CN1320031C - Polyamide containing isosorbide unit and process for preparing same - Google Patents
Polyamide containing isosorbide unit and process for preparing same Download PDFInfo
- Publication number
- CN1320031C CN1320031C CNB200510079892XA CN200510079892A CN1320031C CN 1320031 C CN1320031 C CN 1320031C CN B200510079892X A CNB200510079892X A CN B200510079892XA CN 200510079892 A CN200510079892 A CN 200510079892A CN 1320031 C CN1320031 C CN 1320031C
- Authority
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- China
- Prior art keywords
- nitro
- diacid chloride
- isosorbide
- called
- fluoronaphthalene
- 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.)
- Expired - Fee Related
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 14
- 229920002647 polyamide Polymers 0.000 title claims abstract description 14
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical group O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims description 78
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 136
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 150000004985 diamines Chemical class 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 229960002479 isosorbide Drugs 0.000 claims description 76
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- -1 dinitro compound Chemical class 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 239000006096 absorbing agent Substances 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 4
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 4
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 claims description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 3
- LSACNADXSMNMJS-UHFFFAOYSA-N 1-chloro-3-nitronaphthalene Chemical compound C1=CC=CC2=CC([N+](=O)[O-])=CC(Cl)=C21 LSACNADXSMNMJS-UHFFFAOYSA-N 0.000 claims description 3
- QLIOCENRPBJEPI-UHFFFAOYSA-N 1-chloro-4-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=C(Cl)C2=C1 QLIOCENRPBJEPI-UHFFFAOYSA-N 0.000 claims description 3
- ASXDLWJNLAXOEA-UHFFFAOYSA-N 1-chloro-5-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1Cl ASXDLWJNLAXOEA-UHFFFAOYSA-N 0.000 claims description 3
- ZROFLSNLBFQHLM-UHFFFAOYSA-N 1-chloro-6-nitronaphthalene Chemical compound ClC1=CC=CC2=CC([N+](=O)[O-])=CC=C21 ZROFLSNLBFQHLM-UHFFFAOYSA-N 0.000 claims description 3
- GGHRRMKLOHCQEP-UHFFFAOYSA-N 1-chloro-7-nitronaphthalene Chemical compound C1=CC=C(Cl)C2=CC([N+](=O)[O-])=CC=C21 GGHRRMKLOHCQEP-UHFFFAOYSA-N 0.000 claims description 3
- QOHQXCPALCHOID-UHFFFAOYSA-N 1-chloro-8-nitronaphthalene Chemical compound C1=CC(Cl)=C2C([N+](=O)[O-])=CC=CC2=C1 QOHQXCPALCHOID-UHFFFAOYSA-N 0.000 claims description 3
- MTSIRTDZHYZHBJ-UHFFFAOYSA-N 1-fluoro-3-nitronaphthalene Chemical compound C1=CC=CC2=CC([N+](=O)[O-])=CC(F)=C21 MTSIRTDZHYZHBJ-UHFFFAOYSA-N 0.000 claims description 3
- XVDSBUCGMJBTNO-UHFFFAOYSA-N 1-fluoro-4-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=C(F)C2=C1 XVDSBUCGMJBTNO-UHFFFAOYSA-N 0.000 claims description 3
- UTIRKPWIJBXLEC-UHFFFAOYSA-N 1-fluoro-5-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1F UTIRKPWIJBXLEC-UHFFFAOYSA-N 0.000 claims description 3
- ZYFOQCIEMAASRK-UHFFFAOYSA-N 1-fluoro-6-nitronaphthalene Chemical compound FC1=CC=CC2=CC([N+](=O)[O-])=CC=C21 ZYFOQCIEMAASRK-UHFFFAOYSA-N 0.000 claims description 3
- BQVFKTIDTJOUHT-UHFFFAOYSA-N 1-fluoro-7-nitronaphthalene Chemical compound C1=CC=C(F)C2=CC([N+](=O)[O-])=CC=C21 BQVFKTIDTJOUHT-UHFFFAOYSA-N 0.000 claims description 3
- ZLOVVWJPFBKRTI-UHFFFAOYSA-N 1-fluoro-8-nitronaphthalene Chemical compound C1=CC(F)=C2C([N+](=O)[O-])=CC=CC2=C1 ZLOVVWJPFBKRTI-UHFFFAOYSA-N 0.000 claims description 3
- ZPFNCCOUGPMGHT-UHFFFAOYSA-N 2-chloro-6-nitronaphthalene Chemical compound C1=C(Cl)C=CC2=CC([N+](=O)[O-])=CC=C21 ZPFNCCOUGPMGHT-UHFFFAOYSA-N 0.000 claims description 3
- CECBPKQCQKJAAC-UHFFFAOYSA-N 2-chloro-7-nitronaphthalene Chemical compound C1=CC(Cl)=CC2=CC([N+](=O)[O-])=CC=C21 CECBPKQCQKJAAC-UHFFFAOYSA-N 0.000 claims description 3
- VQYAEJWTLQMEFS-UHFFFAOYSA-N 2-fluoro-6-nitronaphthalene Chemical compound C1=C(F)C=CC2=CC([N+](=O)[O-])=CC=C21 VQYAEJWTLQMEFS-UHFFFAOYSA-N 0.000 claims description 3
- LIHIRYIUXIHNIN-UHFFFAOYSA-N 2-fluoro-7-nitronaphthalene Chemical compound C1=CC(F)=CC2=CC([N+](=O)[O-])=CC=C21 LIHIRYIUXIHNIN-UHFFFAOYSA-N 0.000 claims description 3
- FDBCEJTXDLBXOX-UHFFFAOYSA-N 3-chloro-1-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC(Cl)=CC2=C1 FDBCEJTXDLBXOX-UHFFFAOYSA-N 0.000 claims description 3
- ARQWZKZNEKWQTR-UHFFFAOYSA-N 3-fluoro-1-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC(F)=CC2=C1 ARQWZKZNEKWQTR-UHFFFAOYSA-N 0.000 claims description 3
- ALQUEFFIWUNSDY-UHFFFAOYSA-N 6-chloro-1-nitronaphthalene Chemical compound ClC1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 ALQUEFFIWUNSDY-UHFFFAOYSA-N 0.000 claims description 3
- FWQJIKQKMWNTEE-UHFFFAOYSA-N 6-fluoro-1-nitronaphthalene Chemical compound FC1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 FWQJIKQKMWNTEE-UHFFFAOYSA-N 0.000 claims description 3
- KDRQBCWKGFOWRO-UHFFFAOYSA-N 7-chloro-1-nitronaphthalene Chemical compound C1=C(Cl)C=C2C([N+](=O)[O-])=CC=CC2=C1 KDRQBCWKGFOWRO-UHFFFAOYSA-N 0.000 claims description 3
- QCCBLNQFHYGKEL-UHFFFAOYSA-N 7-fluoro-1-nitronaphthalene Chemical compound C1=C(F)C=C2C([N+](=O)[O-])=CC=CC2=C1 QCCBLNQFHYGKEL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 230000005526 G1 to G0 transition Effects 0.000 abstract description 2
- 239000013307 optical fiber Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Polyamides (AREA)
Abstract
The present invention relates to polyamide containing isosorbitol units, which belongs to the technical field of macromolecular materials. The structure of the polyamide is disclosed in the specification. The present invention uses a preparation method that a diamine monomer containing isosorbitol and a diacid chloride are reacted to synthesize polyamide. The polyamide prepared by the present invention has good solubility, good film forming performance and good mechanical performance, and has the advantages of good thermal stability, high decomposition temperature and convenient processing. The present invention can be used in optical plastics, can manufacture CD or DVD base materials, lenses, dashboard windows or hoods, prism reflectors, thin membranes, sheet materials, or optical fiber, etc. In addition, the polyamide has optical activity, and can be used in chiral stationary phases, chiral separation membranes, etc.
Description
Technical field
The present invention relates to a kind of polymeric amide that contains isoscrbierite unit and preparation method thereof, belong to technical field of polymer materials.
Background technology
Isosorbide (1,4:3,6-two dehydration-D-sorbyl alcohols) as the dewatered product of sorbyl alcohol, have abundant, the special advantages such as chirality feature, degradable and Heat stability is good of raw material sources, therefore great application prospect is arranged at aspects such as liquid crystal, optical plasticss.(the CN1298343 of E. I. Du Pont de Nemours and Co, CN1298346, CN1298416, CN1298417A, CN1298426) invented a series of polyester that contain Isosorbide, this polyester utilizes the condensation reaction of aromatic diacid and glycol, producing the polyester that reduced concentration viscosity is at least 0.15dL/g-0.35dL/g,, can obtain more full-bodied polyester with itself and other thermosetting polyester blend.Because its excellent properties, this polyester can be used to optical plastics, can make CD (CD), high definition CD (DVD), CD or base material (DVD), lens, panel board window or outer cover, prism reflector, film, sheet material or optical fiber etc.Patent CN1442460A has invented a kind of coating that contains Isosorbide, this coating utilizes the chirality feature of Isosorbide, can change and variable color with viewing angle, and have good anti-ultraviolet, acid and alkali-resistance, heat-resisting and weather resistance, can be applied to the external coating of multiple material.It is nuclear that patent US20020013483A has synthesized with the Isosorbide with Isosorbide and P-hydroxybenzoic acid, the product that two ends are hydroxyl.In addition, patent US20020115817A1, US20010003359A1, WO 03/027119A1 etc. has synthesized a series of vinylformic acid list dibasic acid esters that contain Isosorbide, these esters and some are had nematic liquid crystal monomer copolymerization, can obtain to have the cross linking membrane of cholesteryl phase, can be used for color filer.
Polymeric amide has excellent heat, power performance, and good chemical stability; But common aromatic polyamide is insoluble to general organic reagent usually, adopts the vitriol oil that processing units is had relatively high expectations in the course of processing, simultaneously, to some special occasions, has limited its application.
Summary of the invention
The objective of the invention is for overcoming the weak point of existing aromatic series or semiaromatic polyamide composition, a kind of polymeric amide that contains isoscrbierite unit and preparation method thereof is proposed, make it have good solubility, film forming properties and mechanical property, have also that thermal stability is good, decomposition temperature is high, and process advantage easily.
The polymeric amide that contains isoscrbierite unit that the present invention proposes, its structure is:
In the following formula, Ar ' is:
In any,
R is any or multiple in the following structure:
Can adopt the diamine monomer and the diacid chloride reaction that contain Isosorbide, the synthetic polymeric amide that obtains:
Wherein, the diamine monomer that contains Isosorbide is by Isosorbide and nitryl aromatic family halogenide etherificate, restores to obtain, and its structure is:
Described nitryl aromatic family halogenide is selected from following all kinds of a kind of:
X＝F，Cl
This structural formula comprises: p-fluoronitrobenzene, a fluoronitrobenzene, o-fluoronitrobenzene, parachloronitrobenzene, m-chloro-nitrobenzene, o-chloronitrobenzene;
X＝F，Cl
This structural formula comprises: 4-nitro-4 '-fluorine biphenyl, 3-nitro-4 '-fluorine biphenyl, 2-nitro-4 '-fluorine biphenyl, 4-nitro-4 '-chlordiphenyl, 3-nitro-4 '-chlordiphenyl, 2-nitro-4 '-chlordiphenyl; (3)
X＝F，Cl
This structural formula comprises: 4-nitro-1-fluoronaphthalene, 4-nitro-2-fluoronaphthalene, 3-nitro-1-fluoronaphthalene, 4-nitro-1-chloronaphthalene, 4-nitro-2-chloronaphthalene, 3-nitro-1-chloronaphthalene;
X＝F，Cl
This structural formula comprises: 5-nitro-1-fluoronaphthalene, 6-nitro-1-fluoronaphthalene, 7-nitro-1-fluoronaphthalene, 8-nitro-1-fluoronaphthalene, 5-nitro-2-fluoronaphthalene, 6-nitro-2-fluoronaphthalene, 7-nitro-2-fluoronaphthalene, 8-nitro-2-fluoronaphthalene, 5-nitro-1-chloronaphthalene, 6-nitro-1-chloronaphthalene, 7-nitro-1-chloronaphthalene, 8-nitro-1-chloronaphthalene, 5-nitro-2-chloronaphthalene, 6-nitro-2-chloronaphthalene, 7-nitro-2-chloronaphthalene, 8-nitro-2-chloronaphthalene.
Above-mentioned diacid chloride monomer comprises a kind of of following structure:
Be called for short diacid chloride B
Be called for short diacid chloride C
(5)
Diacid chloride E is called for short in n=2～16
Be called for short diacid chloride G
Be called for short diacid chloride H
Be called for short diacid chloride I
(13)
Be called for short diacid chloride M
Be called for short diacid chloride N
For can be applicable to diacid chloride composition commonly used of the present invention, be not particularly limited usually, for example aromatic series diacid chloride and aliphatics diacid chloride and comprise above-mentioned deutero-diacid chloride.These diacid chloride compositions can be by the mixture use of two or more diacid chlorides alone or in combination.
The present invention proposes contains polymeric amide of isoscrbierite unit and preparation method thereof, because the polymeric amide for preparing has been introduced alicyclic structure, and Isosorbide has twist structure, stop tightly packed between the molecular chain, therefore increase the free volume of material, and then improved the solvability of material.The polymeric amide that synthetic contains Isosorbide generally has good solubility, dissolves in general polar solvent, and good film forming properties is arranged, and processing is convenient, can prepare film, fiber or the like.In addition, because the thermostability of Isosorbide, the synthetic polymeric amide has high glass transition, can be greater than 200 ℃, and thermal stability is good, and decomposition temperature can be greater than 400 ℃.Diacid chloride rigidity as employing is big, then can reach higher temperature.In addition, though introduced alicyclic structure, the alicyclic of Isosorbide has certain rigid, thereby has the good mechanical performance.In a word, the polymeric amide that contains Isosorbide can be used in the fields such as opticglass, optics owing to its excellent performance.Simultaneously, the chirality feature that it is special is expected to be applied at aspects such as chiral stationary phase, chiral separation films.
Embodiment
Embodiment 1
(1) Isosorbide is dissolved in solvent N, in the dinethylformamide, ratio is: Isosorbide: N, dinethylformamide=1mol: 500mL;
(2) the alkaline matter sodium Metal 99.5 is added in the above-mentioned solution, the mol ratio of adding is: Isosorbide: sodium=1: 2, heated 0.5 hour down at 50 ℃;
(3) in above-mentioned solution, add parachloronitrobenzene, the synthetic dinitro compound that obtains containing Isosorbide, adding mol ratio is: Isosorbide: parachloronitrobenzene=1: 2, temperature of reaction is 60 ℃, reaction times is 6 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of Isosorbide;
(4) dinitro compound that 2g is contained Isosorbide is dissolved in tetrahydrofuran (THF), after 0.15g palladium-carbon catalyst C-Pd is suspended in the 15ml ethanol, it is joined in the tetrahydrofuran solution, under nitrogen protection, 70 ℃, in 20min, drip the 6ml hydrazine hydrate, reacted 4 hours, filtered while hot, rotary evaporation desolventizes, get the diamine monomer product that contains Isosorbide of white solid, productive rate 90%;
(5) add polar solvent N in the diamine monomer that contains Isosorbide of above-mentioned preparation, dinethylformamide, additional proportion are 1mol: 1L;
(6) in above-mentioned solution, add the acid absorber pyridine earlier; add diacid chloride A again, the mol ratio of adding is: diamines: pyridine: diacid chloride=0.9: 0.9: 1, stirred 1 hour under ice-water bath and nitrogen protection; room temperature reaction is 4 hours again, obtains the heavy-gravity polyamide solution.
Embodiment 2
(1) Isosorbide is dissolved in the solvent N,N-dimethylacetamide, ratio is: Isosorbide: N,N-dimethylacetamide=1mol: 1000mL;
(2) the alkaline matter sodium hydride is added in the above-mentioned solution, the mol ratio of adding is: Isosorbide: sodium hydride=1: 4, heated 1 hour down at 80 ℃;
(3) in above-mentioned solution, add p-fluoronitrobenzene, the synthetic dinitro compound that obtains containing Isosorbide, adding mol ratio is: Isosorbide: p-fluoronitrobenzene=1: 3, temperature of reaction is a room temperature, reaction times is 2 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of Isosorbide;
(4) dinitro compound that 2g is contained Isosorbide is dissolved in tetrahydrofuran (THF), after 0.2g palladium-carbon catalyst C-Pd is suspended in the 15ml ethanol, it is joined in the tetrahydrofuran solution, under atmosphere of hydrogen, 85 ℃, reacted filtered while hot 12 hours, rotary evaporation desolventizes, and gets the diamine monomer product that contains Isosorbide of white solid.
(5) add the polar solvent N,N-dimethylacetamide in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 2L;
(6) add the acid absorber pyridine earlier in above-mentioned solution, add diacid chloride B again, the mol ratio of adding is: diamines: pyridine: diacid chloride=1: 1: 1, under room temperature and nitrogen protection, stirred 1 hour, and obtain the heavy-gravity polyamide solution.
Embodiment 3
(1) Isosorbide is dissolved in the solvent dimethyl sulfoxide (DMSO), ratio is: Isosorbide: dimethyl sulfoxide (DMSO)=1mol: 2000mL;
(2) with alkaline matter salt of wormwood, and potassiumiodide adds in the above-mentioned solution on a small quantity, and the mol ratio of adding is: Isosorbide: salt of wormwood=1: 2, heated 0.5 hour down at 120 ℃;
(3) in above-mentioned solution, add m-chloro-nitrobenzene, the synthetic dinitro compound that obtains containing Isosorbide, adding mol ratio is: Isosorbide: m-chloro-nitrobenzene=1: 3, temperature of reaction is 150 ℃, reaction times is 24 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of Isosorbide;
(4) dinitrobenzene product 10mmol and the tin protochloride 100mmol that contains Isosorbide mixes, add 250ml single port flask, and add suitable quantity of water, 250mmol hydrochloric acid is diluted with 100ml water, join in the above-mentioned single port flask, react under 60 ℃ to solution and become clarification.After finishing, reaction transfers pH value to 3 with aqueous sodium hydroxide solution, the elimination throw out, and filtrate transfers pH value to alkalescence with ammoniacal liquor again, and adularescent precipitates separates out, and filters.The solid dmso solution filters.Filtrate is used water precipitation again, and ethyl alcohol recrystallization gets the diamine monomer product that contains Isosorbide of white solid.
(5) add the polar solvent dimethyl sulfoxide (DMSO) in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 3L;
(6) add earlier the acid absorber pyridine in above-mentioned solution, add diacid chloride C again, the mol ratio of adding is: diamines: pyridine: diacid chloride=1.1: 1.1: 1, under 60 ℃ and nitrogen protection, stirred 8 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 4
(1) Isosorbide is dissolved in the solvents tetrahydrofurane, ratio is: Isosorbide: tetrahydrofuran (THF)=1mol: 8000mL;
(2) alkaline matter potassium hydroxide is added in the above-mentioned solution, the mol ratio of adding is: Isosorbide: potassium hydroxide=1: 8, heated 1 hour down at 80 ℃;
(3) in above-mentioned solution, add between fluoronitrobenzene, the synthetic dinitro compound that obtains containing Isosorbide, adding mol ratio is: Isosorbide a: fluoronitrobenzene=1: 4, temperature of reaction is 60 ℃, reaction times is 24 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of Isosorbide;
(4) contain in the water-soluble and alcoholic acid mixing solutions of the dinitrobenzene product 10mmol of Isosorbide and sodium sulphite 40mol, back flow reaction 4 hours, the adularescent precipitation is separated out filtered while hot, the solid ethyl alcohol recrystallization gets the white diamine monomer product that contains Isosorbide.
(5) add the polar solvent N-Methyl pyrrolidone in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 4L;
(6) add the acid absorber triethylamine earlier in above-mentioned solution, add diacid chloride D again, the mol ratio of adding is: diamines: triethylamine: diacid chloride=1.05: 1.05: 1, under room temperature and nitrogen protection, stirred 16 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 5
(1) Isosorbide is dissolved in the solvent N-Methyl pyrrolidone, ratio is: Isosorbide: N-Methyl pyrrolidone=1mol: 4000mL;
(2) the alkaline matter sodium hydride is added in the above-mentioned solution, the mol ratio of adding is: Isosorbide: sodium hydride=1: 4, heated 1 hour down at 80 ℃;
(3) in above-mentioned solution, add o-fluoronitrobenzene, the synthetic dinitro compound that obtains containing Isosorbide, adding mol ratio is: Isosorbide: o-fluoronitrobenzene=1: 4, temperature of reaction is 60 ℃, reaction times is 24 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of Isosorbide;
(4) contain in the water-soluble and alcoholic acid mixing solutions of the dinitrobenzene product 10mmol of Isosorbide and sodium sulphite 30-60mmol, back flow reaction 4 hours, the adularescent precipitation is separated out filtered while hot, the solid ethyl alcohol recrystallization gets the white diamine monomer product that contains Isosorbide.
(5) add the polar solvent N-Methyl pyrrolidone in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 3L;
(6) add the acid absorber triethylamine earlier in above-mentioned solution, add diacid chloride E again, the mol ratio of adding is: diamines: triethylamine: diacid chloride=0.95: 0.95: 1, under room temperature and nitrogen protection, stirred 24 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 6
(1) Isosorbide is dissolved in solvent N, in the dinethylformamide, ratio is: Isosorbide: N, dinethylformamide=1mol: 1000mL;
(2) the alkaline matter sodium hydride is added in the above-mentioned solution, the mol ratio of adding is: Isosorbide: sodium hydride=1: 4, heated 1 hour down at 80 ℃;
(3) in above-mentioned solution, add 4-nitro-4 '-fluorobenzene, the synthetic dinitro compound that obtains containing Isosorbide, adding mol ratio is: Isosorbide: 4-nitro-4 '-fluorobenzene=1: 3, temperature of reaction is 80 ℃, reaction times is 12 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of two dewatering hexitols:
(4) dinitro compound that 2g is contained Isosorbide is dissolved in tetrahydrofuran (THF), after 0.15g palladium-carbon catalyst C-Pd is suspended in the 15ml ethanol, it is joined in the tetrahydrofuran solution, under atmosphere of hydrogen, 65 ℃ of temperature were reacted filtered while hot 12 hours, rotary evaporation removes and desolvates, and obtains the diamine monomer product that white solid contains Isosorbide.
(5) add the polar solvent hexamethylphosphoramide in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 2L;
(6) in above-mentioned solution, add acid absorber triethylamine and pyridine earlier; add diacid chloride F again; the mol ratio that adds is: diamines: triethylamine: pyridine: diacid chloride=1.02: 0.51: 0.51: 1, under room temperature and nitrogen protection, stirred 18 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 7: nitryl aromatic family halogenide adopts o-chloronitrobenzene, and the diacid chloride monomer adopts diacid chloride G, and other technology is identical with embodiment 1.
Embodiment 8: nitryl aromatic family halogenide adopts 3-nitro-4 '-fluorine biphenyl, and the diacid chloride monomer adopts diacid chloride H, and other technology is identical with embodiment 1.
Embodiment 9: nitryl aromatic family halogenide adopts 2-nitro-4 '-fluorine biphenyl, and the diacid chloride monomer adopts diacid chloride I, and other technology is identical with embodiment 1.
Embodiment 10: nitryl aromatic family halogenide adopts 4-nitro-4 '-chlordiphenyl, and the diacid chloride monomer adopts diacid chloride J, and other technology is identical with embodiment 1.
Embodiment 11: nitryl aromatic family halogenide adopts 3-nitro-4 '-chlordiphenyl, and the diacid chloride monomer adopts diacid chloride K, and other technology is identical with embodiment 1.
Embodiment 12: the reductive agent in the reduction reaction is a tin, and the diacid chloride monomer adopts diacid chloride L, and other technology is identical with embodiment 3.
Embodiment 13: the reductive agent in the reduction reaction adopts iron powder, and the diacid chloride monomer adopts diacid chloride M, and other technology is identical with embodiment 3.
Embodiment 14: nitryl aromatic family halogenide adopts 4-nitro-1-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride N, and other technology is identical with embodiment 2.
Embodiment 15: nitryl aromatic family halogenide adopts 4-nitro-2-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride O, and other technology is identical with embodiment 2.
Embodiment 16: nitryl aromatic family halogenide adopts 3-nitro-1-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride P, and other technology is identical with embodiment 2.
Embodiment 17: nitryl aromatic family halogenide adopts 4-nitro-1-chloronaphthalene, and the diacid chloride monomer adopts diacid chloride P and diacid chloride E, and diacid chloride P: diacid chloride E: diamine monomer=0.5: 0.5: 1, other technology is identical with embodiment 2.
Embodiment 18: nitryl aromatic family halogenide adopts 4-nitro-2-chloronaphthalene, and the diacid chloride monomer adopts diacid chloride B and diacid chloride D, and diacid chloride B: diacid chloride D: diamine monomer=0.1: 0.9: 1, other technology is identical with embodiment 2.
Embodiment 19: nitryl aromatic family halogenide adopts 3-nitro-1-chloronaphthalene, and the diacid chloride monomer adopts diacid chloride B and diacid chloride D, and diacid chloride B: diacid chloride D: diamine monomer=0.8: 0.2: 1, other technology is identical with embodiment 2.
Embodiment 20: in the reduction reaction, also add ammonium chloride in original reductive agent, to shorten the reaction times, the diacid chloride monomer adopts diacid chloride D and diacid chloride M, and diacid chloride D: diacid chloride M: diamine monomer=0.2: 0.8: 1, other technology is identical with embodiment 4.
Embodiment 21: the reductive agent in the reduction reaction adopts potassium sulphide, and the diacid chloride monomer adopts diacid chloride D and diacid chloride M, and diacid chloride D: diacid chloride M: diamine monomer=0.4: 0.6: 1, other technology is identical with embodiment 4.
Embodiment 22: nitryl aromatic family halogenide adopts 5-nitro-1-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride D and diacid chloride I, and diacid chloride D: diacid chloride I: diamine monomer=0.1: 0.9: 1, other technology is identical with embodiment 5.
Embodiment 23: nitryl aromatic family halogenide adopts 6-nitro-1-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride K and diacid chloride I, and diacid chloride K: diacid chloride I: diamine monomer=0.9: 0.1: 1, other technology is identical with embodiment 5.
Embodiment 24: nitryl aromatic family halogenide adopts 7-nitro-1-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride K and diacid chloride I, and diacid chloride K: diacid chloride I: diamine monomer=0.4: 0.6: 1, other technology is identical with embodiment 5.
Embodiment 25: nitryl aromatic family halogenide adopts 8-nitro-1-fluoronaphthalene, and the diacid chloride monomer adopts diacid chloride J and diacid chloride D, and diacid chloride J: diacid chloride D: diamine monomer=0.4: 0.6: 1, other technology is identical with embodiment 5.
Embodiment 26: nitryl aromatic family halogenide adopts 5-nitro-2-fluoronaphthalene, the diacid chloride monomer adopts diacid chloride J, diacid chloride B and diacid chloride D, diacid chloride J: diacid chloride B: diacid chloride D: diamine monomer=0.4: 0.4: 0.2: 1, other technology is identical with embodiment 5.
Embodiment 27: nitryl aromatic family halogenide adopts 6-nitro-2-fluoronaphthalene, the diacid chloride monomer adopts diacid chloride J, diacid chloride B and diacid chloride D, diacid chloride J: diacid chloride B: diacid chloride D: diamine monomer=0.5: 0.2: 0.3: 1, other technology is identical with embodiment 5.
Embodiment 28: nitryl aromatic family halogenide adopts 7-nitro-2-fluoronaphthalene, and other technology is identical with embodiment 5.
Embodiment 29: nitryl aromatic family halogenide adopts 8-nitro-2-fluoronaphthalene, and other technology is identical with embodiment 5.
Embodiment 30: nitryl aromatic family halogenide adopts 5-nitro-1-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 31: nitryl aromatic family halogenide adopts 6-nitro-1-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 32: nitryl aromatic family halogenide adopts 7-nitro-1-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 33: nitryl aromatic family halogenide adopts 8-nitro-1-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 34: nitryl aromatic family halogenide adopts 5-nitro-2-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 35: nitryl aromatic family halogenide adopts 6-nitro-2-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 36: nitryl aromatic family halogenide adopts 7-nitro-2-chloronaphthalene, and other technology is identical with embodiment 6.
Embodiment 37: nitryl aromatic family halogenide adopts 8-nitro-2-chloronaphthalene, and other technology is identical with embodiment 6.
Claims (9)
1, a kind of polymeric amide that contains isoscrbierite unit is characterized in that the structure of this polymeric amide is:
In the following formula, Ar ' is:
Or
In any,
R is any or multiple in the following structure:
2, a kind of polyamide preparation method that contains isoscrbierite unit as claimed in claim 1 is characterized in that this preparation method may further comprise the steps:
(1) Isosorbide is dissolved in the solvent, ratio is: Isosorbide: solvent=1mol: 500mL～8000mL;
(2) alkaline matter is added in the above-mentioned solution, the mol ratio of adding is: Isosorbide: alkaline matter=1: 2～8, heated 0.5～1 hour down at 50～80 ℃;
(3) in above-mentioned solution, add nitryl aromatic family halogenide, the synthetic compound that obtains containing the Isosorbide dinitrobenzene, adding mol ratio is: Isosorbide: nitryl aromatic family halogenide=1: 2～4, temperature of reaction is 60～150 ℃, reaction times is 2～24 hours, then reaction solution is poured in the water, leaches solid, use washing with alcohol again, must contain the dinitro compound of Isosorbide;
(4) dinitro compound that will contain Isosorbide with the reductive method carries out nitroreduction, obtains containing the opticity diamine monomer of Isosorbide, and reduction reaction is room temperature～100 ℃, and the reaction times is 3～24 hours;
(5) add polar solvent in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 1L～4L;
(6) in above-mentioned diamine monomer solution, add acid absorber earlier; add diacid chloride again; the mol ratio that adds is: diamine monomer: acid absorber: diacid chloride=1: 1: 0.9～1.1, under 0～60 ℃ and nitrogen protection, stirred 1～24 hour, and obtain the heavy-gravity polyamide solution.
3, method as claimed in claim 2 is characterized in that wherein said solvent is N, dinethylformamide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, tetrahydrofuran (THF) or N-Methyl pyrrolidone.
4, method as claimed in claim 2 is characterized in that wherein said alkaline matter is any in sodium Metal 99.5, potassium hydroxide, salt of wormwood or the sodium hydride.
5, method as claimed in claim 2 is characterized in that wherein said nitryl aromatic family halogenide is any in the following classes of compounds:
This structural formula comprises: p-fluoronitrobenzene, a fluoronitrobenzene, o-fluoronitrobenzene, parachloronitrobenzene, m-chloro-nitrobenzene, o-chloronitrobenzene;
This structural formula comprises: 4-nitro-4 '-fluorine biphenyl, 3-nitro-4 '-fluorine biphenyl, 2-nitro-4 '-fluorine biphenyl, 4-nitro-4 '-chlordiphenyl, 3-nitro-4 '-chlordiphenyl, 2-nitro-4 '-chlordiphenyl;
This structural formula comprises: 4-nitro-1-fluoronaphthalene, 4-nitro-2-fluoronaphthalene, 3-nitro-1-fluoronaphthalene, 4-nitro-1-chloronaphthalene, 4-nitro-2-chloronaphthalene, 3-nitro-1-chloronaphthalene;
(4)
This structural formula comprises: 5-nitro-1-fluoronaphthalene, 6-nitro-1-fluoronaphthalene, 7-nitro-1-fluoronaphthalene, 8-nitro-1-fluoronaphthalene, 5-nitro-2-fluoronaphthalene, 6-nitro-2-fluoronaphthalene, 7-nitro-2-fluoronaphthalene, 8-nitro-2-fluoronaphthalene, 5-nitro-1-chloronaphthalene, 6-nitro-1-chloronaphthalene, 7-nitro-1-chloronaphthalene, 8-nitro-1-chloronaphthalene, 5-nitro-2-chloronaphthalene, 6-nitro-2-chloronaphthalene, 7-nitro-2-chloronaphthalene, 8-nitro-2-chloronaphthalene.
6, method as claimed in claim 2 is characterized in that, the method for described reduction reaction is the reduction of tin, tin protochloride, the iron series compound reduction, and the palladium based compound is that catalyzer reduces under hydrazine hydrate, hydrogen or any with in the sodium sulfide reducing.
7, method as claimed in claim 2 is characterized in that, described polar solvent is N, any in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or the hexamethylphosphoramide.
8, method as claimed in claim 2 is characterized in that, described diacid chloride is that one or more of following classes of compounds use with any mixed,
Above-mentioned diacid chloride monomer comprises a kind of of following structure:
Be called for short diacid chloride A
Be called for short diacid chloride B
(5)
Be called for short diacid chloride I
Be called for short diacid chloride K
Be called for short diacid chloride L
(13)
Be called for short diacid chloride O
Be called for short diacid chloride P.
9, method as claimed in claim 2 is characterized in that wherein said acid absorber is that a kind of in pyridine or the triethylamine or both use with any mixed.
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| US3485819A (en) * | 1968-07-02 | 1969-12-23 | Squibb & Sons Inc | Alpha-amino-cyclohexadienylalkylene-penicillins and cephalosporins |
| CN1298426A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
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| US3485819A (en) * | 1968-07-02 | 1969-12-23 | Squibb & Sons Inc | Alpha-amino-cyclohexadienylalkylene-penicillins and cephalosporins |
| CN1298426A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
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