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优质期刊推荐粘土/羟乙基纤维素层状复合材料的制备及性能表征--《2015年全国高分子学术论文报告会论文摘要集——主题I 高分子组装与超分子体系》2015年
粘土/羟乙基纤维素层状复合材料的制备及性能表征
【摘要】：以粘土(LRD)与羟乙基纤维素(HEC)为原料,采用真空抽滤自组装法,制备了LRD/HEC层状复合膜,并探讨了LRD含量对复合膜的结构及性能的影响。结果如下:当复合膜中LRD含量在0-40 wt%之间时,复合膜的断面呈现模糊的层状结构,复合膜的杨氏模量及断裂强度随LRD含量的增加而快速升高;当复合膜中LRD含量在40-70 wt%之间时,复合膜的断面呈现逐渐清晰的层状结构,复合膜的杨氏模量及断裂强度随LRD含量的增加而缓慢升高,当复合膜中LRD含量达到70%时,复合膜的机械性能达到最优,杨氏模量达到7.09 GPa,断裂强度达到126.66 Mpa,分别比纯HEC膜提高了43倍及5.5倍;当复合膜中LRD含量高于70 wt%时,LRD在复合膜中出现聚集现象,进而导致复合膜的杨氏模量及断裂强度下降。
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【分类号】：TB332【正文快照】：
粘土/羟乙基纤维素层状复合材料的制备及性能表征@周素坤$北京林业大学材料学院
@杨俊$北京林业大学材料学院
@许凤$北京林业大学材料学院以粘土(LRD)与羟乙基纤维素(HEC)为原料,采用真空抽滤自组装法,制备了LRD/HEC层状复合膜,并探讨了LRD含量对复合膜的结构及性能的影响
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京公网安备75号Patent CNB - Copolymerization method of ethane/alpha-alkene - Google PatentsCN BGrantCN Feb 20, 2013Mar 5, 2010Mar 5, 2010.0, CN
B, CN B, CN , CN-B-, CN B, CNB, CN, CN.0, , , , , , , , , , , , ,
(3) , Copolymerization method of ethane/alpha-alkene
B 本发明涉及一种乙烯/α-烯烃共聚合的方法；以构型限制碳桥联单茂金属混合物作催化剂，催化乙烯/α-烯烃共聚合；构型限制碳桥联单茂金属混合物催化剂包含有如下结构通式的构型限制碳桥联单茂金属化合物：R为H或含有1～10个碳原子的叔丁基或烯丙基；R1、R2为H或含有1～10个碳原子的烷基或芳香基；M＝Ti或Zr；Cp＝茂、取代茂、茚或取代茚；构型限制碳桥联单茂金属化合物与其余化合物按摩尔比为5～7∶1；采用富烯与胺基锂反应，锂化后与金属络合，得到含有不同取代基的碳桥联单茂金属混合物；本方法催化用于乙烯/1-己烯、乙烯/1-辛烯以及乙烯/1-癸烯共聚合，长链α-烯烃插入率高。 The present invention relates to an ethylene / α- o a method to limit the configuration of single carbon bridged metallocene catalyst mixture, catalytic ethylene / α- o configuration to limit carbon bridged single metallocene catalyst comprising a mixture of It has the following structural formula configuration limits the single carbon bridged metallocene compound: R is H or t-butyl or allyl group containing 1 to 10 R1, R2 is H or contains from 1 to 10 carbon atoms, M = Ti or Zr; Cp = Mau, substituted metallocene, indene o configuration limits the single carbon bridged metallocene compounds according to the rest of the compound is from 5 to 7:1 using Fu reaction with lithium alkylene amine, metal complex and after lithiated give single carbon bridged metallocenes mixture containing di catalytic present method for ethylene / 1-hexene, ethylene / 1-octene and ethylene / Copolymerization of 1-decene, long chain α- olefin insertion rate.
1. 一种乙烯/a-烯烃共聚合的方法，其特征在于：以构型限制碳桥联单茂金属混合物作催化剂，MAO为助催化剂，铝/锆质量比为1000，在反应温度70°C下反应时间O. 5小时，α -烯烃浓度为O. 40mol/L,乙烯压力O. IMPa,催化乙烯/ α -烯烃共聚合； 构型限制碳桥联单茂金属混合物催化剂包含有如下结构通式的构型限制碳桥联单茂金属化合物： An ethylene / a- olefin polymerization, wherein: the configuration limit to the single carbon bridged metallocene catalyst mixture, MAO as cocatalyst, Al / Zr ratio of 1000 mass, the reaction temperature at 70 ° C reaction time of O. 5 小时, α - olefin concentration of O. 40mol / L, ethylene pressure O. IMPa, Ethylene / α - o configuration to limit carbon bridged single metallocene catalyst comprising a mixture of the following structure Carbon bridge configuration limits the single metallocene compounds of the general formula:
其中：R为H、叔丁基或稀丙基； Rp R2为H或含有I?10个碳原子的烷基或芳香基； M = T i 或Z Cp =茂、取代茂、茚或取代茚； 上式所述的构型限制碳桥联单茂金属化合物与构型限制碳桥联单茂金属混合物中的其余化合物按摩尔比为5?7 ： I ； 构型限制碳桥联单茂金属混合物由如下方法获得： 2OmmoI的叔丁胺或烯丙基胺,溶解于30?60mL的四氢呋喃中，在_50?50°C下搅拌，加入I. 67mol/L的正丁基锂的正己烧溶液12mL,反应4?60小时,加入20mmol的6,6- 二甲基富烯、6，6- 二苯基富烯，反应20?50小时；再加入I. 67mol/L的正丁基锂的正己烷溶液12mL，反应20?50小时后，再加入15?20mmol的四氯化钛和四氢呋喃的络合物或四氯化锆和四氢呋喃的络合物，反应24?72小时，静置，过滤，滤液减压除去溶剂，所得固体用60mL正己烷或二氯甲烷或石油醚洗涤后抽干。 Wherein: R is H, t-bu Rp R2 is H or an alkyl group or an aromatic group I~10 M = T i or Zr; Cp = metallocene, metallocene-substituted, or subst configuration to limit carbon bridged single metallocene compound of the formula and the configuration of the limitations of single carbon bridged metallocene compounds according to the remaining mixture in a molar ratio of 5~7: I; configuration to limit carbon bridged single-mao n-hexyl burning solution 2OmmoI of t-butylamine or allylamine, 30~60mL was dissolved in tetrahydrofuran and stirred at _50~50 ° C was added under I. 67mol / L n-butyllithium: metal mixture obtained by the following method 12mL, reaction is 4~60 hours, 20mmol of 6,6-dimethyl-fulvene, 6,6-diphenyl fulvene, 20~50 adding I. 67mol / L n-butyl lithium n-hexane solution 12mL, 20~50 hours after the reaction, the complex was added 15~20mmol titanium tetrachloride tetrahydrofuran complex or zirconium tetrachloride and tetrahydrofuran, the reaction 24~72 hours, allowed to stand, filtered and the filtrate solvent was removed under reduced pressure, the resulting solid was drained, washed with 60mL methylene chloride or hexane or petroleum ether.
2.根据权利要求I所述的乙烯/ α -烯烃共聚合的方法，其特征在于：构型限制碳桥联单茂金属化合物是： [t-BuNC (Me) 2 ( n 5-C5H4) ] (TiCl2) [t-BuNC (Me) 2 ( n 5-C5H4) ] (ZrCl2) [t-BuNC (C6H5) 2 ( n 5-C5H4) ] (ZrCl2) [H2C = CHCH2NC (Me) 2 ( n 5_C5H4) ] (ZrCl2)。 2. I wherein the ethylene / α Claim - olefin copolymerization, characterized in that: the configuration limits the single carbon bridged metallocene compounds are: [t-BuNC (Me) 2 (n 5-C5H4)] (TiCl2) [t-BuNC (Me) 2 (n 5-C5H4)] (ZrCl2) [t-BuNC (C6H5) 2 (n 5-C5H4)] (ZrCl2) [H2C = CHCH2NC (Me) 2 (n 5_C5H4 )] (ZrCl2).
—种乙烯/ Ct -烯烃共聚合的方法 - Kind of ethylene / Ct - olefin polymerization
技术领域 Technical Field
[0001] 本发明涉及一种利用构型限制碳桥联单茂金属混合物作催化剂，催化乙烯/α -烯烃如乙烯/I-己烯、乙烯/I-辛烯以及乙烯/I-癸烯共聚合的方法。 [0001] The present invention relates to a configuration limit carbon bridged single metallocene catalyst mixture, Ethylene / α - olefins such as ethylene / I- hexene, ethylene / I- octene and ethylene / I- decene total polymerization.
背景技术 Background
[0002] 茂金属催化剂既可以催化乙烯的聚合，又可以催化α -烯烃的立构规整聚合，以及乙烯与α-烯烃的共聚，在新材料的合成领域显示出巨大的生命力。 [0002] The metallocene catalyst can either catalyze the polymerization of ethylene, and can catalyze α - stereoregular polymerization of olefins, and copolymers of ethylene with α- olefin in the synthesis of new materials show great vitality. 其中，乙烯辛烯共聚弹性体E0C，具有良好的力学性能和加工性能，已形成系列产品，并得到了广泛的应用，工业上可采用注射、挤出、吹塑等加工方法成型，又可以用过氧化物等进行化学交联，或采用橡胶加工方法制成弹性体材料。 Among them, ethylene-octene copolymer elastomer E0C, has good mechanical properties and processing performance, has formed a series of products, and has been widely used in the industry can be injection, extrusion, blow molding and other processing methods, they can use peroxide and other chemical crosslinking, or the use of rubber processing method is made of elastomeric material. 因此关于mEOC催化剂的研究进展非常迅速。 Progress on mEOC catalyst therefore very quickly.
[0003] 由茂钛化合物与硼化合物、有机铝化合物组成的茂金属催化剂，具有可调节共聚单体插入量和微观结构等特点；如CN1083846C发明一种新的几何限制结构的茂钛化合物C13H6R1R2R3NR4Ti (R5)： [0003] The metallocene catalyst composed of titanocene compound and a boron compound, an organic aluminum compound composed of a monomer copolymerizable with adjustable insertion amount and mic CN1083846C invention titanocene compound such as a new geometric confinement structure C13H6R1R2R3NR4Ti ( R5):
[0004] [0004]
[0005] 由苯并茚或取代苯并茚经多步反应合成，能与硼化合物及有机铝化合物组成催化剂，催化剂用于烯烃共聚特别是乙烯/辛烯一I共聚、乙烯/苯乙烯共聚。 [0005] in particular ethylene / octene copolymer made of a I-benzoindenyl or substituted benzindenyl synthesized by multi-step reaction, the catalyst can be composed of a boron compound and an organoaluminum compound, a catalyst for olefin copolymer, ethylene / styrene copolymer. 再如CN1049849 (US 5272236 and 5278272)所报道的几何限制结构的茂钛化合物Me2Si (C5Me4)(NCMe3) TiCl2、有机铝和硼化合物组成的催化体系，用于乙烯/辛烯一I共聚合，可得到一种分子量分布窄、共聚单体插入量高且可调、共聚组份分布均一，具有长链支化聚乙烯链结杓的新型乙烯/辛烯一I共聚物。 Titanocene compound Again CN1049849 (US 5272236 and 5278272) reported geometrical confinement structure Me2Si (C5Me4) (NCMe3) TiCl2, consisting of an organoaluminum compound and a boron catalyst system for ethylene / octene A copolymerization I can obtain a narrow molecular weight distribution, the amount of insertion and high monomer copolymerizable adjustable copolymer composition distribution homogeneous, long chain branched polyethylene link scoop novel ethylene / octene copolymer-I. 但美中不足的是这些催化体系稳定性较差，辛烯插入率太低，成本高昂限制其工业应用。 But the drawback is that these catalytic systems less stable, octene insertion rate is too low, the high cost limit its industrial applications.
[0006] CN1328580公开了一种烯烃共聚合用的桥连茂金属，该茂金属催化剂是含芳基取代的桥连部分的有机金属催化剂。 [0006] CN1328580 discloses a combination of an olefin copolymer bridged metallocene, the metallocene catalyst is an organometallic catalyst having a substituted aryl group bridging portion. 该配合物含有包含至少一个烃基甲硅烷基取代基的增溶共价桥连部分。 The complex comprises at least one hydrocarbon group comprising a silyl substituent solubilizing covalent bridging portion. 这些化合物可以下述通式表示： These compounds may be represented by the following general formula:
[0007] [0007]
[0008] 该类型化合物的制备方法，均采取分步合成；制备路线长，产品收率低下。 [0008] The preparation of compounds of this type are taken st prepared long route and the yield is low.
发明内容 DISCLOSURE
[0009] 本发明目的是提供一种构型限制碳桥联单茂金属混合物作催化剂，催化乙烯/α -烯烃如乙烯/I-己烯、乙烯/I-辛烯以及乙烯/I-癸烯共聚合的方法。 [0009] The object of the present invention to provide a configuration list to limit carbon bridged metallocene catalyst mixture, Ethylene / α - olefins such as ethylene / I- hexene, ethylene / I- octene and ethylene / I- decene co-polymerization.
[0010] 本发明所述的碳桥联单茂金属混合物催化剂包括如下结构的化合物： [0010] Single-carbon bridged metallocene catalyst mixture of the present invention comprises a compound of the following structure:
[0011] [0011]
[0012] 其中：R为H或含有I?10个碳原子的烧基、芳香基或稀丙基；叔丁基为优选基团； [0012] wherein: R is H or contains burn group, an aromatic group, or a dilute propyl I~10 t-butyl
[0013] RpR2为H或含有I?10个碳原子的烷基或芳香基；甲基为优选基团。 [0013] RpR2 is H or containing I~10 carbon atoms
preferably a methyl group.
[0014] M = Ti 或Zr [0014] M = Ti or Zr
[0015] Cp =茂、取代茂、茚或取代茚。 [0015] Cp = Mau, replace Mao, indene or substituted indene.
[0016] 这类构型限制碳桥联茂金属化合物包括但不限制于下列化合物： [0016] Such configuration limits carbon bridged metallocene compounds include, but are not limited to the following compounds:
[0017] [t-BuNC (Me) 2 ( η 5_C5H4) ] (TiCl2) [0017] [t-BuNC (Me) 2 (η 5_C5H4)] (TiCl2)
[0018] [t-BuNC (Me) 2 ( n 5_C5H4) ] (ZrCl2) [0018] [t-BuNC (Me) 2 (n 5_C5H4)] (ZrCl2)
[0019] [t-BuNC (CH2) 5 ( n 5_C5H4) ] (ZrCl2) [0019] [t-BuNC (CH2) 5 (n 5_C5H4)] (ZrCl2)
[0020] [t-BuNCH (H2C = CHCH2) ( n 5_C5H4) ] (TiCl2) [0020] [t-BuNCH (H2C = CHCH2) (n 5_C5H4)] (TiCl2)
[0021 ] [t-BuNC (H2C = CHCH2) 2 ( n 5_C5H4) ] (TiCl2) [0021] [t-BuNC (H2C = CHCH2) 2 (n 5_C5H4)] (TiCl2)
[0022] [t-BuNC (H2C = CHCH2) 2 ( n 5_C5H4) ] (ZrCl2) [0022] [t-BuNC (H2C = CHCH2) 2 (n 5_C5H4)] (ZrCl2)
[0023] [H2C = CHCH2NC (Me) 2 ( n 5_C5H4) ] (ZrCl2) [0023] [H2C = CHCH2NC (Me) 2 (n 5_C5H4)] (ZrCl2)
[0024] [t-BuNC (Me) 2 ( n 5-nBuC5H3) ] (TiCl2) [0024] [t-BuNC (Me) 2 (n 5-nBuC5H3)] (TiCl2)
[0025] [H2C = CHCH2NC (Me) 2 ( n 5-nBuC5H3) ] (Zr Cl2) [0025] [H2C = CHCH2NC (Me) 2 (n 5-nBuC5H3)] (Zr Cl2)
[0026] [t-BuNC (Me) 2 ( n 5-nBuC5H3) ] (ZrCl2) [0026] [t-BuNC (Me) 2 (n 5-nBuC5H3)] (ZrCl2)
[0027] [t-BuNC (Me) 2 ( n 5_H2C = CHCH2C5H3) ] (Zr Cl2)。 [0027] [t-BuNC (Me) 2 (n 5_H2C = CHCH2C5H3)] (Zr Cl2).
[0028] 该类混合物的典型制备过程如下： [0028] A typical process for preparing such mixtures as follows:
[0029] 20mmol的叔丁胺或烯丙基胺，溶解于30?60mL的四氢呋喃（THF)中，在-50?50°C下搅拌，加入I. 67mol/L的正丁基锂（n-BuLi)的正己烷溶液12mL，反应4?60小时，加入20mmol的6，6- 二甲基富烯或6，6- 二烯丙基富烯、或者6-氢-6-烯丙基富烯、或者6，6- 二苯基富烯，反应20?50小时；再加入I. 67mol/L的正丁基锂（n_BuLi)的正己烷溶液12mL,反应20?50小时后，再加入15?20mmol的四氯化钛和四氢呋喃的络合物或四氯化锆和四氢呋喃的络合物，反应24?72小时。 [0029] 20mmol of t-butylamine or allylamine, 30~60mL was dissolved in tetrahydrofuran (THF) and stirred at -50~50 ° C was added under I. 67mol / L n-butyl lithium (n-BuLi) The n-hexane solution 12mL, reaction 4~60 hours, 20mmol of 6,6-dimethyl-fulvene or 6,6-diallyl fulvene or fulvene -6-allyl-6- hydrogen, or 6,6-diphenyl fulvene, 20~50 adding I. 67mol / L n-butyl lithium (n_BuLi) in n-hexane 12mL, 20~50 hours after the reaction, the added 15~20mmol complex or a complex of zirconium tetrachloride and titanium tetrachloride tetrahydrofuran and tetrahydrofuran, the reaction 24~72 hours. 静置，过滤，滤液减压除去溶剂，所得固体以30?60mL正己烷或二氯甲烷、或者石油醚洗涤后抽干，得到的固体即为构型限制碳桥联单茂金属混合物。 Standing, was filtered, and the filtrate solvent was removed under reduced pressure, the resulting solid was after 30~60mL hexane or dichloromethane, washed with petroleum ether or drained, the resulting solid is a mixture of the single metallocene limit carbon bridge configuration.
[0030] 本发明的构型限制碳桥联单茂金属混合物的主要成分为碳桥联单茂金属化合物，其中碳桥联单茂金属化合物与构型限制碳桥联单茂金属混合物中的其余化合物按摩尔比为5?7 ： I。 [0030] The configuration of the present invention to limit carbon bridge the single metallocene mixture of the main components of a single carbon bridged metallocene compounds in which the carbon bridged metallocene compound with a single configuration to limit carbon bridged metallocene mixture remaining single compound in a molar ratio of 5~7: I. 在该碳桥联单茂金属化合物的碳桥或茂环上，特别是碳桥上引入取代基如烷基、烯丙基等，可以改变中心金属的化学、立体环境，有效改善催化剂性能。 On the ring carbon bridge or metallocene single carbon bridged metallocene compounds, especially carbon bridge introduction of a substituent such as an alkyl, allyl, etc., can change the central metal chemistry, three-dimensional environment, improve catalyst performance. 在催化乙烯与长链α -烯烃共聚反应如乙烯/I-己烯、乙烯/I-辛烯共聚合时，烯烃聚合活性高，同时长链α -烯烃插入率较高。 In Ethylene and long chain α - olefin copolymerization, such as ethylene / I- hexene, ethylene / I- octene copolymerized, olefin polymerization activity high, and long chain α - olefins higher insertion rates. 例如，以甲苯为溶剂，以实施例I的含[t-BuNC(Me)2( Jl5-C5H4)](ZrCl2)的混合物为催化剂，MAO为助催化剂，在反应温度70°C下反应时间O. 5小时，催化乙烯/辛烯-I共聚合，在铝/锆比为1000，辛烯-I浓度为O. 40mol/L,乙烯压力O. IMPa时，聚合活性为2. 12X106gPE/mol. cat. h.，聚合物中辛烯-I含量5. 19mol%。 For example, with toluene as solvent in Example I containing [t-BuNC (Me) 2 (Jl5-C5H4)] (ZrCl2) catalyst mixture, MAO as cocatalyst, the reaction time O at a reaction temperature of 70 ° C under After 5 hours, Ethylene / octene copolymerization -I, aluminum / zirconium ratio was 1,000, the concentration of octene -I O. 40mol / L, while the ethylene pressure O. IMPa, the polymerization activity is 2. 12X106gPE / mol. cat. h., -I octene polymer content 5. 19mol%.
[0031] 该构型限制碳桥联单茂金属混合物的制备方法，采用富烯与胺基锂反应，直接在茂环上引入胺基，得到碳桥联配体，锂化后与金属络合，合成含有不同取代基的碳桥联单茂金属混合物。 [0031] This configuration limits the single method of producing carbon bridged metallocene mixture, using rich ene reaction with lithium group, introduced amino directly on Mao ring to obtain a carbon bridging ligands and metal complex after lithiated synthesized containing different carbon bridged metallocene mixture of single substituent. 克服了以往桥联催化剂的制备路线长、产品收率低下的缺陷。 To overcome the past bridged catalyst preparation route length, low product yield defects. 该方法以价廉的富烯为起始物，通过连续法反应合成碳桥联单茂金属混合物，合成方法新颖，对中间产物不需要分离处理和纯化，合成路线短，工艺简单，提高了催化剂收率，简化了处理工艺，节约了成本,催化剂收率可达80%以上。 In this method, inexpensive starting material fulvene synthesized carbon bridged metallocene single reaction mixture by continuous, novel synthesis method, the intermediate product does not require separation and purification, synthesis route is short, simple process, improve the catalyst yield, simplifies the treatment process, cost savings, catalyst yield up to 80%.
[0032] 该类碳桥联单茂金属混合物的制备条件为：富烯与叔丁胺或烯丙基胺的摩尔比为I ： I ;富烯与TiCl4或ZrCl4. THF的摩尔比为I : O. 75?I. O ;反应温度为-50?50°C。 [0032] This class of single carbon bridged metallocene mixture preparation conditions were: fulvene with t-butylamine or allylamine molar ratio I: I; fulvene with TiCl4 or ZrCl4 THF molar ratio of I: O.. . 75~I O; reaction temperature is -50~50 ° C.
[0033] 本发明采用碳桥联茂金属混合物/MAO催化剂体系，对乙烯和α -烯烃共聚合获得高活性，可适用于乙烯等α-烯烃的均聚或共聚，特别适用于催化乙烯/己烯-I、催化乙烯/辛烯-I等乙烯与长链α-烯烃的共聚。 [0033] The present invention is a mixture of carbon bridged metallocene / MAO catalyst system, ethylene and α - olefin copolymerization to obtain high activity, and other α- olefins suitable for ethylene homo- or copolymer, is particularly suitable for Ethylene / hexene ene -I, copolymer Ethylene / octene -I ethylene and other olefins with long chain α-.
[0034] 从上述公开技术方案的实际应用看，本发明所述的碳桥联单茂金属混合物具有合成路线短，只需简单的分离纯化，产品收率高，用于催化乙烯与长链α-烯烃共聚时催化活性高，长链α-烯烃插入率高等特点。 [0034] From a practical technical solution disclosed above, the single carbon bridged metallocene mixture of the present invention comprises a synthetic route is short, simple separation and purification, high yield, Ethylene is used with a long chain α - olefin copolymer high catalytic activity, long chain α- olefin insertion rate and so on.
具体实施方式 DETAILED DESCRIPTION
[0035] 茂金属混合物合成 [0035] metallocene mixtures of synthetic
[0036] 实施例I [0036] Example I
[0037]含[t-BuNC (Me) 2 ( n 5_C5H4) ] (ZrCl2)的混合物的合成 Synthesis [0037] containing [t-BuNC (Me) 2 (n 5_C5H4)] (ZrCl2) mixture of
[0038] 取20mmol (I. 46g)的叔丁胺，加入到30mL的THF中，在_10°C下搅拌，加入I. 67M的n-BuLi的正己烷溶液12mL (20mmol)，反应40小时，得到白色浑浊悬浮液，再加入20mmol (2. 14g)的6，6-二甲基富烯，溶液立刻变澄清，反应50小时后加入I. 67M的n_BuLi的正己烷溶液12mL(20mmol)，反应40小时，得到白色浑浊悬浮液，然后O °C条件下加入17mmol (3. 957g)的ZrCl4,继续搅拌反应72小时，溶液上层变澄清，减压除去溶剂，以二氯甲烷洗涤后抽干，得到黄色固体5. 6g，收率为84% ;经1H NMR和元素分析、质谱分析证明产物为含[t-BuNC (Me) 2 ( n 5-C5H4) ] (ZrCl2)的混合物，[t-BuNC (Me) 2 ( n 5-C5H4) ] (ZrCl2)摩尔含量为84. 4%, BP [t-BuNC(Me)2 ( n5-C5H4) ] (ZrCl2)与其余混合物按摩尔比为5. 4 ： I ;混合物熔点为111 ?114°c。 [0038] Take 20mmol (I. 46g) of t-butylamine was added to 30mL of THF, under stirring at _10 ° C, was added 12mL I. 67M n-hexane solution of n-BuLi in (20mmol), reaction of 40 hours, to give turbid white suspension was added 20mmol (2. 14g) of 6,6-dimethyl-fulvene, immediately the solution became clear, I. 67M was added 50 hours after the reaction of n-hexane solution 12mL n_BuLi (20mmol), reaction of 40 hours, to give a white cloudy suspension was then added to 17mmol (3. 957g) of ZrCl4 at O ° C conditions, stirring was continued for 72 hours the reaction, the solution became clear upper layer, the solvent was removed under reduced pressure, washed with dichloromethane drained to give yellow solid 5. 6g, the yield was 84%; by 1H NMR and elemental analysis, mass spectral analysis confirmed that the product containing [2 (n 5-C5H4) t-BuNC (Me)] (ZrCl2) mixture, [t-BuNC (Me) 2 (n 5-C5H4)] (ZrCl2) molar content of 84. 4%, BP [t-BuNC (Me) 2 (n5-C5H4)] (ZrCl2) and the rest of the mixture at a molar ratio of 5.4 : I; melting point of the mixture was 111 ~114 ° c. 1H NMR(DCCl3, δ ) :6. 31 (m，1H，CpH)，6· 07 ((m，2H，CpH)，6· OO (m，1H, CpH)，I. 52 (s,6H, CMe2)，0. 65 (10H, Me3CN)。元素分析值C12H19Cl2NZr ：C 测量值40. 03% ；H测量值6. 34%。 1H NMR (DCCl3, δ):.. 6 31 (m, 1H, CpH), 6 · 07 ((m, 2H, CpH), 6 · OO (m, 1H, CpH), I 52 (s, 6H, . CMe2), 0 65 (10H, Me3CN) Elemental analysis C12H19Cl2NZr: C measured value 40. 03%; H 6.34% measured value.
[0039] 实施例2 [0039] Example 2
[0040]含[t-BuNC (Me) 2 ( n 5_C5H4) ] (TiCl2)的混合物的合成 Synthesis [0040] contain [t-BuNC (Me) 2 (n 5_C5H4)] (TiCl2) a mixture of
[0041] 取20mmol (I. 46g)的叔丁胺，加入到55mL的THF中，在_10°C下搅拌，慢慢加入I. 67M的n-BuLi的正己烷溶液12mL，搅拌反应30小时，得到白色浑浊悬浮液，加入20mmol的6，6-二甲基富烯溶液立刻变澄清，继续搅拌反应50小时，再加入I. 67M的n_BuLi的正己烷溶液12mL，搅拌反应50小时，得到白色悬浮液，然后加入15. 5mmol的TiCl4 -2THF,继续搅拌反应50小时，溶液变为橄榄绿色。 [0041] Take 20mmol (I. 46g) of t-butylamine was added to 55mL of THF, under stirring at _10 ° C, was slowly added 12mL I. 67M n-hexane solution of n-BuLi, the reaction was stirred for 30 hours, to give turbid white suspension was added a solution of 6,6-dimethyl-fulvene 20mmol immediately became clear, stirring was continued for 50 hours, and then n-hexane solution was added 12mL I. 67M of n_BuLi, and the reaction was stirred for 50 hours, to give a white suspension , then added 15. 5mmol of TiCl4 -2THF, stirring was continued for 50 hours the reaction, the solution turned olive green. 减压除去溶剂，加入正己烷萃取过量n-BuLi，剩余固体抽干，得到橄榄绿色固体合计5. 09g，收率80%。 The solvent was removed under reduced pressure, and extracted with n-hexane was added an excess of n-BuLi, the residual solid was drained to give the olive-green solid aggregate 5. 09g, yield 80%. 经1H NMR和元素分析、质谱分析证明产物为含[t-BuNC (Me) 2 ( n 5-C5H4) ] (TiCl2)的混合物，[t-BuNC (Me) 2 ( n 5-C5H4) ] (TiCl2)摩尔含量为83. 8 %，SP [t-BuNC (Me) 2 ( n 5_C5H4) ] (TiCl2)与其余混合物按摩尔比为5. 2 ： I ;混合物熔点为102 ?105°C。 By 1H NMR and elemental analysis, mass spectral analysis confirmed that the product containing [t-BuNC (Me) 2 (n 5-C5H4)] (TiCl2) mixture, [t-BuNC (Me) 2 (n 5-C5H4)] ( TiCl2) molar content of 83. 8%, SP [t-BuNC (Me) 2 (n 5_C5H4)] (TiCl2) with the rest of the mixture at a molar ratio of 5. 2: I; melting point of the mixture was 102 ~105 ° C. 1H NMR(DCCl3, δ ) :6. 42 (m，1H，CpH)，6· 20 ((m，2H，CpH)，6· 03 (m，1H，CpH)，I. 45 (s,6H, CMe2)，0. 60 (s，11H, Me3CN)。元素分析值C12H19Cl2NTi ：C,计算值48. 68%，测量值46. 50% ；H,计算值6. 47%,测量值7.21%。 1H NMR (DCCl3, δ):.. 6 42 (m, 1H, CpH), 6 · 20 ((m, 2H, CpH), 6 · 03 (m, 1H, CpH), I 45 (s, 6H, .. CMe2), 0 60 (s, 11H, Me3CN) Elemental analysis C12H19Cl2NTi: C, 48.68% Calculated, measured value 46. 50%; H, 6.47% Calculated, measured 7.21%.
[0042] 实施例3 [0042] Example 3
[0043]含[t-BuNC (CH2) 5 ( n 5_C5H4) ] (ZrCl2)的混合物的合成 Synthesis [0043] contain [t-BuNC (CH2) 5 (n 5_C5H4)] (ZrCl2) a mixture of
[0044] 取20mmol (I. 46g)的叔丁胺，加入到30mL的THF中，在_10°C下搅拌，加入I. 67M的n-BuLi的正己烷溶液12mL(20mmol)，搅拌反应40小时，得到白色浑浊悬浮液，加入20mmol (2. 48g)的6，6-五亚甲基富烯，溶液变澄清，搅拌反应48小时，再加入I. 67M的n-BuLi的正己烷溶液12mL，搅拌反应50小时，得到白色浑浊悬浮液，再加入18. 8mmol的ZrCl4，搅拌反应72小时；静置后过滤除去白色的LiCl，滤液减压除去溶剂，以二氯甲烷洗涤后抽干得到淡黄色固体产品5. 5g。 [0044] Take 20mmol (I. 46g) of t-butylamine was added to 30mL of THF was stirred at _10 ° C was added under I. 67M n-BuLi in hexane solution 12mL (20mmol), stirred for 40 hours. to give a white cloudy suspension was added 20mmol (2. 48g) in 6,6-pentamethylene fulvene, the solution became clear, the reaction was stirred for 48 hours, then was added 12mL I. 67M n-hexane solution of n-BuLi, the mixture was stirred for 50 hours to obtain a white turbid suspension was added 18. 8mmol of ZrCl4, the reaction was stirred for 72 the white LiCl was removed by filtration after standing, the filtrate solvent was removed under reduced pressure, washed with methylene chloride to give a pale yellow solid drained product 5. 5g. 经测试产物中[t-BuNC(CH2)5( Ji5-C5H4)] (ZrCl2)摩尔含量为84. 5%, BP [t-BuNC(CH2)5( n5-C5H4) ] (ZrCl2)与其余混合物按摩尔比为5. 45 ： I ；混合物熔点为121 ?124 0C。 After testing the product [t-BuNC (CH2) 5 (Ji5-C5H4)] (ZrCl2) molar content of 84. 5%, BP [t-BuNC (CH2) 5 (n5-C5H4)] (ZrCl2) with the rest of the mixture molar ratio of 5. 45: I; the mixture having a melting point 121 ~124 0C. 1H NMR (DCCl3, δ ) :6. 60 (m, 2H, CpH)，6. 13 (m, 1H, CpH)，I. 35(s,9H, NCMe3)，I. 34(m，3H，(CH2)5), I. 60 (m, 3H, (CH2)5), I. 87 (m, 2H, (CH2) 5)，3· 03 (m，2Η，（CH2) 5)。 1H NMR (DCCl3, δ):. 6 60 (m, 2H, CpH), 6 13 (m, 1H, CpH), I 35 (s, 9H, NCMe3), I 34 (m, 3H, (... CH2) 5), I. 60 (m, 3H, (CH2) 5), I. 87 (m, 2H, (CH2) 5), 3 · 03 (m, 2Η, (CH2) 5). 元素分析C15H23Cl2NZr :C 测量值46. 65% ;H 测量值7. 54%。 Elemental analysis C15H23Cl2NZr: C measured value 46. 65%; H 7.54% measured value.
[0045] 实施例4 [0045] Example 4
[0046]含[t-BuNCH (CH2 = CH CH2) ( η 5_C5H4) ] (TiCl2)混合物的合成 Synthesis [0046] containing [t-BuNCH (CH2 = CH CH2) (η 5_C5H4)] (TiCl2) mixture
[0047] 取20mmol (I. 46g)的叔丁胺，加入到40mL的THF中，在15°C下缓缓滴入加入I. 67M的n-BuLi的正己烷溶液12mL，搅拌反应12小时，加入20mmol(3. Ig)的6-氢-6-烯丙基富烯，透明的黄色的液体变为红色液体，搅拌反应48小时，再加入I. 67M的n-BuLi的正己烷溶液12mL，搅拌反应24小时，得到暗红色溶液，再加入18. 5mmol的TiCl4 · 2THF，继续反应72小时；减压除去溶剂，加入石油醚40mL洗涤，得到褐色粉末固体4. 6g，收率为61 %。 [0047] Take 20mmol (I. 46g) of t-butylamine was added to 40mL of THF, at 15 ° C under slowly added dropwise n-hexane solution was added 12mL of I. 67M n-BuLi, the reaction was stirred for 12 hours, was added 20mmol (3. Ig) -6-allyl-6- hydrogen fulvene, yellow transparent liquid becomes red liquid, the reaction was stirred for 48 hours, then was added 12mL I. 67M n-hexane solution of n-BuLi, the reaction was stirred 24 hours to give a dark red solution, then add 18. 5mmol of TiCl4 · 2THF, reaction was continued for 72 the solvent was removed under reduced pressure, washed with 40mL of petroleum ether was added to give a brown powder solid 4. 6g, 61% yield. 经测试产物中[t-BuNCH(CH2 = CH CH2) ( H5-C5H4)] (TiCl2)摩尔含量为86. 8%, BP [t-BuNCH(CH2=CH CH2) (Ii5-C5H4)] (TiCl2)与其余混合物按摩尔比为6.6 ： I。 Tested product [t-BuNCH (CH2 = CH CH2) (H5-C5H4)] (TiCl2) molar content of 86. 8%, BP [t-BuNCH (CH2 = CH CH2) (Ii5-C5H4)] (TiCl2 ) and the rest of the mixture at a molar ratio of 6.6: I.
[0048] 实施例5 [0048] Example 5
[0049]含[t-BuNC (CH2 = CH CH2) 2 ( η 5_C5H4) ] (TiCl2)的混合物合成[0050]取 20mmol (I. 46g)的叔丁胺，加入到50mL 的THF 中，(TC 下加入I. 67M 的n-BuLi的正己烷溶液12mL，搅拌反应60小时，加入20mmol (5. 25g)的6，6-二烯丙基富烯，立刻变深蓝色溶液，反应50小时后加入I. 67M的n-BuLi的正己烷溶液12mL，反应50小时，再加入19. 15mmol的TiCl4 · 2THF，反应48小时；减压除去溶剂，以二氯甲烷洗涤后减压除去，得到红棕色固体。经测试产物中[t-BuNC(CH2 = CH CH2)2( Ii5-C5H4)] (TiCl2)摩尔含量为85. 9%,即[t-BuNC(CH2 = CH CH2)2( Ii5-C5H4)] (TiCl2)与其余混合物按摩尔比为6. I ： I。 [0049] contain [t-BuNC (CH2 = CH CH2) 2 (η 5_C5H4)] (TiCl2) was synthesized [0050] to take 20mmol (I. 46g) of t-butylamine was added to 50mL of THF was added (at TC 12mL I. 67M n-hexane solution of n-BuLi, the reaction was stirred for 60 hours, was added 20mmol (5. 25g) of 6,6-diallyl fulvene, immediately becomes deep blue solution was added 50 hours after the reaction I. 12mL n-BuLi hexane solution of 67M, the reaction 50 hours, then added 19. 15mmol of TiCl4 · 2THF, reacted 48 the solvent was removed under reduced pressure, washed with methylene chloride was removed under reduced pressure to give a red-brown solid was. Test product [t-BuNC (CH2 = CH CH2) 2 (Ii5-C5H4)] (TiCl2) molar content of 85.9%, i.e. [t-BuNC (CH2 = CH CH2) 2 (Ii5-C5H4)] ( TiCl2) with the rest of the mixture at a molar ratio of 6. I: I.
[0051] 实施例6 [0051] Example 6
[0052]含[t-BuNC (C6H5) 2 ( n 5_C5H4) ] (ZrCl2)混合物的合成 [0052] Syntheses [t-BuNC (C6H5) 2 (n 5_C5H4)] (ZrCl2) mixture
[0053]取 20mmol(l· 46g)的叔丁胺，加入到40mL 的THF 中，在(TC下加入I. 67M 的n-BuLi的正己烷溶液12mL，反应48小时，再加入20mmol (4. 67g)的6，6- 二苯基富烯，溶液立刻变深蓝色，反应48小时后加入I. 67M的n-BuLi的正己烷溶液12mL，得到红色溶液，继续反应48小时，再加入20mmol (5. OOg)的ZrCl4,反应50小时，减压除去溶剂，加入石油醚50mL洗涤，过滤除去液体，得到褐色粉末。经测试产物中[t-BuNC(C6H5)2( Ji5-C5H4)] (ZrCl2)摩尔含量为83.6%,即[t-BuNC(C6H5)2 ( n5_C5H4) ] (ZrCl2)与其余混合物按摩尔比为5. I ： I。 [0053] Take 20mmol (l · 46g) of t-butylamine was added to 40mL of THF, n-hexane solution in 12mL (TC was added at the I. 67M n-BuLi, the reaction 48 hours, and then was added 20mmol (4. 67g) The 6,6-diphenyl fulvene, the solution immediately becomes deep blue, I. 67M was added 48 hours after the reaction 12mL n-BuLi in n-hexane, the resulting red solution, reaction was continued for 48 hours, then added 20mmol (5. OOg) of ZrCl4, 50 hours reaction, the solvent was removed under reduced pressure, washed with petroleum ether was added 50mL, liquid was removed by filtration, to give a brown powder. The product has been tested in the [t-BuNC (C6H5) 2 (Ji5-C5H4)] (ZrCl2) moles content of 83.6%, i.e. [t-BuNC (C6H5) 2 (n5_C5H4)] (ZrCl2) and the rest of the mixture at a molar ratio of 5. I: I.
[0054] 实施例7 [0054] Example 7
[0055]含[H2C = CHCH2NC (Me) 2 ( n 5_C5H4) ] (ZrCl2)混合物合成 [0055] contain [H2C = CHCH2NC (Me) 2 (n 5_C5H4)] (ZrCl2) mixtures of synthetic
[0056] 取20mmol的烯丙基胺加入到45mL的THF中，在-20 °C下搅拌，加入I. 67M的n-BuLi的正己烷溶液12mL，反应4. O小时，加入20mmol (2. 14g)的6，6_ 二甲基富烯，反应20小时，再加入I. 67M的n-BuLi的正己烷溶液12mL，反应20小时，-20 V加入20mmol (4. 64g)的ZrCl4,反应24小时，减压除去溶剂，用二氯甲烷洗涤，得到黄色粉末物质。 [0056] 20mmol taken allyl amine was added to 45mL of THF, under stirring at -20 ° C, was added 12mL I. 67M n-hexane solution of n-BuLi, the reaction 4. O h, 20mmol (2. 14g) in dimethyl fulvene 6,6_, 20 hours, and then was added 12mL I. 67M n-hexane solution of n-BuLi, the reaction 20 hours, -20 V was added 20mmol (4. 64g) of ZrCl4, reaction 24 hours, the solvent was removed under reduced pressure, washed with dichloromethane, to give a yellow powder substance. 经测试产物中[H2C = CHCH2NC(Me)2 (Ii5-C5H4)] (ZrCl2)摩尔含量为85. 1%，即[H2C =CHCH2NC (Me) 2 ( n 5_C5H4) ] (ZrCl2)与其余混合物按摩尔比为5. 7 ： I。 After testing the product [H2C = CHCH2NC (Me) 2 (Ii5-C5H4)] (ZrCl2) molar content of 85.1%, ie [H2C = CHCH2NC (Me) 2 (n 5_C5H4)] (ZrCl2) and the rest a mixture of massage Seoul ratio of 5. 7: I.
[0057] 常压下均相催化乙烯与α -烯烃共聚合 [0057] homogeneous catalysis under normal pressure of ethylene with α - olefin polymerization
[0058] 实施例8 [0058] Example 8
[0059] 将有磁力搅拌子、导气管的IOOmL三口瓶用乙烯气体置换3次，依次加入45. 5mL甲苯、3. 12mL辛烯-I、锆含量为2.0μπιο1的实施例I的混合物，助催化剂MAOI. 35mL(l. 50M) [A1/M = 1012]，常压下通入乙烯，70°C下反应30min，用10%的盐酸乙醇终止反应，聚合物转移到烧杯中，静置、过滤，乙醇洗涤至中性，80°C恒温真空干燥，称量聚合物质量2. 12g，聚合活性为2. 12 X IO6g聚合物/mol · cat · h，辛烯-I含量5. 19mol %，共聚物分子量分布指数为2. 06。 [0059] The a magnetic stirrer, three-necked flask airway IOOmL replaced three times with ethylene gas, followed by adding 45. 5mL of toluene, 3. 12mL octene -I, zirconium content of the mixture of Example I, 2.0μπιο1 help The catalyst MAOI. 35mL (l. 50M) [A1 / M = 1012], ethylene was fed under atmospheric pressure, 70 ° C reaction 30min, with 10% hydrochloric acid in ethanol to terminate the reaction, the polymer is transferred to a beaker and allowed to stand, filtered, washed with ethanol until neutral, 80 ° C constant temperature drying in vacuo, weighed polymer mass 2. 12g, the polymerization activity was 2. 12 X IO6g polymer / mol · cat · h, -I octene content 5. 19mol% , a molecular weight distribution index of the copolymer was 2.06.
[0060] 实施例9 [0060] Example 9
[0061] 将有磁力搅拌子、导气管的IOOmL三口瓶用乙烯气体置换3次，依次加入45. 5mL甲苯、3. 12mL辛烯-I、锆含量为10. Oymol的实施例I的混合物，助催化剂MAO [0061] The a magnetic stirrer, three-necked flask airway IOOmL replaced three times with ethylene gas, followed by adding 45. 5mL of toluene, 3. 12mL octene -I, zirconium content of Example 10. Oymol mixture I, cocatalyst MAO
6. 7mL(l. 50M) [A1/M = 1005]，常压下通入乙烯，70°C下反应30min，用10%的盐酸乙醇终止反应，聚合物转移到烧杯中，静置、过滤，乙醇洗涤至中性，80°C恒温真空干燥，称量聚合物质量7. 72g，聚合活性为I. 54 X IO6g聚合物/mol · cat · h，辛烯-I含量5. 44mol %，共聚物分子量分布指数为2. 19。 6. 7mL (l. 50M) [A1 / M = 1005], ethylene was fed under atmospheric pressure, 70 ° C reaction 30min, with 10% hydrochloric acid in ethanol to terminate the reaction, the polymer is transferred to a beaker, allowed to stand, filtered , washed with ethanol until neutral, 80 ° C constant temperature drying in vacuo, weighed polymer mass 7. 72g, the polymerization activity was I. 54 X IO6g polymer / mol · cat · h, -I octene content 5. 44mol%, copolymers of a molecular weight distribution index of 2.19.
[0062] 实施例10 [0062] Example 10
[0063] 操作方法同实施例9，催化剂为实施例2的混合物。 [0063] The method of operation described in Example 9, a mixture of the catalyst of Example 2. 得到聚合物5. 15g，换算活性为I. 03X 106gPE/mol · Cat · h。 To obtain a polymer 5. 15g, conversion activity I. 03X 106gPE / mol · Cat · h. 135°C测13C NMR，I-辛烯插入率为5. 34% mol。 135 ° C measured 13C NMR, I- octene insertion rate of 5. 34% mol.
[0064] 实施例11 [0064] Example 11
[0065] 操作方法同实施例9，催化剂为实施例3的混合物。 [0065] The method of operation described in Example 9, a mixture of the catalyst of Example 3. 得到聚合物I. 423g，换算活性为O. 285X 106gPE/mol · Cat · h。 To obtain a polymer I. 423g, conversion activity of O. 285X 106gPE / mol · Cat · h. 135°C测13C NMR，I-辛烯插入率为4. 98% mol。 135 ° C measured 13C NMR, I- octene insertion rate of 4. 98% mol.
[0066] 实施例12 [0066] Example 12
[0067] 操作方法同实施例9，催化剂为实施例4的混合物。 [0067] The method of operation described in Example 9, a mixture of the catalyst of Example 4. 得到聚合物I. 45g，换算活性为O. 290X 106gPE/mol · Cat · h。 To obtain a polymer I. 45g, in terms of activity of O. 290X 106gPE / mol · Cat · h. 135°C测13C NMR，I-辛烯插入率为5· 64% mol。 135 ° C measured 13C NMR, I- octene insertion rate of 5 · 64% mol.
[0068] 实施例13 [0068] Example 13
[0069] 操作方法同实施例9，催化剂为实施例5的混合物，I-辛烯用量为6mL。 [0069] The method of operation described in Example 9, a mixture of the catalyst of Example 5, I- octene in an amount of 6mL. 得到聚合物3. 156g，换算活性为O. 631X 106gPE/mol · Cat · h。 To obtain a polymer 3. 156g, conversion activity of O. 631X 106gPE / mol · Cat · h. 135°C测13C NMR，1_ 辛烯插入率为 135 ° C measured 13C NMR, 1_ octene insertion rate
5. 08% mol ο 5. 08% mol ο
[0070] 实施例14 [0070] Example 14
[0071] 操作方法同实施例9，催化剂为实施例6的混合物。 [0071] The method of operation described in Example 9, a mixture of the catalyst of Example 6. 得到聚合物I. 152g，换算活性为O. 225X 106gPE/mol · Cat · h。 To obtain a polymer I. 152g, conversion activity of O. 225X 106gPE / mol · Cat · h. 135°C测13C NMR，I-辛烯插入率为4· 44% mol。 135 ° C measured 13C NMR, I- octene insertion rate of 4 · 44% mol.
[0072] 实施例15 [0072] Example 15
[0073] 操作方法同实施例9，催化剂为实施例7的混合物。 [0073] The method of operation described in Example 9, a mixture of the catalyst of Example 7. 得到聚合物I. 001g，换算活性为0. 200X 106gPE/mol · Cat · h。 To obtain a polymer I. 001g, conversion activity was 0. 200X 106gPE / mol · Cat · h. 135°C测13C NMR，I-辛烯插入率为4. 08% mol。 135 ° C measured 13C NMR, I- octene insertion rate of 4. 08% mol. 埃克森美孚化学专利公司Bridge metallocenes for olefine copolymerization中国石油天然气股份有限公司Synthesis of loaded metallocene catalyst1JP特开平8-96.08.06International Classification, C06PublicationC10Request of examination as to substanceC14GrantedRotate}