CN1379793A - 生产两性离子聚胺的方法 - Google Patents
生产两性离子聚胺的方法 Download PDFInfo
- Publication number
- CN1379793A CN1379793A CN00814489A CN00814489A CN1379793A CN 1379793 A CN1379793 A CN 1379793A CN 00814489 A CN00814489 A CN 00814489A CN 00814489 A CN00814489 A CN 00814489A CN 1379793 A CN1379793 A CN 1379793A
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- CN
- China
- Prior art keywords
- polyamine
- alkoxylate
- quaternized
- sulfation
- nitrogen
- 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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- 229920000768 polyamine Polymers 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 49
- 230000019635 sulfation Effects 0.000 claims abstract description 29
- 238000005670 sulfation reaction Methods 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 25
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 17
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 239000011552 falling film Substances 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000005956 quaternization reaction Methods 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 230000001180 sulfating effect Effects 0.000 abstract description 10
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- -1 polyoxyethylene Polymers 0.000 description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- 229940059574 pentaerithrityl Drugs 0.000 description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 10
- 229920001515 polyalkylene glycol Polymers 0.000 description 10
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical compound NCCCN1CCNCC1 UVLSCMIEPPWCHZ-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000005576 amination reaction Methods 0.000 description 8
- 239000007859 condensation product Substances 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Natural products NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 8
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000007046 ethoxylation reaction Methods 0.000 description 5
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 5
- QSINQXYQYVRZKG-UHFFFAOYSA-N n'-(2-aminoethyl)hexane-1,6-diamine Chemical compound NCCCCCCNCCN QSINQXYQYVRZKG-UHFFFAOYSA-N 0.000 description 5
- AEBNSTBDWXUNIE-UHFFFAOYSA-N n'-(3-aminopropyl)hexane-1,6-diamine Chemical compound NCCCCCCNCCCN AEBNSTBDWXUNIE-UHFFFAOYSA-N 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- OQSRMUINIWSZGC-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ylidenemethanamine Chemical compound NC=C1CC=CC=C1 OQSRMUINIWSZGC-UHFFFAOYSA-N 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical group NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 3
- BOGFHOWTVGAYFK-UHFFFAOYSA-N 1-[2-(2-propoxyethoxy)ethoxy]propane Chemical compound CCCOCCOCCOCCC BOGFHOWTVGAYFK-UHFFFAOYSA-N 0.000 description 2
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 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 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical group OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 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 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OMKZWUPRGQMQJC-UHFFFAOYSA-N n'-[3-(dimethylamino)propyl]propane-1,3-diamine Chemical compound CN(C)CCCNCCCN OMKZWUPRGQMQJC-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
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- QTKDDPSHNLZGRO-UHFFFAOYSA-N 4-methylcyclohexane-1,3-diamine Chemical compound CC1CCC(N)CC1N QTKDDPSHNLZGRO-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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Abstract
一种通过将烷氧基化和季铵化的胺硫酸化以及随后中和而生产两性离子聚胺的方法,包括在不存在溶剂的情况下于至多90℃的温度下用含三氧化硫的惰性气体将分子中具有至少两个叔或季氨基氮原子且含有至少一个季铵化氮原子的烷氧基化和季铵化的聚胺以具有100μm-4mm厚度的膜形式连续硫酸化。
Description
本发明涉及一种通过将烷氧基化和季铵化的聚胺硫酸化以及随后中和而生产两性离子聚胺的方法。
发明背景
EP-A-0,111,976和EP-A-0,112,592涉及两性离子聚胺,其例如通过烷氧基化聚亚烷基胺如三亚乙基胺或四亚乙基五胺、季铵化该烷氧基化的聚亚烷基胺以及随后用氯磺酸在惰性溶剂中硫酸化而得到。惰性溶剂以及在反应过程中形成的氯化氢必须从反应产物中除去。
未用硫酸化试剂如氯磺酸或三氧化硫季铵化的烷氧基化胺和烷氧基化聚胺的硫酸化公开于DE-A-2,557,563中。
根据美国专利4,138,371中所述的方法,两性离子单胺通过使1摩尔式RNH2的胺与5-50摩尔环氧乙烷的反应产物与0.5-1.0摩尔季铵化试剂如硫酸二甲酯或烷基卤反应,然后使所得季铵化聚乙氧基化单胺与0.1-2.0摩尔选自氯磺酸、三氧化硫、氨基磺酸和发烟硫酸的硫酸化试剂反应而制备。
在乙氧基化化合物的硫酸化过程中,形成作为副产物的1,4-二噁烷。由于毒性原因,二噁烷应该从硫酸化聚乙二醇中除去。美国专利4,285,881涉及一种通过用水蒸气在25-150℃的温度下在降膜汽提器中处理含二噁烷的混合物而从醚硫酸盐中除去二噁烷的方法。根据其他方法,二噁烷在减压下、以共沸方式或用沸石(zeolithe)从聚乙二醇醚硫酸盐中除去,参见DE-A-3,126,175,DE-A-3,044,488和DE-A-3,740,695。现有技术的硫酸化方法的另一缺点是反应产物或多或少出现着色。
因此本发明的目的是提供一种将烷氧基化和季铵化聚胺硫酸化的方法,该方法得到的反应产物与由现有技术的方法得到的产物相比具有较低含量的二噁烷和较低的色数。
发明概述
上述目的由一种通过将烷氧基化和季铵化的胺硫酸化以及随后中和而生产两性离子聚胺的方法达到,该方法包括在不存在溶剂的情况下于至多90℃的温度下用含三氧化硫的惰性气体将分子中具有至少两个叔或季胺氮原子且含有至少一个季铵化氮原子的烷氧基化和季铵化的聚胺以具有100μm-4mm厚度的膜形式连续硫酸化。该方法优选在降膜反应器中用三氧化磁/空气或氮气(nitro)混合物进行。烷氧基化和季铵化聚胺含有2-10氮原子和每个氮原子含有至少20个烯化氧单元且季铵化程度至少为80%。发明详述
根据本发明,硫酸化分子中具有至少两个叔或季胺氮原子且含有至少一个季铵化氮原子的烷氧基化和季铵化聚胺。硫酸化的产物例如通过烷氧基化和季铵化从具有2-10个氮原子的聚胺得到。
特别有用的聚胺是六亚甲基二胺、双(六亚甲基二胺)和聚醚聚胺。
聚醚聚胺可以是线性或支化的且含有2-10,优选2-6和最优选2-4个氮原子且分子量为100-800,优选120-500。聚醚聚胺可以用下式表述:
H2N-(B-O)m-(D-O)o-(B-O)p-B-NH2 (I)
其中:
B为线性或支化C2-C4-亚烷基,
D为线性、支化或环状的C5-C16-亚烷基,C4-C16-氧杂亚烷基或C5-C16-氮杂亚烷基,
m为0-7,
o为0或1,
p为0-6,条件是m+o+p≥1直到9。
上式I化合物的实例是氢化的氰基甲基化C3-C12-二醇。这些化合物通过首先使二醇与甲醛和氰化氢反应和随后在氨的存在下氢化加成产物而得到。该生产胺的方法下文称为氨基乙基化。这样生产的化合物尤其是1,9-二氨基-3,7-二氧杂壬烷,1,10-二氨基-3,8-二氧杂癸烷,1,12-二氨基-3,10-十二烷和1,14-二氨基-3,12-十四烷。
其他式I化合物是α,ω-二氨基聚亚烷基二醇,其通过氢化氰基甲基化聚亚烷基二醇(氨基乙基化)得到。合适的聚亚烷基二醇优选含有2-10个重复单元且衍生于聚乙二醇、聚丙二醇、聚丁二醇和聚四氢呋喃。聚亚烷基二醇可以以统计分布或以嵌段形式含有重复单元。这类化合物的实例是1,5-二氨基-3-氧杂戊烷、1,8-二氨基-3,6-二氧杂辛烷,1,11-二氨基-3,6,9-三氧杂-十一烷,1,5-二氨基-1,4-二甲基-3-氧杂庚烷,1,8-二氨基-1,4,7-三甲基-3,6-二氧杂癸烷,1,9-二氨基-5-氧杂-壬烷和1,14-二氨基-5,10-二氧杂-十三烷。
式I的其他化合物是氢化的氰基乙基化C2-C12-二醇,其通过使二醇与丙烯腈以约1-2的摩尔比以Michael型加成反应进行反应并在氨存在下氢化如此得到的Michael加成产物而得到。该生产胺的方法在下文称为氨基丙基化。这类化合物的实例是1,10-二氨基-4,7-二氧杂-癸烷,1,10-二氨基-5-甲基-4,7-二氧杂-十一烷,1,11-二氨基-6,6-二甲基-4,8-二氧杂-十三烷,1,12-二氨基-4,9-二氧杂-十二烷和1,14-二氨基-4,11-二氧杂-十四烷。
另一类式I的化合物是氢化的氰基乙基化聚亚烷基二醇,其具有2-10个重复单元。这些化合物通过使聚亚烷基二醇与丙烯腈根据到丙烯腈上的Michael加成以1-2的摩尔比进行反应并氢化加成产物(氨基丙基化)而得到。合适的聚亚烷基二醇是上面所述的那些。这类化合物的实例是1,13-二氨基-4,7,10-三氧杂-十三烷,1,13-二氨基-5,8-二甲基-4,7,10-三氧杂-十一烷,1,16-二氨基-4,7,10,13-四氧杂-十六烷,1,16-二氨基-5,8,11-三甲基-4,7,10,13-四氧杂-十六烷和1,17-二氨基-4,9,14-三氧杂-十七烷。
其他合适的这类胺通过含有含7-10个环氧乙烷单元和2-5个环氧丙烷单元的嵌段共聚物的聚乙二醇、聚丙二醇或聚四氢呋喃的胺化得到,即通过使氨与所述嵌段共聚物在NH2基团与嵌段共聚物的OH端基进行交换的情况下反应而得到。
优选衍生于聚乙二醇和聚乙二醇的氨基乙基化、氨基丙基化或胺化聚亚烷基二醇在端基处与1-2摩尔环氧丙烷或环氧丁烷或聚四氢呋喃反应。在这些聚亚烷基二醇中优选的烯化氧单元总数为3-9,最优选为3-6。
聚醚聚胺可以具有下式:
H2N-(B-O)m-E-(O-B)m-NH2 (II)
其中
B为线性或支化C2-C4-亚烷基,
R2为-H,C1-C6-烷基,
T为,-(O-B)m-O-H
以及
i为1-4,
m为0-7。
式II的聚醚聚胺衍生于支化结构,其可以通过用每个多元醇中的OH基团为1-4分子的环氧乙烷、环氧丙烷、环氧丁烷或其混合物烷氧基化并随后与氨反应以将OH基团转化为NH基团而由具有3-6个羟基的多元醇如甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、季戊四醇、山梨醇和甘露糖醇得到。生产具有间隔基团的式IV的胺的其他方法为氨基甲基化或氨基丙基化具有3-6个羟基的上述多元醇。
该类化合物的实例是1摩尔甘油与3-7摩尔环氧乙烷的胺化反应产物、通过使1摩尔甘油与3摩尔环氧丙烷反应并随后与7摩尔环氧乙烷反应得到的胺化嵌段共聚物、1摩尔三羟甲基丙烷与3-7摩尔环氧乙烷的胺化反应产物、通过使1摩尔三羟甲基丙烷与3摩尔环氧丙烷反应并进一步与7摩尔环氧乙烷反应得到的嵌段共聚物的胺化反应产物、含有4-8个环氧乙烷单元的乙氧基化季戊四醇的胺化反应产物和含有4个环氧丙烷单元和8个环氧乙烷单元的嵌段的烷氧基化季戊四醇的胺化反应产物。特别有用的是含有9个环氧丙烷单元的胺化的丙氧基化三羟甲基丙烷。
式II的优选聚醚聚胺是由甘油、三羟甲基丙烷和季戊四醇得到的那些。尤其优选的是通过氨基丙基化得到的那些。
聚醚聚胺还可以由下式表征:
H2N-(CH2)q-O-E-O-(CH2)q-NH2 (III)
R1为H,CH3,C2H5
以及
q为2或3。
式V的优选胺是通过氨基乙基化甘油、三羟甲基丙烷或季戊四醇得到的反应产物或所述醇的氨基丙基化反应产物,条件是多元醇的所有OH基团分别被氨基乙基化或氨基丙基化。
合适的聚醚聚胺例如可以具有下式:
聚醚聚胺的其他描述可以由下式给出:
H2N-(CH2)q-O-D-O-(CH2)q-NH2 (IV)
其中
D为 -CH2-CH2-CH2-CH2-,-CH2-CH2-O-CH2-CH2-,
-CH2-CH2-CH2-CH2-CH2-CH2-,
q为2或3。
优选的式IV聚胺是选自乙二醇、丙二醇、丁二醇-1,4、己二醇-1,6和二甘醇的双(氨基乙基化)或双(氨基丙基化)醇。
聚胺还可以衍生于线性或支化疏水性聚胺,其可以由下式描述:
其中在式V,VI和VII中,
B为C2-C16-亚烷基,C5-C15-亚环烷基,
D为C4-C16-亚烷基,C5-C15-亚环烷基,
o为1为2以及
其中在式VIII中,R=C1-C22-烷基或C7-C22芳烷基且
n=2-6,以及
α,ω-二胺在氮原子之间具有选自C8-C16-亚烷基和C5-C15-亚环烷基的间隔基团。
特别有用的是选自双(六亚甲基)三胺,N,N’-双(3-氨基丙基)哌嗪,N,N’-双(2-氨基乙基)哌嗪和N,N’-双(3-氨基丙基)六亚甲基二胺的聚胺。
含有C8-C16-亚烷基作为间隔基团的聚胺例如为1,8-二氨基辛烷,1,10-二氨基癸烷和1,12-二氨基十二烷。含有上述式V-VIII的间隔基团的合适聚胺的实例是二亚丙基三胺,三亚丙基四胺,双(六亚甲基)三胺,双(八亚甲基)三胺,氨基乙基亚丙基二胺,氨基乙基亚丁基二胺,氨基乙基六亚甲基二胺,N,N’-双(氨基乙基)亚丙基二胺,N,N’-双(氨基乙基)亚丁基二胺,N,N’-双(氨基乙基)六亚甲基二胺,N,N’-双(氨基丙基)亚乙基二胺,N,N’-双(氨基丙基)亚丁基二胺,N,N’-双(氨基丙基)亚丁基二胺,N,N’-双(氨基丙基)六亚甲基二胺,N,N’-双(氨基丙基)亚乙基二胺,N,N-双(3-氨基丙基)-N-甲基胺,N-(二甲氨基丙基)亚丙基二胺,N,N’-二甲基-1,3-二氨基丙烷,N,N-双(3-氨基丙基)-N-辛基胺和N,N-双(3-氨基丙基)-N-乙基胺。
具有由环状C5-C15-亚烷基组成的间隔基团的聚胺例如为1,3-亚环己基二胺,4-甲基-1,3-亚环己基二胺,2-甲基-1,3-亚环己基二胺,异佛尔酮二胺和4,4’-二氨基(双亚环己基)甲烷。
含有其他环状间隔基团的聚胺例如为o-,m-,和p-二(氨基亚甲基)苯,N,N’-双(氨基乙基)哌嗪,N,N’-双(氨基丙基)哌嗪和N-氨基丙基哌嗪。
优选的聚胺在分子中含有2-6氮原子。该类化合物的实例是乙二胺,丙二胺-1,3,丁二胺-1,4,新戊基二胺,六亚甲基二胺-1,6,二亚乙基三胺,四亚乙基五胺,2-(乙基氨基)乙基胺,3-(甲基氨基)丙基胺,3-(环己基氨基)丙基胺,3-(2-氨基乙基)氨基丙基胺,2-(二乙氨基)乙基胺,3-(二甲氨基)丙基胺,二甲基二亚丙基三胺,4-氨基乙基辛烷-1,8-二胺,3-(二乙氨基)丙基胺,N,N-二乙基-1,4-戊二胺,氨基乙基哌嗪,氨基丙基哌嗪,N,N-双(氨基丙基)己基胺,N,N-二甲基二亚丙基三胺,N,N-双(3-二甲氨基丙基)胺,N,N’-1,2-亚乙基双-(1,3-丙二胺),N-(氨基乙基)哌嗪,N-(2-咪唑)哌嗪,N-乙基哌嗪,N-(羟乙基)哌嗪,N-(氨基丙基)哌嗪,N-(氨基乙基)吗啉,N-(氨基丙基)吗啉,N-(氨基乙基)咪唑,N-(氨基丙基)咪唑,N-(氨基乙基)六亚甲基二胺,N-(氨基丙基)六亚甲基二胺,N-(氨基乙基)亚乙基二胺,N-(氨基丙基)亚乙基二胺,N-(氨基乙基)亚丁基二胺,双(氨基乙基)六亚甲基二胺和双(氨基乙基)亚乙基二胺。
除了上述聚胺外,适合作为生产两性离子聚胺的原料的聚胺是可以通过使如下两种成分反应得到的缩合产物:
(i)脂族或芳脂族单胺或含有2-5个伯、仲或叔氮基团的聚胺,
(ii)选自表卤代醇、具有2-4个缩水甘油基的聚缩水甘油基醚、具有2-4个卤代醇基团的多卤代醇、二羧酸、其酯氯化物、酰胺或酸酐、二异氰酸酯、脲和蜜胺的交联剂,摩尔比(i)∶(ii)为20∶1-1∶1,基于(i)的胺中氨基摩尔量和(ii)的交联剂中反应性基团摩尔量,所述反应导致形成分子量为150-1,500的交联聚胺。
制备缩合产物的合适胺(i)例如为伯C1-C22-烷基胺,C7-C22-芳烷基胺,C6-C22-环烷基胺,单羟基-C2-C4-烷基胺,二羟基-C2-C4-烷基胺,三羟基-C2-C4-烷基胺,线性或支化C2-C12-亚烷基二胺,C8-C22-亚芳烷基二胺,C7-C22-亚环烷基二胺,在氮原子之间含有1-10个烷氧基单元的α,ω-聚醚二胺以及具有2-4个C2-C12-亚烷基胺单元的线性或支化聚亚烷基聚胺。
上述类型的胺的实例是甲基胺,乙基胺,丙基胺,丁基胺,辛基胺,2-乙基己基胺,苄基胺,
乙醇胺,2-羟基丙基胺,2-羟基丁基胺,二乙醇胺,双(2-羟基丙基)胺,双(2-羟基丁基)胺,三乙醇胺,三(2-羟基丙基胺),三(2-羟基丁基胺),
乙二胺,1,3-二氨基丙烷,1,4-二氨基丁烷,1,6-二氨基己烷,1,3-二氨基-3,3-二甲基丙烷,哌嗪,4,9-二氧杂十二烷二胺-1,12,4,7,10-三氧杂十三烷二胺-1,13,4,11-二氧杂十四烷二胺-1,14,具有2-10个乙二醇单元的α,ω-二氨基聚乙二醇,具有2-10个丙二醇单元的α,ω-二氨基聚丙二醇,具有2-10个氧杂亚丁基单元的α,ω-二氨基聚四氢呋喃,异佛尔酮二胺(Isophoronedimine),双(4-氨基环己基)甲烷,1,3-二氨基环己烷,1,3-二氨基-2-甲基环己烷,1,3-二氨基-4-甲基环己烷,o-二(氨基亚甲基)苯,p-二(氨基亚甲基)苯,m-二(氨基亚甲基)苯
二亚乙基三胺,二亚丙基三胺,N-(氨基乙基)亚丙基二胺,N,N-双(氨基丙基)甲基胺,N(氨基乙基)亚丁基二胺,N,N-双(氨基丙基)丁基胺,N,N-双(氨基丙基)辛基胺,N(氨基乙基)六亚甲基二胺,N-(氨基丙基)六亚甲基二胺,双-六亚甲基三胺,N-二甲氨基丙基亚乙基二胺,N-(2-氨基乙基)哌嗪,N-(3-氨基丙基)哌嗪
双(氨基乙基)哌嗪,双(氨基丙基)哌嗪,三亚乙基四胺,四亚乙基五胺,N,N’-双(氨基丙基)亚乙基二胺,三亚丙基四胺,N,N’-双(氨基丙基)亚丁基二胺-1,4,N,N’-双(氨基乙基)六亚甲基二胺,N,N’-双(氨基丙基)六亚甲基二胺
尤其优选用于制备缩合产物的胺是二乙醇胺,双-(2-羟基丙基)胺,1,3-二氨基丙烷,1,4-二氨基丁烷,1,6-二氨基己烷,4,9-二氧杂十二烷二胺-1,12,4,7,10-三氧杂十三烷二胺-1,13,二亚乙基三胺,二亚丙基三胺,双-六亚甲基三胺和双(氨基丙基)哌嗪。
含有至少两个官能基团的合适交联剂(ii)例如为具有至少4个碳原子的α-,ω-或邻(vicinal)二氯链烷烃如1,4-二氯丁烷和1,6-二氯己烷。其他合适的交联剂为缩水甘油基卤化物,如表氯醇,多元醇的双氯代醇醚,多元醇的多氯代醇醚,聚亚烷基二醇的双氯代醇醚,氯甲酸酯,二元饱和二羧酸的氯化物,光气和尤其是不含卤素的交联剂。
优选使用的交联剂为表氯醇和乙二醇、具有2-20个,尤其是2-14个乙二醇单元的聚乙二醇、丙二醇、聚丙二醇、环氧乙烷和环氧丙烷的共聚物、丁二醇-1,4、新戊二醇、己二醇-1,6、间苯二酚、甘油、二甘油和季戊四醇的双氯代醇醚。其他优选的交联剂是三羟甲基丙烷、甘油和季戊四醇的三氯代醇醚以及1摩尔季戊四醇与4摩尔表氯醇的反应产物。为至少双官能且不含卤素的交联剂优选选自:
(1)蜜胺和/或脲,
(2)二元饱和羧酸及各自衍生于该羧酸的酯、酰胺和酸酐,
(3)双环氧化物、聚环氧化物、α,ω-二异氰酸酯如六亚甲基二异氰酸酯
以及所述交联剂的混合物。双环氧化物和聚环氧化物可以由亚烷基二醇和聚乙二醇的双氯代醇醚得到或由多元醇如三羟甲基丙烷和季戊四醇的三和四氯代醇醚得到。
合适的不含卤素的(2)类交联剂的实例是二元饱和羧酸如C4-C12-二羧酸,还有衍生于所述羧酸的盐、二酯和二酰胺。这类酸的实例是琥珀酸、己二酸、对苯二甲酸、邻苯二甲酸和α,ω-十二烷酸。
可以考虑的二羧酸的酯优选衍生于具有1-4个碳原子的醇。合适的二羧酸酯的实例是琥珀酸二甲酯、琥珀酸二乙酯、琥珀酸二异丙酯、琥珀酸二正丙酯、琥珀酸二异丁酯、己二酸二甲酯、己二酸二乙酯和己二酸二异丙酯。
合适的二羧酸酐的实例是邻苯二甲酸酐和琥珀酸酐。
优选的第(3)类化合物是乙二醇、具有2-20个环氧乙烷单元的聚乙二醇、丙二醇、聚丙二醇醚、环氧乙烷和环氧丙烷的共聚物、丁二醇-1,4、新戊二醇、己二醇-1,6和间苯二酚的双缩水甘油基醚以及二异氰酸酯如六亚甲基二异氰酸酯。
还优选使用交联剂的混合物,例如
-乙二醇的二缩水甘油醚与乙二醇的双氯代醇醚的混合物,
-具有2-20个乙二醇单元的聚乙二醇的二缩水甘油醚与具有2-20个乙二醇单元的聚乙二醇的双氯代醇醚的混合物
交联的聚胺可以通过使至少一种(i)类化合物与至少一种(ii)类化合物反应得到。该反应可以直接(in substance)、以在惰性溶剂中的溶液或以在含水介质中的分散液或在惰性溶剂中进行。
优选的这类聚胺是其中交联的聚胺骨架通过如下两种成分反应得到的那些
(i)选自二乙醇胺、双(2-羟基丙基)胺、1,3-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷、4,9-二氧杂十二烷二胺-1,12、4,7,10-三氧杂十三烷二胺-1,13、二亚乙基三胺、二亚丙基三胺、双(六亚甲基)三胺和双(氨基丙基)哌嗪的胺
(ii)选自表氯醇、C2-C6-亚烷基二醇的双氯代醇醚、具有2-14个乙二醇单元的聚乙二醇的双氯代醇醚、三羟甲基丙烷的三氯代醇醚、甘油的三氯代醇醚、季戊四醇的四氯代醇醚、乙二醇的双缩水甘油基醚、具有2-14个乙二醇单元的聚乙二醇的双缩水甘油基醚、三羟甲基丙烷的三缩水甘油基醚、季戊四醇的四缩水甘油基醚、脲、蜜胺、己二酸、对苯二甲酸、邻苯二甲酸、α,ω-十二烷酸和六亚甲基二异氰酸酯的交联剂。
为了制备用于用三氧化硫硫酸化的原料,将上述聚胺烷氧基化,然后季铵化。聚烷氧基化的产物具有下式的基团:
-(A)n-H (IX) 或
其中
A为环氧乙烷单元、环氧丙烷单元、环氧丁烷单元和四氢呋喃单元,且n为1-50的数。
它们通过使上述聚胺之一或其混合物与至少一种C2-C4-烯化氧或四氢呋喃以其比率使得每一聚胺分子含有至少20个,优选50-200个烯化氧单元进行反应而制备。环氧乙烷和环氧丙烷是优选的烷氧基化试剂。若将烯化氧的混合物加成于氨基氮上,则聚合的烯化氧可以以统计分布或以嵌段存在。例如可以首先加入10-20个环氧乙烷单元/聚胺中的NH基团,然后加入5-10个环氧丙烷单元,反之亦然。
最优选单独使用环氧乙烷或使用1-15%环氧丙烷或1-10%环氧丁烷分别与85-99、90-99%环氧乙烷的组合。若使用环氧乙烷与环氧丙烷或环氧丁烷的组合,优选环氧丙烷或环氧丁烷首先与聚胺的NH和OH-基团反应,然后加入环氧乙烷。优选将聚胺乙氧基化。
为了生产具有式X端基的聚胺,每个所述聚胺的NH基团加入至多1个缩水甘油单元,以使至少50%至100%的聚胺的NH基团被一个缩水甘油单元取代。该反应产物然后如上所述被烷氧基化。
烷氧基化聚胺通过与季铵化试剂反应而被季铵化。合适的季铵化试剂是例如C1-C22-烷基卤、C7-C22-芳烷基卤、硫酸C1-C2-二烷基酯或烯化氧。季铵化试剂的实例是硫酸二甲酯、硫酸二乙酯、甲基氯、乙基氯、甲基溴、乙基溴、丁基溴、己基氯、苄基氯、苄基溴、环氧乙烷或环氧丙烷。最优选的季铵化试剂是硫酸二烷基酯,尤其是硫酸二甲酯和硫酸二乙酯。可以季铵化高达100%的聚醚聚胺的叔氮原子。季铵化程度例如是10-100%,优选至少80%和更优选大于90%至100%。在大多数情况下,完全季铵化烷氧基化的聚胺。
用于硫酸化步骤的原料是每分子含有2-10个氮原子和至少20个烯化氧单元且季铵化程度至少为80%的烷氧基化和季铵化聚胺。更优选烷氧基化和季铵化聚胺每分子含有2-6个氮原子和50-200个烯化氧单元且季铵化程度大于90%。最优选将完全季铵化的烷氧基化聚胺用作硫酸化的原料。
上述原料在不存在溶剂的情况下硫酸化。但可以用如下化合物稀释烷氧基化和季铵化聚胺,该化合物降低所述聚胺的粘度并与三氧化硫反应生成用于织物洗涤剂或清洁组合物中的产物。该类化合物例如是二甲苯、枯烯、烷氧基化醇、单胺或酰胺。烷氧基化和季铵化的聚胺的粘度在20-1,500mPas范围内,最优选40-800mPas(在60℃的温度下于Brookfield粘度计中测定)。
烷氧基化和季铵化的聚胺以具有100μm-4mm,优选200μm-2mm厚度的膜形式在至多90℃的温度下用含三氧化硫的惰性气体连续硫酸化。空气和氮气是硫酸化步骤的最优选惰性气体。硫酸化可以用含有1-10重量%三氧化硫的三氧化硫/空气混合物或含有1-10重量%三氧化硫的三氧化硫/氮气混合物进行。惰性气体优选被加热到进行硫酸化的温度且随后与气态三氧化硫混合。空气或氮气与三氧化硫的混合物优选含有1.2-4重量%的三氧化硫。该反应通常在根据降膜原理操作的反应器中进行。硫酸化可以在各种类型的降膜反应器中进行。例如将烷氧基化和季铵化的聚胺导入垂直放置的反应器的顶部并将含三氧化硫的惰性气体导入该反应器的底部。这意味着硫酸化优选逆流进行。这类反应器公开于<阴离子表面活性剂>,表面活性剂科学丛书,第56卷,第647-697页(1996)(引作参考)。
在另一优选的方法中,烷氧基化季聚胺被导入多管垂直放置的反应器顶部,而含三氧化硫的惰性气体也从顶部导入。这意味着硫酸化也可以在管式反应器中并流进行。
反应温度通常为20-80℃,优选50-70℃。三氧化硫和惰性气体的混合物通常含有20-60m3,优选35-45m3惰性气体/kg三氧化硫。烷氧基化和季铵化的聚胺的羟基端基与三氧化硫的摩尔比例如为1.0∶0.2-1.0∶1.2。
硫酸化所必需的三氧化硫量可以通过测量反应产物的酸值而控制。若烷氧基化和季铵化聚胺的硫酸化在第一次通过时不完全,则可以将反应产物转移到其他反应器中在上面所给温度范围内进行后反应。后反应可以在比反应温度高或低的温度下进行。优选将在第一次通过时得到的硫酸化产物导入至少一个其他降膜反应器中进行后反应。后反应可以在根据降膜原理操作的反应器中连续进行或在搅拌容器中断续进行。
两性离子聚胺的重均分子量Mw至多为9,000,优选1,500-7,500且更优选2,000-7,000。两性离子聚醚聚胺可溶于水中或至少易分散于水中。它们是净阴离子性的,即阴离子电荷(SO3H基团)的平均数目超过源于季铵化胺基的阳离子电荷的平均数目的倍数例如大于1.2,更优选大于1.5且最优选大于1.8。
与由现有技术方法生产的那些两性离子产物相比,本发明方法得到的两性离子产物含有较低的二噁烷-1,4且还具有较好的色数。
用碱如碱金属氢氧化物、碱土金属氢氧化物、氨和胺中和硫酸化的烷氧基化和季铵化聚胺。碱优选以水溶液使用。合适的碱例如是氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、氢氧化钙、氢氧化镁、吗啉、乙醇胺、二乙醇胺、三乙醇胺、环己基胺和二环己基胺。
两性离子聚胺在衣用洗涤剂组合物中用作添加剂,提供改进的亲水性泥土、尤其是粘土除去效果。它们还可以用于清洁剂、化妆品和药物制剂中并用于照相工业中。
季铵化和硫酸化的程度由1H-NMR测定。胺值根据DIN 16 945由胺滴定测定。色数根据DIN 4630测定。
实施例1
将1摩尔六亚甲基二胺与96摩尔环氧乙烷的反应产物用硫酸二甲酯完全季铵化,然后用含7.0体积%三氧化硫的三氧化硫/空气混合物在一个管式垂直放置的管式降膜反应器(长95cm,内径5cm)中于55℃的温度下连续硫酸化。将700g/h的烷氧基化和季铵化的六亚甲基二胺导入反应器的顶部并以具有1.2mm平均厚度的膜形式向下移动,与55℃的三氧化硫/空气混合物(52g/h三氧化硫和190l/h空气)并流接触。烷氧基化和季铵化的六亚甲基二胺中OH基团与三氧化硫的硫酸化比例为1∶0.92。供入降膜反应器中的三氧化硫量通过在反应器底部得到的硫酸化产物的酸值控制。酸值为48。
收集在反应器底部得到的硫酸化的烷氧基化和季铵化六亚甲基二胺并通过将750g硫酸化产物加入到45ml 25重量%强度的氢氧化钠水溶液和700ml水的混合物中而分批中和,同时维持反应混合物的温度为30℃。然后通过进一步加入氢氧化钠水溶液而将反应混合物的pH调节为10。反应混合物含有750ppm二噁烷且根据Gardner的色数(在50重量%强度的溶液中测定)为1.4。反应产物含有1.5重量%尚未硫酸化的原料。实施例2
将1摩尔4,7-二氧杂十二烷二胺和80摩尔环氧乙烷的反应产物用硫酸二甲酯完全季铵化,然后用含6.0体积%三氧化硫的三氧化硫/氮气混合物在实施例1所述的降膜反应器中于55℃的温度下连续硫酸化。将700g/h的烷氧基化和季铵化的二胺导入反应器的顶部并以具有1.3mm平均厚度的膜形式向下移动,与55℃的三氧化硫/氮气混合物(43g/h三氧化硫和190l/h氮气)连续并流接触。烷氧基化和季铵化二胺中OH基团与三氧化硫的硫酸化比例为1∶0.79。供入降膜反应器中的三氧化硫量通过在反应器底部得到的硫酸化产物的酸值控制。将酸值调为40。
收集在反应器底部得到的硫酸化的烷氧基化和季铵化二胺并通过将750g硫酸化产物加入到45ml 25重量%强度的氢氧化钠水溶液和700ml水的混合物中而分批中和,同时维持反应混合物的温度为30℃。然后通过进一步加入氢氧化钠水溶液而将反应混合物的pH调节为10。反应混合物含有575ppm二噁烷且根据Gardner的色数(在50重量%强度的水溶液中测定)为1.0。反应产物含有2.3重量%尚未硫酸化的原料。
实施例3
将通过使2摩尔4,7-二氧杂十二烷二胺和1摩尔表氯醇缩合得到的缩合产物用120摩尔环氧乙烷乙氧基化。然后将乙氧基化缩合产物用硫酸二甲酯完全季铵化。如此得到的乙氧基化和季铵化缩合产物然后用含6.6体积%三氧化硫的三氧化硫/氮气混合物在实施例1所述的降膜反应器中于60℃的温度下连续硫酸化。将700g/h的烷氧基化和季铵化的缩合产物加热到48℃并导入反应器的顶部,以具有1.6mm平均厚度的膜形式向下移动并与60℃的三氧化硫/氮气混合物(48g/h三氧化硫和190l/h氮气)连续并流接触。该反应在60℃的温度下进行。烷氧基化和季铵化产物中OH基团与三氧化硫的硫酸化比例为1∶0.95。供入反应器中的三氧化硫量通过在反应器底部得到的硫酸化产物的酸值控制。酸值为50。
收集在反应器底部得到的硫酸化的烷氧基化和季铵化缩合产物并通过将750g硫酸化产物加入到45ml 25重量%强度的氢氧化钠水溶液和700ml水的混合物中而分批中和,同时维持反应混合物的温度为30℃。然后通过进一步加入氢氧化钠水溶液而将反应混合物的pH调节为10。反应混合物含有约600ppm二噁烷且根据Gardner的色数(在50重量%强度的水溶液中测定)为1.6。反应产物含有2.7重量%尚未硫酸化的原料。
Claims (10)
1.一种通过将烷氧基化和季铵化的胺硫酸化以及随后中和而生产两性离子聚胺的方法,包括在不存在溶剂的情况下于至多90℃的温度下用含三氧化硫的惰性气体将分子中具有至少两个叔或季氮原子且含有至少一个季铵化氮原子的烷氧基化和季铵化的聚胺以具有100μm-4mm厚度的膜形式连续硫酸化。
2.如权利要求1所要求的方法,其中该方法在根据降膜原理操作的反应器中进行。
3.如权利要求1所要求的方法,其中硫酸化在根据降膜原理操作的反应器中进行且其中在第一次通过时得到的反应产物被导入至少一个其他反应器中以进行后反应。
4.如权利要求1所要求的方法,其中在至少一个其他降膜反应器中连续进行后反应。
5.如权利要求1所要求的方法,其中硫酸化用含有1-10体积%三氧化硫的三氧化硫/空气或氮气混合物进行。
6.如权利要求1所要求的方法,其中硫酸化用含有1.2-4体积%三氧化硫的三氧化硫/空气或氮气混合物进行。
7.如权利要求1所要求的方法,其中烷氧基化和季铵化聚胺每分子含有2-10个氮原子和至少20个烯化氧单元且季铵化程度至少为80%。
8.如权利要求1所要求的方法,其中烷氧基化和季铵化聚胺每分子含有2-6个氮原子和50-200个烯化氧单元且季铵化程度大于90%。
9.如权利要求1所要求的方法,其中烷氧基化聚胺被完全季铵化。
10.如权利要求1所要求的方法,其中烷氧基化和季铵化聚胺的羟基端基与三氧化硫的摩尔比为1.0∶0.2-1.0∶1.2。
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