JP4540679B2 - ポリアミドの連続製造方法 - Google Patents
ポリアミドの連続製造方法 Download PDFInfo
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- JP4540679B2 JP4540679B2 JP2006552523A JP2006552523A JP4540679B2 JP 4540679 B2 JP4540679 B2 JP 4540679B2 JP 2006552523 A JP2006552523 A JP 2006552523A JP 2006552523 A JP2006552523 A JP 2006552523A JP 4540679 B2 JP4540679 B2 JP 4540679B2
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- reactor
- gas
- chamber
- polyamide
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- 239000004952 Polyamide Substances 0.000 title claims description 44
- 229920002647 polyamide Polymers 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 40
- 238000010924 continuous production Methods 0.000 title claims description 5
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- 239000007788 liquid Substances 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 51
- 239000007791 liquid phase Substances 0.000 claims description 34
- 239000012071 phase Substances 0.000 claims description 33
- 239000012736 aqueous medium Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 125000005219 aminonitrile group Chemical group 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
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- 230000008569 process Effects 0.000 claims description 17
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- 239000011541 reaction mixture Substances 0.000 claims description 15
- -1 cyclic lactam Chemical class 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
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- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
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- 125000003277 amino group Chemical group 0.000 description 10
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- 125000004432 carbon atom Chemical group C* 0.000 description 6
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
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- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 3
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- JJMDCOVWQOJGCB-UHFFFAOYSA-N 5-aminopentanoic acid Chemical compound [NH3+]CCCCC([O-])=O JJMDCOVWQOJGCB-UHFFFAOYSA-N 0.000 description 2
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- 239000007848 Bronsted acid Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
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- ZLHYDRXTDZFRDZ-UHFFFAOYSA-N epsilon-aminocaproamide Chemical compound NCCCCCC(N)=O ZLHYDRXTDZFRDZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NJNQDCIAOXIFTB-UHFFFAOYSA-N ethyl 6-aminohexanoate Chemical compound CCOC(=O)CCCCCN NJNQDCIAOXIFTB-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TZJVWRXHKAXSEA-UHFFFAOYSA-N methyl 6-aminohexanoate Chemical compound COC(=O)CCCCCN TZJVWRXHKAXSEA-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- YSRFBCIGFNFMPS-UHFFFAOYSA-N naphthalene-1,3,5,7-tetracarboxylic acid Chemical compound C1=C(C(O)=O)C=C(C(O)=O)C2=CC(C(=O)O)=CC(C(O)=O)=C21 YSRFBCIGFNFMPS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- QXOYPGTWWXJFDI-UHFFFAOYSA-N nonanedinitrile Chemical compound N#CCCCCCCCC#N QXOYPGTWWXJFDI-UHFFFAOYSA-N 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- CHGYKYXGIWNSCD-UHFFFAOYSA-N pyridine-2,4,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=NC(C(O)=O)=C1 CHGYKYXGIWNSCD-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- ISIQQQYKUPBYSL-UHFFFAOYSA-N undecanedinitrile Chemical compound N#CCCCCCCCCCC#N ISIQQQYKUPBYSL-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
-
- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
水性媒体を、垂直方向の長手軸に沿って3カ所以上から反応器に導入することを特徴とするポリアミドの連続製造方法により達成されることを見出した。
上記の反応器(1)は、
液漏れ防止底部プレート(5)によって相互に分離され、長手方向に相互に重ねて配置された少なくとも2基のチャンバー(4)を有し、且つ
各々のチャンバー(4)は、直下のチャンバー(4)に液体用配管(6)を介して連結され、液体の生成物流が最も下側のチャンバー(4)の液体用配管(6)を介して取り出され、
各々のチャンバー(4)内の液面より上側の気体空間(7)は、直上に配置されたチャンバー(4)に接続され、その接続は、液面より下側で気体出口用オリフィス(11)を有するガス分配器(9)に通じる1本以上の導管(8)を用いることによって行われ、
チャンバー(4)には、ガス分配器(9)の周囲に垂直に配置され、上端部が液面より下側に、下端部がチャンバー(4)の液漏れ防止底部プレート(5)より上側に在り、そしてチャンバー(4)をガスが流れ込む1以上の空間(13)とガスが流れ込まない1以上の空間(14)とに分割する少なくとも1枚のガイド板(12)が設けられている。
(1)90〜400℃、好ましくは180〜310℃の温度及び0.1〜35×106Pa、好ましくは1〜10×106Paの圧力の条件下、反応器中において、アミノニトリル又はジニトリルとジアミン又はその混合物を、適宜他のポリアミド形成性モノマー及び/又はオリゴマーと一緒に、水性媒体を用いて反応させて、反応混合物を得る段階、
(2)更に反応混合物を、150〜400℃、好ましくは200〜300℃の温度及び段階1の圧力より低い圧力の条件下で反応させ、その際、温度と圧力を、第1の気相及び第1の液相が得られるように選択し、そして第1の気相を、第1の液相から分離する段階、及び
(3)第1の液相を、90〜370℃、好ましくは200〜300℃の温度及び0.1〜30×106Paの圧力の条件下で水又は水性媒体を含む気相又は液相と混合して、生成混合物を得る段階、を含んでいる。
(4)生成混合物を、200〜280℃の温度及び段階3が行われた場合には段階3より低い圧力にて後縮合し、その際、温度及び圧力を、水及びアンモニアを含む第2の気相と、ポリアミドを含む第2の液相と、を得るように選択する段階、を含む。
50〜99.99質量%、好ましくは80〜90質量%の6−アミノカプロニトリル、
0.01〜50質量%、好ましくは1〜30質量%の、C4〜C10−α,ω−脂肪族ジカルボン酸、C8〜C12−芳香族ジカルボン酸及びC5〜C8−シクロアルカンジカルボン酸から選択される少なくとも1種のジカルボン酸、
0〜50質量%、好ましくは0〜30質量%の炭素原子数4〜10のα,ω−ジアミン、
0〜50質量%、好ましくは0〜30質量%のα,ω−C2〜C12−ジニトリル、
0〜50質量%、好ましくは0〜30質量%のα,ω−C5〜C12−アミノ酸又は対応のラクトン、
0〜10質量%の少なくとも1種の無機酸又はその塩、
(但し、個々の質量%の合計は100%である)。
R2、R3が相互に独立して、それぞれ水素、C1〜C12アルキル又はC5〜C8シクロアルキルを表し、
mが3、4、5、6、7、8、9、10、11又は12を表す。]
で表されるアミノカルボン酸化合物との混合物を含む。
少なくとも1種のアミノアルキルニトリルを過剰の抽出水と一緒に加熱して、約250〜約350℃の範囲の温度及び約4〜30×106Paの範囲の圧力とし、その際に、圧力及び温度は、合成混合物が単一の液相として存在するように相互に調節され、そしてニトリル基の転化率は、使用されるアミノアルキルニトリルに対して、95モル%以下であり、これにより反応混合物を得る。
枝分かれ剤又は架橋剤として、3官能性アミン又はカルボン酸。少なくとも3官能性のアミン又はカルボン酸の適例は、EP−A0345648に開示されている。少なくとも3官能性のアミンは、カルボン酸基と反応可能なアミノ基を少なくとも3個有している。これは、カルボン酸基を有していないのが好ましい。この少なくとも3官能性のカルボン酸は、アミンと反応可能で、かつ例えばエステル等のその誘導体の状態で存在することもできるカルボン酸基を少なくとも3個有している。カルボン酸は、カルボン酸基と反応可能なアミノ基を含んでいないのが好ましい。カルボン酸の適例としては、トリメシン酸、三量化脂肪酸(例えばオレイン酸から調製され、かつ50〜60個の炭素原子を有する)、ナフタレンポリカルボン酸(例えば、ナフタレン−1,3,5,7−テトラカルボン酸)である。カルボン酸は、規定された有機化合物であり、高分子量化合物でないのが好ましい。
このR1がH又は−(CH2)n−NR2 2を表わし、
このR2がH又は−(CH2)n−NR3 2を表わし、
このR3がH又は−(CH2)n−NH2を表わし、
nが2〜6までの整数を表わし、そして
xが2〜14までの整数を表す。]
を有しているのが好ましい。
全長4.5m及び内径10cmであり、二酸化チタン触媒が充填され、そして80バールで断熱運転される送り管(流管)に、20kg/hのACNと、14.6kg/hの、91質量%の水、8質量%のカプロラクタムモノマー及び1質量%のカプロラクタムダイマーからなる抽出水と、の導入流を底部から供給した。導入流の温度は208℃であった。85℃の温度を有する5.3kg/hの抽出水(導入流の抽出水に類似の組成)の連続流を、反応器の高さ1mから導入した。更に、反応器の高さ2mから抽出水を側部供給した。この場合、計量導入速度は、第1の側部計量導入の場合の抽出水と同じ組成及び温度と組み合わせ、2.1kg/hであった。
比較実施例1を本願実施例1と同様の方法で行ったが、抽出水の側部計量導入は行わなかった、すなわち、導入流は、20kg/hのACNと、22kg/hの、91質量%の水、8質量%のカプロラクタムモノマー及び1質量%のカプロラクタムダイマーからなる抽出水と、をちょうど含んでいた。導入流の温度は208℃であった。カルボキシル末端基の濃度がアミノ末端基の濃度に対して15.4%であるN6プレポリマーを、流管の末端において、全有機成分の合計に対して、23kg/hの速度で得た。
比較実施例2を本願実施例1と同様の方法で行ったが、抽出水の代わりに、完全イオン非含有水(脱イオン水)を使用した。従って、導入流は、22kg/hのACNと、13.3kg/hの完全イオン非含有水を含んでいた。完全イオン非含有水を、第1の側部供給の場合には4.8kg/hの速度で、そして第2の側部供給の場合には1.9kg/hの速度で連続的に供給した。カルボキシル末端基の濃度がアミノ末端基の濃度に対して17.2%であるN6プレポリマーを、流管の末端において、全有機成分の合計に対して、23kg/hの速度で得た。
比較実施例3を本願実施例1と同様の方法で行ったが、抽出水の代わりに、完全イオン非含有水を使用した。流通反応装置において側部計量導入を行わなかった。従って、導入流は、22kg/hのACNと、20kg/hの完全イオン非含有水を含んでいた。導入温度を再び208℃とした。カルボキシル末端基の濃度がアミノ末端基の濃度に対して14.5%であるN6プレポリマーを、流管の末端において、全有機成分の合計に対して、23kg/hの速度で得た。
Claims (10)
- 垂直方向の長手軸を有し、その長手方向に実質的な流れが生じる反応器おいて、アミノニトリル又はジニトリルとジアミン又はその混合物を、適宜他のポリアミド形成性モノマー及び/又はオリゴマーと一緒に、ポリアミドの製造からポリマーを水で抽出することにより得られる水性モノマー及びオリゴマー抽出物からなる水性媒体を用いて反応させることにより、ポリアミド、そのオリゴマー又はその、適宜他の反応生成物との混合物を製造する連続方法であって、
水性媒体を、垂直方向の長手軸に沿って3カ所以上から反応器に導入することを特徴とするポリアミドの連続製造方法。 - 水性媒体を、垂直方向の長手軸に沿って3〜20カ所から反応器に導入することを特徴とする請求項1に記載の方法。
- 反応器は、流管、TVA反応器、並流式若しくは向流式で運転させるマルチチャンバー反応器、又は反応蒸留装置若しくは非反応蒸留装置である請求項1又は2に記載の方法。
- 反応器は、マルチチャンバー反応器であるか、或いはアミノニトリル又はジニトリルとジアミン又はその混合物が、適宜他のポリアミド形成性モノマー及び/又はオリゴマーと一緒に供給され、且つ一方の端部から水性媒体の一部分が供給され、水性媒体の他の部分が連続的に添加され、他方の端部から、ポリアミド、そのオリゴマー又はその混合物を含む反応混合物が排出される流管である請求項3に記載の方法。
- 以下の段階:
(1)180〜310℃の温度及び1〜10×106Paの圧力の条件下、反応器中において、アミノニトリル又はジニトリルとジアミン又はその混合物を、適宜他のポリアミド形成性モノマー及び/又はオリゴマーと一緒に、水性媒体を用いて反応させて、反応混合物を得る段階、
(2)更に反応混合物を、200〜300℃の温度及び段階1の圧力より低い圧力の条件下で反応させ、その際、温度と圧力を、第1の気相及び第1の液相が得られるように選択し、そして第1の気相を、第1の液相から分離する段階、及び
(3)第1の液相を、200〜300℃の温度及び0.1〜30×106Paの圧力の条件下で水及び水性媒体を含む気相又は液相と混合して、生成混合物を得る段階、
を含む請求項1〜4のいずれか1項に記載の方法。 - 段階3に加え又は段階3の代わりに、以下の段階:
(4)生成物混合物を、200〜280℃の温度及び段階3が行われた場合には段階3より低い圧力にて後縮合し、その際、温度及び圧力を、水及びアンモニアを含む第2の気相と、ポリアミドを含む第2の液相と、を得るように選択する段階、
を含む請求項5に記載の方法。 - 固定床の形の金属酸化物触媒を段階1又は段階3において、或いは段階1及び段階3において利用する請求項5又は6に記載の方法。
- 垂直に配置された長手軸を有する反応器(1)を利用し、且つ該反応器(1)において、反応生成物を底部から除去し、形成したアンモニア及び形成した他の低分子量化合物並びに水を頂部(2)から取り出し、且つ
前記反応器(1)は、
液漏れ防止底部プレート(5)によって相互に分離され、長手方向に相互に重ねて配置された少なくとも2基のチャンバー(4)を有し、且つ
各々のチャンバー(4)は、直下のチャンバー(4)に液体用配管(6)を介して連結され、液体の生成物流が最も下側のチャンバー(4)の液体用配管(6)を介して取り出され、
各々のチャンバー(4)内の液面より上側の気体空間(7)は、直上に配置されたチャンバー(4)に接続され、その接続は、液面より下側で気体出口用オリフィス(11)を有するガス分配器(9)に通じる1本以上の導管(8)を用いることによって行われ、
チャンバー(4)には、ガス分配器(9)の周囲に垂直に配置され、上端部が液面より下側に、下端部がチャンバー(4)の液漏れ防止底部プレート(5)より上側に在り、そしてチャンバー(4)をガスが流れ込む1以上の空間(13)とガスが流れ込まない1以上の空間(14)とに分割する少なくとも1枚のガイド板(12)が設けられていることを特徴とする請求項3又は4に記載の方法。 - 水性媒体の固体含有量は2〜30質量%の範囲であり、固体の少なくとも50質量%は、ラクタム、及び使用されるアミノニトリルから誘導された2〜6環員のオリゴマーの環式ラクタムである請求項1〜8のいずれか1項に記載の方法。
- 水性媒体のみを少なくとも2カ所の相互に異なる位置から反応器に導入する請求項1〜9のいずれか1項に記載の方法。
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DE836938C (de) | 1950-08-26 | 1952-04-17 | Basf Ag | Verfahren zur Herstellung von Amionitrilen |
DE3602376A1 (de) | 1986-01-28 | 1987-07-30 | Basf Ag | Verfahren zur herstellung von (epsilon)-caprolactam |
DE3710803A1 (de) | 1987-03-31 | 1988-10-20 | Basf Ag | Verfahren zur entfernung von caprolactam und dessen oligomeren aus solches enthaltendem polyamidgranulat |
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DE19635077A1 (de) | 1996-08-30 | 1998-03-05 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von Polyamiden aus omega-Aminoalkylnitrilen |
ATE253610T1 (de) | 1997-08-28 | 2003-11-15 | Du Pont | Verfahren zur herstellung von polyamiden |
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