CN116600967A - 连续制备聚酰胺预聚物的方法 - Google Patents
连续制备聚酰胺预聚物的方法 Download PDFInfo
- Publication number
- CN116600967A CN116600967A CN202180076150.9A CN202180076150A CN116600967A CN 116600967 A CN116600967 A CN 116600967A CN 202180076150 A CN202180076150 A CN 202180076150A CN 116600967 A CN116600967 A CN 116600967A
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- China
- Prior art keywords
- extruder
- polyamide
- polycondensation
- residence time
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229920002647 polyamide Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- -1 C12 lactam Chemical class 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 5
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 3
- 238000012565 NMR experiment Methods 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000003918 potentiometric titration Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 125000004112 carboxyamino group Chemical group [H]OC(=O)N([H])[*] 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 description 20
- 239000000047 product Substances 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 238000011955 best available control technology Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920006017 homo-polyamide Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- ROFWOEQFASWFTK-UHFFFAOYSA-N 1-cyclohexylpropylcyclohexane Chemical compound C1CCCCC1C(CC)C1CCCCC1 ROFWOEQFASWFTK-UHFFFAOYSA-N 0.000 description 1
- GSJAEHIASJBUKQ-UHFFFAOYSA-N 1-methyl-1-[2-(1-methylcyclohexyl)propan-2-yl]cyclohexane Chemical compound CC1(CCCCC1)C(C)(C)C1(CCCCC1)C GSJAEHIASJBUKQ-UHFFFAOYSA-N 0.000 description 1
- YDBHSDRXUCPTQQ-UHFFFAOYSA-N 1-methylcyclohexan-1-amine Chemical compound CC1(N)CCCCC1 YDBHSDRXUCPTQQ-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 1
- CPAUKJYZQPARFR-UHFFFAOYSA-N 2-n,2-n'-dicyclohexylpropane-2,2-diamine Chemical compound C1CCCCC1NC(C)(C)NC1CCCCC1 CPAUKJYZQPARFR-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- SBLKVIQSIHEQOF-UPHRSURJSA-N Octadec-9-ene-1,18-dioic-acid Chemical compound OC(=O)CCCCCCC\C=C/CCCCCCCC(O)=O SBLKVIQSIHEQOF-UPHRSURJSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 229920004497 WACKER® AK 1000 SILICONE FLUID Polymers 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- OTKFKCIRTBTDKK-UHFFFAOYSA-N [3-(aminomethyl)-5-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1C(CN)C2C(CN)CC1C2 OTKFKCIRTBTDKK-UHFFFAOYSA-N 0.000 description 1
- YMUAXKYTHNCMAS-UHFFFAOYSA-N [butyl(nitroso)amino]methyl acetate Chemical compound CCCCN(N=O)COC(C)=O YMUAXKYTHNCMAS-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- IZKZIDXHCDIZKY-UHFFFAOYSA-N heptane-1,1-diamine Chemical compound CCCCCCC(N)N IZKZIDXHCDIZKY-UHFFFAOYSA-N 0.000 description 1
- FBQUUIXMSDZPEB-UHFFFAOYSA-N hexadecane-1,1-diamine Chemical compound CCCCCCCCCCCCCCCC(N)N FBQUUIXMSDZPEB-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 description 1
- 229940116918 octadecenedioic acid Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XGSHEASGZHYHBU-UHFFFAOYSA-N tetradecane-1,1-diamine Chemical compound CCCCCCCCCCCCCC(N)N XGSHEASGZHYHBU-UHFFFAOYSA-N 0.000 description 1
- FRXCPDXZCDMUGX-UHFFFAOYSA-N tridecane-1,1-diamine Chemical compound CCCCCCCCCCCCC(N)N FRXCPDXZCDMUGX-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- C08G69/04—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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/425—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders using three or more screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- C08G69/04—Preparatory processes
- C08G69/06—Solid state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及连续制备聚酰胺预聚物的方法,该聚酰胺预聚物的溶液粘度为0.25dL/g至0.70dL/g之间,其根据ISO 307:2007在20℃下在间甲酚中测量,该方法的特征在于,其包括基于一种或多种聚酰胺前体单体的缩聚步骤,所述缩聚步骤在包括至少两个同向旋转的输送螺杆的挤出机中进行,所述至少一种单体在未溶于溶剂或水中的情况下预先以固体或液体形式加入所述挤出机中,并且所述缩聚步骤在不提取在所述缩聚期间形成的水的情况下进行。
Description
技术领域
本专利申请涉及通过缩聚来连续制备聚酰胺预聚物的方法,以及适用于实施这种方法的挤出机。
背景技术
聚酰胺(PA)通常通过分批法,在反应器中通过二胺与二羧酸、或氨基酸、或内酰胺的缩聚而制备,在分批法中加入所述单体并在压力下加热,直到获得足够粘度的混合物。单体经常以水溶液添加,并且在缩聚期间存在和/或形成的水必须通过将反应器置于减压下来去除。
然而,聚酰胺的摩尔质量由于其“活性”性质而难以控制/管理,因为在反应器排空期间,在反应器排空开始和结束时产物无法具有相同的摩尔质量(相同的粘度)。
如果超过了目标摩尔质量,就不再可返回,并且对于所生产的整个批次,产物都被“降级(déclassé)”。
此外,分批法是较资本密集的方法(对于每年生产的一定量的产品),并且较不生态(更多的能量和水消耗、更多的气态流出物和废物的产生,等等)。
此外,去除水也经常导致所添加的单体的损失,特别是在二胺与二羧酸的缩聚的情况下,这需要使用过量的单体,因此导致该方法的成本增加。
最近,已经开发了用于连续合成的方法。
因此,专利EP 2,877,516描述了连续合成重均分子量(Mw)大于或等于14,000g/mol的聚酰胺的方法。这种方法需要至少两次排水操作,并且不产生预聚物,而是产生聚合物。
美国专利8,765,902描述了用于连续制备6T/6I共聚酰胺的方法。这种方法需要蒸发水,并且不产生预聚物,而是产生聚合物。
专利EP 0410,650描述了通过二胺和二羧酸的缩聚来连续制备预聚物的方法。这种方法需要蒸发水。
因此,需要克服上述问题,并且本发明的目的之一是提出制备聚酰胺预聚物的方法,该方法比现有技术的方法更简单、更快、更可靠并且更便宜。
因此,本发明涉及连续制备聚酰胺预聚物的方法,该预聚物在溶液中的粘度在0.25dL/g至0.70dL/g之间,其根据ISO 307:2007在20℃下在间甲酚中测量,
其特征在于,所述方法包括由一种或多种聚酰胺前体单体缩聚的步骤,所述缩聚步骤在包括至少两个同向旋转的输送螺杆的单一挤出机中进行,所述单体在未溶于溶剂或水中的情况下预先以固体或液体形式加入,并且所述缩聚步骤在不提取形成的副产物、尤其是在所述缩聚期间形成的水的情况下进行。
因此,本发明人发现,可在该不需要去除水的情况下,特别是通过将挤出机置于真空下,找到材料在挤出机中的停留时间与挤出机中的反应温度之间的折衷。
事实上,在挤出机中将预聚物置于真空下以去除水是一个技术难题,因为由于低粘度,介质倾向于发泡,并且在真空管线中非常容易上升。因此,这会导致堵塞和真空有效性损失。
由于在挤出机中停留时间总是相同的,因此对于给定挤出温度,所形成的产物总是具有相同的数均摩尔质量(Mn)或相同的粘度。
所形成的产物也可在线表征,这使得可通过反馈来修改方法参数,以保证对最终产物的适当控制。
在整个说明书中,术语预聚物具有与术语低聚物相同的含义。
术语预聚物表示数均分子量Mn小于10,000g/mol、特别是1,000至9,000、特别是1,500至7,000、更特别是2,000至5,000g/mol的聚酰胺。
Mn特别地通过如下测定:藉由溶液中的电位滴定测定的末端官能团水平和所述预聚物的官能度的计算,或NMR试验(Postma et al.Polymer,47,1899–1911(2006))。
Mn也可通过尺寸排阻色谱法测定。
在通过缩聚进行的聚合中,特别是二胺和二羧酸的缩聚或包含羧酸官能团和胺官能团两者的单一单体的缩聚中,每个步骤都是缩合反应,所述缩合反应在消除小分子(称为反应副产物,诸如H2O)的情况下进行,这取决于所涉及的单体。
在本发明的方法中,在反应期间没有消除所形成的副产物、特别是所形成的水,这意味着挤出机不具有用于排出通过缩聚反应在发生反应的螺杆上方形成的反应副产物(在大多数情况下是水)的任何装置。
特别地,挤出机不具有任何脱气装置,或用于去除所形成的缩聚副产物、特别是所形成的水的任何装置,该装置由以下组成:在大气压力下的在外部的出口,或连接到使得可在反应期间在挤出机中形成低压区的装置、诸如真空泵的出口。
尽管如此,挤出机配备有用于在反应完成后并因此在螺杆之后返回到大气压力的装置。
所使用的挤出机包括至少两个输送螺杆。
根据本发明的制备聚酰胺的方法包括以下连续步骤,所有步骤都在挤出机内进行:
在加入所选择的单体之后,熔融固体可熔单体的步骤,将如此熔融的单体和液体单体、液体和/或不可熔固体单体混合的步骤,
和通过对由输送螺杆输送的材料进行剪切操作而进行的缩聚步骤。熔融和混合步骤可组合在单一步骤中。
在优选的方式中,还进行在熔融和混合步骤之间以及在混合和缩聚步骤之间通过在输送螺杆上输送材料来形成连续更新的盖或密封件的步骤。有利地,由进行中的材料形成的盖或密封件填充了可用于材料通过的所有体积,并形成了对蒸气、特别是对可能产生的单体蒸气气密密封的区域。
在挤出机中,每个输送螺杆均由不同的元件组成,这些元件在输送方向上相互跟随。这些不同的元件在旋转轴上彼此相邻放置。在同向旋转的挤出机中,所有的输送螺杆都沿同一方向转动,该方向通常对应于逆时针方向。在线型挤出机的情形中,元件彼此相邻地位于单条直线中,或者在环形挤出机的情形中,位于一个圆中。构成挤出机的不同输送螺杆都具有相同的直径,该直径沿输送螺杆始终保持恒定。最常见的是,该直径属于18至134mm的范围。
在专利EP 2,877,516中特别描述了这种挤出机,其中排除了用于减压或用于提取所形成的副产物的元件,所述元件在本发明的方法中不存在。
作为聚酰胺前体的单体根据其自然外观以固体或液体形式预先加入,但在任何情况下都不溶于任何溶剂或水中。
表述“预先”意指在缩聚反应开始之前加入单体。
在本发明的上下文中,在没有事先反应和没有事先制备相应盐的情况下加入单体。
关于聚酰胺
用于定义聚酰胺的命名法在ISO 1874-1:2011标准“Plastics-Polyamide(PA)Moulding And Extrusion Materials-Part 1:Designation”中描述,并且是技术人员所熟知的。
聚酰胺可为任何聚酰胺,无论它是脂族、脂环族、芳族或半芳族聚酰胺。
所述聚酰胺可为均聚酰胺或共聚酰胺。
有利地,所述聚酰胺是均聚酰胺。
所述芳族聚酰胺特别是通过可选自间苯二甲胺(MXD,CAS号:1477-55-0)或对苯二甲胺(PXD,CAS号:539-48-0)的芳胺与特别地选自对苯二甲酸、间苯二甲酸和萘酸的芳族二羧酸的缩聚而获得的。
任选地用脲单元改性的所述半芳族聚酰胺可特别是如EP1,505,099中所述的式X/YAr的半芳族聚酰胺,特别是式A/XT的半芳族聚酰胺,其中A选自由氨基酸单体获得的单元、由内酰胺单体获得的单元、和对应于式(Ca二胺)·(Cb二酸)的单元,二者均代表单体,其中a代表二胺的碳原子数,b代表二酸的碳原子数,a和b各自在4和36之间、有利地在9和18之间,单元(Ca二胺)选自线型或支化脂族二胺、脂环族二胺、和烷基芳族二胺,并且所述单元(Cb二酸)选自线型或支化脂族二酸、脂环族二酸和芳族二酸;
X.T表示由Cx二胺和对苯二甲酸的缩聚获得的单元,其中x表示Cx二胺的碳原子数,x在6和36之间、有利地在9和18之间,特别是具有式A/6T、A/9T、A/10T或A/11T的聚酰胺,A如上文所定义,特别是聚酰胺PA 6/6T、PA 66/6T、PA 6I/6T、PA MPMDT/6T、PA MXDT/6T、PAPA11/10T、PA 5T/10T、PA 11/5T/10T、PA 11/6T/10T、PA MXDT/10T、PA MPMDT/10T、PABACT/10T、PA BACT/6T、PA BACT/10T/6T、PA 11/BACT/10T、PA 11/BACT/6T、PA 11/MPMDT/10T和PA 11/MXDT/10T,和嵌段共聚物,尤其是聚酰胺/聚醚(PEBA)。
T对应于对苯二甲酸,MXD对应于间苯二甲胺,MPMD对应于甲基五亚甲基二胺,BAC对应于双(氨基甲基)环己烷。
所述脂环族聚酰胺特别是通过以下单体的缩聚获得:脂环族二胺与脂族二羧酸、或脂族二胺与脂环族二羧酸、或脂环族二胺与脂环族二羧酸。
脂环族二胺可选自例如:双(3,5-二烷基-4-氨基环己基)-甲烷、双(3,5-二烷基-4-氨基环己基)乙烷、双(3,5-二烷基-4-氨基环己基)丙烷、双(3,5-二烷基4-氨基环己基)-丁烷、双-(3-甲基-4-氨基环己基)-甲烷、或通常称为“BMACM”或“MACM”(并且在下文中表示为B)的3′-二甲基-4,4′-二氨基-二环己基甲烷、通常称为“PACM”(并且在下文中表示为P)的对-双(氨基环己基)-甲烷、通常称为“PACP”的亚异丙基二(环己胺)、异佛尔酮二胺(在下文中表示为IPD)和通常称为“BAMN”的2,6-双(氨基甲基)降冰片烷。
这些脂环族二胺的非详尽列表见出版物“Cycloaliphatic Amines”(Encyclopaedia of Chemical Technology,Kirk-Othmer,4th Edition(1992),pp.386–405)。
脂环族二羧酸可包含以下碳骨架:降冰片基甲烷、环己烷、环己基甲烷、二环己基甲烷、双环己基丙烷、二(甲基环己基)或二(甲基环己基)丙烷。
脂族二胺和脂族二羧酸与下文所述的脂族聚酰胺一样。
所述脂族聚酰胺可得自如下的一种或多种单体的缩聚,所述单体是至少一种C6至C18、特别是C6至C12、更特别是C10至C12羧酸,特别是11-氨基十一烷酸。
所述脂族聚酰胺可来源于如下的一种或多种单体的缩聚,所述单体是至少一种C6至C18、特别是C6至C12、更特别是C10至C12内酰胺,特别是月桂基内酰胺。
所述脂族聚酰胺可来源于如下的一种或多种单体的缩聚,所述单体是至少一种C6至C18、特别是C6至C12、更特别是C10至C12脂族二胺,与至少一种C6至C18、特别是C6至C12、更特别是C10至C12脂族二羧酸。
所使用的脂族二胺是具有包含至少6个碳原子的线型主链的脂族二胺。
若必要,则该线型主链可包括一个或多个甲基和/或乙基取代基;在后一种构型中,这被称为“支化脂族二胺”。在主链不包括任何取代基的情况下,脂族二胺被称为“线型脂族二胺”。
当该二胺是线型脂族二胺时,其特别对应于式H2N-(CH2)x-NH2,并且可选自例如己二胺、庚二胺、辛二胺、壬二胺、癸二胺、十一烷二胺、十二烷二胺,十三烷二胺、十四烷二胺、十六烷二胺和十八碳烯二胺。刚刚提到的线型脂族二胺都可为标准ASTM D6866意义上的生物来源。
当该二胺是支化脂族二胺时,它可特别地是2-甲基戊二胺、2-甲基-1,8-辛二胺或三亚甲基(2,2,4-或2,4,4)-己二胺。
二羧酸可选自线型或支化脂族二羧酸。
有利地,二胺是线型脂族二胺。
当二羧酸是脂族和线型的时,它可选自己二酸(6)、庚二酸(7)、辛二酸(8)、壬二酸(9)、癸二酸(10)、十一烷二酸(11)、十二烷二酸(12)、十三烷二酸(13)、十四烷二酸(14)、十六烷二酸(16)、十八烷二酸(18)、十八碳烯二酸(18)。
有利地,聚酰胺是半芳族、脂环族或半芳族聚酰胺。
更有利的是,所述聚酰胺是半芳族或脂族的,特别地所述聚酰胺是脂族的。
更有利地,聚酰胺是脂族的,并且由单一氨基羧酸或单一内酰胺获得,特别地其由11-氨基十一烷酸或月桂基内酰胺获得,特别地其由11-氨基十一烷酸获得。
关于方法
优选地,根据本发明的方法获得的聚酰胺的平均聚合度(DPn)小于50、特别是小于或等于45、特别是在5和45之间。
有利地,根据本发明的方法获得的聚酰胺的平均聚合度(DPn)为8至40、特别是12至30。
术语“平均聚合度(DPn)”是指聚合物链中存在的结构单元的平均数量。
平均聚合度(DPn)通常根据下式由聚酰胺的数均分子量(Mn)来评估:
[数学式1]
DPn=Mn/M0
其中
Mn是聚酰胺的数均分子量
M0是单体的数均分子量
有利地,根据本发明的方法获得的聚酰胺的重均分子量(Mn)小于10,000g/mol、特别是在1,000和9,000g/mol之间、特别是1,500至7,000g/mol、更特别是2,000至5.000g/mol。
重均分子量可通过尺寸排阻色谱法测定。
在一个实施方式中,所述挤出机包括2到12个同向旋转的输送螺杆。
在该实施方式的第一变体中,所述挤出机是包括两个同向旋转的输送螺杆的双螺杆挤出机。
有利地,在该第一变体中,所述方法在220至340℃之间、优选260至300℃的温度下进行。
在该第一变体的一个实施方式中,材料在挤出机中在220℃至340℃之间的温度下的停留时间允许进行缩聚反应,以便达到所需的平均聚合度。
有利地,所需聚合度为8至40、特别是12至30。
在该第一变体的一个实施方式中,材料在挤出机中在220℃至340℃之间的温度下的停留时间允许进行缩聚反应,以便达到0.25至0.7dL/g之间的期望粘度。
在该实施方式的第二变体中,所述挤出机是环形多螺杆挤出机,其包括同向旋转的的至少6个输送螺杆、特别是12个输送螺杆。
在该第二变体的一个实施方式中,材料在挤出机中在220℃至340℃之间的温度下的停留时间允许进行缩聚反应,以便达到所需的平均聚合度。
有利地,所需聚合度在8至40之间、特别是12至30。
在该第二变体的一个实施方式中,材料在挤出机中在220℃至340℃之间的温度下的停留时间允许进行缩聚反应,以便达到0.25至0.7dL/g之间的期望粘度。
有利地,材料在第一或第二变体的挤出机中的停留时间大于或等于1分钟、并且特别是在1至10分钟之间、特别是在2至6分钟之间。
在两种变体中的一种或另一种的另一个实施方式中,挤出机的流量大于或等于10kg/h、特别是大于或等于15kg/h、特别是大于或等于30kg/h、更特别地大于或等于50kg/h。
有利地,所使用的具有大于或等于10kg/h、特别是大于或等于15kg/h、特别是大于或等于30kg/h、更特别是大于或等于50kg/h的流量的挤出机是包括6至12个同向旋转的输送螺杆、特别是12个同向旋转的输送螺杆的挤出机。
在一个实施方式中,包括6至12个同向旋转的输送螺杆、特别是12个同向旋转的输送螺杆的具有上述流量的挤出机的长度大于或等于30L/D、特别是30至100L/D。
在另一个实施方式中,在本发明的方法中,在挤出机中的缩聚期间加入至少一种添加剂。
可给出一种或多种颜料或染料作为添加剂的实例。
还可提及选自以下的一种或多种添加剂:催化剂、抗缩孔剂或铺展剂、还原剂、抗氧化剂、增强填料、UV稳定剂、流化剂、腐蚀抑制剂或其混合物。
在根据本发明的方法的一个实施方式中,在所述方法期间进行在线分析。
在该后一个实施方式的第一变体中,如果在线分析表征了所得产物具有所需特性、特别是所需聚合度,则不修改该方法的操作参数、特别是挤出机的停留时间和温度对。
在该后一个实施方式的第二变体中,如果在线分析表征了所得产物不具有所需特性、尤其是所需聚合度,则修改该方法的操作参数、特别是挤出机的停留时间和温度对,以使得可获得具有所需特性、特别是所需聚合度的产品。
根据另一个方面,本发明涉及可通过如上文所定义的方法获得的产品。
因此,该产品对应于通过以上定义的方法获得的预聚物。
根据另一个方面,本发明涉及适于实施如上文所定义的方法的挤出机。
实施例:
实施例1(对比)
在一个批次中制备预聚物的一般程序:
向14升高压釜反应器中加入5kg的以下原材料:
-500g水,
-二胺和二羧酸和/或氨基酸,
-0.1g的WACKER AK1000消泡剂(来自Wacker Silicones)。
将封闭的反应器清除其残余氧,然后加热至230℃的材料温度。在这些条件下搅拌30分钟后,反应器中形成的加压蒸气在60分钟内逐渐松弛,同时逐渐调整材料的材料温度,使得其在大气压下稳定在Tf+10℃。
低聚物(预聚物)然后通过底部阀排空,然后在水浴中冷却,然后研磨。
根据该程序,在不使用二胺或二羧酸的情况下由呈固态的11-氨基十一烷酸(CAS2432-99-7)制备Mn=3000且粘度为0.40的PA11预聚物,其中停留时间(超过1小时)比本发明的实施例2和3中所描述的方法的停留时间(在1至5分钟之间)长得多。
实施例2(本发明):
在几种温度和流量条件下(表1至表6),在直径D=18mm(长度=40D或60D)的ZSK18Ml双螺杆挤出机(Coporion)或直径D=32mm(长度=40D)的Evolum32HT双螺杆挤出机(EV32 Clextral)上由呈固态的11-氨基十一烷酸(CAS 2432-99-7)制备PA11预聚物,而不提取缩聚期间形成的副产物:
ZSK18双螺杆挤出机:
[表1]
温度分布(℃):
[表2]
AT=环境温度
[表3]
温度分布(℃):
[表4]
AT=环境温度
EV32双螺杆挤出机:
[表5]
温度分布(℃):
[表6]
实施例3(本发明):
在几种温度和流量条件下(表7至表12),在直径D=19mm(长度=36D或100D)的包括12个螺杆的RE1 XPV(Extricom)挤出机或直径D=31mm(长度=55D)的包括12个螺杆的RE3 XPV(Extricom)挤出机上由呈固态的11-氨基十一烷酸(CAS 2432-99-7)制备PA11预聚物,而不提取缩聚期间形成的副产物:
包括12个螺杆的RE1 XPV挤出机:
[表7]
温度分布(℃):
[表8]
AT=环境温度
[表9]
温度分布(℃):
[表10]
AT=环境温度
包括12个螺杆的RE3 XPV挤出机:
[表11]
温度分布(℃):
[表12]
本发明的连续方法使得可制备具有所需溶液粘度的PA11预聚物,其中停留时间为几分钟(1至5分钟之间),远低于在分批法中获得PA11预聚合物所需的停留时间(超过一小时)。
Claims (13)
1.连续制备聚酰胺预聚物的方法,所述聚酰胺预聚物在溶液中的粘度在0.25dL/g至0.70dL/g之间,其根据ISO 307:2007在20℃下在间甲酚中测量,
所述配制的聚酰胺预聚物具有小于10,000g/mol、特别是在1,000和9,000g/mol之间、特别是1,500至7,000g/mol、更特别是2,000至5,000g/mol的重均分子量(Mn),其通过如下测定:藉由溶液中的电位滴定测定的末端官能团水平和所述预聚物的官能度的计算,或NMR试验,或尺寸排阻色谱法,
其特征在于,所述方法包括由一种或多种聚酰胺前体单体缩聚的步骤,所述缩聚步骤在包括至少两个同向旋转的输送螺杆的单一挤出机中进行,所述单体在未溶于溶剂或水中的情况下预先以固体或液体形式加入,并且所述缩聚步骤在不提取形成的副产物、尤其是在所述缩聚期间形成的水的情况下进行,所述挤出机不具有任何脱气装置,特别是通过向后者添加惰性气体,或用于去除所形成的缩聚副产物、特别是所形成的水的任何装置,所述装置由以下组成:在大气压力下的在外部的出口,或连接到使得可在反应期间在所述挤出机中产生低压区的装置、诸如真空泵的出口。
2.根据权利要求1所述的方法,其特征在于,所得聚酰胺的平均聚合度(DPn)小于50、特别是小于或等于45、特别是5至45,其根据下式由聚酰胺的数均分子量(Mn)测定:
[数学式1]
DPn=Mn/M0
其中
Mn,如权利要求1中所定义的聚酰胺的数均分子量,
M0,单体的数均分子量。
3.根据权利要求1或2中的一项所述的方法,其特征在于,所述聚酰胺是脂族聚酰胺。
4.根据权利要求3所述的方法,其特征在于,所述单体是至少一种C6至C18、特别是C6至C12、更特别是C10至C12羧基氨基酸,特别是11-氨基十一烷酸。
5.根据权利要求3所述的方法,其特征在于,所述单体是至少一种C6至C18、特别是C6至C12、更特别是C10至C12内酰胺,特别是月桂基内酰胺。
6.根据权利要求3所述的方法,其特征在于,所述单体是至少一种C6至C18、特别是C6至C12、更特别是C10至C12脂族二胺,和至少一种C6至C18、特别是C6至C12、更特别是C10至C12脂族二羧酸。
7.根据权利要求1至6中的一项所述的方法,其特征在于,所述挤出机是具有两个同向旋转的输送螺杆的双螺杆挤出机。
8.根据权利要求7所述的方法,其特征在于,所述方法在220和340℃之间、优选260和300℃之间的温度下进行。
9.根据权利要求8所述的方法,其特征在于,材料在所述挤出机中在220℃和340℃之间的温度下的停留时间允许进行缩聚反应,以便达到所需的平均聚合度,所述停留时间大于或等于1分钟。
10.根据权利要求1至6中的一项所述的方法,其特征在于,所述挤出机是包括至少6个同向旋转的螺杆、特别是12个同向旋转的螺杆的环形多螺杆挤出机。
11.根据权利要求10所述的方法,其特征在于,材料在所述挤出机中在220℃和340℃之间的温度下的停留时间允许进行缩聚反应,以便达到所需的平均聚合度,所述停留时间大于或等于1分钟。
12.根据权利要求7至11中的一项所述的方法,其特征在于,所述材料在所述挤出机中的停留时间大于或等于1分钟、并且特别是在1和10分钟之间,特别是在2和6分钟之间。
13.根据权利要求1至12中的一项所述的方法,其特征在于,在所述挤出机中的缩聚期间加入至少一种添加剂。
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