CN1023647C - 用于烯烃/一氧化碳共聚的新型催化剂组合物及共聚方法 - Google Patents
用于烯烃/一氧化碳共聚的新型催化剂组合物及共聚方法 Download PDFInfo
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 13
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Abstract
新型催化剂组合物，该组合物的特征在于其含下列组分：
a.一种钯化合物，b.一种pKa小于2的酸的阴离子，其前提条件是该酸不能是氢卤酸，
c.一种含一个磷原子和一个或多个不带氢的氮原子、而且其中每个氮原子都是通过一个桥中至少含一个碳原子的有机桥基与磷原子相连的化合物。
Description
本发明涉及适用于制备一氧化碳与一种或多种烯属不饱和化合物的共聚物的新型催化剂组合物。
在一氧化碳与一种或多种烯属不饱和有机化合物（简称A）生成的高分子量线型共聚物中，单体单元是交替排列的，它含有通式为-（CO）-A′-的单元，式中A′代表来自所用单体A的单体单元。该类共聚物可用基于以下组分的催化剂组合物制备：
a.一种钯化合物，
b.一种pka小于2的酸的阴离子，其前提条件是该酸不能是氢卤酸，
c.一种三（烃基）膦。
本专利申请人对这类催化剂组合物所进行的研究表明，当用膦作组分c时，其中至少有一个烃基被含一个多个不带氢的氮原子的基团取代，其活性可大大提高，该基团的构型是磷/氮化合物中的每个氮原子都是通过一个桥中至少含一个碳原子的有机桥基与磷原子相连的。本专利申请人更为概括地发现，下面这类催化剂组合物对一氧化碳与一种或多种烯属不饱和有机化合物的共聚有引人注目的活性：该类催化剂组合物可以上述（a）和（b）组分为基础，但组分（c）是一种含一个磷原子和一个或多个不带氢的氮原子、而且其中每一个氮原子都是通过一个桥中至少含一个碳原子的有机桥基与磷原子相连的化合物。
由组分（a）、（b）和上述作为组分（c）的磷/氮化合物所组成的催化剂组合物是新型的。
因此本专利申请涉及含下列组分的新型催化剂组合物：
a.一种钯化合物，
b.一种pka小于2的酸的阴离子，其前提条件是该酸不能是氢卤酸，
c.一种含一个磷原子和一个或多个不带氢的氮原子、而且其中每一个氮原子都是通过一个桥中至少含一个碳原子的有机桥基与磷原子相连的化合物。
本专利申请还涉及利用这些催化剂组合物制备一氧化碳与一种或多种烯属不饱和化合物的共聚物的方法和涉及所制得的共聚物以及至少部分地采用这些共聚物而制得的成型制品。
用作组分（a）的钯化合物宜为羧酸钯盐，最好是乙酸钯。催化剂组合物组分（b）中的pka小于2（于18℃在水溶液中测定）的酸的例子有硫酸、磺酸（如对甲苯碘酸）和羧酸（如三氟乙酸）。尤为可取的是对甲苯磺酸和三氟乙酸。组分（b）在催化剂组合物中的用量，按每克原子钯计，宜为0.5～200当量，最好为1.0～100当量。组分（b）可以酸或盐的形式加入催化剂组合物中，适合的盐的例子有非贵重过滤金属的盐。采用
非贵重过滤金属的盐的形式作组分（b）时最好采用铜盐。也可根据需要，使组分（a）和（b）结合成为单一化合物。这样的化合物的例子是配合物Pd（CH3CN）2（O3S-C6H4-CH3）2，它可由氯化钯与对甲苯磺酸银盐，或乙酸钯与对甲苯磺酸在乙腈中起反应而制得。
本发明的催化剂组合物的组分（c）最好是磷/氮化合物，它可看作是三苯膦中至少有一个苯基被含一个或多个氮原子的基团取代的衍生物。磷原子与每个氮原子相连的有机桥基在桥中最好至多含三个碳原子。最好采用这样的磷/氮化合物，它可看作是三苯膦中不多于1个的苯基、被含不多于一个的氮原子的基团所取代而得到的衍生物。
可看作是由三苯膦衍生而来的、即通过用含一个氮原子的基团取代三苯膦中的一个苯基而得到的、且其中连接磷原子与氮原子的桥基只含一个碳原子的磷/氮化合物的例子有：
2-吡啶基-二苯膦，
2-（二苯基-膦基）-1-甲基-1-吡咯，
1-（二苯基-膦基）-N-N-二苯基甲酰胺，
1-[（二苯基-膦基）-甲基]-2，5-琥珀酸亚胺。
可看作是由三苯膦衍生而来的、即通过用含一个氮原子的基团取代三苯膦中的一个苯基而得到的、且其中连接磷原子与氮原子的桥基含两个碳原子的磷/氮化合物的例子有：
1-[2-（二苯基-膦基）乙基]-2-吡咯烷酮，
2-（苯基-膦基）-N，N-二苯基乙酰胺，
（2-异氰基-乙基）二苯膦，
8-（二苯基-膦基）-喹啉，
邻-（二苯基-膦基）-N，N-二甲基苯胺，
2-（二苯基-膦基）三乙基胺，
2-[（二苯基-膦基）甲基]-吡啶，
N-[（二苯基-膦基）甲基]-二乙基胺。
可看作是由三苯膦衍生而来的、即通过用含一个氮原子的基团取代三苯膦中的一个苯基而得到的、且其中连接磷原子与氮原子的桥基含三个碳原子的磷/氮化合物的例子有：
2-氰基-乙基-二苯膦，
2-[2-（二苯基-膦基）乙基]-吡啶，
2-[（二苯基-膦基）甲基]-N，N-二甲基苯扎明，
2-（二苯基-膦基）-N，N-二甲基苯甲胺，
2-（二苯基-膦基）-N，N-二乙基苯扎明，
3-（二苯基-膦基）-N，N-二甲基丙酰胺。
可看作是由三苯膦衍生而来的、即通过用含一个氮原子的基团取代三苯膦中的两个或三个苯基而得到的磷/氮化合物的例子有双（2-吡啶基）苯膦和三（2-氰基乙基）膦。
可看作是由三苯膦衍生而来的、即通过用含多个氮原子的基团取代三苯膦中的一个苯基而得到的磷/氮化合物的例子有2-（二苯基-膦基）-1，3，5-三嗪。
本发明的引人注意的催化剂组合物可采用下列五种磷/氮化合物中的任一种作为组分（c）：
2-氰基-乙基-二苯膦，
三（2-氰基-乙基）膦，
2-吡啶基-二苯膦，
双（2-吡啶基）苯膦，
3-（二苯基-膦基）-N，N-二甲基丙酰胺。
本发明的催化剂组合物中，磷/氮化合物的用量按每摩尔钯化合物计宜为0.1～100摩尔，最好为0.5～50摩尔。
最好在本发明的催化剂组合物中还加入醌作为组分（d）。除取代的或未取代的苯醌之外，其它醌和取代的或未取代的萘醌和蒽醌也是适用的。最好采用苯醌，特别是1，4-苯醌。醌的用量按每克原子钯计宜为1～10000摩尔，最好为10～5000摩尔。
采用本发明的催化剂组合物的聚合反应最好在液体稀释剂中进行。低级醇（如甲醇和乙醇）是十分适用的液体稀释剂。聚合反应也可选择在气相中进行。
仅由碳和氢组成的和除碳和氢之外还有一个或多个杂原子的烯属不饱和有机化合物都可借助于本发明的催化剂组合物与一氧化碳进行共聚。本发明的催化剂组合物最好用于制备一氧化碳与一种或多种烯属不饱和烃的共聚物。适用的烃类单体的例子有乙烯和其它α-烯烃（如丙烯，丁烯-1，己烯-1和辛烯-1）以及苯乙烯和烷基取代的苯乙烯（如对-甲基苯乙烯和对-乙基苯乙烯）。本发明的催化剂组合物特别适用于制备一氧化碳与乙烯的共聚物和制备一氧化碳与乙烯和另一种烯属不饱和烃（特别是丙烯）的三元共聚物。
制备共聚物时催化剂组合物的用量可以在很大
的范围内变动。最好每摩尔要进行共聚的烯属不饱和化合物所用的催化剂的量中应含10-7～10-3，最好是10-6～10-4克原子钯。
共聚物的制备宜在20～200℃温度和1～200巴压力下进行，最好在30～150℃和20～100巴的条件下进行。在共聚反应混合物中，烯属不饱和有机化合物与一氧化碳的摩尔比宜为10∶1～1∶5，最好为5∶1～1∶2。用于按照本发明的方法制备共聚物的一氧化碳不必是纯的，它可含诸如氢、二氧化碳和氮之类的杂质。
现借助于以下的实施例对本发明加以说明。
实施例1
一氧化碳/乙烯共聚物的制备方法如下：将含有50毫升甲醇、0.1毫摩尔乙酸钯、2.0毫摩尔对甲苯磺酸和0.3毫摩尔三苯膦的催化剂溶液装入一采用磁性搅拌的250毫升高压釜中。在抽空除去高压釜中的所有空气之后，在压力下将乙烯通入直至压力达30巴，接着将一氧化碳通入，直至压力达60巴。然后将高压釜内的反应化合物加热至110℃。5小时后通过使反应物冷却至室温，然后卸除压力以终止聚合反应。滤出所生成的共聚物，用甲醇洗涤并在室温下进行真空干燥。聚合速率为5克共聚物/克钯/小时。
实施例2
一氧化碳/乙烯共聚物的制备方法大体上与实施例1的共聚物相同，所不同的是：
a.催化剂溶液含0.2毫摩尔而不是0.1毫摩尔乙酸钯，含0.5毫摩尔2-氰基-乙基-二苯膦，而不是0.3毫摩尔三苯膦。
b.反应温度为80℃，而不是110℃。
聚合速率为23.6克共聚物/克钯/小时。
实施例3
一氧化碳/乙烯共聚物的制备方法大体上与实施例1的共聚物相同，所不同的是：
a.催化剂溶液含0.2毫摩尔而不是0.1毫摩尔乙酸钯，含0.5毫摩尔三（2-氰基-乙基）膦，而不是0.3毫摩尔三苯膦，
b.反应温度为100℃，而不是110℃。
聚合速率为40克共聚物/克钯/小时。
实施例4
一氧化碳/乙烯共聚物的制备方法大体上与实施例1的共聚物相同，所不同的是：
a.催化剂溶液含3.0毫摩尔2-吡啶基-二苯膦，而不是0.3毫摩尔三苯膦，而且多含20毫摩尔1，4-苯醌，
b.反应温度为80℃，而不是110℃。
聚合速率为100克共聚物/克钯/小时。
实施例5
一氧化碳/乙烯共聚物的制备方法大体上与实施例1的共聚物相同，所不同的是：
a.催化剂溶液含3.0毫摩尔双（2-吡啶基）苯膦，而不是0.3毫摩尔三苯膦，而且多含20毫摩尔1，4-苯醌，
b.反应温度为100℃，而不是110℃。
聚合速率为37.8克共聚物/克钯/小时。
实施例6
一氧化碳/乙烯共聚物的制备方法大体上与实施例1的共聚物相同，所不同的是：
a.催化剂溶液含0.15毫摩尔双3-（二苯基-膦基）-N，N-二甲基丙酰胺，而不是0.3毫摩尔三苯膦，而且多含1.0毫摩尔而不是2.0毫摩尔的对甲苯磺酸。
b.反应温度为105℃，而不是110℃。
聚合速率为28.3克共聚物/克钯/小时。
进行13C-NMR分析的结果表明，按照实施例1～6的方法制备而得的一氧化碳/乙烯共聚物具有线型交替结构，所以它是由化学式-CO-（C2H4）-单元组成。共聚物的溶点为257℃。在实施例1～6之中，实施例2-6是本发明的实施例。实施例1是在本发明的范围之外的，放在本专利申请中是为了进行比较
实施例1中用三苯膦作为催化剂组合物的组分（c），反应是在110℃下进行的，实施例2-6中采用了本发明的用一磷/氮化合物作为组分（c）的催化剂组合物，反应是在80～105℃下进行的。实施例1与实施例2-6的比较表明，采用本发明的催化剂组合物时能在较低的温度下达到高的反应速率。
Claims (7)
1、一种宜用于一氧化碳和一种或多种烯属不饱和有机化合物的混合物聚合的新型催化剂组合物，该组合物的特征在于它由下列组分组成：
a.一种钯化合物，
b.一种pka小于2的酸的阴离子，其前提条件是该酸不能是氢卤酸，
c.一种含一个磷原子和一个或多个不带氢的氮原子、而且其中每个氮原子都是通过一个桥中含至少一个碳原子的有机桥基与磷原子相连的化合物，所述化合物是通过仅用含一个或多个氮原子的基团取代三芳基膦中至少一个芳基而获得的。
2、权利要求1所述的催化剂组合物，其特征在于用一种可看作是由三苯膦衍生而来的、即通过用含一个或多个氮原子的基团取代三苯膦中的至少一个苯基而得到的磷/氮化合物作为组分（c）。
3、权利要求2所述的催化剂组合物，其特征在于用一种可看作是由三苯膦衍生而来的、即通过用仅含一个氮原子的基团取代三苯膦中的至少一个苯基而得到的磷/氮化合物作为组分（c）。
4、权利要求3所述的催化剂组合物，其特征在于组分（c）采用从2-氰基-乙基-二苯膦、2-吡啶基-二苯膦和3-（二苯基-膦基）-N，N-二甲基丙酰胺中选取的一种磷/氮化合物。
5、权利要求2所述的催化剂组合物，其特征在于组分（c）采用从三（2-氰基-乙基）膦和双（2-吡啶基）苯膦中选取的一种磷/氮化合物。
6、权利要求1至5中任一项所述的催化剂组合物用于一氧化碳与一种或多种烯属不饱和有机化合物的混合物共聚中。
7、权利要求6所述的应用，其特征是所用的烯属不饱和化合物为乙烯，或乙烯与丙烯的混合物。
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| US (1) | US4859764A (zh) |
| EP (1) | EP0259914B1 (zh) |
| JP (1) | JPH0822916B2 (zh) |
| CN (1) | CN1023647C (zh) |
| AT (1) | ATE73152T1 (zh) |
| AU (1) | AU592449B2 (zh) |
| BR (1) | BR8704273A (zh) |
| CA (1) | CA1305695C (zh) |
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| CA1331173C (en) * | 1986-12-05 | 1994-08-02 | Eit Drent | Process for the carbonylation of acetylenically unsaturated compounds |
| US4880902A (en) * | 1987-08-27 | 1989-11-14 | Shell Oil Company | Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst |
| GB8723602D0 (en) * | 1987-10-08 | 1987-11-11 | British Petroleum Co Plc | Polyketones |
| GB8723603D0 (en) * | 1987-10-08 | 1987-11-11 | British Petroleum Co Plc | Polyketones |
| US4948870A (en) * | 1988-05-27 | 1990-08-14 | Shell Oil Company | Polymerization process |
| KR0148012B1 (ko) * | 1989-03-03 | 1998-08-17 | 오노 알버어스 | 신규한 포스핀으로 구성되는 촉매시스템 및 이를 이용한 아세틸렌형 또는 올레핀형 불포화화합물의 카르보닐화방법 |
| US5099062A (en) * | 1989-03-03 | 1992-03-24 | Shell Oil Company | Carbonylation catalyst and process |
| KR0144567B1 (ko) * | 1989-03-03 | 1998-07-15 | 오노 알버어스 | 카르보닐화촉매시스템 |
| US5103043A (en) * | 1989-03-03 | 1992-04-07 | Shell Oil Company | Carbonylation catalyst system |
| US5061785A (en) * | 1989-03-29 | 1991-10-29 | Shell Oil Company | Polymerization of carbon monoxide/olefin with tertiary aliphatic monophosphine catalyst |
| GB9002521D0 (en) * | 1990-02-05 | 1990-04-04 | Shell Int Research | Carbonylation catalyst system |
| US5166411A (en) * | 1990-02-05 | 1992-11-24 | Shell Oil Company | Carbonylation catalyst system |
| US5179225A (en) * | 1990-02-05 | 1993-01-12 | Shell Oil Company | Carbonylation catalyst system |
| NL9002223A (nl) * | 1990-10-12 | 1992-05-06 | Shell Int Research | Katalysatorcomposities. |
| US5218084A (en) * | 1990-12-11 | 1993-06-08 | Shell Oil Company | Polymerization of carbon monoxide/propylene with aromatic amine |
| GB9111583D0 (en) * | 1991-05-30 | 1991-07-24 | Shell Int Research | Carbonylation catalyst system |
| CA2139123A1 (en) * | 1992-06-26 | 1994-01-06 | Hendrik Ter Maat | Polyketone yarn and method of manufacturing same |
| US5820806A (en) * | 1993-01-13 | 1998-10-13 | Akzo Nobel Nv | Process for the preparation of polyketone fibers |
| DE69727460T2 (de) * | 1996-04-04 | 2004-07-01 | Bp Chemicals Ltd. | Eine verbindung, die in einer katalytischen zusammensetzung verwendbar ist |
| JP2002503769A (ja) | 1998-02-12 | 2002-02-05 | アコルディス インダストリアル ファイバース ベスローテン フェンノートシャップ | ポリケトン繊維の製造方法 |
| WO2005072061A2 (en) | 2004-02-02 | 2005-08-11 | Biosight Ltd. | Conjugates for cancer therapy and diagnosis |
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| US2495286A (en) * | 1949-06-08 | 1950-01-24 | Du Pont | Interpolymers of carbon monoxide and method for preparing the same |
| GB1081304A (en) * | 1965-03-23 | 1967-08-31 | Ici Ltd | Improvements in or relating to chemical compounds |
| US3689460A (en) * | 1971-03-04 | 1972-09-05 | Shell Oil Co | Interpolymers of carbon monoxide and process for preparing same |
| US3694412A (en) * | 1971-03-04 | 1972-09-26 | Shell Oil Co | Process for preparing interpolymers of carbon monoxide in the presence of aryl phosphine-palladium halide complex |
| GB2058074B (en) * | 1979-08-23 | 1983-10-12 | Secr Defence | Palladium complexes |
| EP0086281B2 (en) * | 1981-12-02 | 1988-10-19 | Shell Internationale Researchmaatschappij B.V. | Preparation of carbamates using a palladium-containing catalyst |
| ATE49010T1 (de) * | 1983-04-06 | 1990-01-15 | Shell Int Research | Verfahren zur herstellung von polyketonen. |
| GB8428347D0 (en) * | 1984-11-09 | 1984-12-19 | Shell Int Research | Dimerization of olefins |
| EP0170311B1 (en) * | 1984-07-30 | 1989-02-01 | Shell Internationale Researchmaatschappij B.V. | Process for the dimerization of olefins |
| NL8403035A (nl) * | 1984-10-05 | 1986-05-01 | Shell Int Research | Werkwijze ter bereiding van polyketonen. |
| IN166314B (zh) * | 1985-08-29 | 1990-04-07 | Shell Int Research | |
| IN168056B (zh) * | 1986-03-05 | 1991-01-26 | Shell Int Research | |
| IN168306B (zh) * | 1986-03-05 | 1991-03-09 | Shell Int Research | |
| EP0246683A3 (en) * | 1986-05-13 | 1988-01-27 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of polymers |
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| Publication number | Publication date |
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| CA1305695C (en) | 1992-07-28 |
| BR8704273A (pt) | 1988-04-12 |
| ATE73152T1 (de) | 1992-03-15 |
| DE3777027D1 (de) | 1992-04-09 |
| EP0259914B1 (en) | 1992-03-04 |
| JPS6356524A (ja) | 1988-03-11 |
| CN87105647A (zh) | 1988-03-02 |
| ES2033296T3 (es) | 1993-03-16 |
| AU592449B2 (en) | 1990-01-11 |
| JPH0822916B2 (ja) | 1996-03-06 |
| AU7724887A (en) | 1988-02-25 |
| EP0259914A1 (en) | 1988-03-16 |
| US4859764A (en) | 1989-08-22 |
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