CN109348733A - 用于制造有机电荷传输膜的方法 - Google Patents
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- CN109348733A CN109348733A CN201680086675.XA CN201680086675A CN109348733A CN 109348733 A CN109348733 A CN 109348733A CN 201680086675 A CN201680086675 A CN 201680086675A CN 109348733 A CN109348733 A CN 109348733A
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
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- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- 241000790917 Dioxys <bee> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- GWJBEJFEFFWFBI-UHFFFAOYSA-N acenaphthylen-1-ylmethanol Chemical group C1=CC(C(CO)=C2)=C3C2=CC=CC3=C1 GWJBEJFEFFWFBI-UHFFFAOYSA-N 0.000 description 1
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- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WWECJGLXBSQKRF-UHFFFAOYSA-N n,n-dimethylformamide;methanol Chemical compound OC.CN(C)C=O WWECJGLXBSQKRF-UHFFFAOYSA-N 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/26—Nitrogen
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
- H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/135—Cross-linked structures
-
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Abstract
一种聚合物,其具有至少4,000的Mn且包含式NAr1Ar2Ar3的化合物的聚合单元,其中Ar1、Ar2和Ar3独立地为C6‑C50芳族取代基;Ar1、Ar2和Ar3共同含有至少2个氮原子和至少9个芳族环;并且Ar1、Ar2和Ar3中的至少一个含有与芳族环连接的乙烯基。
Description
技术领域
本发明涉及一种用于制备有机电荷传输膜的方法。
背景技术
需要一种用于制造用于平板有机发光二极管(OLED)显示器的有机电荷传输膜的有效方法。溶液加工是通过将OLED溶液沉积到衬底上以形成薄膜然后进行交联和聚合来制造大型平板OLED显示器的主要技术之一。目前,可溶液加工的聚合材料是可交联的有机电荷传输化合物。例如,US7037994公开了一种抗反射成膜制剂,其包含至少一种含有乙酰氧基甲基苊烯或羟基甲基苊烯重复单元的聚合物和在溶剂中的热或光酸产生剂(TAG,PAG)。然而,此参考文献并没有公开本文所描述的制剂。
发明内容
本发明提供了一种聚合物,其具有至少4,000的Mn且包含式NAr1Ar2Ar3的化合物的聚合单元,其中Ar1、Ar2和Ar3独立地是C6-C50芳族取代基;Ar1、Ar2和Ar3共同含有至少2个氮原子和至少9个芳族环;并且Ar1、Ar2和Ar3中的至少一个含有与芳族环连接的乙烯基。
具体实施方式
除非另有规定,否则百分比是重量百分比(重量%)并且温度是以℃为单位。除非另有规定,否则操作在室温(20-25℃)下进行。沸点是在大气压(约101kPa)下测量。分子量是以道尔顿为单位并且聚合物的分子量是通过尺寸排阻色谱法使用聚苯乙烯标准物来测定。
如本文所用,术语“芳族取代基”是指具有至少一个芳族环,优选至少两个芳族环的取代基。含有两个或更多个稠环的环状部分被认为是单芳族环,条件是环状部分中的所有环原子都是芳族系统的一部分。例如,萘基、咔唑基和吲哚基被认为是单芳族环,但芴基被认为含有两个芳族环,因为芴的9位处的碳原子不是芳族系统的一部分。
优选地,式NAr1Ar2Ar3的化合物不含芳基甲氧基键。芳基甲氧基键是具有两个与氧原子连接的苄基碳原子的醚键。苄基碳原子是如下碳原子,所述碳原子不是芳族环的一部分并且其与具有5至30个(优选5至20个)碳原子的芳族环,优选苯环的环碳连接。优选地,化合物不含如下键,所述键仅具有一个与氧原子连接的苄基碳原子。优选地,芳基甲氧基键是醚、酯或醇。优选地,式NAr1Ar2Ar3的化合物不具有醚键,其中任一碳是苄基碳,优选根本没有醚键。
优选地,式NAr1Ar2Ar3的化合物含有至少10个芳族环;优选至少11;优选不超过20、优选不超过17、优选不超过14个芳族环。优选地,Ar2和Ar3各自独立地含有至少10个碳原子,优选至少15、优选至少20;优选不超过45、优选不超过42、优选不超过40个碳原子。优选地,Ar1含有不超过35个碳原子,优选不超过25、优选不超过15个碳原子。脂族碳原子,例如C1-C6烃基取代基或非芳族环碳原子(例如,芴的9-碳上的甲基基团),包括在Ar取代基中的碳原子的总数中。Ar基团可含有杂原子,优选N、O或S;优选Ar基团不含氮以外的杂原子。优选地,在式NAr1Ar2Ar3的化合物中仅存在一个乙烯基。优选地,化合物在稠环系统上不具有乙烯基,所述系统例如芴基、咔唑基或吲哚基。优选地,Ar基团包含联苯基、芴基、亚苯基、咔唑基和吲哚基取代基中的一种或多种;各自任选地含有烷基取代基。在本发明的一个优选实施例中,Ar1、Ar2和Ar3中的两个通过至少一个共价键连接。这种情况的一个实例是如下所示的优选实施例的结构
其中Ar4和Ar7独立地是C5-C20芳族取代基,其与上述结构中的咔唑单元连接并且还与氮原子连接;Ar5、Ar6、Ar8和Ar9独立地为C5-C25芳族取代基;并且Ar1、Ar4、Ar7、Ar5、Ar6、Ar8和Ar9中的至少一个含有与芳族环连接的乙烯基。优选地,Ar4和Ar7独立地是C5-C15芳族取代基,优选C5-C10芳族取代基;优选Ar4和Ar7相同。优选地,Ar5、Ar6、Ar8和Ar9独立地是C6-C20芳族取代基,优选C9-C20芳族取代基。优选地,Ar5、Ar6、Ar8和Ar9选自由以下组成的群组:联苯基、芴基、咔唑基和吲哚基,各自任选地含有烷基取代基。优选地,仅Ar1含有乙烯基。优选地,Ar1是C6-C25芳族取代基,优选C6-C20芳族取代基。
当芳基取代基中的一个中的氮原子是三芳基胺氮原子时,Ar1、Ar2和Ar3基团可以用不同的方式来定义,其取决于哪个氮原子被认为是式NAr1Ar2Ar3中的氮原子。在这种情况下,氮原子和Ar基团应解释为满足权利要求书的限制。
优选地,Ar1、Ar2和Ar3共同含有不超过5个氮原子,优选不超过4、优选不超过3。
“有机电荷传输化合物”是能够接收电荷并通过电荷传输层传输电荷的材料。电荷传输化合物的实例包括“电子传输化合物”(其是能够接收电子并通过电荷传输层传输电子的电荷传输化合物)和“空穴传输化合物”(其是能够通过电荷传输层传输正电荷的电荷传输化合物)。优选有机电荷传输化合物。优选地,有机电荷传输化合物具有至少50重量%芳族环(以所有芳族环的分子量除以总分子量所测量;与芳族环稠合的非芳族环包括在芳族环的分子量中),优选至少60%、优选至少70%、优选至少80%、优选至少90%。优选地,聚合物包含有机电荷传输化合物
在本发明的优选实施例中,所使用的一些或全部材料(包括溶剂和聚合物)富含超过氚天然同位素丰度的氚。本文中所出现的所有化合物名称和结构意欲包括所有部分或完全氚化的类似物。
优选地,聚合物具有至少6,000的Mn,优选至少8,000、优选至少10,000、优选至少20,000;优选不大于10,000,000、优选不大于1,000,000、优选不大于500,000、优选不大于300,000、优选不大于200,000。优选地,聚合物包含至少60%(优选至少80%、优选至少95%)含有至少五个芳族环,优选至少六个芳族环的聚合单体;其他不具有这种特征的单体也可能存在。
优选地,如在固体基础上通过液相色谱法/质谱法(LC/MS)所测量,聚合物的纯度为至少99%、优选至少99.5%、优选至少99.7%。优选地,本发明的制剂含有不超过10ppm的金属,优选不超过5ppm。
可用于本发明的优选聚合物包括,例如以下结构。
不必一定是电荷传输化合物的交联剂也可以包括在制剂中。优选地,这些交联剂具有至少60重量%芳族环(如先前所定义),优选至少70重量%、优选至少75重量%。优选地,交联剂具有3至5个可聚合基团,优选3或4。优选地,可聚合基团是与芳族环连接的乙烯基。下面显示了优选的交联剂
优选地,如通过气相色谱法-质谱法(GC/MS)所测量,用于制剂中的溶剂具有至少99.8%的纯度,优选至少99.9%。优选地,相对于聚合物使用CHEMCOMP v2.8.50223.1所计算,溶剂具有小于1.2,优选小于1.0的RED值(根据汉森溶解度参数所计算的相对能量差)。优选的溶剂包括芳族烃和芳族-脂族醚,优选具有6至20个碳原子的那些。苯甲醚、二甲苯和甲苯是特别优选的溶剂。
优选地,用于制备膜的制剂的固体百分比,即相对于制剂总重量的聚合物的百分比为0.5至20重量%;优选至少0.8重量%、优选至少1重量%、优选至少1.5重量%;优选不超过15重量%、优选不超过10重量%、优选不超过7重量%、优选不超过4重量%。优选地,溶剂的量为至少80至99.5重量%;优选地至少85重量%、优选地至少90重量%、优选地至少93重量%、优选地至少94重量%;优选地不超过99.2重量%、优选地不超过99重量%、优选地不超过98.5重量%。
优选地,式NAr1Ar2Ar3的化合物通过已知方法使用自由基引发剂来聚合,例如偶氮化合物、过氧化物或具有结构R1R2R3C-CR4R5R6的烃基引发剂,其中R1至R6独立地为氢或C1-C20烃基(优选C1-C12),其中不同的R基团可以连接以形成环结构,条件是R1、R2和R3的至少一个为芳基,并且R4、R5和R6中的至少一个为芳基。当使用烃基引发剂时,优选聚合温度为20-100℃。
本发明进一步涉及包含本发明的聚合物的有机电荷传输膜和一种用于生产其的方法,所述方法是通过将制剂涂布在表面上,优选是其他有机电荷传输膜,以及铟-锡-氧化(ITO)玻璃或硅晶片。通过以下来形成膜:将制剂涂布在表面上,在50至150℃(优选80至120℃)的温度下预烘焙,优选少于5分钟,然后在120至280℃的温度下进行热退火;优选至少140℃、优选至少160℃、优选至少170℃;优选不大于230℃、优选不大于215℃。
优选地,根据本发明生产的聚合物膜的厚度为1nm至100微米,优选至少10nm、优选至少30nm,优选不大于10微米、优选不大于1微米、优选不大于300nm。旋涂膜厚度主要由溶液中的固体含量和旋转速率来测定。例如,在2000rpm的旋转速率下,2重量%、5重量%、8重量%和10重量%的聚合物制剂溶液分别使得膜厚为30nm、90nm、160nm和220nm。烘烤并退火后,湿膜收缩5%或小于5%。
实例
4-(3-(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛的合成:向圆底烧瓶中装入N-(4-(9H-咔唑-3-基)苯基)-N-([1,1′-联苯基]-4-基)-9,9-二甲基-9H-芴-2-胺(2.00g,3.32mmol,1.0当量)、4-溴苯甲醛(0.737g,3.98mmol,1.2当量)、CuI(0.126g,0.664mmol,0.2当量)、碳酸钾(1.376g,9.954mmol,3.0当量)和18-冠-6(86mg,10mol%)。将烧瓶用氮气冲洗并连接到回流冷凝器。添加10.0mL干燥、脱气的1,2-二氯苯,并将混合物回流48小时。用饱和水性NH4Cl淬灭冷却的溶液,并用二氯甲烷萃取。将合并的有机部分干燥,并通过蒸馏除去溶剂。通过硅胶色谱法(已烷/氯仿梯度)纯化粗残余物,得到作为亮黄色固体(2.04g,87%)的产物。1H NMR(500MHz,CDCl3)δ10.13(s,1H),8.37(d,J=2.0Hz,1H),8.20(dd,J=7.7,1.0Hz,1H),8.16(d,J=8.2Hz,2H),7.83(d,J=8.1Hz,2H),7.73-7.59(m,7H),7.59-7.50(m,4H),7.50-7.39(m,4H),7.39-7.24(m,10H),7.19-7.12(m,1H),1.47(s,6H)。13C NMR(126MHz,CDCl3)δ190.95,155.17,153.57,147.21,146.98,146.69,143.38,140.60,140.48,139.28,138.93,135.90,135.18,134.64,134.46,133.88,131.43,128.76,127.97,127.81,126.99,126.84,126.73,126.65,126.54,126.47,125.44,124.56,124.44,124.12,123.98,123.63,122.49,120.96,120.70,120.57,119.47,118.92,118.48,110.05,109.92,46.90,27.13。
(4-(3-(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑9-基)苯基)甲醇的合成。在氮气层下,向圆底烧瓶中装入4-(3-(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛(4.36g,6.17mmol,1.00当量)。将材料溶解于40mL 1∶1 THF/EtOH中。分批添加硼氢化钠(0.280g,7.41mmol,1.20当量),并且将材料搅拌3小时(通过TLC显示原材料的消耗)。用1M HCl小心地淬灭反应混合物,并用部分二氯甲烷萃取产物。用饱和水性碳酸氢钠洗涤合并的有机部分,用MgSO4干燥并浓缩成粗残余物。通过色谱法(己烷/二氯甲烷梯度)纯化材料,得到作为白色固体(3.79g,85%)的产物。1H NMR(500MHz,CDCl3)δ8.35(s,1H),8.19(dt,J=7.8,1.1Hz,1H),7.73-7.56(m,11H),7.57-7.48(m,2H),7.48-7.37(m,6H),7.36-7.23(m,9H),7.14(s,1H),4.84(s,2H),1.45(s,6H)。13C NMR(126MHz,CDCl3)δ155.13,153.56,147.24,147.02,146.44,141.27,140.60,140.11,140.07,138.94,136.99,136.33,135.06,134.35,132.96,128.73,128.44,127.96,127.76,127.09,126.96,126.79,126.62,126.48,126.10,125.15,124.52,123.90,123.54,123.49,122.46,120.66,120.36,120.06,119.43,118.82,118.33,109.95,109.85,64.86,46.87,27.11。
N-([1,1′-联苯基]-4-基)-9,9-二甲基-N-(4-(9-(4-(((4-乙烯基苄基)氧基)甲基)苯基)-9H-咔唑-3-基)苯基)-9H-芴-2-胺(比较单体)的合成:在氮气填充的手套箱中,向100mL圆底烧瓶中装入(4-(3-(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯基)甲醇(4.40g,6.21mmol,1.00当量)和35mL THF。分批添加氢化钠(0.224g,9.32mmol,1.50当量),并将混合物搅拌30分钟。连接回流冷凝器,将单元密封并从手套箱中除去。注入4-乙烯基苄基氯(1.05mL,7.45mmol,1.20当量),并将混合物回流直至消耗原材料(TLC)。冷却(冰浴)反应混合物并用异丙醇小心地淬灭。添加饱和水性NH4Cl,并用乙酸乙酯萃取产物。用盐水洗涤合并的有机部分、用MgSO4干燥、过滤、浓缩并通过二氧化硅色谱法(己烷/乙酸乙酯梯度)纯化,得到作为白色固体(3.49g,67%)的产物。1H NMR(400MHz,CDCl3)δ8.35(s,1H),8.18(dt,J=7.8,1.0Hz,1H),7.74-7.47(m,14H),7.47-7.35(m,11H),7.35-7.23(m,9H),7.14(s,1H),6.73(dd,J=17.6,10.9Hz,1H),5.76(dd,J=17.6,0.9Hz,1H),5.25(dd,J=10.9,0.9Hz,1H),4.65(s,4H),1.45(s,6H)。13C NMR(101MHz,CDCl3)δ155.13,153.56,147.25,147.03,146.43,141.28,140.61,140.13,138.94,137.64,137.63,137.16,137.00,136.48,136.37,135.06,134.35,132.94,129.21,128.73,128.05,127.96,127.76,126.96,126.94,126.79,126.62,126.48,126.33,126.09,125.14,124.54,123.89,123.54,123.48,122.46,120.66,120.34,120.04,119.44,118.82,118.31,113.92,110.01,109.90,72.33,71.61,46.87,27.11。
4-(3,6-双(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛的合成:将4-(3,6-二溴-9H-咔唑-9-基)苯甲醛(6.00g,17.74mmol)、N-([1,1′-联苯基]-4-基)-9,9-二甲基-N-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼杂环戊烷-2-基)苯基)-9H-芴-2-胺(15.70g,35.49mmol)、Pd(PPh3)3(0.96g)、7.72g K2CO3、100mLTHF和30mL H2O的混合物在氮气下在80℃下加热过夜。冷却到室温后,在真空下除去溶剂并且用二氯甲烷萃取残余物。然后通过硅胶柱色谱法用石油醚和二氯甲烷作为洗脱液获得产物,以得到所需产物(14.8g,产率92%)。1H NMR(CDCl3,ppm):10.14(s,1H),8.41(d,2H),8.18(d,2H),7.86(d,2H),7.71(dd,2H),7.56-7.68(m,14H),7.53(m,4H),7.42(m,4H),7.26-735(m,18H),7.13-7.17(d,2H),1.46(s 12H)。
(4-(3,6-双(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯基)甲醇:4-(3,6-双(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯甲醛(10.0g,8.75mmol)溶解于80mL THF和30mL乙醇中。在氮气气氛下经2小时添加NaBH4(1.32g,35.01mmol)。接着,添加水性氢氯酸溶液直至pH 5且保持搅拌混合物30min。在真空下除去溶剂并且用二氯甲烷萃取残余物。然后在真空下干燥产物并在无进一步纯化的情况下用于下一步中。
B单体的合成:将0.45g 60%NaH添加到100mL干燥的10.00g(4-(3,6-双(4-([1,1′-联苯基]-4-基(9,9)-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑-9-基)苯基)甲醇的DMF溶液中。在室温下搅拌1小时后,通过针筒添加2.00g 1-(氯甲基)-4-乙烯基苯。在N2下在60℃下将溶液搅拌,并通过TLC跟踪。在消耗原材料后,将溶液冷却并倒入冰水中。用水、乙醇和石油醚分别过滤和洗涤后,得到粗产物,并在50℃下在真空烘箱中干燥过夜,然后通过快速硅胶柱色谱法用二氯甲烷和石油醚(1∶3至1∶1)的洗脱液的梯度进化来纯化。将得自乙酸乙酯的粗产物通过再结晶和柱色谱法进一步纯化,其能够使纯度为99.8%。ESI-MS(m/z,Ion):1260.5811,(M+H)+.1H NMR(CDCl3,ppm):8.41(s,2H),7.58-7.72(m,18H),7.53(d,4H),7.38-7.50(m,12H),7.25-7.35(m,16H),7.14(d,2H),6.75(q,1H),5.78(d,1H),5.26(d,1H),4.68(s,4H),1.45(s,12H)。
A单体的合成:在N2气氛下,将PPh3CMeBr(1.45g,4.0mmol)装入装备有搅拌器的三颈圆底烧瓶中,向其中添加180mL无水THF。将悬浮液置于冰浴中。然后将t-BuOK(0.70g,6.2mmol)缓慢添加到溶液中,反应混合物变为亮黄色。使反应再反应3小时。之后,将4-(3,6-双(4-([1,1′-联苯基]-4-基(9,9-二甲基-9H-芴-2-基)氨基)苯基)-9H-咔唑将-9-基)苯甲醛(2.0g,1.75mmol)装入烧瓶中并在室温下搅拌过夜。用2N HCl淬灭混合物,并用二氯甲烷萃取,并将有机层用去离子水洗涤三次,并经无水Na2SO4干燥。浓缩滤液,并在硅胶柱上用作为洗脱液的二氯甲烷和石油醚(1∶3)纯化。将得自二氯甲烷和乙酸乙酯的粗产物进一步重结晶,纯度为99.8%。ESI-MS(m/z,Ion):1140.523,(M+H)+.。1H NMR(CDCl3,ppm):8.41(s,2H),7.56-7.72(m,18H),7.47-7.56(m,6H),7.37-7.46(m,6H),7.23-7.36(m,18H),6.85(q,1H),5.88(d,1H),5.38(d,1H),1.46(s,12H)。
用于HTL单体的自由基聚合的一般方案:
在手套箱中,将HTL单体(1.00当量)溶解于苯甲醚(电子级别,0.25M)中。将混合物加热至70℃,并注入AIBN溶液(在甲苯中0.20M,5mol%)。搅拌混合物直至完全消耗单体,至少24小时(可添加2.5mol%部分的AIBN溶液以完全转化)。用甲醇(10x体积的苯甲醚)沉淀聚合物并通过过滤分离。用另外部分的甲醇冲洗过滤的固体。将过滤的固体重新溶解于苯甲醚中,并将沉淀/过滤序列重复两次多。将分离的固体置于50℃下的真空烘箱中过夜以除去残余溶剂。
用于HTL聚合物的分子量数据:
凝胶渗透色谱法(GPC)研究进行如下。使2mg HTL聚合物溶解于1mL THF中。将溶液通过0.20μm聚四氟乙烯(PTFE)针筒过滤器过滤,并将50μl滤液注入GPC系统。使用以下分析条件:泵:WatersTM e2695分离模块,标称流动速率为1.0mL/min;洗脱液:飞世尔科技公司(Fisher Scientific)HPLC级别THF(未稳定);注入器:Waters e2695分离模块;管柱:来自聚合物实验室公司(Polymer Laboratories Inc)的两个5μm混合C管柱,保持在40℃下;检测器:昭和(Shodex)RI-201差异折射率(DRI)检测器;校准:来自聚合物实验室公司的17种聚苯乙烯标准材料,在3,742kg/mol至0.58kg/mol范围内拟合3阶多项式曲线。
单体 | M<sub>n</sub> | M<sub>w</sub> | M<sub>z</sub> | M<sub>z+1</sub> | M<sub>w</sub>/M<sub>n</sub> |
比较均聚物 | 17,845 | 38,566 | 65,567 | 95,082 | 2.161 |
A均聚物 | 15,704 | 61,072 | 124,671 | 227,977 | 3.89 |
B均聚物 | 21,482 | 67,058 | 132,385 | 226,405 | 3.12 |
HTL均聚物膜研究-溶剂正交性:
1)HTL均聚物溶液的制备:将HTL均聚物固体粉末直接溶解于苯甲醚中以制造2重量%的储备溶液。将溶液在N2下在80℃下搅拌5至10min以完全溶解。
2)制备热退火HTL均聚物膜:在使用之前,将Si晶片通过紫外-臭氧预处理2min。将数滴上述过滤HTL溶液沉积到预处理的Si晶片上。通过以500rpm旋涂5秒然后以2000rpm旋涂30秒来获得薄膜。然后将所得膜转移到N2吹扫箱中。在100℃下预烘烤“湿”膜1min以除去大部分残余苯甲醚。随后,将膜在160至235℃下热退火10至20min。
3)热退火HTL均聚物膜上的条带测试:热退火HTL膜的“初始”厚度使用M-2000D椭偏仪(J.A.Woollam Co.,Inc.)进行测量。然后,将数滴邻二甲苯或苯甲醚添加到膜上以形成胶泥。90秒后,以3500rpm分离邻二甲苯/苯甲醚溶剂30秒。使用椭偏仪立即测量膜的“条带”厚度。然后将膜转移到N2吹扫箱中,随后在100℃下通过后烘烤1min以除去膜中的任何溶胀溶剂。使用椭偏仪测量“最终”厚度。使用柯西(Cauchy)模型测定膜厚度,并对1cm×1cm区域中的9=3×3点进行平均。
“-条带”=“条带”-“初始”:由于溶剂汽提导致的初始膜损失
“-PSB”=“最终”-“条带”:溶胀溶剂的进一步膜损失
“-总计”=“-条带”+“-PSB”=“最终”-“初始”:由于溶剂汽提和溶胀导致的总膜损失
应用条带测试来研究HTL均聚物正交溶解度。对于完全耐溶剂的HTL膜,溶剂汽提后的总膜损失应<1nm,优选<0.5nm。
汇总表:B均聚物条带测试结果(邻二甲苯和苯甲醚作为汽提溶剂)
用于单体A的聚合物的耐溶剂性数据:
热退火:190℃/20min
第1次1.5min邻二甲苯汽提(顶部);第二次5min邻二甲苯汽提(底部)
热退火:205℃/10min
第1次1.5min邻二甲苯汽提(顶部);第二次5min邻二甲苯汽提(底部)
用于单体B的聚合物的耐溶剂性数据:
热退火:190℃/20min
第1次1.5min邻二甲苯汽提(顶部);第二次5min邻二甲苯汽提(底部)
热退火:205℃/10min
第1次1.5min邻二甲苯汽提(顶部);第二次5min邻二甲苯汽提(底部)
SP-37和SP-40膜均与1.5和5min的邻二甲苯汽提正交。
发光装置的制备
按顺序用溶剂乙醇、丙酮和异丙醇清洁氧化铟锡(ITO)玻璃衬底(2×2cm),且接着用UV臭氧清洁剂处理15min。在手套箱中将来自Plextronics公司的空穴注入层(HIL)材料PlexcoreTM OC AQ-1200从水溶液旋涂到ITO衬底上且在150[℃下退火20min。其后,对于比较蒸发HTL、N-([1,1′-联苯基]-4-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-9H-芴-2-胺,将衬底转移到热蒸发器中以便沉积HTL、发射材料层(EML)、电子转移层(ETL)和阴极;对于溶液法的本发明HTL,从苯甲醚溶液沉积HTL材料(可溶聚合物)且在150℃下退火10min以除去有机溶剂。此后,聚合物HTL的交联可在加热板上在手套箱中在205℃下进行10min。接着,按顺序沉积后续磷光绿色(Ph-Green)EML、ETL和阴极。最终这些装置在测试之前密封。
用于OLED装置的电流-电压-亮度(J-V-L)特征,即,驱动电压(V)、亮度效率(Cd/A)和1000尼特和50mA/cm2亮度下的国际照明委员会(international commission onillumination,CIE)数据以及15000尼特持续10小时的寿命用KeithlyTM 238高电流源测量单元和柯尼卡美能达公司(Konica Minolta Company)的CS-100A颜色和亮度仪进行且在表2中列出。通过经校准的CCD摄谱收集OLED装置的电致发光(EL)光谱且对于所有四个OLED装置实例都固定在516nm下。
HTL材料 | 10mA/cm<sup>2</sup>处的电压 | 100mA/cm<sup>2</sup>处的电压 |
比较均聚物 | 2.7 | 4.3 |
单体A均聚物 | 3.4 | 5.0 |
单体B均聚物 | 3.8 | 5.4 |
Claims (9)
1.一种聚合物,其具有至少4,000的Mn且包含式NAr1Ar2Ar3的化合物的聚合单元,其中Ar1、Ar2和Ar3独立地为C6-C50芳族取代基;Ar1、Ar2和Ar3共同含有至少2个氮原子和至少9个芳族环;并且Ar1、Ar2和Ar3中的至少一个含有与芳族环连接的乙烯基。
2.根据权利要求1所述的聚合物,其具有6,000至1,000,000的Mn。
3.根据权利要求2所述的聚合物,其中式NAr1Ar2Ar3的所述化合物含有总共10至20个芳族环。
4.根据权利要求3所述的聚合物,其中Ar2和Ar3各自独立地含有至少20个碳原子,并且Ar1含有不超过20个碳原子。
5.根据权利要求4所述的聚合物,其中Ar基团不含氮以外的杂原子。
6.根据权利要求5所述的聚合物,其中在式NAr1Ar2Ar3的所述化合物中仅存在一个乙烯基。
7.根据权利要求6所述的聚合物,其中Ar基团包含联苯基、芴基、亚苯基、咔唑基和吲哚基中的一种或多种。
8.一种电子装置,其包含一种或多种根据权利要求1所述的聚合物。
9.一种发光装置,其包含一种或多种根据权利要求1所述的聚合物。
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CN109891617A (zh) * | 2016-11-07 | 2019-06-14 | 陶氏环球技术有限责任公司 | 聚合电荷转移层和包含其的有机电子装置 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002124389A (ja) * | 2000-10-16 | 2002-04-26 | Jsr Corp | 有機エレクトロルミネッセンス素子 |
US20120018710A1 (en) * | 2009-02-26 | 2012-01-26 | Idemitsu Kosan Co., Ltd. | Novel polymerizable monomer and polymer of the polymerizable monomer, and material for organic device, hole injection/transport material and organic electroluminescent element each comprising the polymer |
US20150084031A1 (en) * | 2009-03-11 | 2015-03-26 | Idemitsu Kosan Co., Ltd. | Novel polymerizable monomer, and material for organic device, hole injection/transport material, material for organic electroluminescence element and organic electroluminescent element each comprising polymer (polymeric compound) of the polymerizable monomer |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01215070A (ja) * | 1988-02-24 | 1989-08-29 | Canon Inc | 有機太陽電池 |
US20110245429A1 (en) * | 2008-12-10 | 2011-10-06 | Neil Gough | Cross Linked Organic Conductive Layer |
JP2010150425A (ja) * | 2008-12-25 | 2010-07-08 | Idemitsu Kosan Co Ltd | 新規重合性単量体とその重合体、それを用いた有機デバイス用材料、及び有機エレクトロルミネッセンス素子 |
JP2011105643A (ja) * | 2009-11-17 | 2011-06-02 | Idemitsu Kosan Co Ltd | 重合性単量体、及びそれを用いて得られる高分子化合物、有機デバイス用材料、有機エレクトロルミネッセンス素子用材料、並びに有機デバイス、有機エレクトロルミネッセンス素子 |
CN101885834B (zh) * | 2010-07-16 | 2012-06-27 | 华南理工大学 | 含4,5-乙撑基-2,7-咔唑的共轭聚合物及其制备方法与应用 |
JP2012062450A (ja) * | 2010-09-17 | 2012-03-29 | Idemitsu Kosan Co Ltd | 新規重合性単量体と高分子化合物、それを用いた有機デバイス用材料、有機エレクトロルミネッセンス用材料、有機デバイス及び有機エレクトロルミネッセンス素子 |
CN103382246B (zh) * | 2012-05-04 | 2016-09-07 | 海洋王照明科技股份有限公司 | 芴/咔唑基共聚物、其制备方法以及聚合物发光二极管 |
JP2016119320A (ja) * | 2013-03-01 | 2016-06-30 | 出光興産株式会社 | 重合性単量体、その重合体を含む有機デバイス用材料、正孔注入輸送材料、及び有機エレクトロルミネッセンス素子用材料、並びに有機エレクトロルミネッセンス素子 |
JP6613298B2 (ja) * | 2014-08-21 | 2019-11-27 | ダウ グローバル テクノロジーズ エルエルシー | ポリマー電荷移送層及びそれを含む有機電子装置 |
-
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- 2016-06-28 JP JP2018564309A patent/JP2019518847A/ja active Pending
- 2016-06-28 WO PCT/CN2016/087414 patent/WO2018000180A1/en active Application Filing
- 2016-06-28 CN CN201680086675.XA patent/CN109348733A/zh active Pending
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002124389A (ja) * | 2000-10-16 | 2002-04-26 | Jsr Corp | 有機エレクトロルミネッセンス素子 |
US20120018710A1 (en) * | 2009-02-26 | 2012-01-26 | Idemitsu Kosan Co., Ltd. | Novel polymerizable monomer and polymer of the polymerizable monomer, and material for organic device, hole injection/transport material and organic electroluminescent element each comprising the polymer |
US20150084031A1 (en) * | 2009-03-11 | 2015-03-26 | Idemitsu Kosan Co., Ltd. | Novel polymerizable monomer, and material for organic device, hole injection/transport material, material for organic electroluminescence element and organic electroluminescent element each comprising polymer (polymeric compound) of the polymerizable monomer |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109891617A (zh) * | 2016-11-07 | 2019-06-14 | 陶氏环球技术有限责任公司 | 聚合电荷转移层和包含其的有机电子装置 |
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JP2019518847A (ja) | 2019-07-04 |
US20190148664A1 (en) | 2019-05-16 |
KR20190020070A (ko) | 2019-02-27 |
WO2018000180A1 (en) | 2018-01-04 |
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