CN1260271C - 通过双金属氰化物催化制备的脂族聚碳酸酯均聚物和共聚物 - Google Patents
通过双金属氰化物催化制备的脂族聚碳酸酯均聚物和共聚物 Download PDFInfo
- Publication number
- CN1260271C CN1260271C CNB02815262XA CN02815262A CN1260271C CN 1260271 C CN1260271 C CN 1260271C CN B02815262X A CNB02815262X A CN B02815262XA CN 02815262 A CN02815262 A CN 02815262A CN 1260271 C CN1260271 C CN 1260271C
- Authority
- CN
- China
- Prior art keywords
- cyclic carbonate
- aliphatic polycarbonate
- dmc catalysts
- metal cyanide
- double metal
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyethers (AREA)
Abstract
本发明涉及脂族聚碳酸酯均聚物和共聚物,它们是通过DMC催化方法由环状碳酸酯的开环均聚或共聚获得的。
Description
本发明涉及通过DMC催化方法由环状碳酸酯的开环均聚或共聚获得的脂族聚碳酸酯均聚物和共聚物。
用于含氧环状单体开环聚合的双金属氰化物(DMC)催化剂已问世很久了。DMC催化剂在通过环氧化物与含有活泼氢原子的起始化合物的加聚反应制备聚醚多元醇方面具有特别的市场价值(参见例如US-A 3 404109,US-A 3 829 505,US-A 3 941 849和US-A 5 158 922),因为DMC催化剂的使用使得带有双键端基的单官能团聚醚,即所谓的一元醇的比例相对使用碱催化剂按传统方法制备的聚醚多元醇而言降低了。而且如US-A 5 470 813,EP-A 700 949,EP-A 743 093,EP-A 761708,WO 97/40086,WO 98/16310和WO 00/47649中所述的改进的高活性DMC催化剂具有特别高的活性,允许以非常低的催化剂浓度(25p pm或更低)制备聚醚多元醇,因此不必再将催化剂从终产物中分离出来。此外,DMC催化剂也使其它含氧环状单体如氧杂环丁烷(US-A 3 278457,US-A 3 404 109)、环状酸酐(US-A 5 145 883,US-A 3 538 043)或内酯(US-A 5 032 671)的均聚和共聚成为可能。
脂族聚碳酸酯均聚物和共聚物均适于作为热塑性体系的添加剂。而且,脂族OH-官能化聚碳酸酯广泛用作构造聚氨酯和聚氨酯-脲弹性体的羟基组分。制备脂族聚碳酸酯的通常方法是二醇与来自短链醇的碳酸二烷基酯、二氧杂环戊酮或碳酸二苯基酯进行酯交换。这些反应可被催化剂,特别是碱、锡和钛化合物加速(参见例如Kunststoffhandbuch,3/1卷,聚碳酸酯,Hanser Verlag,Münich,1992,118页起)。
现在已经发现脂族聚碳酸酯均聚物和共聚物可以通过DMC催化方法由环状碳酸酯的开环均聚或共聚获得。
因此本发明涉及脂族聚碳酸酯均聚物和共聚物,它们全部或部分是通过DMC催化方法由环状碳酸酯的开环均聚或共聚获得的。
适宜的环状碳酸酯具有通式(I)或(II):
其中m,n,p和q彼此独立地代表0,1,2,3,4,5或6并且R1和R2代表H、C1-6-烷基、C3-6-链烯基、C1-6-烷或烯氧基-C1-6-烷基,特别是H、CH3和C2H5。
优选使用的环状碳酸酯(I)或(II)为1,3-丙二醇碳酸酯、新戊二醇碳酸酯、1,4-丁二醇碳酸酯和季戊四醇或己二醇的二聚碳酸酯。特别优选的是6元环碳酸酯,特别是新戊二醇碳酸酯。
原则上适宜的DMC催化剂是已知的并且在上面引用的现有技术中有详细描述。例如在US-A 5 470 813,EP-A 700 949,EP-A 743 093,EP-A 761 708,WO 97/40086,WO 98/16310和WO 00/47649中所述的改进的高活性DMC催化剂是优选使用的。EP-A 700 949中所述的高活性DMC催化剂是典型的实例,它们除了含有双金属氰化物(例如六氰基钴(III)酸锌)和有机络合物配体(例如叔丁醇)外,还含有数均分子量大于500g/mol的聚醚。
DMC催化的环状碳酸酯的开环均聚或共聚一般在20-200℃,优选在40-180℃,特别优选在80-160℃进行。反应可以在总压力为0.001-20bar下进行。聚合可以以本体(substance)或在惰性有机溶剂如甲苯或THF中进行。溶剂的量一般占待制备聚合物量的10-30wt%。
以待制备聚合物的量为基准,催化剂的浓度一般为0.0005-1wt%,优选为0.001-0.1wt%,特别优选为0.001-0.05wt%。
聚合可连续或不连续进行,例如以间歇或半间歇方法进行。
DMC催化的环状碳酸酯的开环均聚或共聚任选在一种或多种含有活泼氢原子的起始化合物存在下进行。以这种方式可以制备出适于作为构造聚氨酯体系的多元醇成分的OH-官能化的脂族聚碳酸酯均聚物和共聚物。
分子量为18-10,000g/mol并且含有1-8个羟基基团的化合物优选用作含有活泼氢原子的起始化合物。实例为水、乙醇、丁醇、乙二醇、二甘醇、三甘醇、1,2-丙二醇、1,4-丁二醇、己二醇、双酚A、三羟甲基丙烷、甘油、季戊四醇、山梨糖醇、蔗糖、降解淀粉、聚醚多元醇和聚酯多元醇。
DMC催化的环状碳酸酯的开环聚合可以均聚方式进行,任选在一种或多种含有活泼氢原子的起始化合物存在下进行。
DMC催化的环状碳酸酯的开环聚合也可以共聚方式进行,也任选在一种或多种含有活泼氢原子的起始化合物存在下进行。无规共聚和嵌段共聚均是可能的。
在无规共聚中,DMC催化的环状碳酸酯的开环聚合是在任意一种或多种适于以DMC催化剂催化聚合的其他单体存在下进行。特别适于与环状碳酸酯进行无规共聚的是环氧化物,特别是环氧乙烷、环氧丙烷和环氧丁烷及其混合物,氧杂环丁烷,环状酸酐如邻苯二甲酸酐,环状酯如己内酯,和丙交酯。
在制备聚碳酸酯嵌段共聚物时,根据本发明,脂族聚碳酸酯嵌段是通过DMC催化的环状碳酸酯的开环聚合获得的。优选的嵌段共聚物为聚(酯-嵌段-碳酸酯)共聚物和聚(醚-嵌段-碳酸酯)共聚物,其中酯或醚嵌段可通过任意方法或催化剂方法获得。
在本方法的优选实施方案中,首先通过已知方法由DMC催化的环氧化物,特别是环氧丙烷和/或环氧丙烷/环氧乙烷混合物与上述含有活泼氢原子的起始化合物的加聚反应制备聚醚多元醇,然后使含有活性DMC催化剂的聚醚多元醇与环状碳酸酯根据本发明的方法进行开环反应。在该反应中,聚醚多元醇的仲羟基基团可完全或部分转化为伯羟基基团,后者与异氰酸酯基团的反应性更强。因此这些聚(醚-碳酸酯)多元醇在用于聚氨酯方面具有极大的价值。
实施例
实施例1
在一个带有搅拌器和回流冷凝器的可加热平底广口瓶中,在氩气下加入20g聚丙二醇起始化合物(数均分子量=1,000g/mol)和4mg DMC催化剂(包含六氰基钴酸锌、叔丁醇和数均分子量为1000g/mol的聚丙二醇;EP-A 700 949中有述)并加热至105℃。然后在105℃常压下于3小时内连续计量加入20g环氧丙烷。当加入了所有的环氧丙烷时,加入5.2g新戊二醇碳酸酯并随后在150℃常压下搅拌1小时。然后在150℃/1mbar下蒸馏1小时除去挥发性组分;随后使混合物冷却至环境温度。
得到微黄色透明产物。1H-和13C-NMR分析显示聚丙二醇中28%的仲羟基基团与新戊二醇碳酸酯进行开环反应形成伯羟基基团。
实施例2
在一个带有搅拌器和回流冷凝器的可加热平底广口瓶中,在氩气下加入20g聚丙二醇起始化合物(数均分子量=1,000g/mol)和2mg实施例1中所用的DMC催化剂并加热至105℃。然后在105℃常压下于3小时内连续计量加入20g环氧丙烷。当加入了所有的环氧丙烷时,加入5.2g新戊二醇碳酸酯并随后在150℃常压下搅拌5小时。然后在150℃/1mbar下蒸馏1小时除去挥发性组分;随后使反应混合物冷却至环境温度。
得到带淡黄色的透明产物。1H-和13C-NMR分析显示,聚丙二醇中47%的仲羟基基团与新戊二醇碳酸酯进行开环反应形成伯羟基基团。
实施例3
在一个带有搅拌器和回流冷凝器的可加热平底广口瓶中,在氩气下加入20g聚丙二醇起始化合物(数均分子量=1,000g/mol)和2mg实施例1中所用的DMC催化剂并加热至105℃。然后在105℃常压下于3小时内连续计量加入20g环氧丙烷。当加入了所有的环氧丙烷时,加入15.6g新戊二醇碳酸酯并随后在150℃常压下搅拌1小时。然后在150℃/1mbar下蒸馏1小时除去挥发性组分;随后使反应混合物冷却至环境温度。
得到带淡黄色的且浑浊(由于未反应的新戊二醇碳酸酯)的产物。1H-和13C-NMR分析显示,聚丙二醇中70%的仲羟基基团与新戊二醇碳酸酯进行开环反应形成伯羟基基团。
Claims (8)
1.制备脂族聚碳酸酯均聚物或共聚物的方法,该方法包括环状碳酸酯在双金属氰化物催化剂的存在下进行开环均聚或共聚的步骤。
3.根据权利要求1的方法,其中环状碳酸酯为新戊二醇碳酸酯。
4.根据权利要求1的方法,其中所用双金属氰化物催化剂包含六氰基钴(III)酸锌。
5.根据权利要求1的方法,其中所用双金属氰化物催化剂包含叔丁醇。
6.根据权利要求1的方法,其中双金属氰化物催化的环状碳酸酯的开环均聚或共聚是在一种或多种含有活泼氢原子的起始化合物存在下进行的。
7.制备OH-官能化的脂族聚碳酸酯均聚物或共聚物的方法,包括环状碳酸酯在双金属氰化物催化剂存在下进行开环的步骤。
8.根据权利要求7的方法,其中首先通过双金属氰化物催化的环氧化物与含有活泼氢原子的起始化合物的加聚反应制备聚醚多元醇,然后使含有活性双金属氰化物催化剂的聚醚多元醇与环状碳酸酯进行开环反应。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10138216.2 | 2001-08-03 | ||
DE10138216A DE10138216A1 (de) | 2001-08-03 | 2001-08-03 | Aliphatische Polycarbonathomo- und -copolymere durch DMC-Katalyse |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1538981A CN1538981A (zh) | 2004-10-20 |
CN1260271C true CN1260271C (zh) | 2006-06-21 |
Family
ID=7694330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB02815262XA Expired - Fee Related CN1260271C (zh) | 2001-08-03 | 2002-07-22 | 通过双金属氰化物催化制备的脂族聚碳酸酯均聚物和共聚物 |
Country Status (15)
Country | Link |
---|---|
US (2) | US6646100B2 (zh) |
EP (1) | EP1432751B1 (zh) |
JP (1) | JP2004536953A (zh) |
KR (1) | KR20040030910A (zh) |
CN (1) | CN1260271C (zh) |
AT (1) | ATE366766T1 (zh) |
BR (1) | BR0211678A (zh) |
CA (1) | CA2455996A1 (zh) |
DE (2) | DE10138216A1 (zh) |
HK (1) | HK1070666A1 (zh) |
HU (1) | HUP0401198A3 (zh) |
MX (1) | MXPA04001002A (zh) |
PL (1) | PL367101A1 (zh) |
RU (1) | RU2004106538A (zh) |
WO (1) | WO2003014186A1 (zh) |
Families Citing this family (59)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6762278B2 (en) * | 2002-02-04 | 2004-07-13 | Basf Corporation | Process for the copolymerization of alkylene oxides and carbon dioxide using suspensions of multi-metal cyanide compounds |
US6806348B2 (en) * | 2003-02-11 | 2004-10-19 | Basf Corporation | Process for removing and regenerating a double metal cyanide (DMC) catalyst from a polymer polyol |
US6713599B1 (en) | 2003-03-31 | 2004-03-30 | Basf Corporation | Formation of polymer polyols with a narrow polydispersity using double metal cyanide (DMC) catalysts |
JP4413226B2 (ja) | 2003-09-12 | 2010-02-10 | ビーエーエスエフ ソシエタス・ヨーロピア | 高分岐型または超分岐型の高官能性ポリカルボナート、その製造方法および使用方法 |
DE102004051241A1 (de) | 2004-10-20 | 2006-05-04 | Basf Ag | Fließfähige Polyamide mit hyperverzweigten Polyestern/Polycarbonaten |
DE102004054632A1 (de) * | 2004-11-11 | 2006-05-18 | Basf Ag | Polymerblends aus Polyestern und linearen oligomeren Polycarbonaten |
DE102005009166A1 (de) | 2005-02-25 | 2006-08-31 | Basf Ag | Hochfunktionelle, hoch- oder hyperverzweigte Polycarbonate sowie deren Herstellung und Verwendung |
US7268204B2 (en) * | 2005-03-29 | 2007-09-11 | Basf Corporation | Complex of a multimetal cyanide compound and methods of forming polyethercarbonate polyols |
US7671228B2 (en) * | 2005-03-29 | 2010-03-02 | Basf Corporation | Method of forming a polyethercarbonate polyol using a CO2-philic compound or substituent |
US20060223973A1 (en) * | 2005-03-29 | 2006-10-05 | Basf Corporation | Method of forming a polyethercarbonate polyol |
EP2058352B1 (en) * | 2006-08-31 | 2011-11-09 | Asahi Glass Company, Limited | Method of purifying polyether compound |
DE502007004885D1 (de) | 2006-12-19 | 2010-10-07 | Basf Se | Thermoplastische formmassen mit verbesserter duktilität |
US7666973B2 (en) * | 2007-07-30 | 2010-02-23 | Tyco Healthcare Group Lp | Carbonate copolymers |
US8309646B2 (en) | 2007-11-19 | 2012-11-13 | Basf Se | Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability |
PT2225337T (pt) | 2007-11-19 | 2017-11-27 | Basf Se | Utilização de polímeros muito ramificados em dispersões poliméricas para tintas brilhantes |
MY150270A (en) | 2007-11-20 | 2013-12-31 | Basf Se | Use of thermoplastic molding materials for gid/wit |
ES2400735T3 (es) | 2007-11-28 | 2013-04-11 | Basf Se | Mezcla de estabilizador líquido |
CN102027030B (zh) | 2008-03-14 | 2013-11-27 | 巴斯夫欧洲公司 | 粗孔聚氨酯弹性体 |
JP2011528745A (ja) * | 2008-07-23 | 2011-11-24 | ビーエーエスエフ ソシエタス・ヨーロピア | ポリマーを製造するための2−イソプロピル−2−アルキル−1,3−プロパンジオールの使用 |
EP2159240A2 (de) | 2008-09-01 | 2010-03-03 | Basf Se | Plastisch verformbare Polyurethanschaumstoffe |
KR20110069169A (ko) | 2008-10-13 | 2011-06-22 | 바스프 에스이 | 모노필라멘트를 제조하기 위한 방법 및 모노필라멘트의 용도 |
DE102008058224A1 (de) | 2008-11-19 | 2010-05-20 | Lanxess Deutschland Gmbh | Leichtbauteil in Hybridbauweise |
DE102008058225A1 (de) | 2008-11-19 | 2010-07-08 | Lanxess Deutschland Gmbh | Leichtbauteil in Hybridbauweise |
DE102009005763A1 (de) | 2009-01-23 | 2010-07-29 | Lanxess Deutschland Gmbh | Rahmenseitenteil einer Kraftfahrzeug Karosserie |
ATE517149T1 (de) | 2009-05-11 | 2011-08-15 | Basf Se | Verstärkte styrolcopolymere |
DE102009034767A1 (de) * | 2009-07-25 | 2011-01-27 | Lanxess Deutschland Gmbh & Co. Kg | Organoblechstrukturbauteil |
US8263715B2 (en) | 2009-08-28 | 2012-09-11 | International Business Machines Corporation | Hydrogel compositions and methods of preparation thereof |
EP2503986B1 (de) | 2009-11-26 | 2015-09-09 | Basf Se | Verwendung von hochverzweigten polycarbonaten in kosmetischen und dermatologischen formulierungen |
US20110123473A1 (en) * | 2009-11-26 | 2011-05-26 | Basf Se | Use of highly-branched polycarbonates in cosmetic and dermatological formulations |
KR20120114294A (ko) | 2009-12-09 | 2012-10-16 | 바스프 에스이 | 난용성 활성 성분을 가용화하기 위한 알콕실화 과분지형 폴리카르보네이트 |
ES2583302T3 (es) | 2010-02-18 | 2016-09-20 | Basf Se | Dispersión polimérica que contiene un policarbonato altamente ramificado con grupos insaturados de ácido graso |
US20110237693A1 (en) * | 2010-03-23 | 2011-09-29 | Basf Se | Blends made of polyarylene ethers and of polyarylene sulfides |
JP5808394B2 (ja) | 2010-05-05 | 2015-11-10 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | インサート部材およびプラスチック外被を含んでなる構成部材ならびにその製造方法 |
EP2395039A1 (de) | 2010-05-21 | 2011-12-14 | Basf Se | Polymeres Flammschutzmittel |
EP2552993B1 (en) * | 2010-07-15 | 2014-07-16 | Total Research & Technology Feluy | Isocyanate-free method for preparing poly(carbonate-urethane) or poly(ester-urethane) |
DE102010043409A1 (de) | 2010-11-04 | 2012-05-10 | Bayer Materialscience Aktiengesellschaft | Verfahren zur Herstellung von Polycarbonatpolyolen durch immortale Polymerisation von cyclischen Carbonaten |
WO2012084762A1 (de) | 2010-12-20 | 2012-06-28 | Bayer Materialscience Ag | Verfahren zur herstellung von polyetherpolyolen |
CA2840520A1 (en) | 2011-06-30 | 2013-01-03 | Bayer Intellectual Property Gmbh | Process for preparing high molecular weight polyether polyols |
KR101909320B1 (ko) * | 2011-08-25 | 2018-10-17 | 다우 글로벌 테크놀로지스 엘엘씨 | 이중 금속 시아니드 촉매의 존재 하에 에틸렌 카르보네이트의 중합에 의한 옥시에틸렌 단위를 갖는 폴리에테르 알콜의 제조 방법 |
CA2859566A1 (en) | 2011-12-20 | 2013-06-27 | Bayer Intellectual Property Gmbh | Hydroxy-aminopolymers and method for producing same |
EP2671893A1 (de) | 2012-06-06 | 2013-12-11 | Bayer MaterialScience AG | Verfahren zur Herstellung von Omega-Hydroxy-Aminopolymeren |
EP2876121A1 (de) | 2013-11-22 | 2015-05-27 | Bayer MaterialScience AG | Einsatz von Urethan-Alkoholen zur Herstellung von Polyetherpolyolen |
EP2886572A1 (de) | 2013-12-17 | 2015-06-24 | Bayer MaterialScience AG | Einsatz von Urethan-Alkoholen zur Herstellung von Polyethercarbonatpolyolen |
EP3230341A4 (en) * | 2014-12-08 | 2018-11-14 | Sang-Hyun Pyo | Aliphatic polycarbonates and production methods from cyclic carbonates thereof |
CA2972304C (en) | 2014-12-23 | 2023-10-03 | Basf Se | Hyperbranched polymer modified with isocyanate linker and mix of short and long chain alkyl polyether |
JP2018517029A (ja) | 2015-05-21 | 2018-06-28 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 超分岐ポリカーボネートポリオールの調製及びそれらの使用 |
EP3098252A1 (de) | 2015-05-26 | 2016-11-30 | Covestro Deutschland AG | Einsatz von alkoholen, die mindestens zwei urethangruppen enthalten, zur herstellung von polyethercarbonatpolyolen |
EP3098251A1 (de) | 2015-05-26 | 2016-11-30 | Covestro Deutschland AG | Einsatz von alkoholen, die mindestens zwei urethangruppen enthalten, zur herstellung von polyetherpolyolen |
SG11201801151YA (en) | 2015-08-26 | 2018-03-28 | Covestro Deutschland Ag | Method for producing high molecular weight polyoxyalkylene polyols |
CN108368200B (zh) | 2015-10-16 | 2021-09-17 | 巴斯夫欧洲公司 | 能量固化性高反应性多乙烯基醚或丙烯酸酯官能树脂 |
US9562135B1 (en) | 2015-12-21 | 2017-02-07 | Covestro Llc | Polyether carbonates by DMC catalysis |
SG11201809538TA (en) | 2016-05-13 | 2018-11-29 | Covestro Deutschland Ag | Method for the preparation of polyoxyalkylene polyols |
DK3515478T3 (da) | 2016-09-21 | 2024-05-21 | Nextcure Inc | Antistoffer til SIGLEC-15 og fremgangsmåder til anvendelse deraf |
US10053533B1 (en) | 2017-04-13 | 2018-08-21 | Presidium Usa, Inc. | Oligomeric polyol compositions |
JP7150256B2 (ja) | 2018-04-19 | 2022-10-11 | 国立大学法人北海道大学 | 環状カーボネート開環重合による重合体の製造方法 |
EP3747927A1 (de) | 2019-06-05 | 2020-12-09 | Covestro Deutschland AG | Verfahren zur kontinuierlichen herstellung von polyoxyalkylenpolyolen |
EP3889204A1 (de) * | 2020-04-02 | 2021-10-06 | Covestro Deutschland AG | Verfahren zur herstellung eines polyoxyalkylencarbonatpolyols |
CN116134063A (zh) | 2020-07-23 | 2023-05-16 | 巴斯夫欧洲公司 | 低温常压下脲二酮的开环的应用 |
CN112175168B (zh) * | 2020-10-14 | 2021-12-14 | 上海交通大学 | 一种三元共聚物、嵌段聚合物以及三元共聚物的合成方法 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1063525A (en) | 1963-02-14 | 1967-03-30 | Gen Tire & Rubber Co | Organic cyclic oxide polymers, their preparation and tires prepared therefrom |
US3278457A (en) | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
NL6602632A (zh) | 1965-03-01 | 1966-09-02 | ||
US3829505A (en) | 1970-02-24 | 1974-08-13 | Gen Tire & Rubber Co | Polyethers and method for making the same |
US3941849A (en) | 1972-07-07 | 1976-03-02 | The General Tire & Rubber Company | Polyethers and method for making the same |
GB8528071D0 (en) * | 1985-11-14 | 1985-12-18 | Shell Int Research | Polycarbonates |
DE3723194A1 (de) * | 1987-07-14 | 1989-01-26 | Bayer Ag | Verfahren zur herstellung von aliphatischen polycarbonaten |
GB8905768D0 (en) * | 1989-03-13 | 1989-04-26 | Ici Plc | Compositions of matter |
JP3097854B2 (ja) | 1989-05-12 | 2000-10-10 | 旭硝子株式会社 | ポリウレタン類の製造方法 |
US5032671A (en) | 1990-09-04 | 1991-07-16 | Arco Chemical Technology, Inc. | Preparation of lactone polymers using double metal cyanide catalysts |
US6080801A (en) * | 1990-09-13 | 2000-06-27 | Klaus Draenert | Multi-component material and process for its preparation |
US5158922A (en) | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5470813A (en) | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US5712216A (en) | 1995-05-15 | 1998-01-27 | Arco Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
US5482908A (en) | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5545601A (en) | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
US5627120A (en) | 1996-04-19 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5714428A (en) | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
DE19905611A1 (de) | 1999-02-11 | 2000-08-17 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
-
2001
- 2001-08-03 DE DE10138216A patent/DE10138216A1/de not_active Withdrawn
-
2002
- 2002-07-22 DE DE50210468T patent/DE50210468D1/de not_active Expired - Fee Related
- 2002-07-22 BR BR0211678-2A patent/BR0211678A/pt not_active IP Right Cessation
- 2002-07-22 EP EP02794510A patent/EP1432751B1/de not_active Expired - Lifetime
- 2002-07-22 HU HU0401198A patent/HUP0401198A3/hu unknown
- 2002-07-22 KR KR10-2004-7001608A patent/KR20040030910A/ko not_active Application Discontinuation
- 2002-07-22 MX MXPA04001002A patent/MXPA04001002A/es active IP Right Grant
- 2002-07-22 CN CNB02815262XA patent/CN1260271C/zh not_active Expired - Fee Related
- 2002-07-22 WO PCT/EP2002/008131 patent/WO2003014186A1/de active IP Right Grant
- 2002-07-22 CA CA002455996A patent/CA2455996A1/en not_active Abandoned
- 2002-07-22 JP JP2003519131A patent/JP2004536953A/ja active Pending
- 2002-07-22 RU RU2004106538/04A patent/RU2004106538A/ru not_active Application Discontinuation
- 2002-07-22 PL PL02367101A patent/PL367101A1/xx not_active Application Discontinuation
- 2002-07-22 AT AT02794510T patent/ATE366766T1/de not_active IP Right Cessation
- 2002-07-30 US US10/208,536 patent/US6646100B2/en not_active Expired - Fee Related
-
2003
- 2003-09-02 US US10/653,526 patent/US6806345B2/en not_active Expired - Fee Related
-
2005
- 2005-04-18 HK HK05103295A patent/HK1070666A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
RU2004106538A (ru) | 2005-07-27 |
DE50210468D1 (de) | 2007-08-23 |
US20030032761A1 (en) | 2003-02-13 |
JP2004536953A (ja) | 2004-12-09 |
US6806345B2 (en) | 2004-10-19 |
EP1432751B1 (de) | 2007-07-11 |
CA2455996A1 (en) | 2003-02-20 |
MXPA04001002A (es) | 2004-08-11 |
HK1070666A1 (en) | 2005-06-24 |
US20040044174A1 (en) | 2004-03-04 |
DE10138216A1 (de) | 2003-02-20 |
HUP0401198A2 (hu) | 2004-09-28 |
EP1432751A1 (de) | 2004-06-30 |
HUP0401198A3 (en) | 2005-11-28 |
BR0211678A (pt) | 2004-11-09 |
ATE366766T1 (de) | 2007-08-15 |
KR20040030910A (ko) | 2004-04-09 |
CN1538981A (zh) | 2004-10-20 |
US6646100B2 (en) | 2003-11-11 |
PL367101A1 (en) | 2005-02-21 |
WO2003014186A1 (de) | 2003-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1260271C (zh) | 通过双金属氰化物催化制备的脂族聚碳酸酯均聚物和共聚物 | |
CN1183180C (zh) | 具有高伯羟基含量的长链聚醚多元醇 | |
US11149117B2 (en) | Alkylene oxide polymerization using a double metal cyanide catalyst complex and a magnesium, group 3-group 15 metal or lanthanide series metal compound | |
Luo et al. | Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis | |
US8134022B2 (en) | Polyether carbonate polyols made via double metal cyanide (DMC) catalysis | |
US5032671A (en) | Preparation of lactone polymers using double metal cyanide catalysts | |
CN102933637B (zh) | 活化用于制备聚醚碳酸酯多元醇的双金属氰化物催化剂的方法 | |
CN101108896B (zh) | 耐高含水量的聚醚生产方法 | |
EP2997071B1 (en) | Method and catalyst system for preparing polymers and block copolymers | |
CN1670007A (zh) | 在双金属氰化物催化工艺中起始物进料流的酸化 | |
EP2513192A1 (en) | Method for continuously producing low equivalent weight polyols using double metal cyanide catalysts | |
CN103764715A (zh) | 通过碳酸乙二醇酯在双金属氰化物催化剂的存在下的聚合制备具有氧亚乙基单元的聚醚醇的方法 | |
CN1487000A (zh) | 活性起始混合物及相关方法 | |
CN115584018B (zh) | 一种聚酯i-聚酯ii-聚碳酸酯三嵌段共聚物的制备方法 | |
Colomb et al. | Heterogeneous catalytic ring opening polymerization of 2, 2‐dimethyltrimethylene carbonate with metal alkoxides as initiators in protic conditions | |
CN1974630A (zh) | 中、高分子量烯丙基聚醚单元醇的制备方法 | |
Zhang et al. | Copolymerization of c1 building blocks with epoxides | |
EP1448663A1 (en) | Process for the alkoxylation of organic compounds | |
Iwasa | Studies on Design and Synthesis of Efficient Metal Catalysts for Precise Ring-Opening Polymerization of Cyclic Monomers | |
Isnard | Synthesis of sustainable polyesters via ring opening polymerization promoted by phenoxy-imine aluminum complexes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1070666 Country of ref document: HK |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |