CN118006126A - Liquid crystal polyamide-imide alloy material and preparation method thereof - Google Patents
Liquid crystal polyamide-imide alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN118006126A CN118006126A CN202410253942.4A CN202410253942A CN118006126A CN 118006126 A CN118006126 A CN 118006126A CN 202410253942 A CN202410253942 A CN 202410253942A CN 118006126 A CN118006126 A CN 118006126A
- Authority
- CN
- China
- Prior art keywords
- alloy material
- imide
- polyamide
- liquid crystal
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 98
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 96
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 95
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 44
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 34
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 24
- -1 carboxyl compound Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 150000004984 aromatic diamines Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 12
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000007112 amidation reaction Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- VOSLIUIVGWBSOK-UHFFFAOYSA-N 1-n-phenylbenzene-1,2,4-triamine Chemical compound NC1=CC(N)=CC=C1NC1=CC=CC=C1 VOSLIUIVGWBSOK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical group 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 229960004109 potassium acetate Drugs 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229960000314 zinc acetate Drugs 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000013329 compounding Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101000609255 Homo sapiens Plasminogen activator inhibitor 1 Proteins 0.000 description 3
- 102100039418 Plasminogen activator inhibitor 1 Human genes 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 101000609261 Homo sapiens Plasminogen activator inhibitor 2 Proteins 0.000 description 2
- 101000596046 Homo sapiens Plastin-2 Proteins 0.000 description 2
- 101000762938 Homo sapiens TOX high mobility group box family member 4 Proteins 0.000 description 2
- 102100039419 Plasminogen activator inhibitor 2 Human genes 0.000 description 2
- 102100026749 TOX high mobility group box family member 4 Human genes 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 2
- RQHMQURGSQBBJY-UHFFFAOYSA-N (2,2-dichloroacetyl) 2,2-dichloroacetate Chemical compound ClC(Cl)C(=O)OC(=O)C(Cl)Cl RQHMQURGSQBBJY-UHFFFAOYSA-N 0.000 description 1
- LEDMBFYDMKOSPL-UHFFFAOYSA-N 1-(2-hydroxyphenyl)cyclohexa-3,5-diene-1,2-diol Chemical compound OC1C=CC=CC1(O)C1=CC=CC=C1O LEDMBFYDMKOSPL-UHFFFAOYSA-N 0.000 description 1
- 101001090688 Homo sapiens Lymphocyte cytosolic protein 2 Proteins 0.000 description 1
- 102100034709 Lymphocyte cytosolic protein 2 Human genes 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present disclosure provides a liquid crystal polyamide-imide alloy material, wherein the alloy material is calculated by mass percent and totals 100%, and the alloy material comprises the following components: 62-95% of polyamide-imide; 5-35% of liquid crystal polyester; 3-8% of a compatilizer; 0.1-2% of auxiliary agent, and the preparation method of the liquid crystal polyamide-imide alloy material is also provided.
Description
Technical Field
The disclosure belongs to the technical field of polymer material preparation, and particularly relates to a liquid crystal polyamide-imide alloy material and a preparation method thereof.
Background
Polyamide-imide (PAI) is an engineering material with excellent performance, has the characteristics of heat resistance, wear resistance, self-lubricity, low dielectric property, mechanical property, small thermal expansion coefficient, chemical stability and the like, and is widely applied to the fields of aviation, aerospace, transportation, chemical industry, power industry and the like. However, due to the presence of amide groups, there is still a certain limitation in the field of application of heat resistance and low water absorption. In addition, polyamide-imide has poor flowability in the molding process, and is easy to generate the phenomenon of insufficient injection when thin-wall parts are molded.
In order to overcome the limitations of polyamide-imide materials, the related art has attempted to compound polyamide-imide with other polymers to prepare alloy materials with better properties. However, polyamide-imide has poor compatibility with most polymers, which results in phase separation of the composite material at the interface, severely affecting the properties of the material. In addition, the phase separation phenomenon is further exacerbated by the fact that different polymers often repel each other and are incompatible during compounding.
Therefore, how to effectively prepare the polyamide-imide alloy material, solve the compatibility problem, improve the heat resistance and the fluidity of the alloy material and reduce the water absorption rate, and become the technical problem to be solved at present.
Disclosure of Invention
In view of this, to solve at least one technical problem described and other aspects in the related art, the present disclosure provides a liquid crystal polyamide-imide alloy material, wherein the alloy material comprises the following components in percentage by mass, in total 100):
According to the embodiment of the disclosure, the polyamide-imide is a copolymer of an aromatic diamine monomer and an aromatic dianhydride monomer through amidation reaction, and the molar ratio of the aromatic diamine monomer to the aromatic dianhydride monomer is 1:1;
The aromatic diamine monomer is one or more of 2,2 '-bis (trifluoromethyl) -4,4' -biphenyl diamine, m-phenylenediamine, p-phenylenediamine and 2, 4-diaminodiphenylamine;
The aromatic dianhydride monomer is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 1,2, 4-trimellitic anhydride acyl chloride, 1,2, 4-trimellitic anhydride and pyromellitic dianhydride.
According to the embodiment of the disclosure, the liquid crystal polyurethane is an esterification product obtained by esterification reaction of a carboxyl compound containing an aromatic ring and a hydroxyl compound containing an aromatic ring, and the molar ratio of hydroxyl to carboxyl is 1:1;
The carboxyl compound containing aromatic ring is selected from one or more of p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid and isophthalic acid;
The hydroxyl compound containing aromatic ring is selected from one or more of p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, hydroquinone and 4,4' -biphenol.
According to embodiments of the present disclosure, the compatibilizer is one or more of bisphenol a epoxy resin, maleic anhydride grafts, glycidyl triglycerides;
the auxiliary agent is one or more of an antioxidant, a lubricant, a heat stabilizer and an antistatic agent.
According to embodiments of the present disclosure, the tensile strength of the alloy material is 45 to 73MPa;
the water absorption rate of the alloy material is 0.5-2.3%;
the thermal decomposition temperature of the alloy material is 375-488 ℃;
The glass transition temperature of the alloy material is 239-286 ℃.
In another aspect of the present disclosure, a method for preparing the above-described liquid crystal polyamide-imide alloy material is provided, comprising:
Uniformly mixing polyamide-imide, liquid crystal polyester, a compatilizer and an auxiliary agent, adding the mixture into a double-screw extruder, and extruding and granulating to obtain liquid crystal polyamide-imide alloy particles;
and (3) placing the alloy particles into a rotary drum, and performing tackifying reaction in the gradual heating process to obtain the liquid crystal polyamide-imide alloy material.
According to an embodiment of the present disclosure, a method for synthesizing polyamide-imide includes:
Adding an aromatic diamine monomer and an aromatic dianhydride monomer into a reaction kettle in proportion, adding a first solvent to control the solid content of the aromatic diamine monomer and the aromatic dianhydride monomer in the first solvent, gradually heating to a reaction temperature, and performing amidation reaction to obtain polyamide-imide, wherein the solid content of the aromatic diamine monomer and the aromatic dianhydride monomer is controlled by the first solvent, wherein the solid content of the aromatic diamine monomer and the aromatic dianhydride monomer is obtained by the polyamide-imide:
The first solvent is any one of N-methylpyrrolidone, dimethylacetamide, N-dimethylacetamide, dimethylbenzene and tetrahydrofuran;
the solid content is 10-15%;
the amidation reaction temperature is 100-140 ℃;
the amidation reaction time is 3-6 h.
According to an embodiment of the present disclosure, a method for synthesizing a liquid crystal polyester includes:
adding a carboxyl compound containing an aromatic ring and a hydroxyl compound containing an aromatic ring into a reaction kettle in proportion, adding a catalyst and a second solvent, gradually heating to a reaction temperature, and vacuumizing for esterification reaction to obtain liquid crystal polyester, wherein:
The catalyst is one or more of zinc acetate, manganese acetate, potassium acetate, cobalt acetate, dibutyl tin oxide and antimonous oxide, and the weight of the catalyst accounts for 100-1000 ppm of the total feeding amount of carboxyl compounds containing aromatic rings and hydroxyl compounds containing aromatic rings;
the second solvent is anhydride;
The esterification reaction temperature is 300-350 ℃;
The esterification reaction time is 2-4 h.
According to the embodiment of the disclosure, the temperature from a feeding port to an extrusion die head of the twin-screw extruder is 260-280 ℃, 270-290 ℃, 280-310 ℃, 300-330 ℃, 320-340 ℃ and 330-350 ℃ respectively;
the speed of the twin screw extruder main machine was 200 rpm.
According to the embodiment of the disclosure, a material baffle plate and a heating resistor ring are arranged inside the rotary drum;
The tackifying reaction is solid phase tackifying;
The reaction temperature of the tackifying reaction is 200-300 ℃;
the reaction time of the tackifying reaction is 8-16 h.
The liquid crystal polyamide-imide alloy material and the preparation method thereof provided by the embodiment of the disclosure are prepared by mixing liquid crystal polyester, polyamide-imide, a compatilizer and an auxiliary agent in proportion. The addition of the compatilizer can realize the compounding of the polyamide-imide and the liquid crystal polyester, and the liquid crystal polyester containing an aromatic ring structure is introduced into an amide molecular chain of the polyamide-imide so as to improve the heat resistance and the flow property of the alloy material, and simultaneously reduce the water absorption rate, so that the alloy material has the characteristics of the liquid crystal polyester and the polyamide-imide and has better comprehensive performance.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the embodiments.
The endpoints of the ranges and any values disclosed in this disclosure are not limited to the precise range or value, and such range or value should be understood to encompass values approaching those range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, and are to be considered as specifically disclosed in this disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
The polyamide-imide material used at present has heat-resistant aromatic hetero-imide ring and flexible amide group, so that the polyamide-imide material has good heat resistance, wear resistance and the like. However, the existence of the amide group influences the application of the amide in the fields of higher temperature resistance and lower water absorption to a certain extent, and meanwhile, the fluidity is not ideal, so that the performance and the application range of the product are influenced. To overcome these limitations, other polymers have been used in the related art to compound with polyamide-imide to produce alloy materials with better properties. However, the poor compatibility between polyamide-imide and most polymers results in phase separation of the composite material at the interface, severely affecting the properties of the material.
In the course of realizing the present disclosure, it was found that liquid crystalline polyesters have a rigid aromatic ring structure, which exhibits excellent heat resistance, creep resistance, low water absorption and chemical stability, while having excellent mechanical properties and flowability. Therefore, the liquid crystal polyamide-imide alloy material with the characteristics of the liquid crystal polyester and the polyamide-imide is prepared by mixing the liquid crystal polyester, the polyamide-imide, the compatilizer and the auxiliary agent in proportion.
The present disclosure provides a liquid crystal polyamide-imide alloy material, wherein the alloy material is calculated by mass percent and totals 100%, and the alloy material comprises the following components:
According to the disclosed embodiment, the liquid crystal polyester, the polyamide-imide, the compatilizer and the auxiliary agent are mixed in proportion to prepare the liquid crystal polyamide-imide alloy material. The addition of the compatilizer realizes the compounding of the polyamide-imide and the liquid crystal polyester, and introduces the aromatic ring structure of the liquid crystal polyester into the amide molecular chain of the polyamide-imide, thereby improving the heat resistance and the flow property of the alloy material. Meanwhile, the water absorption of the alloy material is reduced, so that the alloy material has the characteristics of liquid crystal polyester and polyamide-imide, and has better comprehensive performance.
According to the embodiment of the disclosure, the polyamide-imide is a copolymer of an aromatic diamine monomer and an aromatic dianhydride monomer through amidation reaction, and the molar ratio of the aromatic diamine monomer to the aromatic dianhydride monomer is 1:1;
The aromatic diamine monomer is one or more of 2,2 '-bis (trifluoromethyl) -4,4' -biphenyl diamine, m-phenylenediamine, p-phenylenediamine and 2, 4-diaminodiphenylamine;
The aromatic dianhydride monomer is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 1,2, 4-trimellitic anhydride acyl chloride, 1,2, 4-trimellitic anhydride and pyromellitic dianhydride.
According to the embodiment of the disclosure, the liquid crystal polyurethane is an esterification product obtained by esterification reaction of a carboxyl compound containing an aromatic ring and a hydroxyl compound containing an aromatic ring, and the molar ratio of hydroxyl to carboxyl is 1:1;
The carboxyl compound containing aromatic ring is selected from one or more of p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid and isophthalic acid;
The hydroxyl compound containing aromatic ring is selected from one or more of p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, hydroquinone and 4,4' -biphenol.
According to the embodiment of the disclosure, the compatilizer is one or more of bisphenol A epoxy resin, maleic anhydride graft and glycidyl triglyceride, and the structure of the polyamide-imide and the structure of the liquid crystal polyester are greatly different, so that the compatibility is poor. The addition of the compatilizer can weaken the interfacial tension between two polymers, blur the interface layer and help to promote more uniform mixing and dispersing effects, and secondly, the compatilizer can bridge the two polymers (namely polyamide-imide and liquid crystal polyester) to form stronger chemical bonding, so that the mechanical property of the composite material is improved. The auxiliary agent is one or more of an antioxidant, a lubricant, a heat stabilizer and an antistatic agent. Different functional additives are added in the preparation process of the alloy material, so that the performance of the alloy material can be further optimized, and the processing efficiency and the use safety of the alloy material are improved. For example, the addition of the antioxidant can delay the aging process of the alloy material, improve the weather resistance and the stability of the alloy material and prolong the service life of the alloy material; the flowability of the material can be improved by adding the lubricant, and friction and abrasion are reduced; the heat stabilizer is added to improve the heat stability of the alloy material, prevent the alloy material from thermal decomposition or oxidation reaction at high temperature, and improve the stability and durability of the material in a high-temperature environment; the antistatic agent can reduce static accumulation on the surface of the composite material and prevent the material from generating static spark or adsorbing dust.
According to embodiments of the present disclosure, the tensile strength of the alloy material may be 45 to 73MPa, for example, 45MPa, 60MPa, 65MPa, 70MPa, 73MPa, etc., the water absorption of the alloy material may be 0.5 to 2.3%, for example, 0.5%, 1.0%, 1.5%, 2.0%, 2.3%, etc., the thermal decomposition temperature of the alloy material may be 375 to 488 ℃, for example, 375 ℃, 390 ℃, 400 ℃, 450 ℃, 488 ℃, etc., and the glass transition temperature of the alloy material may be 239 to 286 ℃, for example, 239 ℃, 250 ℃, 270 ℃, etc. The liquid crystal polyamide-imide alloy material prepared in the method has good mechanical property and high decomposition temperature resistance, can bear the high-temperature and high-pressure molding process, and simultaneously maintains stable structure and performance, so that the liquid crystal polyamide-imide alloy material is suitable for molding or injection molding. In addition, the reduction of the water absorption rate also widens the application of the liquid crystal polyamide-imide alloy material in the field of low water absorption.
In another aspect of the present disclosure, a method for preparing the above-described liquid crystal polyamide-imide alloy material is provided, comprising:
Adding polyamide-imide, liquid crystal polyester, compatilizer and auxiliary agent into a mixer according to a proportion, uniformly mixing, adding into a double-screw extruder, extruding and granulating to obtain liquid crystal polyamide-imide alloy particles; and (3) placing the alloy particles into a rotary drum, and performing tackifying reaction in the gradual heating process to obtain the liquid crystal polyamide-imide alloy material.
According to the embodiment of the invention, in the preparation process, the polyamide-imide, the liquid crystal polyester, the compatilizer and the auxiliary agent raw materials are uniformly mixed, and then the solid-phase tackifying is carried out on the alloy material by using the rotary drum, so that the molecular chain arrangement of the alloy material is more regular and orderly, the strength and the thermal stability of the material are further improved, and the liquid crystal polyamide-imide alloy material with more excellent performance is obtained. Specifically, the total mass percentage is 100 percent, and polyamide-imide, liquid crystal polyester, compatilizer and auxiliary agent are mixed according to the following mass percentage, wherein the mass percentage of polyamide-imide is 62 to 95 percent; 5-35% of liquid crystal polyester; 3-8% of a compatilizer; 0.1 to 2 percent of auxiliary agent. When the liquid crystal polyester is too much, uneven distribution is generated between the liquid crystal polyester and the polyamide-imide, thereby affecting the flow property of the material, and possibly generating uneven flow or flow defects. When the compatibilizer is too much, interfacial adhesion of the material is lowered, thereby lowering tensile strength, melting point and heat resistance of the alloy material. The components are evenly mixed and then added into a double-screw extruder through a weightless scale, and the liquid crystal polyamide-imide alloy particles are obtained through extrusion and granulation, wherein the temperature of the double-screw extruder from a feeding port to an extrusion die head is 260 ℃ to 280 ℃,270 ℃ to 290 ℃,280 ℃ to 310 ℃,300 ℃ to 330 ℃,320 ℃ to 340 ℃,330 ℃ to 350 ℃ and the rotating speed of a host machine is 200 revolutions per minute. Alloy particles are placed in the rotary drum, and a material baffle plate and a heating resistor ring are arranged in the rotary drum, so that stirring of materials can be enhanced, and heating of the materials is more uniform. The drum is gradually heated under vacuum to carry out tackifying reaction, thus obtaining the liquid crystal polyamide-imide alloy material. The solid phase tackifying reaction is solid phase tackifying, and the solid phase tackifying does not need to use a large amount of solvent or water, so that the environmental pollution and the energy consumption are reduced. Simultaneously, the materials uniformly roll in the rotary drum, so that the contact area and the reaction time of the materials and the surface of the rotary drum are increased, and the tackifying effect is improved. The reaction temperature of the tackifying reaction is 200 to 300 ℃, for example, 200 ℃, 220 ℃, 250 ℃,270 ℃,300 ℃ and the like, and the reaction time of the tackifying reaction is 8 to 16 hours, for example, 8 hours, 12 hours, 14 hours, 16 hours and the like.
According to an embodiment of the present disclosure, a method for synthesizing polyamide-imide includes: the method comprises the steps of adding an aromatic diamine monomer and an aromatic dianhydride monomer into a reaction kettle in proportion, adding a first solvent to control the solid content of the aromatic diamine monomer and the aromatic dianhydride monomer in the first solvent, wherein the first solvent is any one of N-methylpyrrolidone, dimethylacetamide, N-dimethylacetamide, dimethylbenzene and tetrahydrofuran. The solid content is 10 to 15%, for example, 10%, 12%, 13%, 14%, 15%, etc. The excessively high solid content may cause aggregation during precipitation of polyamide-imide particles, and poor dispersibility, so that the molecular weight distribution is uneven, and the excessively low solid content may cause an increase in the amount of solvent wasted and a decrease in the yield of polyamide-imide. In nitrogen atmosphere, the temperature is gradually increased to the reaction temperature, and then amidation reaction is carried out to obtain a viscous polymer, wherein the amidation reaction temperature is 100-140 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like, and the amidation reaction time is 3-6 h, for example, 3h, 4h, 5h, 6h and the like. The viscous polymer was washed in deionized water to give a dark yellow solid, which was then dried under vacuum at 120℃for 8h to give a polyamide-imide.
According to an embodiment of the present disclosure, a method for synthesizing a liquid crystal polyester includes: and (3) adding the carboxyl compound containing the aromatic ring and the hydroxyl compound containing the aromatic ring into a reaction kettle in proportion, adding a catalyst and a second solvent, gradually heating to the reaction temperature under the protection of nitrogen atmosphere, and vacuumizing for esterification reaction to obtain the liquid crystal polyester. The catalyst is one or more of zinc acetate, manganese acetate, potassium acetate, cobalt acetate, dibutyl tin oxide and antimonous oxide, and the weight of the catalyst accounts for 100-1000 ppm of the total feeding amount of carboxyl compounds containing aromatic rings and hydroxyl compounds containing aromatic rings, and can be 100ppm, 300ppm, 500ppm, 800ppm, 1000ppm and the like. The catalyst and the catalyst concentration have higher catalytic activity and selectivity in the synthesis reaction of the liquid crystal polyester, can promote the esterification reaction, and are favorable for obtaining high-quality liquid crystal polyester products. The second solvent is anhydride, specifically at least one of acetic anhydride, propionic anhydride, butyric anhydride, dichloroacetic anhydride and maleic anhydride, and the use of anhydride as solvent can perform acylation reaction in the preparation process of the liquid crystal polyester, and acyl groups with stability can be introduced into the polyester molecular chain through the acylation reaction, so that the thermal stability and chemical stability of the liquid crystal polyester are further improved. The esterification reaction temperature is 300 to 350 ℃, for example, 300 ℃, 310 ℃, 330 ℃, 350 ℃ and the like, and the esterification reaction time is 2 to 4 hours, for example, 2 hours, 3 hours, 4 hours and the like.
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the embodiments. The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The examples are not intended to identify specific techniques or conditions, but are conventional and may be carried out according to techniques or conditions described in the literature in this field or according to product specifications.
Synthesis of liquid crystal polyester:
Example 1:
70% by mole of parahydroxybenzoic acid and 30% by mole of 2-hydroxy-6-naphthoic acid were fed into the reaction vessel, followed by 300ppm of potassium acetate and 105% by mole of acetic anhydride (relative to the total amount of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid) based on the total amount of the materials (parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid). Stirring is started after nitrogen replacement, the temperature is gradually increased to 310 ℃, the liquid crystal polyester is obtained after vacuum reaction for 1 hour and discharged, and the liquid crystal polyester is crushed into 10 meshes for standby. The melting point of the prepared liquid crystal polyester is 271 ℃, and the liquid crystal polyester is marked as LCP1#.
Example 2:
Raw materials of 60% mole fraction of parahydroxybenzoic acid, 20% mole fraction of 2-hydroxy-6-naphthoic acid, 10% mole fraction of terephthalic acid and 10% mole fraction of biphenol were added to a reaction vessel, followed by addition of cobalt acetate in an amount of 300ppm based on the total feed of raw materials (parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid, biphenol) and 105% mole fraction of acetic anhydride (relative to the total amount of parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid and biphenol). Stirring after nitrogen replacement, gradually heating to 330 ℃, discharging after vacuum reaction for 1 hour, and crushing the mixture into 10 meshes for later use; the melting point of the obtained liquid crystal polyester is 323 ℃, and the obtained liquid crystal polyester is marked as LCP2#.
Synthesis of polyamide-imide:
Example 3:
A feed of 50 mole fraction of p-phenylenediamine and 50 mole fraction of trimellitic anhydride acid chloride was added to the reaction vessel, followed by addition of an N-methylpyrrolidone solution to control the solids content of the feed (p-phenylenediamine, trimellitic anhydride acid chloride) in the solution to 15%. Stirring is started after nitrogen replacement, and the temperature is gradually increased to 120 ℃ at the same time, and the viscous polymer is obtained after 4 hours of reaction. The viscous polymer was poured into deionized water to precipitate a yellow solid, washed three times with deionized water, and dried at 120℃for 4 hours for use, to give a polyamide-imide having a glass transition temperature of 243℃and designated PAI1#.
Example 4:
50 mole percent of 2, 4-diaminodiphenylamine and 50 mole percent of 1,2, 4-trimellitic anhydride were added to the reaction vessel, followed by addition of an N, N-dimethylacetamide solution to control the solid content of the starting materials (2, 4-diaminodiphenylamine, 1,2, 4-trimellitic anhydride) in the solution to 15%. Stirring is started after nitrogen replacement, and the temperature is gradually increased to 120 ℃ at the same time, and the viscous polymer is obtained after 4 hours of reaction. The viscous polymer was poured into deionized water to precipitate a yellow solid, washed three times with deionized water, and dried at 120℃for 4 hours for use, to give a polyamide-imide having a glass transition temperature of 255℃and designated PAI2#.
Preparation of a liquid crystal polyamide-imide alloy material:
example 5:
The mass fraction composition of each component in this example 5 is as follows:
The method for preparing the liquid crystal polyamide-imide alloy material comprises the following steps: PAI1#, LCP1#, triglycidyl, antioxidant and lubricant (auxiliary agent) are added into a mixer to be mixed uniformly, and the mixture is added into a double-screw extruder through a weightless scale after being fully mixed, wherein the temperature from a feeding port to an extrusion die head of the extruder is 260 ℃,275 ℃,280 ℃,285 ℃,285 ℃ and the rotating speed of a host machine is 200 revolutions per minute, and liquid crystal polyamide-imide alloy particles are obtained through water cooling, bracing and granulating. Then transferring the alloy particles into a rotary drum, and gradually heating to 245 ℃ under vacuum state to react for 8 hours to obtain the liquid crystal polyamide-imide alloy material.
Example 6:
In comparison with example 5, the mass fraction composition of each component in this example is as follows:
other preparation processes are the same as in example 5, and the liquid crystal polyamide-imide alloy material is prepared.
Example 7:
In comparison with example 5, the mass fraction composition of each component in this example is as follows:
other preparation processes are the same as in example 5, and the liquid crystal polyamide-imide alloy material is prepared.
Example 8:
In comparison with example 5, the mass fraction composition of each component in this example is as follows:
other preparation processes are the same as in example 5, and the liquid crystal polyamide-imide alloy material is prepared.
Example 9:
The mass fraction of each component in this embodiment is as follows:
Adding PAI 2#, LCP 2#, epoxy resin, antioxidant and lubricant into a mixer, mixing uniformly, adding into a double-screw extruder through weightlessness weighing, respectively, cooling by water, bracing and granulating from a feeding port to an extrusion die head at 260 ℃,275 ℃,280 ℃,285 ℃,285 ℃ and a host rotation speed of 200 rpm to obtain liquid crystal polyamide-imide alloy particles. Then transferring the alloy particles into a rotary drum, and gradually heating to 245 ℃ under vacuum state to react for 8 hours to obtain the liquid crystal polyamide-imide alloy material.
Example 10:
In comparison with example 9, the mass fraction composition of each component in this example is as follows:
Other preparation processes are the same as in example 9, and a liquid crystal polyamide-imide alloy material is prepared.
Example 11:
In comparison with example 9, the mass fraction composition of each component in this example is as follows:
Other preparation processes are the same as in example 9, and a liquid crystal polyamide-imide alloy material is prepared.
Example 12:
In comparison with example 9, the mass fraction composition of each component in this example is as follows:
Other preparation processes are the same as in example 9, and a liquid crystal polyamide-imide alloy material is prepared.
The compositions of all the liquid-crystalline polyamide-imide alloy materials in examples 5 to 12 are shown in Table 1.
TABLE 1
The performance parameters of all the polyamide-imide and liquid crystal polyamide-imide alloy materials of examples 3 to 12 were measured as follows:
Preparation of test bars:
All the liquid crystal polyester, polyamide-imide and liquid crystal polyamide-imide alloy materials in examples 3 to 12 were dried in an oven at 130℃for 6 hours, and then injection molded into test bars by an injection molding machine at 320℃under 30MPa for 8 seconds and at 160 ℃.
Tensile strength: determined according to the method of ISO 527-2;
Water absorption rate: measured according to the method of ISO 62;
thermal performance: measured according to the method of ISO 11357.
All test results are shown in table 2.
TABLE 2
Note that: t d-5% -the temperature corresponding to 5% of thermal weight loss.
As can be seen from the performance tests of the polyamide-imide PAI1# and PAI2# splines of examples 3-4 and the liquid crystal polyamide-imide alloy material splines of examples 5-12, the liquid crystal polyamide-imide alloy materials obtained in examples 5-12 were improved in tensile strength, heat resistance and glass transition temperature, and reduced in water absorption, as compared with the polyamide-imide materials not subjected to compounding. With the increase of the content of the liquid crystal polyester, an aromatic ring structure is successfully introduced into an amide molecular chain of the polyamide-imide. Due to the stability of the aromatic ring structure, the high rigidity and strength are provided for the liquid crystal polyester, so that the glass transition temperature of the alloy material is improved, and the heat resistance of the alloy material is further improved. In addition, the hydrophobicity of the aromatic ring structure helps to reduce the water absorption of the liquid crystalline polyesters and liquid crystalline polyamide-imide alloys, which remain stable in a wet environment, where the alloy material prepared in example 12 performs best in all respects. The liquid crystal polyamide-imide alloy material with excellent comprehensive performance is successfully prepared by compounding the liquid crystal polyester and the polyamide-imide, and the application of the alloy material in the aspects of electronics, electrics, aerospace, aviation and the like is expanded.
While the foregoing is directed to embodiments of the present disclosure, other and further details of the invention may be had by the present application, it is to be understood that the foregoing description is merely exemplary of the present disclosure and that no limitations are intended to the scope of the disclosure, except insofar as modifications, equivalents, improvements or modifications may be made without departing from the spirit and principles of the present disclosure.
Claims (10)
1. A liquid crystalline polyamide-imide alloy material, wherein the alloy material amounts to 100% in mass percent, the alloy material comprising the following components:
2. The alloy material according to claim 1, wherein the polyamide-imide is a copolymer of an aromatic diamine monomer and an aromatic dianhydride monomer through amidation reaction, and the molar ratio of the aromatic diamine monomer to the aromatic dianhydride monomer is 1:1;
the aromatic diamine monomer is one or more of 2,2 '-bis (trifluoromethyl) -4,4' -biphenyl diamine, m-phenylenediamine, p-phenylenediamine and 2, 4-diaminodiphenylamine;
the aromatic dianhydride monomer is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 1,2, 4-trimellitic anhydride acyl chloride, 1,2, 4-trimellitic anhydride and pyromellitic dianhydride.
3. The alloy material according to claim 1, wherein the liquid crystal polyurethane is an esterification product obtained by esterification of a carboxyl compound containing an aromatic ring and a hydroxyl compound containing an aromatic ring, and the molar ratio of hydroxyl to carboxyl is 1:1;
the carboxyl compound containing the aromatic ring is selected from one or more of p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid and isophthalic acid;
the hydroxyl compound containing the aromatic ring is selected from one or more of p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, hydroquinone and 4,4' -biphenol.
4. The alloy material according to claim 1, wherein,
The compatilizer is one or more of bisphenol A epoxy resin, maleic anhydride graft and glycidyl triglyceride;
The auxiliary agent is one or more of an antioxidant, a lubricant, a heat stabilizer and an antistatic agent.
5. The alloy material according to claim 1, wherein,
The tensile strength of the alloy material is 45-73 MPa;
The water absorption rate of the alloy material is 0.5-2.3%;
the thermal decomposition temperature of the alloy material is 375-488 ℃;
the glass transition temperature of the alloy material is 239-286 ℃.
6. A method of preparing the liquid crystal polyamide-imide alloy material of any one of claims 1-5, comprising:
Uniformly mixing polyamide-imide, liquid crystal polyester, a compatilizer and an auxiliary agent, adding the mixture into a double-screw extruder, and extruding and granulating to obtain liquid crystal polyamide-imide alloy particles;
and (3) placing the alloy particles into a rotary drum, and performing tackifying reaction in the gradual heating process to obtain the liquid crystal polyamide-imide alloy material.
7. The preparation method according to claim 6, wherein the synthesis method of the polyamide-imide comprises:
Adding an aromatic diamine monomer and an aromatic dianhydride monomer into a reaction kettle in proportion, adding a first solvent to control the solid content of the aromatic diamine monomer and the aromatic dianhydride monomer in the first solvent, gradually heating to a reaction temperature, and carrying out amidation reaction to obtain the polyamide-imide, wherein:
The first solvent is any one of N-methylpyrrolidone, dimethylacetamide, N-dimethylacetamide, dimethylbenzene and tetrahydrofuran;
the solid content is 10-15%;
The amidation reaction temperature is 100-140 ℃;
the amidation reaction time is 3-6 h.
8. The preparation method of claim 6, wherein the synthetic method of the liquid crystal polyester comprises the following steps:
Adding a carboxyl compound containing an aromatic ring and a hydroxyl compound containing an aromatic ring into a reaction kettle in proportion, adding a catalyst and a second solvent, gradually heating to a reaction temperature, and vacuumizing for esterification reaction to obtain the liquid crystal polyester, wherein the catalyst and the second solvent are selected from the group consisting of:
The catalyst is one or more of zinc acetate, manganese acetate, potassium acetate, cobalt acetate, dibutyl tin oxide and antimonous oxide, and the weight of the catalyst accounts for 100-1000 ppm of the total feeding amount of the carboxyl compound containing the aromatic ring and the hydroxyl compound containing the aromatic ring;
The second solvent is anhydride;
the esterification reaction temperature is 300-350 ℃;
the esterification reaction time is 2-4 h.
9. The preparation method according to claim 6, wherein,
The temperature from a feeding port to an extrusion die head of the double-screw extruder is 260-280 ℃, 270-290 ℃, 280-310 ℃, 300-330 ℃, 320-340 ℃ and 330-350 ℃ respectively;
The rotating speed of the main machine of the double-screw extruder is 200 revolutions per minute.
10. The preparation method according to claim 6, wherein,
A material baffle plate and a heating resistor ring are arranged in the rotary drum;
The tackifying reaction is solid phase tackifying;
The reaction temperature of the tackifying reaction is 200-300 ℃;
The reaction time of the tackifying reaction is 8-16 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410253942.4A CN118006126A (en) | 2024-03-06 | 2024-03-06 | Liquid crystal polyamide-imide alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410253942.4A CN118006126A (en) | 2024-03-06 | 2024-03-06 | Liquid crystal polyamide-imide alloy material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118006126A true CN118006126A (en) | 2024-05-10 |
Family
ID=90945200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410253942.4A Pending CN118006126A (en) | 2024-03-06 | 2024-03-06 | Liquid crystal polyamide-imide alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118006126A (en) |
-
2024
- 2024-03-06 CN CN202410253942.4A patent/CN118006126A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI794452B (en) | Liquid crystalline polyester liquid composition, method for producing liquid crystalline polyester film and liquid crystalline polyester film | |
| TWI448505B (en) | Camera module with liquid crystal polyester resin composition | |
| TWI444427B (en) | Camera module with liquid crystal polyester resin composition | |
| CN100362036C (en) | Aromatic liquid-crystalline polyester | |
| JP6411702B1 (en) | Totally aromatic liquid crystal polyester resin | |
| JP4169322B2 (en) | Totally aromatic liquid crystal polyester resin molding | |
| EP1081173B1 (en) | Process for producing aromatic liquid crystalline polyester and film thereof | |
| WO2020166651A1 (en) | Liquid crystal polyester powder, liquid crystal polyester composition, film producing method, and laminate producing method | |
| JP2010031256A (en) | Resin composition and molded article using the same | |
| JP6025241B2 (en) | Method for producing foam molded article and resin composition | |
| WO2020166644A1 (en) | Film and laminate | |
| JP2020132849A (en) | Liquid crystal polyester powder, liquid crystal polyester composition, production method of film, and production method of laminate | |
| JP4034019B2 (en) | Method for producing liquid crystalline polyester | |
| CN111655795A (en) | Resin composition | |
| TWI785251B (en) | Preparation method for liquid crystalline resin microparticles | |
| WO2007052955A1 (en) | Method of preparing wholly aromatic polyester | |
| CN113501941B (en) | Thermotropic liquid crystal polyester material and preparation method thereof | |
| WO2012105469A1 (en) | Liquid-crystal polyester and manufacturing process therefor | |
| JP2004143270A (en) | Liquid-crystal polyester resin composition | |
| US20120329975A1 (en) | Method for producing liquid crystal polyester | |
| WO2013114763A1 (en) | Method for producing resin composition | |
| CN118006126A (en) | Liquid crystal polyamide-imide alloy material and preparation method thereof | |
| JP2014506952A (en) | Method for producing wholly aromatic liquid crystal polyester resin, resin produced by the production method, and compound containing the resin | |
| JP3909149B2 (en) | Totally aromatic thermotropic liquid crystal copolyester and composition thereof | |
| TWI524978B (en) | Liquid crystal resin composition, liquid crystal resin composition, and liquid crystal resin manufacturing apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |