CN108178906A - A kind of liquid crystal polymer/polyphenylene sulfide alloy material and preparation method thereof - Google Patents
A kind of liquid crystal polymer/polyphenylene sulfide alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN108178906A CN108178906A CN201711432215.0A CN201711432215A CN108178906A CN 108178906 A CN108178906 A CN 108178906A CN 201711432215 A CN201711432215 A CN 201711432215A CN 108178906 A CN108178906 A CN 108178906A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- polyphenylene sulfide
- crystal polymer
- alloy material
- repetitive unit
- 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
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 49
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 49
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 47
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 46
- 239000000956 alloy Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000003252 repetitive effect Effects 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 13
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 4
- 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 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 polyphenylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229920005621 immiscible polymer blend Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of liquid crystal polymer/polyphenylene sulfide alloy materials and preparation method thereof, are made of the raw material of following weight percent meter：Liquid crystal polyester 69% 93.9%；Polyphenylene sulfide 5% 20%；Toughening compatilizer 1% 10%；Auxiliary agent 0.1% 1%.The invention has the advantages that：1st, the present invention uses liquid crystal polymer and polyphenylene sulfide as raw material, and add toughening compatilizer, auxiliary agent, makes liquid crystal polymer and polyphenylene sulfide compound in the molten state.2nd, in liquid crystal polymer/polyphenylene sulfide alloy material of the invention, the addition of polyphenylene sulfide, so that it has relatively low dielectric constant and dielectric loss angle tangent under high frequency environment, composite material maintains liquid crystal polymer and the performance of polyphenylene sulfide in itself simultaneously, thus the composite material has excellent comprehensive performance.
Description
Technical field
The present invention relates to a kind of Liquid Crystal Polymer alloys material, specially a kind of liquid crystal polyester/polyphenylene sulfide alloy material
And the preparation method of this alloy material, belong to liquid crystal polymer technical field of composite materials.
Background technology
Thermotropic liquid crystal polymer (TLCP) is a kind of high-performance polymer material, and the component available for manufacture includes electrical
It is used as with electric power connector, circuit board, motor insulation shell fast, for various purposes, motor vehicle assembly, cooker/baking tray, replacement ceramics
For high temperature light socket and light-emitting diode housing and/or mounting.
TLCP is usually with its excellent melt-processed shaping characteristic, intrinsic anti-flammability and at high temperature all multi-purpose
It is famous on the way.But liquid crystal polymer (LCP) is used alone, and also there is the shortcomings of rigidity is general, and dielectric constant is high under high frequency.
Polyphenylene sulfide (PPS) full name is polyphenylene thioether, is the thermoplastic resin that thiophenyl is carried in molecular backbone, is one
The crystalline polymer of kind.The electrical property of PPS is very prominent, dielectric constant and dielectric loss angle tangent all than relatively low, and
And change in larger frequency and temperature range little.
But PPS is polysulfide ether structure, differs larger with the polyester construction of TLCP, generally Immiscible Polymer Blends.Between the two
Compatibility is to prepare the critical issue of alloy material.Using compatilizer, ternary compatible system is formed, is most common increase-volume side
Method.But its selection to compatilizer, the requirement of component ratio are very high.
Invention content
The purpose of the invention is to provide a kind of liquid crystal polymer/polyphenylene sulfide alloy material.To solve existing LCP high
The problem of dielectric constant and dielectric loss angle tangent are higher under frequency use environment.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of liquid crystal polymer/polyphenylene sulfide alloy material is made of the raw material of following weight percent meter：
Liquid crystal polymer in the present invention is to show the liquid crystal polyester of liquid crystal liquid crystal property in the molten state, used in the present invention
The fusing point of liquid crystal polyester is at 200~350 DEG C, preferably 220~300 DEG C.The melt viscosity of liquid crystal polyester used in the present invention
Usually in 10~100Pas, preferably 25~45Pas.
Liquid crystal polyester is the liquid crystal polyester formed using aromatic compound as starting monomer, and fragrance is preferably used only
The Wholly aromatic liquid crystal polyester that compounds of group is formed as starting monomer.
The typical example of the liquid crystal polyester of the present invention can use aromatic hydroxy-carboxylic and selected from by aromatic series dicarboxyl
The liquid crystal polyester that at least each a kind of compound in the combination that acid and aromatic diol are formed is polymerize and formed.
Part or all of above-mentioned aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic diol can be independently
Ground is their polymerizable derivative.
The polymerizable derivative of the compound with hydroxyl as aromatic hydroxy-carboxylic, aromatic diol etc,
It may be exemplified the acylate that hydroxyl is acylated, acyloxy is transformed to and is formed.
Liquid crystal polyester preferably has the repetitive unit (hereinafter referred to as " repetitive unit represented by formula (1), formula (2) and formula (3)
(1) ", " repetitive unit (2) " and " repetitive unit (3) ")：
Formula (1)-O-Ar1-CO-
Formula (2)-CO-Ar2-CO-
Formula (3)-O-Ar3-O-
In formula, Ar1, Ar2 and Ar3 separately represent phenylene, naphthylene or biphenylene.
In the combination of the above each repetitive unit for forming liquid crystal polyester：
Repetitive unit (1) is preferred from the repetitive unit of P-hydroxybenzoic acid or 6-Hydroxy-2-naphthoic acid.Repetitive unit
(2) it is preferred from the repetition list of terephthalic acid (TPA), phthalic acid, M-phthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyl dicarboxylic acid
Member.Repetitive unit (3) is preferred from the repetitive unit of hydroquinone, 4,4 '-dihydroxybiphenyl.
The content of repetitive unit (1) is usually 30 moles of more than %, preferably 42~88 moles of %, and more preferable 58~72 rub
You are %.The content of repetitive unit (2) is usually 30 moles of % hereinafter, it is preferred that 6~30 moles of %, more preferable 9~21 moles of %.Weight
The content of multiple unit (3) is usually 30 moles of % hereinafter, it is preferred that 6~30 moles of %, more preferable 9~21 moles of %.
The ratio between the content of repetitive unit (2) and the content of repetitive unit (3) usual 0.9/1~1/0.9 is preferably identical
's.
Repetitive unit (1)~(3) in liquid crystal polyester are separately a kind of repetitive unit or two or more repetitive unit
Combination.
It is 200-260 DEG C that the polyphenylene sulfide that the present invention uses, which selects selective freezing temperature,；Melt flow rate (MFR) is 100-
1050g/10min, preferably 220-240 DEG C of crystallization temperature；Melt flow rate (MFR) is 250-750g/10min.
The toughening compatilizer is more for that can interact with liquid crystal polymer and polyphenylene sulfide or both
Functional compounds, can be physical compatilizer or chemically solubilizer, the present invention use Ethylene-butyl acrylate-methyl
Glycidyl acrylate ternary atactic copolymer (PTW).
In addition, the composite material of the present invention can contain the auxiliary agent for not influencing material property, including lubricant (such as advanced fat
Fat acid metal salt, pentaerythritol esters compound), antioxidant, heat stabilizer, UV absorbers, antistatic agent and conduction
One or more of carbon black.
Above-mentioned liquid crystal polymer/polyphenyl thioether composite material (and can accordingly be set with well known melt molding method
It is standby), including being injection moulded, squeezing out (when particularly forming sheet material, film or pipe), blowing and sinter molding.
The preparation method of above-mentioned liquid crystal polymer/polyphenylene sulfide condensation material, its step are as follows：
Liquid crystal polyester and polyphenylene sulfide are dried in vacuo 2~15 hours at 105 DEG C~200 DEG C, preferably 120 DEG C~
It is dried in vacuo 4~8 hours at 180 DEG C, it is added in into double screw extruder extrusion using Weightlessness balance according to a certain percentage, is granulated.
Double screw extruder from spout to extrusion die temperature be 280 DEG C~300 DEG C respectively, 240 DEG C~280 DEG C, 240 DEG C~280
DEG C, 260 DEG C~300 DEG C, 280 DEG C~300 DEG C, 280 DEG C~310 DEG C, engine speed is 300 revs/min.Performance test test specimen is used
Injection molding machine is injection moulded.
The invention has the advantages that：1st, the present invention uses liquid crystal polymer and polyphenylene sulfide as raw material, and add
Toughening compatilizer, auxiliary agent make liquid crystal polymer and polyphenylene sulfide compound in the molten state, wherein, the toughening compatilizer of addition
It increases the compatibility between liquid crystal polymer and polyphenylene sulfide, increases liquid crystal polymer and polyphenylene sulfide two is alternate is mutually dissolved
Ability；By adding in lubricant, to improve the dispersion effect and processing performance of each component in material.2nd, liquid crystal of the invention gathers
Close object/polyphenylene sulfide alloy material in, the addition of polyphenylene sulfide so that its under high frequency environment have relatively low dielectric constant with
Dielectric loss angle tangent, while composite material maintains liquid crystal polymer and the performance of polyphenylene sulfide in itself, thus this is compound
Material has excellent comprehensive performance.
Specific embodiment
It is further illustrated the present invention below by embodiment and comparative example, in the case where not violating spirit of the invention, the present invention
It should be not limited to the content that following embodiment is specifically expressed.
Properties of product test method：
The present invention uses differential scanning calorimeter (DSC 8000, PerkinElmer companies of the U.S.) test fusing point (Tm), it presses
It is tested according to ASTM D3418 methods.The present invention is tested using capillary rheometer (RH 2200, Malvern companies of Britain)
Melt viscosity (MV) is tested according to ASTM D3835 methods.The present invention uses Melt Flow Rate Measurer (MF50, Italy
CEAST companies) test melt flow rate (MFR) (g/10min), it is tested according to ASTM D1238 methods.
In the present invention, tensile strength (TS) is measured by ASTM D638 methods, rate of extension 5mm/min.Izod notches rush
Hit intensity (IS) is tested with ASTM D256 methods, sample thickness 3.2mm.Heat distortion temperature (HDT) passes through ASTM D648 methods
It measures, applies load 1.82MPa.
In the present invention, permittivity ε is pressed with dielectric loss angle tangent tan δ by dielectric constant dielectric loss test instrument
60250 methods of IEC measure.
Production Example 1
It is first that P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, hydroquinone and acetic anhydride is anti-in 120~130 DEG C of constant temperature
It answers 1 hour, was then raised to 185~195 DEG C in 2 hours, then isothermal reaction 0.5~1 hour, acetylization reaction terminates；Then
The acetate that acetylization reaction is obtained carries out melt polycondensation reaction with terephthalic acid (TPA), and by polymerization temperature liter in 3 hours
To predetermined temperature, polymerisation is made constantly to carry out；Then constant temperature makes polymerisation tend to complete；In order to make point of liquid crystal polyester
Son amount is sufficiently high, and reaction late phase reaction system will apply high vacuum and keep high temperature；When the torque of blender is raised to predetermined journey
Degree is passed through nitrogen immediately, terminates polymerisation；Increase nitrogen pressure to 2kg/cm2, release liquid crystal polyester, the liquid crystal that will be obtained
Polyester carries out the measure of fusing point and melt viscosity.The monomer ratio for preparing above-mentioned liquid crystal polyester is as follows：P-hydroxybenzoic acid 36 rubs
You are %, 44 moles of % of 6-Hydroxy-2-naphthoic acid, 10 moles of % of hydroquinone, 10 moles of % of terephthalic acid (TPA).Prepare the liquid of gained
The fusing point of brilliant polyester (label is in following tables) is 281 DEG C, melt viscosity 52Pas.
Embodiment 1-6 and comparative example 1-2 are formulated referring to table 1, and the wherein PPS trades mark are 1470C/F-T, and Zhejiang is new and into share
Co., Ltd；Compatilizer isPTW, E.I.Du Pont Company.
Liquid crystal polymer, PPS is 4 hours dry at 150 DEG C.Dried material is claimed by the proportioning of table 1 by weightlessness
Material is added in into extruding pelletization in double screw extruder.Extruder includes transfer element, kneading member, low-pressure area (to make to gather
Volatile ingredient that may be present in object is closed to discharge under vacuum) and mouth mold.Extruder is from spout to extrusion die temperature point
It it is not 280 DEG C, 250 DEG C, 250 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, engine speed is 300 revs/min.Liquid crystal polymer Masterbatch
Mouth mold is left, is cooled down through water-carrying groove, pelletizing.
Liquid crystal polymer/polyphenyl thioether composite material particle is after 150 DEG C dry 3~5 hours, with injection moulding method system
The batten of standby test performance.310 DEG C, injection pressure 60MPa, 5~10sec of injection time of injection temperature, cooling time 5~
10sec, 90~110 DEG C of mould temperature.The batten of injection formed carries out performance survey after 50% relative humidity, 23 DEG C are placed at least 24 hours
Examination, the performance tested are listed in table 2.Table 1
| Composition | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 |
| TLCP | % | 70 | 89 | 83 | 80 | 77 | 90 | 0 | 95 |
| PPS | % | 20 | 8 | 12 | 15 | 18 | 7 | 95 | 0 |
| Compatilizer | % | 9 | 2 | 4 | 4 | 4 | 2 | 4 | 4 |
| Antioxidant | % | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Lubricant | % | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| It amounts to | % | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Experimental results are referring to table 2.
Table 2
It can be seen that from Examples 1 to 6 and comparative example 1~2：Liquid crystal polymer/the polyphenylene sulfide obtained in Examples 1 to 6
Ether composite material has many advantages, such as that high intensity, high rigidity, heat resistance are good, compared with pure liquid crystal polymer it can be found that
The present invention solve in the prior art LCP under high frequency use environment dielectric constant with dielectric loss angle tangent is higher asks
Topic, maintains the excellent performances of LCP.Therefore liquid crystal polymer/polyphenylene sulfide alloy material of the present invention has excellent
Mechanics, dielectric properties, can materials electric as manufacture, various refractory investment parts in high frequency communications.
Claims (15)
1. a kind of liquid crystal polymer/polyphenylene sulfide alloy material, it is characterised in that：By the raw material group of following weight percent meter
Into：
2. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 1, it is characterised in that：The liquid
The fusing point of brilliant polyester is 200~350 DEG C, and the melt viscosity is 10~100Pas.
3. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 2, it is characterised in that：The liquid
The fusing point of brilliant polyester is 220~300 DEG C；The melt viscosity is 25~45Pas.
4. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 1, it is characterised in that：The liquid
Brilliant polyester is the liquid crystal polyester that is formed using aromatic compound as starting monomer or using only aromatic compound as original
The Wholly aromatic liquid crystal polyester that material list body forms.
5. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 1, it is characterised in that：Liquid crystal polyester
Repetitive unit represented by with formula (1), formula (2) and formula (3)：
Formula (1)-O-Ar1-CO-
Formula (2)-CO-Ar2-CO-
Formula (3)-O-Ar3-O-
In formula, Ar1, Ar2 and Ar3 separately represent phenylene, naphthylene or biphenylene.
6. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 5, it is characterised in that：Repetitive unit
(1) it is preferred from the repetitive unit of P-hydroxybenzoic acid or 6-Hydroxy-2-naphthoic acid；Repetitive unit (2) is preferred to benzene two
Formic acid, phthalic acid, M-phthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyl dicarboxylic acid repetitive unit；Repetitive unit (3) is preferred
Repetitive unit from hydroquinone, 4,4 '-dihydroxybiphenyl.
7. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 5, it is characterised in that：Repetitive unit
(1) content is 30 moles of more than %, and the content of repetitive unit (2) is usually 30 moles of % hereinafter, the content of repetitive unit (3)
Usually 30 moles of below %.
8. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 7, it is characterised in that：Repetitive unit
(1) content is 42~88 moles of %, and (2 content is 6~30 moles of % to repetitive unit, and (3 content is 6~30 to repetitive unit
Mole %.
9. a kind of liquid crystal polymer/polyphenylene sulfide alloy material according to claim 7, it is characterised in that：Unit (2)
The ratio between content and the content of repetitive unit (3) usual 0.9/1~1/0.9.
10. a kind of liquid crystal polymer/polyphenylene sulfide alloy material stated according to claim 1, it is characterised in that：The polyphenyl
The crystallization temperature of thioether is 200-260 DEG C；Melt flow rate (MFR) is 100-1050g/10min.
11. a kind of liquid crystal polymer/polyphenylene sulfide alloy material stated according to claim 10, it is characterised in that：The polyphenyl
220-240 DEG C of the crystallization temperature of thioether；Melt flow rate (MFR) is 250-750g/10min.
12. a kind of liquid crystal polymer/polyphenylene sulfide alloy material stated according to claim 1, it is characterised in that：The toughening
Compatilizer is Ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
13. a kind of liquid crystal polymer/polyphenylene sulfide alloy material stated according to claim 1, it is characterised in that：The present invention's answers
Condensation material contains the auxiliary agent for not influencing material property, including lubricant, antioxidant, heat stabilizer, UV absorbers, anti-quiet
One or more of electric agent and conductive black.
14. the preparation method of one of the arbitrary liquid crystal polymer/polyphenylene sulfide condensation materials of claim 1-13, feature exist
In：Its step are as follows：
Liquid crystal polyester and polyphenylene sulfide at 105 DEG C~200 DEG C are dried in vacuo 2~15 hours, it is made according to a certain percentage
Double screw extruder extrusion is added in Weightlessness balance, is granulated；Double screw extruder from spout to extrusion die temperature be 280 respectively
DEG C~300 DEG C, it is 240 DEG C~280 DEG C, 240 DEG C~280 DEG C, 260 DEG C~300 DEG C, 280 DEG C~300 DEG C, 280 DEG C~310 DEG C, main
Machine rotating speed is 300 revs/min.
15. the preparation method of a kind of liquid crystal polymer/polyphenylene sulfide alloy material stated according to claim 14, feature exist
In：Liquid crystal polyester is dried in vacuo 4~8 hours with polyphenylene sulfide at 120 DEG C~180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711432215.0A CN108178906A (en) | 2017-12-26 | 2017-12-26 | A kind of liquid crystal polymer/polyphenylene sulfide alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711432215.0A CN108178906A (en) | 2017-12-26 | 2017-12-26 | A kind of liquid crystal polymer/polyphenylene sulfide alloy material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108178906A true CN108178906A (en) | 2018-06-19 |
Family
ID=62547130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711432215.0A Pending CN108178906A (en) | 2017-12-26 | 2017-12-26 | A kind of liquid crystal polymer/polyphenylene sulfide alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108178906A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500058A (en) * | 2020-05-09 | 2020-08-07 | 宁波长阳科技股份有限公司 | Liquid crystal polymer film for flexible printed circuit board |
| CN112694752A (en) * | 2020-12-24 | 2021-04-23 | 珠海万通特种工程塑料有限公司 | High-performance antistatic PPS composite material and preparation method and application thereof |
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| CN114316522A (en) * | 2021-12-29 | 2022-04-12 | 中国科学院长春应用化学研究所 | High-performance liquid crystal polymer composite material and application thereof |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
| US12294185B2 (en) | 2019-09-10 | 2025-05-06 | Ticona Llc | Electrical connector formed from a polymer composition having a low dielectric constant and dissipation factor |
| US12441879B2 (en) | 2019-08-21 | 2025-10-14 | Ticona Llc | Polymer composition for laser direct structuring |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140233A (en) * | 2011-02-18 | 2011-08-03 | 金发科技股份有限公司 | Low warpage liquid crystal polymer composition and preparation method thereof |
| CN103087524A (en) * | 2013-03-04 | 2013-05-08 | 四川华通特种工程塑料研究中心有限公司 | Polyphenyl thioether sheet with electrical insulation properties and preparation method thereof |
| CN106751624A (en) * | 2016-12-29 | 2017-05-31 | 上海普利特化工新材料有限公司 | A kind of liquid crystal polymer Masterbatch and preparation method thereof |
-
2017
- 2017-12-26 CN CN201711432215.0A patent/CN108178906A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140233A (en) * | 2011-02-18 | 2011-08-03 | 金发科技股份有限公司 | Low warpage liquid crystal polymer composition and preparation method thereof |
| CN103087524A (en) * | 2013-03-04 | 2013-05-08 | 四川华通特种工程塑料研究中心有限公司 | Polyphenyl thioether sheet with electrical insulation properties and preparation method thereof |
| CN106751624A (en) * | 2016-12-29 | 2017-05-31 | 上海普利特化工新材料有限公司 | A kind of liquid crystal polymer Masterbatch and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡隆伟等: "《紧固件材料手册》", 31 December 2014, 中国宇航出版社 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12441879B2 (en) | 2019-08-21 | 2025-10-14 | Ticona Llc | Polymer composition for laser direct structuring |
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11705641B2 (en) | 2019-08-21 | 2023-07-18 | Ticoan Llc | Antenna system including a polymer composition having a low dissipation factor |
| US12136762B2 (en) | 2019-08-21 | 2024-11-05 | Ticona Llc | Polymer composition for use in an antenna system |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US12428522B2 (en) | 2019-09-10 | 2025-09-30 | Ticona Llc | Polymer composition for laser direct structuring |
| US12294185B2 (en) | 2019-09-10 | 2025-05-06 | Ticona Llc | Electrical connector formed from a polymer composition having a low dielectric constant and dissipation factor |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US12107617B2 (en) | 2019-09-23 | 2024-10-01 | Ticona Llc | RF filter for use at 5G frequencies |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
| US12035467B2 (en) | 2020-02-26 | 2024-07-09 | Ticona Llc | Circuit structure |
| CN111500058A (en) * | 2020-05-09 | 2020-08-07 | 宁波长阳科技股份有限公司 | Liquid crystal polymer film for flexible printed circuit board |
| WO2021227505A1 (en) * | 2020-05-09 | 2021-11-18 | 宁波长阳科技股份有限公司 | Liquid crystal polymer film for flexible printed circuit board |
| CN112694752A (en) * | 2020-12-24 | 2021-04-23 | 珠海万通特种工程塑料有限公司 | High-performance antistatic PPS composite material and preparation method and application thereof |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
| US12230865B2 (en) | 2021-02-18 | 2025-02-18 | Ticona Llc | Polymer composition for use in an antenna system |
| CN114316522A (en) * | 2021-12-29 | 2022-04-12 | 中国科学院长春应用化学研究所 | High-performance liquid crystal polymer composite material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108178906A (en) | A kind of liquid crystal polymer/polyphenylene sulfide alloy material and preparation method thereof | |
| TWI765153B (en) | Resin moldings and electrical and electronic parts containing wholly aromatic liquid crystal polyester resin whose loss tangent can be reduced by heat treatment | |
| TW500765B (en) | Thermoplastic resin composition and heat-resistant tray for IC | |
| JP6900151B2 (en) | All-aromatic liquid crystal polyester resins, molded products, and electrical and electronic components | |
| CN111936547B (en) | Liquid crystal polyester resin, method for producing the same, and molded article formed therefrom | |
| JP5366533B2 (en) | Thermoplastic resin composition | |
| JPWO2020138277A1 (en) | A resin composition and a resin molded product comprising the resin composition | |
| JP7703301B2 (en) | Resin composition and resin molded article made from said resin composition | |
| CN110724367B (en) | A liquid crystal polymer/PET in-situ composite polyester material that can be extruded into a film and its preparation method | |
| JP2015059178A (en) | Liquid crystalline polyester resin composition and molded article comprising the same | |
| CN113121962B (en) | Polytetrafluoroethylene/liquid crystal polymer composite material and preparation method thereof | |
| CN110066502A (en) | A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility | |
| WO2023186187A1 (en) | Liquid crystal polymer, and preparation method and use therefor | |
| Paszkiewicz et al. | Characterization of polypropylene/poly (2, 6-dimethyl-1, 4-phenylene oxide) blends with improved thermal stability | |
| CN102719082B (en) | Polyphenyl ether/ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof | |
| CN102134495A (en) | High-fluidity liquid crystal polymer composition and preparation method thereof | |
| CN108264741A (en) | A kind of liquid crystal polyester/nylon composite materials and preparation method thereof | |
| CN108276746A (en) | A kind of liquid crystal polyester/nylon alloy material and preparation method thereof | |
| CN113004663A (en) | Low-dielectric alloy material and preparation method and application thereof | |
| CN103374199B (en) | A kind of polyetheretherketone/polyimide/polyphenylene sulfide ternary alloy and its preparation method | |
| CN110845935A (en) | Small motor insulation powder and preparation method thereof | |
| JP2013014757A (en) | Thermally conductive resin composition | |
| JP2013014758A (en) | Thermally conductive resin composition | |
| CN104650560A (en) | PC/PBT blend alloy with excellent electric and heat conduction and flame retardance | |
| JP2024061926A (en) | Liquid crystal polyester resin composition, and molded article made from the same |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180619 |