CN1990513A - 生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 - Google Patents
生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 Download PDFInfo
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- CN1990513A CN1990513A CNA2006101699659A CN200610169965A CN1990513A CN 1990513 A CN1990513 A CN 1990513A CN A2006101699659 A CNA2006101699659 A CN A2006101699659A CN 200610169965 A CN200610169965 A CN 200610169965A CN 1990513 A CN1990513 A CN 1990513A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/10—Carbocyclic compounds
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- Polymerisation Methods In General (AREA)
Abstract
本发明涉及一种通过在引发剂存在下在有机溶剂中在回流条件下自由基聚合至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体而生产乙烯基内酰胺共聚物的方法,其中在至少90mol%疏水性单体已经完全反应时将至少10mol%N-乙烯基内酰胺加入聚合混合物中。
Description
技术领域
本发明涉及一种通过至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体在有机溶剂中的自由基聚合生产这些单体的水溶性共聚物的方法以及可以通过该方法得到的共聚物及其应用。
背景技术
通过自由基聚合由N-乙烯基内酰胺和疏水性共聚单体生产共聚物是已知的。该类共聚物的生产在有机溶剂如醇类或具有高溶剂含量的水和有机溶剂的混合物中进行。通常而言,聚合在溶剂回流下进行。与N-乙烯基内酰胺相比更易挥发的疏水性单体以此方式进入气相和冷凝液中。
对于许多应用目的而言,需要溶于水中得到清澈溶液,即浓度为5重量%的溶液的FNU值应<20的共聚物。然而,存在的问题是单体的不同反应性和不同极性可能导致疏水性单体浓度增加,这导致能够由疏水性单体形成不是水溶性的均聚物。甚至在500-1000ppm的小量下,该类均聚物也导致共聚物水溶液浑浊。疏水性单体浓度的增加尤其可能出现在气相和冷凝液中,还可能出现在反应器壁上和聚合介质的表面上。
US 5,395,904描述了通过根据进料方法的受控聚合而聚合乙烯基吡咯烷酮和乙酸乙烯酯。使用可能包含至多50重量%水的醇性溶剂。
US 5,319,041描述了通过根据进料方法的聚合制备乙烯基吡咯烷酮和乙酸乙烯酯的共聚物,其中控制聚合温度。
US 5,502,136描述了一种根据进料方法生产乙烯基吡咯烷酮和乙酸乙烯酯的共聚物的方法,其中经由通过特殊数学式定义的方案控制进料。
US 4,520,179和US 4,554,311描述了以过氧新戊酸叔丁酯作为引发剂在水或水/醇混合物中聚合乙烯基吡咯烷酮和乙酸乙烯酯。其中所用引发剂允许生产具有窄分子量分布的共聚物,这得不到FNU值<20的水溶性产物。
EP-A 161描述了一种生产乙烯基吡咯烷酮和乙酸乙烯酯的共聚物的方法,其中在聚合之后用特殊引发剂进行后聚合。然而,聚合物具有高残留含量的乙酸乙烯酯且并不足够非浑浊。
EP-A 795 567描述了通过在水溶液中聚合而生产乙烯基内酰胺和疏水性单体的共聚物。
EP-A公开了溶于水中得到清澈溶液的乙烯基吡咯烷酮和乙烯基酯的共聚物的生产,其中在聚合过程中的特定点进行溶剂交换以除去挥发性成分。该方法较复杂。
DE-A 22 18 935描述了N-乙烯基吡咯烷酮与各种水溶性和水不溶性共聚单体的共聚。这里使用水不溶性引发剂,它们以在共聚物的水溶液中的细碎悬浮液形式使用。然而,在水不溶性共聚单体的情况下,这同样不能得到FNU值<20的所需水溶性共聚物。
发明内容
因此,本发明的目的是提供一种通过在有机溶剂中的自由基共聚来生产至少一种亲水性N-乙烯基内酰胺和至少一种疏水性共聚单体的透明水溶性共聚物的改进方法。
根据本发明,该目的通过在引发剂存在下在有机溶剂中在回流条件下自由基聚合至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体而实现,其中在至少90mol%疏水性单体已经完全反应时将至少5mol%N-乙烯基内酰胺加入聚合混合物中。
具体实施方式
合适的水溶性乙烯基内酰胺为N-乙烯基吡咯烷酮、3-甲基-N-乙烯基吡咯烷酮、4-甲基-N-乙烯基吡咯烷酮、5-甲基-N-乙烯基吡咯烷酮、N-乙烯基吡啶酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺,优选N-乙烯基吡咯烷酮。乙烯基内酰胺的用量为30-90重量%,优选50-90重量%。
本发明方法适于生产其中疏水性单体含量基于单体混合物为10-70重量%,优选10-50重量%的单体混合物的水溶性聚合物。合适的疏水性单体是在水中的溶解度为1-100g/l的那些。合适的疏水性单体例如为乙酸乙烯酯、丙酸乙烯酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙基酯、丙烯酸正丁基酯、丙烯酸叔丁基酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯腈或甲基丙烯腈。疏水性单体尤其为在大气压力下的沸点为60-130℃的聚合温度范围的那些,从而使它们能够在聚合条件下蒸发。甚至在稍低于聚合温度的沸点下,在与溶剂具有足够溶混性的情况下疏水性单体也能随在聚合条件下沸腾的溶剂进入气相中。疏水性单体在这里可以作为与溶剂的共沸混合物或作为与溶剂的物理混合物进入气相中。优选的疏水性单体是乙酸乙烯酯。
可以提到的自由基引发剂例如为过氧化二烷基或二芳基,如过氧化二叔戊基、过氧化二枯基、二(叔丁基过氧异丙基)苯、2,5-二(叔丁基过氧)-2,5-二甲基己烷、过氧化叔丁基枯烯、2,5-二(叔丁基过氧)-2,5-二甲基-3-己烯、1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-二(叔丁基过氧)环己烷、2,2-二(叔丁基过氧)丁烷或过氧化二叔丁基,脂族和芳族过氧酯,如过氧新癸酸枯基酯、2-过氧新癸酸2,4,4-三甲基戊基酯、过氧新癸酸叔戊基酯、过氧新癸酸叔丁基酯、过氧新戊酸叔戊基酯、过氧新戊酸叔丁基酯、过氧-2-乙基己酸叔戊基酯、过氧-2-乙基己酸叔丁基酯、过氧二乙基乙酸叔丁基酯、1,4-二(叔丁基过氧)环己烷、过氧异丁酸叔丁基酯、过氧-3,5,5-三甲基己酸叔丁基酯、过氧乙酸叔丁基酯、过氧苯甲酸叔戊基酯或过氧苯甲酸叔丁基酯,过氧化二链烷酰或二苯甲酰,如过氧化二异丁酰、过氧化二(3,5,5-三甲基己酰)、过氧化二月桂酰、过氧化二癸酰、2,5-二(2-乙基己酰过氧)-2,5-二甲基己烷或过氧化二苯甲酰,以及过氧碳酸酯,如过氧二碳酸二(4-叔丁基环己基)酯、过氧二碳酸二(2-乙基己基)酯、过氧二碳酸二叔丁基酯、二乙酰过氧二碳酸酯、过氧二碳酸二肉豆蔻基酯、过氧异丙基碳酸叔丁基酯或过氧-2-乙基己基碳酸叔丁基酯。所用的易溶于油的偶氮引发剂例如为2,2’-偶氮二(异丁腈)、2,2’-偶氮二(2,4-二甲基戊腈)或4,4’-偶氮二(4-氰基戊酸)。
所用自由基引发剂优选为选自如下的化合物:过氧-2-乙基己酸叔丁基酯(Trigonox21;来自Akzo Nobel的Trigonox牌号)、过氧-2-乙基己酸叔戊基酯(Trigonox121)、过氧苯甲酸叔丁基酯(TrigonoxC)、过氧苯甲酸叔戊基酯、过氧乙酸叔丁基酯(TrigonoxF)、过氧-3,5,5-三甲基己酸叔丁基酯(Trigonox42 S)、过氧异丁酸叔丁基酯、过氧二乙基乙酸叔丁基酯(Trigonox27)、过氧新戊酸叔丁基酯(Trigonox25)、过氧异丙基碳酸叔丁基酯(TrigonoxBPIC)、2,5-二甲基-2,5-二(叔丁基过氧)己烷(Trigonox101)、过氧化二叔丁基(TrigonoxB)、氢过氧化枯基(TrigonoxK)和过氧-2-乙基己基碳酸叔丁基酯(Trigonox117)。当然还可以使用上述自由基引发剂的混合物。
引发剂基于单体的用量为0.02-15mol%,优选0.05-3mol%。在本发明方法中,引发剂取决于溶解度以在C1-C4醇中的溶液使用。在这些溶液中,引发剂的浓度基于溶剂为0.02-2mol%,优选0.1-2mol%。
合适的聚合介质是极性有机溶剂。该溶剂必须亲水,以使它可以与乙烯基内酰胺以任何混合比溶混。此外,该溶剂应在聚合条件下沸腾,从而可以形成回流。合适的例如为脂族或芳族卤代烃类,如氯仿、四氯化碳、六氯乙烷、二氯乙烷、四氯乙烷、氯苯,以及液态C1-或C2-氯氟烃类,脂族C2-C5腈类,如乙腈、丙腈、丁腈或戊腈,线性或环状脂族C3-C7酮类,如丙酮、甲基乙基酮、甲基异丁基酮、2-或3-己酮、2-、3-或4-庚酮、环戊酮、环己酮,线性或环状脂族醚类,如二异丙基醚、1,3-或1,4-二烷、四氢呋喃或乙二醇二甲基醚,碳酸酯,如碳酸二乙酯,以及内酯,如丁内酯、戊内酯或己内酯。合适的一元醇、二元醇或多元醇尤其是C1-C8醇类、C2-C8链烷二醇以及C3-C10三醇或多元醇。其实例是甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、正戊醇、2-戊醇、3-戊醇,以及乙二醇、1,2-丙二醇或1,3-丙二醇。
所用单烷氧基醇尤其为被C1-C6烷氧基取代的上述C1-C8醇、C2-C8链烷二醇和C3-C10三醇。其实例是甲氧基甲醇、2-甲氧基乙醇、2-甲氧基丙醇、3-甲氧基丙醇、2-甲氧基丁醇、3-甲氧基丁醇、4-甲氧基丁醇、2-乙氧基乙醇、2-乙氧基丙醇、3-乙氧基丙醇、2-乙氧基丁醇、3-乙氧基丁醇、4-乙氧基丁醇、2-异丙氧基乙醇、2-异丙氧基丙醇、3-异丙氧基丙醇、2-异丙氧基丁醇、3-异丙氧基丁醇、4-异丙氧基丁醇、2-(正丙氧基)乙醇、2-(正丙氧基)丙醇、3-(正丙氧基)丙醇、2-(正丙氧基)丁醇、3-(正丙氧基)丁醇、4-(正丙氧基)丁醇、2-(正丁氧基)乙醇、2-(正丁氧基)丙醇、3-(正丁氧基)丙醇、2-(正丁氧基)丁醇、3-(正丁氧基)丁醇、4-(正丁氧基)丁醇、2-(仲丁氧基)乙醇、2-(仲丁氧基)丙醇、3-(仲丁氧基)丙醇、2-(仲丁氧基)丁醇、3-(仲丁氧基)丁醇、4-(仲丁氧基)丁醇、2-(叔丁氧基)乙醇、2-(叔丁氧基)丙醇、3-(叔丁氧基)丙醇、2-(叔丁氧基)丁醇、3-(叔丁氧基)丁醇、4-(叔丁氧基)丁醇。
特别合适的是C1-C4醇,优选乙醇或异丙醇。特别优选使用异丙醇作为溶剂。
聚合通常在5-9的中性pH下进行。必要的话,通过加入碱如氨、三乙胺、三乙醇胺或氢氧化钠溶液,或酸如盐酸、乳酸、草酸、乙酸或甲酸来调节和/或维持该pH。
若需要较低分子量,则可以通过在聚合混合物中加入调节剂来产生。合适的调节剂例如为醛类,如甲醛、乙醛、丙醛、正丁醛和异丁醛,甲酸,甲酸铵,硫酸羟铵和磷酸羟铵。此外,可以使用以有机键合形式包含硫的调节剂。这些调节剂例如为二正丁基硫、二正辛基硫、二苯基硫、二异丙基二硫化物、二正丁基二硫化物、二正己基二硫化物、二乙酰二硫化物和二叔丁基三硫化物。优选调节剂包含SH基团形式的硫。该类调节剂的实例是正丁基硫醇、正己基硫醇或正十二烷基硫醇。特别优选水溶性的含硫聚合调节剂,如亚硫酸氢盐、二亚硫酸盐(disulfite)以及诸如巯基乙酸乙酯、半胱氨酸、2-巯基乙醇、1,3-巯基丙醇、3-巯基-1,2-丙二醇、1,4-巯基丁醇、巯基乙酸、3-巯基丙酸、巯基琥珀酸、硫甘油、二乙醇硫化物、硫二甘醇、乙硫基乙醇、硫脲和二甲亚砜的化合物。其他合适的调节剂是烯丙基化合物,如烯丙醇或烯丙基溴,苄基化合物,如苄基氯,或烷基卤化物,如氯仿或四氯甲烷。在优选实施方案中,将调节剂计量加入反应混合物中,合适的话以在C1-C4醇中的溶液。
本发明方法的进行应使得在至少90mol%疏水性单体已经完全反应时将至少10mol%N-乙烯基内酰胺加入聚合混合物中。
在本发明方法中,将单体,合适的话以在C1-C4醇中的溶液,计量加入反应混合物中(进料方法)。在本发明的一个实施方案中,首先引入至多20mol%,优选至多15mol%,尤其至多10mol%的水溶性N-乙烯基内酰胺I(基于N-乙烯基内酰胺I的总量)和少量引发剂溶液和溶剂,优选乙醇或异丙醇。然后将该混合物升至反应温度并与剩余的引发剂溶液和合适的话调节剂同时连续或分几次计量加入剩余量的单体。通常而言,计量加料在2-14小时,优选3-12小时,理想的是4-11小时内进行(取决于所用批料大小和浓度)。单体在反应混合物中的浓度基于反应混合物为10-80重量%,优选20-75重量%,尤其25-70重量%。此时,在反应混合物已经升至所需反应温度之后允许连续或分几次加入引发剂溶液,尤其是在2.5-16小时,优选3.5-14小时,尤其5-12.5小时内加入。
在待聚合的疏水性单体总用量中至少90mol%聚合之后,加入另外量I-占待聚合的乙烯基内酰胺总用量的5-25mol%-的乙烯基内酰胺,以使加料以线性或可变的物料流连续进行或分几次分批进行,该量I的加入应使该量I的乙烯基内酰胺的加料在疏水性单体的总加料时间的110-150%后完成。若加料以可变物料流连续进行,则在该量I的加料时间的50%内将该量I的至少60%加入反应混合物中。若该量I的加料分几次分批进行,则取决于以小时计算的绝对加料时间将该量分成3-7等份,从而同样可以在该量I的加料时间的50%内将该量I的至少60%加入反应混合物中,其中第一份加料在该量I的加料时间为零时加入反应混合物中。若加料以线性物料流连续进行,则同样可以在开始连续计量加料之前在该量I的加料时间为零时将该量I的全部量的5-10%分批加入反应混合物中。
除了本发明的该方法外,可以将其他使本发明聚合物溶液的浊度最小化的已知方法与该方法结合,条件是它们与这里所述的方法不矛盾。
聚合反应在回流条件下进行。就此而言,回流条件是指液态聚合混合物沸腾且易于挥发的组分如溶剂和/或疏水性单体蒸发并因冷却而再次冷凝。回流通过控制温度和压力而维持。
反应温度通常为60-90℃,但也可以高达130℃。该反应可以在大气压力下、在自生压力下或在保护性气体表压下进行。在保护性气体表压的情况下,调节压力以使沸腾总是存在。本领域熟练技术人员可以使用相对蒸气压确定合适的压力范围。压力在这里通常不超过2MPa。聚合可以在0.05-2MPa,优选0.08-1.2MPa,尤其是0.1-0.8MPa的压力下进行。
聚合在装有搅拌装置的蒸发器中进行。合适的搅拌装置是锚式搅拌器、螺旋桨搅拌器、交叉叶片搅拌器、Mik搅拌器或本领域熟练技术人员已知适于溶液聚合的其他搅拌器。此外,还存在一个或多个用于计量加入单体、引发剂溶液和合适的话调节剂(溶液)的进料装置。
此外,该蒸发器在其中不存在液态聚合混合物而是存在气相的反应器上部区域装有冷凝器。
在聚合条件下,考虑到它们的较低沸点,溶剂和/或疏水性单体部分进入气相中,而较高沸点的N-乙烯基内酰胺保留在液态聚合相中。取决于溶剂的选择,气相还可以仅由疏水性单体组成。在冷凝器中,溶剂和/或疏水性单体的气相冷凝并因此形成所谓的回流。
在聚合反应之后,需要的话加入一种或多种聚合引发剂并将聚合物溶液加热到例如聚合温度或高于聚合温度的温度,以完成聚合。合适的是上述偶氮引发剂,还有所有其他适于在醇性溶液中的自由基聚合的常规引发剂,例如过氧化物、氢过氧化物、过氧化二硫酸盐、过碳酸盐、过氧酯和过氧化氢。这样将聚合反应进行到转化率为99.9%。在聚合过程中形成的溶液通常包含10-70重量%,优选15-60重量%的聚合物。在聚合之后,还可以将所得溶液进行物理后处理,例如蒸汽蒸馏或用氮气汽提,从而从溶液中除去随蒸汽挥发的溶剂或杂质。此外,还可以用过氧化氢、亚硫酸钠/氢过氧化叔丁基等对溶液进行化学后处理或漂白。
合适的话可以通过对应于现有技术的干燥方法将通过蒸汽蒸馏得到的共聚物的水溶液转化成固体粉末。合适的干燥方法是适合由水溶液进行干燥的那些。优选的方法例如为喷雾干燥、喷雾流化床干燥、转鼓干燥和带式干燥。同样可以使用冻干和冷冻浓缩。
借助本发明方法可以确保共聚单体都总是维持均匀的浓度且不会发生只有一种单体的过浓,从而如前所述防止形成水不溶性均聚物。
所得聚合物通常具有的K值(在浓度为1重量%的水溶液或乙醇溶液中在25℃下测定)为10-100,尤其是15-90,特别优选20-80。K值的测定描述于H.Fikentscher,“Systematik der Cellulosen auf Grund ihrerViskositt in Lsung”[基于溶液粘度的纤维素体系],Cellulose-Chemie13(1932),58-64和71-74和Encyclopedia of Chemical Technology,第21卷,第2版,427-428(1970)中。
它们的透明溶解性的度量是浊度单位FNU(或NTU),该单位在浓度为5重量%的聚合物水溶液中在25℃下测量并通过用作为人造不透明剂的福尔马肼(formazin)校准而确定。准确的方法在下列实施例中给出。根据本发明得到的聚合物具有的FNU值<20,尤其<10,优选<7,特别优选<5。
由本发明方法得到的聚合物尤其用于化妆品和药物制剂中,例如在发蜡添加剂、头发定型添加剂或喷发胶添加剂中作为增稠剂或成膜剂,用于皮肤化妆品制剂、免疫化学品中或在药物制剂中用作活性成分释放剂。此外,根据本发明生产的聚合物可以用作农业化学的助剂,例如用于种子涂敷或用于缓慢释放肥料配制剂。这些聚合物还适合作为工业应用的涂料,例如用于涂敷纸张或塑料,或用于热熔粘合剂。此外,这些聚合物适合作为转印用粘合剂、润滑添加剂、金属表面防锈剂或除锈剂、防垢剂或除垢剂、从含油的水中回收石油过程中的辅助剂、石油和天然气生产以及石油和天然气运输过程中的辅助剂、废水清洁剂、粘合剂原料、洗涤添加剂和照相工业中的辅助剂。
下列实施例用于说明本发明,但不限制本发明。
实施例
共聚物水溶液的浊度通过浊度法测量(根据DIN 38404的改性方法)测定。在该方法中,以光度法测定由测量溶液所散射的光,光散射由光束与溶液中的颗粒或液滴之间的相互作用引起,这些颗粒或液滴的数目和尺寸构成了浊度。这里所测量的量为浊度单位FNU(或NTU),其在浓度为5重量%的聚合物水溶液中在25℃下测量并通过用作为人造不透明剂的福尔马肼(formazin)校准而确定。FNU值越高,该溶液越浑浊。
实施例1-5通用程序:
进料分配
初始进料 进料1 见实施例
进料2 见实施例
进料1 异丙醇 230ml
乙烯基吡咯烷酮 见实施例
乙酸乙烯酯 见实施例
进料2 异丙醇 30ml
过新戊酸叔丁基酯75% 2g
进料3 乙烯基吡咯烷酮 见实施例
进料4 异丙醇 30ml
过新戊酸叔丁基酯75% 1g
(Trigonox 25)
在体积为2L的搅拌反应器中进行聚合。初始进料用氮气吹扫10分钟,然后加热到聚合温度T(℃)(内部温度)。在距离T差10%的(℃)温度下开始进料1和2。进料1在v小时内计量加入,进料2在x小时内计量加入。如所述在y小时内计量加入进料3。然后将该混合物后聚合1小时。当进料2完成时,将该混合物加热到比T高10-15%的内部温度(℃)。然后在80℃下将进料4在z小时内计量加入。当进料4完成时,将该混合物在该比T高10-15%的温度(℃)下再后聚合b小时。然后首先通过热蒸馏除去溶剂,然后通过蒸汽蒸馏除去溶剂,并通过添加水产生所述固体含量。
固体含量,重量%
K值在浓度为1%的乙醇溶液中测量
GC分析:乙烯基吡咯烷酮,ppm;乙酸乙烯酯,ppm;
外观:颜色、粘度、透明度(FNU值)
以mol%表示的数据指所述进料物质的总量。
实施例1
VP/VAc=55.5∶44.5 mol mol%
初始进料: VP 0.142 8.471
VAc 0.173 9.953
进料1 VP 1.286 76.634
VAc 1.563 90.047
进料3 VP 0.250 14.895
聚合温度:78℃
进料时间:进料1:v=4小时 进料3:y=2小时
进料3的开始:进料1结束后
引发剂进料:进料2:x=6小时 进料4:z=0.5小时
后聚合:a=2小时,b=1小时
固体含量:35.4重量%
K值:32.4,在浓度为1%的乙醇溶液中测量
GC分析:乙烯基吡咯烷酮<50ppm;乙酸乙烯酯<50ppm;
外观:浅黄色,清澈,FNU值:8
实施例2
VP/VAc=70∶30 mol mol%
初始进料: VP 0.179 7.807
VAc 0.116 9.050
进料1 VP 1.801 78.465
VAc 1.171 90.950
进料3 VP 0.315 13.727
聚合温度:78℃
进料时间:进料1:v=3.5小时 进料3:y=1.5小时
进料3的开始:进料1结束后
引发剂进料:进料2:x=5.5小时 进料4:z=0.5小时
后聚合:a=2小时,b=1小时
固体含量:37.1重量%
K值:30.5,在浓度为1%的乙醇溶液中测量
GC分析:乙烯基吡咯烷酮<50ppm;乙酸乙烯酯<62ppm;
外观:浅黄色,清澈,FNU值:1
实施例3
VP/VAc=30∶70 mol mol%
初始进料: VP 0.077 7.807
VAc 0.272 9.050
进料1 VP 0.772 78.465
VAc 2.732 90.950
进料3 VP 0.135 13.727
聚合温度:78℃
进料时间:进料1:v=5小时 进料3:y=2.5小时
进料3的开始:进料1开始后4.5小时
引发剂进料:进料2:x=7.5小时 进料4:z=1小时
后聚合:a=2小时,b=1.5小时
固体含量:36.3重量%
K值:33.7,在浓度为1%的乙醇溶液中测量
GC分析:乙烯基吡咯烷酮<51ppm;乙酸乙烯酯71ppm;
外观:浅黄色,清澈,FNU值:9
实施例4
VP/VAc=60∶40 mol mol%
初始进料: VP 0.154 7.807
VAc 0.155 9.050
进料1 VP 1.544 78.465
VAc 1.561 90.950
进料3 VP 0.270 13.727
聚合温度:78℃
进料时间:进料1:v=4小时 进料3:y=1.8小时
进料3的开始:进料1结束后
引发剂进料:进料2:x=6小时
进料4:z=1小时,分3次(0、25分钟后、1小时后)
后聚合:a=2小时,b=1.5小时
固体含量:32.8重量%
K值:34.2,在浓度为1%的乙醇溶液中测量
GC分析:乙烯基吡咯烷酮<50ppm;乙酸乙烯酯<50ppm;
外观:浅黄色,清澈,FNU值:3
实施例5
VP/VAc=50∶50 mol mol%
初始进料: VP 0.128 7.807
VAc 0.194 9.050
进料1 VP 1.286 78.465
VAc 1.951 90.950
进料3 VP 0.225 13.727
聚合温度:78℃
进料时间:进料1:v=4.5小时 进料3:y=2小时
进料3的开始:进料1开始后4小时
引发剂进料:进料2:x=6.5小时 进料4:z=1小时
后聚合:a=2小时,b=1.5小时
固体含量:34.3重量%
K值:31.4,在浓度为1%的乙醇溶液中测量
GC分析:乙烯基吡咯烷酮<50ppm;乙酸乙烯酯<50ppm;
外观:浅黄色,清澈,FNU值:2
Claims (8)
1.一种通过在引发剂存在下在有机溶剂中在回流条件下自由基聚合至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体而生产乙烯基内酰胺共聚物的方法,其中在至少90mol%疏水性单体已经完全反应时将至少10mol%N-乙烯基内酰胺加入聚合混合物中。
2.根据权利要求1的方法,其中所用疏水性共聚单体为在水中的溶解度为1-100g/l的单体。
3.根据权利要求1或2的方法,其中所用疏水性共聚单体为在大气压力下的沸点为60-150℃的单体。
4.根据权利要求1-3中任一项的方法,其中所用疏水性共聚单体为选自由乙酸乙烯酯、丙酸乙烯酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙基酯、丙烯酸正丁基酯、丙烯酸叔丁基酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯腈和甲基丙烯腈组成的组的单体。
5.根据权利要求1-4中任一项的方法,其中所用疏水性共聚单体为乙酸乙烯酯。
6.根据权利要求1-5中任一项的方法,其中所用N-乙烯基内酰胺为N-乙烯基吡咯烷酮。
7.根据权利要求1-6中任一项的方法,其中聚合在60-150℃的温度下进行。
8.根据权利要求1-7中任一项的方法,其中所用有机溶剂为醇。
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JP (1) | JP2007169651A (zh) |
CN (1) | CN1990513B (zh) |
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US7572870B2 (en) * | 2005-12-23 | 2009-08-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
US7572871B2 (en) * | 2005-12-23 | 2009-08-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
US7847044B2 (en) * | 2005-12-23 | 2010-12-07 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer by polymerization under increased pressure |
DE102007052412A1 (de) * | 2006-11-29 | 2008-06-05 | Basf Se | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren |
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DE2218935C3 (de) * | 1972-04-19 | 1980-01-31 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von wäßrigen Lösungen von N-Vinylpyrrolidonpolymerisaten |
DE2730017A1 (de) * | 1977-07-02 | 1979-01-18 | Basf Ag | Verfahren zur reduzierung der restmonomerengehalte bei der polymerisation von vinyllactamen und vinylestern |
US4520179A (en) * | 1982-09-20 | 1985-05-28 | Gaf Corporation | Preparation of vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
US4554311A (en) * | 1982-09-20 | 1985-11-19 | Gaf Corporation | Method of preparing an aqueous solution comprising vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
DE3931681A1 (de) * | 1989-09-22 | 1991-04-04 | Basf Ag | Verfahren zur herstellung von in wasser klaren copolymerisaten |
US5319041A (en) * | 1993-03-26 | 1994-06-07 | Isp Investments Inc. | Process for the preparation of vinylpyrrolidone/vinyl acetate copolymers |
US5395904A (en) * | 1993-12-07 | 1995-03-07 | Isp Investments Inc. | Process for providing homogeneous copolymers of vinylpyrrolidone and vinyl acetate which form clear aqueous solutions having a high cloud point |
US5502136A (en) * | 1994-12-28 | 1996-03-26 | Isp Investments Inc. | Process for making substantially homogeneous copolymers of vinyl pyrrolidone and vinyl acetate which form clear aqueous solutions |
DE19609864A1 (de) * | 1996-03-13 | 1997-09-18 | Basf Ag | Verfahren zur Herstellung von wasserlöslichen Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren |
DE102004022256A1 (de) * | 2004-05-04 | 2005-12-01 | Basf Ag | Verfahren zur Herstellung von überwiegend aus Vinylformamid aufgebauten Polymeren |
-
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- 2006-12-22 JP JP2006345255A patent/JP2007169651A/ja not_active Withdrawn
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JP2007169651A (ja) | 2007-07-05 |
US20070149737A1 (en) | 2007-06-28 |
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