CN101815743B - 含有乙烯亚胺单元的氨基烷基乙烯基醚、其制备方法及其用途 - Google Patents
含有乙烯亚胺单元的氨基烷基乙烯基醚、其制备方法及其用途 Download PDFInfo
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- -1 Amino alkyl vinyl ethers Chemical class 0.000 title claims abstract description 44
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 16
- 239000011707 mineral Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 22
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 8
- 150000001350 alkyl halides Chemical class 0.000 claims description 8
- JPVNTYZOJCDQBK-UHFFFAOYSA-N 3-ethenoxypropan-1-amine Chemical compound NCCCOC=C JPVNTYZOJCDQBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 claims description 2
- 150000002466 imines Chemical group 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 150000008050 dialkyl sulfates Chemical class 0.000 abstract 1
- 235000005985 organic acids Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- MNHKUCBXXMFQDM-UHFFFAOYSA-N 4-[(4-nitrophenyl)methyl]pyridine Chemical compound C1=CC([N+](=O)[O-])=CC=C1CC1=CC=NC=C1 MNHKUCBXXMFQDM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- 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
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
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- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
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Abstract
本发明涉及含有烯化亚胺单元的式(I)的氨基烷基乙烯基醚：H2C＝CH-O-X-NH-[Al-]n-H，其中[Al-]n表示具有n个烯化亚胺单元的直链或支链的低聚烯化亚胺链，n是至少为1的数值，并且X表示直链或支链的C2-C6亚烷基基团；本发明还涉及单体I与无机酸或有机酸的盐，及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物；涉及通过氨基-C2-C6-烷基乙烯基醚与烯化亚胺的加成来制备式(I)化合物的方法；并涉及含有烯化亚胺单元的式(I)氨基烷基乙烯基醚用作单体以制备造纸工业中所用聚合物的用途、用作抗微生物涂料、用于洗涤剂中和用于处理金属表面的用途。
Description
本发明涉及含有乙烯亚胺单元的下式的氨基烷基乙烯基醚，
H2C＝CH-O-X-NH-[Al-]n-H (I)，
其中
[Al-]n为具有n个烯化亚胺单元的直链或支链的低聚烯化亚胺链，
n是至少为1的数值，并且
X表示直链或支链的C2-C6亚烷基基团，
本发明还涉及单体I的盐及其季铵化产物、其制备方法，及其作为用于制备造纸工业中所用聚合物的单体、用作抗微生物涂料、用于洗涤剂中和用于处理金属表面的用途。
WO-A-01/36500公开了含有烯化亚胺单元的下式单体：
其中
R为氢或C1--C4-烷基，
[Al-]m为具有m个烯化亚胺单元的直链或支链的低聚烯化亚胺链，
m为一个1-20的整数，并且低聚烯化亚胺链中数均m值为至少1.5，
Y为一种无机酸的阴离子等价物，并且
n为一个1≤n≤m的数值。
优选上述式中m的数均值为至少2.1、通常为2.1至8的单体或单体混合物。它们可通过将烯键式不饱和羧酸与低聚烯化亚胺——优选为低聚物混合物的形式——反应而得到。如果合适，可将所得产物用无机酸HY转化为酸加成盐。所述单体可在引发自由基聚合的引发剂的存在下于水性介质中聚合，得到用作造纸中助剂的均聚物和共聚物。
本发明目的为提供具有烯化亚胺单元的其他单体。
本发明的该目的由下述物质实现：含有烯化亚胺单元的下式氨基烷基乙烯基醚，以及单体I与无机酸或有机酸的盐、及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，
H2C＝CH-O-X-NH-[Al-]n-H (I)，
其中
[Al-]n为具有n个烯化亚胺单元的直链或支链的低聚烯化亚胺链，
n是至少为1的数值，并且
X为直链或支链的C2-C6亚烷基基团，
条件是不包括乙烯基氧乙基乙二胺、氨基丙基氨基乙基乙烯基醚和3-(3-氨基丙基氨基)丙基乙烯基醚。
直链低聚烯化亚胺链[Al-]n可例如借助下式描述：
-[CHR′-CHR″-NH-]n-H (II)，
其中n是至少为1的数值，并且R’和R”为单价有机基团，例如C1--C4烷基、苯基或氢。R’和R”优选为氢。
支链低聚烯化亚胺结构[Al-]n可例如借助下式表示：
其中p为0或不同于0的整数1、2、3等，q和r彼此独立地为不同于0的整数，并且p+q+r+1的总和为n。式III代表一个单支链的低聚烯化亚胺单元[Al-]n，但也可具有多个支链。
优选这样的含有烯化亚胺单元的式I氨基烷基乙烯基醚，以及单体I与无机酸或有机酸的盐、及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，其中
[Al-]n为n个乙烯亚胺单元，
n为一个2-20的数值，并且
X为C3-C4亚烷基基团。
特别优选这样的含有烯化亚胺单元的式I的氨基烷基乙烯基醚，以及单体I与无机酸或有机酸的盐、及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，其中
[Al-]n为n个乙烯亚胺单元，
n为一个3-15的数值，并且
X为基团-CH2-CH2-CH2-。
对于单体I与无机酸或有机酸的盐，其中所存在氮原子中的至少一个、优选其中所存在氮原子中的多个或全部(即式I中的n+1个)以质子化形式存在。因此它们可被部分中和或全部中和。用于形成盐的有例如：无机酸，如盐酸、硫酸、磷酸、膦酸或硝酸，或者有机酸，如甲酸、乙酸、丙酸、苯磺酸、氨基磺酸或对甲苯磺酸。
单体I的季铵化产物可通过单体I与季铵化试剂——例如C1-C18烷基卤化物或硫酸二烷基酯——的反应得到。单体I所含氮原子中的至少一个在季铵化产物中以季铵化的形式存在。季铵化单体I含有例如2至最多n+1个季铵化氮原子，n具有上式I中所述含义。适宜的季铵化试剂有，例如氯代甲烷、氯代乙烷、1-氯丙烷、2-氯丙烷、1-氯丁烷、2-氯丁烷、1-氯己烷、环己基氯、苄基氯、溴代甲烷、碘代甲烷、溴代乙烷、碘代乙烷、硫酸二甲酯和硫酸二乙酯。
含有烯化亚胺单元的式I氨基烷基乙烯基醚、以及单体I与无机酸或有机酸的盐、及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，可通过以下方式得到：使至少一种烯化亚胺与氨基-C2-C6烷基乙烯基醚进行加成反应，其中每摩尔乙烯基醚使用至少1mol烯化亚胺；将该加合物用无机酸或有机酸中和来制备盐；并使它们与C1-C18烷基卤化物或硫酸二烷基酯反应来制备季铵化产物。
在本发明方法的一个优选实施方案中，使乙烯亚胺与氨基-C3-C4烷基乙烯基醚进行加成反应，其中每摩尔乙烯基醚与2-20mol乙烯亚胺进行加成反应。
特别优选摩尔比为1∶3至15的氨基丙基乙烯基醚与乙烯亚胺的反应产物。在1H-NMR谱中，它们在2.54-2.78ppm处显示出多重峰，其为氨基烷基乙烯基醚中与氨基相邻的质子(-CH2-NH2)的信号和在与乙烯亚胺低聚的形式中该基团的质子的信号。与乙烯亚胺低聚的氨基丙基乙烯基醚在n＝6.8的低聚程度下具有9.0meq/g的阳离子电荷密度(在pH为8、浓度为0.1g/kg并且温度为20℃下的水溶液中测得)。
烷基乙烯基醚与烯化亚胺的反应优选在一种催化剂——例如无机酸——的存在下于水性介质中进行。优选使用硫酸作为催化剂。例如，将1摩尔催化剂(例如硫酸)首先与60-85mol(优选70-75mol)氨基烷基乙烯基醚进行反应，然后使乙烯亚胺与部分以铵盐形式存在的所述氨基烷基乙烯基醚进行加成反应。该反应混合物的pH在例如≥6.5、优选8-11的范围内。反应温度为例如55-105℃。通常在60-80℃、特别是65-75℃的温度范围内。
烯化亚胺(优选乙烯亚胺)与氨基烷基乙烯基醚的加成反应以例如下述方式进行：将至少一种氨基烷基乙烯基醚在室温下溶于水中，向该水溶液中添加一种催化剂例如硫酸，将该混合物在搅拌的情况下加热至反应温度，并在连续搅拌的情况下将烯化亚胺连续或按份计量添加至初始形成的混合物中从而使烯化亚胺以可控方式反应，并可调节反应温度。根据批量的大小，为该目的所需的反应时间在实验室规模上为例如10分钟至3小时。反应终点，即当在反应混合物中无法再检测到烯化亚胺的时间，借助于乙烯亚胺与4-(4-硝基苄基)吡啶的反应确定，参见R.Preussmann，H.Schneider and F.Epple，Arzneimittel-Forschung，第19卷，1059-1073(1969)。在所述试验中，根据深紫色用4-(4-硝基苄基)吡啶检测乙烯亚胺。如果该测试为阴性，则反应完成。该反应混合物可直接使用。但是，也可将乙烯亚胺与氨基烷基乙烯基醚的加合物从反应混合物中分离出来，例如通过除去水分离出来。
本发明的含有烯化亚胺单元的氨基烷基乙烯基醚为可通过自由基引发剂而聚合的单体。因此它们可用作制备造纸工业用聚合物的单体。摩尔质量Mw最高达30000的聚合物适宜用作例如造纸中杂质
和细粉料(Feinstoff)的固定剂。也可将式I单体的聚合物用作抗微生物涂料、用于洗涤剂中和用于处理金属表面。
实施例1
在装配有搅拌器、温度计和计量装置的四颈烧瓶中，将30g(0.296mol)氨基丙基乙烯基醚(CH2＝CH-O-CH2-CH2-CH2-NH2)溶于16g去离子水中并与5g浓硫酸(0.051mol)混合。pH为8.5。将该混合物在氮气气氛中于搅拌下加热至65℃的温度。一旦达到该温度，就在1小时内计量添加161ml浓度60％的乙烯亚胺(89.4g，2.079mol)的水溶液。然后将该混合物在65-70℃的温度下再搅拌4小时。该时间之后，在该反应混合物中借助于上述Preussmann试验不再检测到乙烯亚胺。该反应结束后，反应混合物的pH为11。
实施例2
在装配有剧烈搅拌器、回流冷凝器和温度计的四颈烧瓶中，将78.2g(0.772mol)氨基丙基乙烯基醚(CH2＝CH-O-CH2-CH2-CH2-NH2)溶于41.7g去离子水中并用10％的浓硫酸缓慢调节至pH为11。将该混合物在氮气气氛中于搅拌下加热至65℃的温度。一旦达到该温度，就在1小时内计量添加360ml浓度60％的乙烯亚胺(199.7g，4.644mol)的水溶液。然后将该混合物在65℃下再保持1小时，然后在85℃下再搅拌4小时。最后，将该混合物再在回流下加热3小时。该时间之后，在该反应混合物中借助于上述Preussmann试验不再检测到乙烯亚胺。
实施例3
在装配有剧烈搅拌器、回流冷凝器和温度计的四颈烧瓶中，将180g(1.776mol)氨基丙基乙烯基醚(CH2＝CH-O-CH2-CH2-CH2-NH2)溶于25g去离子水中并用10％的浓硫酸缓慢调节至pH为11。将该混合物在氮气气氛中于搅拌下加热至65℃的温度。一旦达到该温度，就在1小时内计量添加276ml浓度60％的乙烯亚胺(153.3g，3.565mol)的水溶液。然后将该混合物在70℃下搅拌30分钟。最后，将该混合物再在回流下加热5小时。该时间之后，在该反应混合物中借助于上述Preussmann试验不再检测到乙烯亚胺。
Claims (7)
1.一种含有烯化亚胺单元的下式氨基烷基乙烯基醚以及单体I与无机酸或有机酸的盐，及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，
H2C＝CH-O-X-NH-[Al-]n-H (I)，
其中
[Al-]n为具有n个烯化亚胺单元的直链或支链的低聚烯化亚胺链，
n是一个至少为1的数值，并且
X表示直链或支链的C2-C6亚烷基基团，
条件是不包括乙烯基氧乙基乙二胺、氨基丙基氨基乙基乙烯基醚和3-(3-氨基丙基氨基)丙基乙烯基醚。
2.权利要求1的含有烯化亚胺单元的氨基烷基乙烯基醚以及单体I与无机酸或有机酸的盐，及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，其中，在式I中，
[Al-]n为n个乙烯亚胺单元，
n为一个2-20的数值，并且
X为C3-C4亚烷基基团。
3.权利要求1或2的含有烯化亚胺单元的氨基烷基乙烯基醚以及单体I与无机酸或有机酸的盐，及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物，其中，在式I中，
[Al-]n为n个乙烯亚胺单元，
n为一个3-15的数值，并且
X为基团-CH2-CH2-CH2-。
4.一种制备权利要求1的含有烯化亚胺单元的氨基烷基乙烯基醚、以及单体I与无机酸或有机酸的盐、及单体I与烷基卤化物或硫酸二烷基酯的季铵化产物的方法，其中至少一种烯化亚胺与氨基-C2-C6烷基乙烯基醚进行加成反应，每摩尔乙烯基醚使用至少1mol烯化亚胺，将该加合物用无机酸或有机酸中和来制备盐，并使它们与C1-C18烷基卤化物或硫酸二烷基酯反应来制备季铵化产物。
5.权利要求4的方法，其中乙烯亚胺与氨基-C3-C4烷基乙烯基醚进行加成反应，每摩尔乙烯基醚与2-20mol乙烯亚胺进行加成反应。
6.权利要求4的方法，其中氨基丙基乙烯基醚与乙烯亚胺以1∶3至15的摩尔比进行反应。
7.权利要求1至3之一的含有烯化亚胺单元的氨基烷基乙烯基醚用作制备造纸工业用聚合物的单体、用作抗微生物涂料、用于洗涤剂中和用于处理金属表面的用途。
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| WO2001036500A1 (de) * | 1999-11-19 | 2001-05-25 | Basf Aktiengesellschaft | Verfahren zur herstellung von wasserlöslichen polymeren mit oligoalkylenimin-seitenketten |
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| JP2006282764A (ja) * | 2005-03-31 | 2006-10-19 | Fuji Photo Film Co Ltd | インク組成物及びそれを用いた画像形成方法、記録物 |
| WO2009047148A1 (de) | 2007-10-01 | 2009-04-16 | Basf Se | Blockcopolymere umfassend eine polyalkylenoxideinheit sowie mindestens eine terminale polyalkylenimineinheit |
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| WO2001036500A1 (de) * | 1999-11-19 | 2001-05-25 | Basf Aktiengesellschaft | Verfahren zur herstellung von wasserlöslichen polymeren mit oligoalkylenimin-seitenketten |
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