DE3419749A1 - Thermotropic, aromatic polyesters of high rigidity and toughness, process for their preparation, and their use for the production of mouldings, filaments, fibres and films - Google Patents
Thermotropic, aromatic polyesters of high rigidity and toughness, process for their preparation, and their use for the production of mouldings, filaments, fibres and filmsInfo
- Publication number
- DE3419749A1 DE3419749A1 DE19843419749 DE3419749A DE3419749A1 DE 3419749 A1 DE3419749 A1 DE 3419749A1 DE 19843419749 DE19843419749 DE 19843419749 DE 3419749 A DE3419749 A DE 3419749A DE 3419749 A1 DE3419749 A1 DE 3419749A1
- Authority
- DE
- Germany
- Prior art keywords
- molar ratio
- mol
- thermotropic
- condensed
- 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.)
- Withdrawn
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 51
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000465 moulding Methods 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 11
- 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 abstract description 8
- 239000000835 fiber Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006085 branching agent Substances 0.000 claims description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 abstract description 2
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 239000000155 melt Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
- 239000011654 magnesium acetate Substances 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000005168 4-hydroxybenzoic acids Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 229940119177 germanium dioxide Drugs 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 2
- XSAVLGOTFYRGCX-UHFFFAOYSA-N 3-ethyl-4-hydroxybenzoic acid Chemical compound CCC1=CC(C(O)=O)=CC=C1O XSAVLGOTFYRGCX-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- LTFHNKUKQYVHDX-UHFFFAOYSA-N 4-hydroxy-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1O LTFHNKUKQYVHDX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DTQQMULENZFWGF-UHFFFAOYSA-N 2-ethyl-4-hydroxybenzoic acid Chemical compound CCC1=CC(O)=CC=C1C(O)=O DTQQMULENZFWGF-UHFFFAOYSA-N 0.000 description 1
- BBMFSGOFUHEVNP-UHFFFAOYSA-N 4-hydroxy-2-methylbenzoic acid Chemical compound CC1=CC(O)=CC=C1C(O)=O BBMFSGOFUHEVNP-UHFFFAOYSA-N 0.000 description 1
- IPXDGHZTUBSPSG-UHFFFAOYSA-N 4-hydroxy-2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1C1=CC=CC=C1 IPXDGHZTUBSPSG-UHFFFAOYSA-N 0.000 description 1
- LPADJMFUBXMZNL-UHFFFAOYSA-N 4-hydroxy-3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(C=2C=CC=CC=2)=C1 LPADJMFUBXMZNL-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005264 High molar mass liquid crystal Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process 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
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- AKTIAGQCYPCKFX-FDGPNNRMSA-L magnesium;(z)-4-oxopent-2-en-2-olate Chemical compound [Mg+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AKTIAGQCYPCKFX-FDGPNNRMSA-L 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 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
- C08G63/605—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 the hydroxy and carboxylic groups being bound to aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Thermotrope aromatische Polyester mit hoher SteifigkeitThermotropic aromatic polyester with high rigidity
und Zähigkeit, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Filamenten, Fasern und Folien Die Erfindung betrifft hochmolekulare thermotrope vollaromatische Polyester mit hoher Steifigkeit, Schlagzähigkeit und günstiger Schmelzviskosität, ein Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Filamenten, Fasern und Folien.and toughness, method of making them and their uses for the production of moldings, filaments, fibers and films The invention relates to high molecular weight, fully aromatic, thermotropic polyester with high stiffness and impact strength and favorable melt viscosity, a method for their preparation and their use for the production of moldings, filaments, fibers and foils.
Als "thermotrop" bezeichnet man solche Substanzen, die flüssig-kristalline Schmelzen bilden. Thermotrope Polykondensate sind hinreichend bekannt, vergleiche z.B.Substances that are liquid-crystalline are called "thermotropic" Form melts. Thermotropic polycondensates are well known, compare e.g.
F. E. McFarlane et al., Liquid Crystal Polymers II, Contemporary Topics in Polymer Science, Vol. 2, Plenum Publishing Corporation, 1977; W. J. Jackson und H.F. Kuhfuss, J. Polymer Science, Polymer Chem. Ed. 14, 2042 (1976); W. C. Wooten et al. in A. Ciferri "Ultra-high Modulus Polymers", Applied Science Publ., London 1979, S. 362 f.; A. Blumstein et al., "Liquid Crystalline Order in Polymers", Academic Press 1978; J. Preston, Angew. Makromol. Chem. 109/110, S. 1-19 (1982); A. Ciferri, W.R. Krigbaum, R. B. Meyer "Polymer Liquid Crystals", Academic Press, New York, 1982; EP 1185, 1340, 8855, 11 640, 15 856, 17 310, 18 145, 18 709, 22 344, 44 205, 49 615; US 3 991 013, 3 991 014, 4 066 620, 4 067 852, 4 083 829, 4 107 143; WO 79/797, 79/1034, 79/1040.F. E. McFarlane et al., Liquid Crystal Polymers II, Contemporary Topics in Polymer Science, Vol. 2, Plenum Publishing Corporation, 1977; W. J. Jackson and H.F. Kuhfuss, J. Polymer Science, Polymer Chem. Ed. 14: 2042 (1976); W. C. Wooten et al. in A. Ciferri "Ultra-high Modulus Polymers", Applied Science Publ., London 1979, p. 362 f .; A. Blumstein et al., "Liquid Crystalline Order in Polymers ", Academic Press 1978; J. Preston, Angew. Makromol. Chem. 109/110, pp. 1-19 (1982); A. Ciferri, W.R. Krigbaum, R. B. Meyer, "Polymer Liquid Crystals", Academic Press, New York, 1982; EP 1185, 1340, 8855, 11 640, 15 856, 17 310, 18 145, 18 709, 22,344,44,205, 49,615; U.S. 3,991,013, 3,991,014, 4,066,620, 4,067,852, 4,083,829, 4,107,143; WO 79/797, 79/1034, 79/1040.
Der flüssig-kristalline Zustand von Polymerschmelzen läßt sich mit Hilfe eines Polarisationsmikroskops untersuchen: Für die Untersuchungen war das Okular mit einem Aufsatz ausgerüstet, der eine Fotodiode im Brennpunkt der Okularlinse angeordnet enthielt. Anhand eines nachgeschalteten Meßverstärkers mit Regeleinrichtung wurde der Meßwert am eingeschalteten Mikroskop bei parallel angeordneten Nicolschen Prismen in Abwesenheit einer Materialprobe auf 100 Skalenteile eingestellt. Bei gekreuzten Nicolschen Prismen ergab sich dann ein Wert von 0,01 Skalenteilen.The liquid-crystalline state of polymer melts can be determined with Examine with the help of a polarizing microscope: That was for the examinations Eyepiece equipped with an attachment that has a photodiode in the focal point of the eyepiece lens arranged contained. Using a downstream measuring amplifier with control device the measured value on the switched on microscope was at parallel arranged Nicol prisms set to 100 divisions in the absence of a material sample. With crossed Nicol prisms, the result was a value of 0.01 scale divisions.
Die Schichtdicke der untersuchten Polykondensatschmelzen betrug 100 ßm.The layer thickness of the examined polycondensate melts was 100 ßm.
Die Untersuchung der Polykondensate erfolgte nach dem Aufschmelzen der Proben bei Temperaturen zwischen 280 und 4000C. Sofern in diesem gesamten Bereich oder in einem Teil davon eine Aufhellung der zwischen den gekreuzten Nicolschen Prismen beobachteten Schmelze auftrat, wurde das Polykondensat als thermotrop flüssigkristallin eingestuft.The polycondensates were examined after melting of the samples at temperatures between 280 and 4000C. Unless in this entire area or in a part of it a lightening of the between the crossed Nicols Prisms observed melt occurred, the polycondensate was as thermotropic liquid crystalline classified.
Die flüssig-kristallinen Polykondensate zeigen in der Meßanordnung Werte über 1 Skalenteil, meist Werte von 3 bis 90 Skalenteilen. Für amorphe Schmelzen z.B.The liquid-crystalline polycondensates show in the measuring arrangement Values over 1 scale division, mostly values from 3 to 90 scale divisions. For amorphous melts e.g.
aromatische Polycarbonate, wurden dagegen Werte von weniger als 0,1 Skalenteil gefunden.aromatic polycarbonates, on the other hand, have values of less than 0.1 Scale division found.
Die oben beschriebene Methode ist für eine Schnellbestimmung im Laboratorium besonders geeignet und liefert in nahezu allen Fällen zweifelsfreie Ergebnisse. In Zweifelsfällen kann es dagegen sinnvoll sein, das Vorhandensein flüssig-kristalliner Komponenten mittels Röntgenweitwinkelstreuung in der Schmelze nachzuweisen, wie es z.B. bei G.W. Gray und P.A. Windsor, "Plastic Crystals, Physico-Chemical Properties and Methods of Investigation", insbesondere Chapter 3, John Wiley & Sons, New York, Sydney, Toronto 1974 beschrieben ist.The method described above is for a rapid determination in the laboratory particularly suitable and provides unequivocal results in almost all cases. In cases of doubt, however, it can be useful to determine the presence of liquid-crystalline Detect components by means of wide-angle X-ray scattering in the melt, such as it e.g. at G.W. Gray and P.A. Windsor, "Plastic Crystals, Physico-Chemical Properties and Methods of Investigation ", particularly Chapter 3, John Wiley & Sons, New York, Sydney, Toronto 1974.
Die DE-OS 20 25 971 betrifft hochmolekulare voll-aromatische Polyester auf Basis von p-Hydroxybenzoesäure, aromatischen Dicarbonsäuren (wie Terephthal- oder Isophthalsäure) und Diphenolen (wie Hydrochinon oder 4,4'-Dihydroxybiphenyl). Aufgrund der verwendeten Komponenten sind diese Polyester thermotrop; sie können z.B. zu Fasern verarbeitet werden. Von den 13 Polyestern der Beispiele schmilzt ein einziger unter 3000C. Diese Polyester sind also schlecht verarbeitbar.DE-OS 20 25 971 relates to high molecular weight fully aromatic polyesters based on p-hydroxybenzoic acid, aromatic dicarboxylic acids (such as terephthalic or isophthalic acid) and diphenols (such as hydroquinone or 4,4'-dihydroxybiphenyl). Because of the components used, these polyesters are thermotropic; you can e.g. processed into fibers. Of the 13 polyesters of the examples, melts a single one below 3000C. These polyesters are therefore difficult to process.
Formkörper, die aus flüssig-kristalliner Schmelze hergestellt werden, weisen mechanische Festigkeiten auf, wie sie normalerweise bei unverstärkten, aus isotroper Schmelze verarbeiteten Polykondensaten nicht gefunden werden; jedoch läßt die Zähigkeit solcher Formkörper manche Wünsche offen (vgl. US 42 42 496, EP 44 175, W.J. Jackson jr., Brit. Polym. J. 12, 154 (1980)).Moldings made from liquid-crystalline melt have mechanical strengths as they normally do with unreinforced polycondensates processed by isotropic melt cannot be found; however lets the toughness of such shaped bodies leaves much to be desired (cf. US 42 42 496, EP 44 175, W.J. Jackson Jr., Brit. Polym. J. 12, 154 (1980)).
Durch eigene Untersuchungen wurde bestätigt, daß thermötrope Polyester hoher Festigkeit in der Regel geringe Zähigkeit und thermotrope Polyester hoher Zähigkeit in der Regel weniger ausgeprägte Festigkeit besitzen.Our own investigations have confirmed that thermotropic polyester high strength usually low toughness and thermotropic polyesters higher Toughness usually have less pronounced strength.
Aufgabe der Erfindung war es daher, thermotrope vollaromatische Polyester bereitzustellen, die gegenüber den Polyestern der DE-OS 20 25 971 besser verarbeitbar sind und dennoch hervorragende mechanische Eigenschaften aufweisen.The object of the invention was therefore to provide thermotropic, fully aromatic polyesters to provide which, compared to the polyesters of DE-OS 20 25 971, are easier to process and yet have excellent mechanical properties.
Weitere Aufgabe der Erfindung war es, thermotrope vollaromatische Polyester zur Verfügung zu stellen, die durch thermoplastische Verformung zu Formteilen verarbeitet werden können, welche sowohl hohe mechanische Festigkeit als auch hohe Zähigkeit besitzen.Another object of the invention was to provide fully aromatic thermotropic To make polyester available, through thermoplastic deformation into molded parts can be processed, which both high mechanical strength and high Possess tenacity.
Bevorzugte neue thermotrope vollaromatische Polyester sollten bei einer Temperatur unterhalb 3700C, vorzugsweise unterhalb 3500C, insbesondere unterhalb 3300C thermoplastisch verarbeitbar sein.Preferred new thermotropic fully aromatic polyesters should be at a temperature below 3700C, preferably below 3500C, in particular below 3300C can be processed thermoplastically.
Bevorzugte neue thermotrope voll-aromatische Polyester sollten eine Schlagzähigkeit von mindestens 20, vorzugsweise von mindestens 30, insbesondere von mindestens 40 kJ/m2 besitzen. Außerdem sollten diese bevorzugten Polyester eine Kerbschlagzähigkeit von mindestens 10, vorzugsweise von mindestens 20, insbesondere von mindestens 25 kJ/m2 haben. Weiterhin sollten diese bevorzugten Polyester einen Biege-E-Modul von mindestens 7500, vorzugsweise von mindestens 8500, insbesondere von mindestens 10000 MPa besitzen.Preferred new thermotropic fully aromatic polyesters should be one Impact strength of at least 20, preferably of at least 30, in particular of at least 40 kJ / m2. In addition, these preferred polyesters should be Notched impact strength of at least 10, preferably of at least 20, in particular of at least 25 kJ / m2. Furthermore, these preferred polyesters should be one Flexural modulus of elasticity of at least 7500, preferably of at least 8500, in particular of at least 10,000 MPa.
Uberraschenderweise wurde gefunden, daß voll-aromatische Polyester, die einkondensierte Reste von p-Hydroxybenzoesäure, Iso- und Terephthalsäure, Hydrochinon und 3,4'- und/oder 4,4'-Dihydroxydiphenyl, -diphenylether und/oder -diphenylsulfid enthalten, die gewünschte Kombination vorteilhafter Eigenschaften besitzen.Surprisingly, it was found that fully aromatic polyesters, the condensed residues of p-hydroxybenzoic acid, iso- and terephthalic acid, hydroquinone and 3,4'- and / or 4,4'-dihydroxydiphenyl, diphenyl ether and / or diphenyl sulfide contain the desired combination of advantageous properties.
Gegenstand der Erfindung sind thermotrope voll-aromatische Polyester auf Basis von (a) (gegebenenfalls substituierter) p-Hydroxybenzoesäure, (b) Iso- und Terephthalsäure, (c) Hydrochinon und (d) 3,4'- und/oder 4,4' -Dihydroxydiphenyl, 3,4'- und/oder 4,4'-Dihydroxydiphenylether und/oder 3,4'- und/oder 4,4'-Dihydroxydiphenylsulfid, wobei das Molverhältnis der einkondensierten Reste a/b 80 : 20 bis 50 :50, vorzugsweise 70 : 30 bis 55 : 45, insbesondere 65 : 35 bis 60 : 40, das Molverhältnis der einkondensierten Reste b/c/d 20:10:10 bis 50:48:2, vorzugsweise 30:22:8 bis 45:41:4, insbesondere 35:29:6 bis 40:35:5, das Molverhältnis der einkondensierten Reste b/(c+d) = 0,95 bis 1,05 und der Terephthalsäureanteil der Komponente (b) bis zu 50 Mol-%, vorzugsweise 1 bis 40 Mol-%, bezogen auf (b), betragen.The invention relates to thermotropic, fully aromatic polyesters based on (a) (optionally substituted) p-hydroxybenzoic acid, (b) iso- and terephthalic acid, (c) hydroquinone and (d) 3,4'- and / or 4,4'-dihydroxydiphenyl, 3,4'- and / or 4,4'-dihydroxydiphenyl ether and / or 3,4'- and / or 4,4'-dihydroxydiphenyl sulfide, where the molar ratio of the condensed radicals a / b is 80:20 to 50:50, preferably 70:30 to 55:45, in particular 65:35 to 60:40, the molar ratio of the condensed Remainders b / c / d 20:10:10 to 50:48: 2, preferably 30:22: 8 to 45: 41: 4, especially 35: 29: 6 to 40: 35: 5, the molar ratio of the condensed radicals b / (c + d) = 0.95 to 1.05 and the terephthalic acid content of component (b) up to 50 mol%, preferably 1 to 40 mol%, based on (b).
Bevorzugte (a) p-Hydroxybenzoesäuren sind durch C1-C4 -Alkyl., C1-C4 -Alkoxy, C6 -C10-Aryl oder C7-C 12-Alkylaryl (wie Phenyl, Tolyl, Naphthyl), oder Halogen (vorzugsweise Chlor) kernsubstituierte p-Hydroxybenzoesäuren, wie z.B. 4-Hydroxy-2-methylbenzoesäure, 4-Hydroxy-3-methylbenzoesäure, 2-Ethyl-4-hydroxybenzoesäure, 3-Ethyl-4-hydroxybenzoesäure, 4-Hydroxy-2-phenylbenzoesäure, 4-Hydroxy-3-phenylbenzoesäure oder 3-Chlor-4-hydroxybenzoesäure, vorzugsweise jedoch unsubstituierte p-Hydroxybenzoesäure selbst.Preferred (a) p-hydroxybenzoic acids are through C1-C4-alkyl., C1-C4 -Alkoxy, C6 -C10-aryl or C7-C 12-alkylaryl (such as phenyl, tolyl, naphthyl), or Halogen (preferably chlorine) ring-substituted p-hydroxybenzoic acids, such as 4-hydroxy-2-methylbenzoic acid, 4-hydroxy-3-methylbenzoic acid, 2-ethyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid, 4-hydroxy-2-phenylbenzoic acid, 4-hydroxy-3-phenylbenzoic acid or 3-chloro-4-hydroxybenzoic acid, but preferably unsubstituted p-hydroxybenzoic acid itself.
Die erfindungsgemäßen Polyester können die Reste der Verbindungen (a) bis (d) in statistischer Verteilung, in Segmenten oder in Blöcken enthalten. Betreffend Komponente (a) ist darauf zu achten, daß längere Blöcke den Schmelzpunkt und die Schmelzviskosität stark erhöhen können.The polyesters according to the invention can be the radicals of the compounds (a) to (d) contained in statistical distribution, in segments or in blocks. Regarding component (a) care should be taken that longer blocks reach the melting point and can greatly increase the melt viscosity.
Als Endgruppen können die erfindungsgemäßen Polyester -COOH, -H, -OH, -OC6H5, Acyloxy oder von Kettenabbrechern herrührende Reste enthalten. Bevorzugte Kettenabbrecher sind monofunktionelle aromatische Hydroxylverbindungen, wie 4-Hydroxydiphenyl, p-Nonylphenol, 4-(1,1,3,3-Tetramethylbutyl)-phenol, B-Naphthol, und aromatische Monocarbonsäuren, wie Diphenylcarbonsäuren und Naphthalincarbonsäuren. Kettenabbrecher können in Mengen von 0,5 bis 5 Mol-%, bezogen auf die Summe der Komponenten a und b, eingesetzt werden.The polyesters according to the invention -COOH, -H, -OH, -OC6H5, acyloxy or radicals derived from chain terminators. Preferred Chain terminators are monofunctional aromatic hydroxyl compounds such as 4-hydroxydiphenyl, p-Nonylphenol, 4- (1,1,3,3-tetramethylbutyl) -phenol, B-naphthol, and aromatic Monocarboxylic acids such as diphenylcarboxylic acids and naphthalenecarboxylic acids. Chain breaker can be used in amounts of 0.5 to 5 mol%, based on the sum of components a and b.
Gegebenenfalls können auch verzweigende drei- oder höherfunktionelle - vorzugsweise aromatische - Monomere in Mengen von 0,1 bis 1 Mol-%, bezogen auf die Summe der Komponenten a und b, wie z.B. Phloroglucin, 1,3,5-Benzoltricarbonsäure und 3,5-Dihydroxybenzoesäure, eingesetzt werden.If necessary, branching three- or higher-functional ones can also be used - preferably aromatic - monomers in amounts of 0.1 to 1 mol%, based on the sum of components a and b, such as phloroglucinol, 1,3,5-benzenetricarboxylic acid and 3,5-dihydroxybenzoic acid can be used.
Die erfindungsgemäßen Polyester besitzen in der Regel eine inhärente Viskosität von mindestens 0,5, vorzugsweise von mindestens 1,0, dl/g (gemessen an einer Lösung von 5 mg Polyester/ml p-Chlorphenol bei 450C). Sollten Polyester in p-Chlorphenol unlöslich sein, wird angenommen, daß sie die angegebene Mindestviskosität besitzen; sie sind somit erfindungsgemäß, sofern sie den Parametern des Hauptanspruchs genügen.The polyesters according to the invention generally have an inherent one Viscosity of at least 0.5, preferably of at least 1.0 dl / g (measured on a solution of 5 mg polyester / ml p-chlorophenol at 450C). Should polyester be in If p-chlorophenol is insoluble, it is believed that it has the specified minimum viscosity own; they are therefore according to the invention provided they meet the parameters of the main claim suffice.
Die erfindungsgemäßen Polyester besitzen vorzugsweise eine Schmelzviskosität von weniger als 1000 Pa.s, ge--1 messen bei einer Schergeschwindigkeit von 103 sec unter Verwendung einer Düse mit einem Länge/Durchmesserverhältnis von 20 bei einer Temperatur von weniger als 3700C, vorzugsweise weniger als 3300C.The polyesters according to the invention preferably have a melt viscosity of less than 1000 Pa.s, measured at a shear rate of 103 sec using a nozzle with a length / diameter ratio of 20 at a Temperature less than 3700C, preferably less than 3300C.
Die erfindungsgemäßen Polyester können nach verschiedenen Verfahren hergestellt werden, z.B. durch Kondensation bzw. Umesterung der reaktiven Derivate der Verbindungen (a) bis (d), z.B. ihrer Ester bzw. Säurechloride, und anschließende Polykondensation.The polyesters according to the invention can by various methods can be produced, e.g. by condensation or transesterification of the reactive derivatives of the compounds (a) to (d), e.g. their esters or acid chlorides, and subsequent Polycondensation.
Beispiele für bevorzugte Ausgangsverbindungen sind also ihre Arylester, ihre Acylester und ihre Säurechloride.Examples of preferred starting compounds are their aryl esters, their acyl esters and their acid chlorides.
Nach einem bevorzugten Syntheseverfahren werden die niederen Acylester, vorzugsweise die Acetate, der Verbindungen (a), (c) und (d) mit Iso- und Terephthalsäure (b) umgesetzt, wobei die Acylester auch in situ hergestellt werden können.According to a preferred synthesis process, the lower acyl esters, preferably the acetates of the compounds (a), (c) and (d) with iso- and terephthalic acid (b) implemented, the acyl esters can also be prepared in situ.
Diese Reaktionen können in der Schmelzphase durchgeführt werden; möglich ist jedoch auch die Reaktion in Gegenwart eines flüssigen wärmeüberleitenden Mediums, das einen hohen Siedepunkt hat.These reactions can be carried out in the melt phase; possible however, the reaction in the presence of a liquid heat-transferring medium is also possible, that has a high boiling point.
Die Reste der Verbindungen (a) bis (d) werden im Verhältnis der Ausgangskomponenten in den Polyester eingebaut.The radicals of the compounds (a) to (d) are in the ratio of the starting components built into the polyester.
Die erfindungsgemäßen Polyester sind vorzugsweise frei von Carbonatgruppen.The polyesters according to the invention are preferably free from carbonate groups.
Es kann zweckmäßig sein,sowohl die Kondensations- bzw. Umesterungsreaktionen als auch die Polykondensationsreaktionen katalytisch zu beschleunigen. Derartige Katalysatoren sind bekanntlich z.B. Lewis-Säuren und Halogenwasserstoffsäuren; Oxide, Hydride, Hydroxide, Halogenide, Alkoholate, Phenolate, Salze anorganischer oder organischer Säuren (vorzugsweise Carbonsäuresalze), Komplexsalze oder Mischsalze der Erdalkalimetalle, wie z.B. Magnesium, Calcium; der Nebengruppenelemente, wie z.B. Vanadium, Titan, Mangan, Cobalt, Nickel, Zink, Lanthan, Cer, Zirkonium oder der Elemente aus anderen Gruppen des Periodensystems, wie z.B. Germanium, Zinn, Blei und Antimon oder auch die Alkalimetalle oder Erdalkali- metalle selbst, insbesondere Natrium, Natriumhydroxid, Lithiumacetat, Natriumacetat, Kaliumacetat, Calciumacetat, Magnesiumacetat, Cobaltacetat, Zinkacetat, Calciumbenzoat, Magnesiumacetylacetonat, Zinkacetylacetonat, Vanadyl-C1-C8-alkoxide, Titanalkoxide wie Titantetrabutylat, Titantetrapropylat, Alkoxytitansilikate, Zirkoniumbutylat, Zirkoniumpropylat, Titantetraphenolat, Natriumphenolat, Germaniumdioxid, Antimontrioxid, Dialkyl- und Diarylzinnoxid, Di-butylzinn-diacetat, Di-butyl-dimethoxy-zinn. Besonders bevorzugt sind Magnesium-, Mangan-, Natrium-, Kalium- und Zinkacetat.It can be useful to carry out both the condensation and transesterification reactions as well as accelerating the polycondensation reactions catalytically. Such Catalysts are known to include, for example, Lewis acids and hydrohalic acids; Oxides, Hydrides, hydroxides, halides, alcoholates, phenolates, salts of inorganic or organic acids (preferably carboxylic acid salts), complex salts or mixed salts the alkaline earth metals such as magnesium, calcium; of the subgroup elements, such as e.g. vanadium, titanium, manganese, cobalt, nickel, zinc, lanthanum, cerium, zirconium or the elements from other groups of the periodic table, such as germanium, tin, Lead and antimony or the alkali metals or alkaline earth metals itself, especially sodium, sodium hydroxide, lithium acetate, sodium acetate, potassium acetate, Calcium acetate, magnesium acetate, cobalt acetate, zinc acetate, calcium benzoate, magnesium acetylacetonate, Zinc acetylacetonate, vanadyl C1-C8 alkoxides, titanium alkoxides such as titanium tetrabutylate, Titanium tetrapropylate, alkoxytitanium silicates, zirconium butylate, zirconium propylate, titanium tetraphenolate, Sodium phenolate, germanium dioxide, antimony trioxide, dialkyl and diaryl tin oxide, di-butyltin diacetate, Di-butyl-dimethoxy-tin. Magnesium, manganese, sodium, Potassium and zinc acetate.
Die Katalysatormengen betragen vorzugsweise 0,001 bis 1, insbesondere 0,01 bis 0,2, Gew.-%, bezogen auf das Gesamtgewicht der eingesetzten Monomeren.The amounts of catalyst are preferably from 0.001 to 1, in particular 0.01 to 0.2% by weight, based on the total weight of the monomers used.
Die erfindungsgemäßen Polyester können bei Temperaturen von 160 bis 3700C hergestellt werden, wobei man im allgemeinen die Reaktion bei niedrigen Temperaturen beginnt und im Verlaufe der Reaktionsfortschreitung kontinuierlich die Temperatur erhöht. Bei nachlassender Reaktionsgeschwindigkeit kann ein Vakuum angelegt werden, wobei der Druck vorzugsweise kontinuierlich von Normaldruck bis ca. 0,1 mbar gesenkt wird.The polyesters according to the invention at temperatures from 160 to 3700C, whereby the reaction is generally carried out at low temperatures begins and as the reaction progresses continuously the temperature elevated. If the reaction rate slows down, a vacuum can be applied, the pressure preferably being lowered continuously from normal pressure to about 0.1 mbar will.
Das erhaltene Produkt kann -vorzugsweise in Granulatform - einer Festphasennachkondensation unter vermindertem Druck bei Temperaturen von 200 bis 3000C unterworfen werden; nach 1 bis 25 Stunden haben sich das Molekulargewicht erhöht und die daraus resultierenden Eigenschaften des Polyesters merklich verbessert.The product obtained can undergo a solid phase post-condensation, preferably in granulate form subjected under reduced pressure at temperatures from 200 to 3000C; after 1 to 25 hours, the molecular weight and the resulting increases Properties of the polyester noticeably improved.
Weiterer Gegenstand der Erfindung ist also ein Verfahren zur Herstellung der neuen Polyester durch Umsetzung der Komponenten (a) bis (d) bzw. ihrer reaktionsfähigen Derivate, die auch in situ hergestellt werden können, gegebenenfalls in Gegenwart von Kettenabbrechern, Verzweigungsmitteln und Katalysatoren, bei Temperaturen von 160 bis 3700C, gegebenenfalls unter vermindertem Druck.The invention also relates to a method for production of the new polyesters by reacting components (a) to (d) or their reactive ones Derivatives which can also be prepared in situ, optionally in the presence of chain terminators, branching agents and catalysts, at temperatures of 160 to 3700C, optionally under reduced pressure.
Die erfindungsgemäßen thermotropen Polyester können infolge ihrer relativ geringen Schmelzviskosität vorteilhaft aus der Schmelze zu Spritzgußformteilen, Filamenten, Fasern, Bändern und Filmen verarbeitet werden, wobei durch auftretende Scherkräfte eine Molekülorientierung erzielt wird, die in hohem Maße von der Stärke der Scherkräfte beeinflußt wird. Desweiteren zeigen sie eine ausgeprägte Strukturviskosität, das heißt, daß die Schmelzviskosität bei Erhöhung der Scherkräfte stark abfällt. Geeignete Verarbeitungsverfahren sind Spritzguß, Extrusion, Pressen und Schmelzspinnen.The thermotropic polyesters according to the invention can as a result of their relatively low melt viscosity advantageous from the melt to injection molded parts, Filaments, fibers, ribbons and films are processed, being occurring through Shear forces a molecular orientation is achieved, which is to a large extent dependent on the strength the shear forces is influenced. Furthermore, they show a pronounced structural viscosity, that is, the melt viscosity drops sharply as the shear forces increase. Suitable processing methods are injection molding, extrusion, pressing and melt spinning.
Aus den erfindungsgemäßen Polyestern können Formteile hoher Zugfestigkeit, außerordentlicher Zähigkeit und großer Dimensionsstabilität hergestellt werden. Da die Polyester außerordentlich chemikalienresistent und flammwidrig sind, eignen sie sich bevorzugt zur Herstellung von - elektrotechnischen Artikeln, wie z.B. Isolatoren, gedruckten Schaltungen, Steckkontakten, Armaturenteilen, - Teilen chemisch-technischer Apparate, wie z.B. Rohren, Behälterauskleidungen, Rotoren, Gleitlagern, Dichtungen, - Teilen der Flugzeuginnenausstattung, - Teilen medizinisch-technischer Geräte, wie z.B. Bauteilen von Klimaanlagen, Ventilteilen.Moldings with high tensile strength, extraordinary toughness and great dimensional stability. Since the polyesters are extremely chemical-resistant and flame-retardant, they are suitable it is preferred for the production of - electrotechnical articles such as insulators, printed circuits, plug contacts, fittings, - parts chemical-technical Apparatus such as pipes, container linings, rotors, plain bearings, seals, - Parts of the aircraft interior, - Parts of medical-technical devices, such as e.g. components of air conditioning systems, valve parts.
Die erfindungsgemäßen Polyester können aber auch als Uberzugs- und Beschichtungsmaterial (pulverförmig oder dispergiert) verwendet werden. Auch zur Herstellung verstärkter oder gefüllter Formmassen mit einem Verstärker- bzw. Füllstoffgehalt von 5 bis 65 Gew.-%, bezogen auf verstärkte bzw. gefüllte Formmasse, sind sie bestens geeignet.The polyesters according to the invention can also be used as a coating and Coating material (powder or dispersed) can be used. Also for Production of reinforced or filled molding compounds with a reinforcement or filler content from 5 to 65% by weight, based on reinforced or filled molding compound, they are ideal suitable.
Weiterer Gegenstand der Erfindung ist also die Verwendung der neuen Polyester zur Herstellung von Formkörpern, Filamenten, Fasern und Filmen.Another object of the invention is the use of the new Polyester for the production of moldings, filaments, fibers and films.
Beispiele Die Prüfung der Schlagzähigkeit an und Kerbschlagzähigkeit ak erfolgte an Normkleinstäben gemäß DIN 53 453 (ISO/R 179) bei 230C jeweils an 10 Prüfkörpern.Examples Testing of impact strength and notched impact strength ak was carried out on standard small bars in accordance with DIN 53 453 (ISO / R 179) at 230C 10 test pieces.
Die Bestimmung der Biegefestigkeit wurde an Normkleinstäben gemäß DIN 53 452 (ISO R 178) durchgeführt. Der Biege-E-Modul wurde gemäß DIN 53 457 ermittelt.The flexural strength was determined on standard small bars in accordance with DIN 53 452 (ISO R 178) carried out. The flexural modulus of elasticity was determined in accordance with DIN 53 457.
Die Zugfestigkeit wurde gemäß DIN 53 455 (ISO/R 527), der Zug-E-Modul gemäß DIN 53 457 gemessen. Die Messung der Wärmeformbeständigkeit erfolgte durch Bestimmungen der Vicat-B-Erweichungstemperatur gemäß DIN 53 460 (ISO 306).The tensile strength was according to DIN 53 455 (ISO / R 527), the tensile modulus of elasticity measured according to DIN 53 457. The heat resistance was measured by Determination of the Vicat B softening temperature according to DIN 53 460 (ISO 306).
Vergleich 1 In ein 1 l-Planschliffgefäß mit Planschliffdeckel, Rührer, Stickstoffeinleitung und einem Destillationsaufsatz, der mit einem Kühler verbunden war, wurden die folgenden Substanzen eingewogen: 2,4 Mol =A 331,49 g p-Hydroxybenzoesäure, 1,44 Mol = 239,23 g Isophthalsäure, 1,44 Mol e 158,56 g Hydrochinon, 6,33 Mol e 646,23 g Acetanhydrid, 0,1 g Magnesiumacetat (wasserfrei) und 0,15 g Antimontrioxid.Comparison 1 In a 1 l flat jointed vessel with a flat jointed lid, stirrer, Nitrogen inlet and a distillation head connected to a condenser the following substances were weighed out: 2.4 mol = A 331.49 g p-hydroxybenzoic acid, 1.44 moles = 239.23 g isophthalic acid, 1.44 moles e, 158.56 g hydroquinone, 6.33 moles e 646.23 g acetic anhydride, 0.1 g magnesium acetate (anhydrous) and 0.15 g antimony trioxide.
Unter Stickstoffatmosphäre wurde mittels Salzbad auf 1700C erhitzt. Sobald die Destillation von Essigsäure nachließ (nach ca. 45 Minuten), wurde die Temperatur im Reaktionsgefäß im Verlauf einer Stunde auf 250"C und im Verlauf einer weiteren Stunde auf 3300C erhöht.The mixture was heated to 170 ° C. by means of a salt bath under a nitrogen atmosphere. As soon as the distillation of acetic acid subsided (after about 45 minutes), the temperature in the reaction vessel to 250 "C. over the course of one hour and increased to 3300C over the course of a further hour.
Nach Beendigung der Destillation wurde der Druck im Verlauf von 30 Minuten bis auf ca. 1 mbar gesenkt.After the completion of the distillation, the pressure became in the course of 30 Minutes reduced to approx. 1 mbar.
Während dieser Vakuumphase nahm die Viskosität der entstandenen Polymerschmelze stark zu. Die Schmelze wurde daher langsamer gerührt.During this vacuum phase, the viscosity of the polymer melt formed increased strong too. The melt was therefore stirred more slowly.
Am Ende dieser Phase war eine Gesamtmenge von 709 g Essigsäure (enthält restliches Acetanhydrid) aufgefangen worden.At the end of this phase, a total of 709 g of acetic acid (contains remaining acetic anhydride) has been collected.
Der erhaltene hell-braune Polyester wurde gemahlen und bei 250"C einer Festphasennachkondensation unterworfen (bei einem Vakuum von ca. 1 mbar/24 Stunden). Die inhärente Viskosität des so erhaltenen Polyesters betrug 1,2 dl/g. Im Bereich von 3000C bis 4000C wurde eine optisch anisotrope Schmelzphase beobachtet.The light brown polyester obtained was ground and at 250 "C one Subject to solid phase post-condensation (at a vacuum of approx. 1 mbar / 24 hours). The inherent viscosity of the polyester thus obtained was 1.2 dl / g. In the area from 3000C to 4000C an optically anisotropic melt phase was observed.
Vergleich 2 In das in Vergleich 1 beschriebene Reaktionsgefäß wurden die folgenden Substanzen eingefüllt: 2,4 Mol =A 33,149 p-Hydroxybenzoesäure, 1,44 Mol e 239,23 g Isophthalsäure, 1,2 Mol e 132,13 g Hydrochinon, 0,24 Mol = 48,48 g 4,4'-Dihydroxydiphenyl, 6,33 Mol =A 646,23 g Acetanhydrid, 0,15 g Zinkacetat und 0,2 g Germaniumdioxid.Comparison 2 In the reaction vessel described in Comparison 1 were filled with the following substances: 2.4 mol = A 33.149 p-hydroxybenzoic acid, 1.44 Mol e 239.23 g isophthalic acid, 1.2 mol e 132.13 g hydroquinone, 0.24 mol = 48.48 g 4,4'-dihydroxydiphenyl, 6.33 mol = A 646.23 g acetic anhydride, 0.15 g zinc acetate and 0.2 g germanium dioxide.
Das im Vergleich 1 beschriebene Temperatur-Zeit-Programm wurde befolgt. Es wurde ein hellbeiger Polyester mit bei 3000C guter Schmelzfließfähigkeit erhalten. Das Produkt wurde gemahlen und im Vakuum (ca. 1 mbar) bei 2500C in fester Phase nachkondensiert (24 Stunden).The temperature-time program described in comparison 1 was followed. A light beige polyester with good melt flowability at 3000C was obtained. The product was ground and in a vacuum (approx. 1 mbar) at 2500C in the solid phase post-condensed (24 hours).
Die inhärente Viskosität des Polyesters betrug 2,09 dl/g.The inherent viscosity of the polyester was 2.09 dL / g.
Polarisationsmikroskopisch wurde eine optisch anisotrope Schmelzphase im Bereich von 300 bis 4000C beobachtet.An optically anisotropic melt phase became apparent under the polarization microscope observed in the range of 300 to 4000C.
Beispiel 1 In die im Vergleich 1 beschriebene Reaktionsapparatur wurden die folgenden Substanzen eingewogen: 2,4 Mol =A 331,49 g p-Hydroxybenzoesäure, 1,2 Mol =A 199,36 g Isophthalsäure, 0,24 Mol = 33,87 g Terephthalsäure, 1,2 Mol = 132,13 g Hydrochinon, 0,24 Mol e 44,64 g 4,4'Dihydroxydiphenyl, 6,33 Mol e 646,23 g Acetanhydrid, 0,2 g Magnesiumacetat und 0,2 g Germaniumdioxid.Example 1 In the reaction apparatus described in comparison 1 were the following substances weighed out: 2.4 mol = A 331.49 g of p-hydroxybenzoic acid, 1.2 Mol = A 199.36 g isophthalic acid, 0.24 mol = 33.87 g terephthalic acid, 1.2 mol = 132.13 g hydroquinone, 0.24 mol e 44.64 g 4,4'-dihydroxydiphenyl, 6.33 mol e 646.23 g acetic anhydride, 0.2 g magnesium acetate and 0.2 g germanium dioxide.
Nach dem in Vergleich 1 beschriebenen Temperatur-Zeit-Programm wurde ein hellbeiges Produkt mit guter Schmelzfließfähigkeit erhalten. Das Produkt wurde gemahlen und im Vakuum (ca. 1 mbar) in fester Phase nachkondensiert (24 Stunden).According to the temperature-time program described in comparison 1 obtained a light beige product with good melt flowability. The product was ground and post-condensed in a vacuum (approx. 1 mbar) in the solid phase (24 hours).
Die inhärente Viskosität des Polyesters betrug 2,8 dl/g.The inherent viscosity of the polyester was 2.8 dL / g.
Im Bereich von 290 bis 4000C wurde ein optisch anisotrope Schmelzphase beobachtet.In the range from 290 to 4000C an optically anisotropic melt phase became observed.
Beispiele 2-8 Zur Herstellung der in Tabelle 1 aufgelisteten Polyester wurde die im Vergleich 1 beschriebene Reaktionsapparatur und das dort beschriebene Verfahren verwendet. Tabelle 1 Beispiel PHB (b) (c) (d) Komponent d Inhärente anisotrope (Mol) (Mol) (Mol) (Mol) Viskosität Phase (dl/g) 2 2,6 1,2 IS 1,2 0,2 4,4'-DOD 2,82 270°C - 400°C 0,2 TS 3 2,8 1,1 IS 1,1 0,2 4,4'-DOD 2,54 300°C - 400°C 0,2 TS 4 2,94 1,06 IS 1,05 0,21 4,4'-DOD 2,3 290°C - 400°C 0,2 TS 5 2,94 0,96 IS 1,05 0,21 4,4'-DOD 3,14 300°C - 400°C 0,3 TS 6 2,8 1,0 IS 1,1 0,2 4,4'-DOD 1,9 280°C - 400°C 0,3 TS 7 2,6 1,2 IS 1,2 0,2 4,4'-DODE 1,98 260°C - 400°C 0,2 TS 8 2,6 1,2 IS 1,2 0,2 4,4'-DODS 2,94 310 - 400°C 0,2 TS PHB = p-Hydroxybenzoesäure DOD = Dihydroxydiphenyl IS = Isophthalsäure TS = Terephthalsäure DODE = Diydroxydiphenylether DODS = Dihydroxydiphenylsulfid Zur Prüfung der mechanischen Eigenschaften wurden aus den Polyestern der Vergleiche 1 und 2 und der Beispiele 1 bis 8 durch Spritzguß Normkleinstäbe hergestellt.Examples 2-8 For the preparation of the polyesters listed in Table 1 the reaction apparatus described in comparison 1 and that described there Method used. Table 1 Example PHB (b) (c) (d) component d Inherent anisotropic (mol) (mol) (mol) (mol) viscosity phase (dl / g) 2 2.6 1.2 IS 1.2 0.2 4.4'-DOD 2.82 270 ° C - 400 ° C 0.2 TS 3 2.8 1.1 IS 1.1 0.2 4.4'-DOD 2.54 300 ° C - 400 ° C 0.2 TS 4 2.94 1.06 IS 1.05 0.21 4,4'-DOD 2.3 290 ° C - 400 ° C 0.2 TS 5 2.94 0.96 IS 1.05 0.21 4.4'-DOD 3.14 300 ° C - 400 ° C 0.3 TS 6 2.8 1.0 IS 1.1 0.2 4,4'-DOD 1.9 280 ° C - 400 ° C 0.3 TS 7 2.6 1.2 IS 1.2 0.2 4.4'-DODE 1.98 260 ° C - 400 ° C 0.2 TS 8 2.6 1.2 IS 1.2 0.2 4.4'-DODS 2.94 310 - 400 ° C 0.2 TS PHB = p-hydroxybenzoic acid DOD = dihydroxydiphenyl IS = isophthalic acid TS = terephthalic acid DODE = diydroxydiphenyl ether DODS = dihydroxydiphenyl sulfide For testing the mechanical properties were made from the polyesters of Comparisons 1 and 2 and Examples 1 to 8 Injection molding standard small bars manufactured.
Die Verarbeitung der Polyester erfolgte bei Temperaturen zwischen 290 und 3300C. In Tabelle 2 sind die gemessenen Werte aufgeführt.The polyester was processed at temperatures between 290 and 3300C. Table 2 shows the measured values.
Tabelle 2 Beispiel Vicat B an/ak Biegefestig- Biege-E- Viskosität (°C) (kJ/m²) keit (MPa) Modul (MPa) (Pa.s)xx Vergleich 1 140 8/6 150 6.500 800/300°C Vergleich 2 142 51x/39x 174 7.200 600/280°C 1 143 48x/42x 194 10.300 700/290°C 2 133 43x/30x 179 8.900 500/280°C 3 135 58x/37x 188 10.100 200/320°C 4 138 46x/42x 195 10.600 250/320°C 5 144 32x/42x 197 12.300 190/320°C 6 141 55x/44x 192 10.900 280/320°C 7 128 65x/38x 195 10.300 300/300°C 8 147 35x/26x 188 11.200 290/320°C X = angebrochen XX = Schmelzviskosität bei einer Schergeschwindigkeit von 10³ sec-1 bei der jeweils angegebenen Temperatur Beispiel 9 In einen beheizbaren 25 l-Kessel aus V4A-Stahl mit Rührer, Stickstoffeinleitung und Destillationsaufsatz wurden die folgenden Substanzen eingefüllt: 31,2 Mol # 4.309 g p-Hydroxybenzoesäure, 14,4 Mol # 2.392 g Isophthalsäure, 2,4 Mol =A 399 g Terephthalsäure, 14,4 Mol e 1.586 g Hydrochinon, 2,4 Mol e 447 g 4,4'-Dihydroxydiphenyl, 76,8 Mol 9 7.841 g Acetanhydrid, 5 g Magnesiumacetat und 2 g Gemaniumdioxid.Table 2 Example Vicat B an / ak Biegefestig-Biege-E-Viscosity (° C) (kJ / m²) speed (MPa) Module (MPa) (Pa.s) xx comparison 1 140 8/6 150 6,500 800/300 ° C Comparison 2 142 51x / 39x 174 7,200 600/280 ° C 1 143 48x / 42x 194 10,300 700/290 ° C 2 133 43x / 30x 179 8,900 500/280 ° C 3 135 58x / 37x 188 10,100 200/320 ° C 4 138 46x / 42x 195 10,600 250/320 ° C 5 144 32x / 42x 197 12,300 190/320 ° C 6 141 55x / 44x 192 10,900 280/320 ° C 7 128 65x / 38x 195 10,300 300/300 ° C 8 147 35x / 26x 188 11,200 290/320 ° C X = partial XX = melt viscosity at a shear rate of 10³ sec-1 at the specified temperature Example 9 In a heatable 25 l kettle made of V4A steel with stirrer, nitrogen inlet and distillation attachment the following substances were poured in: 31.2 mol # 4,309 g of p-hydroxybenzoic acid, 14.4 mol # 2,392 g isophthalic acid, 2.4 mol = A 399 g terephthalic acid, 14.4 mol e 1,586 g hydroquinone, 2.4 mol e 447 g 4,4'-dihydroxydiphenyl, 76.8 mol 9 7,841 g Acetic anhydride, 5 g magnesium acetate and 2 g gemanium dioxide.
Nach dreimaligem Evakuieren und anschließendem Belüften mit Stickstoff wurde der Kessel auf 1700C aufgeheizt.After evacuating three times and then venting with nitrogen the boiler was heated to 1700C.
Dabei wurde Stickstoff mit einer Durchflußgeschwindigkeit von 20 l/h übergeleitet. Nach 2,5 Stunden bei 1700C wurde die Temperatur innerhalb von 30 Minuten auf 2000C anschließend innerhalb von 1,5 Stunden auf 2500C, dann innerhalb von 1,5 Stunden weiter auf 300°C erhöht. Bei 3000C wurde zunächst ca. 1 Stunde bei Normaldruck gehalten und dann der Druck im Verlauf von 1,5 Stunden bis auf 20 mbar erniedrigt. Der Kessel wurde mit Stickstoff belüftet, das Produkt durch ein Bodenventil herausgedrückt und granuliert.Nitrogen was used at a flow rate of 20 l / h transferred. After 2.5 hours at 1700C, the temperature rose within 30 minutes to 2000C then within 1.5 hours to 2500C, then within 1.5 Hours further increased to 300 ° C. At 3000C it was initially about 1 hour at normal pressure held and then the pressure reduced to 20 mbar in the course of 1.5 hours. The kettle was vented with nitrogen and the product was forced out through a bottom valve and granulated.
Das so isolierte hell-beige Produkt wurde im Vakuum (ca. 1 mbar) bei 2400C in fester Phase nachkondensiert (24 Stunden).The light beige product isolated in this way was in vacuo (approx. 1 mbar) at 2400C post-condensed in the solid phase (24 hours).
Die inhärente Viskosität des Polyesters betrug 1,4 dl/g.The inherent viscosity of the polyester was 1.4 dL / g.
Im Bereich von 3100C bis 4000C bildete das Produkt eine optisch anisotrope Schmelzphase.In the range from 3100C to 4000C, the product was optically anisotropic Melting phase.
Zur Prüfung der mechanischen Eigenschaften wurden aus dem Polyester durch Spritzguß Biege- und Zugstäbe hergestellt. Folgende Werte wurden gemessen: an: 76* kJ/m2 ak = 48* kJ/m2 Biegefestigkeit: 222 MPa Biege-E-Modul: 11.100 MPa Zugfestigkeit: 188 MPa Zug-E-Modul: 23.800 MPa Vicat B-Temperatur: 1400CThe polyester was used to test the mechanical properties bending and tension rods produced by injection molding. The following values were measured: an: 76 * kJ / m2 ak = 48 * kJ / m2 Flexural strength: 222 MPa Flexural modulus: 11,100 MPa Tensile strength: 188 MPa Tensile modulus: 23,800 MPa Vicat B temperature: 1400C
Claims (7)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843419749 DE3419749A1 (en) | 1984-05-26 | 1984-05-26 | Thermotropic, aromatic polyesters of high rigidity and toughness, process for their preparation, and their use for the production of mouldings, filaments, fibres and films |
| US06/627,965 US4603190A (en) | 1983-07-16 | 1984-07-03 | Thermotropic aromatic polyesters having high rigidity and toughness, process for the production thereof and the use thereof for the production of moulded articles, filaments, fibres and films |
| DE8484107690T DE3461383D1 (en) | 1983-07-16 | 1984-07-03 | Thermotropic aromatic polyesters having a high rigidity and resilience, process for their production, their use in the production of moulded articles, filaments, fibres and sheets |
| EP84107690A EP0134956B2 (en) | 1983-07-16 | 1984-07-03 | Thermotropic aromatic polyesters having a high rigidity and resilience, process for their production, their use in the production of moulded articles, filaments, fibres and sheets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843419749 DE3419749A1 (en) | 1984-05-26 | 1984-05-26 | Thermotropic, aromatic polyesters of high rigidity and toughness, process for their preparation, and their use for the production of mouldings, filaments, fibres and films |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3419749A1 true DE3419749A1 (en) | 1985-11-28 |
Family
ID=6236964
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19843419749 Withdrawn DE3419749A1 (en) | 1983-07-16 | 1984-05-26 | Thermotropic, aromatic polyesters of high rigidity and toughness, process for their preparation, and their use for the production of mouldings, filaments, fibres and films |
Country Status (1)
| Country | Link |
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| DE (1) | DE3419749A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664972A (en) * | 1986-04-23 | 1987-05-12 | E. I. Du Pont De Nemours And Company | Optically anisotropic melt forming aromatic copolyesters based on t-butylhydroquinone |
| EP0237358A3 (en) * | 1986-03-14 | 1988-07-20 | Mitsui Petrochemical Industries, Ltd. | Melt-moldable wholly aromatic polyester |
| EP0314976A3 (en) * | 1987-10-31 | 1989-11-02 | Bayer Ag | Thermotropic aromatic polyesters with a higher thermal stability, process for their preparation and their use in the preparation of moulding compositions, filaments, fibres and films |
| EP0257558B1 (en) * | 1986-08-28 | 1992-01-02 | BASF Aktiengesellschaft | Wholly aromatic thermotropic polyesters |
| 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 |
-
1984
- 1984-05-26 DE DE19843419749 patent/DE3419749A1/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0237358A3 (en) * | 1986-03-14 | 1988-07-20 | Mitsui Petrochemical Industries, Ltd. | Melt-moldable wholly aromatic polyester |
| US4664972A (en) * | 1986-04-23 | 1987-05-12 | E. I. Du Pont De Nemours And Company | Optically anisotropic melt forming aromatic copolyesters based on t-butylhydroquinone |
| EP0257558B1 (en) * | 1986-08-28 | 1992-01-02 | BASF Aktiengesellschaft | Wholly aromatic thermotropic polyesters |
| EP0314976A3 (en) * | 1987-10-31 | 1989-11-02 | Bayer Ag | Thermotropic aromatic polyesters with a higher thermal stability, process for their preparation and their use in the preparation of moulding compositions, filaments, fibres and films |
| US4912193A (en) * | 1987-10-31 | 1990-03-27 | Bayer Aktiengesellschaft | Thermotropic aromatic polyester based on p-hydroxy benzoic acid, 4,4'-dihydroxy diphenyl, terephthalic acid, and isophthalic acid |
| 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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