CN112934266A - 乙烯齐聚催化剂的制备方法及其齐聚 - Google Patents
乙烯齐聚催化剂的制备方法及其齐聚 Download PDFInfo
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- CN112934266A CN112934266A CN202011426960.6A CN202011426960A CN112934266A CN 112934266 A CN112934266 A CN 112934266A CN 202011426960 A CN202011426960 A CN 202011426960A CN 112934266 A CN112934266 A CN 112934266A
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- zirconium
- catalyst composition
- oligomerization
- catalyst
- ethylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 55
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- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001408 amides Chemical class 0.000 claims abstract description 22
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- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
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- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 claims description 3
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
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- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 claims description 2
- VDJJKYYENYIHFF-UHFFFAOYSA-J oxolane;tetrachlorozirconium Chemical group C1CCOC1.C1CCOC1.Cl[Zr](Cl)(Cl)Cl VDJJKYYENYIHFF-UHFFFAOYSA-J 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
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- 238000005649 metathesis reaction Methods 0.000 description 3
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- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical group CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 2
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- 150000001241 acetals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/22—Organic complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明描述了用作用于乙烯齐聚的催化剂体系的催化剂组合物,所述催化剂组合物提供高活性并生产具有宽的重量百分比分布即C4至C16的线性齐聚物产物。催化剂组合物包含锆酰胺化合物、有机铝化合物和添加剂。本发明还提供了锆酰胺化合物的制备方法,所述方法包括在有机溶剂的存在下使具有式ZrXm.nTHF的锆组分与式RCONR'R”的经取代的酰胺反应,其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,其中R、R'和R”为饱和或不饱和的脂族C1‑C10烃或芳族C6‑C14烃。
Description
技术领域
本发明涉及用作用于乙烯齐聚的催化剂体系的催化剂组合物,所述催化剂组合物提供高活性并生产具有宽的重量百分比分布即C4至C16的线性齐聚物产物。催化剂组合物包含锆酰胺化合物、有机铝化合物和添加剂。本发明还提供了锆酰胺化合物的制备方法,所述方法包括在有机溶剂的存在下使具有式ZrXm.nTHF的锆组分与式RCONR'R”的经取代的酰胺反应,其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
背景技术
线性α-烯烃(Linear alpha-olefin,LAO)是在伯位或α位处具有末端双键的烯烃或烯。双键的位置决定化学特性,并且可以经历烯烃的所有反应,包括加成、易位(metathesis)、聚合等。
极多用途的线性α-烯烃被用作用于清洁剂、合成润滑剂、增塑剂、表面活性剂和聚烯烃的前体。线性α-烯烃在聚乙烯的生产中被用作共聚单体。
线性α-烯烃制备主要基于乙烯的齐聚。乙烯齐聚过程产生具有末端双键的链长为4、6、8等的偶数碳编号的烯烃的混合物。非常期望具有末端双键,但无法排除内部烯烃形成。此外,存在一些量的聚合物。乙烯齐聚中的关键因素是得到期望的选择性、α-烯烃的纯度和产物分布,因此催化剂体系和工艺条件起重要的作用。用于生产线性α-烯烃的各种类型的催化剂体系在本领域中是公知的。
Exxon的US 4,361,714描述了包含卤化锆以及二烷基锌和有机铝化合物的催化剂体系。齐聚在烃溶剂的介质中在约50℃至约200℃的温度下且在3.5MPa至10.5MPa的乙烯压力下进行。然而,该催化剂的主要缺点是在烃溶剂中的溶解性差,并且大量产生作为副产物的蜡和高分子量聚乙烯,这导致严重的反应器堵塞。
Idemitsu的US 4,783,573描述了在基于锆配合物的催化剂体系的存在下合成具有长链长的线性α-烯烃,所述催化剂体系在干燥苯溶剂中使用无水四氯化锆以及铝倍半氯化物和三乙基铝。使用包含杂原子的有机化合物(例如烷基二硫化物、硫醚、噻吩和伯胺)作为慢化剂(moderator),以及在120℃下且在3.5MPa的压力下进行齐聚。该方法的主要缺点是四氯化锆在烃溶剂中的溶解性差、反应温度高以及其对轻质α-烯烃的选择性相对低。
Exxon的US 4,855,525公开了二元催化剂体系,其包含一般式(ZrCl4.CH3COOR)2的烷基烷酸锆和式RnAlX3-n的有机铝化合物。该催化剂的主要缺点是产生不期望量的高分子量聚乙烯。
Idemitsu的US 5,260,500描述了使用醇作为第三组分的基于锆的催化剂体系。在该方法中,防止催化剂组分污染到产物中以生产高纯度α-烯烃。该体系的主要缺点是聚合物的产生和C20+馏分的高产率。
US 5,496,783公开了通过将锆化合物与选自缩酮和缩醛的有机化合物和烃基-铝卤化物混合而获得的催化剂体系。对于乙烯齐聚评估该催化剂,并显示出对分别具有4、6、8和10个碳原子的轻质α-烯烃的良好选择性。产物分布特别朝向1-丁烯的产生,其中最佳实施例中的选择性为43重量%。该催化剂的另一个缺点是低活性和形成聚合物痕量,其最终积聚并导致反应器堵塞并阻碍长时间生产运行。
SABIC的US 8,653,316和9,050,587公开了包含一般式ZrCl4-m(R1COO)m的羧酸锆和式R2nAlX3-n的有机铝化合物的催化剂。对于乙烯齐聚评估添加电子供体以得到对催化剂体系的选择性和低分子量线性α-烯烃的纯度的协同作用的该发明催化剂体系。然而,催化剂体系的主要缺点是C20+馏分的高产率。
发明目的
本发明的主要目的是提供用作用于乙烯齐聚的催化剂体系的催化剂组合物,其可以生产具有高纯度的线性α-烯烃。
本发明的另一个目的是提供用于制备齐聚催化剂体系的方法,所述齐聚催化剂体系可以生产具有高纯度的线性α-烯烃。
此外,本发明的目的是生产具有高纯度的线性α-烯烃。
此外,本发明的目的是生产宽重量百分比分布的线性α-烯烃。
此外,本发明的目的是使乙烯齐聚而没有形成聚合物。
发明内容
用于以高纯度获得α-烯烃的乙烯齐聚主要通过有效的催化剂体系来实现。当助催化剂和反应条件支持齐聚时,催化剂的性质主要决定在齐聚期间可实现什么。因此,非常期望合适的催化剂。
因此,本发明提供了用作用于乙烯齐聚的催化剂体系的催化剂组合物,所述催化剂组合物包含具有一般式ZrXm.n(RCONR'R”)的锆酰胺化合物、有机铝化合物和添加剂,其中X为卤素原子;m为值等于或小于4的整数;n为等于或小于2的数;R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
在本发明的特征之一中,锆酰胺化合物为四氯双(N,N-二异丁基乙酰胺)锆(ZrCl4.2{CH3CON[CH2CH(CH3)2]2})。
在本发明的特征之一中,有机铝化合物选自烷基铝、三烯基铝、二烷基铝卤化物、烷基铝倍半卤化物、二烷基铝氢化物、部分氢化烷基铝、铝氧烷、二烷基铝醇盐及其混合物,其中:
(i)烷基铝为三烷基铝,并且选自三乙基铝、三异丙基铝、三异丁基铝、三正丁基铝、三正己基铝和三正辛基铝;
(ii)三烯基铝为三异戊二烯基铝(triisoprenyl aluminum);
(iii)二烷基铝卤化物选自二乙基铝氯化物、二丁基铝氯化物、二异丁基铝氯化物和二乙基铝溴化物;
(iv)烷基铝倍半卤化物选自乙基铝倍半氯化物、丁基铝倍半氯化物和乙基铝倍半溴化物;
(v)二烷基铝氢化物选自二乙基铝氢化物和二丁基铝氢化物;
(vi)部分氢化烷基铝选自乙基铝二氢化物和丙基铝二氢化物;
(vii)铝氧烷选自甲基铝氧烷、异丁基铝氧烷、四乙基铝氧烷和四异丁基铝氧烷;以及
(viii)二烷基铝醇盐为二乙基铝乙醇盐。
在本发明的另一个特征中,铝与锆的摩尔比为5:1至100:1。
在本发明的又一个特征中,添加剂选自氢、酯、醚、胺、酸酐和硫化合物。在优选特征之一中,添加剂选自乙酸乙酯、乙酰乙酸乙酯、苯甲酸乙酯、苯甲醚、四氢呋喃、1,2-二噁烷、噻吩及其混合物。
在本发明的又一个特征中,锆化合物与添加剂的摩尔比为1:0.1至1:10。
本发明还提供了用作用于乙烯齐聚的催化剂体系的催化剂组合物的制备方法,所述方法包括将锆酰胺化合物与有机铝化合物和添加剂一起添加,以及锆酰胺化合物通过在有机溶剂的存在下使锆组分与经取代的酰胺反应来制备,
其中:
锆酰胺化合物具有式:
ZrXm.n(RCONR'R”)
其中X为卤素原子;m为值等于或小于4的整数;n为等于或小于2的数;R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃,
锆组分具有式:
ZrXm.nTHF
其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,以及
经取代的酰胺具有式:
RCONR'R”
其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
本发明还提供了锆酰胺化合物的制备方法,所述方法包括在有机溶剂的存在下使具有式ZrXm.nTHF的锆组分与式RCONR'R”的经取代的酰胺反应,其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
在特征之一中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中锆组分为四氯双(四氢呋喃)锆ZrCl4.2THF。
在特征之一中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中锆酰胺化合物具有式ZrXm.2RCONR'R”,其中X可以为氯或溴;m为值等于或小于4的整数。
在特征之一中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中经取代的酰胺通过包括使酰卤与溶剂化剂和经取代的胺接触以获得经取代的酰胺的过程来制备。
在又一个特征中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中酰卤由RCOX表示,其中R选自H、可以与环状环连接的C1-C20线性或支化烷基、C6-C14芳基、C3-C15环烷基、C1-C20烷氧基,可以包含或可以不包含杂原子,以及X选自卤素。在优选特征之一中,酰卤为乙酰氯。
在又一个特征中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,经取代的胺由R'R”NH表示,其中R'和R”为可以与环状环连接的C1-C20线性或支化烷基、C6-C14芳基、C3-C15环烷基,可以包含或可以不包含杂原子,以及R'和R”可以相同或不同。在优选特征之一中,经取代的胺为N,N-二异丁基胺。
在特征之一中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中经取代的酰胺为N,N-二异丁基乙酰胺。
在又一个特征中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中锆组分与经取代的酰胺的摩尔比为0.1至5。
在又一个特征中,本发明涉及催化剂组合物的制备方法或锆酰胺的制备方法,其中反应在20℃至170℃范围内的温度下进行。
在本发明的特征之一中,有机溶剂选自二乙醚、二氯甲烷、四氢呋喃、氯苯、甲苯、邻氯甲苯、二甲苯、氯仿和环己烷。
本发明还提供了用于乙烯的齐聚而没有形成聚合物的方法,所述方法包括在乙烯齐聚条件下在惰性有机溶剂中使乙烯与催化剂组合物接触以获得在4至30个碳原子范围内的齐聚物的分子量范围内具有90摩尔%或更大的高线性度的线性α-烯烃。
在本发明的特征之一中,惰性有机溶剂选自未经取代或经卤素取代的芳族烃溶剂;脂族烷烃;脂环族烃化合物;卤代烷烃及其混合物,其中:
(i)芳族烃溶剂选自甲苯、苯、二甲苯、氯苯、二氯苯和氯甲苯;
(ii)脂族烷烃选自戊烷、己烷、庚烷、辛烷、壬烷和癸烷;
(iii)脂环族烃化合物选自环己烷和十氢化萘;以及
(iv)卤代烷烃选自二氯乙烷和二氯丁烷。
具体实施方式
本发明描述了用作用于乙烯齐聚的催化剂体系的催化剂组合物,所述催化剂组合物包含具有一般式ZrXm.n(RCONR'R”)的锆酰胺化合物、有机铝化合物和添加剂,其中X为卤素原子;m为值等于或小于4的整数;n为等于或小于2的数;R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
锆酰胺化合物与有机铝化合物和添加剂一起用作用于乙烯齐聚的催化剂体系,从而提供高活性并生产具有宽的重量百分比分布即C4至C16的线性齐聚物产物。
在本发明的一个特征中,锆酰胺化合物通过在有机溶剂的存在下使具有式ZrXm.nTHF的锆组分与式RCONR'R”的经取代的酰胺反应来制备,其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。在一个实施方案中,锆组分具有式ZrXm.nTHF,其中X可以为氯或溴;m为值等于或小于4的整数以及n为等于或小于2的数。最优选的锆组分为四氯双(四氢呋喃)锆ZrCl4.2THF。在一个实施方案中,经取代的酰胺具有式RCONR'R”,其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
因此,本发明还提供了用于制备经取代的酰胺的方法,所述方法包括使由RCOX表示的酰卤与溶剂化剂和经取代的胺接触以获得经取代的酰胺。在一个实施方案中,溶剂化剂可以为芳族或脂族的且本质上为极性或非极性的,实例不限于二乙醚苯、癸烷、煤油、乙苯、氯苯、二氯苯、甲苯、邻氯甲苯、二甲苯、二氯甲烷、氯仿、环己烷等。在一个实施方案中,酰卤由RCOX表示,其中R为H、可以与环状环连接的C1-C20线性或支化烷基、C6-C14芳基、C3-C15环烷基、C1-C20烷氧基,可以包含或可以不包含杂原子,以及X选自卤素。也可以使用酰卤的混合物。在另一个实施方案中,经取代的胺由R'R”NH表示,其中R'和R”为可以与环状环连接的C1-C20线性或支化烷基、C6-C14芳基、C3-C15环烷基,可以包含或可以不包含杂原子。也可以使用经取代的胺的混合物。R'和R”可以相同或不同。在本发明的一个特征中,将酰卤添加到溶剂化剂中,然后逐滴添加经取代的胺。在该添加期间,保持温度使得不允许放热将温度升高2℃。按照安全性方面,该步骤是重要的,因为向胺中添加酰卤是相当放热的置换反应。
描述了锆酰胺化合物的制备方法。在本发明的一个特征中,锆组分与经取代的酰胺的摩尔比为约0.1至5,优选0.5至2。在另一个特征中,反应温度为约20℃至约170℃,优选约50℃至约120℃。在另一个特征中,锆酰胺化合物可以直接使用或在纯化之后使用。在又一个特征中,锆酰胺化合物优选为四氯双(N,N-二异丁基乙酰胺)锆(ZrCl4.2{CH3CON[CH2CH(CH3)2]2})。
在本发明的一个特征中,锆酰胺化合物与有机铝化合物和添加剂一起用作用于乙烯齐聚的催化剂体系,从而提供高活性并生产具有宽的重量百分比分布即C4至C16的线性齐聚物产物。在又一个特征中,有机铝化合物包括但不限于烷基铝,例如三烷基铝,例如三乙基铝、三异丙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝;三烯基铝,例如三异戊二烯基铝;二烷基铝卤化物,例如二乙基铝氯化物、二丁基铝氯化物、二异丁基铝氯化物和二乙基铝溴化物;烷基铝倍半卤化物,例如乙基铝倍半氯化物、丁基铝倍半氯化物和乙基铝倍半溴化物;二烷基铝氢化物,例如二乙基铝氢化物和二丁基铝氢化物;部分氢化烷基铝,例如乙基铝二氢化物和丙基铝二氢化物;以及铝氧烷,例如甲基铝氧烷、异丁基铝氧烷、四乙基铝氧烷和四异丁基铝氧烷;二乙基铝乙醇盐;优选二乙基铝氯化物和乙基铝倍半氯化物。也可以使用有机铝化合物的混合物。
铝与锆的摩尔比为约5:1至约100:1,优选约10:1至约70:1。
锆化合物与添加剂的摩尔比为1:0.1至1:10。
在又一个特征中,用于乙烯的齐聚的催化剂生产在期望的分子量范围即4至30个碳原子的齐聚物内具有高线性度例如约90摩尔%或更大的线性α-烯烃。
在一个实施方案中,乙烯的齐聚优选在惰性有机溶剂中进行。惰性有机溶剂包括未经取代或经卤素取代的芳族烃溶剂,例如甲苯、苯、二甲苯、氯苯、二氯苯、氯甲苯等;脂族烷烃,例如戊烷、己烷、庚烷、辛烷、壬烷、癸烷等;脂环族烃化合物,例如环己烷、十氢化萘等;卤代烷烃,例如二氯乙烷、二氯丁烷等。可以使用溶剂的混合物。
本发明中使用的催化剂或催化剂组合物提供了许多优点,例如:锆酰胺化合物是稳定的化合物并且容易制备。当与助催化剂和添加剂一起使用时,该化合物容易溶解。催化剂提供高活性和具有宽的重量百分比分布即C4至C16的线性齐聚物产物形成的高生产率。用于制备锆酰胺化合物的方法使用ZrCl4.2THF作为起始化合物,ZrCl4.2THF容易获得、非常便宜且易于处理。由于2摩尔的酰胺足以置换ZrCl4.2THF中的2摩尔THF并合成需要的式ZrXm.2RCONR'R”的催化剂,因此不需要过量的酰胺。经取代的酰胺在溶剂化剂中使用酰氯和胺来合成,并且在没有进一步纯化或重结晶的情况下使用。
实施例
本文中包括以下实施例仅用于说明性目的。本领域技术人员将理解,可以在不改变本发明的实质的情况下在本发明中做出许多修改。
N,N-二异丁基乙酰胺的制备
在100ml圆底烧瓶中,将乙酰氯(1摩尔)添加在二乙醚中,然后逐滴添加N,N-二异丁基胺(1.5摩尔)。保持温度使得不允许放热将温度升高2℃。持续添加1小时,然后搅拌1.5小时。在完成反应并除去醚层之后,使用酸化水然后是盐水来中和未反应的胺。通过在真空下蒸发然后干燥将醚从层中除去。产率约85%。NMR:0.92ppm(12H),2.20(4H),2.38(2H),7.23-7.26(8H)。
四氯双(N,N-二异丁基乙酰胺)锆(ZrCl4.2{CH3CON[CH2CH(CH3)2]2}的制备
在100ml圆底烧瓶中,将ZrCl4.2THF(1摩尔)和N,N-二异丁基乙酰胺(2摩尔)添加在甲苯中,并在110℃下回流6小时。在冷却时,沉淀出白色固体,并通过经由在真空下蒸发除去甲苯将其分离。将白色固体在真空中进一步干燥。产率约90%。实测值(%):C,41.18;H,7.44;N,4.86;Cl,24.6;Zr,15.91;C20H42O2N2Cl4Zr。计算值(%):C,41.61;H,7.28;N,4.85;Cl,24.62;Zr,15.80。
使用四氯双(N,N-二异丁基乙酰胺)锆的乙烯的齐聚
在配备有氮气的装料烧瓶中,添加200ml干燥甲苯,然后添加四氯双(N,N-二异丁基乙酰胺)锆(0.25mmol)。将该深棕色混合物搅拌15分钟,观察到催化剂溶解。然后向溶液中添加纯的EASC(Al/Zr=17.5),然后添加作为添加剂的乙酸乙酯。此时,观察到催化剂完全溶解。在30℃下将该深棕色溶液装入预处理的反应器中。使齐聚在80℃和30巴乙烯压力下进行60分钟。在收回澄清液体之后,将其用10ml甲醇处理以使催化剂体系淬灭。没有蜡形成以及聚合物形成,并且如果检测到聚合物,其仅是痕量。
表1中提供了使用不同条件的乙烯齐聚和条件的细节。使用的添加剂为乙酸乙酯(EA)。助催化剂为亚乙基铝倍半氯化物(ethylene aluminum sesquichloride,EASC)。
缩写:
1.EASC=亚乙基铝倍半氯化物
2.DEAC=二乙基铝氯化物
3.EA=乙酸乙酯
4.ZrCl4.2THF=四氯双(四氢呋喃)锆
5.ZrCl4=四氯化锆
6.Zr((CH3)2CHCH2COO)4=四异丁酸锆
7.TEAL=三乙基铝氯化物
8.TIPA=三异戊二烯基铝
9.DBAH=二丁基铝氢化物
10.DEAE=二乙基铝乙醇盐
11.MAO=甲基铝氧烷
表1
上表描述了当经历乙烯的齐聚时催化剂体系的不同特性。
如从表1中看出,根据本发明的实施例的齐聚实验产生具有含有大量C4至C10的改善的α-烯烃分布(重量百分比)的新催化剂的类似的活性。另外地,与比较例的结果相比,LAO馏分的纯度显著改善。
表2
使用不同类型的烷基铝用于乙烯的齐聚的工作实施例
表3
使用不同摩尔比的烷基铝用于乙烯的齐聚的工作实施例
表4
使用不同添加剂用于使用EASC作为助催化剂且添加剂为0.125mmol的乙烯的齐聚的工作实施例
表5
使用不同摩尔比的EA用于使用EASC作为助催化剂且Al/Zr摩尔比为17.5的乙烯的齐聚的工作实施例
Claims (16)
1.一种用作用于乙烯齐聚的催化剂体系的催化剂组合物,所述催化剂组合物包含具有一般式ZrXm.n(RCONR'R”)的锆酰胺化合物、有机铝化合物和添加剂,其中X为卤素原子;m为值等于或小于4的整数;n为等于或小于2的数;R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
2.根据权利要求1所述的催化剂组合物,其中所述锆酰胺化合物为四氯双(N,N-二异丁基乙酰胺)锆(ZrCl4.2{CH3CON[CH2CH(CH3)2]2})。
3.根据前述权利要求中任一项所述的催化剂组合物,其中所述有机铝化合物选自烷基铝、三烯基铝、二烷基铝卤化物、烷基铝倍半卤化物、二烷基铝氢化物、部分氢化烷基铝、铝氧烷、二烷基铝醇盐及其混合物,其中:
(i)所述烷基铝为三烷基铝,并且选自三乙基铝、三异丙基铝、三异丁基铝、三正丁基铝、三正己基铝和三正辛基铝;
(ii)所述三烯基铝为三异戊二烯基铝;
(iii)所述二烷基铝卤化物选自二乙基铝氯化物、二丁基铝氯化物、二异丁基铝氯化物和二乙基铝溴化物;
(iv)所述烷基铝倍半卤化物选自乙基铝倍半氯化物、丁基铝倍半氯化物和乙基铝倍半溴化物;
(v)所述二烷基铝氢化物选自二乙基铝氢化物和二丁基铝氢化物;
(vi)所述部分氢化烷基铝选自乙基铝二氢化物和丙基铝二氢化物;
(vii)所述铝氧烷选自甲基铝氧烷、异丁基铝氧烷、四乙基铝氧烷和四异丁基铝氧烷;以及
(viii)所述二烷基铝醇盐为二乙基铝乙醇盐。
4.根据前述权利要求中任一项所述的催化剂组合物,其中铝与锆的摩尔比为5:1至100:1。
5.根据前述权利要求中任一项所述的催化剂组合物,其中所述添加剂选自酯、醚、胺、酸酐和硫化合物。
6.根据前述权利要求中任一项所述的催化剂组合物,其中所述添加剂选自乙酸乙酯、乙酰乙酸乙酯、苯甲酸乙酯、苯甲醚、四氢呋喃、1,2-二噁烷、噻吩及其混合物。
7.根据前述权利要求中任一项所述的催化剂组合物,其中锆化合物与所述添加剂的摩尔比为1:0.1至1:10。
8.一种根据权利要求1所述的用作用于乙烯齐聚的催化剂体系的催化剂组合物的制备方法,所述方法包括将锆酰胺化合物与有机铝化合物和添加剂一起添加,以及所述锆酰胺化合物通过在有机溶剂的存在下使锆组分与经取代的酰胺反应来制备,
其中:
所述锆酰胺化合物具有式:
ZrXm.n(RCONR'R”)
其中X为卤素原子;m为值等于或小于4的整数;n为等于或小于2的数;R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃,
所述锆组分具有式:
ZrXm.nTHF
其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,以及
所述经取代的酰胺具有式:
RCONR'R”
其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
9.一种根据权利要求1所述的用作用于乙烯齐聚的催化剂体系的催化剂组合物的锆酰胺化合物的制备方法,所述方法包括在有机溶剂的存在下使具有式ZrXm.nTHF的锆组分与具有式RCONR'R”的经取代的酰胺反应,其中X为卤素原子;m为值等于或小于4的整数以及n为等于或小于2的数,其中R、R'和R”为饱和或不饱和的脂族C1-C10烃或芳族C6-C14烃。
10.根据权利要求9所述的锆酰胺化合物的制备方法,其中,所述锆组分为四氯双(四氢呋喃)锆ZrCl4.2THF。
11.根据权利要求9所述的锆酰胺化合物的制备方法,其中,所述经取代的酰胺为N,N-二异丁基乙酰胺。
12.根据前述权利要求9至11中任一项所述的锆酰胺化合物的制备方法,其中,锆组分与经取代的酰胺的摩尔比为0.1至5。
13.根据前述权利要求9至12中任一项所述的锆酰胺化合物的制备方法,其中,反应在20℃至170℃范围内的温度下进行。
14.根据前述权利要求9至13中任一项所述的锆酰胺化合物的制备方法,其中,所述有机溶剂选自二乙醚、二氯甲烷、四氢呋喃、氯苯、甲苯、邻氯甲苯、二甲苯、氯仿和环己烷。
15.一种用于乙烯的齐聚而没有形成聚合物的方法,包括在乙烯齐聚条件下在惰性有机溶剂中使乙烯与根据权利要求1至7中任一项所述的催化剂组合物接触以获得在4至30个碳原子范围内的齐聚物的分子量范围内具有90摩尔%或更大的高线性度的线性α-烯烃。
16.根据权利要求15所述的方法,其中所述惰性有机溶剂选自未经取代或经卤素取代的芳族烃溶剂;脂族烷烃;脂环族烃化合物;卤代烷烃及其混合物,其中:
(i)所述芳族烃溶剂选自甲苯、苯、二甲苯、氯苯、二氯苯和氯甲苯;
(ii)所述脂族烷烃选自戊烷、己烷、庚烷、辛烷、壬烷和癸烷;
(iii)所述脂环族烃化合物选自环己烷和十氢化萘;以及
(iv)所述卤代烷烃选自二氯乙烷和二氯丁烷。
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KR102392332B1 (ko) | 2021-06-08 | 2022-04-28 | 에스케이씨솔믹스 주식회사 | 블랭크 마스크 및 이를 이용한 포토마스크 |
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RU2759004C1 (ru) | 2021-11-08 |
IN201921051272A (zh) | 2022-01-06 |
US11344871B2 (en) | 2022-05-31 |
EP3834932A1 (en) | 2021-06-16 |
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JP7212027B2 (ja) | 2023-01-24 |
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