CN1322220A - 二氧化碳和氧化烯的单羧酸终止的聚合物 - Google Patents
二氧化碳和氧化烯的单羧酸终止的聚合物 Download PDFInfo
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Abstract
一种可用作表面活性剂的聚合物组合物,其通过氧化烯(如氧化乙烯)、二氧化碳和单羧酸链终止剂(如含有脂肪烷基的单羧酸链终止剂)的反应而形成。
Description
发明背景
现有技术描述了很多由二氧化碳和氧化烯的反应形成的聚合物体系。
在授予H.C.Stevens的美国专利3,248,415中，教导了高分子量聚碳酸酯可以由二氧化碳和1，2-环氧化物形成。这些聚碳酸酯如第1栏第42-46行教导用羟基终止。
更近的授予R.F.Harris的美国专利4,745,162描述了表面活性剂的合成，其为具有酸端基的聚(碳酸亚烷基酯)多元醇。这些化合物为醇终止的物质且具有如下通式
R-(OC(O)OC2H4OC2H4)m-(OC2H4)n-(OI)k-OH其中R为烷基，如脂肪烷基，且其中m可以为约1-约40，n可以为约O-200，k可以为约0-约8。部分I为来自二醇或多元醇的未取代或取代残基。通过醇终止的物质与二元酸反应得到酸官能的聚(碳酸亚烷基酯)多元醇。
发明概述
本发明涉及由氧化烯、二氧化碳和单羧酸链终止剂的反应形成的聚合物组合物。本发明优选实施方案的描述
本发明依赖于二氧化碳、氧化烯(优选氧化乙烯)和单羧酸链终止剂的反应在优选的实施方案中产生下式的终产物：
RC(O)O(R′OC(O)O)m-(R′O)n)x-H其中R为烷基，优选含有约8-约18个碳原子的脂肪烷基，其中各R′独立地为含2-4个，优选2或3个碳原子的亚烷基，其中各m和n为1-约30，且其中x为约1-约30。这些组合物的分子量为约500-约4,000。在这些组合物中碳酸酯(“m”)与醚键(“n”)的总比率为约5∶95至约60∶40且脂肪酸与羟基的端基比为约15∶85至约40∶60。应注意m和n的值对于各单元x可变化。若未以其他方式提及，则本文本中给出的m和n的值为所有m和n个基团的数均值。
本发明的产物可以使用现有技术已知常用于生产二氧化碳/氧化烯聚合物组合物的技术来形成。在本发明组合物的制备中可以使用宽范围的催化剂。已发现有用的众知催化剂是锌盐，如戊二酸锌。还可以使用下列额外物质作为该反应的催化剂：碱(土)金属碳酸盐，如钠、钾和/或钙的碳酸盐；碱(土)金属氢氧化物，如钠、钾和/或钙的氢氧化物；或叔胺，如N-烷基吗啉中的一种或多种。还可以使用碱金属和/或碱土金属的锡酸盐，如三水合锡酸钠和三水合锡酸钾。催化剂可以约0.5％至约15％的量使用，基于用于该反应中的氧化烯重量。
用于本发明的合适氧化烯试剂包括环氧化物如氧化乙烯、氧化丙烯和1，2-氧化丁烯。若需要，可以使用氧化烯混合物和/或氧化烯的组成可以在工艺过程中改变。若使用2种或更多种氧化烯，则各R′的值可随工艺条件而改变。优选仅使用一种氧化烯。
合适的单官能羧酸链终止剂包括C2-C20烷基羧酸。优选使用C8-C18烷基羧酸，如月桂酸、硬脂酸和油酸。然而也可以使用其他羧酸。待用于本发明方法中的酸可以呈混合物形式，例如可从天然源得到。
用于进行该反应的优选溶剂为二氯甲烷，但可以将其他溶剂用于该聚合反应。若需要，可以不使用溶剂。
在进行该反应时，将氧化烯、链终止剂、催化剂、溶剂(若使用)和二氧化碳加入设计成耐高压的反应容器中。将该反应容器密封，升温至约60℃至约150℃，优选约110-130℃。在与二氧化碳反应的过程中将压力维持为约7至约60barg，优选约10-25barg。
本发明组合物可用作表面活性剂。
优选链终止剂具有疏水基团(如脂肪烷基)，而该低聚物结构的其余部分为亲水性的(且是潜在可生物降解的)，因为存在来自二氧化碳试剂的部分。
本发明由下列实施例说明。实施例1
本实施例说明用于聚合反应以生产本发明产物的催化剂的制备。
将50g戊二酸在200ml甲醇中的溶液缓慢加入25g氧化锌在175ml甲醇中的搅拌淤浆中。该酸加完后，维持搅拌，将混合物加热到60℃并保持4小时。过滤分离固体，用250ml甲醇洗涤两次并在60℃下真空干燥12小时。实施例2
本实施例说明使用实施例1所制备的催化剂生产本发明产物的聚合反应。
在装备有搅拌器、热电偶、气体导入口和排气口的1升高压釜中进行聚合。通用聚合程序如下：首先将10.2g戊二酸锌和链终止剂-月桂酸(2.5g)加入高压釜中，将其密封并用少量氮气流在95℃下吹扫密封的高压釜4小时。然后向该系统中加入300ml二氯甲烷溶剂和100g氧化乙烯并用7.1巴CO2加压。然后将高压釜加热到120℃的所需反应温度。向高压釜中加入额外的CO2直至压力为18.5-32.1巴，并不关闭CO2气体进料以维持压力。
反应结束后，将反应器冷却至室温，并释放压力。为了在打开高压釜之前蒸除氧化乙烯，将其再次加热到60℃，使排气管连接涤气塔开口。下一实施例中的表1说明使用的反应条件。实施例3
本实施例说明使用的回收和提纯程序。
如下处理含二氯甲烷的聚合物和齐聚物：首先，若需要的话再次加入二氯甲烷至约300ml.使用分液漏斗进行两次3.7％重量HCl的洗涤而除去催化剂。另外用水洗涤两次，用0.1M NaOH洗涤两次并最后用水洗涤两次。然后将聚合物分成两部分：甲醇可溶部分和甲醇不溶部分。这通过在搅拌下将二氯甲烷溶液缓慢加入甲醇中完成。除去甲醇不溶部分并在真空烘箱中干燥。在本实施例中，甲醇可溶部分是唯一需要的产物且通过蒸发溶剂而分离。聚合条件和甲醇可溶产物的表征数据列于下表1中：
表1：聚合条件和甲醇可溶产物特性
注：所有操作使用10.2g戊二酸锌催化剂
| 操作 | 条件 | 产物 | ||||||
| # | LA | 时间 | 温度 | 压力 | 甲醇可溶物 | LA/OH | MW | 结构 |
| g | Hr | ℃ | 巴 | g | g/mol | m∶n | ||
| 1 | 2.5 | 18 | 123 | 19 | 51.1 | 16/84 | 1100 | 13∶87 |
| 2 | 5.0 | 18 | 119 | 18.4 | 31.1 | 39/61 | 400 | 8∶92 |
| 3 | 1.25 | 18.5 | 120 | 19 | 40.8 | 14/86 | 900 | 13∶87 |
| 4 | 5 | 18 | 120 | 25 | 34.9 | 37/63 | 600 | 13∶87 |
| 5 | 5 | 18 | 120 | 32.1 | 32.3 | 40/60 | 700 | 15∶85 |
MW和m∶n比：由NMR测定
结构：碳酸酯(m)和醚(n)键之比
LA：月桂酸
LA/OH：由NMR测定的端基之比实施例4
本实施例说明在前一实施例中形成的甲醇可溶产物的表面性能。
由Fisher Autotensionmat表面张力分析仪测量表面张力。样品的临界胶束浓度(CMC)与表面张力一起示于表2中。低CMC和低表面张力的产物说明它们具有良好的表面性能：
表2：CO2 齐聚物的表面性能
实施例5
| 操作 | 表面性能 | |
| # | CMC，g/100ml | 表面张力@0.1％重量，mN/m |
| 1 | 0.025 | 33.3 |
| 2 | 0.014 | 28.8 |
| 3 | 0.028 | 31.4 |
| 4 | 0.023 | 32.5 |
| 5 | 0.025 | 31.2 |
将实施例2和3的通用聚合和产物回收程序用于本实施例。
在本实施例中，所有聚合在60-95℃的较低温度下进行且得到甲醇可溶产物和甲醇不溶性高聚物。表3和4说明聚合条件和产物特性。
表3：聚合条件和甲醇可溶产物特性
注：操作4：比例：催化剂/链终止剂＝10g/1g
| 操作 | 条件 | 产物产量 | 甲醇可溶产物 | |||||
| # | 时间 | 温度 | 压力 | 甲醇不溶物 | 甲醇可溶物 | ηinh | MW | 结构 |
| 小时 | ℃ | 巴 | 克 | 克 | ml/g | g/mol | m∶n | |
| 6 | 4 | 85 | 25 | 16.5 | 7.8 | 0.41 | 1400 | 17∶83 |
| 7 | 6 | 95 | 14.3 | 31.1 | 12.1 | 0.20 | 900 | 45∶55 |
| 8 | 4 | 60 | 57.1 | 7.9 | 3.4 | 0.092 | 1000 | 80∶20 |
| 9 | 4 | 85 | 25 | 49.3 | 6.4 | 0.305 | 2100 | 28∶72 |
| 10 | 4 | 85 | 25 | 36.1 | 5.8 | 0.12 | 900 | 55∶45 |
MW：由NMR测定
结构：碳酸酯(m)与醚(n)键之比
表4：CO2 齐聚物的表面性能
注：π＝γ溶剂-γ溶液。对水而言，使用72mN/m的γ溶剂。对于γ溶液，使用浓度高于CMC的值的平均。实施例6
| 操作 | 表面性能 | |
| # | CMC，g/100ml | π，mN/m |
| 6 | 0.01 | 44 |
| 7 | 0.002 | 42 |
| 9 | 0.01 | 42 |
| 10 | 0.005 | 48 |
下表说明根据OECD的试验指南(Ecotoxicology andEnvironmental Safety，24，319-327(1992))由密封瓶试验测试的碳酸亚烷基酯齐聚物各自的生物降解百分数：
样品的结构式如下：
| 样品 | 生物降解(％) | |||||||
| # | m/n | R/OH | Mn | 0天 | 7天 | 14天 | 21天 | 28天 |
| 6 | 14/86 | 23/77 | 2,400 | 0 | 3 | 20 | 40 | 52 |
| 4 | 28/72 | 57/43 | 2,100 | 0 | 15 | 40 | 47 | 57 |
| 7 | 43/53 | 53/47 | 1,400 | 0 | 20 | 38 | 55 | 63 |
| 5 | 55/45 | 52/48 | 900 | 0 | 45 | 67 | 72 | 78 |
R-{[C2H4OC(O)O]m-[C2H4O]n}x-H其中R＝CH3(CH2)10C(O)O-；m＝1-5；n＝1-25；和x＝1-30。
结果表明所有测试的碳酸亚烷基酯齐聚物是可生物降解的。对比例6
该实施例用于提供本发明和含于授予R.F.Harris的美国专利4,745,162实施例1和2中的某些公开内容之间的对比。
将碳酸亚乙酯(33.2g，0.38mol)、正十二烷醇(5.96g，0.037mol)和三水合锡酸钠催化剂(0.38g)加入装备有搅拌器、冷凝器、热电偶的三颈烧瓶中并将所得反应混合物维持在氮气氛下，同时加热到160℃并保持21小时。反应之后，通过将产物与丙酮(100ml)和4g CELATOMFW-60过滤剂一起搅拌3小时，然后过滤并除去溶剂而除去催化剂。产物的产量为20.7g。
NMR分析表明产物具有如下特性：碳酸酯∶醚键之比：36∶64；十二烷基∶OH的端基之比：42∶58；分子量：600g/mol；表面张力：36.2mN/m；以及CMC：0.016g/100ml。
前述实施例仅用于说明本发明的某些实施方案且因此不应认为限制本发明。所要求保护的范围如下列权利要求书所述。
Claims (9)
1.一种聚合物组合物，通过氧化烯、二氧化碳和单羧酸链终止剂的反应形成。
2.如权利要求1所述的组合物，其中链终止剂含有脂肪烷基。
3.如权利要求1或2所述的组合物，其中氧化烯为氧化乙烯。
4.如权利要求1-3中任一项所述的组合物，其中氧化烯为氧化乙烯且链终止剂为在其烷基中含约8至约18个碳原子的单羧酸。
5.一种聚合物组合物，具有如下结构：
RC(O)O(R′OC(O)O)m-(R′O)n)x-H其中R为含约8至约18个碳原子的脂肪烷基，各R′独立地为含2-4个碳原子的亚烷基，其中m和n为1至约30，x为约1至约30，且m与n之比为约5∶95至约60∶40。
6.如权利要求5所述的组合物，其中多于50％，优选基本上所有的R′基团含两个碳原子。
7.如权利要求5所述的组合物，其中多于50％，优选基本上所有的R′基团含三个碳原子。
8.如权利要求6所述的组合物，其中R为含约8至约18个碳原子的脂肪烷基且m与n之比为约5∶95至约60∶40。
9.如权利要求7所述的组合物，其中R为含约8至约18个碳原子的脂肪烷基且m与n之比为约5∶95至约60∶40。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/137,919 | 1998-08-20 | ||
| US09/137,919 US6100372A (en) | 1998-08-20 | 1998-08-20 | Monocarboxylic acid-terminated polymers of carbon dioxide and an alkylene oxide |
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| Publication Number | Publication Date |
|---|---|
| CN1322220A true CN1322220A (zh) | 2001-11-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99811778.1A Pending CN1322220A (zh) | 1998-08-20 | 1999-08-09 | 二氧化碳和氧化烯的单羧酸终止的聚合物 |
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| Country | Link |
|---|---|
| US (1) | US6100372A (zh) |
| EP (1) | EP1117722A1 (zh) |
| JP (1) | JP2003531221A (zh) |
| CN (1) | CN1322220A (zh) |
| WO (1) | WO2000014141A1 (zh) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143306A (zh) * | 2013-05-27 | 2015-12-09 | Lg化学株式会社 | 制备聚亚烷基碳酸酯的方法 |
| CN105518053A (zh) * | 2013-05-01 | 2016-04-20 | 诺沃梅尔公司 | 脂族聚碳酸酯组合物和方法 |
| CN105745017A (zh) * | 2013-11-04 | 2016-07-06 | Lg化学株式会社 | 有机锌催化剂及其制备方法 |
| CN105814112A (zh) * | 2013-08-26 | 2016-07-27 | 萨索尔化学品（美国）有限公司 | 基于脂族聚碳酸酯的表面活性剂 |
| US9732187B2 (en) | 2013-11-18 | 2017-08-15 | Lg Chem, Ltd. | Manufacturing method of polyalkylene carbonate resin |
| US9751981B2 (en) | 2013-10-30 | 2017-09-05 | Lg Chem, Ltd. | Manufacturing method of organic zinc catalyst and manufacturing method of polyalkylene carbonate resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19932292A1 (de) | 1999-07-10 | 2001-01-11 | Henkel Kgaa | Polyestercarbonate |
| GB201111928D0 (en) | 2011-07-12 | 2011-08-24 | Norner As | Process |
| TR201202779A2 (tr) | 2012-03-12 | 2013-10-21 | Petkim Petrokimya Holding Anonim Sirketi | Polietilen karbonat üretim yöntemi. |
| EP2664641B1 (en) | 2012-05-18 | 2018-04-25 | Petkim Petrokimya Holding Anonim Sirekti | Method for producing polyethylene carbonate with metal salts |
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| US3248415A (en) * | 1963-01-16 | 1966-04-26 | Pittsburgh Plate Glass Co | Method of preparing high molecular weight polycarbonates |
| US4066630A (en) * | 1977-01-10 | 1978-01-03 | Air Products And Chemicals, Inc. | End capped polyalkylene carbonates having improved thermal stability |
| US4137280A (en) * | 1978-04-19 | 1979-01-30 | Air Products And Chemicals, Inc. | Polyalkylene carbonates as processing aids for polyvinyl chloride |
| US4488982A (en) * | 1980-07-23 | 1984-12-18 | Texaco Development Corp. | Low foaming nonionic polyether polycarbonate surfactants and functional fluids |
| US4686276A (en) * | 1985-12-30 | 1987-08-11 | The Dow Chemical Company | Process for preparing poly (alkylene carbonates) |
| US4665136A (en) * | 1986-04-07 | 1987-05-12 | Air Products And Chemicals, Inc. | Process for producing novel block alkylene polycarbonate copolymers |
| US5015753A (en) * | 1986-07-14 | 1991-05-14 | The Dow Chemical Company | Process for preparing poly(alkylene carbonate) monoahls and polyahls useful as surfactants |
| US4895970A (en) * | 1986-07-14 | 1990-01-23 | The Dow Chemical Company | Poly(alkylene carbonate) monoahls and polyahls useful as surfactants |
| US4745162A (en) * | 1986-09-22 | 1988-05-17 | The Dow Chemical Company | Poly(alkylene carbonate) polyahls having on the average up to one acid-terminal moiety and salts thereof |
| US4956424A (en) * | 1986-10-02 | 1990-09-11 | The Dow Chemical Company | Novel poly (alkylene carbonate) polyahls having more than one pendant acid group |
| US4866143A (en) * | 1988-04-21 | 1989-09-12 | Basf Corporation | Novel surfactants based on poly(alkylene carbonate)s |
| US4948845A (en) * | 1988-04-21 | 1990-08-14 | Basf Corporation | Novel surfactants based on poly(alkylene carbonate)s |
| US4943677A (en) * | 1989-06-08 | 1990-07-24 | Air Products And Chemicals, Inc. | Making poly(alkylene carbonates) of controlled molecular weight |
| US5232633A (en) * | 1992-06-19 | 1993-08-03 | Lever Brothers | Sulfoethyl carbonate wetting agents and their use in detergent compositions |
| IL110787A0 (en) * | 1993-08-27 | 1994-11-11 | Sandoz Ag | Biodegradable polymer, its preparation and pharmaceutical composition containing it |
-
1998
- 1998-08-20 US US09/137,919 patent/US6100372A/en not_active Expired - Fee Related
-
1999
- 1999-08-09 CN CN99811778.1A patent/CN1322220A/zh active Pending
- 1999-08-09 JP JP2001576396A patent/JP2003531221A/ja active Pending
- 1999-08-09 WO PCT/EP1999/005763 patent/WO2000014141A1/en not_active Application Discontinuation
- 1999-08-09 EP EP99964478A patent/EP1117722A1/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105518053A (zh) * | 2013-05-01 | 2016-04-20 | 诺沃梅尔公司 | 脂族聚碳酸酯组合物和方法 |
| CN105143306A (zh) * | 2013-05-27 | 2015-12-09 | Lg化学株式会社 | 制备聚亚烷基碳酸酯的方法 |
| CN105814112A (zh) * | 2013-08-26 | 2016-07-27 | 萨索尔化学品（美国）有限公司 | 基于脂族聚碳酸酯的表面活性剂 |
| CN105814112B (zh) * | 2013-08-26 | 2019-03-08 | 萨索尔化学品(美国)有限责任公司 | 基于脂族聚碳酸酯的表面活性剂 |
| US9751981B2 (en) | 2013-10-30 | 2017-09-05 | Lg Chem, Ltd. | Manufacturing method of organic zinc catalyst and manufacturing method of polyalkylene carbonate resin |
| CN105745017A (zh) * | 2013-11-04 | 2016-07-06 | Lg化学株式会社 | 有机锌催化剂及其制备方法 |
| US9803048B2 (en) | 2013-11-04 | 2017-10-31 | Lg Chem, Ltd. | Organic zinc catalyst and preparation method thereof |
| US9732187B2 (en) | 2013-11-18 | 2017-08-15 | Lg Chem, Ltd. | Manufacturing method of polyalkylene carbonate resin |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000014141A8 (en) | 2000-06-15 |
| US6100372A (en) | 2000-08-08 |
| WO2000014141A1 (en) | 2000-03-16 |
| JP2003531221A (ja) | 2003-10-21 |
| EP1117722A1 (en) | 2001-07-25 |
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