CN111073223A - Modified liquid crystal polyester resin compound and preparation method thereof - Google Patents
Modified liquid crystal polyester resin compound and preparation method thereof Download PDFInfo
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- CN111073223A CN111073223A CN201911353208.0A CN201911353208A CN111073223A CN 111073223 A CN111073223 A CN 111073223A CN 201911353208 A CN201911353208 A CN 201911353208A CN 111073223 A CN111073223 A CN 111073223A
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified liquid crystal polyester resin compound and a preparation method thereof. The modified liquid crystal polyester resin compound is prepared from 50-80 parts by weight of liquid crystal polyester resin, 3-10 parts by weight of ethylene copolymer elastomer, 5-15 parts by weight of mica and 0-30 parts by weight of filler. Because the ethylene copolymer elastomer can be grafted with the liquid crystal polyester resin to improve the activity of the liquid crystal polyester resin, and the mica can ensure that the obtained compound has the characteristics of low warpage and low shrinkage, the modified liquid crystal polyester resin compound has the advantages that the ethylene copolymer elastomer and the mica are added, and the adhesion of the modified liquid crystal polyester resin compound is obviously enhanced under the synergistic effect of the ethylene copolymer elastomer and the mica, so that the bonding strength of the modified liquid crystal polyester resin compound with other materials is favorably improved, and the falling-off condition is avoided.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified liquid crystal polyester resin compound and a preparation method thereof.
Background
Liquid Crystal Polymer (LCP) is a novel high-performance special engineering plastic developed in the early 80 s. LCP self-organizes at a molecular level according to production conditions, and is classified into three types, thermotropic liquid crystal, lyotropic liquid crystal, and photo-induced liquid crystal. In either type of LCP, the molecular backbone of the LCP is provided with a large number of rigid benzene ring structures due to the aromatic thermoplastic polyester, which determines the specific physicochemical characteristics and processing properties of the LCP. Because of the high degree of regularity of the molecular chains of the LCP, the liquid of the LCP solution becomes water-like when heated to crystallization temperature with a slight shear force, which makes it easier to mold thin-walled miniaturized connector parts.
However, the molecular chain of LCP is too regular, resulting in poor surface adhesion, low strength when bonding with other materials, and sometimes even falling off during use, which affects the stability of the device.
Disclosure of Invention
The invention aims to provide a modified liquid crystal polyester resin compound, which aims to solve the problem of poor adhesiveness of the existing liquid crystal polyester resin.
The invention also aims to provide a preparation method of the modified liquid crystal polyester resin compound.
It is still another object of the present invention to provide a method for preparing wholly aromatic liquid crystalline polyester resin.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a modified liquid crystal polyester resin compound is prepared from the following raw materials in parts by weight:
in a preferred embodiment of the present invention, the liquid crystal polyester resin is a wholly aromatic liquid crystal polyester resin.
In a preferred embodiment of the present invention, the wholly aromatic liquid crystalline polyester resin comprises at least one of the following repeating units:
repeating units of aromatic diol: OArO,
Repeating units of aromatic diamine: HNArNH,
Repeating unit of aromatic hydroxylamine: HNArO,
Repeating units of aromatic dicarboxylic acid: OCArCO,
Repeating units of aromatic hydroxycarboxylic acid: OArCO,
Repeating units of aromatic aminocarboxylic acid: HNArCO;
wherein Ar is at least one selected from the group consisting of phenylene, biphenylene, naphthalene, and an aromatic compound in which two phenylenes are bonded to each other, and an aromatic compound in which at least one hydrogen of the phenylene, biphenylene, naphthalene, and aromatic compound in which two phenylenes are bonded to each other is substituted.
In a preferred embodiment of the present invention, the filler is at least one selected from glass fiber, whisker, wollastonite, talc, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate, and silica.
The invention also provides a preparation method of the wholly aromatic liquid crystal polyester resin, which comprises the following steps:
selecting at least two monomers to carry out polycondensation reaction to synthesize a wholly aromatic liquid crystal polyester prepolymer;
carrying out solid-phase polycondensation on the wholly aromatic liquid crystal polyester prepolymer to obtain wholly aromatic liquid crystal polyester resin;
wherein the monomer is selected from at least one of aromatic diol, aromatic diamine and aromatic hydroxylamine, and at least one of aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid and aromatic aminocarboxylic acid.
As a preferred technical solution of the present invention, the polycondensation reaction is a solution polycondensation reaction or a bulk polycondensation reaction.
In a preferred embodiment of the present invention, the monomer is pretreated with an acylating agent before the polycondensation reaction.
In a preferred embodiment of the present invention, the solid phase polycondensation is performed under an inert atmosphere or under vacuum.
The invention also provides a preparation method of the modified liquid crystal polyester resin compound, which comprises the following steps:
providing liquid crystal polyester resin, ethylene copolymer elastomer, mica and filler according to the raw material formula of the modified liquid crystal polyester resin compound;
and drying the liquid crystal polyester resin, the ethylene copolymer elastomer, the mica and the filler, mixing, melting, mixing, extruding, drawing, cooling and granulating to obtain the modified liquid crystal polyester resin compound.
As a preferred technical scheme of the invention, the temperature of the drying treatment is 100-160 ℃.
As a preferable technical scheme of the invention, the drying treatment time is 4-8 h.
Because the ethylene copolymer elastomer can perform graft copolymerization with the liquid crystal polyester resin, the ethylene copolymer elastomer is added into the liquid crystal polyester resin, and a branched chain or a functional lateral group can be added on an original highly regular molecular chain of the liquid crystal polyester resin, so that the regularity of the molecular chain of the liquid crystal polyester resin is reduced, the activity of the liquid crystal polyester resin is improved, and the adhesion of the liquid crystal polyester resin is improved. Meanwhile, mica is added into the modified liquid crystal polyester resin compound, and the hexagonal layered crystal structure of the mica has the characteristics of low warpage and low shrinkage, so that the surface of the modified liquid crystal polyester resin compound is smoother, and the improvement of the attaching degree is facilitated. In addition, the inventors have unexpectedly found that the ethylene copolymer elastomer and the mica also have a synergistic effect, and the two modify the liquid crystal polyester resin together, so that the adhesiveness of the obtained modified liquid crystal polyester resin can be further improved.
The modified liquid crystal polyester resin compound is obtained by melt mixing, extrusion, bracing, cooling and granulation, and the ethylene copolymer elastomer and the liquid crystal polyester resin can be subjected to sufficient graft copolymerization reaction through the melt mixing, so that the prepared modified liquid crystal polyester resin has excellent adhesive property, and the method has the advantages of simple process, easy control of production conditions and contribution to large-scale production.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight in the embodiment of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as encompassing the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a modified liquid crystal polyester resin compound which is prepared from the following raw materials in parts by weight:
the addition amount of the liquid crystal polyester resin is 50-70 parts. If the addition amount of the liquid crystal polyester resin is too small, the fluidity of the obtained modified liquid crystal polyester resin compound is low, the original purpose of using a liquid crystal material cannot be achieved, and the liquid crystal polyester resin compound is not beneficial to practical application; if the amount of the liquid crystal polyester resin added is too large, the fluidity of the resulting modified liquid crystal polyester resin composite is too high, and it is difficult to improve the adhesion, which is not favorable for achieving the object of the present invention. In some embodiments, typical but non-limiting amounts of liquid crystalline polyester resin may be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts.
The wholly aromatic liquid crystal polyester resin has the advantages of high temperature resistance and strong fluidity, and therefore, in some embodiments, the wholly aromatic liquid crystal polyester resin is used as the liquid crystal polyester resin, so that the modified liquid crystal polyester resin keeps a higher melting point and has good high temperature resistance.
Preferably, the wholly aromatic liquid crystalline polyester resin includes at least one of the following repeating units:
repeating units of aromatic diol: OArO,
Repeating units of aromatic diamine: HNArNH,
Repeating unit of aromatic hydroxylamine: HNArO,
Repeating units of aromatic dicarboxylic acid: OCArCO,
Repeating units of aromatic hydroxycarboxylic acid: OArCO,
Repeating units of aromatic aminocarboxylic acid: HNArCO;
wherein Ar is at least one selected from the group consisting of phenylene, biphenylene, naphthalene, and an aromatic compound in which two phenylenes are bonded to each other, and an aromatic compound in which at least one hydrogen in the aromatic compound in which phenylene, biphenylene, naphthalene, and two phenylenes are bonded to each other is substituted.
The wholly aromatic liquid crystalline polyester resin used in the present invention may be a commercially available wholly aromatic liquid crystalline polyester resin as it is, or a wholly aromatic liquid crystalline polyester resin prepared by the following steps:
s1, selecting at least two monomers to carry out polycondensation reaction to synthesize a wholly aromatic liquid crystal polyester prepolymer;
s2, carrying out solid phase polycondensation on the wholly aromatic liquid crystal polyester prepolymer to obtain wholly aromatic liquid crystal polyester resin;
wherein the monomer is selected from at least one of aromatic diol, aromatic diamine and aromatic hydroxylamine, and at least one of aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid and aromatic aminocarboxylic acid.
Preferably, the polycondensation reaction in S1 is a solution polycondensation reaction or a bulk polycondensation reaction. In the solution polycondensation reaction, because the solvent exists, the reaction temperature can be reduced, the reaction condition is stabilized, the insoluble monomer is favorably dissolved, and the reaction rate is improved; the high-purity polymer can be obtained by the bulk polycondensation without adding a solvent or a dispersing agent, and the method has the advantage of simple operation.
Further, in order to promote the polycondensation reaction, the monomer may be pretreated with an acylating agent to improve the reactivity of the monomer.
Still further, the acylating agent is an acetylating agent. This is because the acylating agent has the highest activity and is more favorable for the acylation reaction.
In S2, since solid-phase polycondensation is carried out by heating the prepolymer to a temperature not lower than the glass transition temperature but lower than the melting point, in some embodiments, heating with a hot plate, hot air, high-temperature fluid, or the like may be used to supply an appropriate amount of heat to the prepolymer.
Preferably, the solid phase polycondensation is carried out under an inert atmosphere or under vacuum conditions, either by removing by-products from the reaction process by inert gas or vacuum, or by making the polymer chain ends sufficiently reactive.
Because the ethylene copolymer elastomer can perform graft copolymerization with the liquid crystal polyester resin, the ethylene copolymer elastomer is added into the liquid crystal polyester resin, and a branched chain or a functional lateral group can be added on an original highly regular molecular chain of the liquid crystal polyester resin, so that the regularity of the molecular chain of the liquid crystal polyester resin is reduced, the activity of the liquid crystal polyester resin is improved, and the adhesion of the liquid crystal polyester resin is improved. In some embodiments, the ethylene copolymer elastomer is preferably BF-E from Sumitomo, Japan. The BF-E has an epoxy group in the molecular structure, and hydroxyl and carboxyl in the molecular chain of the liquid crystal polyester resin can perform a ring-opening reaction with the epoxy group with high reaction activity, so that the BF-E is grafted to the liquid crystal polyester resin through a covalent bond, and the activity of the liquid crystal polyester resin is further improved.
The addition amount of the ethylene copolymer elastomer of the present invention is 3 to 10 parts. If the addition amount of the ethylene copolymer elastomer is too small, sufficient branched chains or functional side groups cannot be added on the molecular chain of the liquid crystal polyester resin, and accordingly, the regularity of the liquid crystal polyester resin is not changed greatly and the activity is not improved obviously; if the amount of the ethylene copolymer elastomer added is too large, the content of the liquid-crystalline polyester resin as a matrix is reduced accordingly, resulting in deterioration of the flowability of the resulting modified liquid-crystalline polyester resin, which affects the practical use thereof. Typical, but non-limiting, amounts of ethylene copolymer elastomer added may be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts in some embodiments.
The hexagonal layered crystal structure of the mica has the characteristics of low warpage and low shrinkage, so that the surface of the modified liquid crystal polyester resin compound can be smoother by adding the mica, the bonding degree of the modified liquid crystal polyester resin compound and other materials is favorably improved, and the mica is prevented from falling off in the using process. In some embodiments, the mica is added in a powdered form, preferably T001 from Yokou pearlescent elmwood, Inc.
The addition amount of the mica of the invention is 5 to 15 parts. If the addition amount of mica is too small, the improvement on the flatness of the obtained modified liquid crystal polyester resin compound is not obvious, and correspondingly, the fitting degree of the modified liquid crystal polyester resin compound and other materials is also poor; if the amount of mica added is too large, the content of the liquid-crystalline polyester resin as a matrix is reduced accordingly, resulting in deterioration of the flowability of the resulting modified liquid-crystalline polyester resin, which affects the practical use thereof. Typical but non-limiting amounts of mica added may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts in some embodiments.
In addition, the inventor finds in experiments that the ethylene copolymer elastomer and the mica have a synergistic effect, and the modified liquid crystal polyester resin can be added into the liquid crystal polyester resin for modification, so that the adhesiveness of the obtained modified liquid crystal polyester resin can be further improved.
The filler can improve the mechanical properties of the obtained modified liquid crystal polyester resin compound, so that the modified liquid crystal polyester resin compound has enough mechanical strength. The addition amount of the filler is 0-30 parts. The mica has certain mechanical properties, so the modified liquid crystal polyester resin compound can be prepared by adding a proper amount of the filler according to the actual condition without adding the filler or according to the addition amount of the mica. In some embodiments, typical but non-limiting amounts of filler may be 0 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts.
Preferably, the filler is at least one selected from the group consisting of glass fiber, whisker, wollastonite, talc, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate and silica.
According to the invention, the liquid crystal polyester resin is used as a base material, and the ethylene copolymer elastomer is added into the liquid crystal polyester resin, so that a branched chain or a functional side group can be added on an originally highly regular molecular chain of the liquid crystal polyester resin, thereby reducing the regularity of the molecular chain of the liquid crystal polyester resin, improving the activity of the liquid crystal polyester resin and improving the adhesion of the liquid crystal polyester resin. Meanwhile, mica is added into the modified liquid crystal polyester resin compound, and the hexagonal layered crystal structure of the mica has the characteristics of low warpage and low shrinkage, so that the surface of the modified liquid crystal polyester resin compound is smoother, and the improvement of the attaching degree is facilitated. In addition, the ethylene copolymer elastomer and the mica also have a synergistic effect, and the ethylene copolymer elastomer and the mica jointly modify the liquid crystal polyester resin, so that the adhesiveness of the obtained modified liquid crystal polyester resin can be further improved.
The embodiment of the invention also provides a preparation method of the modified liquid crystal polyester resin compound, which comprises the following steps:
s01, providing liquid crystal polyester resin, ethylene copolymer elastomer, mica and filler according to the raw material formula of the modified liquid crystal polyester resin compound;
s02, drying and mixing the liquid crystal polyester resin, the ethylene copolymer elastomer, the mica and the filler, and carrying out melt mixing, extrusion, bracing, cooling and granulation to obtain the modified liquid crystal polyester resin compound.
In step S02, the liquid crystal polyester resin, the ethylene copolymer elastomer, the mica, and the filler are dried to remove impurities on the surfaces of the respective materials. In some embodiments, the temperature of the drying treatment is 100-160 ℃, and the drying efficiency can be improved on the premise of not influencing the properties of the modified liquid crystal polyester resin composite by controlling the drying condition at a proper temperature; the drying time is 4-8 h to ensure the drying effect. Specifically, typical but not limiting drying treatment temperatures may be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃; typical but not limiting drying treatment times may be 4h, 5h, 6h, 7h, 8 h.
The modified liquid crystal polyester resin compound is obtained by melt mixing, extrusion, bracing, cooling and granulation, and the ethylene copolymer elastomer and the liquid crystal polyester resin can be subjected to sufficient graft copolymerization reaction through the melt mixing, so that the prepared modified liquid crystal polyester resin has excellent adhesive property, and the method has the advantages of simple process, easy control of production conditions and contribution to large-scale production.
In order to clearly understand the details of the above-described implementation and operation of the present invention for those skilled in the art and to significantly embody the advanced performance of the embodiments of the present invention, the above-described technical solution is illustrated by a plurality of embodiments below.
Example 1
The components and the contents of the modified liquid crystal polyester resin compound are shown in table 1, wherein the liquid crystal polyester resin is selected from wholly aromatic liquid crystal polyester resin (purchased from Jiangsu Wott Special materials manufacturing Co., Ltd.), the ethylene copolymer elastomer is selected from BF-E, mica is selected from mica powder, and the filler is selected from talcum powder.
The preparation method of the modified liquid crystal polyester resin compound comprises the following steps:
taking 75 parts by weight of wholly aromatic liquid crystal polyester resin, 0 part by weight of BF-E, 10 parts by weight of mica powder and 15 parts by weight of talcum powder, and drying for 6 hours at 110 ℃; and putting the dried wholly aromatic liquid crystal polyester resin, BF-E, mica powder and talcum powder into an automatic mixer for uniform mixing, then putting into a double-screw extruder for melt mixing, and obtaining the modified liquid crystal polyester resin compound through extrusion, bracing, cooling and granulation.
Example 2
The difference between the embodiment and the embodiment 1 is that the mass ratio of the wholly aromatic liquid crystal polyester resin, BF-E, mica powder and talcum powder is 75:3:7:15, and the rest is the same as the embodiment 1.
Example 3
The difference between the embodiment and the embodiment 1 is that the mass ratio of the wholly aromatic liquid crystal polyester resin, BF-E, mica powder and talcum powder is 70:5:10:15, and the rest is the same as the embodiment 1.
Example 4
The difference between the embodiment and the embodiment 1 is that the mass ratio of the wholly aromatic liquid crystal polyester resin, BF-E, mica powder and talcum powder is 65:10:10:15, and the rest is the same as the embodiment 1.
Example 5
The difference between the embodiment and the embodiment 1 is that the mass ratio of the wholly aromatic liquid crystal polyester resin, BF-E, mica powder and talcum powder is 75:10:0:15, and the rest is the same as the embodiment 1. Comparative example 1
The difference between the present example and example 1 is that the mass ratio of the wholly aromatic liquid crystalline polyester resin, BF-E, mica powder and talc powder is 75:0:0:25, and the other operations are the same as example 1.
TABLE 1 addition amount of each component of examples 1 to 5 and comparative example 1
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Liquid crystalline polyester resin | 75 | 75 | 70 | 65 | 75 | 75 |
| Ethylene copolymer elastomer | 0 | 3 | 5 | 10 | 10 | 0 |
| Mica | 10 | 7 | 10 | 10 | 0 | 0 |
| Filler material | 15 | 15 | 15 | 15 | 15 | 25 |
In order to verify the properties of the modified liquid crystal polyester resin composites prepared in examples 1 to 5 of the present invention and comparative example 1, the modified liquid crystal polyester resin composites obtained in examples 1 to 5 and comparative example 1 were injection-molded using an injection molding machine as injection molding raw materials, and the properties of the modified liquid crystal polyester resin composites obtained in examples 1 to 5 and comparative example 1 were tested and evaluated by adhesion strength.
The adhesion strength was tested using ASTM standard bent bars. The modified liquid crystal polyester resin composites obtained in examples 1 to 5 and comparative example 1 were first injection-molded into a bar and adhered to a PA66 bar with an adhesive area of 12.5 mm. times.12.5 mm using Henkel 3128NH, and the adhered sample was left to cure at 80 ℃ for 30 minutes and tested for adhesive strength at the adhered part using an Instron tester after cooling, the results of which are shown in Table 2.
TABLE 2 results of Performance test of modified liquid-crystalline polyester resin composites obtained in examples 1 to 5 and comparative example 1
As can be seen from Table 2, the formulation of comparative example 1 has no ethylene copolymer elastomer and mica, the bonding strength is only 0.6MPa, and example 1 has 10% mica on the basis of comparative example 1, so that the bonding strength is improved; example 5 the adhesive strength was also improved by adding 10% of the ethylene copolymer elastomer based on comparative example 1. Examples 2 to 4 were conducted by adding not only mica but also 3%, 5% and 10% of ethylene copolymer elastomer, respectively, and the adhesive strength of the resulting modified liquid-crystalline polyester resin composite was gradually increased as the content of the ethylene copolymer elastomer was increased, and in addition, it was found that the adhesion of the liquid-crystalline polyester was synergistically enhanced by the mica and the ethylene copolymer elastomer.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The modified liquid crystal polyester resin compound is characterized by being prepared from the following raw materials in parts by weight:
2. the modified liquid crystal polyester resin compound according to claim 1, wherein the liquid crystal polyester resin is a wholly aromatic liquid crystal polyester resin.
3. The modified liquid crystal polyester resin compound according to claim 2, wherein the wholly aromatic liquid crystal polyester resin comprises at least one of the following repeating units:
repeating units of aromatic diol: -O-Ar-O-),
Repeating units of aromatic diamine: -HN-Ar-NH-),
Repeating unit of aromatic hydroxylamine: -HNArO-,
repeating units of aromatic dicarboxylic acid: -OC-Ar-CO-),
Repeating units of aromatic hydroxycarboxylic acid: -O-Ar-CO-),
Repeating units of aromatic aminocarboxylic acid: -HN-Ar-CO-;
wherein Ar is at least one selected from the group consisting of phenylene, biphenylene, naphthalene, and an aromatic compound in which two phenylenes are bonded to each other, and an aromatic compound in which at least one hydrogen of the phenylene, biphenylene, naphthalene, and aromatic compound in which two phenylenes are bonded to each other is substituted.
4. The modified liquid-crystalline polyester resin composite of any one of claims 1 to 3, wherein said filler is at least one selected from the group consisting of glass fiber, whisker, wollastonite, talc, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate and silica.
5. A method for preparing wholly aromatic liquid crystal polyester resin is characterized by comprising the following steps:
selecting at least two monomers to carry out polycondensation reaction to synthesize a wholly aromatic liquid crystal polyester prepolymer;
carrying out solid-phase polycondensation on the wholly aromatic liquid crystal polyester prepolymer to obtain wholly aromatic liquid crystal polyester resin;
wherein the monomer is selected from at least one of aromatic diol, aromatic diamine and aromatic hydroxylamine, and at least one of aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid and aromatic aminocarboxylic acid.
6. The method of preparing wholly aromatic liquid crystalline polyester resin according to claim 5, wherein the polycondensation reaction is a solution polycondensation reaction or a bulk polycondensation reaction.
7. The method of preparing wholly aromatic liquid crystalline polyester resin according to claim 5, wherein the monomer is pretreated with an acylating agent before the polycondensation reaction.
8. The method of preparing wholly aromatic liquid crystalline polyester resin according to claim 5, wherein the solid phase polycondensation is performed under an inert atmosphere or under vacuum conditions.
9. A preparation method of a modified liquid crystal polyester resin compound is characterized by comprising the following steps:
a raw material formulation of the modified liquid crystal polyester resin composite according to any one of claims 1 to 4, wherein the raw material formulation comprises a liquid crystal polyester resin, an ethylene copolymer elastomer, mica and a filler;
and drying the liquid crystal polyester resin, the ethylene copolymer elastomer, the mica and the filler, mixing, melting, mixing, extruding, drawing, cooling and granulating to obtain the modified liquid crystal polyester resin compound.
10. The method for preparing a modified liquid crystal polyester resin composite according to claim 9, wherein the temperature of the drying treatment is 100 ℃ to 160 ℃; and/or the presence of a gas in the gas,
the drying time is 4-8 h.
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| US20120199790A1 (en) * | 2009-10-21 | 2012-08-09 | Samsung Fine Chemicals Co., Ltd. | Wholly aromatic liquid crystal polyester resin compound, preparation method thereof, parts for optical pickup, and preparation method thereof |
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| CN109796730A (en) * | 2018-12-29 | 2019-05-24 | 江苏沃特特种材料制造有限公司 | Liquid-crystal polyester resin compound with shock resistance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120199790A1 (en) * | 2009-10-21 | 2012-08-09 | Samsung Fine Chemicals Co., Ltd. | Wholly aromatic liquid crystal polyester resin compound, preparation method thereof, parts for optical pickup, and preparation method thereof |
| KR20120052647A (en) * | 2010-11-16 | 2012-05-24 | 삼성정밀화학 주식회사 | Wholly aromatic liquid crystalline polyester resin compound with enhanced fluidity |
| CN103987784A (en) * | 2011-12-28 | 2014-08-13 | 东丽株式会社 | Polyphenylene sulfide resin composition, molded article of polyphenylene sulfide resin composition, and method for producing polyphenylene sulfide resin composition |
| CN109796730A (en) * | 2018-12-29 | 2019-05-24 | 江苏沃特特种材料制造有限公司 | Liquid-crystal polyester resin compound with shock resistance and preparation method thereof |
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