CN1875052B - 水溶性聚羟氨基醚及其制备方法 - Google Patents
水溶性聚羟氨基醚及其制备方法 Download PDFInfo
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- CN1875052B CN1875052B CN2004800316526A CN200480031652A CN1875052B CN 1875052 B CN1875052 B CN 1875052B CN 2004800316526 A CN2004800316526 A CN 2004800316526A CN 200480031652 A CN200480031652 A CN 200480031652A CN 1875052 B CN1875052 B CN 1875052B
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- water
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
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- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 5
- -1 isopropylidene diphenylene Chemical group 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 40
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- 150000001412 amines Chemical class 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
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- VIATXXYHBGHTMA-UHFFFAOYSA-N n-(hydroxyamino)oxyhydroxylamine Chemical compound ONONO VIATXXYHBGHTMA-UHFFFAOYSA-N 0.000 claims description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
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- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims 1
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- 125000004427 diamine group Chemical group 0.000 claims 1
- 229910001867 inorganic solvent Inorganic materials 0.000 claims 1
- 239000003049 inorganic solvent Substances 0.000 claims 1
- PODAMDNJNMAKAZ-UHFFFAOYSA-N penta-2,3-diene Chemical group CC=C=CC PODAMDNJNMAKAZ-UHFFFAOYSA-N 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 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 claims 1
- 239000000047 product Substances 0.000 description 24
- 239000011541 reaction mixture Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 16
- 125000002947 alkylene group Chemical group 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
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- 230000009477 glass transition Effects 0.000 description 8
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- 238000006116 polymerization reaction Methods 0.000 description 6
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- 239000004215 Carbon black (E152) Substances 0.000 description 4
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及一种含有具有聚环氧烷侧链的共聚羟氨基醚的水溶性聚合物,所述聚合物的水溶液和制备共聚羟氨基醚的方法。
Description
技术背景
本发明涉及水溶性聚合物。水溶性聚合物用于许多用途,包括改进的石油炼制、金属加工液润滑和食品工业中的胶凝剂。已知的是,来自油井和气井的大量水的产生构成了从地下储层中回收烃的总回收中的主要花费之一,并且一些水溶性聚合物降低了这种产水量。参看,例如,Treybig等,美国专利6,569,983和Ahmed等,美国专利6,051,670。
还公知的是,已经使用聚合物和胶化或交联水溶性聚合物改变地下岩层的渗透性以提高注水操作的效力。通常,将聚合物注入岩层并使其渗入具有最高透水性的区域。还提出了下述理论,即聚合物阻隔了岩层中的透水区域,由此减少了与油一起产生的水量。现有聚合物,例如聚丙烯酰胺,确实降低了产水量,但是它们也降低了产油量。
理想的是提供可降低产水量但不会影响产油量的水溶性聚合物。
发明概述
在第一方面,本发明是一种水溶性聚合物,其含有具有聚环氧烷侧链的共聚羟氨基醚。
在第二方面,本发明是一种含有水流体和第一方面的水溶性聚合物的组合物。
在第三方面,本发明是一种制备第一方面的水溶性聚合物的方法,其包括使(1)伯胺、双(仲)二胺或单-胺-官能化聚(环氧烷)或它们的混合物与(2)二环氧甘油醚、二环氧基官能化的聚(环氧烷)或它们的混合物在足以使这些胺部分与环氧部分反应形成含有胺键、醚键和侧羟基部分的聚合物主链的条件下反应。
在第四方面,本发明是一种制备第一方面的水溶性聚合物的方法,其包括任选在起到终止剂作用的单官能亲核体存在的情况下,并任选在催化剂和/或溶剂存在的情况下,使当量或过量的双官能胺或其混合物与过量或当量的双酚的二环氧甘油醚或其混合物反应。
在第五方面,本发明是一种制备第一方面的水溶性聚合物的方法,其包括在足以使胺部分与环氧部分反应形成含有胺键、醚键和侧羟基部分的聚合物主链的条件下,将选自伯胺、双(仲)二胺或单-胺-官能化聚(环氧烷)或它们的混合物的胺溶于有机或非有机溶剂,在胺溶液中加入选自二环氧甘油醚、二环氧基官能化的聚(环氧烷)或它们的混合物的环氧化物,其中胺氢当量与环氧化物当量比为1.01∶1至1.1∶1。
根据下列详述和权利要求,本发明的其它方面变得显而易见。
发明详述
优选地,共聚羟氨基醚表示为下式:
其中R是氢或烷基;R1是芳族或取代芳族部分;Y是不含环氧基的有机部分,而z是任选含有环氧基的有机部分;x是0-0.99;n是5-400;每个A独立地为下式之一所示的氨基:
其中R2是烃基或取代烃基;R3是C2-C10亚烃基或取代亚烃基;R4是C2-C20亚烃基或取代亚烃基,其中取代基为羟基、氰基、卤素、芳氧基、烷基酰氨基、芳基酰氨基、烷基羰基或芳基羰基;且每个B表示为下式:
其中R5是烃基;R6是氢、甲基、乙基、烃基、或它们的混合物;当q大于40时x是0-0.99;但当q小于40时x小于0.2或大于0.8。
对于本发明,术语“烃基”是指如烷基、环烷基、芳烷基或芳基的单价烃,术语“亚烃基”是指如亚烃基、亚环烃基、亚芳烃基或亚芳基的二价烃。
在本发明的更优选具体实施方式中,R是氢;R1是异亚丙基二亚苯基、1,4-亚苯基、1,3-亚苯基、亚甲基二亚苯基、硫代二苯撑(thidodiphenylene)、羰基二亚苯基、或它们的混合物;R2是甲基、乙基、苯基、苄基、2-羟乙基、3-羟丙基、2-羟丙基、2,3-二羟丙基、2-(乙酰氨基)乙基、或它们的混合物;R3和R4独立地为亚乙基、1,2-亚丙基、1,2-亚丁基、或它们的混合物;R5C1-C20烷基。
在本发明的最优选具体实施方式中,R1是异亚丙基二亚苯基,R2是2-羟乙基;R5是氢、甲基、乙基、丙基、丁基、苄基或它们的混合物;R6是氢和甲基的混合物;Y和Z是N-(2-羟乙基)哌嗪基或双(2-羟乙基)氨基,q是20-50,且n是10-25。
可以通过常规方法从反应混合物中回收该水溶性聚合物。例如,可以用如二甲基甲酰胺的适宜溶剂稀释含有该聚合物和任选溶剂的反应混合物,冷却至室温,并将聚合物沉淀到非溶剂中以将其分离。然后通过用非溶剂洗涤或多次洗涤来提纯沉淀的聚合物。通过过滤收集聚合物,用合适的非溶剂洗涤,然后干燥。也可以结合温度和真空条件通过溶剂挥发来从溶液中回收该水溶性聚合物。
在本发明的实践中可以使用的多官能胺包括双仲胺和伯胺。
可以在本发明的实践中用于制备聚合物的伯胺包括苯胺和取代苯胺,例如,4-(甲酰氨基)苯胺、4-甲基苯胺、4-甲氧基苯胺、4-叔丁基苯胺、3,4-二甲氧基苯胺、3,4-二甲基苯胺;烷基胺和取代烷基胺,例如丁胺和苄胺;和链烷醇胺,例如,2-氨基乙醇和1-氨基丙-2-醇。优选的伯胺是苯胺、4-甲氧基苯胺、4-叔丁基苯胺、丁胺和2-氨基乙醇。最优选的伯胺是2-氨基乙醇。
可以在本发明的实践中用于制备聚合物的双仲胺包括哌嗪和取代哌嗪,例如二甲基哌嗪和2-甲基酰氨基哌嗪;双(N-甲氨基)苯、1,2-双(N-甲氨基)乙烷、以及N,N′-双(2-羟乙基)乙二胺。优选的双仲胺是哌嗪、二甲基哌嗪、和1,2-(N-甲氨基)乙烷。最优选的双仲胺是哌嗪。
可以在本发明的实践中用于制备聚合物的胺官能化聚(环氧烷)包括下列通式所示的那些材料:
其中R6是氢、甲基、乙基、烃基或它们的混合物;R5是烃基,q是1至1000。这类胺的典型例子是Huntsman制造的“M”系列JeffamineTM产品。它们的制备通常如下:使环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物与脂族醇引发剂聚合,然后将所得末端羟基转化成胺部分。
环氧官能化的聚(环氧烷)也可以在本发明的实践中用于制备该聚合物,而且它们可以与双酚的二环氧甘油醚混合。合适的环氧官能化的聚(环氧烷)是下列通式所示的那些材料:
其中R1是氢、甲基、或它们的混合物;y是1至40。这类环氧化物的典型例子是Dow Chemical Company制造的“700”系列D.E.R.TM环氧树脂。它们的合成如下:使环氧乙烷、环氧丙烷或它们的混合物与氢氧化物引发剂聚合,然后使所得聚(环氧烷)二醇与环氧氯丙烷反应。
可以在本发明的实践中用于制备聚合物的二环氧甘油醚包括9,9-二(4-羟苯基)芴、4,4′-亚甲基双酚(双酚F)、氢醌、间苯二酚、4,4′-磺酰基联苯酚、4,4′-硫代联苯酚、4,4′-氧联苯酚、4,4′-二羟基二苯甲酮、四溴异亚丙基联苯酚、二羟基二硝基亚芴基二亚苯基、4,4′-联苯酚、4,4′-二羟基氧化联苯、二(4-羟苯基)甲烷、α.,α.-双(4-羟苯基)乙基苯、2,6-二羟基萘和4,4′-异亚丙基双酚(双酚A)和含有酰胺的双酚的二环氧甘油醚,例如N,N′-双(羟苯基)亚烷基二羟酰胺、N,N′-双(羟苯基)亚芳基二羟酰胺、二(羟基苯甲酰氨基)链烷或双(羟基苯甲酰氨基)芳烃、N-(羟苯基)羟基苯甲酰胺、2,2-双(羟苯基)乙酰胺、N,N′-双(3-羟苯基)戊二酰胺,N,N′-二(3-羟苯基)己二酰二胺、1,2-双(4-羟基苯甲酰氨基)乙烷、1,3-双(4-羟基苯甲酰氨基)苯、N-(4-羟苯基)-4-羟基苯基酰胺、和2,2-双(4-羟苯基)-乙酰胺。更优选的二环氧甘油醚是9,9-二(4-羟苯基)芴、氢醌、间苯二酚、4,4′-磺酰基联苯酚、4,4′-硫代联苯酚、4,4′-氧联苯酚、4,4′-二羟基二苯甲酮、双酚F、四溴异亚丙基联苯酚、二羟基二硝基亚芴基二亚苯基、4,4′-联苯酚、4,4′-二羟基氧化联苯、二(4-羟苯基)甲烷、α.,α.-双(4-羟苯基)乙基苯、2,6-二羟基萘和4,4′-异亚丙基双酚(双酚A)的二环氧甘油醚,最优选的二环氧甘油醚是4,4′-氧联苯酚、4,4′-二羟基二苯甲酮、9,9-二(4-羟苯基)芴和双酚F的二环氧甘油醚。
可用于本发明的实践的起到终止剂作用的单官能亲核体包括仲胺、硫化氢、氨、氢氧化铵、羟基芳烃(hydroxyarene)、芳族醚盐、羧酸、羧酸盐、硫醇或硫醇盐。优选地,羟基芳烃是酚、甲酚、甲氧基苯酚、或4-叔丁基酚;芳族醚盐是苯酚钠或苯酚钾;羧酸是乙酸或苯甲酸;羧酸盐是乙酸钠、苯甲酸钠、乙基己酸钠、乙酸钾、苯甲酸钾、乙基己酸钾、或乙基己酸钙;硫醇是3-巯基-1,2-丙二醇或苯硫醇;且硫醇盐是苯硫醇钠或苯硫醇钾。单官能亲核体选自二乙醇胺、N-(2-羟乙基)哌嗪、哌啶(piperadine)、二乙胺、二丙胺或二苄胺。
优选的催化剂包括金属氢氧化物、季铵盐或季鏻盐。尤其优选的催化剂包括氢氧化钠、氢氧化钾、氢氧化铵、乙酸乙基三苯鏻、溴化四丁铵和氯化双(三苯基亚膦基)铵。
最有利的进行反应的条件取决于各种因素,包括具体的反应剂、溶剂和所用催化剂,但是一般而言,反应在非氧化气氛(例如氮气覆盖)下,优选在40℃至190℃的温度,更优选在50℃至150℃的温度下进行。反应可以在不加溶剂或其它稀释剂的情况下进行。然而,在某些情况下,为了确保在这些温度下获得均匀的反应混合物,可以理想地使用惰性有机溶剂或水作为这些反应剂的溶剂。适宜溶剂的例子包括二丙甘醇甲醚,作为DowanolTM DPM购得,其是The Dow ChemicalCompany的产品,还包括醚或羟基醚,例如二甘醇二甲醚、三甘醇二甲醚、二甘醇乙醚、二甘醇甲醚、二丙甘醇甲醚、丙二醇苯醚、丙二醇甲醚、和三丙甘醇甲醚、以及类似1-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺的质子酰胺溶剂,和它们的混合物。
最优选的是聚环氧烷链中所含的环氧乙烷多于环氧丙烷。聚亚烷基侧链的长度可以是1个烯化氧单元至1000个烯化氧单元,优选2个烯化氧单元至500个烯化氧单元,更优选5个烯化氧单元至250个烯化氧单元,最优选为10个烯化氧单元至100个烯化氧单元。
优选地,共聚羟氨基醚具有1000至500,000,更优选2000至250,000,最优选5000至100,000的分子量。可以通过N-H对环氧基比率的偏化学计量或通过在聚合过程开始时或在聚合过程之中或最后加入前述单官能终止剂来控制共聚物分子量。
有利地,含有聚合物重复单元的聚环氧烷的用量为1至99摩尔%,更优选1至25摩尔%。
共聚羟氨基醚的水溶液可以表现出浊点或更低的临界溶解温度(LCST),以使共聚羟氨基醚的水溶液在低于水的沸点的一定温度下,优选在室温下流动,并在升高的温度下变得更粘和/或胶凝,并可能在视觉上从透明转变成模糊/不透明/浑浊。术语浊点是可用于描述视觉转变的术语。此处所用的术语“LCST”描述了当溶液温度升高时,聚合物溶液经历从一相(均质溶液)转变成至少两相体系(富含聚合物的相和更富含溶剂的相)的相变时的温度。可以在聚羟氨基醚的水溶液中加入盐、酸或碱来改变浊点或LCST。浊点或LCST也可能随水溶液中聚羟氨基醚的浓度以及聚羟氨基醚分子量的改变而改变。
下列实施例用于举例说明本发明并不应该看成限制本发明的范围。除非另行说明,所有的份数和百分比都是按重量计。
在实施例中使用下列材料:
D.E.R.TM 332THE DOW CHEMICAL COMPANY制造的高纯双酚A二环氧甘油醚。
JEFFAMINETM XTJ506Huntsman制造的聚氧化烯单胺,其中环氧丙烷/环氧乙烷比率为~3/19,且分子量约为1000。
JEFFAMINETM M2070 Huntsman制造的聚氧化烯单胺,其中环氧丙烷/环氧乙烷比率为~10/32,且分子量约为2000。
实施例1 溶液,D.E.R.332/MEA/JEFFAMINE XTJ506 100/80/20 (m/m/m),DP~15,羟乙基哌嗪
在一个1升树脂锅中加入D.E.R.332(180.00克,EEW 171)、JEFFAMINE XTJ506(101.75克,Mn~1030),乙醇胺(24.10克)、1-(2-羟乙基)哌嗪(8.60克)和无水N,N-二甲基乙酰胺(250毫升)。首先将在正(positive)氮气下搅拌过的反应混合物升温至大约45℃。当初始放热消退时,将反应设定点升至75℃,并在温度上升稳定之后,将设定点升至140℃并在此温度保持大约1小时。用N,N-二甲基乙酰胺冷却反应混合物,随后在大约95℃在真空下去除N,N-二甲基乙酰胺。产物具有0.18dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为6℃。制备该产物的20wt%水溶液,其在室温下具有低粘度并基本是澄清的;在大约50℃溶液变成半透明/不透明白色和高粘度软凝胶;当将溶液冷却至室温时,它再次变成低粘度和基本澄清。
实施例2溶液,D.E.R.332/MEA/JEFFAMINE XTJ506 100/85/15 (m/m/m),DP~25,羟乙基哌嗪
在一个100毫升树脂锅中加入D.E.R.332(76.00克,EEW 171)、JEFFAMINE XTJ506(35.59克,Mn~1031),乙醇胺(10.93克)、1-(2-羟乙基)哌嗪(2.28克)和无水N,N-二甲基乙酰胺(150毫升)。首先将在正氮气下搅拌过的反应混合物升温至大约45℃。当初始放热消退时,将反应设定点升至75℃,并在温度上升稳定之后,将设定点升至140℃并在此温度保持大约1.25小时。用N,N-二甲基乙酰胺冷却反应混合物,随后在大约95℃在真空下去除N,N-二甲基乙酰胺。产物具有0.23dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为13℃。在室温下制备该产物的15wt%水溶液,其在大约50℃变成半透明白色凝胶。
实施例3溶液,D.E.R.332/MEA/JEFFAMINE XTJ506 100/85/15 (m/m/m)
在一个1升树脂锅中加入D.E.R.332(12.000克,EEW 171)、Jeffamine XTJ506(5.426克,Mn~1031),乙醇胺(1.822克)、和无水N,N-二甲基乙酰胺(25毫升)。首先将在正氮气下搅拌过的反应混合物升温至大约45℃。当初始放热消退时,将反应设定点升至75℃,并在温度上升稳定之后,将设定点在小于升至100℃达3/4小时以下,将设定点升至140℃并在此温度保持大约3.25小时。将反应混合物在100℃放置过夜。在炼聚锅中加入在N,N-二甲基乙酰胺(2毫升)中的乙醇胺(0.026克)并在100℃三分钟后,将温度升至140℃达大约2小时,随后冷却。随后在大约95℃在真空下去除N,N-二甲基乙酰胺。产物具有0.33dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为16℃。在反应中没有使用终止剂。制备该产物的20wt%水溶液。
实施例4溶液,D.E.R.332/MEA/JEFFAMINE XTJ506 100/88.75/11.25 (m/m/m)
在一个100毫升树脂锅中加入D.E.R.332(13.000克,EEW 171)、Jeffamine XTJ506(4.409克,Mn~1031),乙醇胺(2.061克)、和无水N,N-二甲基乙酰胺(25毫升)。首先将在正氮气下搅拌过的反应混合物升温至大约45℃。当初始放热消退时,将反应设定点升至75℃,并在温度上升稳定之后,将设定点升至100℃达1/2小时以下,将设定点升至140℃并在此温度保持大约3小时。将反应混合物在100℃放置过夜。在炼聚锅中加入在N,N-二甲基乙酰胺(2毫升)中的乙醇胺(0.022克)并将温度升至140℃达大约1.5小时。将产物在冰水中沉淀、水洗,并在真空炉中以大约55℃干燥。产物具有0.34dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为31℃。在反应中没有使用终止剂。所得聚合物不溶于水。
实施例5溶液,D.E.R.332/MEA/Jeffarnine XTJ506 100/92.5/7.5 (m/m/m)
在一个100毫升树脂锅中加入D.E.R.332(14.000克,EEW 171)、Jeffamine XTJ506(3.165克,Mn~1031),乙醇胺(2.313克)、和无水N,N-二甲基乙酰胺(25毫升)。首先将在正氮气下搅拌过的反应混合物升温至大约45℃。当初始放热消退时,将反应设定点升至75℃,并在温度上升稳定之后,将设定点升至100℃达大约1小时,将设定点升至140℃并在此温度保持大约3.25小时。将反应混合物在100℃放置过夜。在炼聚锅中加入在N,N-二甲基乙酰胺(2毫升)中的乙醇胺(0.022克)并将温度升至140℃达大约1小时,随后加入N,N-二甲基乙酰胺(10毫升)并冷却。将产物在冰水中沉淀、水洗,并在真空炉中以大约55℃干燥。产物具有0.46dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为46℃。在反应中没有使用终止剂。所得聚合物不溶于水。
实施例6溶液,D.E.R.332/MEA/Jeffamine XTJ506 100/80/20 (m/m/m),DP~15,羟乙基哌嗪
在一个1升树脂锅中加入D.E.R.332(345.15克,EEW 172.7)、Jeffamine XTJ506(189.24克,Mn~1010),乙醇胺(45.78克)和1-(2-羟乙基)哌嗪(16.27克)。在正氮气下,搅拌过的反应的初始设定点为45℃。反应混合物开始自热,同时进行冷却以使温度保持在大约140-150℃以下。在升温消退后,使反应在140℃保持30分钟,然后将产物冷却至室温。产物具有0.19dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为6℃。在大约40℃下,将312.5克产物逐份加入搅拌过的含水(1193.1克)和乙酸(1.37克)的2升树脂锅中,由此制备该产物的水溶液。随后将氢氧化钠水溶液(45.5毫升,0.50N)与10毫升水漂洗液一起加入该溶液中。
实施例7溶液,D.E.R.332/MEA/JEFFAMINE M2070 100/87.5/12.5 (m/m/m),DP~13.7,二乙醇胺
在一个1升树脂锅中加入D.E.R.332(317.97克,EEW 172.7)、JEFFAMINE M2070(223.39克,Mn~2083),乙醇胺(45.86克)和二乙醇胺(13.15克)。在正氮气下,搅拌过的反应的初始设定点为45℃。反应混合物开始自热,同时进行冷却以使温度保持在大约140-150℃以下。在升温消退后,使反应在140℃保持30分钟,然后将产物冷却至室温。产物具有0.17dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为2℃。在大约40℃下,将312.5克产物逐份加入搅拌过的含水(1193.1克)和乙酸(1.37克)的2升树脂锅中,由此制备该产物的水溶液。随后将氢氧化钠水溶液(45.5毫升,0.50N)与10毫升水漂洗液一起加入该溶液中。
实施例8溶液,D.E.R.332/MEA/JEFFAMINE M2070 100/85/15 (m/m/m)
在一个100毫升树脂锅中加入D.E.R.332(10克,EEW 171)、JEFFAMINE M2070(8.932克,Mn~2083),乙醇胺(1.484克)和无水N-甲基吡咯烷酮(20毫升)。首先将在正氮气下搅拌过的反应混合物升温至大约45℃。当初始放热消退时,将反应设定点升至75℃,并在温度上升稳定之后,将设定点升至100℃达2小时,将设定点升至140℃并在此温度保持大约3.25小时。将反应混合物在100℃放置过夜。在炼聚锅中加入在N,N-二甲基乙酰胺(2毫升)中的乙醇胺(0.026克)并在100℃30分钟后,将温度升至140℃达大约3.75小时,随后冷却至100℃过夜。在炼聚锅中加入在2毫升N-甲基吡咯烷酮中的乙醇胺(0.017克)并在100℃30分钟后,并将温度升至140℃达大约4.25小时并冷却。产物不在水中沉淀。产物在冷异丙醇中沉淀并用冷异丙醇和室温异丙醇洗涤,并将产物在真空中在大约110℃干燥。产物具有0.75dL/g的特性粘度(N,N-二甲基甲酰胺,30.0℃,0.5g/dL)。以10℃/分钟加热速率通过DSC测定的半高玻璃化转变为大约-15℃。在反应中没有使用终止剂。
实施例9水聚合,D.E.R.332/MEA/JEFFAMINE M2070和DEA
在一个30加仑不锈钢反应器中加入8137.5克水并以100RPM’s开始混合。加入JEFFAMINE M2070(6437.1克,Mn~1040)、乙醇胺(1321.5克)和二乙醇胺(378.9克),然后加热至54-63℃。压力为19.1-21.7PSIA,并将混合增至200RPM’s。通过2加仑不锈钢(SS 316)加料罐经1小时48分钟加入D.E.R.332(9084克,EEW 172.7)。将反应混合物蒸煮34分钟,然后经过31分钟加入水(133.8磅)。将所得溶液混合1小时39分钟,然后冷却至25℃,并通过25micro Nomex袋滤器系统过滤到聚乙烯容器中。
实施例10Dowanol PM聚合,D.E.R.332/MEA/JEFFAMINE M2070 和DEA
在一个30加仑不锈钢反应器(SS 316)中加入8137.5克DowanolPM并以100RPM’s开始混合。加入JEFFAMINE M2070(6437.1克,Mn~1040)、乙醇胺(1321.5克)和二乙醇胺(378.9克),然后加热至87-91.6℃。压力为19.1-21.7PSIA,并将混合增至200RPM’s。通过2加仑不锈钢(SS 316)加料罐经1小时34分钟加入D.E.R.332(9084克,EEW 172.7)。将反应混合物在89-101℃蒸煮2小时43分钟,然后经过36分钟加入水(133.7磅)。将所得溶液在67.1-89℃和150RPM’s下混合1小时,然后冷却至26℃,并通过25micro Nomex袋滤器系统过滤到聚乙烯容器中。
Claims (18)
1.一种水溶性聚合物,其含有具有聚环氧烷侧链的共聚羟氨基醚;其中所述水溶性聚合物由下式表示:
其中R是氢;R1独立地是异亚丙基二亚苯基、1,4-亚苯基、1,3-亚苯基、亚甲基二亚苯基、硫代二苯撑、羰基二亚苯基、或它们的混合物;每个Y和z独立地为双(2-羟乙基)氨基或N-(2-羟乙基)哌嗪基;n是5-400;每个A独立地为下式之一所示的氨基:
其中R2独立地为甲基、乙基、苯基、苄基、2-羟乙基、3-羟丙基、2-羟丙基、2,3-二羟丙基、2-(乙酰氨基)乙基、或它们的混合物;R3和R4独立地为亚乙基、1,2-亚丙基、1,2-亚丁基、或它们的混合物;且每个B表示为下式:
其中R5是C1-C20烷基;每个R6独立地是氢、烃基、或它们的混合物;q是1至1000;当q大于40时x是0-0.99;但当q小于40时x为0至小于0.2或大于0.8至0.99。
2.根据权利要求1所述的聚合物,其中R6是氢和甲基的混合物;q是20-50,且n是10-25。
3.根据权利要求2所述的聚合物,其中R1是异亚丙基二亚苯基,R2是2-羟乙基。
4.根据权利要求2所述的聚合物,其中每个R5独立地为氢、甲基、乙基、丙基、丁基、苄基或它们的混合物;Y和Z是双(2-羟乙基)氨基。
5.根据权利要求1所述的聚合物,其中所述R6独立地为氢、甲基、乙基、或它们的混合物。
6.一种制备权利要求1所述的水溶性聚合物的方法,其包括(1)任选在单官能亲核体存在的情况下,并任选在催化剂和/或溶剂存在的情况下,使当量或过量的双官能胺或其混合物与过量或当量的双酚的二环氧甘油醚或其混合物反应;或(2)任选在起到终止剂作用的单官能亲核体存在的情况下,并任选在催化剂和/或溶剂存在的情况下,使当量或过量的双官能胺或其混合物与过量或当量的双酚的二环氧甘油醚或其混合物反应;或(3)在足以使胺部分与环氧部分反应形成含有胺键、醚键和侧羟基部分的聚合物主链的条件下,将选自伯胺、双仲二胺或单-胺-官能化聚环氧烷或它们的混合物的胺溶于有机或无机溶剂,在胺溶液中加入二环氧甘油醚,其中胺氢当量与环氧化物当量比为0.9∶1至1.2∶1。
7.根据权利要求6所述的方法,其中非有机溶剂是水,且单官能亲核体选自仲胺、硫化氢、氨、氢氧化铵、单官能化酚、芳族醚盐、羧酸、羧酸盐、硫醇或硫醇盐。
9.根据权利要求6所述的方法,其中单官能亲核体选自二乙醇胺、N-(2-羟乙基)哌嗪、哌啶、二乙胺、二丙胺或二苄胺。
10.根据权利要求6所述的方法,其中单官能亲核体选自酚、乙酸或丙酸,催化剂选自鏻或铵盐。
11.根据权利要求6所述的方法,其中溶剂选自1-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、水、二甘醇二甲醚、三甘醇二甲醚、二甘醇乙醚、二甘醇甲醚或丙二醇甲醚。
12.根据权利要求8所述的方法,其中所述R6独立地为氢、甲基、乙基、或它们的混合物。
13.一种根据权利要求6所述的方法制备的水溶性聚合物。
14.一种含有水流体和权利要求1所述的水溶性聚合物的组合物。
15.一种含有下式所示聚合物的水溶液:
其中R是氢;R1独立地是异亚丙基二亚苯基、1,4-亚苯基、1,3-亚苯基、亚甲基二亚苯基、硫代二苯撑、羰基二亚苯基、或它们的混合物;每个Y和z独立地为双(2-羟乙基)氨基或N-(2-羟乙基)哌嗪基;n是5-400;每个A独立地为下式之一所示的氨基:
其中每个R2独立地为甲基、乙基、苯基、苄基、2-羟乙基、3-羟丙基、2-羟丙基、2,3-二羟丙基、2-(乙酰氨基)乙基、或它们的混合物;R3和R4独立地为亚乙基、1,2-亚丙基、1,2-亚丁基、或它们的混合物;且每个B表示为下式:
其中R5是C1-C20烷基;每个R6独立地是氢、烃基、或它们的混合物;q是1至1000;当q大于40时x是0-0.99;但当q小于40时x为0至小于0.2或大于0.8至0.99。
16.根据权利要求15所述的水溶液,其中粘度随温度升高而升高。
17.根据权利要求15所述的水溶液,其中所述R6独立地为氢、甲基、乙基、或它们的混合物。
18.一种包括将权利要求1所述的聚合物溶于水的方法,该水任选含有酸、碱、盐、溶剂或它们的混合物。
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PCT/US2004/023265 WO2005035627A1 (en) | 2003-09-12 | 2004-07-19 | Water-soluble polyhydroxyaminoether and process for preparing the same |
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CN1875052A CN1875052A (zh) | 2006-12-06 |
CN1875052B true CN1875052B (zh) | 2010-05-26 |
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CN2004800316526A Expired - Fee Related CN1875052B (zh) | 2003-09-12 | 2004-07-19 | 水溶性聚羟氨基醚及其制备方法 |
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EP (1) | EP1692208B1 (zh) |
KR (2) | KR101335890B1 (zh) |
CN (1) | CN1875052B (zh) |
BR (1) | BRPI0413967B1 (zh) |
CA (1) | CA2533166C (zh) |
TW (1) | TWI370145B (zh) |
WO (1) | WO2005035627A1 (zh) |
Families Citing this family (26)
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US20050059794A1 (en) * | 2003-09-12 | 2005-03-17 | Glass Terry W. | Water-soluble polyhydroxyaminoether and process for preparing the same |
US7759436B2 (en) * | 2006-10-26 | 2010-07-20 | Basf Coatings Gmbh | Film-former of resin with nonionic metal coordinating structure and crosslinker-reactive group |
US9179367B2 (en) * | 2009-05-26 | 2015-11-03 | Qualcomm Incorporated | Maximizing service provider utility in a heterogeneous wireless ad-hoc network |
EP2333000A1 (de) * | 2009-12-11 | 2011-06-15 | BYK-Chemie GmbH | Polyethermodifizierte Epoxid-Amin-Addukte als Netz- und Dispergiermittel |
WO2011133415A1 (en) * | 2010-04-23 | 2011-10-27 | Lubrizol Advanced Materials, Inc. | Dispersant composition |
US8763700B2 (en) | 2011-09-02 | 2014-07-01 | Robert Ray McDaniel | Dual function proppants |
US9725645B2 (en) | 2011-05-03 | 2017-08-08 | Preferred Technology, Llc | Proppant with composite coating |
US9290690B2 (en) | 2011-05-03 | 2016-03-22 | Preferred Technology, Llc | Coated and cured proppants |
US9562187B2 (en) | 2012-01-23 | 2017-02-07 | Preferred Technology, Llc | Manufacture of polymer coated proppants |
WO2013134067A1 (en) * | 2012-03-06 | 2013-09-12 | Trw Automotive U.S. Llc | Method and apparatus for diagnosing inertia sensor |
US9169430B2 (en) | 2012-10-30 | 2015-10-27 | Ecolab Usa Inc. | Chemical treatment method and additive used to treat fines migration and flow through porous media |
US9518214B2 (en) | 2013-03-15 | 2016-12-13 | Preferred Technology, Llc | Proppant with polyurea-type coating |
US10100247B2 (en) | 2013-05-17 | 2018-10-16 | Preferred Technology, Llc | Proppant with enhanced interparticle bonding |
WO2015017140A1 (en) | 2013-07-31 | 2015-02-05 | Dow Global Technologies Llc | Foam-free synthesis of co-polyhydroxyaminoether |
US20150197682A1 (en) | 2014-01-16 | 2015-07-16 | Clearwater International, Llc | Anti-gel agent for polyhydroxyetheramines, gel stabilized polyhydroxyetheramine solutions, and methods for making and using same |
US10253609B2 (en) | 2014-04-29 | 2019-04-09 | Ecolab Usa Inc. | Permeability of subterranean reservoirs using acid diversion |
US9790422B2 (en) | 2014-04-30 | 2017-10-17 | Preferred Technology, Llc | Proppant mixtures |
US9862881B2 (en) | 2015-05-13 | 2018-01-09 | Preferred Technology, Llc | Hydrophobic coating of particulates for enhanced well productivity |
AR104606A1 (es) | 2015-05-13 | 2017-08-02 | Preferred Tech Llc | Partícula recubierta |
JP2018521176A (ja) * | 2015-06-23 | 2018-08-02 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングBASF Coatings GmbH | 受動的不透明化用の水性樹脂溶液 |
KR102000896B1 (ko) * | 2015-12-25 | 2019-07-16 | 도레이 카부시키가이샤 | 말단 변성 폴리아미드 수지 및 그의 제조 방법 |
WO2017223490A1 (en) | 2016-06-24 | 2017-12-28 | Dow Global Technologies Llc | Method for reducing the permeability of a subterranean formation to aqueous-based fluids |
WO2018005343A1 (en) | 2016-06-29 | 2018-01-04 | Dow Global Technologies Llc | Method for modifying the permeability to water of a subterranean formation |
US11208591B2 (en) | 2016-11-16 | 2021-12-28 | Preferred Technology, Llc | Hydrophobic coating of particulates for enhanced well productivity |
US10696896B2 (en) | 2016-11-28 | 2020-06-30 | Prefferred Technology, Llc | Durable coatings and uses thereof |
CN114716985A (zh) * | 2022-01-25 | 2022-07-08 | 湖北菲特沃尔科技有限公司 | 一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法 |
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US5464924A (en) * | 1994-01-07 | 1995-11-07 | The Dow Chemical Company | Flexible poly(amino ethers) for barrier packaging |
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US5567748A (en) * | 1991-12-17 | 1996-10-22 | The Dow Chemical Company | Water compatible amine terminated resin useful for curing epoxy resins |
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US5962093A (en) * | 1997-10-22 | 1999-10-05 | The Dow Chemical Company | Thermally stable polyetheramines |
US6051671A (en) * | 1998-03-24 | 2000-04-18 | Nova Chemicals Ltd. | Clean containers |
CA2362329A1 (en) * | 1999-02-11 | 2000-08-17 | Huntsman Petrochemical Corporation | Method for treatment of waste water |
US6569983B1 (en) * | 2001-12-20 | 2003-05-27 | Ondeo Nalco Energy Services, L.P. | Method and composition for recovering hydrocarbon fluids from a subterranean reservoir |
US7504438B1 (en) * | 2001-12-20 | 2009-03-17 | Nalco Company | Demulsifiers, their preparation and use in oil bearing formations |
US20050059794A1 (en) * | 2003-09-12 | 2005-03-17 | Glass Terry W. | Water-soluble polyhydroxyaminoether and process for preparing the same |
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2003
- 2003-09-12 US US10/662,089 patent/US20050059794A1/en not_active Abandoned
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2004
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- 2004-07-19 KR KR1020127010764A patent/KR101335890B1/ko not_active IP Right Cessation
- 2004-07-19 KR KR1020067007033A patent/KR20060130030A/ko not_active Application Discontinuation
- 2004-07-19 CN CN2004800316526A patent/CN1875052B/zh not_active Expired - Fee Related
- 2004-07-19 BR BRPI0413967-4A patent/BRPI0413967B1/pt not_active IP Right Cessation
- 2004-07-19 WO PCT/US2004/023265 patent/WO2005035627A1/en active Application Filing
- 2004-07-19 CA CA2533166A patent/CA2533166C/en not_active Expired - Lifetime
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2007
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2008
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US5464924A (en) * | 1994-01-07 | 1995-11-07 | The Dow Chemical Company | Flexible poly(amino ethers) for barrier packaging |
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CN1875052A (zh) | 2006-12-06 |
KR101335890B1 (ko) | 2013-12-02 |
BRPI0413967A (pt) | 2006-10-31 |
KR20060130030A (ko) | 2006-12-18 |
US7893136B2 (en) | 2011-02-22 |
US20050059794A1 (en) | 2005-03-17 |
WO2005035627A1 (en) | 2005-04-21 |
BRPI0413967B1 (pt) | 2021-04-13 |
US20100113690A1 (en) | 2010-05-06 |
EP1692208B1 (en) | 2016-10-05 |
TW200523286A (en) | 2005-07-16 |
EP1692208A1 (en) | 2006-08-23 |
CA2533166C (en) | 2012-09-25 |
KR20120058625A (ko) | 2012-06-07 |
US7678872B2 (en) | 2010-03-16 |
US20090005503A1 (en) | 2009-01-01 |
US20080045642A1 (en) | 2008-02-21 |
TWI370145B (en) | 2012-08-11 |
CA2533166A1 (en) | 2005-04-21 |
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