CS265213B2 - Process for preparing block copolymere of polyamide-6 - Google Patents
Process for preparing block copolymere of polyamide-6 Download PDFInfo
- Publication number
- CS265213B2 CS265213B2 CS859339A CS933985A CS265213B2 CS 265213 B2 CS265213 B2 CS 265213B2 CS 859339 A CS859339 A CS 859339A CS 933985 A CS933985 A CS 933985A CS 265213 B2 CS265213 B2 CS 265213B2
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- lactam
- solution
- viscosity
- barium
- mixture
- Prior art date
Links
- 229920002292 Nylon 6 Polymers 0.000 title claims description 9
- 229920001577 copolymer Polymers 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000012693 lactam polymerization Methods 0.000 claims abstract description 42
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 37
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052788 barium Inorganic materials 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 68
- -1 2-oxo-1-pyrrolidinyl Chemical group 0.000 claims description 47
- 239000003999 initiator Substances 0.000 claims description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 21
- 229920001400 block copolymer Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 239000003623 enhancer Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- IQDSKLHRKYTKKY-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Ca+2].[O-]C1=NCCCCC1.[O-]C1=NCCCCC1 IQDSKLHRKYTKKY-UHFFFAOYSA-L 0.000 claims description 2
- WWIVCNJPGNAPMY-UHFFFAOYSA-L barium(2+);3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Ba+2].[O-]C1=NCCCCC1.[O-]C1=NCCCCC1 WWIVCNJPGNAPMY-UHFFFAOYSA-L 0.000 claims 1
- TUPYJTFUIPWHBL-UHFFFAOYSA-L barium(2+);3,4-dihydro-2h-pyrrol-5-olate Chemical compound [Ba+2].[O-]C1=NCCC1.[O-]C1=NCCC1 TUPYJTFUIPWHBL-UHFFFAOYSA-L 0.000 claims 1
- FNWDMTDFCYUSKG-UHFFFAOYSA-L calcium;3,4-dihydro-2h-pyrrol-5-olate Chemical group [Ca+2].[O-]C1=NCCC1.[O-]C1=NCCC1 FNWDMTDFCYUSKG-UHFFFAOYSA-L 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- WUZDBCQTGVJJMD-UHFFFAOYSA-L strontium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Sr+2].[O-]C1=NCCCCC1.[O-]C1=NCCCCC1 WUZDBCQTGVJJMD-UHFFFAOYSA-L 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 58
- 150000003951 lactams Chemical class 0.000 abstract description 32
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 89
- 230000001965 increasing effect Effects 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000007792 addition Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 239000004952 Polyamide Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000003438 strontium compounds Chemical class 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- YPKNNJOFXHHNON-UHFFFAOYSA-L magnesium;2-oxopyrrolidine-1-carboxylate Chemical compound [Mg+2].[O-]C(=O)N1CCCC1=O.[O-]C(=O)N1CCCC1=O YPKNNJOFXHHNON-UHFFFAOYSA-L 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002243 precursor Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- PIANPMBGAQMIBP-UHFFFAOYSA-L strontium;2-oxopyrrolidine-1-carboxylate Chemical compound [Sr+2].[O-]C(=O)N1CCCC1=O.[O-]C(=O)N1CCCC1=O PIANPMBGAQMIBP-UHFFFAOYSA-L 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- KEOZCAIGSRBLGC-UHFFFAOYSA-L calcium;2-oxopyrrolidine-1-carboxylate Chemical compound [Ca+2].[O-]C(=O)N1CCCC1=O.[O-]C(=O)N1CCCC1=O KEOZCAIGSRBLGC-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000252233 Cyprinus carpio Species 0.000 description 1
- 201000005569 Gout Diseases 0.000 description 1
- 241001648319 Toronia toru Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- UJPWWRPNIRRCPJ-UHFFFAOYSA-L strontium;dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Sr+2] UJPWWRPNIRRCPJ-UHFFFAOYSA-L 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002023 wood Substances 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
- C08G69/20—Anionic polymerisation characterised by the catalysts used
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/682,718 US4595747A (en) | 1984-12-17 | 1984-12-17 | Viscosified lactam polymerization initiator solutions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS933985A2 CS933985A2 (en) | 1988-12-15 |
| CS265213B2 true CS265213B2 (en) | 1989-10-13 |
Family
ID=24740842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS859339A CS265213B2 (en) | 1984-12-17 | 1985-12-16 | Process for preparing block copolymere of polyamide-6 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4595747A (fr) |
| EP (1) | EP0191277A3 (fr) |
| JP (1) | JPS61143431A (fr) |
| KR (2) | KR900004792B1 (fr) |
| AU (1) | AU571760B2 (fr) |
| BR (1) | BR8506314A (fr) |
| CA (1) | CA1232989A (fr) |
| CS (1) | CS265213B2 (fr) |
| DD (2) | DD250321A5 (fr) |
| DK (1) | DK581885A (fr) |
| PT (1) | PT81687B (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8400006A (nl) * | 1984-01-03 | 1985-08-01 | Stamicarbon | Werkwijze voor de condensatie van imide en alkohol. |
| US4596865A (en) * | 1984-12-17 | 1986-06-24 | Monsanto Company | Promotion of ε-caprolactam block copolymerization |
| US4595746A (en) * | 1984-12-17 | 1986-06-17 | Monsanto Company | Promotion of ε-caprolactam polymerization with lactam magnesium halide catalyst and 2-oxo-1-pyrrolidinyl groups |
| US4677189A (en) * | 1986-03-11 | 1987-06-30 | Dsm Rim Nylon Vof | Lactam polymerization initiators |
| FR2619385B1 (fr) * | 1987-08-11 | 1992-01-17 | Atochem | Poudre de polyamide constituee de particules a structure " rose des sables ". procede d'obtention de la poudre de polyamide |
| CA2090201A1 (fr) * | 1992-03-06 | 1993-09-07 | Norman L. Holy | Polyamides degradables |
| KR102142733B1 (ko) * | 2012-07-06 | 2020-08-07 | 란세스 도이치란트 게엠베하 | 캐스트 폴리아미드의 제조를 위한 촉매, 상기 촉매의 제조 방법 및 그의 용도 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862262A (en) * | 1973-12-10 | 1975-01-21 | Monsanto Co | Lactam-polyol-acyl polyactam terpolymers |
| US4031164A (en) * | 1974-06-06 | 1977-06-21 | Monsanto Company | Lactam-polyol-polyacyl lactam terpolymers |
| DE3273792D1 (en) * | 1981-06-16 | 1986-11-20 | Monsanto Co | Process for the preparaton of nylon block polymers |
-
1984
- 1984-12-17 US US06/682,718 patent/US4595747A/en not_active Expired - Fee Related
-
1985
- 1985-12-16 AU AU51270/85A patent/AU571760B2/en not_active Ceased
- 1985-12-16 BR BR8506314A patent/BR8506314A/pt unknown
- 1985-12-16 EP EP85870184A patent/EP0191277A3/fr not_active Withdrawn
- 1985-12-16 CA CA000497759A patent/CA1232989A/fr not_active Expired
- 1985-12-16 PT PT81687A patent/PT81687B/pt unknown
- 1985-12-16 JP JP60281246A patent/JPS61143431A/ja active Pending
- 1985-12-16 CS CS859339A patent/CS265213B2/cs unknown
- 1985-12-16 DD DD85295901A patent/DD250321A5/de unknown
- 1985-12-16 KR KR1019850009447A patent/KR900004792B1/ko not_active Expired
- 1985-12-16 DK DK581885A patent/DK581885A/da not_active Application Discontinuation
- 1985-12-16 DD DD85284387A patent/DD241607A5/de unknown
-
1989
- 1989-12-22 KR KR1019890018659A patent/KR900004795B1/ko not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| KR860004944A (ko) | 1986-07-16 |
| DK581885D0 (da) | 1985-12-16 |
| BR8506314A (pt) | 1986-08-26 |
| EP0191277A2 (fr) | 1986-08-20 |
| PT81687A (en) | 1986-01-01 |
| KR900004792B1 (ko) | 1990-07-05 |
| US4595747A (en) | 1986-06-17 |
| JPS61143431A (ja) | 1986-07-01 |
| AU571760B2 (en) | 1988-04-21 |
| CA1232989A (fr) | 1988-02-16 |
| DD241607A5 (de) | 1986-12-17 |
| DD250321A5 (de) | 1987-10-08 |
| PT81687B (en) | 1987-05-06 |
| DK581885A (da) | 1986-06-18 |
| AU5127085A (en) | 1986-06-26 |
| EP0191277A3 (fr) | 1988-03-23 |
| KR900004795B1 (ko) | 1990-07-05 |
| CS933985A2 (en) | 1988-12-15 |
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