CN1033861C - 用天冬氨酸制备杂聚琥珀酰亚胺的方法 - Google Patents
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Abstract
杂聚琥珀酰亚胺制备方法包括制成聚(烷二醇)，天冬氨酸及必要时的一或多种其它氨基酸的聚合混合物，将该混合物加热到高温以及将混合物保持在高温下以形成杂聚琥珀酰亚胺。
Description
本发明涉及杂聚琥珀酰亚胺制备方法，尤其是在聚(烷二醇)中用天冬氨酸及必要时的其它氨基酸制备杂聚琥珀酰亚胺的方法。
已知几种制备纯聚琥珀酰亚胺的方法，纯聚琥珀酰亚胺水解成聚(氨基酸)时可用作吸收剂，硬表面清洁剂，及起锅炉和冷却塔水处理剂，助洗剂，防成膜剂，分散剂，螯合剂和除垢剂作用的洗涤添加剂，但所有制备纯聚琥珀酰亚胺的已知方法的缺点在于工艺时间太长，原料昂贵或要求处理给制造工艺带来许多困难的固体物料。
US 5 057597(Koskan)公开了在氮气氛中至少180℃下将氨基酸搅拌流化3-6小时而制成纯聚琥珀酰亚胺的固相方法，其中得到的聚琥珀酰亚胺再水解成聚(氨基酸)。
US 4839461(Boehmke et al.)公开了将马来酸或马来酸酐与氨液以1∶1-1.5的mol比混合制成聚(天冬氨酸)的方法，其中得到的混合物加热到120-150℃，形成的铵盐和马来酸液蒸发而得结晶浆料并使其熔融，这期间蒸出冷凝和结晶水而得聚(天冬氨酸)多孔物质，整个工艺要求6-8小时才能完成。
转让给Ajinomoto的日本专利52-0088773B公开了制备聚(天冬氨酸)的溶剂法，其中在一或多种有机溶剂中用天冬氨酸酐的氢卤酸盐，而所用溶剂为有机酸如丙酸，丁酸或戊酸；醇如叔丁醇和叔戊醇；酯如乙酸乙酯丁酯；酮如甲基异丁基酮和环己酮；醚如四氢呋喃和二恶烷；卤代烃如二氯乙烷和二氯苯；烃如甲苯，二甲苯和萘烷以及酰胺如二甲基甲酰胺，但这些溶剂可能引起另外的危害，费用支出，气味和毒性并要求清除后才能得最终产品。
合成聚琥珀酰亚胺和聚(氨基酸)的现有方法费时，复杂或要求使用大量挥发性有机溶剂或惰性气体。本文及权利要求书中“杂聚琥珀酰亚胺”指聚合物链中含琥珀酰亚胺基团并可含其它基团的聚合物料，而“纯聚琥珀酰亚胺”指仅含琥珀酰亚胺基团的聚合物料。
本发明目的是提出溶剂法制备杂聚琥珀酰亚胺的方法。
本发明另一目的是提出不需要产品分离步骤的溶剂法制备杂聚琥珀酰亚胺的方法。
本发明提出杂聚琥珀酰亚胺制备方法，其中：
a)制成聚(烷二醇)，天冬氨酸及必要时的一或多种其它氨基酸的聚合混合物；
b)将混合物加热到高温；以及
c)将混合物保持在高温下以形成杂聚琥珀酰亚胺。
本发明所用聚(烷二醇)为反应温度下为流体的产品，合适例子包括聚(丁二醇)，聚(乙二醇)和聚(丙二醇)，而且其一或两端还可连羧酸，1-30碳烷基，胺，1-10碳烷基胺或其任何组合，优选为二乙二醇，聚(乙二醇)，有端甲基的聚(乙二醇)或聚(丙二醇)，其分子量最高约30000，优选约300-约20000，更优选约1000-约15000，而其加入聚合混合物中的用量以马来酰胺酸重量计为2-约90wt％，优选约20-约90wt％，更优选约30-约85wt％。
除天冬氨酸而外，还可用最多80wt％(以天冬氨酸重量计)一或多种其它氨基酸按本发明方法制成杂聚琥珀酰亚胺，优选其它氨基酸为丙氨酸，赖氨酸，天冬酰胺，甘氨酸或谷氨酸，其用量以马来酰胺酸重量计为5-约70wt％，优选约10-约60wt％。
聚合环境中优选基本上无氧，包括空气中的氧，原因是有氧时缩聚反应的温度下聚(烷二醇)会氧化，变色或降解，而获得这种环境的适宜办法是用惰性气体，优选用氮气密封，吹扫或鼓泡或在减压下进行聚合。
本发明所用高温必须足以引起缩聚，优选温度随反应条件变化，如优选温度随天冬氨酸与聚(烷二醇)的比例增大或随进行缩聚的压力升高而升高，但如在存在共沸溶剂时优选温度可降低，优选高温一般约120-约300℃。
缩合反应形成杂聚琥珀酰亚胺，因此要求去除反应副产物如水或醇以使反应完全，其中去除水的合适办法是向聚合混合物中加一或多种共沸溶剂如甲苯，二甲苯或四氢化萘并从聚合混合物中去除共沸馏出物，而另一除水办法是向聚合混合物中加一或多种干燥剂如硅铝酸盐，其它办法是用惰性气体向聚合混合物中鼓泡或吹扫聚合混合物表面或在减压下进行聚合。
聚合可间歇或连续地行，其中适宜的反应器包括间歇反应罐，连续搅拌反应罐，活塞流反应器，反应管和刮壁反应器，其中反应温度必须足以驱除缩合反应中形成的水，该温度可根据是否用共沸溶剂和进行聚合的压力是低于大气压，大气压或超过大气压的情况变化。
本发明方法得到的产品为杂聚琥珀酰亚胺在聚(烷二醇)中的溶液，悬浮液或分散液，其中聚(烷二醇)可用于宜用杂聚琥珀酰亚胺的许多领域如用于洗涤剂配方，因此在产品用于洗涤剂时无需将聚琥珀酰亚胺从聚(烷二醇)分出的分离步骤，而且必要时还可用任何常见方法，优选将产品与碱水溶液氢氧化钠或碳酸钠水溶液接触而使杂聚琥珀酰亚胺水解成相应的聚(氨基酸)如聚(天冬氨酸)。
实施例1
制备纯聚琥珀酰亚胺
向装有磁性搅拌棒，Dewar冷凝器和氮报出入管的100ml三颈圆底烧瓶中加5.0gL-天冬氨酸和5.0g分子量8000的聚(乙二醇)甲基醚，其中烧瓶用氮气连续吹扫并在190℃油浴中浸泡15小时后冷至室温，然后经1H NMR谱分析表明未余下天冬氨酸，生成的纯聚琥珀酰亚胺再用稀碳酸钠水溶液水解而形成聚(天冬氨酸)并经1H NMR谱分析得到证实。
Claims (13)
1.杂聚琥珀酰亚胺制备方法，其中包括：
a)制成聚(烷二醇)、天冬氨酸及必要时的一或多种其它氨基酸的聚合混合物，所述聚(烷二醇)选自聚(丁二醇)、聚(乙二醇)和聚(丙二醇)以及一或两端还连有羧酸、1-30碳烷基、胺、1-10碳烷基胺或其任何组合端基的聚(丁二醇)、聚(乙二醇)和聚(丙二醇)；
b)将混合物加热到120℃-250℃的高温；以及
c)将混合物保持在此高温下以形成杂聚琥珀酰亚胺。
2.权利要求1的方法，其中聚(烷二醇)选自二乙二醇、聚(乙二醇)、端连甲基的聚(乙二醇)和聚(丙二醇)。
3.权利要求1的方法，其中聚(烷二醇)为聚(乙二醇)。
4.权利要求1的方法，其中聚合混合物中以天冬氨酸计含2-90wt％聚(烷二醇)。
5.权利要求1的方法，其中聚合混合物中以天冬氨酸计含20-90wt％聚(烷二醇)。
6.权利要求1的方法，其中聚合混合物中以天冬氨酸计含30-85wt％聚(烷二醇)。
7.权利要求1的方法，其中一或多种其它氨基酸选自丙氨酸、甘氨酸、赖氨酸、天冬酰胺和谷氨酸。
8.权利要求1的方法，其中一或多种其它氨基酸为丙氨酸。
9.权利要求1的方法，其中聚合混合物中以天冬氨酸计含最多80wt％一或多种氨基酸。
10.权利要求1的方法，其中聚合混合物中以天冬氨酸计含5-70wt％一或多种氨基酸。
11.权利要求1的方法，其中聚合混合物中以天冬氨酸计含10-60wt％一或多种氨基酸。
12.权利要求1的方法，其中还包括将杂聚琥珀酰亚胺水解成相应聚(氨基酸)。
13.权利要求1的方法，其中混合物保持在基本上无氧高温环境中。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/911,866 US5380817A (en) | 1992-07-10 | 1992-07-10 | Process for preparing polysuccinimides from aspartic acid |
| US07/911,866 | 1992-07-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1082065A CN1082065A (zh) | 1994-02-16 |
| CN1033861C true CN1033861C (zh) | 1997-01-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN93108565A Expired - Fee Related CN1033861C (zh) | 1992-07-10 | 1993-07-10 | 用天冬氨酸制备杂聚琥珀酰亚胺的方法 |
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|---|---|
| US (2) | US5380817A (zh) |
| EP (1) | EP0578449B1 (zh) |
| JP (1) | JPH06211982A (zh) |
| KR (1) | KR940005713A (zh) |
| CN (1) | CN1033861C (zh) |
| AT (1) | ATE152746T1 (zh) |
| AU (1) | AU666194B2 (zh) |
| BR (1) | BR9302725A (zh) |
| CA (1) | CA2099462A1 (zh) |
| DE (1) | DE69310446T2 (zh) |
| ES (1) | ES2102600T3 (zh) |
| MX (1) | MX9303793A (zh) |
| NZ (1) | NZ247842A (zh) |
| TW (1) | TW274554B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5380817A (en) * | 1992-07-10 | 1995-01-10 | Rohm And Haas Company | Process for preparing polysuccinimides from aspartic acid |
| ATE171715T1 (de) * | 1993-04-23 | 1998-10-15 | Rhodia Chimie Sa | Polyanhydroasparaginsäure und seine bioabbaubaren hydrolyseprodukte |
| US5484945A (en) * | 1993-08-24 | 1996-01-16 | Mitsui Toatsu Chemicals, Inc. | Preparation process of polysuccinimide |
| CA2132112A1 (en) * | 1993-09-21 | 1995-03-22 | David Elliott Adler | Acid catalyzed process for preparing amino acid polymers |
| US5681920A (en) * | 1994-06-28 | 1997-10-28 | Donlar Corporation | Process for production of a polysuccinimide and derivatives thereof |
| US5552517A (en) * | 1995-03-03 | 1996-09-03 | Monsanto Company | Production of polysuccinimide in an organic medium |
| DE19545678A1 (de) | 1995-12-07 | 1997-06-12 | Goldschmidt Ag Th | Copolymere Polyaminosäureester |
| JPH09165447A (ja) | 1995-12-15 | 1997-06-24 | Mitsubishi Chem Corp | ポリアスパラギン酸共重合体及びその製造方法 |
| US5856427A (en) * | 1996-01-16 | 1999-01-05 | Solutia Inc. | Process for the production of polysuccinimide |
| US5981691A (en) * | 1997-04-23 | 1999-11-09 | University Of South Alabama | Imide-free and mixed amide/imide thermal synthesis of polyaspartate |
| DE19822603A1 (de) | 1998-05-20 | 1999-11-25 | Goldschmidt Ag Th | Pigmentpasten enthaltend hydrophob modifizierte Polyasparaginsäurederivate |
| DE19822600C2 (de) | 1998-05-20 | 2003-08-21 | Goldschmidt Ag Th | Copolymere, hydrophob modifizierte Polyasparaginsäureester mit erhöhter Molekularmasse |
| DE19822604A1 (de) | 1998-05-20 | 1999-11-25 | Goldschmidt Ag Th | Kondensationsprodukte enthaltend polyethermodifizierte Monoester und/oder -amide alpha, beta-ungesättigter Dicarbonsäuren, ihre Herstellung und Verwendung |
| DE60027833T2 (de) | 1999-09-10 | 2007-04-26 | Nippon Shokubai Co., Ltd. | Verfahren zur Herstellung von Polyasparaginsäure |
| US6878797B2 (en) * | 2002-04-19 | 2005-04-12 | Board Of Trustees Of Michigan State University | Synthesis and applications of polymaleimide |
| CN100351286C (zh) * | 2006-01-24 | 2007-11-28 | 北京化工大学 | 一种聚天门冬氨酸树脂的制备方法 |
| EP2271732B1 (en) | 2008-04-28 | 2013-04-17 | Dow Global Technologies LLC | Polyalkylene glycol lubricant composition |
| CN102002152B (zh) * | 2010-10-27 | 2013-06-12 | 中国科学院长春应用化学研究所 | 脂肪族二元酸-1,2-丙二醇聚酯及其制备方法 |
| CN120329530A (zh) * | 2024-01-16 | 2025-07-18 | 元素驱动(杭州)生物科技有限公司 | 含有环酰亚胺结构的聚酯聚合物 |
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| US2306918A (en) * | 1940-02-15 | 1942-12-29 | Research Corp | Amine reaction product |
| US3052655A (en) * | 1958-08-01 | 1962-09-04 | Sidney W Fox | Thermal polymerization of amino acid mixtures containing aspartic acid or a thermal precursor of aspartic acid |
| GB1064417A (en) * | 1963-12-09 | 1967-04-05 | Kyowa Hakko Kogyo Kk | Process for the preparation of copolypeptides |
| US3846380A (en) * | 1972-10-31 | 1974-11-05 | M Teranishi | Polyamino acid derivatives and compositions containing same |
| IT1000589B (it) * | 1972-12-26 | 1976-04-10 | Ajinomoto Kk | Procedimento per preparare un poli amminoacido |
| JPS528873A (en) * | 1975-07-09 | 1977-01-24 | Matsushita Electric Ind Co Ltd | Maximum demand monitor indication unit |
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| US5057597A (en) * | 1990-07-03 | 1991-10-15 | Koskan Larry P | Process for the manufacture of anhydro polyamino acids and polyamino acids |
| US5371177A (en) * | 1992-07-10 | 1994-12-06 | Rohm And Haas Company | Process for preparing polysuccinimides from maleamic acid |
| US5371179A (en) * | 1992-07-10 | 1994-12-06 | Rohm And Haas Company | Polysuccinimide polymers and process for preparing polysuccinimide polymers |
| US5380817A (en) * | 1992-07-10 | 1995-01-10 | Rohm And Haas Company | Process for preparing polysuccinimides from aspartic acid |
| US5319145A (en) * | 1992-07-10 | 1994-06-07 | Rohm And Haas Company | Method for preparing polysuccinimides with a rotary tray dryer |
| US5219952A (en) * | 1992-09-18 | 1993-06-15 | Donlar Corporation | Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia |
| US5296578A (en) * | 1992-09-18 | 1994-03-22 | Donlar Corporation | Production of polysuccinimide and polyaspartic acid from maleic anhydride and ammonia |
| US5393868A (en) * | 1992-10-13 | 1995-02-28 | Rohm And Haas Company | Production of polysuccinimide by thermal polymerization of maleamic acid |
-
1992
- 1992-07-10 US US07/911,866 patent/US5380817A/en not_active Expired - Fee Related
-
1993
- 1993-06-10 AU AU40154/93A patent/AU666194B2/en not_active Ceased
- 1993-06-10 NZ NZ247842A patent/NZ247842A/en unknown
- 1993-06-21 JP JP5149000A patent/JPH06211982A/ja not_active Withdrawn
- 1993-06-24 MX MX9303793A patent/MX9303793A/es not_active IP Right Cessation
- 1993-06-30 CA CA002099462A patent/CA2099462A1/en not_active Abandoned
- 1993-06-30 BR BR9302725A patent/BR9302725A/pt not_active Application Discontinuation
- 1993-07-02 AT AT93305212T patent/ATE152746T1/de not_active IP Right Cessation
- 1993-07-02 ES ES93305212T patent/ES2102600T3/es not_active Expired - Lifetime
- 1993-07-02 DE DE69310446T patent/DE69310446T2/de not_active Expired - Fee Related
- 1993-07-02 EP EP93305212A patent/EP0578449B1/en not_active Expired - Lifetime
- 1993-07-05 TW TW082105338A patent/TW274554B/zh active
- 1993-07-09 KR KR1019930012927A patent/KR940005713A/ko not_active Withdrawn
- 1993-07-10 CN CN93108565A patent/CN1033861C/zh not_active Expired - Fee Related
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1994
- 1994-08-25 US US08/296,337 patent/US5484878A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69310446T2 (de) | 1997-10-09 |
| TW274554B (zh) | 1996-04-21 |
| ES2102600T3 (es) | 1997-08-01 |
| ATE152746T1 (de) | 1997-05-15 |
| EP0578449B1 (en) | 1997-05-07 |
| MX9303793A (es) | 1994-02-28 |
| JPH06211982A (ja) | 1994-08-02 |
| CA2099462A1 (en) | 1994-01-11 |
| US5484878A (en) | 1996-01-16 |
| EP0578449A1 (en) | 1994-01-12 |
| AU666194B2 (en) | 1996-02-01 |
| NZ247842A (en) | 1995-03-28 |
| KR940005713A (ko) | 1994-03-22 |
| BR9302725A (pt) | 1994-03-01 |
| US5380817A (en) | 1995-01-10 |
| DE69310446D1 (de) | 1997-06-12 |
| AU4015493A (en) | 1994-01-13 |
| CN1082065A (zh) | 1994-02-16 |
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