CN113621222A - Low-melting-point PBT electromagnetic shielding composite material and preparation method thereof - Google Patents
Low-melting-point PBT electromagnetic shielding composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention relates to a low-melting-point PBT electromagnetic shielding composite material and a preparation method thereof, which comprises the steps of adding PBT base stock master batch, a graphene material and a dispersing agent into a high-speed stirrer for stirring, then adding a compound compatilizer, an inorganic nano material, LCP fibers, flax fibers and carbon fibers for continuous stirring, adding a mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain a modified PBT material; wherein, the PBT base stock master batch is a graft copolymer of PBT and at least one of polytetramethylene glycol and adipic acid, and the compound compatilizer is a compound of one of dihydric alcohol and dibasic acid and the compatilizer. The PBT electromagnetic shielding composite material disclosed by the invention has the characteristics of low melting point, excellent electromagnetic shielding and radar wave absorption.
Description
Technical Field
The invention belongs to the technical field of functional composite materials, and particularly relates to a low-melting-point PBT electromagnetic shielding composite material and a preparation method thereof.
Background
With the rapid development of modern electronic technology, electromagnetic radiation is ubiquitous, and has become the fifth major public hazard for human beings following air pollution, water pollution, solid waste pollution and noise pollution. Environmental pollution caused by electromagnetic radiation can bring a lot of harm to our lives, and on one hand, electromagnetic radiation can cause electromagnetic interference to various electronic devices and information systems, data transmission errors are caused, and various accidents are caused. More seriously, the long-term exposure of the human body to electromagnetic radiation may cause structural changes in cell membranes and proteins, which may damage the biological and nervous systems of the human body. Therefore, it is becoming more and more important to adopt a simple and feasible method to reduce the harm of electromagnetic radiation.
Generally, the reflection and absorption of electromagnetic waves by certain materials or structures are utilized to realize effective protection of electromagnetic radiation, the reflective electromagnetic shielding material usually adopts metal and alloy with high conductivity, but has the defects of high cost, large specific gravity, difficult manufacture into complex shapes and the like, and the high-conductivity metal is adopted as the shielding material, the shielding effect is realized mainly by reflection generated by mismatching of the impedance of incident electromagnetic waves and dielectric materials, and the reflected electromagnetic waves do not disappear or generate strong attenuation, so that secondary electromagnetic pollution is formed, and the thorough prevention and treatment of the electromagnetic pollution are not facilitated. The common absorption type electromagnetic shielding material has a high magnetic loss tangent value, and attenuates and absorbs electromagnetic waves by means of magnetic polarization mechanisms such as magnetic hysteresis loss, core resonance, back effect loss and the like; or because of having higher electric loss tangent value, depend on the electronic polarization or interface polarization attenuation of the medium, absorb the electromagnetic wave, but this kind of shielding material has shielding effectiveness low, problem such as the difficult broadband absorption.
The research and development of electromagnetic shielding composite materials are attracting more and more attention, and novel shielding materials are developed endlessly, but the current electromagnetic shielding composite materials have low shielding effectiveness and cannot fundamentally eliminate electromagnetic waves.
The traditional electromagnetic shielding composite material adopts polyethylene terephthalate, polybutylene terephthalate and the like as matrix resin, and Chinese patent 202010706003.2 discloses a high-strength electromagnetic shielding and heat-conducting PBT/PET nano composite material and a preparation method thereof, wherein the composite material comprises the following components: polybutylene terephthalate, polyethylene terephthalate, toughening agent and graphene-Fe3O4The composite filler, the filler surface treating agent and the antioxidant have excellent electromagnetic shielding effect through the synergistic effect of dielectric loss and magnetic loss, and the shielding mechanism mainly absorbs electromagnetic waves. However, the prepared composite material has the following disadvantages: (1) the prepared composite material has high melting point (generally 225-235 ℃) and poor fluidity, and for PBT parts subjected to secondary injection molding or rubber coating molding, the PBT is easy to carbonize at a higher injection molding temperature, so that the application range of the PBT is limited; (2) the compatibility among the raw materials is not considered in the preparation process, and the performance parameters of the prepared material are further influenced.
Disclosure of Invention
The invention aims to provide a PBT electromagnetic shielding composite material with a low melting point, which has the characteristics of low melting point, excellent electromagnetic shielding and radar wave absorption.
The technical scheme adopted by the invention for solving the problems is as follows: a low-melting-point PBT electromagnetic shielding composite material comprises the following raw materials: PBT base stock master batch, graphene material, inorganic nano material, LCP fiber, flax fiber and carbon fiber; the PBT base stock master batch is a graft copolymer of PBT and at least one of polytetramethylene glycol PTMG and adipic acid AA.
Preferably, the PBT base stock master batch specifically comprises: the PBT is prepared by graft copolymerization of PBT and at least one of polytetramethylene glycol and adipic acid, and then sequentially filtering by a melt filter and granulating by a granulator.
Preferably, the graphene material is graphene or graphene oxide.
Preferably, the inorganic nano material is at least one of nano calcium carbonate, talcum powder, silicon dioxide, titanium dioxide and sepiolite raw ore.
Preferably, the carbon fiber is added with polyether ketone PEK.
More preferably, the addition amount of the polyether ketone PEK is 1-3% of the mass of the carbon fiber.
Preferably, the mass ratio of the inorganic nano material to the LCP fibers to the flax fibers to the carbon fibers is 1-2: 2-4.
The invention also aims to provide a preparation method of the low-melting-point PBT electromagnetic shielding composite material, which comprises the following steps:
(1) Weighing the raw material components in proportion;
(2) adding the PBT base material master batch, the graphene material and the dispersing agent into a high-speed stirrer according to the parts by weight, and stirring for 60-120 min at 40-60 ℃;
(3) adding a compound compatilizer, an inorganic nano material, LCP fibers, flax fibers and carbon fibers into the mixture obtained in the step (2), and continuously stirring the mixture for 60 to 120min at the temperature of between 40 and 60 ℃;
(4) adding the mixture obtained in the step (3) into a double-screw extruder, controlling the rotating speed of screws to be 100-250 r/min and the temperature to be 180-260 ℃, and carrying out melt extrusion granulation to obtain a modified PBT material;
wherein the compound compatilizer is a compound of one of dihydric alcohol and dibasic acid and the compatilizer.
Preferably, the PBT base material master batch, the graphene material, the dispersing agent, the compound compatilizer, the inorganic nano material, the LCP fiber, the flax fiber and the carbon fiber are sequentially 50-70 parts, 3-5 parts, 1-3 parts, 3-5 parts, 3-6 parts and 6-12 parts by weight.
Preferably, the dispersant is a bisamide dispersant, and the compatilizer is a maleic anhydride styrene copolymer, maleic anhydride or a silane coupling agent.
Compared with the prior art, the invention has the advantages that:
(1) the PBT and the polytetramethylene glycol or adipic acid are subjected to graft copolymerization, so that the melting point of the PBT is greatly reduced, the fluidity of the PBT is improved, the compatibility between the raw materials is modified by the compatilizer and the dispersing agent, and particularly, the compatibility is greatly improved by adopting a compound of one of dihydric alcohol and dibasic acid and the compatilizer.
(2) According to the invention, the inorganic nano material, the LCP fiber, the flax fiber and the carbon fiber are used as filling materials, so that the final modified PBT material realizes layered radar wave absorption, the carbon fiber is added with the polyether ketone, the radar absorption effect can be greatly improved, the graphene is uniformly filled in the material, and the modified PBT material has excellent radar wave absorption characteristic and high wave absorption performance, and is suitable for the fields of wave absorption materials, antistatic materials, electromagnetic shielding and the like.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The low-melting-point PBT electromagnetic shielding composite material comprises the following raw materials in parts by weight: 60 parts of PBT base stock master batch, 4 parts of graphene, 4 parts of nano calcium carbonate, 4 parts of LCP fiber, 4 parts of flax fiber, 8 parts of carbon fiber added with polyether ketone (the addition amount of the polyether ketone is 1 percent of the mass of the carbon fiber), 2 parts of dispersant vinyl bis stearamide and 4 parts of compound compatilizer; the PBT base stock master batch specifically comprises the following components: and after graft copolymerization of the PBT and the adipic acid, filtering the mixture by a melt filter and granulating the mixture by a granulator in sequence to obtain the PBT/adipic acid graft copolymer.
A preparation method of a low-melting-point PBT electromagnetic shielding composite material comprises the following steps:
(1) Weighing the raw material components in proportion;
(2) adding the PBT base material master batch, the graphene and the vinyl bis-stearamide into a high-speed stirrer according to the parts by weight, and stirring for 100min at 50 ℃;
(3) adding a compound compatilizer, inorganic nano materials, LCP fibers, flax fibers and carbon fibers into the mixture obtained in the step (2), and continuously stirring the mixture for 100min at the temperature of 60 ℃;
(4) and (4) adding the mixture obtained in the step (3) into a double-screw extruder, controlling the rotating speed of the screws to be 150r/min and the temperature to be 230 ℃, and performing melt extrusion granulation to obtain the modified PBT material.
The compound compatilizer is a compound of dihydric alcohol and a compatilizer maleic anhydride styrene copolymer, and the mass ratio of the dihydric alcohol to the compatilizer is 1: 3.
example 2
A low-melting-point PBT electromagnetic shielding composite material comprises the following raw materials: 55 parts of PBT base stock master batch, 3.5 parts of graphene, 3 parts of nano calcium carbonate, 3 parts of LCP (liquid Crystal Polymer) fiber, 3 parts of flax fiber, 6 parts of carbon fiber added with polyether ketone (the addition amount of the polyether ketone is 2 percent of the mass of the carbon fiber), 1.5 parts of dispersant vinyl bis stearamide and 3 parts of compound compatilizer; the PBT base stock master batch specifically comprises the following components: and after graft copolymerization of the PBT and the polytetramethylene glycol, filtering the mixture by a melt filter and granulating the mixture by a granulator in sequence to obtain the PBT/PBT alloy material.
A preparation method of a low-melting-point PBT electromagnetic shielding composite material comprises the following steps:
(1) weighing the raw material components in proportion;
(2) adding the PBT base material master batch, the graphene material and the vinyl bis-stearamide into a high-speed stirrer according to the parts by weight, and stirring for 80min at 60 ℃;
(3) adding a compound compatilizer, inorganic nano materials, LCP fibers, flax fibers and carbon fibers into the mixture obtained in the step (2), and continuously stirring the mixture for 80min at the temperature of 60 ℃;
(4) and (4) adding the mixture obtained in the step (3) into a double-screw extruder, controlling the rotating speed of the screws to be 200r/min and the temperature to be 230 ℃, and performing melt extrusion granulation to obtain the modified PBT material.
The compound compatilizer is a compound of diacid and compatilizer maleic anhydride styrene copolymer, and the mass ratio of the diacid to the compatilizer is 1: 3.
example 3
A low-melting-point PBT electromagnetic shielding composite material comprises the following raw materials: 68 parts of PBT base stock master batch, 3.5 parts of graphene, 5 parts of silicon dioxide, 5 parts of LCP (liquid Crystal Polymer) fiber, 5 parts of flax fiber, 10 parts of carbon fiber added with polyether ketone (the addition amount of the polyether ketone is 1 percent of the mass of the carbon fiber), 2.5 parts of dispersant vinyl bis stearamide and 4.5 parts of compound compatilizer; the PBT base stock master batch specifically comprises the following components: and after graft copolymerization of the PBT and the adipic acid, filtering the mixture by a melt filter and granulating the mixture by a granulator in sequence to obtain the PBT/adipic acid graft copolymer.
A preparation method of a low-melting-point PBT electromagnetic shielding composite material comprises the following steps:
(1) weighing the raw material components in proportion;
(2) adding the PBT base material master batch, the graphene and the vinyl bis-stearamide into a high-speed stirrer according to the parts by weight, and stirring for 120min at 40 ℃;
(3) adding a compound compatilizer, inorganic nano materials, LCP fibers, flax fibers and carbon fibers into the mixture obtained in the step (2), and continuously stirring the mixture for 110min at the temperature of 50 ℃;
(4) and (4) adding the mixture obtained in the step (3) into a double-screw extruder, controlling the rotating speed of the screws to be 200r/min and the temperature to be 240 ℃, and performing melt extrusion granulation to obtain the modified PBT material.
The compound compatilizer is a compound of dihydric alcohol and a compatilizer maleic anhydride styrene copolymer, and the mass ratio of the dihydric alcohol to the compatilizer is 1: 3.
the melting points of the prepared modified PBT materials of the example 1, the example 2 and the example 3 are 124 ℃, 125 ℃ and 124 ℃.
Comparative example 1
The only difference from example 1 is: carbon fibers with added polyetherketone were not added.
Comparative example 2
The only difference from example 1 is: no polyetherketone was added.
Comparative example 3
The only difference from example 1 is: nano calcium carbonate is not added.
Comparative example 4
The only difference from example 1 is: flax fibers were not added.
Comparative example 5
The only difference from example 1 is: no LCP fibers were added.
Comparative example 6
The only difference from example 1 is: no glycol was added.
Comparative example 7
The only difference from example 1 is: no adipic acid was added, i.e.the PBT was not graft copolymerized.
The melting point of the modified PBT material of comparative example 7 was 225 ℃.
The PBT modified materials obtained in the examples 1-3 and the comparative examples 1-6 are subjected to electromagnetic shielding and radar wave absorption performance tests, the test samples are prepared into samples with the thickness of 150mm multiplied by 150mm and the thickness of 3mm, the free space method is adopted for testing, the electromagnetic wave shielding performance and the electromagnetic wave absorption performance are obtained according to the following formulas (a) to (f), and the test results are shown in the following table:
electromagnetic wave shielding property (dB) =20log [ S ]21] （a）
S21= transmission/incident electric field strength (b)
S11= reflected/incident electric field strength (c)
Transmittance (%) = S21 2×100 （d）
Reflectance (%) = S11 2×100 （e）
Absorptance (%) = 100-transmittance-reflectance (f)
| Shielding (dB) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| 70GHz | -40 dB | -45 dB | -43 dB | -10 dB | -23 dB | -15 dB | -25 dB | -18dB | -33 dB |
| 77 GHz | -42 dB | -45 dB | -43 dB | -10 dB | -24 dB | -15 dB | -25 dB | -18 dB | -33 dB |
| 79 GHz | -42 dB | -45 dB | -44 dB | -11 dB | -24 dB | -16 dB | -27 dB | -20 dB | -34 dB |
| 85 GHz | -45 dB | -46 dB | -46 dB | -11 dB | -26 dB | -17 dB | -28 dB | -24dB | -35 dB |
| Absorbency (%) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| 70GHz | 60% | 63% | 62% | 19% | 30% | 37% | 31% | 33% | 45% |
| 77 GHz | 61% | 63% | 63% | 19% | 31% | 38% | 32% | 34% | 45% |
| 79 GHz | 61% | 64% | 63% | 20% | 31% | 38% | 32% | 35% | 46% |
| 85 GHz | 63% | 65% | 66% | 21% | 32% | 40% | 33% | 36% | 46% |
As can be seen from the above table, the modified PBT materials prepared in examples 1-3 have obvious electromagnetic wave shielding property and radar wave absorption property at 70-85 GHz, and compared with example 1, the modified PBT material prepared without adding the dihydric alcohol has poor electromagnetic wave shielding property and radar wave absorption property, which indicates that the compatibility is reduced without adding the dihydric alcohol, and further the radar wave absorption property of the final product is influenced.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (10)
1. The PBT electromagnetic shielding composite material with the low melting point is characterized in that: the method comprises the following raw materials: PBT base stock master batch, graphene material, inorganic nano material, LCP fiber, flax fiber and carbon fiber; the PBT base stock master batch is a graft copolymer of PBT and at least one of polytetramethylene glycol and adipic acid.
2. The electromagnetic shielding composite material of PBT with low melting point of claim 1, which is characterized in that: the PBT base stock master batch specifically comprises the following components: the PBT is prepared by graft copolymerization of PBT and at least one of polytetramethylene glycol and adipic acid, and then sequentially filtering by a melt filter and granulating by a granulator.
3. The electromagnetic shielding composite material of PBT with low melting point of claim 1, which is characterized in that: the graphene material is graphene or graphene oxide.
4. The electromagnetic shielding composite material of PBT with low melting point of claim 1, which is characterized in that: the inorganic nano material is at least one of nano calcium carbonate, talcum powder, silicon dioxide, titanium dioxide and sepiolite raw ore.
5. The electromagnetic shielding composite material of PBT with low melting point of claim 1, which is characterized in that: the carbon fiber is added with polyether ketone.
6. The PBT electromagnetic shielding composite material with low melting point of claim 4, wherein: the addition amount of the polyether ketone is 1-3% of the mass of the carbon fiber.
7. The electromagnetic shielding composite material of PBT with low melting point of claim 1, which is characterized in that: the mass ratio of the inorganic nano material to the LCP fibers to the flax fibers to the carbon fibers is 1-2: 2-4.
8. The preparation method of the low-melting-point PBT electromagnetic shielding composite material is characterized by comprising the following steps of: the method comprises the following steps:
(1) weighing the raw material components in proportion;
(2) adding the PBT base material master batch, the graphene material and the dispersing agent into a high-speed stirrer according to the parts by weight, and stirring for 60-120 min at 40-60 ℃;
(3) Adding a compound compatilizer, an inorganic nano material, LCP fibers, flax fibers and carbon fibers into the mixture obtained in the step (2), and continuously stirring the mixture for 60 to 120min at the temperature of between 40 and 60 ℃;
(4) adding the mixture obtained in the step (3) into a double-screw extruder, controlling the rotating speed of screws to be 100-250 r/min and the temperature to be 180-260 ℃, and carrying out melt extrusion granulation to obtain a modified PBT material;
wherein the compound compatilizer is a compound of one of dihydric alcohol and dibasic acid and the compatilizer.
9. The preparation method of the low-melting-point PBT electromagnetic shielding composite material according to claim 8, characterized by comprising the following steps: the PBT base material master batch comprises, by weight, 50-70 parts of PBT base material master batch, 3-5 parts of graphene material, 3-5 parts of dispersing agent, 1-3 parts of inorganic nano material, 3-5 parts of LCP fiber, 3-6 parts of flax fiber and 6-12 parts of carbon fiber in sequence.
10. The preparation method of the low-melting-point PBT electromagnetic shielding composite material according to claim 8, characterized by comprising the following steps: the dispersant is a bisamide dispersant, and the compatilizer is a maleic anhydride styrene copolymer, maleic anhydride or a silane coupling agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111454546A (en) * | 2020-04-26 | 2020-07-28 | 诺思贝瑞新材料科技（苏州）有限公司 | Electromagnetic shielding composite material and preparation method thereof |
| CN111925630A (en) * | 2020-07-21 | 2020-11-13 | 浙江大学 | High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof |
| CN112940464A (en) * | 2021-02-03 | 2021-06-11 | 浙江通力新材料科技股份有限公司 | High-performance PBT/PET electromagnetic shielding composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111454546A (en) * | 2020-04-26 | 2020-07-28 | 诺思贝瑞新材料科技（苏州）有限公司 | Electromagnetic shielding composite material and preparation method thereof |
| CN111925630A (en) * | 2020-07-21 | 2020-11-13 | 浙江大学 | High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof |
| CN112940464A (en) * | 2021-02-03 | 2021-06-11 | 浙江通力新材料科技股份有限公司 | High-performance PBT/PET electromagnetic shielding composite material and preparation method thereof |
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Application publication date: 20211109 |