CN101203534B - 酶分解聚合物中的残留甲酰胺 - Google Patents
酶分解聚合物中的残留甲酰胺 Download PDFInfo
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- CN101203534B CN101203534B CN2006800222053A CN200680022205A CN101203534B CN 101203534 B CN101203534 B CN 101203534B CN 2006800222053 A CN2006800222053 A CN 2006800222053A CN 200680022205 A CN200680022205 A CN 200680022205A CN 101203534 B CN101203534 B CN 101203534B
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- Prior art keywords
- methane amide
- enzyme
- vinyl
- acid
- urase
- 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.)
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种减少由N-乙烯基甲酰胺单体通过聚合生产的制剂(Z)中的甲酰胺含量的方法。
Description
本发明涉及一种减少由N-乙烯基甲酰胺单体构成的聚合物制剂中的甲酰胺的方法。
背景技术
乙烯基甲酰胺的聚合物和共聚物溶液可包含作为源自其制备的杂质的甲酰胺。甲酰胺浓度通常可为500-20 000ppm。对许多应用领域如化妆品而言,希望降低甲酰胺含量。取决于应用领域,希望降低至小于500ppm以下至小于10ppm的水平。同时必要的是所应用的方法不改变聚合物结构,尤其是必须不通过水解聚合物的甲酰胺侧链而产生氨基。
已经证明通过物理除臭方法如蒸馏、蒸气汽提或气体汽提而降低聚合物溶液的甲酰胺含量的尝试是不适合的。
WO 00/09573描述了通过用酸或碱处理聚合物而将甲酰胺水解为甲酸盐和氨。然而,该程序没有产生令人满意的结果,因为水解不充分,或聚合物的显著比例的甲酰胺单元同样被水解。
通过氧化或还原除去甲酰胺的尝试同样是不成功的。用许多试剂将其化学转化的尝试同样不成功。
在所有这些情况下,或者不存在甲酰胺的转化,或者引发聚合物上不希望的副反应如分子量降低、交联或水解。
已知能够水解甲酰胺的各种酶:刀豆脲酶(Jack beanurease)[EC 3.5.1.51]高活性地催化脲水解,明显较低活性地催化甲酰胺水解为甲酸和氨(Dixon等人,Can.J.Biochem.1980,58 1335-1344;Fishbein,Biochim.Biophys.Acta 1977,484,433-442;Blakeley and Zerner,J.Mol.Cat.1984,23,263-292)。
Greenwood等人(FEMS Microbiol.Lett.1998,160,131-135)描述了来自Methylophilus methylotrophus[EC 3.5.1.5]的能够在水溶液中使甲酰胺水解的脲酶。
Clarke(Adv.Microbial Physiol.1970,4,179-222)研究了来自绿脓杆菌(Pseudomonas aeruginosa)的脂族酰胺酶的底物特异性。这需要在活性测定中研究各种脂族酰胺如甲酰胺、乙酰胺。
Wyborn等人(Eur.J.Biochem.1996,240,314-322;Microbiology1994,140,191-195)研究了来自Methylophilus methylotrophus的甲酰胺酶。在提纯酶和异种表达的过程中进行甲酰胺水解活性测定。
Cornelius等人(J.General Microbiol.,1981,125,367-374)描述了来自Alcaligenes eutrophus的两种酰胺酶。在活性测定中对甲酰胺和其它脂族酰胺研究了底物特异性。
发明目的
本发明的目的为在使得聚合物结构不受攻击的温和条件下减少含水聚合物制剂中的甲酰胺含量。
发明内容
本发明涉及一种通过使酶分类E.C.3.5的水解酶与制剂(P)接触而减少由N-乙烯基甲酰胺单体通过聚合制备的(P)中的甲酰胺含量的方法。
适合本发明方法的水解酶为作用于非肽碳氮键的那些水解酶(E.C.分类3.5.x.x.)。
其中优选与线性酰胺反应的水解酶分类[EC 3.5.1.x],非常特别优选脲酶分类[E.C.3.5.1.5.]和甲酰胺酶分类[EC 3.5.1.49]。
特别合适的脲酶为来自刀豆的脲酶,其为来自乳酸杆菌(Lactobacillus),尤其是发酵乳酸杆菌(Lactobacillus fermentum)的脲酶(“酸性脲酶”)和来自杆菌(Bacillus),尤其是巴氏芽孢杆菌(Bacillus pasteurii)的脲酶。
特别合适的甲酰胺酶为开头由Wyborn等人所述的来自Methylophilusmethylotrophus的甲酰胺酶。
酶可以各种纯度水平的提纯形式用于本发明方法中,或作为较不纯的萃取物如豆粉(刀豆粉;可市购)使用。酶优选作为固体使用。
酶可以纯净形式或作为多种不同酶的混合物(“鸡尾酒”)使用。
取决于方法程序,可将溶解形式的酶与(P)接触,或将酶施加至常规载体并使其以固定形式与(P)接触。
在本发明方法中使用的水解酶的量取决于酶制剂的纯度。对本发明方法而言,酶的典型用量为每g聚合物固体10-10 000单位,优选100-1000单位。一单位定义为在pH=7.5和25℃下每分钟水解1μmol脲的酶的量。这些酶的量仅为大约的指导量,尤其是当反应条件如温度和诱导时间改变时,其也可向上或向下偏移。对本发明的具体转化最佳的水解酶量可通过常规的系列试验容易地建立。
本发明方法可适用于包含N-乙烯基甲酰胺单元的所有聚合物。就此而言,合适的是N-乙烯基甲酰胺的均聚物和共聚物及其接枝共聚物。适合于N-乙烯基甲酰胺的可行共聚单体的实例为其它N-乙烯基羧酰胺如N-乙烯基-N-甲基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-正丙基甲酰胺、N-乙烯基-N-异丙基甲酰胺、N-乙烯基-N-异丁基甲酰胺、N-乙烯基-N-甲基丙酰胺、N-乙烯基-N-丁基乙酰胺和N-乙烯基-N-甲基丙酰胺。
适合N-乙烯基甲酰胺的其它共聚单体为具有3-8个C原子的单烯属不饱和羧酸,以及这些单体的水溶性盐。该组单体例如包括丙烯酸、甲基丙烯酸、二甲基丙烯酸、乙基丙烯酸、马来酸、柠康酸、亚甲基丙二酸、烯丙基乙酸、乙烯基乙酸、巴豆酸、富马酸、中康酸和衣康酸。该组的优选使用单体为丙烯酸、甲基丙烯酸、马来酸或所述羧酸的混合物,尤其是丙烯酸和甲基丙烯酸的混合物。不饱和羧酸可以游离形式和以例如用氢氧化钠溶液、氢氧化钾溶液、氢氧化钙或氨部分或完全中和形式聚合。
其它合适的共聚单体的实例为所述羧酸的酯、酰胺和腈。丙烯酸酯和甲基丙烯酸酯优选源自具有1-4个碳原子的饱和单羟基醇或包含2-4个碳原子的饱和二羟基醇。
这些酯的实例为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯和源自异构丁醇的丙烯酸和甲基丙烯酸的酯,以及丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、丙烯酸羟基异丁酯和甲基丙烯酸羟基异丁酯。
还应提及丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-叔丁基丙烯酰胺、丙烯腈、甲基丙烯腈、丙烯酸二甲基氨基乙酯、甲基丙烯酸二甲基氨基乙酯、丙烯酸二乙基氨基乙酯、甲基丙烯酸二乙基氨基乙酯,以及最后提及的单体与羧酸或无机酸的盐,以及季铵化产物。
作为可用于N-乙烯基甲酰胺共聚的共聚单体,额外可使用乙烯酯如甲酸乙烯酯、乙酸乙烯酯和丙酸乙烯酯。还合适的是N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、1-乙烯基咪唑、2-甲基-1-乙烯基咪唑和4-甲基-1-乙烯基咪唑、乙烯基磺酸、烯丙基磺酸、甲基烯丙基磺酸、苯乙烯磺酸、乙烯膦酸、烯丙基膦酸和二烯丙基二甲基氯化铵。当然也可使用所述单体的混合物。
所述共聚单体的单元例如可构成1-99摩尔%的含N-乙烯基甲酰胺的共聚物。
此外也可以使得聚合在分子中具有至少两个烯属不饱和非共轭双键的化合物存在下进行,以使N-乙烯基甲酰胺的均聚物和共聚物改性。聚合中包含这些单体具有增加聚合物分子量的效果。
特别合适的实例为亚烷基二丙烯酰胺如亚甲基二丙烯酰胺和N,N’-丙烯酰基乙二胺、N,N’-二乙烯基亚乙基脲、N,N’-二乙烯基亚丙基脲、乙叉基二3-(N-乙烯基吡咯烷酮)、N,N′-二乙烯基二咪唑基-(2,2′)丁烷和1,1′-二(3,3′-乙烯基苯并咪唑啉-2-酮)-1,4-丁烷。其它合适的交联剂例如为亚烷基二醇二(甲基)丙烯酸酯如乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、四乙二醇二甲基丙烯酸酯、二甘醇丙烯酸酯、二甘醇甲基丙烯酸酯,芳族二乙烯基化合物如二乙烯基苯和二乙烯基甲苯,以及丙烯酸乙烯酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、二乙烯基二烷、季戊四醇三烯丙基醚,以及交联剂的混合物。交联剂的用量基于用于聚合的单体为0.1-10重量%,优选1-4重量%。
改性的另一可行性由将N-乙烯基甲酰胺接枝至其它聚合物上而提供。该类接枝聚合物通过在接枝基质存在下,以上述方式使N-乙烯基甲酰胺,合适的话与其它上述共聚单体一起聚合而制备。
US-A-5334287例如描述了将N-乙烯基甲酰胺接枝至基于糖的天然物质上。就此而言,合适的接枝基质为单糖和寡糖如葡萄糖、果糖、半乳糖、核糖、甘露糖、蔗糖、乳糖和棉子糖,或多糖如果胶、藻酸铵、甲壳质、脱乙酰壳多糖、肝素、琼脂、阿拉伯树胶、刺槐豆胶、瓜耳豆胶、黄原胶、葡聚糖等,以及戊聚糖如木聚糖和阿聚糖。还合适的是来自下列的天然淀粉:玉米淀粉、土豆淀粉、小麦淀粉、米淀粉、木薯淀粉、西米淀粉、高粱淀粉、树薯淀粉、豌豆淀粉和具有至少80重量%支链淀粉含量的淀粉如蜡质玉米淀粉或蜡质土豆淀粉,酶或水解降解的淀粉如白糊精和黄糊精以及麦芽糖糊精,或氧化淀粉如双醛淀粉。
最后,在该系列中还应提及化学改性的糖如羧甲基纤维素。
适合作为接枝基质的其它聚合物为包含氧化烯单元的那些,尤其是可通过使氧化乙烯、氧化丙烯、氧化正丁烯、氧化异丁烯或四氢呋喃聚合而获得的C2-C4氧化烯的均聚物和共聚物。这类聚氧化烯描述在DE-A-19515943中。这些聚合物还可为C2-C4氧化烯与主要为长链醇、酚类、羧酸和胺的加成产物。DE-A-19526626公开了在包含饱和的C1-C4羧酸的乙烯酯如甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯和正丁酸乙烯酯的单元和/或乙烯醇单元的聚合物上的相应的接枝聚合物。
包含N-乙烯基甲酰胺单元的聚合物通过已知的溶液、沉淀、悬浮或乳液聚合方法,并使用在聚合条件下保持自由基的化合物而制备。聚合温度通常为例如30-200℃,优选40-110℃。合适的引发剂例如为偶氮和过氧化合物,以及通常的氧化还原引发剂体系如过氧化氢和肼的组合。这些体系合适的话可额外包含少量重金属盐。优选使用水溶性偶氮化合物如2,2’-偶氮二(2-甲基丙酰胺)二盐酸盐、2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)和2,2’-偶氮二(2-甲基-N-苯基丙酰胺)二盐酸盐作为聚合引发剂。低K值聚合物通过在调节剂如巯基化合物、烯丙基化合物、醛或肼存在下方便地进行聚合而制备。
可以该方式获得的聚合物具有10-300,优选30-250的K值。K值通过H.Fikentscher,Cellulose-Chemie,第13卷,58-64和71-74(1932)的方法,在pH为7和25℃的温度和0.1重量%的聚合物浓度下,在5%浓度的氯化钠水溶液中测定。
在以该方式制备的聚合物中的甲酰胺浓度为10-100 000ppm。典型的值为5000-10 000ppm。本发明方法现在使该甲酰胺含量显著减少。
使水解酶与(P)接触的反应温度可在约5℃至至多100℃的宽范围内选择。优选选择的温度为所用水解酶具有高催化活性的温度,其通常为10-40℃,优选20-35℃。然而,如果使用来自嗜热微生物的水解酶或特定选择的耐热的酶,则反应温度还可明显更高。
本发明的pH范围通常为3-10,优选4-8。最佳范围取决于所用水解酶的pH稳定性。
反应时间极大地取决于酶的所选择用量、温度和(P)中聚合物的浓度,以及所需的“残留甲酰胺含量”。反应时间通常为数小时至至多数天,优选5-24小时。
在本发明方法中,聚合物制剂通常存在于水分散体或溶剂,优选缓冲溶剂中。(P)可呈分散体或优选分子溶液的形式。在制剂(P)中的聚合物的量可在约1重量%至至多99重量%,优选5-50重量%,特别优选10-30重量%聚合物的宽范围内调节。
本发明方法可不连续地或连续地进行。在不连续(分批)程序中,酶可在紧邻聚合之后或在分离和合适的话提纯聚合物之后加入。在甲酰胺已通过水解酶降解之后,取决于使用目的,可从反应介质中除去酶。然而,酶还可留在反应介质中并仅在需要时例如通过加热或通过酸化介质而失活。
对本发明优选实施方案中的连续程序而言,使用负载型酶与聚合物制剂(P)接触。例如,可将负载型水解酶填充入柱中,将(P)在所需反应条件下泵送通过该柱。对特定应用而言,还可串联酶反应器级联,以特别有效地减少甲酰胺。
使用本发明方法可显著降低由N-乙烯基甲酰胺通过聚合制备的聚合物制剂中的甲酰胺含量,并因此获得小于50ppm,优选小于20ppm,尤其是小于10ppm的残留甲酰胺含量。
实施例部分:
除非另有说明,酶活性单位指将脲水解为氨。
水溶液中甲酰胺含量由HPLC定量。
实施例1:
用刀豆粉萃取物降解残留的甲酰胺
用水萃取刀豆粉(由Sigma提供),通过离心澄清并通过超滤浓缩。获得每ml含有1101U脲酶的萃取物。
将各种量的该脲酶萃取物加入16重量%的聚(乙烯基甲酰胺)水溶液(批料的总质量为50g),并在40℃和7.0的pH下搅拌。酶通过酸化变性以停止反应。
酶的量[kU] | 反应时间 | 残留甲酰胺含量[ppm] |
无无5510101515 | 0小时24小时6小时24小时6小时24小时6小时24小时 | 160017009904206008032040 |
实施例2:
用刀豆粉的冷冻干燥产物降解残留甲酰胺
将实施例1中所述的萃取物冷冻干燥。获得活性为17926U/g的含脲酶的粉末。
将各种量的该脲酶粉末加入50g的16重量%的聚(乙烯基甲酰胺)水溶液,并在40℃和7.0的pH下搅拌。酶通过酸化变性以停止反应。
酶的量[kU] | 反应时间 | 残留甲酰胺含量[ppm] |
无1.252.55101515 | 24小时24小时24小时24小时24小时6小时24小时 | 170079039010010230<10 |
实施例3:
用大豆粉的萃取物降解残留的甲酰胺
用水萃取大豆粉(由Sigma提供),通过离心澄清并通过超滤浓缩。获得每ml含有292U脲酶的萃取物。
将各种量的该脲酶萃取物加入16重量%的聚(乙烯基甲酰胺)水溶液(批料的总质量为50g),并在40℃和7.0的pH下搅拌。酶通过酸化变性以停止反应。
酶的量[kU] | 反应时间 | 残留甲酰胺含量[ppm] |
无557.3 | 24小时6小时24小时6小时 | 170012206101150 |
实施例4:
用市售脲酶降解残留甲酰胺
来自剑豆的提纯的脲酶可购自Fluka(序列号94282)。水解脲的活性为每mg蛋白质约35单位。
将各种量的该脲酶萃取物加入16重量%的聚(乙烯基甲酰胺)水溶液(批料的总质量为50g),并在40℃和7.0的pH下搅拌。酶通过酸化变性以停止反应。
酶的量 | 残留甲酰胺含量[ppm] |
无28.5mg(1kU)57mg(2kU)114ng(4kU)171mg(6kU)229mg(8kU) | 150057017014<10<10 |
实施例5:
在不同温度和时间以及比实施例4高的聚合物浓度下用市售脲酶降解残留的甲酰胺
来自剑豆的提纯的脲酶可购自Fluka(序列号94282)。水解脲的活性为每mg蛋白质约35单位。
将各种量的该脲酶萃取物加入32重量%的聚(乙烯基甲酰胺)水溶液(批料的总质量为150g),并在40℃和7.0的pH下搅拌。酶通过酸化变性以停止反应。
酶的量 | 8小时后的残留甲酰胺含量[ppm] | 24小时后的残留甲酰胺含量[ppm] | 72小时后的残留甲酰胺含量[ppm] |
07.5kU15KU30kU60kU | --1170610140 | 3400-2702540 | -2207020- |
实施例6:
用来自巴氏芽孢杆菌的市售脲酶降解残留甲酰胺
来自巴氏芽孢杆菌的提纯的脲酶可购自Sigma(序列号U7127)。水解脲的活性为每mg蛋白质约197单位。
将各种量的该脲酶萃取物加入16重量%的聚(乙烯基甲酰胺)水溶液(批料的总质量为20g),并在40℃和7.5的pH下搅拌。酶通过酸化变性以停止反应。
酶的量 | 残留甲酰胺含量[ppm] |
无10kU20kU | 1200400120 |
Claims (7)
1.一种通过使酶分类E.C.3.5的水解酶与制剂(P)接触而减少由N-乙烯基甲酰胺单体通过聚合制备的(P)中的甲酰胺含量的方法,其中所述水解酶为来自刀豆的脲酶。
2.根据权利要求1的方法,其中使(P)和水解酶在3-10的pH下接触。
3.根据权利要求1的方法,其中使(P)和水解酶在5-100℃的温度下接触。
4.根据权利要求1的方法,其中(P)呈水溶液形式。
5.根据权利要求1的方法,其中(P)为N-乙烯基甲酰胺的均聚物。
6.根据权利要求1的方法,其中所述方法连续进行。
7.根据权利要求1的方法,其中将所述甲酰胺含量降至低于50ppm。
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PCT/EP2006/063353 WO2006136554A1 (de) | 2005-06-21 | 2006-06-20 | Enzymatischer abbau von restformamid in polymeren |
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CN1307595A (zh) * | 1998-06-25 | 2001-08-08 | Cytec技术有限公司 | 从聚酰胺制备物中除去不需要的单酰胺化合物的方法 |
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JPH03252406A (ja) * | 1990-03-01 | 1991-11-11 | Kuraray Co Ltd | 高分子化合物のアミド基を分解する方法 |
DE19836992A1 (de) * | 1998-08-14 | 2000-02-17 | Basf Ag | Verfahren zur Eliminierung von Formamid aus N-Vinylformamideinheiten enthaltenden Polymerisaten |
JP4366132B2 (ja) * | 2003-08-26 | 2009-11-18 | 住友化学株式会社 | N−置換ホルムアミド類の加水分解酵素 |
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EP0272025A2 (en) * | 1986-12-16 | 1988-06-22 | Zeneca Limited | Process for the decomposition of acrylamide |
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JP5006875B2 (ja) | 2012-08-22 |
ES2376250T3 (es) | 2012-03-12 |
CN101203534A (zh) | 2008-06-18 |
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