into magnetic sheet and is laminated with copper sheet on the surface after 40 minutes under 250 ℃～300 ℃ temperature.The suitable frequency range unit of this product is 3000～1000 megahertzes.
Example 14
With the blend after 40 minutes under 120 ℃～180 ℃ temperature of the cobalt complex of 4 parts of diaminourea phenylates, 1 part of nickel-zinc ferrite, 0.5 part of titanium dioxide, 0.5 part of barium titanate and 4 parts of polyethylene, injection mo(u)lding, and with vacuum sputtering at surface-coated one deck gold film.The suitable band limits of this product is 20～3000 megahertzes.
Example 15
With 4 parts of iron-cobalt-silicon boron alloy powder, 0.5 part of alundum (Al, 0.2 part of titanium dioxide and 0.3 part of glass dust and 3 parts of polyethylene to benzene dioxime copper complex, 2 parts of iron-baseds, blend was hot pressed into magnetic sheet, bar magnet or magnet ring after 30 minutes under 120 ℃～180 ℃ temperature.The suitable band limits of this product is 20～3000 megahertzes.
The above-mentioned part example of the present invention is as shown in table 1 with the performance test data and the relevant price contrast situation of existing dielectric substrate.
The sexual valence data contrast of table 1 macromolecule magnetic of the present invention polymer base material and existing dielectric substrate
| Commercially available dielectric substrate | Polymeric substrate | |||||||
| Ceramic substrate | Dielectric substrate (polytetrafluoroethylene composite base plate) | Polymeric substrate (polytetrafluoroethylene) | Macromolecule magnetic polymer base material of the present invention | |||||
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | ||||
| Proportion | ?????＞6.0 | ?????＞4.0 | ????1.8～2.0 | ???????1.10～1.20 | ??1.10～1.20 | ???1.05～1.10 | ???1.05～1.10 | ???1.10～1.20 |
| Price (minimum) | 2 yuan/cm 2 | 1 yuan/cm 2 | 200 yuan/kg (5mm sheet material) | 0.3 unit/cm 2 | 0.3 unit/cm | 0.25 unit/cm 2 | 0.28 unit/cm 2 | 0.3 unit/cm 2 |
| Processing technology | Sintering, evaporation chromium, copper facing | Copper sheet is covered in hot pressing | Copper sheet is covered in hot pressing | Copper is covered in 150～350 ℃ of extrusion molding, injection moulding or hot pressing, vacuum sputtering, plastics plated film or hot pressing | Copper is covered in 150～350 ℃ of hot pressing | Copper is covered in 150～300 ℃ of injection mouldings, extrusion molding or hot pressing | Copper is covered in 150～320 ℃ of hot pressing | 150～330 ℃ of injection moulding hot pressing |
| Processability | Crisp firmly | Crisp firmly | Processability is good | Processability is good | Processability is good | Processability is good | Processability is good | Processability is good |
| Dielectric constant (ε ') | ?????10～15 | ?????5～15 | ???????2～3 | ?????????5～15 | ????5～10 | ?????5～13 | ??????5～13 | ??????4～12 |
| ?????tgδ ε | ?????1×10 -4 | ????1×10 -3 | ?????1×10 -4 | ??????1×10 -3--4 | ???2.1×10 -3 | ????2.3×10 -3 | ????6.5×10 -4 | ???6.5×10 -4 |
| Permeability (μ ') | ????????1 | ???????1 | ????????1 | ?????????3～5 | ????3～5 | ?????3～5 | ??????3～5 | ??????3～5 |
| Magnetic loss tg δ μ | ????????- | ???????- | ????????- | ????????1×3 -4 | ???0.5×10 -3 | ???1.5×10 -3 | ????7.5×10 -4 | ???7.0×10 -4 |
| Physical dimension | Thin, little, heavy | Thin, little, heavy | Gently, greatly | Gently, thin, little | Gently, thin, little | Gently, thin, little | Gently, thin, little | Gently, thin, little |
| Cover the copper sheet substrate and peel off intensity | ????????- | (1.2N/cm Taixing, Jiangsu insulating material factory product) | (1.0N/cm commercially available prod, morning twilight chemical plant, Chengdu) | (1.5N/cm this law sample) | ???1.4N/cm | ????1.2N/cm | ?????1.2N/cm | ????1.1N/cm |
| Practical example | Microstrip circuit | The microstrip circuit antenna loads | Antenna loads | Microstrip circuit microstrip antenna antenna loads | The microstrip circuit microstrip antenna | The little band of microstrip antenna loads | Little band antenna loaded microstrip electric wire that bursts at the seams | Little live line antenna loads |
Claims (6)
1. macromolecule magnetic polymer base material material, it is characterized in that it being through blend or mediate modification and become by at least a with the conventional thermoplastic resin material in following component A and the B component, wherein total consumption of component A and B component is 10%～70% of a total weight, the plastics resin material that all the other are used for modification
Said component A can be for any contains the organometallic polymer magnetic material of the ferrocene composition of amido, amino or carbonyl in ferrocene phenylenediamine, ferrocene ethylenediamine, ferrocene benzidine, ferrocene diketone, ferrocene dialdehyde, ferrocene diaminourea phenylate and the ferrocene MDA, or the metal complex of the metal organic low molecular magnetic material of said ferrocene composition, metal wherein can be any in iron, cobalt, nickel, copper, zinc, calcium, magnesium, gallium, yttrium, the gadolinium;
Said B component can be the metal complex of any micromolecule glycol, diamines (ammonia), two hydrazines or dioxime in ethylene glycol, hexylene glycol, benzene dimethanol, ethylenediamine, hexamethylene diamine, benzidine, MDA, chrysoidine, the diaminourea phenylate, and metal wherein can be any in iron, cobalt, nickel, copper, zinc, calcium, magnesium, gallium, yttrium, the gadolinium;
The thermoplastic resin material of said routine can be in powdery, granular or bar-shaped polyethylene, polypropylene, polystyrene, Merlon, polyurethane, polysulfones, polyphenylene sulfide, polymethyl methacrylate, polyphenylene oxide, polyester terephthalate, epoxy resin, unsaturated-resin, the polytetrafluoroethylene any.
2. macromolecule magnetic polymer base material material as claimed in claim 1, it is characterized in that to be incorporated as 0～20% conventional pulverous carbonyl iron of raw material total weight, carbonyl nickel, permalloy, soft magnetic ferrite, the dilval of crystalline state, amorphous alloy, titanium oxide, silica, barium titanate, strontium titanates, the aluminium oxide sapphire, tantalum oxide, muscovite, quartzy, pottery, any inorganic constituents in the glass, soft magnetic ferrite wherein can be nickel-zinc ferrite, manganese-zinc ferrite, tri-iron tetroxide, α-di-iron trioxide, in γ-di-iron trioxide any, amorphous alloy wherein can be the iron-cobalt-silicon boron alloy of iron-based, the iron nickel molybdenum boron alloy that iron is Ni-based, in the cobalt ferronickel silicon boron alloy of cobalt-based any.
3. macromolecule magnetic polymer base material material as claimed in claim 1 is characterized in that can adding in case of necessity the titanate ester of total weight 2～10%, in the silane coupling agent any in the thermoplastic resin material of said routine.
4. the macromolecule magnetic polymer base material made from the described macromolecule magnetic of claim 1 polymer base material material is characterized in that for through extrusion molding, the en plaque that injection moulding or hot pressing became, bar-shaped or ring-type section bar.
5. the macromolecule magnetic polymer base material that macromolecule magnetic polymer base material material as claimed in claim 4 is made, what it is characterized in that said section bar surface-coatedly has a conductive material layer.
6. the macromolecule magnetic polymer base material that macromolecule magnetic polymer base material material as claimed in claim 5 is made is characterized in that said electric conducting material rete is copper, gold or silver-colored material layer.
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|---|---|---|---|
| CNB991147111A CN1134030C (en) | 1999-03-17 | 1999-03-17 | Magnetic polymer base material and shapes of the material |
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|---|---|---|---|
| CNB991147111A CN1134030C (en) | 1999-03-17 | 1999-03-17 | Magnetic polymer base material and shapes of the material |
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|---|---|
| CN1267893A true CN1267893A (en) | 2000-09-27 |
| CN1134030C CN1134030C (en) | 2004-01-07 |
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| CN108695590A (en) * | 2017-10-14 | 2018-10-23 | 丹阳市遥控天线厂 | A kind of manufacture craft of antenna for mobile phone |
| CN108736143A (en) * | 2017-10-18 | 2018-11-02 | 丹阳市遥控天线厂 | A kind of television antenna manufacture craft |
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