CN106083906A - 催化环酯聚合的咪硼唑金属配合物及其应用 - Google Patents
催化环酯聚合的咪硼唑金属配合物及其应用 Download PDFInfo
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- CN106083906A CN106083906A CN201610546839.4A CN201610546839A CN106083906A CN 106083906 A CN106083906 A CN 106083906A CN 201610546839 A CN201610546839 A CN 201610546839A CN 106083906 A CN106083906 A CN 106083906A
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- Prior art keywords
- metal complex
- borazol
- miaow
- atom
- cyclic ester
- Prior art date
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- Pending
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- 125000000217 alkyl group Chemical group 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 9
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- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
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- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 5
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- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
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- 238000004440 column chromatography Methods 0.000 description 5
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- 229920000642 polymer Polymers 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QBAKBJNOARBSGP-UHFFFAOYSA-N n-[2-(benzylideneamino)ethyl]-1-phenylmethanimine Chemical compound C=1C=CC=CC=1C=NCCN=CC1=CC=CC=C1 QBAKBJNOARBSGP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
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- QYZARPHMTGMEOZ-UHFFFAOYSA-N Cl.Cl.N1=CNC2=C1C=CC=C2.[F] Chemical compound Cl.Cl.N1=CNC2=C1C=CC=C2.[F] QYZARPHMTGMEOZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 241001597008 Nomeidae Species 0.000 description 3
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- 239000004793 Polystyrene Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
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- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- YAZDSTCFFRZJLW-UHFFFAOYSA-N 2-hydroxyicosa-2,4,6,8-tetraenoic acid Chemical compound CCCCCCCCCCCC=CC=CC=CC=C(O)C(O)=O YAZDSTCFFRZJLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
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- 150000003950 cyclic amides Chemical class 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明公开了催化环酯聚合的咪硼唑金属配合物及其应用,涉及有机化学催化技术领域,尤其涉及一种与咪硼唑配位的金属催化剂。所述的咪硼唑金属配合物为具有式(I)结构的化合物。本发明公开的配合物应用在催化环酯聚合反应。该催化剂相比传统锡催化剂具有极高的催化活性,即所述的咪硼唑金属配合物无论在本体聚合还是溶液聚合中均体现了强催化活性,且催化聚合的产物具有分子量分布窄的特点。
Description
技术领域
本发明涉及有机化学催化技术领域,尤其涉及一种与咪硼唑配位的金属催化剂。
背景技术
在环境问题严重、石油资源短缺的形势下,生物降解塑料得到了广泛的关注。由于其良好的生物降解性、生物相容性和低毒性,脂肪族聚酯正成为生物可降解材料领域研究的热点。其中,在组织工程和药物控释载体方面有巨大应用前景的聚己内酯(PCL)更是受到了很多关注。PCL最早在上世纪30年代,由Carothers等人通过ε-己内酯(ε-CL)的开环聚合反应(Ring-opening polymerization,ROP)制备得到。聚己内酯是疏水性、半结晶聚合物,其结晶度随着聚合物分子质量下降,聚合物可在微生物作用下降解。考虑到PCL主要应用于医学和药剂学,因此,制备PCL的有效ROP催化体系一直是重要的研究方向。
以开环聚合机理区分,应用于环酯开环聚合的催化剂包括遵循配位-插入机理的金属催化剂以及通过活化单体或引发剂的有机催化剂。其中符合配位-插入机理的锡(Sn)类金属盐对开环聚合制备聚酯的产业化具有巨大的影响。德国的Kricheldorf等对锡类催化机理进行了深入的研究,涉及锡类催化剂对多种环酯单体的作用机制,包括丙交酯、己内酯、三亚甲基碳酸酯等(Polymer,1995,36(6):1253-1259.)。Kricheldorf等认为锡类金属盐的催化活性来自于金属中心空sp3d2轨道:在二丁基二异辛酸锡(Bu2SnOct2)中,金属中心有两个空sp3d2轨道,辛酸基团作为配位基,反应活性受位阻效应而减弱;而异辛酸亚锡(SnOct2)具有三个空sp3d2轨道,路易斯酸酸性更强,催化活性更高,更适合应用于产业化生产(Macromolecules,1988,21(2):286-293.)。相对而言,利用不同活化机制的有机催化剂在控制程度上体现出优势,却在催化活性上不及传统金属盐。
目前,应用于内酯配位开环聚合的催化剂体系主要包括辛酸亚锡、金属铝、钙、镁、锌、钛族络合物和IIIB金属络合物等。开环聚合制备聚己内酯的催化剂中,最为典型的是辛酸亚锡,小分子量的醇可以作为(共)引发剂控制聚合物分子量及分子量分布。但是,上述催化剂体系或者活性较高但产物分子量分布宽,或者分子量分布窄但活性低,均难以兼顾活性高和分子量分布窄的特点。
硼酸在催化方面的应用相当广泛,从基础有机反应,到碳骨架的构建,硼烷类的缺电子键对于调控底物基团电子分布,有着显著作用。Benkovic等发现,硼唑合成过程中,从原料至产物,以硼原子为中心,硼氧键或者与硼烷连接的其他杂原子均具有极强的吸电子能力(J.Am.Chem.Soc.2013,135:14544-14547)。这启示我们利用强吸电子配体,增强金属中心的亲电能力,从而活化内酯羰基氧原子。
发明内容
鉴于现有技术中存在上述技术问题,本发明提供了一种催化环酯聚合的咪硼唑金属配合物及其应用,该金属配合物属于硼唑金属配合物,其能够高效催化ε-己内酯的开环聚合,具有高催化活性,并得到分子量分布较窄的聚己内酯产物。
本发明所述的咪硼唑金属配合物采用了如下技术方案。
本发明提供一种催化环酯聚合的咪硼唑金属配合物,所述的咪硼唑金属配合物为具有式(I)结构的化合物:
其中,R1、R2、R3、R4中,至少包括3个氢原子;当R1、R2、R3、R4分别不为氢原子时,R1、R2、R3、R4可各自独立地选为C1-C12的链状烷烃基、C3-C8的环烷烃基、C2-C8的烯烃基、C2-C5的炔烃基、氟原子、氯原子、溴原子、R8、R9各自独立地选为C1-C5的烷烃基、C1-C5的烷氧基或氢原子;
R5为氢原子或者R6、R7中,至少包括1个氢原子,当R6、R7分别不为氢原子时,R6、R7可选为C1-C12的链状烷烃基、C3-C8的环烷烃基、C2-C8的烯烃基、C2-C5的炔烃基、氟原子、氯原子、溴原子、硝基、苄氧基;M为Sn或Zn,优选Sn。
优选所述的R1、R2、R3、R4中,至少包括3个氢原子;当R1、R2、R3、R4分别不为氢原子时,R1、R2、R3、R4可各自独立地选为C1-C6的直链烷烃基、C3-C8的支链烷烃基、C3-C6的环烷烃基、氟原子、氯原子、溴原子、苯基、苄基;
具体的所述的咪硼唑金属配合物如表1所示的结构:
表1
R5为氢原子或者其中,R6、R7中,至少包括1个氢原子,当R6、R7分别不为氢原子时,R6、R7可选为C1-C4的直链烷烃基、氟原子;M为Sn或Zn。
合成所述咪硼唑金属配合物的方法为:
以1,2-氧硼杂环戊烷或2-氯-1,2-氧硼杂环戊烷为硼环原料,并溶解于DMF中,加热到60℃,加入多聚甲醛作为羰基原料,反应至体系澄清后,加入乙二胺的芳香族衍生物,或在加入氟苯并嗪、氯化钙及苯酚反应后加入乙二胺的芳香族衍生物,共混反应后,向体系滴加氯化亚锡或氯化锌,析出白色粉末,过滤得粗产品后,柱层析纯化得到所述咪硼唑金属配合物。
催化环酯聚合反应的方法为:
将环酯单体置于烧瓶,加入咪硼唑金属配合物与共引发剂,油浴加热,恒温反应;
或将环酯单体置于烧瓶,以有机溶剂溶解,再加入咪硼唑金属配合物与共引发剂,室温反应。
所述共引发剂,为MeOH、EtOH、nPrOH、iPrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3中的一种或几种。上述醇与所述的咪硼唑金属配合物摩尔比可在很大的范围内变化:(0.1-10)℃1。聚合物的分子量可通过上述醇与配合物摩尔比来控制,在0.1万-20万范围内精确可调节、分子量分布介于1.01-1.20,具有活性聚合特点。
在所述的咪硼唑金属配合物的应用中还包括稳定熔融工艺,熔融工艺中的稳定剂为三烷基亚磷酸,烷基亚磷酸、芳香族亚磷酸、空间受阻的环状芳香族化合物、空间受阻的二亚磷酸化合物、羟基苯丙酸、羟苄基化合物、苯甲醇、亚烷基双酚、烷基酚、氨基酸、硫醚、空间受阻的氨基化合物、对苯二酚中的一种或几种混合物。
在所述的咪硼唑金属配合物的应用中还包括稳定熔融工艺,熔融工艺中的除水剂为粘土、氧化铝、硅胶、沸石、氯化钙、碳酸钙、硫酸钠、碳酸氢钙、碳酸氢钠、碳酸氢钾中的一种或几种混合物。也可以在阻聚剂中添加受阻(烷基,芳基,酚基)酰肼、芳香族或脂肪族的酰胺单羟酸或者二羟酸、环酰胺、脂肪族或芳香族的腙醛或者二腙醛、二酰基酰肼衍生物。
所述的咪硼唑金属配合物,除了可以在熔融工艺中制备聚己内酯,还可以在有机溶剂中制备聚己内酯,所述有机溶剂为苯、甲苯、二甲苯、N,N-二甲基甲酰胺、三氯甲烷、二氯甲烷、乙腈、吡啶、二甲亚砜、1,4-二氧己环中的一种、呋喃、四氢呋喃。反应混合液可在另一种极性溶剂中析出固体粉末。
本发明中所述的环酯结构是选自具有式(III)结构的环状化合物单体中的一种或几种:
其中,A为[-(CR8R9)-];R8、R9选自H,具有1~5个碳原子的烷基和具有1~5个碳原子并被卤原子或羟基取代的烷基中的相同或不同基团;x选自O或N;或者是选自具有式(IV)结构的环状化合物单体中的一种或几种:
其中,A、B为[-(CR10R11)-]n,n为2~6的整数,A和B可以相同也可以不同;R10、R11选自H、具有1~5个碳原子的烷基、具有1~5个碳原子并被卤原子或羟基取代的烷基;x选自O或NH。
有益效果:
本发明提供了一种硼唑金属配合物催化剂,该催化剂相比传统锡催化剂具有极高的催化活性,即所述的咪硼唑金属配合物无论在本体聚合还是溶液聚合中均体现了强催化活性,且催化聚合的产物具有分子量分布窄的特点。
1、本发明首次将含硼金属盐用于环酯的开环聚合;
2、本发明所述的咪硼唑金属配合物对ε-己内酯具有高催化活性,其活性高于目前所有报道中的传统锡盐及有机催化剂;
3、使用本发明所述的咪硼唑金属配合物催化ε-己内酯及其他内酯及交酯单体聚合的产物分子量分布较窄,且可以调节分子量大小,具有活性聚合特点。
具体实施方式
为了进一步说明本发明,下面结合实施例对本发明优选实施方案进行描述,但是这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
合成方法(化合物序号代表核磁数据表中结构)
化合物1:将1,2-氧硼杂环戊烷(2.212g)溶解于DMF(100mL)中,油浴60℃下缓慢加入多聚甲醛(1.236g),60℃下反应至体系澄清。加入N,N′-双(苯基亚甲基)-1,2-乙二胺(3.235g),在室温下反应6小时后,缓慢滴加氯化亚锡(4.226g)的DMF溶液,至体系析出白色固体后继续反应2小时。反应结束后,静置过滤,减压抽干溶剂,得到的粗产物进行柱层析分离(石油醚/二氯甲烧=1/1)得到黄色产物,产率88.2%。
化合物2:将1,2-氧硼杂环戊烷(2.212g)溶解于DMF(100mL)中,油浴60℃下缓慢加入多聚甲醛(1.236g),60℃下反应至体系澄清。加入N,N′-双(苯基亚甲基)-1,2-乙二胺(3.235g),在室温下反应6小时后,缓慢滴加氯化亚锌(3.656g)的DMF溶液,至体系析出白色固体后继续反应2小时。反应结束后,静置过滤,减压抽干溶剂,得到的粗产物进行柱层析分离(石油醚/二氯甲烧=1/1)得到黄色产物,产率79.5%。
化合物3:将2-氯-1,2-氧硼杂环戊烷(3.011g)溶解于DMF(100mL)中,油浴60℃下缓慢加入多聚甲醛(1.236g),100℃下反应至体系澄清。加入苯磺酸(4.252g)的乙腈溶液与氯化钙(0.5g),搅拌至体系呈乳状,静止、过滤。在滤液中加入N,N′-双(苯基亚甲基)-1,2-乙二胺(3.235g),在室温下反应8小时后,缓慢滴加氯化亚锡(4.226g)的DMF溶液,至体系析出白色固体后继续反应2小时。反应结束后,静置过滤,减压抽干溶剂,得到的粗产物进行柱层析分离(石油醚/二氯甲烧=1/2)得到黄色产物,产率79.8%。
化合物4:将2-氯-1,2-氧硼杂环戊烷(3.011g)溶解于DMF(100mL)中,油浴60℃下缓慢加入多聚甲醛(1.236g),60℃下反应至体系澄清,体系反复抽真空三次。加入氟苯并嗪(3.122g)的乙腈溶液、氯化钙(0.5g)及苯酚(3.122g),搅拌至体系呈乳状,静止、过滤。加入N,N′-双(苯基亚甲基)-1,2-乙二胺(3.235g),在45℃反应24小时后,缓慢滴加氯化亚锡(4.226g)的DMF溶液,至体系析出白色固体后继续反应2小时。反应结束后,静置过滤,减压抽干溶剂,得到的粗产物进行柱层析分离(正己烷/乙酸乙酯=4/1)得到白色粉末,产率81.2%。
化合物5:将2-氯-1,2-氧硼杂环戊烷(3.011g)溶解于DMF(100mL)中,油浴60℃下缓慢加入多聚甲醛(1.236g),60℃下反应至体系澄清,体系反复抽真空三次。加入氟苯并嗪(3.122g)的乙腈溶液、氯化钙(0.5g)及苯酰氯(3.211g),搅拌至体系呈乳状,静止、过滤。滤液加入N,N′-双(苯基亚甲基)-1,2-乙二胺(3.235g),在室温下搅拌反应6小时后,缓慢滴加氯化亚锡(4.226g)的DMF溶液,至体系析出白色固体后继续反应2小时。反应结束后,静置过滤,减压抽干溶剂,得到的粗产物进行柱层析分离(石油醚/二氯甲烧=1/1)得到黄色产物,产率82.2%。
核磁数据表(300MHz,CDCl3):
实施例1-5
实施例1-5采用了不同的金属配合物作为催化剂,在相同的反应条件下进行本体聚合。分别为5.7g(50mmol)的ε-己内酯分别置于50mL烧瓶,加入0.1mmol金属配合物,0.1mmol苯甲醇。120℃下油浴加热。恒温反应15min,冷却,取样分析,使用液相色谱测定转化率,使用GPC测定分子量(聚苯乙烯为标样)。实施例1-10的实验结果见表1。
实施例1-5中所述的ε-己内酯的单体为己内酯生产过程中精馏后纯度较高的产品。
表1不同催化剂作用下的本体聚合反应
实施例6-10
实施例6-10中采用上述实施例4中的金属配合物作为催化剂,在不同温度条件下进行本体聚合。分别将5.7g(50mmol)的ε-己内酯分别置于50mL烧瓶,加入0.1mmol实施例1中金属配合物,0.1mmol苯甲醇。5种温度下油浴加热,恒温反应15min,冷却,取样分析,使用液相色谱测定转化率,使用GPC测定分子量(聚苯乙烯为标样)。实施例6-10的实验结果见表2。
实施例6-10中所述的ε-己内酯的单体为己内酯生产过程中精馏后纯度较高的产品。
表2不同温度下的聚合结果
实施例11-16
实施例11-16中采用上述实施例4中的金属配合物作为催化剂,在不同催化剂用量条件下进行本体聚合。分别将5.7g(50mmol)的ε-己内酯分别置于50mL烧瓶,加入实施例2中金属配合物5个批次质量,0.1mmol苯甲醇。在120℃下油浴加热。恒温反应20min,冷却,取样分析,转化率以液相色谱测得,分子量以GPC测得(聚苯乙烯为标样)。实施例11-16的实验结果见表3。
实施例11-16中所述的ε-己内酯的单体为己内酯生产过程中精馏后纯度较高的产品。
表3金属配合物不同用量对聚合率的影响
实施例17-26
实施例17-26中采用上述实施例1中的金属配合物作为催化剂,在不同有机溶剂条件下进行溶液聚合。分别将5.7g(50mmol)的ε-己内酯分别置于50mL烧瓶,加入不同有机溶剂15mL。加入实施例4中金属配合物0.5mmol,0.5mmol苯甲醇。室温恒温反应1小时,取样分析,转化率以液相色谱测得,终产物倒入冰甲醇中析出白色固体,分子量以GPC测得(聚苯乙烯为标样)。实施例17-26的实验结果见表4。
实施例17-26中所述的ε-己内酯的单体为己内酯生产过程中精馏后纯度较高的产品。
表4:不同有机溶剂中聚合情况
实施例27-30
实施例26-29采用上述实施例9的金属配合物作为催化剂,催化4种不同的环酯进行本体聚合。分别将4种,5g的环酯分别置于50mL烧瓶,加入1mg实施例3中阻聚剂,120℃下油浴加热,反应4小时,冷却,取样分析环酯的含量。以此来计算环酯转化率(即聚合率),实施例26-29的实验结果见表5。
表5不同环酯单体的聚合
Claims (8)
1.一种催化环酯聚合的咪硼唑金属配合物,其特征在于,所述的催化环酯聚合的咪硼唑金属配合物是具有式(I)所示的结构的化合物:
其中,R12、R13中,至少包括1个氢原子;当R12、R13分别不为氢原子时,R12、R13各自独立地选为C1-C12的链状烷烃基、C3-C8的环烷烃基、C2-C8的烯烃基、C2-C5的炔烃基、氟原子、氯原子、溴原子、R8、R9各自独立地选为C1-C5的烷烃基、C1-C5的烷氧基或氢原子;
R14为氢原子或者其中,R6、R7中,至少包括1个氢原子,当R6、R7分别不为氢原子时,R6、R7可选为C1-C12的链状烷烃基、C3-C8的环烷烃基、C2-C8的烯烃基、C2-C5的炔烃基、氟原子、氯原子、溴原子、硝基、苄氧基;
M为Sn或Zn。
2.根据权利要求1所述的咪硼唑金属配合物,其特征在于,所述的R12、R13中,至少包括1个氢原子;当R12、R13分别不为氢原子时,R12、R13各自独立地选为C1-C3的直链烷烃基、氟原子、氯原子、溴原子、苯基、苄基;
R14为氢原子或者其中,R6、R7中,至少包括1个氢原子,当R6、R7分别不为氢原子时,R6、R7可选为C1-C3的直链烷烃基、氟原子、氯原子、溴原子、硝基、苄氧基;
M为Sn或Zn。
3.根据权利要求1所述的咪硼唑金属配合物,其特征在于,所述的含碱的金属配合物是具有表1中结构的化合物:
表1
。
4.一种根据权利要求1至3任意一项所述的咪硼唑金属配合物IV的应用,其特征在于,所述的咪硼唑金属配合物应用于环酯结构化合物的开环聚合。
5.根据权利要求4所述的应用,其特征在于,催化环酯聚合反应的方法为:
将环酯单体置于烧瓶,加入咪硼唑金属配合物与共引发剂,油浴加热,恒温反应;
或将环酯单体置于烧瓶,以有机溶剂溶解,再加入咪硼唑金属配合物与共引发剂,室温反应。
6.根据权利要求5所述的应用,其特征在于,所述的环酯单体是选自具有式(III)所示的结构的环状化合物单体中的一种或几种:
其中,A为[-(CR8R9)-];R8、R9选自H,具有1~5个碳原子的烷基和具有1~5个碳 原子并被卤原子或羟基取代的烷基中的相同或不同基团;X选自O或N;或者是选自具有式(IV)结构的环状化合物单体中的一种或几种:
其中,A、B为[-(CR10R11)-]n,n为2~6的整数,A和B可以相同也可以不同;
R10、R11选自H、具有1~5个碳原子的烷基、具有1~5个碳原子并被卤原子或羟基取代的烷基;X选自O或NH。
7.根据权利要求5所述的应用,其特征在于,所述的共引发剂为MeOH、EtOH、nPrOH、1PrOH、 nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3中的一种。
8.根据权利要求5所述的应用,其特征在于,所述的有机溶剂为苯、甲苯、二甲苯、N,N-二甲基甲酰胺、三氯甲烷、二氯甲烷、乙腈、吡啶、二甲亚砜、1,4-二氧己环中的一种、呋喃、四氢呋喃。
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CN105968332A (zh) * | 2016-07-12 | 2016-09-28 | 安徽红太阳新材料有限公司 | 催化环酯聚合的苯并硼唑金属配合物及其应用 |
CN110092899A (zh) * | 2019-05-23 | 2019-08-06 | 大连汇鹏达化工有限公司 | 一种苯丙氨酸亚锡配合物的用途 |
CN110092899B (zh) * | 2019-05-23 | 2021-04-06 | 大连汇鹏达化工有限公司 | 一种苯丙氨酸亚锡配合物的用途 |
CN113087882A (zh) * | 2020-01-08 | 2021-07-09 | 浙江大学 | 一种具有多硼中心的有机催化体系和应用 |
CN113087882B (zh) * | 2020-01-08 | 2023-08-01 | 浙江大学 | 一种具有多硼中心的有机催化体系和应用 |
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