CN105837807A - Liquid crystal polyester and its molded composition and use - Google Patents
Liquid crystal polyester and its molded composition and use Download PDFInfo
- Publication number
- CN105837807A CN105837807A CN201610068348.3A CN201610068348A CN105837807A CN 105837807 A CN105837807 A CN 105837807A CN 201610068348 A CN201610068348 A CN 201610068348A CN 105837807 A CN105837807 A CN 105837807A
- Authority
- CN
- China
- Prior art keywords
- temperature
- melting
- liquid crystal
- crystallization
- crystal polyester
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 132
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000002844 melting Methods 0.000 claims abstract description 115
- 230000008018 melting Effects 0.000 claims abstract description 115
- 238000012360 testing method Methods 0.000 claims abstract description 20
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- 238000002425 crystallisation Methods 0.000 claims description 65
- 230000008025 crystallization Effects 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000000465 moulding Methods 0.000 claims description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 238000005917 acylation reaction Methods 0.000 claims description 28
- 239000012763 reinforcing filler Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 22
- 239000000155 melt Substances 0.000 claims description 19
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 16
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 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 5
- -1 4' -biphenol Chemical compound 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010425 asbestos Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229910052895 riebeckite Inorganic materials 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims 1
- 229910000271 hectorite Inorganic materials 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 230000010933 acylation Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 229920000106 Liquid crystal polymer Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VGCSPGQZLMQTHC-UHFFFAOYSA-N (2,2-dibromoacetyl) 2,2-dibromoacetate Chemical compound BrC(Br)C(=O)OC(=O)C(Br)Br VGCSPGQZLMQTHC-UHFFFAOYSA-N 0.000 description 1
- 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
- IYXUFOCLMOXQSL-UHFFFAOYSA-N (2,2-difluoroacetyl) 2,2-difluoroacetate Chemical compound FC(F)C(=O)OC(=O)C(F)F IYXUFOCLMOXQSL-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- TVPCUVQDVRZTAL-UHFFFAOYSA-N 2-ethylhexanoyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(=O)C(CC)CCCC TVPCUVQDVRZTAL-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention discloses a liquid crystal polyester and its molded composition and use. The liquid crystal polyester comprises repeated structural units [I]-[IV]. A differential scanning calorimetry (DSC) test proves that the liquid crystal polyester has a double enthalpy ratio delta H greater than or equal to 0.1 and less than or equal to 0.9 defined in the formula (1) of delta H=H(melting enthalpy)/H(crystalline enthalpy) and preferably, the double enthalpy ratio delta H is greater than or equal to 0.2 and less than or equal to 0.7. The liquid crystal polyester has a double enthalpy ratio delta H greater than or equal to 0.1 and less than or equal to 0.9. The liquid crystal polyester and the liquid crystal polyester molded composition have good fluidity and excellent melting characteristics. A small thin wall molded product has high stability and is especially suitable for a thin wall electronic product.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a liquid crystal polyester, a molding composition composed of the liquid crystal polyester and application of the liquid crystal polyester.
Background
Thermotropic Liquid Crystal Polymer (TLCP) as a high-performance special engineering plastic has excellent mechanical properties, good fluidity, heat resistance, chemical corrosion resistance, flame retardance and electrical insulation performance, and is widely applied in the fields of electronic and electric appliances, small-sized precise thin-wall parts and the like at present. The preparation method usually adopts a high-temperature melt polymerization method, but due to the self-polymerization of monomers such as HBA and the like or the branching and crosslinking reaction of molecular chains, the melt processability and the physical properties of a final liquid crystal product are poor, particularly the flowability of resin is seriously influenced, so that the liquid crystal polyester molding composition has the conditions of insufficient mold filling and the like in the molding process, and the application of a liquid crystal polymer in thin-walled parts of electronic and electric appliances is seriously influenced.
Researches on inhibition of self-polymerization of HBA and control of occurrence of side reactions such as cross-linking in high temperature polymerization process have been important issues in research and industry, for example, patents CN1673249A, CN 104004170A, CN104098760A and CN104098761A mention that decarboxylation and self-polymerization of HBA are inhibited by adding 4-methylbenzenesulfonic acid, water or acetic acid, and the above methods have certain improvement effect on intrinsic viscosity of liquid crystal polymer.
As shown in the above patents, the intrinsic viscosity of the liquid crystal polyester has become a general means in the industry to characterize the relative molecular mass and molecular chain motion characteristics of the liquid crystal polyester, and indirectly reflect the fluidity of the final liquid crystal polyester. However, the difference in intrinsic viscosity is not the only factor affecting the flowability of the polymer. The raw material monomer has different structures or proportions, the degree of self-polymerization of the monomers, the change of molecular weight and molecular chain sequence structure, whether molecular chain segments are uniform or not, the entanglement or branching degree of the molecular chains, the movement capability, the crystallization structure and the speed of the molecular chains, the preparation process and the like all influence the fluidity of the polymer.
Differential Scanning Calorimetry (DSC) is one of the most commonly used thermal analyzers, and is used to characterize the melting and crystallization process of polymers, reflect the relationship between molecular chain structures and crystallization, and directly determine the melting or crystallization behavior of DSC in the process of temperature rise or temperature decrease. The applicant continuously researches and further discovers that the liquid crystal polyester with a specific melting crystallization enthalpy ratio, namely within a double enthalpy ratio range, has a specific molecular chain structure and a specific crystallization state, so that the liquid crystal polyester has excellent processing flowability and mechanical properties.
Disclosure of Invention
The primary object of the present invention is to provide a liquid crystalline polyester having high flowability, which has a double enthalpy ratio Δ H within a specific range and remarkably improved processing flowability.
Another object of the present invention is to provide a molding composition comprising the above liquid-crystalline polyester.
The invention is realized by the following technical scheme:
a liquid crystal polyester comprising repeating structural units represented by the following formulae [ I ] to [ IV ]:
the amount of the structural unit [ I ] derived from parahydroxybenzoic acid is 40mol% or more and 80mol% or less, based on 100mol% of the total amount of the repeating units; the amount of structural units [ II ] derived from 4, 4' -biphenol is 10mol% or more and 30mol% or less; the total amount of the structural unit [ III ] derived from terephthalic acid and the structural unit [ IV ] derived from isophthalic acid is 10mol% or more and 32mol% or less; the ratio of the amount of the structural unit [ II ] to the total molar amount of the structural units [ III ] and [ IV ] is 1:1, wherein the molar ratio of the structural unit [ IV ] derived from isophthalic acid to the structural unit [ III ] derived from terephthalic acid is preferably 0.1 to 0.49, and the sum of the molar percentages of the structural units [ I ], [ II ], [ III ] and [ IV ] is 100%;
wherein, a Differential Scanning Calorimetry (DSC) test is adopted, the temperature is increased to the highest temperature of a melting point plus 30 ℃ from room temperature at the temperature rising rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a crystallization curve of the liquid crystal polyester is obtained, the crystallization starting temperature and the crystallization finishing temperature of a crystallization peak are selected, and the crystallization peak area is calculated to be H (crystallization enthalpy); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature rise rate of 20 ℃/min again to obtain a second melting curve of the liquid crystal polyester, the melting starting temperature and the melting finishing temperature of a melting peak are selected, and the melting peak area is calculated to be H (melting enthalpy), wherein the liquid crystal polyester meets the condition that the double enthalpy ratio delta H defined by the following formula (1) is more than or equal to 0.1, less than or equal to 0.9, preferably more than or equal to 0.2 and less than or equal to 0.7;
(1) Δ H = H (melting enthalpy)/H (crystallization enthalpy).
The DSC double enthalpy ratio delta H is the ratio of the melting enthalpy and the crystallization enthalpy of the liquid crystal polyester crystal, and the physical significance of the actual reaction is the relationship between the damage of the liquid crystal polyester crystal structure and the difficulty degree of molecular chain crystallization and the molecular chain structure of the liquid crystal polyester. The crystallization behavior and the crystal melting behavior are closely related to the structural characteristics of the molecular chain, no interaction exists among ideal molecular chains, the molecular chain structure is regular, the internal rotation capacity is high, the flexibility is high, the movement of the molecular chain has no resistance such as friction and the like, the molecular chain moves freely, and the perfect fluidity is shown, so that the molecular chain crystallization capacity is high, and the crystal structure is compactly and regularly stacked. However, in the actual synthesis of liquid crystal polyester, due to the difference in the structure or ratio of the raw material monomers, the degree of self-polymerization of the monomers, the change in molecular weight and molecular chain sequence structure, whether the molecular chain segments are uniform and the molecular chain is regular, the entanglement or branching degree of the molecular chain is high or low, the rotation capacity of the molecular chain is high or low, the motion capacity of the molecular chain, the preparation process and other factors influence the molecular chain structure of the finally prepared liquid crystal polyester to be greatly different, the arrangement and crystallization behavior of the molecular chain and the destructive behavior of the crystal structure are greatly changed, as shown in the melting enthalpy and crystallization enthalpy change of DSC, the enthalpy change has certain fluctuation, and the fluctuation of the enthalpy change just reflects the structural characteristics of the molecular chain and the macroscopic fluidity change of the liquid crystal polyester caused by the fluctuation.
According to the invention, researches show that when the DSC enthalpy ratio delta H of the liquid crystal polyester is more than or equal to 0.1 and less than or equal to 0.9, particularly more than or equal to 0.2 and less than or equal to 0.7, the self-polymerization segment or molecular chain branching crosslinking of HBA is obviously weakened, the liquid crystal polyester has higher fluidity, the melting characteristic is excellent, the molding stability of a small thin-wall molding product is high, and when the delta H is more than 0.9, the processing fluidity is poor due to the change of the molecular chain structure and the crystallization behavior.
In order to complete the preparation of the high-fluidity liquid crystal polyester, the melt viscosity of the liquid crystal polyester is 10 Pa.s-35 Pa.s, preferably 15 Pa.s-30 Pa.s, and the melt viscosityTesting with capillary rheometer at 0-30 deg.C above melting point and with shear rate of 1000S-1Measured using a die having an inner diameter of 1mm and a length of 40 mm.
The melting point of the liquid crystalline polyester should be as high as possible from the viewpoint of heat resistance, but the melting point of the liquid crystalline polymer of the present invention is 310 ℃ to 390 ℃, preferably 330 ℃ to 380 ℃ from the viewpoint of the heating capacity of the molding equipment at the time of melt processing of the polymer. And the melting point is measured by DSC, the temperature is raised to the highest temperature of the melting point plus 30 ℃ under the condition of the temperature raising rate of 20 ℃/min from the room temperature, the temperature is lowered to the room temperature at the rate of 20 ℃/min after staying for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ again at the temperature raising rate of 20 ℃/min after the test sample stays for 3min at the room temperature, the second melting curve of the liquid crystal polyester is obtained, and the melting peak value of the curve is selected as the melting point.
The content of each structural unit can be calculated by the following method: 500mg of liquid-crystalline polyester or molding composition thereof are metered into a 25ml volumetric flask, 2.5ml of NaOH/CH with a concentration of 5mol/L are added3And adding 10ml of dehydrated dimethyl sulfoxide into the OH solution. Thoroughly hydrolyzing at 60 deg.C under nitrogen atmosphere, shaking for more than 18 hr, dissolving in water, acidifying with hydrochloric acid, and freeze drying. Taking appropriate amount of hydrolysate to NMR (nuclear magnetic resonance) tube, performing 1H-NMR measurement, and calculating peak area ratio derived from each structural unit.
The preparation method of the liquid crystal polyester comprises the following steps:
a. under the condition of nitrogen pressurization, taking p-hydroxybenzoic acid, 4' -biphenol, terephthalic acid and isophthalic acid as raw materials, and carrying out acylation reaction under the action of an acylating agent, wherein the pressure is kept between 0.2MPa and 0.6 MPa;
b. after the acylation reaction is finished, reducing the pressure in the reaction kettle to 10KPa-30KPa, quickly discharging acetic acid and unreacted acetic anhydride molecules from the rectification column, when the receiving amount of the acetic acid reaches more than 50% of a theoretical value, quickly heating to 200 ℃ or more, maintaining the reduced pressure condition, raising the temperature of a reaction system program to the highest reaction temperature, further reducing the pressure to 50KPa-100KPa, and carrying out melt polycondensation to obtain a prepolymer;
c. and cooling, solidifying and granulating the prepolymer, and carrying out solid-phase polymerization in a solid-phase polymerization container to obtain liquid crystal polyester particles.
The phenolic hydroxyl group contained in the raw material monomer is preferably acylated with a fatty acid anhydride before melt polycondensation. The fatty acid anhydride is not particularly limited, and any of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, 2-ethylhexanoic anhydride, dichloroacetic anhydride, dibromoacetic anhydride, difluoroacetic anhydride, maleic anhydride, and succinic anhydride may be used, or a mixture of two or more thereof may also be used. From the viewpoint of production cost, acetic anhydride, propionic anhydride or butyric anhydride is preferable, and acetic anhydride is more preferable. The molar ratio of the amount of the fatty acid anhydride to the phenolic hydroxyl groups used is (1 to 1.2): 1, and the amount of the fatty acid anhydride used is preferably 1.02 to 1.10 times by equivalent from the viewpoint of producing low outgassing and solder blister resistance.
The first stage of the preparation method of the liquid crystal polyester is an acylation reaction stage, the phenolic hydroxyl of the main monomer component is subjected to acylation reaction by the acylating agent, and the acylation process is mainly characterized in that, the pressure of the reaction kettle is kept between 0.2MPa and 0.6MPa in the acylation process in a nitrogen pressurization mode, wherein the magnitude of the holding pressure is not particularly limited, but the acylation reaction temperature must be controlled within the acylation temperature range required for the process, the purpose is to ensure that acetic anhydride and acetic acid products are boiled violently by a pressurizing mode, acetic acid is generated by the self-polymerization reaction of the p-hydroxybenzoic acid acylate, the volume of acetic acid gas is increased, whereas an increase in pressure causes the chemical reaction to proceed in the direction of a decrease in gas volume, so that the self-polymerization reaction is moderately suppressed, meanwhile, the boiling acetic anhydride increases the probability of collision with the monomer and ensures the balance of acylation reaction of phenolic hydroxyl. The second stage is an ester exchange polymerization stage, the whole reaction process is a decompression reaction, the vacuum pumping is carried out to reduce the pressure to 10KPa-30KPa, wherein the decompression is realized by pumping by a vacuum pump, the pressure is not particularly limited, but the requirement of the temperature programming rate must be met. After acylation is finished, acetic acid molecules are required to be rapidly discharged to meet the requirement of rapid temperature rise, a large amount of acetic acid molecules are gasified into fog due to nitrogen pressurization in an acylation stage, then, air is pumped out by a vacuum pump for decompression, a large amount of acetic acid and unreacted acetic anhydride are discharged from a reaction kettle, the discharged acetic acid flows into an acetic acid receiving tank under the cooling action of a heat exchanger, when the receiving amount of the acetic acid reaches more than 50% of a theoretical value, the temperature rise rate is increased, the reaction temperature of the reaction kettle is rapidly raised to 200 ℃ or more, and the reaction enters the condensation reaction of an acylation group of a phenolic hydroxyl group and a carboxylic acid group to inhibit self-polymerization of a monomer. In the ester exchange polymerization stage, a decompression mode is adopted, after the reaction temperature reaches the highest reaction temperature, the vacuum degree of the reaction kettle is increased, and then the pressure is further reduced to 50Kpa-100Kpa, so that by-products generated in the reaction, such as phenol and other small molecules, are continuously discharged from the reaction kettle under the decompression effect, the molecular chain rearrangement or branching probability is reduced, and the branching crosslinking reaction of the molecular chain is reduced. The acylation reaction is usually carried out at 100 ℃ to 180 ℃ for 30 minutes to 20 hours, and preferably at 120 ℃ to 160 ℃ for 40 minutes to 5 hours. The melt polycondensation can be carried out under the action of a catalyst, and the catalyst is a conventionally known catalyst for polyester polymerization and can be a metal salt catalyst, such as potassium acetate, sodium acetate, magnesium acetate, zinc acetate, antimony trioxide, tetrabutyl titanate and the like.
The melt polycondensation can be carried out under an inert gas atmosphere; the polycondensation may be carried out in a batch or continuous mode or in a combined mode. After the acylation reaction is finished, heating at the speed of 0.1-150 ℃/min to quickly heat the reaction kettle to 200 ℃ or above, and entering a melt polycondensation stage; the melt polycondensation is carried out at a temperature in the range of 130 to 400 ℃, preferably 160 to 370 ℃, wherein the maximum reaction temperature is more preferably the melting point of the liquid crystalline polyester +30 ℃.
The polymerization vessel used for the melt polycondensation may be a polymerization vessel having a known shape. The vertical polymerization tank is preferably used, and the stirring paddle can be a turbine blade, a double-helix blade or a multi-stage paddle blade, and is preferably a turbine blade.
After the melt polycondensation, the melt viscosity of the prepolymer is preferably 10pa.s or less, from the viewpoint of facilitating the discharge of the prepolymer in a molten state from the polymerization vessel. The melt viscosity is measured by a Dynisco LCR7000 type capillary rheometer, the measurement temperature is more than the melting point by 30 ℃, and the shear rate is 1000S-1Measured using a die having an inner diameter of 1mm and a length of 40 mm.
After the melt polycondensation, the discharge of the prepolymer is preferably carried out under an inert gas atmosphere such as a nitrogen gas atmosphere, that is, by adding an inert gas to the polymerization vessel and increasing the pressure, the occurrence of side reactions can be suppressed while suppressing the increase in the molecular weight of the prepolymer (suppressing the melt viscosity of the prepolymer). The apparatus for discharging the prepolymer in a molten state may be selected from a valve, an extruder and a gear pump, solidify the prepolymer while continuously conveying it in one direction, and may be cut or pulverized downstream in the conveying direction by means of a wire cutter, a sheet cutter or a pulverizer. The prepolymer particles or powder obtained after cutting or crushing are not particularly limited, but preferably 0.1mm to 5 mm.
The acylation reaction and the transesterification polymerization may be carried out continuously in the same reactor or in different reaction vessels.
The solid-phase polymerization is preferably carried out under the conditions that the vacuum degree is 0.1Pa to 50KPa or inert protective gas such as nitrogen is introduced, the polymerization temperature is about 0 to 340 ℃, and the reaction time is 0.5 to 40 hours. The solid-phase polymerization may be carried out in a static state with or without stirring.
A great deal of experimental data according to the invention show that the self-polymerization of the monomers mainly occurs under low temperature conditions, such as temperatures below 200 ℃, while the reactions of branching, crosslinking and the like of the molecular chains are mainly concentrated under high temperature conditions, such as temperatures above 300 ℃; therefore, the optimal preparation process is adopted, and the reaction of the two temperature sections is well controlled, which is the key for controlling the sequence structure arrangement of molecular chains and also the key for ensuring the prepared liquid crystal polyester to have better processing fluidity. The invention adopts the improved preparation process, effectively controls the reaction of each temperature section, and avoids the processing fluidity problem caused by the self-polymerization of the monomer or the branching and crosslinking of the molecular chain. And experimental data is collated to find that the liquid crystal polyester prepared by the process of the invention and the molding composition thereof show higher fluidity when the enthalpy ratio delta H is in a preferred range through DSC to the crystallization enthalpy and the melting enthalpy, but the processing fluidity is deteriorated due to the change of the molecular weight structure and the crystal structure when the enthalpy ratio delta H is higher than the preferred range of the invention.
The adjusted polymerization process is mainly characterized in that the reaction is divided into two stages, the first stage is the acylation stage of the monomer, the pressure maintaining reaction is carried out in the acylation process, and the pressure is kept between 0.2MPa and 0.6 MPa; the second stage is ester exchange polymerization stage, and the whole reaction process is decompression reaction, and the vacuum pumping is carried out until the pressure is reduced to 10KPa-30 KPa. The purpose of the combined pressure and pressure reduction process is to effectively solve the problem of a series of side reactions generated in two reaction temperature ranges, thereby preparing the liquid crystal polyester with excellent processing fluidity and the molding composition thereof.
The invention also provides a liquid crystal polyester molding composition, which comprises 30 to 99.9 weight parts of liquid crystal polyester, 1 to 70 weight parts of reinforcing filler and 0 to 20 weight parts of other additives and/or other polymers; wherein,
the liquid crystal polyester is composed of repeating structural units of the following formulas (I) to (IV):
the amount of the structural unit [ I ] derived from parahydroxybenzoic acid is 40mol% or more and 80mol% or less, based on 100mol% of the total amount of the repeating units; the amount of structural units [ II ] derived from 4, 4' -biphenol is 10mol% or more and 30mol% or less; the total amount of the structural unit [ III ] derived from terephthalic acid and the structural unit [ IV ] derived from isophthalic acid is 10mol% or more and 32mol% or less; the ratio of the amount of the structural unit [ II ] to the total molar amount of the structural units [ III ] and [ IV ] is 1:1, wherein the molar ratio of the structural unit [ IV ] derived from isophthalic acid to the structural unit [ III ] derived from terephthalic acid is preferably 0.1 to 0.49, and the sum of the molar percentages of the structural units [ I ], [ II ], [ III ] and [ IV ] is 100%;
wherein, a Differential Scanning Calorimetry (DSC) test is adopted, the temperature is increased to the highest temperature of a melting point plus 30 ℃ from room temperature at the temperature rising rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a crystallization curve of the liquid crystal polyester is obtained, the crystallization starting temperature and the crystallization finishing temperature of a crystallization peak are selected, and the crystallization peak area is calculated to be H (crystallization enthalpy); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature rise rate of 20 ℃/min again to obtain a second melting curve of the liquid crystal polyester, the melting starting temperature and the melting finishing temperature of a melting peak are selected, and the melting peak area is calculated to be H (melting enthalpy), wherein the liquid crystal polyester meets the condition that the double enthalpy ratio delta H defined by the following formula (1) is more than or equal to 0.1, less than or equal to 0.9, preferably more than or equal to 0.2 and less than or equal to 0.7;
(1) Δ H = H (melting enthalpy)/H (crystallization enthalpy).
The liquid crystal polyester molding composition of the invention is slightly lower than the fluidity of the resin due to the addition of various fillers, so that the enthalpy ratio delta H of the molding composition is slightly improved, but the comparative test data shows that when the enthalpy ratio delta H of the molding composition is less than 1.0, the processing fluidity of the molding composition is still better than that of the liquid crystal polyester composition in the comparative test.
According to the liquid crystal polyester molding composition, a Differential Scanning Calorimetry (DSC) test is adopted, the temperature is increased to the highest temperature of a melting point plus 30 ℃ from room temperature at the temperature rise rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a crystallization curve of the liquid crystal polyester molding composition is obtained, the crystallization starting temperature and the crystallization finishing temperature of a crystallization peak are selected, and the crystallization peak area is calculated to be H (crystallization enthalpy); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature rise rate of 20 ℃/min again to obtain a second melting curve of the liquid crystal polyester molding composition, the melting starting temperature and the melting finishing temperature of a melting peak are selected, and the melting peak area is calculated to be H (melting enthalpy), wherein the liquid crystal polyester molding composition meets the double enthalpy ratio delta H defined by the following formula (1) and is more than or equal to 0.2 and less than 1.0, preferably more than or equal to 0.5 and less than or equal to 0.9;
(1) Δ H = H (melting enthalpy)/H (crystallization enthalpy).
Wherein the reinforcing filler is fibrous, and the average length of the reinforcing filler is 0.01-20 mm, preferably 0.1-6 mm; the length-diameter ratio of the composite material is 5: 1-2000: 1, preferably 30: 1-600: 1; when the size of the fibrous reinforcing filler is selected within the above range, the liquid-crystalline polyester composition exhibits not only good melt-processing fluidity but also high heat distortion temperature and high rigidity.
The content of the reinforcing filler is too low, so that the mechanical property of the liquid crystal polyester molding composition is poor; the content of the reinforcing filler is too high, and the surface of the liquid crystal polyester molding composition product is seriously floated, so that the appearance of the product is influenced. The content of the reinforcing filler is preferably 10 to 50 parts by weight, more preferably 15 to 40 parts by weight;
the reinforcing filler is inorganic reinforcing filler or organic reinforcing filler.
The inorganic reinforcing filler comprises one or more of glass fiber, potassium titanate fiber, metal-clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal curing fiber, asbestos fiber, alumina fiber, silicon carbide fiber, gypsum fiber or boron fiber, and is preferably glass fiber. The use of the glass fiber can improve not only the moldability of the liquid crystal polyester composition but also mechanical properties such as tensile strength, flexural strength or flexural modulus, and heat resistance such as heat distortion temperature at which the thermoplastic resin composition is molded.
The organic reinforcing filler includes, but is not limited to, liquid crystal polyester fibers and/or carbon fibers.
The reinforcing filler is in a non-fibrous shape having an average particle diameter of 0.001 μm to 50 μm, which results in poor melt processability of the liquid crystal polyester resin when the average particle diameter of the reinforcing filler is less than 0.001 μm; when the average particle diameter of the reinforcing filler is more than 50 μm, poor surface appearance of injection molded articles may result. It is selected from one or more of potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, talcum powder, carbon black, gypsum, asbestos, zeolite, sericite, kaolin, montmorillonite, clay, lithium montmorillonite, synthetic mica, aluminosilicate, silica, titanium oxide, alumina, zinc oxide, zirconium oxide, iron oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, barium sulfate, magnesium sulfate, calcium carbonate, mica, quartz powder, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass bead, ceramic bead, boron nitride or silicon carbide.
The liquid crystal polyester composition according to the embodiment of the present invention may further contain a common processing aid selected from the group consisting of an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a mold release agent, a colorant containing a dye or a pigment, a plasticizer, and an antistatic agent, as long as the effects of the present invention are not impaired. Or a liquid crystalline polyester having another structure or a polymer other than the liquid crystalline polyester may be blended, and the other polymer may be one or more of wholly aromatic or semi-aromatic thermotropic liquid crystalline polymer, aromatic or semi-aromatic polyamide, polyether ether ketone, polyether sulfone, polyolefin homopolymer or copolymer, and the like. By such a combination, predetermined characteristics can be further provided.
The method of blending the reinforcing filler, the processing aid, and the like into the liquid crystal polyester according to the embodiment of the present invention is not particularly limited, and dry blending, a solution mixing method, addition of polymerization of the liquid crystal polyester, melt kneading, and the like can be used, and among them, melt kneading is preferable. Such as kneaders, single-or twin-screw extruders, rubber roll extruders, etc., of which twin-screw extruders are preferably used. The temperature for melt kneading is not less than the melting point of the liquid crystal polyester and not more than the melting point +50 ℃.
As the kneading method, a method of kneading by collectively charging the liquid crystal polyester, the reinforcing filler and other processing aids from a post-charging machine; the method may be any of a method of kneading the liquid crystal polyester and other processing aid agent by penetrating them from a post-feeder and adding the reinforcing filler from a side feeder, a method of preparing a liquid crystal polyester composition master batch containing the liquid crystal polyester and other processing aid agent at a high concentration, and then kneading the master batch, the liquid crystal polyester and the reinforcing filler to a predetermined concentration, and the like.
The liquid crystal polyester composition according to the embodiment of the present invention is a melt-molded article known in the art, such as injection molding, injection compression molding, extrusion molding, blow molding, and compression molding. The molded article described here may be various film products such as injection molded articles, extrusion molded articles, press molded articles, sheets, tubes, unstretched films, uniaxially stretched films, biaxially stretched films, various fibers such as unstretched yarns and super-stretched yarns, and the like. In the case of injection molding, the effects of the present invention can be remarkably obtained, and therefore, it is preferable.
The molded article of the liquid crystalline polyester or the liquid crystalline polyester molding composition obtained by the present invention can be applied to electric and electronic parts such as various gears, various housings, sensors, LED lamps, connectors, sockets, resistors, relay housings, relay bases, relay bobbins, switches, coil bobbins, capacitors, variable capacitor housings, optical pickups, resonators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts, FDD holders, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related parts, VTR parts, television parts, irons, hair dryers, electric rice cooker parts, microwave oven parts, etc, Audio equipment parts such as audio, laser disks, and optical disks, lighting parts, refrigerator parts, air conditioning parts, typewriter parts, and word processor parts, and various bearings such as home and business electric parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, washing jigs, oilless bearings, stern bearings, and water bearings, motor parts, machine-related parts such as igniters and typewriters, optical equipment such as microscopes, binoculars, cameras, and clocks, and precision machine-related parts; various valves such as alternator terminals, alternator connectors, IC regulators, potentiometer bases for dimmers, exhaust valves, various pipes for fuel-related systems, exhaust systems, and intake systems, intake nozzle snorkels, intake manifolds, fuel pumps, engine cooling water connectors, carburetor bodies, carburetor spacers, exhaust gas sensors, cooling water sensors, oil temperature sensors, throttle position sensors, crank position sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, motor insulators for electric windows, etc., for vehicle use, heater warm air flow control valves, brush holders for radiator motors, water pump impellers, turbine blades, wiper motor-related parts, power distributors, starter switches, starter relays, wiring harnesses for transmissions, window washer nozzles, etc, Automobile and vehicle-related components such as air conditioner panel switch boards, fuel-related solenoid valve coils, fuse connectors, horn terminals, electrical component insulating plates, stepping motor rotors, lamp rings, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device housings are particularly useful for printed wiring boards, small and thin-walled electronic components, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention discovers, through research, that the DSC enthalpy ratio delta H of the liquid crystal polyester is more than or equal to 0.1 and less than or equal to 0.9, and the liquid crystal polyester has higher fluidity, excellent melting property and high molding stability of small thin-wall molded products because of the specific molecular chain structure and the crystallization state.
(2) In the whole synthesis process, the invention combines the polymerization process of pressurization and depressurization, can effectively control the acylation efficiency of hydroxyl, effectively prevent the side reactions of monomer self-polymerization, molecular chain entanglement, branching and crosslinking and the like in the polymerization process, control the ordered arrangement of the molecular chains of the liquid crystal polyester, and prepare the liquid crystal polyester with higher fluidity and the molding composition thereof.
(3) The preparation method provided by the invention is simple to operate, the product is easy to obtain, the production period is short, and the preparation method is suitable for industrial production.
Detailed Description
The raw materials, acylating agent, catalyst, glass fiber, mica, calcium stearate and other auxiliary agents used in the examples of the present invention are all commercially available.
The necessary performance characterization and test methods of the invention are as follows:
(1) melting point, melting enthalpy and crystallization enthalpy test: measuring by adopting DSC 200F 3 manufactured by NETZSCH company, heating to the highest temperature of melting point +30 ℃ from room temperature at a heating rate of 20 ℃/min, staying at the temperature for 3min, cooling to room temperature at a rate of 20 ℃/min to obtain a crystallization curve, selecting the crystallization starting temperature and the crystallization finishing temperature of a crystallization peak, and calculating the crystallization peak area as H (crystallization enthalpy); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature rise rate of 20 ℃/min again to obtain a second melting curve of the polyester, the melting peak value of the curve is selected to be the melting point, the melting starting temperature and the melting ending temperature of the melting peak are selected, the melting peak area is calculated to be H (melting enthalpy), and the double enthalpy ratio delta H is calculated according to the following formula:
Δ H = H (melting enthalpy)/H (crystallization enthalpy).
(2) Fluidity: the flowability of the liquid crystalline polyester is characterized by the length of a rod-shaped sheet injection molding body with the dimension of width and thickness of 5 x 0.45mm, the injection molding temperature is near the melting point, and the flowability of the liquid crystalline polyester and the molding composition thereof is measured by taking the length average value of 30 rod-shaped sheet injection molding bodies as a parameter. The longer the length of the injection-molded article of the rod-shaped sheet, the better the flowability, under the same injection-molding conditions.
(3) Melt viscosity: the liquid crystal polyester is tested by a DyniscoLCR7001 type capillary rheometer, the diameter of a neck ring is 1mm, the length of the neck ring is 40mm, the liquid crystal polyester has the temperature of 20 ℃ above the melting temperature and the shear rate of 1000s-1The viscosity under the conditions is the melt viscosity.
Examples
1
The following monomer raw materials, acylating agent and catalyst were charged into a polymerization reactor equipped with a stirrer, reflux condenser, monomer feed port, nitrogen gas inlet port, thermometer and torque sensor.
P-hydroxybenzoic acid 1180 g (60 mol%) HBA
(II) 530.1 g (20 mol%) of 4, 4' -biphenol BP
(III) terephthalic acid 402.1 g (17 mol%) TA
(IV) isophthalic acid 70.9 g (3 mol%) IA
Acylating agent: 1527 g of acetic anhydride
Catalyst: 115 mg of magnesium acetate
After the feeding is finished, completely replacing the atmosphere in the reaction container with nitrogen, raising the temperature of the reaction system to 150 ℃ under the protection of nitrogen, keeping the nitrogen pressure at 0.2MPa, and refluxing at the temperature for 2 hours to perform acylation reaction; after the acylation reaction is finished, starting a vacuum pump to reduce the pressure in the reaction kettle to 10KPa-30KPa, quickly discharging acetic acid and unreacted acetic anhydride molecules from a rectification column to meet the process requirement of quick temperature rise, when the receiving amount of the acetic acid reaches more than 50% of a theoretical value, quickly raising the temperature to 200 ℃, keeping the pressure reduction condition, raising the temperature of the reaction system to the maximum temperature of 360 ℃ within 6 hours, continuously discharging small molecules of acetic acid, particularly phenol and other by-products causing molecular chain rephotography and branching during the period, and then reducing the pressure to 50KPa within 30 minutes; when the stirring torque reaches a preset value, considering that the reaction is finished, and taking out a product in the reactor at the moment; cooling the product to room temperature, crushing the product by a crusher, heating the product from the room temperature to 290 ℃ in 10 hours under the vacuum degree of less than 200Pa, and maintaining the temperature for 10 hours; the product obtained by the above method was observed by a polarization microscope, and was found to be a liquid crystal polymer showing optical anisotropy in a molten state. The melting temperature, melt viscosity, storage modulus release rate, and rod-shaped injection-molded body length of the liquid-crystalline polyester are shown in Table 1.
Examples 2-5 ：According to the formula shown in table 1, after the acylation reaction is finished, starting a vacuum pump to reduce the pressure in the reaction kettle to 10KPa-30KPa, quickly discharging acetic acid and unreacted acetic anhydride molecules from a rectification column to meet the process requirement of quick temperature rise, when the acetic acid receiving amount reaches more than 50% of a theoretical value, quickly raising the temperature to 210 ℃, keeping the reduced pressure condition, raising the temperature of the reaction system to 370 ℃ within 6 hours, continuously discharging acetic acid, particularly small molecules of byproducts such as phenol and the like which cause molecular chain rearrangement and branching during the period, and then reducing the pressure to 60KPa within 30 minutes; the rest of the procedure is the same as in example 1; the melting point, melt viscosity, double enthalpy ratio and rod length of the liquid crystalline polyester are shown in Table 1.
Examples 6-12 ：According to the formula shown in Table 1, after the acylation reaction is finished, a vacuum pump is started to reduce the pressure in the reaction kettle to 10KPa to 30KPa, acetic acid and unreacted acetic anhydride molecules are quickly discharged from a rectifying column to meet the process requirement of quick temperature rise, when the receiving amount of the acetic acid reaches more than 50 percent of the theoretical value, the temperature is quickly raised to 220 ℃, the reduced pressure condition is maintained, the reaction system is heated to 380 ℃ within 6 hours, and the highest temperature of the reaction system, particularly the highest temperature of phenol and the like is continuously discharged during the period of time to causeMolecular chain rearrangement and branched by-product micromolecules, and then decompressing to 70KPa within 30 minutes; the rest of the procedure is the same as in example 1; the melting point, melt viscosity, storage modulus release rate, and rod fluid length of the liquid crystalline polyester are shown in Table 1.
Comparative examples 1-3 ：After the feeding is finished, completely replacing the atmosphere in the reaction container with nitrogen, raising the temperature of the reaction system to 140 ℃ under the protection of nitrogen, and maintaining the temperature for reflux for 2 hours to carry out acylation reaction; after the acylation reaction is finished, discharging acetic acid and unreacted acetic anhydride molecules from the rectifying column, heating the reaction system to the maximum temperature of 360 ℃ within 6 hours while continuously discharging the acetic acid, and then reducing the pressure to 30KPa within 30 minutes; when the stirring torque reaches a preset value, considering that the reaction is finished, and taking out a product in the reactor at the moment; cooling the product to room temperature, crushing the product by a crusher, heating the product from the room temperature to 290 ℃ in 10 hours under the vacuum degree of less than 200Pa, and maintaining the temperature for 10 hours; the product obtained by the above method was observed by a polarization microscope, and was found to be a liquid crystal polymer showing optical anisotropy in a molten state. The melting point, melt viscosity, enthalpy ratio and rod length of the liquid crystalline polyester are shown in Table 1.
TABLE 1
From the above results, it can be seen that the liquid-crystalline polyesters in examples having a enthalpy ratio Δ H of 0.1 or more and 0.9 or less have a rod length significantly higher than that of comparative examples, indicating that the liquid-crystalline polyesters in examples have high flowability.
In addition, it can be seen from the examples and comparative examples that even under the conditions of the same structure and ratio of the raw material monomers and similar melt viscosity, the liquid crystal polyesters in different ranges of the bi-enthalpy ratio have distinct difference in the length of the rod-shaped injection body due to the difference in the molecular chain structure and the crystalline form, i.e., the liquid crystal polyesters with different bi-enthalpy ratios exhibit different flowability.
Examples
13-24
Comparative example
4-7
: preparation of liquid-crystalline polyester moulding compositions
According to the proportion shown in the table 2, the liquid crystal polyester prepared in the examples 1-12 and the comparative example is dried in vacuum at 150 ℃ for more than 12h, then resin and auxiliary agents are added into an extruder from a main feeding port of a double-screw extruder by a high-speed mixer, other auxiliary agents such as glass fiber, mica, calcium stearate and the like are added into the extruder from a side feeding port of the double-screw extruder according to the proportion, and the liquid crystal polyester composition is obtained by melting and mixing, extruding at a proper screw barrel temperature, granulating, cooling and solidifying in annular cooling air of enough long air flow; the melting point, melt viscosity, enthalpy ratio and rod length of the liquid crystal polyester composition were measured, respectively, and the results are shown in Table 2.
TABLE 2
As can be seen from the results in Table 2, the liquid crystal polyester molding compositions of the examples have significantly higher flowability than comparative examples due to the use of liquid crystal polyester resins having a enthalpy ratio Δ H of 0.1 or more and 0.9 or less, which are significantly changed in molecular chain structure and crystalline morphology, and are particularly suitable for application in thin-walled electronic parts.
Claims (15)
1. A liquid crystal polyester comprising repeating structural units represented by the following formulae [ I ] to [ IV ]:
the amount of the structural unit [ I ] derived from parahydroxybenzoic acid is 40mol% or more and 80mol% or less, based on 100mol% of the total amount of the repeating units; the amount of structural units [ II ] derived from 4, 4' -biphenol is 10mol% or more and 30mol% or less; the total amount of the structural unit [ III ] derived from terephthalic acid and the structural unit [ IV ] derived from isophthalic acid is 10mol% or more and 32mol% or less; the ratio of the amount of the structural unit [ II ] to the total molar amount of the structural units [ III ] and [ IV ] is 1:1, wherein the molar ratio of the structural unit [ IV ] derived from isophthalic acid to the structural unit [ III ] derived from terephthalic acid is preferably 0.1 to 0.49, and the sum of the molar percentages of the structural units [ I ], [ II ], [ III ] and [ IV ] is 100%;
wherein, a Differential Scanning Calorimetry (DSC) test is adopted, the temperature is increased to the highest temperature of a melting point plus 30 ℃ from room temperature at the temperature rising rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a crystallization curve of the liquid crystal polyester is obtained, the crystallization starting temperature and the crystallization finishing temperature of a crystallization peak are selected, and the crystallization peak area is calculated to be H (crystallization enthalpy); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature rise rate of 20 ℃/min again to obtain a second melting curve of the liquid crystal polyester, the melting starting temperature and the melting finishing temperature of a melting peak are selected, and the melting peak area is calculated to be H (melting enthalpy), wherein the liquid crystal polyester meets the condition that the double enthalpy ratio delta H defined by the following formula (1) is more than or equal to 0.1, less than or equal to 0.9, preferably more than or equal to 0.2 and less than or equal to 0.7;
(1) Δ H = H (melting enthalpy)/H (crystallization enthalpy).
2. The liquid crystalline polyester of claim 1, wherein the melt viscosity of the liquid crystalline polyester is 10pa.s to 35pa.s, preferably 15pa.s to 30pa.s, the melt viscosity is measured by a capillary rheometer at a temperature of 0 to 30 ℃ above the melting point and at a shear rate of 1000S-1Measured using a die having an inner diameter of 1mm and a length of 40 mm.
3. The liquid crystalline polyester of claim 1, wherein: the melting point of the liquid crystal polyester is 310-390 ℃, preferably 330-380 ℃, the melting point is measured by DSC, the temperature is raised to the highest temperature of the melting point plus 30 ℃ from room temperature under the condition of the temperature raising rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a test sample is kept for 3min at the room temperature and then is raised to the highest temperature of the melting point plus 30 ℃ at the temperature raising rate of 20 ℃/min, a second melting curve of the liquid crystal polyester is obtained, and the melting peak value of the curve is selected as the melting point.
4. The method for producing a liquid-crystalline polyester according to any one of claims 1 to 3, comprising the steps of:
a. under the condition of nitrogen pressurization, taking p-hydroxybenzoic acid, 4' -biphenol, terephthalic acid and isophthalic acid as raw materials, and carrying out acylation reaction under the action of an acylating agent, wherein the pressure is kept between 0.2MPa and 0.6 MPa;
b. after the acylation reaction is finished, reducing the pressure in the reaction kettle to 10KPa-30KPa, quickly discharging acetic acid and unreacted acetic anhydride molecules from the rectification column, when the receiving amount of the acetic acid reaches more than 50% of a theoretical value, quickly heating to 200 ℃ or more, maintaining the reduced pressure condition, raising the temperature of a reaction system program to the highest reaction temperature, further reducing the pressure to 50KPa-100KPa, and carrying out melt polycondensation to obtain a prepolymer;
c. and cooling, solidifying and granulating the prepolymer, and carrying out solid-phase polymerization in a solid-phase polymerization container to obtain liquid crystal polyester particles.
5. The method for producing a liquid-crystalline polyester according to claim 4, wherein the temperature of the acylation reaction in the step a is 100 to 180 ℃, preferably 120 to 160 ℃, and the reaction time is 30 minutes to 20 hours, preferably 40 minutes to 5 hours.
6. The method for preparing liquid crystalline polyester according to claim 4, wherein in the step b, after the acylation reaction is finished, the temperature is raised at a rate of 0.1 ℃/min to 150 ℃/min, the temperature of the reaction kettle is rapidly raised to 200 ℃ or more, and the reaction kettle enters a melt polycondensation stage, wherein the melt polycondensation temperature is 130 ℃ to 400 ℃, preferably 160 ℃ to 370 ℃.
7. The method of claim 4, wherein the solid-phase polymerization is carried out under a vacuum of 0.1Pa to 50KPa or under inert gas such as nitrogen gas, the polymerization temperature is 0 to 340 ℃, and the reaction time is 0.5 to 40 hours.
8. A liquid crystalline polyester molding composition comprising a liquid crystalline polyester according to any of claims 1 to 3 comprising 30 to 99.9 parts by weight of a liquid crystalline polyester, 1 to 70 parts by weight of a reinforcing filler and 0 to 20 parts by weight of other auxiliaries and/or other polymers; wherein,
the liquid crystal polyester is composed of repeating structural units of the following formulas (I) to (IV):
the amount of the structural unit [ I ] derived from parahydroxybenzoic acid is 40mol% or more and 80mol% or less, based on 100mol% of the total amount of the repeating units; the amount of structural units [ II ] derived from 4, 4' -biphenol is 10mol% or more and 30mol% or less; the total amount of the structural unit [ III ] derived from terephthalic acid and the structural unit [ IV ] derived from isophthalic acid is 10mol% or more and 32mol% or less; the ratio of the amount of the structural unit [ II ] to the total molar amount of the structural units [ III ] and [ IV ] is 1:1, wherein the molar ratio of the structural unit [ IV ] derived from isophthalic acid to the structural unit [ III ] derived from terephthalic acid is preferably 0.1 to 0.49, and the sum of the molar percentages of the structural units [ I ], [ II ], [ III ] and [ IV ] is 100%;
wherein, a Differential Scanning Calorimetry (DSC) test is adopted, the temperature is increased to the highest temperature of a melting point plus 30 ℃ from room temperature at the temperature rising rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a crystallization curve of the liquid crystal polyester is obtained, the crystallization starting temperature and the crystallization finishing temperature of a crystallization peak are selected, and the crystallization peak area is calculated to be H (crystallization enthalpy); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature raising rate of 20 ℃/min again to obtain a second melting curve of the liquid crystal polyester, the melting starting temperature and the melting finishing temperature of a melting peak are selected, and the melting peak area is calculated to be H (melting enthalpy), wherein the liquid crystal polyester satisfies the condition that the double enthalpy ratio defined by the following formula (1) is more than or equal to 0.1, less than or equal to 0.9, preferably more than or equal to 0.2 and less than or equal to 0.7;
(1) Δ H = H (melting enthalpy)/H (crystallization enthalpy).
9. The liquid crystalline polyester molding composition of claim 8, wherein the liquid crystalline polyester has a melt viscosity of 10pa.s to 35pa.s, preferably 15pa.s to 30pa.s, as measured by capillary rheometer, a temperature of 0 to 30 ℃ above the melting point, and a shear rate of 1000S-1Measured using a die having an inner diameter of 1mm and a length of 40 mm.
10. The liquid crystalline polyester molding composition of claim 8, wherein: the melting point of the liquid crystal polyester is 310-390 ℃, preferably 330-380 ℃, the melting point is measured by DSC, the temperature is raised to the highest temperature of the melting point plus 30 ℃ from room temperature under the condition of the temperature raising rate of 20 ℃/min, the temperature is kept for 3min and then is reduced to the room temperature at the rate of 20 ℃/min, a test sample is kept for 3min at the room temperature and then is raised to the highest temperature of the melting point plus 30 ℃ at the temperature raising rate of 20 ℃/min, a second melting curve of the liquid crystal polyester is obtained, and the melting peak value of the curve is selected as the melting point.
11. The liquid crystalline polyester molding composition of claim 8, wherein the reinforcing filler is fibrous in shape and has an average length of 0.01mm to 20mm, preferably 0.1mm to 6 mm; the length-diameter ratio of the composite material is 5: 1-2000: 1, preferably 30: 1-600: 1; the content of the reinforcing filler is preferably 10 to 50 parts by weight, more preferably 15 to 40 parts by weight; the reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler, the inorganic reinforcing filler comprises one or more of but not limited to glass fiber, potassium titanate fiber, metal clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal curing fiber, asbestos fiber, alumina fiber, silicon carbide fiber, gypsum fiber or boron fiber, and preferably glass fiber; the organic reinforcing filler includes, but is not limited to, liquid crystal polyester fibers and/or carbon fibers.
12. The liquid crystalline polyester molding composition of claim 8, wherein the reinforcing filler is in the form of non-fibers having an average particle size of 0.001 to 50 μm and is selected from one or more of potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, talc, carbon black, gypsum, asbestos, zeolite, sericite, kaolin, montmorillonite, clay, hectorite, synthetic mica, aluminosilicate, silica, titanium oxide, alumina, zinc oxide, zirconia, iron oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, barium sulfate, magnesium sulfate, calcium carbonate, mica, quartz powder, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, or silicon carbide.
13. The liquid crystalline polyester molding composition of claim 8, wherein the other additives are selected from one or more of antioxidants, heat stabilizers, UV absorbers, lubricants, mold release agents, colorants, plasticizers, or antistatic agents.
14. The liquid-crystalline polyester molding composition according to any of claims 8 to 13, wherein the liquid-crystalline polyester molding composition is characterized in that the temperature is raised from room temperature to the highest temperature of the melting point +30 ℃ at a temperature raising rate of 20 ℃/min by a Differential Scanning Calorimetry (DSC) test, the temperature is kept at the temperature for 3min and then is lowered to room temperature at a rate of 20 ℃/min to obtain the crystallization curve of the liquid-crystalline polyester molding composition, the crystallization starting temperature and the crystallization ending temperature of the crystallization peak are selected, and the crystallization peak area is calculated as H (enthalpy of crystallization); after the test sample stays at room temperature for 3min, the temperature is raised to the highest temperature of the melting point plus 30 ℃ at the temperature raising rate of 20 ℃/min again to obtain a second melting curve of the liquid crystal polyester molding composition, the melting starting temperature and the melting finishing temperature of a melting peak are selected, and the melting peak area is calculated to be H (melting enthalpy), wherein the liquid crystal polyester molding composition meets the condition that the double enthalpy ratio defined by the following formula (1) is more than or equal to 0.2 and less than 1.0, preferably more than or equal to 0.5 and less than or equal to 0.9;
(1) Δ H = H (melting enthalpy)/H (crystallization enthalpy).
15. Use of a liquid crystalline polyester molding composition according to any of claims 8 to 14 in the field of electronics.
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| CN112250846A (en) * | 2020-10-30 | 2021-01-22 | 金发科技股份有限公司 | Liquid crystal polyester, liquid crystal polyester composition and application |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| JP7703650B2 (en) | 2020-10-26 | 2025-07-07 | ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー | Liquid crystal polymer compositions, articles and methods of manufacture |
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| 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 |
| CN116462940B (en) * | 2023-03-20 | 2024-03-19 | 深圳市富恒新材料股份有限公司 | Low-warpage antibacterial PET material and preparation method thereof |
| CN117024719B (en) * | 2023-10-07 | 2024-01-30 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and fiber concrete |
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| CN105837807B (en) * | 2016-02-01 | 2019-03-29 | 金发科技股份有限公司 | A kind of liquid crystal polyester and the moulding compound being made from it and its application |
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| US20010014708A1 (en) * | 1999-03-30 | 2001-08-16 | Nippon Petrochemical Co., Ltd. | Method of producing thermotropic liquid crystalline copolyester, thermotropic liquid crystalline copolyester composition obtained by the same method, and molding made of the same composition |
| CN1340591A (en) * | 2000-08-29 | 2002-03-20 | 住友化学工业株式会社 | Liquid crystal polyester and its preparation method |
| CN101875762A (en) * | 2008-12-25 | 2010-11-03 | 住友化学株式会社 | Liquid crystal polyester resin composition and connector using same |
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| WO2017133448A1 (en) * | 2016-02-01 | 2017-08-10 | 金发科技股份有限公司 | Liquid crystal polyester, moulding composition consisting thereof and use thereof |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| JP7703650B2 (en) | 2020-10-26 | 2025-07-07 | ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー | Liquid crystal polymer compositions, articles and methods of manufacture |
| CN112250846A (en) * | 2020-10-30 | 2021-01-22 | 金发科技股份有限公司 | Liquid crystal polyester, liquid crystal polyester composition and application |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017133448A1 (en) | 2017-08-10 |
| CN105837807B (en) | 2019-03-29 |
| CN109824875A (en) | 2019-05-31 |
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