CN1087316C - 寡胺或聚胺的烷氧基化物的制备方法 - Google Patents
寡胺或聚胺的烷氧基化物的制备方法 Download PDFInfo
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- CN1087316C CN1087316C CN95195536A CN95195536A CN1087316C CN 1087316 C CN1087316 C CN 1087316C CN 95195536 A CN95195536 A CN 95195536A CN 95195536 A CN95195536 A CN 95195536A CN 1087316 C CN1087316 C CN 1087316C
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- oxide
- polyamine
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- 229920000768 polyamine Polymers 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229920001281 polyalkylene Polymers 0.000 claims description 3
- -1 N-substituted carboxamides Chemical class 0.000 abstract description 8
- 150000003462 sulfoxides Chemical class 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- 150000003457 sulfones Chemical class 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 1
- 150000002170 ethers Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 150000001414 amino alcohols Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical group CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Chemical group 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001223 polyethylene glycol Chemical group 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000003527 tetrahydropyrans Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
寡胺或聚胺的烷氧基化物的制备分二步进行，在其第一步，在有水、醇或酸或其混合物存在而无中性或碱性催化剂存在的情况下，在寡胺或聚胺上每个NH基加成1分子烯化氧。在其第二步，去除水和酸后，在有一种传统的中性或碱性催化剂存在的情况下，进行与进一步的烯化氧的反应。其中在第二步进行前，加入一种来自以下组群的有机溶剂或稀释剂或其混合物：(a)醇和酚和它们的烷氧基化物，(b)以氧化乙烯、氧化丙烯、环氧丁烷或其混和物为基体的聚醇，(c)N-取代的羧酰胺，(d)烷醇一元胺和烷醇聚胺和它们的烷氧基化物，(e)寡胺或聚胺的其它烷氧基化物，(f)芳香烃，(g)脂族烃，(h)醚，(i)砜或亚砜。
Description
本发明涉及一种分二步制备寡胺或聚胺的烷氧基化物的改善方法，其中，第一步，在有水、醇或酸或它们的混合物存在而无中性或碱性催化剂存在的情况下，在寡胺或聚胺上每个NH基加成一分子烯化氧。第二步，去除水和酸后，在有传统的中性或碱性催化剂存在的情况下，与进一步的烯化氧进行反应。
DE-B2227546揭示了一种分两步制备烷氧基化聚亚烷基亚胺的方法，其中，第一步，聚亚烷基聚胺在有1-50重量％的水存在的情况下，与足量的烯化氧作用，生成相应的氨基醇，其中键合氢原子的氮原子上的所有原子价被饱和。第二步，在去除水后，加入一种碱性催化剂，随后进行进一步的烷氧基化。
众所周知，在第二步中氨基醇的进一步反应必须在没有水存在的情况下进行，因为如果不是这样就有许多不想要的带乙二醇或聚乙二醇结构的副产物过量生成。但是，纯聚合氨基醇的进一步烷氧基化作用，例如在熔化状态下，仅仅非常慢地发生。尤其是在进一步反应发生初始，产生的高粘度状态难以控制和克服，这导致反应时间和产物的巨大变化，产物随粘度不同而有很大差异。
本发明的目的是找出反应条件，在此条件下，来自所描述制备方法第一步的聚合氨基醇能以一种经济和有效的方式，在短反应时间下被烷氧基化而生成可重现的产物。
我们发现这一目的可通过开头所定义的方法达到，其特征在于，在第二步进行之前，加入以下组群中的一种有机溶剂或稀释剂或它们的混和物：
(a)醇和酚和它们的烷氧基化物
(b)以氧化乙烯、氧化丙烯、环氧丁烷或其混和物为基础的聚醇
(c)N-取代的羧酰胺
(d)链烷醇一元胺和链烷醇聚胺和它们的烷氧基化物
(e)寡胺或聚胺的其它烷氧基化物
(f)芳香烃
(g)脂族烃
(h)醚
(i)砜或亚砜
所述溶剂或稀释剂优选以2～400重量份的量加入，尤其优选5～200重量份，特别是10～100重量份，以来自第一步的加合物的重量为基础。
合适的醇和酚或它们的烷氧基化物(a)的实例是C1-C8-烷醇，尤其是C1-C4-烷醇，例如甲醇、乙醇、n-丙醇、异丙醇、n-丁醇、异丁醇、仲丁醇、叔丁醇、n-戊醇、n-己醇、n-庚醇、n-辛醇或2-乙基己醇、环己醇、苯甲醇、多元醇例如乙二醇或丙二醇；酚例如未取代酚、甲酚或萘酚，特别是在酚的情况中，其与每羟基1～30摩尔，尤其是2～15摩尔氧化乙烯、氧化丙烯、环氧丁烷的反应产物或其混和物。
聚二醇(b)的实施例是二甘醇、三甘醇、四甘醇和聚乙二醇，其平均分子量为200～2000，尤其是300～1000；此外还有二丙二醇、三丙二醇、四丙二醇和聚丙二醇，其平均分子量为270～2000，尤其是350～1000；此外还有二丁二醇、三丁二醇、四丁二醇和聚丁二醇，其平均分子量为320～2000，尤其是400～1000。
尤其合适的N-取代开链或环状羧酰胺(c)是N，N-二甲基甲酰胺、N，N-二丁基甲酰胺、N，N二甲基乙酰胺和N-甲基吡咯烷酮。
合适的链烷醇一元胺和聚胺或它们的烷氧基化物(d)的实施例是一乙醇胺、二乙醇胺、三乙醇胺、一-n-丙醇胺、二-n-丙醇胺、三-n-丙醇胺、一异丙醇胺、二异丙醇胺、三异丙醇胺、四乙醇乙二胺或四乙醇丙二胺，其与每羟基1～30摩尔，尤其是2～15摩尔氧化乙烯、氧化丙烯、环氧丁烷的反应产物或其混和物。
寡胺或聚胺的其它烷氧化物(e)是指与按照本发明制备的烷氧基化物同类型的产物。
尤其合适的芳香烃(f)是苯、甲苯、二甲苯、1，3，5-三甲基苯、苯乙烯、1，2-二氢化茚、茚和主要或唯一包括这些类型的芳香烃的工业芳香族馏分，例如石脑油(一种烷基苯的混和物)和重溶剂石脑油。尤其有意义的是二甲苯，这是指同分异构的纯o-、m-和p-二甲苯和它们的工业混和物。
脂族烃(g)的实施例是戊烷、己烷、庚烷、环戊烷、环己烷和主要或仅包括这些类型的脂族烃的工业脂肪族馏分，例如在35～110℃范围内蒸馏出来的石油醚。
尤其合适的醚官能度为1或更多，优选1或2的开链或环状醚(h)是二乙醚、二-n-丙醚、二异丙醚、二-n-丁基醚、甲基叔丁基醚、二甲氧基乙烷、四氢吡喃、四氢呋喃和二氧杂环己烷。
开链或环状砜或亚砜(i)的实施例是二甲砜、二乙砜、环丁砜、3-环丁砜、二甲亚砜。
按照本发明优选应用的溶剂和稀释剂是从组群(b)(c)(d)(f)和(h)中得来的。尤其合适的按照本发明的方法被烷氧基化的寡胺或聚胺是每个分子含3～10个氮原子，优选为3～7个的聚亚烷基聚胺，例如二亚乙基三胺、三亚乙基四胺或四亚乙基五胺，此外还有重均分子量为600～10,000,000优选2000～7,000,000的聚乙烯胺，此外还有重均分子量为2000～50,000优选5000～25,000的聚乙烯亚胺。
适合按照本发明进行烷氧基化作用的是所有常用的1，2-烯化氧，尤其是氧化乙烯，氧化丙烯和环氧丁烷。其中可使用1，2-或2，3-环氧丁烷，还有氧化苯乙烯、氧化环己烯和所述烯化氧的混和物。
在序言中提出的按照本发明分二步进行烷氧基化的方法以一种传统的方式进行。在其第一步，按化学计量进行每个NH基加成一分子烯化氧的反应。反应优选在水中进行，水通常是起始胺的最佳溶剂，或者在一种含水介质中进行。反应通常在高温下，例如50～130℃，尤其是70～120℃和例如1.1～10巴尤其是2～5巴的压力下进行，例如在一个压热器中进行。可以单独存在于反应介质中或优选与水一起作为溶剂或反应促进剂的醇和/或酸的实例是C1-C4-烷醇，例如前面在(a)下面提到的那些，以及传统的无机酸，例如盐酸或硫酸，或者传统的羧酸如乙酸。
在第二步，去除水和酸以及必要的话，如果在这一步不要求醇作为溶剂或稀释剂，去除醇后，加入一种传统的中性或碱性催化剂。合适的和优选的碱性催化剂尤其是碱金属氢氧化物例如NaOH和KOH和碱金属醇化物例如钠或钾的甲醇化物、乙醇化物、异丙氧化物和叔丁氧化物。可以提及的中性催化剂的实例是层化合物，例如未改良的和改良了的水滑石。第二步一般在高温例如70-180℃尤其是90-150℃下和在与第一步类似的压力下进行，例如也在一个压热器中进行。
在第二步进行前，通过使用按照本发明加入的溶剂或稀释剂进行共沸蒸馏或者在加入溶剂或稀释剂之前进行减压蒸馏或者在加入溶剂或稀释剂之后进行减压蒸馏，以去除水和酸以及必要的话去除醇。有可能在第一步之前、之中或之后加入溶剂或稀释剂，在此溶剂或稀释剂必须有一个足够高的沸点。
按照本发明的方法制备寡胺或聚胺的烷氧基化物是可能的，该烷氧基化物有任意数量的烯化氧单元对应每个初始NH基。在此优选的是3～300烯化氧单元每个初始NH基，尤其是4～200，特别是10～100烯化氧单元每个初始NH基。
在按照本发明加入的溶剂或稀释剂的存在下可大大改善对第二步烷氧基化的控制，因为在相反情况下出现的粘度问题被避免了，尤其是反应时间短得多。
在进行第二步前，通过共沸蒸馏去除水时，水的去除比从例如熔体中去除水要快得多，并且几乎完全。尤其令人吃惊的是相对无极性和质子惰性的溶剂，例如来自(f)组的那些，适合导致所要求的来自烷氧基化第一步的高极性化合物，也就是相应的氨基醇中水的去除。
按照本发明的方法获得的产物可用于尤其是破坏原油乳化。在此，在许多情况下，还含有所用溶剂或稀释剂的产物，其破坏原油乳化要比那些未用所描述的溶剂或稀释剂就已制备，随后向其中加入这些试剂而获得的类似产物的破坏效果更好一些。这样一种协合效应已通过将类似的、市场上可买到的、未用所描述的溶剂或稀释剂而制备的烷氧化寡胺或聚胺与所述溶剂或稀释剂混合而测试出来，因此本申请同样涉及这样一些还含有所用溶剂或稀释剂的烷氧基化的寡胺或聚胺用以破坏原油乳化。
实施例1a
聚乙烯亚胺在水中的一烷氧基化(第一步)和添加二甲苯后通过共沸蒸馏去除水
43克重均分子量为约20,000的聚乙烯亚胺与43克水一起导入一个压热器中。然后，在90～100℃温度和最大4巴的压力下搅拌的同时，加入58克氧化丙烯，历时30分钟。在此温度下再搅拌一个小时后，混合物冷却至约80℃，加入20克50重量％的KOH水溶液和100克二甲苯，通过共沸蒸馏去除所有水。
实施例1b
在有二甲苯存在的情况下进一步烷氧基化(第二步)
来自实施例1a的产物母体与约2610克氧化丙烯在一个压热器中，在130-140℃温度和直至约4.5巴的压力下反应。反应时间为1230分钟。比较实施例a
在第二步前不添加二甲苯，重复实施例1a和1b。在此实例中，在120℃温度和将压力降至10毫巴下进行蒸馏，水被去除。第二步的反应时间是3600分钟。
实施例2a
聚乙烯亚胺在水中的一烷氧基化(第一步)
43克重均分子量为约20,000的聚乙烯亚胺与43克水一起导入一个压热器中。然后，在90～100℃温度和最大4巴压力下搅拌的同时，加入58克氧化丙烯，历时30分钟。在此温度下再搅拌1小时后，加入20克50重量％的KOH水溶液。通过将压力降至约10毫巴和将温度升高至120℃进行蒸馏，历时5小时，水被完全去除。
实施例2b
在有四氢呋喃存在的情况下进一步烷氧基化(第二步)
实施例2a的产物母体已冷却至60℃，与100克四氢呋喃混合并与进一步的氧化丙烯反应，就象实施例1b中那样。此实施例中的反应时间为1190分钟。
实施例2c
在有N，N-二丁基甲酰胺存在的情况下进一步烷氧基化(第二步)
实施例2a的产物母体已冷却至60℃，与100克N，N-二丁基甲酰胺混合并与进一步的氧化丙烯反应，就象实施例1b中那样。此实施例中的反应时间为1250分钟。
实施例3a
聚乙烯亚胺在水和聚丙二醇中的一烷氧基化(第一步)
43克重均分子量为约20,000的聚乙烯亚胺与43克水和50克平均分子量为约600的聚丙二醇一起导入一个压热器中。然后，在90-100℃温度和最大4巴的压力下搅拌的同时，加入58克氧化丙烯，历时30分钟。在此温度下再搅拌1小时后，混合物冷却至约80℃，加入20克50重量％的KOH水溶液，通过将压力降至10毫巴和在不高于120℃温度下，去除所有水。
实施例3b
在有聚丙二醇存在的情况下进一步烷氧基化(第二步)
实施例3a的产物母体与进一步的氧化丙烯反应，就象实施例1b中那样。此实施例中的反应时间为1300分钟。
实施例4a
聚乙烯亚胺在水和三乙醇胺中的一烷氧基化(第一步)
重复实施例3a，差别在于用50克三乙醇胺代替聚丙二醇。
实施例4b
在有三乙醇胺存在的情况下进一步烷氧基化(第二步)
实施例4a的产物母体与进一步的氧化丙烯反应，就象实施例1b中那样。此实施例中的反应时间为1260分钟。
Claims (3)
1.一种分二步制备寡胺或聚胺的烷氧基化物的方法，其中每个分子带3～10个氮原子的聚亚烷基聚胺、重均分子量为600～10,000,000的聚乙烯胺或重均分子量为2000～50,000的聚乙烯亚胺被用作寡胺或聚胺，在其第一步，在有水或水与醇和/或酸的混合物存在而无中性或碱性催化剂存在的情况下，在寡胺或聚胺上每个NH基加成1分子烯化氧，在其第二步，去除水和酸后，在有一种传统的中性或碱性催化剂存在的情况下，进行与进一步的烯化氧的反应，其中在第二步进行前，加入一种来自以下组群的有机溶剂或稀释剂或其混合物：(f)芳香烃。
2.根据权利要求1的方法，其中加入的有机溶剂或稀释剂的量为2～400重量份，以来自第一步的加合物的重量为基础。
3.根据权利要求1或2的方法，氧化乙烯、氧化丙烯、环氧丁烷或其混合物被用作烯化氧。
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| DE102009041983A1 (de) * | 2009-09-17 | 2011-04-07 | Clariant International Ltd. | Alkoxylierte Trialkanolaminkondensate und deren Verwendung als Emulsionsspalter |
| EP2797873B1 (en) * | 2011-12-29 | 2015-12-09 | Taminco | Process for the production of choline hydroxide |
| BR102017022800A2 (pt) * | 2017-10-23 | 2019-05-07 | Oxiteno S A Ind E Comercio | processo de alcoxilação de uma composição polimérica e uso de uma composição polimérica alcoxilada |
| WO2020121031A1 (en) | 2018-12-12 | 2020-06-18 | Sabic Global Technologies B.V. | Polyethylenimine as a new emulsion breaker for quench water systems |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907701A (en) * | 1972-06-07 | 1975-09-23 | Basf Ag | Demulsifying crude oil emulsions |
| FR2335492A1 (fr) * | 1975-12-19 | 1977-07-15 | Bayer Ag | Procede perfectionne pour preparer des polyamines aromatiques polycycliques par condensat-acide d'amines aromatiques avec le formaldehyde |
| US4705834A (en) * | 1983-12-28 | 1987-11-10 | Basf Aktiengesellschaft | Crosslinked oxyalkylated polyalkylenepolyamines |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1027869C (zh) * | 1991-07-23 | 1995-03-15 | 中国石油天然气总公司胜利设计院 | 阳离子聚醚型反相破乳剂的制备方法 |
| DE4136661A1 (de) * | 1991-11-07 | 1993-05-13 | Basf Ag | Erdoelemulsionsspalter |
-
1994
- 1994-10-06 DE DE4435688A patent/DE4435688A1/de not_active Withdrawn
-
1995
- 1995-09-26 BR BR9509248A patent/BR9509248A/pt not_active IP Right Cessation
- 1995-09-26 CA CA002201782A patent/CA2201782C/en not_active Expired - Fee Related
- 1995-09-26 WO PCT/EP1995/003809 patent/WO1996011225A1/de not_active Application Discontinuation
- 1995-09-26 ES ES95935382T patent/ES2131336T3/es not_active Expired - Lifetime
- 1995-09-26 MX MX9702367A patent/MX198647B/es unknown
- 1995-09-26 DE DE59505927T patent/DE59505927D1/de not_active Expired - Lifetime
- 1995-09-26 AU AU37425/95A patent/AU3742595A/en not_active Abandoned
- 1995-09-26 DK DK95935382T patent/DK0784645T3/da active
- 1995-09-26 US US08/809,720 patent/US5846453A/en not_active Expired - Lifetime
- 1995-09-26 CN CN95195536A patent/CN1087316C/zh not_active Expired - Fee Related
- 1995-09-26 JP JP51229296A patent/JP3955319B2/ja not_active Expired - Fee Related
- 1995-09-26 EP EP95935382A patent/EP0784645B1/de not_active Expired - Lifetime
- 1995-09-26 CN CNB011435739A patent/CN100415855C/zh not_active Expired - Fee Related
- 1995-09-26 KR KR1019970702216A patent/KR970706335A/ko not_active Application Discontinuation
-
1997
- 1997-04-04 FI FI971418A patent/FI971418A0/fi unknown
- 1997-04-04 NO NO971540A patent/NO971540D0/no not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907701A (en) * | 1972-06-07 | 1975-09-23 | Basf Ag | Demulsifying crude oil emulsions |
| FR2335492A1 (fr) * | 1975-12-19 | 1977-07-15 | Bayer Ag | Procede perfectionne pour preparer des polyamines aromatiques polycycliques par condensat-acide d'amines aromatiques avec le formaldehyde |
| US4705834A (en) * | 1983-12-28 | 1987-11-10 | Basf Aktiengesellschaft | Crosslinked oxyalkylated polyalkylenepolyamines |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0784645T3 (da) | 1999-11-01 |
| BR9509248A (pt) | 1997-10-21 |
| JPH10506945A (ja) | 1998-07-07 |
| CN1375543A (zh) | 2002-10-23 |
| CA2201782C (en) | 2000-11-28 |
| FI971418A (fi) | 1997-04-04 |
| ES2131336T3 (es) | 1999-07-16 |
| MX9702367A (es) | 1997-06-28 |
| DE4435688A1 (de) | 1996-04-11 |
| CN1160409A (zh) | 1997-09-24 |
| EP0784645B1 (de) | 1999-05-12 |
| NO971540L (no) | 1997-04-04 |
| NO971540D0 (no) | 1997-04-04 |
| CN100415855C (zh) | 2008-09-03 |
| MX198647B (es) | 2000-09-18 |
| DE59505927D1 (de) | 1999-06-17 |
| KR970706335A (ko) | 1997-11-03 |
| WO1996011225A1 (de) | 1996-04-18 |
| US5846453A (en) | 1998-12-08 |
| JP3955319B2 (ja) | 2007-08-08 |
| EP0784645A1 (de) | 1997-07-23 |
| CA2201782A1 (en) | 1996-04-18 |
| FI971418A0 (fi) | 1997-04-04 |
| AU3742595A (en) | 1996-05-02 |
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