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CN1185787A - 作为烯烃聚合催化剂的氮杂硼啉基金属配合物 - Google Patents

作为烯烃聚合催化剂的氮杂硼啉基金属配合物 Download PDF

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CN1185787A
CN1185787A CN96194219A CN96194219A CN1185787A CN 1185787 A CN1185787 A CN 1185787A CN 96194219 A CN96194219 A CN 96194219A CN 96194219 A CN96194219 A CN 96194219A CN 1185787 A CN1185787 A CN 1185787A
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zirconium
halogen
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S·纳吉
R·克里沙穆蒂
B·P·艾斯尔顿
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Lyondell Chemical Co
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Abstract

公开了一种具有通式(Ⅰ)的催化剂,其中L是或(a)的配体,L是L、Cp、Cp*、茚基、芴基、NR2、OR或卤素,L可桥连到L;X是卤素、NR2、OR或C1－C12烷基,M是锆或铪,R是C1－C12烷基或C6－C12芳基,R1是R、C6－C12烷芳基、C6－C12芳烷基、氢或Si(R)3,R2是R1卤素、COR、COOR、SOR或SOOR,R3是R2、OR、N(R)2、SR或稠合环系,Cp是环戊二烯基,Cp*是五甲基环戊二烯基,n是0—3,LB是任意的路易丝碱。还公开了一种制备聚α－烯烃的方法,包括聚合α－烯烃单体,使用诸如上述通式的催化剂,其中M可以是钛、锆或铪。

Description

作为烯烃聚合催化剂的氮杂硼啉基金属配合物
发明背景
本发明涉及用于乙烯和其它烯烃均聚和共聚的催化剂，本发明特别涉及有一个过渡金属以π-键键合到含氮杂硼啉环(azaboroline ring)的配体上的催化剂。
直到最近，制备聚烯烃主要用传统的齐格勒催化剂体系。这些催化剂一般含有含过渡金属的化合物和一种或多种有机金属化合物。例如，用诸如三氯化钛和二乙基氯化铝或四氯化钛、三氯氧钒和三乙基铝的混合物的齐格勒催化剂制备聚乙烯。这些催化剂是廉价的，但它们的活性低，因此必须以高浓度使用。结果，有时需要从聚合物中除去催化剂残留物，这增加了生产费用。中和剂和稳定剂必须加入到聚合物中以消除催化剂残余物的有害影响。除去催化剂残余物不完全会使聚合物有黄色或灰色，并且降低其使用价值和长期稳定性。例如，含氯的残留物可使聚合物加工设备被腐蚀。另外，齐格勒催化剂制备的聚合物有宽的分子量分布，这对于诸如注塑的一些应用是不希望的。它们在α-烯烃共聚单体的结合方面效果也不好。共聚单体结合不好使得很难控制聚合物密度。可能需要大量过量的共聚单体以得到一定的密度，许多更高级的α-烯烃——诸如1-辛烯——可能只以很低的水平结合，若有的话。
尽管从齐格勒催化剂体系发现以来已有了实质性均改进，这些催化剂现已被最近发现的茂金属催化剂体系代替。茂金属催化剂一般含有带一个或多个环戊二烯环配体的过渡金属化合物。当它们与有机金属化合物——诸如烷基铝，与惯用的齐格勒催化剂使用——使用时，活性很低，而当它们与作为助催化剂的铝氧烷使用时有非常高的活性。活性一般高得以至于催化剂残渣不必从聚合物中除去。另外，它们制备的聚合物有高的分子量和窄的分子量分布。它们也能很好地使α-烯烃共聚单体结合。但是，在更高温度下，茂金属催化剂趋于制备较低分子量的聚合物。因此，它们可用于在约80-95℃进行的乙烯气相和淤浆聚合，但在约150-250℃进行的乙烯溶液聚合中通常效果不良。在溶液中进行乙烯的聚合是理想的，因为这种聚合能适用于分子量和密度范围宽并使用多种不同共聚单体的聚合物的制备而有很大灵活性。可制备在多种不同应用中使用的聚合物。例如，用于食品的包装的防护膜的高分子量、高密度聚乙烯(PE)膜，以及有好的韧性和高冲击强度的、低密度乙烯共聚物。本发明概述
我们还发现新的一类基于一种氮杂硼啉环结构并含过渡金属的催化剂。本发明的催化剂具有不寻常的高活性，这意味着它们可以非常小的量使用。它们还很适合于将共聚单体结合入该聚合物中。它们在更高的温度有好的活性，并因此预期可用于乙烯的溶液聚合。
我们还发现，用本发明催化剂聚合的单体的氢原子敏感性比用其它催化剂好。即，当将本发明催化剂用于聚合单体时，在存在的氢量上的小小变动就对所得聚合物的分子量有大的影响。优选实施方案的描述
本发明的催化剂具有通式
Figure A9619421900061
其中L是通式为的配体，L′是L、Cp、Cp*、茚基、芴基、NR2、OR或卤素，L可桥连到L′，X是卤素、NR2、OR或C1-C12烷基，M是钛、锆或铪，R是C1-C12烷基或C6-C12芳基，R1是R、C6-C12烷芳基、C6-C12芳烷基、氢或Si(R)3，R2是R1、卤素、COR、COOR、SOR或SOOR，R3是R2、OR、N(R)2、SR或稠合环系，Cp是环戊二烯基，Cp*是五甲基环戊二烯基。
L′配体优选是Cp、Cp*或L，因为那些化合物易于制备并有好的活性。X基优选是卤素，最优选氯，因为那些化合物更易于获得。R基优选是C1-C4烷基，R1基优选是C3-C12烷基或芳基，R2基优选是叔丁基或三甲基甲硅烷基，R3基优选是氢或甲基，因为那些化合物更易制备。可用作R3的稠环结构的例子包括金属M优选锆，因为锆催化剂使活性和稳定性很好地相结合。
任意地，L可被桥连到L′。可用于桥连两个配体的基团包括亚甲基、亚乙基、1，2-亚苯基、二甲基甲硅烷基、二苯基甲硅烷基、二乙基甲硅烷基和甲基苯基甲硅烷基。通常在催化剂中只用单桥。认为桥连配体改变了催化活性过渡金属周围的几何学并且提高了催化剂活性和其它性质，诸如共聚单体结合性和热稳定性。
在通式中，LB是任意的路易斯碱。可使用最高到等摩尔量(与M一起)的碱。一般不优选使用路易斯碱，因为它有降低催化剂活性的倾向。但是，它也有提高催化剂稳定性的倾向，因此，包括它可能是理想的，取决于使用催化剂的方法。碱可以是制备含氮杂硼啉的化合物中的残余溶剂，或可以分别将其加入以提高催化剂的性能。可在本发明中使用的碱的例子包括醚，诸如乙醚、二丁基醚、四氢呋喃、1，2-二甲氧基乙烷；酯，诸如邻苯二甲酸正丁酯、苯甲酸乙酯和对茴香酸乙酯；叔胺，诸如三乙基胺；膦，诸如三乙基膦、三丁基膦和三苯基膦。
本发明的催化剂可由从市场可得的起始原料制备。不能从市场获得的特别的起始原料可用下文例举的在文献中已知的技术制备。用于催化剂的氮杂硼啉配体的前体，可如文献所述从烯丙胺通过其二价阴离子(由一种强碱生成)与一种烷基硼二卤化物反应来制备(J.Schulze，G.Schmid，有机金属化学杂志(J.Organomet.Chem.)，193，1980，p.83)。
Figure A9619421900081
可使用的强碱的例子包括烷基锂化合物，诸如正丁基锂、甲基锂；氢化物，诸如氢化钠和氢化钾。每摩尔烯丙胺使用2摩尔碱。在室温、在一种烃溶剂——诸如戊烷或己烷——中该反应进行数小时。可以对烯丙胺以1∶1的摩尔比用四甲基乙二胺稳定烷基锂。可用真空分离产物并用蒸馏纯化。
在下一步如文献所述，产物与一种碱——诸如受阻的锂试剂(例如，锂四甲基哌啶)——反应生成氮杂硼啉基阴离子(G.Schmid等人，化学报告(Chem.Ber.)，115，1982，p.3830)：
Figure A9619421900091
在最后一步，第二步的产物被冷却到约-60℃，加入MX4或MCpX3。将反应物温热至室温，当反应物溶解并且LiX沉淀时，反应完成：
Figure A9619421900092
由于催化剂通常与一种有机金属助催化剂结合使用，优选将催化剂溶于一种助催化剂也可溶于其中的溶剂中。例如，如果甲基铝氧烷(MAO)是助催化剂，那么甲苯、二甲苯、苯或乙基苯可作为溶剂使用。其它适合的助催化剂包括式AlR′X(R2)3-X的烷基铝，其中1≤X≤3，R2是氢、卤素或C1-C20烷基或烷氧基，诸如三乙基铝和二氯化乙基铝。优选的助催化剂是MA0，因为它产生高活性，并且生成分子量分布较窄的聚合物。当用于聚合反应时，有机金属助催化剂与催化剂的摩尔比一般在0.01∶1至100000∶1范围，优选1∶1至10000∶1范围。
另一种助催化剂是一种酸盐，含非配位的惰性阴离子(见美国专利US5064802)。这种酸盐一般是非亲核化合物，含有庞大的连在硼或铝原子上的配体，诸如四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)硼酸苯铵、四(五氟苯基)硼酸-N，N-二甲基苯胺、四(五氟苯基)硼酸三苯甲基酯以及它们的混合物。当这些化合物与催化剂反应时，认为生成的阴离子与含金属的阳离子弱配位。酸盐与催化剂的摩尔比可在约0.01∶1至1000∶1范围，但优选约1∶1至10∶1。由于在从催化剂和酸盐制备活性催化剂体系的方法上没有限制，优选在约-78℃至150℃温度范围将它们在一种惰性溶剂中混合。如果需要，也可将其在单体存在下混合。该酸盐可与前文描述的有机金属助催化剂共用。
催化剂和助催化剂可在一种载体上使用，诸如硅胶、氧化铝、氧化硅、氧化镁或二氧化钛，但不优选使用载体，因为它们会在聚合物中留下污染物。但是，可以根据采用的工艺需要载体。例如，一般在气相聚合过程和淤浆聚合过程中需要载体，用于控制所制备聚合物的颗粒尺寸和防止反应器壁结污垢。载体还可提高催化剂的热稳定性。使用载体时，将催化剂和助催化剂溶于溶剂中，沉淀到载体材料上，例如，用蒸发溶剂的方法。助催化剂还可沉积到载体上，或将其与承载的催化剂分别引入反应器。
一旦催化剂已制备，应尽可能迅速地使用，因为它在储存期间会损失一些活性。应在低温下储存催化剂，诸如-100至约20℃。在烯烃单体的聚合中以常规方法使用催化剂。尽管诸如苯乙烯的不饱和单体可用本发明的催化剂聚合，但它特别用于α-烯烃的聚合，诸如丙烯、1-丁烯、1-己烯、1-辛烯和尤其是乙烯。
本催化剂还可以用常规方法用于不饱和单体混合物的共聚，诸如乙烯、丙烯、1-丁烯、1-己烯、1-辛烯等；乙烯和诸如1，3-丁二烯、1，4-己二烯、1，5-己二烯等二烯烃的混合物；乙烯和诸如降冰片烯、亚乙基降冰片烯、乙烯基降冰片烯、降冰片二烯等不饱和共聚单体的混合物。
本发明的催化剂可用于许多不同的聚合过程。其可用于液相的聚合过程(淤浆、溶液、悬浮液、本体相或这些的结合)、高压流体相或气相聚合过程。这些过程可系列使用，或个别地单独使用。聚合反应区的压力可在约15至50000psia范围，温度在约-100至300℃范围。
下列实施例进一步说明本发明。实施例1制备双(1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)二氯合锆和(1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)三氯合锆
将0.438g(3.2mmol)2-甲基-1-叔丁基-Δ3-1，2-氮杂硼啉(根据文献J.Schultze，和G.Schmid，有机金属化学杂志(J.Organomet.Chem.)，1980，193，83-91的方法制备)在6ml干THF中的溶液加入2，2，6，6-四甲基哌啶锂(3.2mmol)的冷(-78℃)溶液中来制备2-甲基-1-叔丁基-1，2-氮杂硼啉基锂。2，2，6，6-四甲基哌啶锂是由等摩尔量的2，2，6，6-四甲基哌啶和正丁基锂/己烷在10mlTHF中反应制备的。冷浴最高热至10℃，进行1.5小时，此后在真空下除去溶剂。用35ml甲苯处理黄色油状残留物，得到黄色淤浆。将其冷却到-60℃，在良好搅拌下加入氯化锆(IV)(0.37g，1.6mmol)。加热该浴至室温，搅拌混合物过夜。真空下蒸发溶剂，用30ml甲苯处理残留物，滤除氯化锂。浓缩甲苯滤液，用己烷(2×15ml)萃取粘稠的黄色残留物并过滤。蒸发己烷滤液，得到0.14g黄色固体。材料的1H NMR谱表明它是两种要求的化合物约2/3的混合物。实施例2制备(η5-环戊二烯基)(1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)二氯合锆方法A
如上所述从2-甲基-1-叔丁基-Δ3-1，2-氮杂硼啉(0.49g，3.5mmol)制备的2-甲基-1-叔丁基-1，2-氮杂硼啉基锂在20ml THF中的溶液用注射器滴加到搅拌的环戊二烯基二氯合锆(0.93g，3.52mmo1)在50ml THF中的冷(-35℃)溶液中。加热该浴至室温，搅拌混合物过夜。在真空中蒸发溶剂，残留物用35ml甲苯萃取并过滤。用10ml甲苯洗涤沉淀，蒸发合并的滤液。生成的粘胶残留物与25ml干己烷一起搅拌，生成米色固体和浅黄色上层清液。过滤混合物，干燥固体，得到棕黄色无定形粉末产物0.77g。材料的1HNMR谱表明它是被一些杂质污染的要求的产物。方法B
将0.438g(3.2mmol)2-甲基-1-叔丁基-Δ3-1，2-氮杂硼啉(根据文献J.Schulze，和G.Schmid，有机金属化学杂志(J.Organomet.Chem.)，1980，193，83-91的方法制备)在10ml干甲苯中的溶液加到2，2，6，6-四甲基哌啶锂(3.2mmol；通过等摩尔量的2，2，6，6-四甲基哌啶和正丁基锂/己烷在15mlTHF中反应制备)的冷(-78℃)溶液中制备2-甲基-1-叔丁基-1，2-氮杂硼啉基锂。在真空中蒸发溶剂，直到起始体积的三分之一，溶液冷却到-78℃，加入35ml干甲苯。良好搅拌澄清的黄色液体，同时用移液管加入环戊二烯基三氯合锆(0.84g，3.2mmol)。加热该浴至室温，搅拌过夜。过滤反应混合物，滤液蒸发至干。在固体残留物中加入20ml甲苯，过滤混合物以从黄色滤液中除去深色不溶物质。浓缩滤液，得到0.34g黄色无定形粉末，其1H NMR谱表明是所需产品。实施例3-11用氮杂硼啉基锆催化剂的乙烯聚合
用根据方法2A制备的催化剂聚合乙烯。在带搅拌的1.7升高压釜中、在80至110℃进行聚合。将干的不含氧的甲苯(840ml)装入清洁、干燥、无氧的反应器。来自Ethyl Corporation的MAO(10％wt，在甲苯中)用于聚合反应。在30℃用注射器加入MAO，MAO的量是在下表中给出的比值的所要求的。反应器被加热至要求的温度，加入足量乙烯使反应器压力达到150psig。在要求的温度和压力平衡反应器。将0.100g产品溶于100ml甲苯制备催化剂溶液。首先将助催化剂注入反应器，再单独注入催化剂。用这种溶液起动聚合，该溶液应提供表中所示的催化剂的量。按需用于保持压力恒定在150psig的要求使乙烯进入反应器，同时生成聚合物。
1小时结束时(如果活性非常高，少于1小时)，停乙烯流，迅速冷却反应器到室温。打开反应器，从甲苯中滤出聚合物。在真空炉中将产品干燥过夜，称重。表1给出了反应条件，表2给出了聚合结果。
表1
实施例 催化剂的量(mmol)   MAO的量(mmol) Al/TM     T(℃)     H2的量(mmol)   丁烯的量(ml)   反应时间(小时)
    3  0.00552     9.0     1630     80     0     0     0.5
    4  0.00138     2.25     1630     80     0     0     0.5
    5  0.00138     4.5     3261     80     0     0     0.5
    6  0.00138     4.5     3261     80     30     0     1
    7  0.00138     4.5     3261     80     30     20     1
    8  0.00276     4.5     1630     110     0     0     1
    9  0.00276     9     3261     110     0     0     1
    10  0.00276     9     3261     110     30     0     1
    11  0.00276     9     3261     110     30     20     1
表2
实施例 聚合物重量(g)     产率(kg/gZr/小时)     MI2(dg/分钟)   MFR   密度(g/ml)   Mw/Mn
    3     61.8     245     0.16   17.0   0.9577     -
    4     42.2     670     0.03   24.2   0.9500     -
    5     43.2     686     0.04   21.3   0.9529     1.79
    6     71.2     566     4.29   28.7   0.9669     -
    7     85.4     678     3.44   25.9   0.9503     5.14
    8     62.2     247     0.92   22.1   0.9589
    9     67.3     267     1.40   15.1   0.9622     1.74
    10     80.5     320     3.56   21.7   0.9660     -
    11     93.7     372     11.56   21.7   0.9483     3.73
上表表明，有宽范围分子量的聚合物可使用本发明的催化剂制备，因为这类催化剂对氢更敏感。
聚合物的熔融指数根据ASTM D-1238条件E和条件F测定。MI2是以2.16kg的重量测定的熔融指数(条件E)。MI20是以21.6kg重量测定的熔融指数(条件F)。MFR是MI20对NI2的比。根据ASTM D-1505测定聚合物密度。在135℃用1，2，4-三氯苯作为溶剂用Waters 150C凝胶渗透色谱测定聚合物的分子量分布。用重均分子量(Mw)和Mw/Mn(数均分子量)的比表征分子量分布。实施例12和13
在150℃、带搅拌的2.0升不锈钢高压釜里进行溶液聚合。将1.0升干的、无氧的IsoparG.(产自Exxon Chemical Company)装入清洁的、干燥的、无氧的反应器中。然后在150℃调节反应器至平衡。用足够的乙烯加压达到乙烯分压为150psig。不加入氢气或共聚单体。在实施例2中所述的催化剂的溶液与在甲苯中含10％甲基铝氧烷(MAO)的溶液混合(产自AlbemarleCorporation，使用时不用进一步纯化)。搅拌该混合物15分钟。将10.0ml这种混合物注入反应器起动聚合反应。在10.0ml中的催化剂和MAO的量与实验条件一起列于表3。向反应器供入乙烯以保持压力恒定。
15分钟结束时停乙烯气流，反应混合物被移至装有一种在IsoparG中的抗氧化剂溶液的容器内。溶液冷却至室温过夜。由真空过滤将聚合物从溶剂过滤。在真空烘箱中干燥过夜并称重。聚合物的重量为12.1g。聚合物MI2为118dg/分。另外的聚合物性质见表2。实施例14-18
以与实施例3-11所述相同的方法进行淤浆聚合。在那些聚合中使用实施例1所述的催化剂。聚合条件列于表3。生成的聚合物的性质列于表4。
表3
实施例 催化剂的量(mmol)   MAO的量(mmol) Al/TM     T(℃)     H2的量(mmol)   丁烯的量(ml)   反应时间(小时)
    12  0.0138     7.5  543     150     0     0     0.25
    13  0.0138     3.8  272     150     0     0     0.25
    14  0.00552     9.0  1630     80     0     0     1.0
    15  0.00552     13.5  2446     80     0     0     1.0
    16  0.00552     13.5  2446     110     0     0     1.0
    17  0.00552     13.5  2446     110     30     0     1.0
    18  0.00552     13.5  2446     110     30     20     1.0
表4
实施例 聚合物重量(g)   产率(kg/gZr/小时)     MI2(dg/分)   MFR   密度(g/ml)
    12     12.1     38     118     23     0.9660
    13     8.8     28     108     25     0.9483
    14     50.9     101     0.04     18.3     0.9609
    15     49.0     97     0.06     15.0     0.9714
    16     39.7     79     203     -     ＞0.9700
    17     34.0     68     111     24.9     ＞0.9700
    18     42.2     84     166     16.7     ＞0.9700
上表表明，催化剂有好的活性，可制备具有很高结晶性和密度的聚合物。低MFR值表明聚合物有窄的分子量分布。

Claims (20)

1.一种通式如下
Figure A9619421900021
的催化剂，其中L是下式的配体，L’是L、Cp、Cp*、茚基、芴基、NR2、OR或卤素，L可桥连到L；
X是卤素、NR2、OR或C1-C12烷基，M是锆或铪，R是C1-C12烷基或C6-C12芳基，R1是R、C6-C12烷芳基、C6-C12芳烷基、氢或Si(R)3，R2是R1、卤素、COR、COOR、SOR或SOOR，R3是R2、OR、N(R)2、SR或稠合环系，Cp是环戊二烯基，Cp*是五甲基环戊二烯基，n是0-3，LB是任意的路易丝碱。
2.根据权利要求1的催化剂，其中L′是Cp、Cp*或L，X是氯。M是锆，R是C1-C4烷基，R1是C3-C12烷基或芳基，R2是叔丁基或三甲基甲硅烷基，R3是氢或甲基。
3.根据权利要求1的催化剂，是双(1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)二氯合锆。
4.根据权利要求1的催化剂，是1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)三氯合锆。
5.一种制备聚α-烯烃的方法，包括聚合α-烯烃单体，使用通式如下的催化剂，其中L是下式的配体，L′是L、Cp、Cp*、茚基、芴基、NR2、OR或卤素，L可桥连到L；
X是卤素、NR2、OR或C1-C12烷基，M是锆、钛或铪，R是C1-C12烷基或C6-C12芳基，R1是R、C6-C12烷芳基、C6-C12芳烷基、氢或Si(R)3，R2是R1、卤素、COR、COOR、SOR或SOOR，R3是R2、OR、N(R)2、SR或稠合环系，Cp是环戊二烯基、Cp*是五甲基环戊二烯基，n是0-3，LB是任意的路易丝碱。
6.根据权利要求5的方法，其中L′是Cp、Cp*或L。
7.根据权利要求5的方法，其中X是卤素。
8.根据权利要求7的方法，其中X是氯。
9.根据权利要求5的方法，其中M是锆。
10.根据权利要求5的方法，其中R是C1-C4烷基。
11.根据权利要求5的方法，其中R1是C3-C12烷基或芳基。
12.根据权利要求5的方法，其中R2是叔-丁基或三甲基甲硅烷基。
13.根据权利要求5的方法，其中R3是氢或甲基。
14.根据权利要求5的方法，其中所述的催化剂与一种有机金属助催化剂一起使用，每摩尔所述催化剂用约0.01-100000摩尔有机金属助催化剂。
15.根据权利要求14的方法，其中所述有机金属助催化剂是甲基铝氧烷。
16.根据权利要求5的方法，其中所述的催化剂与一种含有非配位惰性阴离子的酸盐一起使用，每摩尔所述催化剂用约0.01-1000摩尔含有非配位惰性阴离子的酸盐。
17.根据权利要求16的方法，其中所述的酸盐选自四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)硼酸苯铵、四(五氟苯基)硼酸-N，N-二甲基苯铵、四(五氟苯基)硼酸三苯甲酯以及它们的混合物。
18.一种制备聚α-烯烃的方法，包括聚合α-烯烃单体，使用通式如下的催化剂，其中L是下式
Figure A9619421900042
的配体，L′是L、Cp、Cp*，L可桥连到L；X是氯，M是锆，R是C1-C4烷基，R1是C3-C12烷基或芳基，R2是叔丁基或三甲基甲硅烷基，R3是氢或甲基，Cp是环戊二烯基，Cp*是五甲基环戊二烯基，n是0-3，LB是任意的路易丝碱。
19.根据权利要求18的方法。其中所述催化剂是双(1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)二氯合锆。
20.根据权利要求18的方法，其中所述催化剂是(1-叔丁基-2-甲基-η5-1，2-氮杂硼啉基)三氯合锆。
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CN113388058A (zh) * 2021-06-08 2021-09-14 福州大学 一种利用有机催化剂进行全光谱诱导可控自由基聚合的方法
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CN113388058A (zh) * 2021-06-08 2021-09-14 福州大学 一种利用有机催化剂进行全光谱诱导可控自由基聚合的方法

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