CN113201229A - Liquid crystal polymer composite material and application thereof - Google Patents

Liquid crystal polymer composite material and application thereof Download PDF

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Publication number
CN113201229A
CN113201229A CN202110532057.6A CN202110532057A CN113201229A CN 113201229 A CN113201229 A CN 113201229A CN 202110532057 A CN202110532057 A CN 202110532057A CN 113201229 A CN113201229 A CN 113201229A
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Prior art keywords
liquid crystal
crystal polymer
fibrous filler
fibers
polymer composite
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CN202110532057.6A
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Inventor
周广亮
宋彩飞
刑羽雄
罗德彬
黄国栋
刘尧
肖中鹏
姜苏俊
黄险波
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Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
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Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
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Priority to CN202110532057.6A priority Critical patent/CN113201229A/en
Publication of CN113201229A publication Critical patent/CN113201229A/en
Priority to PCT/CN2022/083073 priority patent/WO2022237349A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a liquid crystal polymer composite material which comprises the following components in parts by weight: 40-95 parts of liquid crystal polymer resin and 5-40 parts of fibrous filler; in the fibrous filler, the fiber with the length of less than 200 mu m accounts for 5-30% of the total weight of the fibrous filler, the fiber with the length of 200-400 mu m accounts for 25-55% of the total weight of the fibrous filler, and the fiber with the length of more than 400 mu m accounts for 15-70% of the total weight of the fibrous filler. The liquid crystal polymer composite material can be applied to the preparation of large-size ultrathin devices, the length of the device in the longest direction is more than 100mm, the thickness of the device can reach less than 5mm, and the dielectric loss is small.

Description

Liquid crystal polymer composite material and application thereof
Technical Field
The invention relates to the technical field of special engineering plastics, in particular to the field of liquid crystal polymer materials, and specifically relates to a liquid crystal polymer composite material and application thereof.
Background
Since liquid crystal polymers have excellent fluidity and dimensional stability, they are widely used in small electronic devices such as electronic connectors, coil bobbins, relays, and the like; in recent years, with the steady development of the technology of domestic liquid crystal polymers and the great improvement of the productivity, the cost is reduced year by year, and the liquid crystal polymers are concerned by the fields of new energy automobiles, communication and the like due to the characteristics of high heat resistance, high rigidity, high fluidity, high dimensional stability, self-flame resistance, high-frequency stable dielectric property and the like, and are used for preparing functional parts or structural parts and the like with complex structures, large sizes and ultra-thin thicknesses; however, when the existing liquid crystal polymer is used for preparing a large-size ultrathin device and is applied to the communication field, the size stability of the large-size ultrathin device needs to be realized by filling a filler; however, the addition of the filler increases the dielectric loss of the device, has a large influence on the integrity of communication signals, and increases the energy consumption.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a liquid crystal polymer composite material and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a liquid crystal polymer composite material comprises the following components in parts by weight: 40-95 parts of liquid crystal polymer resin and 5-40 parts of fibrous filler; in the fibrous filler, the fiber with the length of less than 200 mu m accounts for 5-30% of the total weight of the fibrous filler, the fiber with the length of 200-400 mu m accounts for 25-55% of the total weight of the fibrous filler, and the fiber with the length of more than 400 mu m accounts for 15-70% of the total weight of the fibrous filler.
The inventor finds that in the liquid crystal polymer composite material, the different sizes of the fibrous fillers and the proportion of the different sizes have great influence on the dielectric loss; finally, the liquid crystal polymer composite material is obtained by controlling the size of the fibrous filler and the proportion of different sizes, and has lower dielectric loss. The liquid crystal polymer composite material can be applied to preparation of large-size ultrathin devices, the length of the device in the longest direction is more than 100mm, the thickness of the device can reach less than 5mm, and the dielectric loss is small.
In the invention, because the breaking length of the fibrous filler in the extruder is shortened, the fibrous fillers with different length distributions can be realized by adding fibers with certain length or different length proportions and liquid crystal polymer resin into the extruder together for melt extrusion, or by adding fibers with different lengths into feeding ports at different positions or adding fibers with different proportions into the feeding ports at different positions, and the fibrous fillers can be determined according to the model number, screw combination, feeding port positions, the length of fiber raw materials and the like of the extruder.
Preferably, in the fibrous filler, the fibers with the length of less than 200 μm account for 16-29% of the total weight of the fibrous filler, the fibers with the length of 200-400 μm account for 34-46% of the total weight of the fibrous filler, and the fibers with the length of more than 400 μm account for 25-50% of the total weight of the fibrous filler. The fibrous filler in the above length distribution range produces articles having lower dielectric loss.
Preferably, the fibrous filler comprises at least one of glass fibers, alumina fibers, carbon fibers, potassium titanate fibers, boric acid fibers, quartz fibers, and wollastonite fibers; preferably, the fibrous filler is glass fiber.
Preferably, the liquid crystal polymer resin is a liquid crystal polymer resin having a melting point Tm of 270 ℃ or higher. The liquid crystal polymer with the melting point can meet the preparation requirement of large-size ultrathin parts. More preferably, the liquid crystal polymer resin is a liquid crystal polymer resin having a melting point Tm of 350 ℃ ± 30 ℃. Most preferably, the liquid crystal polymer resin is a liquid crystal polymer resin having a melting point Tm of 350 ℃. + -. 10 ℃. When the melting point range is selected for the liquid crystal polymer resin, the yield of large-size ultrathin parts is higher.
Preferably, the fibrous filler comprises at least one of glass fibers, alumina fibers, carbon fibers, potassium titanate fibers, boric acid fibers, quartz fibers, and wollastonite fibers; more preferably, the fibrous filler is glass fiber. The cross section of the fibrous filler may be one or an optional combination of a circular cross section, an elliptical cross section and a rectangular cross section.
Preferably, the liquid crystal polymer composite material further comprises 5-40 parts by weight of a platy filler; more preferably, the platy filler is mica powder and/or talcum powder; mica powder is most preferred.
The inventor finds that the addition of the flaky mica with the content can improve the plasticity and the mechanical property of the liquid crystal polymer composite material and control lower dielectric loss through research. Preferably, the average particle size of the flaky filler is D50 ═ 20-80 μm. When the particle diameter of the plate-like filler is within this range, the dimensional stability of the liquid crystal polymer can be improved.
Preferably, the fibrous filler has an average diameter of 5 to 20 μm.
The invention also provides application of the liquid crystal polymer composite material in electronic devices.
When the liquid crystal polymer composite material is applied to electronic devices, the length of the device in the longest direction can reach more than 100mm, the thickness of the device can reach less than 5mm, and the dielectric loss is small.
The invention also provides application of the liquid crystal polymer composite material in electronic communication devices.
The invention has the beneficial effects that: the invention provides a liquid crystal polymer composite material and application thereof, in the liquid crystal polymer composite material, the sizes of fibrous fillers are different and the proportions of the sizes have great influence on dielectric loss; finally, the liquid crystal polymer composite material is obtained by controlling the size of the fibrous filler and the proportion of different sizes, and has lower dielectric loss. The liquid crystal polymer composite material can be applied to the preparation of large-size ultrathin devices, the length of the device in the longest direction is more than 100mm, the thickness of the device can reach less than 5mm, and the dielectric loss is small.
Detailed Description
The source information of each raw material in examples and comparative examples is as follows:
liquid crystal polymer resin: a liquid crystal polymer resin which is purchased from special engineering plastics of Zhuhaiwantong, has the model of Vicryst R800 and the melting point Tm of 350 +/-10 ℃;
glass fiber A: purchased from owenskonin, type 923, with an average diameter of 10 μm and an initial average length of 3 mm;
glass fiber B: purchased from owenskon under model number FT771, with an average diameter of 6 μm and an initial average length of 3 mm;
mica powder: commercially available from Japan Kongshiba mica, model AB-25S, and having an average particle diameter D50 of 24 μm.
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The formulations (parts by weight) of the liquid crystal polymer composites of examples 1 to 21 and comparative examples 1 to 10 are shown in Table 1, and the lengths of the glass fibers in the liquid crystal polymer composites of examples and comparative examples were controlled by using different feed rates at different feed ports.
The characterization method of the length and the distribution of the glass fiber comprises the following steps: taking the liquid crystal polymer composite material obtained by the double-screw extruder, and obtaining ash content of the composite material according to ISO 3451-1; placing ash into 100mL of 95% industrial alcohol, dispersing for 2min by an ultrasonic machine, sucking 2mL of the ash from the bottom by a pipette, placing the ash on a clean glass slide, magnifying by 500 times by an optical microscope, photographing, measuring the length of glass fibers, and calculating the length, distribution and weight ratio of the glass fibers by a statistical method.
The liquid crystal polymer composites described in the examples and comparative examples were prepared by the following method:
(1) weighing the components according to the formula proportion;
(2) setting the processing temperature of a double-screw extruder to be 320-380 ℃;
(3) adding liquid crystal polymer resin from a first feeding port in proportion by a metering scale; adding mica powder from a third feeding port in proportion by a metering scale; adding the glass fiber from the second feeding port and the fourth feeding port in proportion by a metering scale;
(4) and (3) blending and modifying the melt by a double-screw extruder, discharging the melt through a die head, cooling the melt by a water tank, and drawing the melt to a granulator for granulation to finally obtain the uniform liquid crystal polymer composite material.
The dielectric loss test method comprises the following steps: the injection moulding machine was injection moulded into 100mm by 2mm square plates and tested for dielectric loss Df at 2.5GHz in accordance with IEC 62562.
TABLE 1
Figure BDA0003067314010000041
Figure BDA0003067314010000051
As can be seen from Table 1, the different sizes of the glass fibers and the proportion of the different sizes of the total fibers have a greater effect on the dielectric loss; it is found that when the glass fibers are filled in the same proportion, the fibers having a length of 200 μm or less account for 5 to 30% of the total weight of the glass fibers, the fibers having a length of 200 μm to 400 μm account for 25 to 55% of the total weight of the glass fibers, and the fibers having a length of 400 μm or more account for 15 to 70% of the total weight of the glass fibers, the liquid crystal polymer composite material has a low dielectric loss, and particularly, when the fibers having a length of 200 μm or less account for 16 to 29% of the total weight of the glass fibers, the fibers having a length of 200 μm to 400 μm account for 34 to 46% of the total weight of the glass fibers, and the fibers having a length of 400 μm or more account for 25 to 50% of the total weight of the glass fibers, a low dielectric loss can be achieved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The liquid crystal polymer composite material is characterized by comprising the following components in parts by weight: 40-95 parts of liquid crystal polymer resin and 5-40 parts of fibrous filler; in the fibrous filler, the fiber with the length of less than 200 mu m accounts for 5-30% of the total weight of the fibrous filler, the fiber with the length of 200-400 mu m accounts for 25-55% of the total weight of the fibrous filler, and the fiber with the length of more than 400 mu m accounts for 15-70% of the total weight of the fibrous filler.
2. The liquid crystalline polymer composite of claim 1, wherein in the fibrous filler, fibers having a length of less than 200 μm account for 16 to 29% of the total weight of the fibrous filler, fibers having a length of 200 to 400 μm account for 34 to 46% of the total weight of the fibrous filler, and fibers having a length of more than 400 μm account for 25 to 50% of the total weight of the fibrous filler.
3. The liquid crystal polymer composite material according to claim 1, wherein the liquid crystal polymer resin is a liquid crystal polymer resin having a melting point Tm of 270 ℃ or higher; preferably, the liquid crystal polymer resin is a liquid crystal polymer resin with a melting point Tm of 350 ℃ +/-30 ℃; more preferably, the liquid crystal polymer resin is a liquid crystal polymer resin having a melting point Tm of 350 ℃. + -. 10 ℃.
4. The liquid crystalline polymer composite of claim 1, wherein the fibrous filler comprises at least one of glass fibers, alumina fibers, carbon fibers, potassium titanate fibers, boric acid fibers, quartz fibers, and wollastonite fibers; preferably, the fibrous filler is glass fiber.
5. The liquid crystalline polymer composite of claim 1, further comprising 5 to 40 parts by weight of a plate-like filler.
6. The liquid crystalline polymer composite of claim 5, wherein the platy filler is mica powder and/or talc powder.
7. The liquid crystal polymer composite according to claim 6, wherein the average particle diameter of the plate-like filler is 20 to 80 μm as D50.
8. The liquid crystalline polymer composite of claim 1, wherein the fibrous filler has an average diameter of 5 to 20 μm.
9. Use of a liquid crystal polymer composite according to any one of claims 1 to 8 in an electronic device.
10. Use of a liquid crystal polymer composite according to any one of claims 1 to 8 in an electronic communication device.
CN202110532057.6A 2021-05-14 2021-05-14 Liquid crystal polymer composite material and application thereof Pending CN113201229A (en)

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CN115433473A (en) * 2022-09-30 2022-12-06 金发科技股份有限公司 Liquid crystal polymer composition and preparation method and application thereof

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Application publication date: 20210803