CN114507419B - Liquid crystal polymer composition and preparation method thereof - Google Patents
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Abstract
The invention relates to a liquid crystal polymer composition, which comprises the following components in parts by weight: 48 to 69.9 parts of liquid crystal polymer resin, 30 to 50 parts of filler and 0.3 to 2 parts of carbon black, wherein the pH value of the carbon black is less than or equal to 3. According to the invention, the carbon black with the pH value less than or equal to 3 is added into the liquid crystal polymer resin composition, so that the prepared liquid crystal polymer resin composition is darker in color and has lower dielectric loss.
Description
Technical Field
The invention relates to a liquid crystal polymer composition and a preparation method thereof, in particular to a thermotropic liquid crystal polymer composition containing carbon black with low dielectric loss requirement and a preparation method thereof, belonging to the technical field of materials.
Background
The thermotropic liquid crystalline polymer composition is colored black by adding carbon black, and is injected into various molded articles, and is used in the fields of electronic and electrical connectors and the like. In order to make the liquid crystalline resin composition black while not affecting its properties, CN1165580 discloses a liquid crystalline polymer composition containing 0.1 to 10wt% of carbon black, which composition has flame retardant properties reaching V-0 grade; JPH07196894 reports a liquid crystalline resin composition obtained by adding carbon black having a pH of 3.5 to 10 to a liquid crystalline polymer resin. JPH10101945A discloses a thermoplastic resin composition containing 0.01 to 10 parts by weight of carbon black having an adsorption amount of dibutyl phthalate (DBP) of 150ml/100g or less. To improve the problem of aggregation of carbon black caused by liquid-crystalline polymer compositions, CN201180069344.2 discloses that the specific surface area measured by BET low-temperature nitrogen adsorption method is 10-40 (m 2 /g) a process for processing carbon black with a liquid crystalline polymer resin to reduce aggregation of the carbon black. CN201110029376 discloses liquid crystalline polymeric resins, platy fillers and a number average particle size of 20-45nmCarbon black composition.
With the development of high frequency communication in recent years, there is a demand for a black thermotropic liquid crystalline polymer composition for use in this field, particularly, a low dielectric loss. However, the dielectric loss of liquid crystal polymer compositions after addition of carbon black generally increases to a greater extent due to the polarity of the carbon black itself and the higher dielectric loss.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a liquid crystal polymer composition and a preparation method thereof, wherein the liquid crystal polymer composition has good black coloring effect and lower dielectric loss.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a liquid crystal polymer composition comprising the following components in parts by weight: 48-69.9 parts of liquid crystal polymer resin, 30-50 parts of filler and 0.3-2 parts of carbon black, wherein the pH value of the carbon black is less than or equal to 3, and the pH value of the carbon black is tested by using GB/T3780.7-2015 standard.
According to the invention, the carbon black with the pH value less than or equal to 3 is added into the liquid crystal polymer resin composition, and the addition amount of the carbon black is reasonably selected, so that the prepared liquid crystal polymer resin composition has darker color and lower dielectric loss.
As a preferred embodiment of the composition of the invention, the pH value of the carbon black is 2-3, and the carbon black with the pH value of 2-3 is selected, so that the prepared liquid crystal polymer composition has low dielectric loss and L value less than or equal to 40 (color black).
As a preferred embodiment of the composition of the present invention, the liquid crystal polymer resin comprises a structural unit represented by the formula (I),
in the liquid crystal polymer resin, the mol percentage of the structural units shown in the formula (I) to the total structural units is 10-25%.
As a preferred embodiment of the composition of the present invention, the liquid crystal polymer resin is prepared by: and (3) carrying out melt polymerization on the hydroxy aromatic acid monomer, the aromatic dicarboxylic acid monomer, the aromatic diphenol monomer and the hydroxy aromatic amine monomer under the action of an acylating agent and a catalyst to prepare a prepolymer, and then carrying out solid-phase polymerization to prepare the liquid crystal polymer resin.
As a preferred embodiment of the composition of the present invention, the hydroxy aromatic acid monomer is at least one of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, the aromatic dicarboxylic acid monomer is at least one of terephthalic acid, isophthalic acid and 2, 6-naphthalene dicarboxylic acid, and the hydroxy aromatic amine monomer is acetaminophen.
As a preferred embodiment of the composition of the invention, the acylating agent is acetic anhydride, and the molar ratio of the acylating agent to the total hydroxyl groups of the hydroxy aromatic acid monomer, the aromatic diphenol monomer and the hydroxy aromatic amine monomer is 1-1.5:1; the catalyst is at least one of dialkyl tin oxide, diaryl tin oxide, alkoxy titanium, alkali and alkaline earth metal salts and Lewis acid salts, and the mass of the catalyst is 0.001-1% of the total mass of hydroxy aromatic acid monomers, aromatic dicarboxylic acid monomers, aromatic diphenol monomers and hydroxy aromatic amine monomers.
Preferably, the molar ratio of the acylating agent to the total hydroxyl groups of the hydroxy aromatic acid monomer, the aromatic diphenol monomer and the hydroxy aromatic amine monomer is 1.02 to 1.1: the catalyst is Zn, K, mg, ca or Co acetate or aromatic acid salt, and the mass of the catalyst is 0.05-0.2% of the total mass of hydroxy aromatic acid monomer, aromatic dicarboxylic acid monomer, aromatic diphenol monomer and hydroxy aromatic amine monomer.
As a preferred embodiment of the composition of the present invention, the reaction conditions for the melt polymerization are: acylating at 120-150 deg.c for 1-3 hr, heating to 0-25 deg.c higher than the melting temperature of the prepolymer at 10-60 deg.c/hr, maintaining the temperature for 10-4 hr to obtain molten prepolymer at 133-101080 Pa, and exhausting from the bottom of the reaction container at 0.05-0.6 MPa to obtain columnar granular prepolymerIn the form of structural particles, spherical or elliptical particles, wherein the columnar structural particles have a cross-sectional area of 7-24mm 2 The length is 3-6mm; the volume of the spherical or elliptic particles is 15-65mm 3 ；
Wherein the granular prepolymer prepared by the above method is at a temperature 10 ℃ higher than the melting temperature thereof for 1000s -1 The melt viscosity measured by a capillary rheometer at a shear rate is 4-8pa.s;
the reaction conditions of the solid-phase polymerization are as follows: heating and polymerizing the granular prepolymer in a reduced pressure or inert gas to obtain liquid crystal polymer resin, wherein the reaction temperature of solid phase polymerization is 10-80 ℃ below the melting temperature of the granular prepolymer, the reaction temperature is preferably 20-60 ℃ below the melting temperature, the pressure is not more than 1000Pa, the pressure is preferably not more than 200Pa, and the reaction time is 1-24 h;
wherein the liquid crystal polymer resin prepared by the method has a melting temperature 20 ℃ higher than the melting temperature of 1000s -1 The melt viscosity, measured by capillary rheometry at shear rate, is between 10 and 100pa.s, preferably between 10 and 50pa.s.
As a preferred embodiment of the composition of the present invention, the carbon black is at least one of channel black, furnace black, lamp black, thermal black; the DBP absorption of the carbon black is 30-80 g/100g, and the carbon black is tested by using GB/T3780.2-2015 standard; the iodine absorption value is 45-65 mg/g, and the test is carried out by using GB/T3780.1-2015 standard.
Preferably, the carbon black is at least one of furnace carbon black and lamp carbon black.
As a preferred embodiment of the composition of the present invention, the filler is at least one of glass fiber, flake and/or granular inorganic filler, and the flake filler is at least one of glass flake, mica and talcum powder; the granular filler is at least one of clay, glass beads, graphite, calcium carbonate, barium sulfate and titanium dioxide.
Preferably, the cross-section of the glass fiber may be one or optionally a combination of a circular cross-section, an elliptical cross-section, a rectangular cross-section.
In a second aspect, the present invention provides a method for preparing the above composition, comprising the steps of: uniformly mixing liquid crystal polymer resin and carbon black, adding the mixture into an extruder from a main feeding port of a double-screw extruder, and adding filler into the extruder from a side feeding port of the double-screw extruder; and (3) melting and mixing under the rotation of a screw, extruding, cooling and granulating to obtain the liquid crystal polymer composition.
As a preferred embodiment of the preparation method of the present invention, the rotation speed of the screw is 350rpm, and the barrel temperature is 290-355 ℃.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the carbon black with the pH value less than or equal to 3 is added into the liquid crystal polymer resin composition, so that the prepared liquid crystal polymer resin composition is darker in color and has lower dielectric loss.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The test method in the embodiment of the invention comprises the following steps:
(1) Melting temperature:
the temperature is raised to the highest temperature of the melting point +30deg.C at a heating rate of 20deg.C/min from the room temperature by DSC 200F3 manufactured by NETZSCH company, the temperature is lowered to the room temperature at a heating rate of 20deg.C/min after the sample stays at the room temperature for 3min, the temperature is raised to the highest temperature of the melting point +30deg.C at a heating rate of 20deg.C/min again after the sample stays at the room temperature for 3min, a second melting curve of the polymer is obtained, and the melting peak is selected to be the melting point.
(2) Dielectric test: < measurement of dielectric loss (2.5 GHz) >)
The liquid crystal polymer resin and the composition thereof were heated and melted at a temperature of from the melting point to +30℃, and injection molded to prepare a test piece in the form of a flat plate of 100 mm. Times.100 mm. Times.2 mm. Regarding the dielectric loss tangent in the in-plane direction of the test piece, the dielectric loss tangent at a frequency of 2.5GHz was measured by the split dielectric resonator method (SPDR method) using a network analyzer E5071C from Keysight Technology Co.
(3) L value:
l-value test method refers to ASTM E313-2010. The specific test method is as follows: the measurement hole of 1 inch was compacted with a test sample having a size of 60mm×60mm×0.8mm, as measured by an automatic color difference meter ColorEye 7000A manufactured by X-rite corporation, and the darkness value measured by the reflection mode was L value, with the darkness being higher as the L value was lower.
Example 1 liquid Crystal Polymer resin 1
A liquid crystal polymer resin comprising a structural unit represented by the formula (I),
in the liquid crystal polymer resin, the mol percentage of the structural units shown in the formula (I) to the total structural units is 20%.
The preparation method of the liquid crystal polymer resin of the embodiment is as follows:
into a 100 liter reaction vessel equipped with a nitrogen inlet and a stirrer with stirring power indication were charged 61.2395kg of parahydroxybenzoic acid (HBA), 27.5200kg of Biphenol (BP), 18.4146kg of terephthalic acid (TPA), 6.1382kg of Isophthalic Acid (IA) and 76.1938kg of Acetic Anhydride (AA), and 15.06g of magnesium acetate. After nitrogen replacement, the reaction temperature was raised to 145 ℃ under nitrogen atmosphere and the reflux reaction was carried out for 3 hours; then heating to 360 ℃ at a speed of 60 ℃ per hour, keeping the temperature for reaction for 30 minutes, and vacuumizing to 200Pa in 30 minutes to continue the reaction until the stirring power reaches a preset value. Then adding nitrogen into the reaction kettle until the pressure is 0.2MPa, discharging through a valve at the bottom of the kettle, passing through a water tank, and cutting into sections with the diameter of 16mm by a granulator 2 Prepolymer particles of length 5 mm.
10kg of the above prepolymer pellets were charged into a 50 liter reactor equipped with a stirrer, and then subjected to solid phase polycondensation at 280℃under a vacuum of 25Pa for 5 hours to obtain a final liquid-crystalline polymer resin 1.
EXAMPLE 2 liquid Crystal Polymer resin 2
A liquid crystal polymer resin comprising a structural unit represented by the formula (I),
in the liquid crystal polymer resin, the mol percentage of the structural unit shown in the formula (I) to the whole structural units is 25%.
The preparation method of the liquid crystal polymer resin of the embodiment is as follows:
into a 100 liter reaction vessel equipped with a nitrogen inlet and a stirrer with stirring power indication, 1.6869kg of parahydroxybenzoic acid (HBA), 60.9038kg of 2-hydroxy-6-naphthoic acid (HNA), 25.5844kg of Biphenol (BP), 22.8259kg of terephthalic acid (TPA) and 62.9641kg of Acetic Anhydride (AA) and 15.06g of magnesium acetate were charged. After nitrogen replacement, the reaction temperature was raised to 145 ℃ under nitrogen atmosphere and the reflux reaction was carried out for 3 hours; then the temperature is raised to 358 ℃ at the speed of 60 ℃ per hour (the highest reaction temperature of the prepolymerization), the reaction is kept at the temperature for 30 minutes, and then the vacuum is pumped to 200Pa in 30 minutes to continue the reaction until the stirring power reaches a preset value. Then adding nitrogen into the reaction kettle until the pressure is 0.2MPa, discharging through a valve at the bottom of the kettle, passing through a water tank, and cutting into sections with the diameter of 16mm by a granulator 2 Prepolymer particles of length 5 mm.
10kg of the above prepolymer pellets were charged into a 50 liter reactor equipped with a stirrer, and then subjected to solid phase polycondensation at 275℃under a vacuum of 25Pa for 5 hours to obtain a final liquid-crystalline polymer tree 2.
EXAMPLE 3 liquid Crystal Polymer resin 3
A liquid crystal polymer resin comprising a structural unit represented by the formula (I),
in the liquid crystal polymer resin, the mol percentage of the structural unit shown in the formula (I) to the total structural units is 11.2 percent.
The preparation method of the liquid crystal polymer resin of the embodiment is as follows:
at the position of being provided with a nitrogen inlet and a beltTo a 100 liter reaction vessel of a stirrer exhibiting stirring power, 65.9614kg of p-hydroxybenzoic acid (HBA), 7.1779kg of 2-hydroxy-6-naphthoic acid (HNA), 15.9100kg of Biphenol (BP), 20.5315kg of terephthalic acid (TPA), 5.7658kg of acetaminophen (APAP) and 75.8369kg of Acetic Anhydride (AA) and 15.06g of magnesium acetate were charged. After nitrogen replacement, the reaction temperature was raised to 145 ℃ under nitrogen atmosphere and the reflux reaction was carried out for 3 hours; then heating to 350 ℃ at a speed of 60 ℃ per hour, keeping the temperature for reaction for 30 minutes, and vacuumizing to 200Pa in 30 minutes to continue the reaction until the stirring power reaches a preset value. Then adding nitrogen into the reaction kettle until the pressure is 0.2MPa, discharging through a valve at the bottom of the kettle, passing through a water tank, and cutting into sections with the diameter of 16mm by a granulator 2 Prepolymer particles of length 5 mm.
10kg of the above prepolymer pellets were charged into a 50 liter reactor equipped with a stirrer, and then subjected to solid phase polycondensation at 270℃under a vacuum of 25Pa for 5 hours to obtain a final liquid-crystalline polymer resin 3.
HBA, HNA, BP, TPA, IPA, APAP, AA and magnesium acetate of examples 1-3 were both purchased from Sigma-Aldrich.
Example 4
A liquid crystal polymer composition comprising the components in parts by weight as shown in table 1. Meanwhile, the L value and dielectric loss of the liquid crystal polymer composition were evaluated by injection molding, and the test results are shown in Table 1.
The preparation method of the liquid crystal polymer composition of the embodiment comprises the following steps:
the liquid crystal polymer resin and the carbon black are added into an extruder from a main feeding port of a double-screw extruder after being uniformly mixed, glass fiber and other fillers are added into the extruder from a side feeding port of the double-screw extruder, and are melted and mixed at a screw speed of 300rpm, the temperature of a screw barrel is 290-350 ℃, and the liquid crystal polymer composition is obtained by extrusion.
Examples 5 to 11
Examples 5 to 11 the parts by weight of the components in the liquid crystal polymer composition are shown in Table 1. Meanwhile, the L value and dielectric loss of the liquid crystal polymer composition were evaluated by injection molding, and the test results are shown in Table 1.
Examples 5 to 11 liquid crystalline polymer compositions were prepared in the same manner as in example 4.
Comparative examples 1 to 3
Comparative examples 1 to 3 the parts by weight of the respective components in the liquid crystal polymer composition are shown in table 1. Meanwhile, the L value and dielectric loss of the liquid crystal polymer composition were evaluated by injection molding, and the test results are shown in Table 1.
Comparative examples 1 to 3 liquid crystal polymer compositions were prepared in the same manner as in example 4.
TABLE 1
In table 1, glass fiber 1: purchased from eurvescening, model 923; glass fiber 2: available from Eurasian under the model FT771. Talc powder was purchased from Liaoning Ai Hai Talc Co., ltd., model PT20; mica powder was purchased from Japan mountain mica company under the model AB-25S and the average particle diameter D50 was 24. Mu.m; carbon Black 1 was purchased from eurolone corporation under the model Black 550, furnace Black; carbon black 2 was purchased from eurolone corporation under the model Printex40, furnace black.
As can be seen from Table 1, the carbon blacks used in examples 4 to 11 have pH values of 2.7 as compared with comparative examples 1 to 3, and the liquid crystal polymer composition comprises the following components in parts by weight: 48-69.9 parts of liquid crystal polymer resin, 30-50 parts of filler and 0.3-2 parts of carbon black, and the prepared liquid crystal polymer composition has smaller L value, relatively lower dielectric loss and better comprehensive performance. The pH of the carbon black used in comparative example 1 was 9.8, and the dielectric loss of the prepared liquid crystal polymer compositions was higher than in examples 4 to 11.
Effect example 1
To examine the influence of the pH of carbon black on the dielectric loss of the liquid crystal polymer composition, test groups 1 to 3 and control groups 1 to 2 were designed. The liquid crystal polymer resins of test groups 1 to 3 and control groups 1 to 2 were the same as those of example 6 in Table 1 in terms of type and amount of liquid crystal polymer resin, type and amount of filler, and amount of carbon black, and only the pH value of carbon black was different. The pH values of the carbon blacks in the test groups 1 to 3 and the control groups 1 to 2 are shown in Table 2. Meanwhile, the L values and dielectric losses of the liquid crystal polymer compositions of test groups 1 to 3 and control groups 1 to 2 were tested, and the test results are shown in Table 2.
TABLE 2
| Test group 1 | Test group 2 | Test group 3 | Control group 1 | Control group 2 | |
| pH of carbon black | 2.5 | 2.7 | 3 | 4 | 8 |
| L value | 38 | 39 | 40 | 41 | 39 |
| Df@2.5GHz | 0.007 | 0.006 | 0.006 | 0.009 | 0.01 |
As is clear from Table 2, when the pH of the carbon black is not more than 3, the dielectric loss of the liquid crystal polymer composition obtained is low, and the L value is not more than 40 (color black).
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A low dielectric loss liquid crystalline polymer composition characterized in that the composition comprises the following components in parts by weight: 48-69.9 parts of liquid crystal polymer resin, 30-50 parts of filler and 0.3-2 parts of carbon black, wherein the pH value of the carbon black is less than or equal to 2.7; the liquid crystal polymer resin comprises a structural unit shown in a formula (I),
in the liquid crystal polymer resin, the mol percentage of the structural units shown in the formula (I) to the total structural units is 10% -25%.
2. The composition of claim 1, wherein the carbon black has a pH of 2 to 2.7.
3. The composition of claim 1, wherein the liquid crystal polymer resin is prepared by a process comprising: preparing a prepolymer by melt polymerization of a hydroxy aromatic acid monomer, an aromatic dicarboxylic acid monomer, an aromatic diphenol monomer and a hydroxy aromatic amine monomer under the action of an acylating agent and a catalyst, and then preparing liquid crystal polymer resin by solid phase polymerization; the aromatic diphenol monomer is biphenol.
4. The composition of claim 3, wherein the hydroxy aromatic acid monomer is at least one of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, the aromatic dicarboxylic acid monomer is at least one of terephthalic acid, isophthalic acid and 2, 6-naphthalene dicarboxylic acid, and the hydroxy aromatic amine monomer is acetaminophen.
5. The composition of claim 3, wherein the acylating agent is acetic anhydride, and the molar ratio of the acylating agent to the total hydroxyl groups of the hydroxy aromatic acid monomer, the aromatic diphenol monomer and the hydroxy aromatic amine monomer is 1-1.5:1; the catalyst is at least one of dialkyl tin oxide, diaryl tin oxide, alkoxy titanium, alkali and alkaline earth metal salts and Lewis acid salts, and the mass of the catalyst is 0.001% -1% of the total mass of hydroxy aromatic acid monomers, aromatic dicarboxylic acid monomers, aromatic diphenol monomers and hydroxy aromatic amine monomers.
6. The composition of claim 1, wherein the carbon black is at least one of channel black, furnace black, lamp black, thermal black, and DBP absorption of 30 to 80g/100g, and iodine absorption of 45 to 65mg/g.
7. The composition of claim 1, wherein the filler is at least one of glass fiber, flake and/or particulate inorganic filler, and the flake filler is at least one of glass flake, mica, talc; the granular filler is at least one of clay, glass beads, graphite, calcium carbonate, barium sulfate and titanium dioxide.
8. The method for preparing the composition according to any one of claims 1 to 7, comprising the steps of: uniformly mixing liquid crystal polymer resin and carbon black, adding the mixture into an extruder from a main feeding port of a double-screw extruder, and adding filler into the extruder from a side feeding port of the double-screw extruder; and (3) melting and mixing under the rotation of a screw, extruding, cooling and granulating to obtain the liquid crystal polymer composition.
9. The method according to claim 8, wherein the rotation speed of the screw is 350rpm, and the barrel temperature is 290-355 ℃.
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| CN115678228B (en) * | 2022-11-04 | 2023-08-18 | 宁波聚嘉新材料科技有限公司 | Antistatic liquid crystal resin composition and film product thereof |
| WO2024138507A1 (en) * | 2022-12-29 | 2024-07-04 | Ticona Llc | Black liquid crystalline polymer composition with low dissipation factor |
| CN117024719B (en) * | 2023-10-07 | 2024-01-30 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and fiber concrete |
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| US9355753B2 (en) * | 2012-12-05 | 2016-05-31 | Ticona Llc | Conductive liquid crystalline polymer composition |
| WO2014099377A1 (en) * | 2012-12-19 | 2014-06-26 | Ticona Llc | Liquid crystalline composition having a dark black color |
| KR102018232B1 (en) * | 2013-02-15 | 2019-09-04 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Resin composition for high dielectric constant materials, molded article containing same, and master batch for coloring |
| JP6165608B2 (en) * | 2013-12-03 | 2017-07-19 | Ｊｘｔｇエネルギー株式会社 | Camera module parts comprising a wholly aromatic liquid crystal polyester resin composition and an injection molded product thereof as constituent members |
-
2020
- 2020-11-16 CN CN202011277536.XA patent/CN114507419B/en active Active
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2021
- 2021-04-30 WO PCT/CN2021/091351 patent/WO2022100030A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| WO2022100030A1 (en) | 2022-05-19 |
| CN114507419A (en) | 2022-05-17 |
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