CN106543153A - 2 imidazoles carbonyl, 2 methyl trimethylene carbonate and its production and use - Google Patents
2 imidazoles carbonyl, 2 methyl trimethylene carbonate and its production and use Download PDFInfo
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- -1 methyl trimethylene Chemical group 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 12
- 239000004417 polycarbonate Substances 0.000 claims abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 17
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical class [H]O* 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- JCQFIMPZAUENFB-UHFFFAOYSA-N ethyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate Chemical compound CCOC(=O)C1(C)COC(=O)OC1 JCQFIMPZAUENFB-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920001963 Synthetic biodegradable polymer Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
本发明提供了一种具有反应活性的新型环状碳酸酯单体2‑咪唑羰基‑2‑甲基三亚甲基碳酸酯，其分子式为C9H10N2O4，分子量为210。该物质的合成路线为：从2，2‑二羟甲基丙酸出发，经关环反应，制备了新型六元环状碳酸酯单体即2‑咪唑羰基‑2‑甲基三亚甲基碳酸酯。本发明所提供的2‑咪唑羰基‑2‑甲基三亚甲基碳酸酯的咪唑羰基具有反应活性，能和一系列带羟基、氨基化合物进行置换反应，用来合成其他六元环状碳酸酯单体，因此能够用于制备多种环状碳酸酯单体。这些环状碳酸酯单体又能够进一步的合成具有良好生物相容性的功能化聚碳酸酯。且本发明原料价格便宜、来源广泛，制备方法简单，具有较高的应用价值。
The invention provides a novel reactive cyclic carbonate monomer 2-imidazolecarbonyl-2-methyltrimethylene carbonate, which has a molecular formula of C 9 H 10 N 2 O 4 and a molecular weight of 210. The synthetic route of this substance is: starting from 2,2-dimethylolpropionic acid, through ring-closing reaction, a new type of six-membered cyclic carbonate monomer, namely 2-imidazolecarbonyl-2-methyltrimethylene carbonate, was prepared ester. The imidazole carbonyl of 2-imidazolecarbonyl-2-methyltrimethylene carbonate provided by the present invention has reactivity, and can carry out displacement reaction with a series of hydroxyl and amino compounds, and is used to synthesize other six-membered cyclic carbonate mono body, so it can be used to prepare a variety of cyclic carbonate monomers. These cyclic carbonate monomers can further synthesize functionalized polycarbonates with good biocompatibility. Moreover, the raw material of the invention is cheap, has wide sources, simple preparation method and high application value.
Description
技术领域technical field
本发明提供了一种生物可降解聚碳酸酯类化合物及其制备方法和用途，尤其涉及2-咪唑羰基-2-甲基三亚甲基碳酸酯，属于生物医用材料领域。The invention provides a biodegradable polycarbonate compound and its preparation method and application, in particular to 2-imidazolecarbonyl-2-methyltrimethylene carbonate, which belongs to the field of biomedical materials.
背景技术Background technique
作为一类人工合成生物可降解高分子材料，脂肪族聚碳酸酯具有良好的生物相容性、生物可降解性和物理机械性能，而且种类很多，在外科手术缝合线、骨固定材料、药物控制释放和组织工程等领域越来越受到重视。脂肪族聚碳酸酯的合成方法主要有酯交换法、光气缩合法、环氧化物和二氧化碳加成聚合法以及环状碳酸酯单体开环聚合法。其中，环状碳酸酯单体开环聚合法具有聚合过程热效应低、聚合速度快和产物分子量高等优点，已经成为合成脂肪族聚碳酸酯最主要的方法。在环状碳酸酯单体中引入不同的功能基团，譬如羧基、氨基、羟基等，能够给脂肪族聚碳酸酯提供进一步的化学修饰。环状碳酸酯单体种类繁多，通过开环聚合可以制备出各种各样脂肪族聚碳酸酯。As a class of synthetic biodegradable polymer materials, aliphatic polycarbonate has good biocompatibility, biodegradability and physical and mechanical properties, and there are many types. It is used in surgical sutures, bone fixation materials, drug control Areas such as release and tissue engineering are receiving increasing attention. The synthesis methods of aliphatic polycarbonate mainly include transesterification, phosgene condensation, addition polymerization of epoxide and carbon dioxide, and ring-opening polymerization of cyclic carbonate monomers. Among them, the ring-opening polymerization method of cyclic carbonate monomer has the advantages of low thermal effect during polymerization, fast polymerization speed and high molecular weight of the product, and has become the most important method for synthesizing aliphatic polycarbonate. The introduction of different functional groups into the cyclic carbonate monomer, such as carboxyl, amino, hydroxyl, etc., can provide further chemical modification to the aliphatic polycarbonate. There are many kinds of cyclic carbonate monomers, and various aliphatic polycarbonates can be prepared by ring-opening polymerization.
发明内容Contents of the invention
本发明提供了一种具有反应活性的新型环状碳酸酯单体，该单体可用于合成多种环状碳酸酯单体，并用于合成生物可降解脂肪族聚碳酸酯。The invention provides a novel cyclic carbonate monomer with reactivity, which can be used to synthesize various cyclic carbonate monomers and biodegradable aliphatic polycarbonate.
实现本发明上述目的所采用的技术方案为：2-咪唑羰基-2-甲基三亚甲基碳酸酯，其结构式为：The technical scheme adopted to realize the above-mentioned purpose of the present invention is: 2-imidazole carbonyl-2-methyl trimethylene carbonate, and its structural formula is:
上述2-咪唑羰基-2-甲基三亚甲基碳酸酯为白色晶体，分子式C9H10N2O4，分子量为210。The above-mentioned 2-imidazolecarbonyl-2-methyltrimethylene carbonate is a white crystal with a molecular formula of C 9 H 10 N 2 O 4 and a molecular weight of 210.
本发明还提供了该材料的制备方法，包括以下步骤：将2，2-二羟甲基丙酸和N'N-羰基二咪唑溶于有机溶剂中，在室温下反应10～14小时，反应产物重结晶纯化后得到2-咪唑羰基-2-甲基三亚甲基碳酸酯。The present invention also provides a preparation method of the material, comprising the following steps: dissolving 2,2-dimethylolpropionic acid and N'N-carbonyldiimidazole in an organic solvent, reacting at room temperature for 10 to 14 hours, and reacting The product was recrystallized and purified to obtain 2-imidazolecarbonyl-2-methyltrimethylene carbonate.
所述有机溶剂为二氯甲烷、三氯甲烷、二甲基甲酰胺、二甲亚砜、乙腈、乙酸乙酯、丙酮或四氢呋喃。The organic solvent is dichloromethane, chloroform, dimethylformamide, dimethyl sulfoxide, acetonitrile, ethyl acetate, acetone or tetrahydrofuran.
重结晶所用的溶剂为四氢呋喃和乙醚的混合溶液。The solvent used for recrystallization is a mixed solution of tetrahydrofuran and ether.
重结晶所用的溶剂为四氢呋喃和乙醚按照1：3体积比混合后的溶液。The solvent used for recrystallization is a solution of tetrahydrofuran and diethyl ether mixed in a volume ratio of 1:3.
本发明所提供的2-咪唑羰基-2-甲基三亚甲基碳酸酯的咪唑羰基具有反应活性，能和一系列带羟基、氨基化合物进行置换反应，用来合成其他六元环状碳酸酯单体，因此能够用于制备多种环状碳酸酯单体。这些环状碳酸酯单体又能够进一步的合成具有良好生物相容性的功能化聚碳酸酯。且本发明原料价格便宜、来源广泛，制备方法简单，具有较高的应用价值。The imidazole carbonyl of the 2-imidazole carbonyl-2-methyl trimethylene carbonate provided by the present invention has reactivity, and can carry out displacement reaction with a series of hydroxyl and amino compounds, and is used to synthesize other six-membered cyclic carbonate mono body, so it can be used to prepare a variety of cyclic carbonate monomers. These cyclic carbonate monomers can further synthesize functionalized polycarbonates with good biocompatibility. Moreover, the raw material of the invention is cheap, has wide sources, simple preparation method and high application value.
附图说明Description of drawings
图1为本发明所提供的2-咪唑羰基-2-甲基三亚甲基碳酸酯的结构式；Fig. 1 is the structural formula of 2-imidazole carbonyl-2-methyl trimethylene carbonate provided by the present invention;
图2为本发明所提供的2-咪唑羰基-2-甲基三亚甲基碳酸酯的合成路线图。Figure 2 is a synthetic route diagram of 2-imidazolecarbonyl-2-methyltrimethylene carbonate provided by the present invention.
具体实施方式detailed description
本发明实施例中所提供的2-咪唑羰基-2-甲基三亚甲基碳酸酯，其结构式如图1所示，该物质的合成路线如图2所示：从2，2-二羟甲基丙酸出发，经关环反应，制备了新型六元环状碳酸酯单体即2-咪唑羰基-2-甲基三亚甲基碳酸酯。下面结合具体实施例本上述合成方法做详细具体的说明：The structural formula of 2-imidazolecarbonyl-2-methyltrimethylene carbonate provided in the examples of the present invention is shown in Figure 1, and the synthetic route of the substance is shown in Figure 2: from 2,2-dimethylol Starting from propionic acid, a new six-membered cyclic carbonate monomer, 2-imidazolecarbonyl-2-methyltrimethylene carbonate, was prepared through ring-closing reaction. Below in conjunction with specific embodiment this above-mentioned synthesis method is described in detail:
实施例1Example 1
本实施例中所采用的合成步骤如下：The synthetic steps adopted in the present embodiment are as follows:
2-咪唑羰基-2-甲基三亚甲基碳酸酯的制备：将2.68克2，2-二羟甲基丙酸、8.11克N，N’-羰基二咪唑和30毫升二氯甲烷置于100毫升圆底烧瓶中，在室温下搅拌12小时。用20毫升5％NaHCO3水溶液和饱和盐水各洗一次，无水硫酸镁干燥。过滤，滤液浓缩除溶剂，并用四氢呋喃和乙醚体积比为1比3的混合溶剂重结晶三次，得到白色晶体，产率为38％。通过红外(FT-IR)、核磁共振谱(1H NMR和13C NMR)和元素分析(EA)表征分析，证实该白色晶体为2-咪唑羰基-2-甲基三亚甲基碳酸酯。FT-IR：v＝1750cm-1(C＝O)，v＝1732cm-1(CON)。1H NMR(CDCl3，ppm)：8.26(s，1H，NCH＝N)，7.57(s，1H，NCH)，7.05(s，1H，NCH)，4.60(d，2H，J＝11.2Hz，CH2)，4.22(d，2H，J＝11.2Hz，CH2)，1.33(s，3H，CH3)。13C NMR(CDCl3，ppm)：171.2，147.9，137.3，130.3，117.5，68.0，46.1，17.2。C9H10N2O4 210.19：Calad.C 51.43，H 4.80，N13.33；Found C 51.65，H 4.72，N 13.17。Preparation of 2-imidazolecarbonyl-2-methyltrimethylene carbonate: 2.68 g of 2,2-dimethylolpropionic acid, 8.11 g of N,N'-carbonyldiimidazole and 30 ml of dichloromethane were placed in 100 mL round bottom flask and stirred at room temperature for 12 hours. Wash with 20 ml of 5% NaHCO 3 aqueous solution and saturated brine, and dry over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to remove the solvent, and recrystallized three times with a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:3 to obtain white crystals with a yield of 38%. Characterized by infrared (FT-IR), nuclear magnetic resonance ( 1 H NMR and 13 C NMR) and elemental analysis (EA), it was confirmed that the white crystal was 2-imidazolecarbonyl-2-methyltrimethylene carbonate. FT-IR: v=1750cm -1 (C=O), v=1732cm -1 (CON). 1 H NMR (CDCl 3 , ppm): 8.26(s, 1H, NCH=N), 7.57(s, 1H, NCH), 7.05(s, 1H, NCH), 4.60(d, 2H, J=11.2Hz, CH 2 ), 4.22 (d, 2H, J = 11.2 Hz, CH 2 ), 1.33 (s, 3H, CH 3 ). 13 C NMR (CDCl 3 , ppm): 171.2, 147.9, 137.3, 130.3, 117.5, 68.0, 46.1, 17.2. C 9 H 10 N 2 O 4 210.19: Calad. C 51.43, H 4.80, N 13.33; Found C 51.65, H 4.72, N 13.17.
实施例2Example 2
本实施例中所采用的合成步骤如下：The synthetic steps adopted in the present embodiment are as follows:
2-咪唑羰基-2-甲基三亚甲基碳酸酯的制备：将2.68克2，2-二羟甲基丙酸、8.11克N，N’-羰基二咪唑和30毫升三氯甲烷置于100毫升圆底烧瓶中，在室温下搅拌12小时。用20毫升5％NaHCO3水溶液和饱和盐水各洗一次，无水硫酸镁干燥。过滤，滤液浓缩除溶剂，并用四氢呋喃和乙醚体积比为1比3的混合溶剂重结晶三次，得到白色晶体2-咪唑羰基-2-甲基三亚甲基碳酸酯，产率为34％。其红外(FT-IR)、核磁共振谱(1H NMR和13C NMR)和元素分析(EA)数据同实施例1。Preparation of 2-imidazolecarbonyl-2-methyltrimethylene carbonate: 2.68 g of 2,2-dimethylolpropionic acid, 8.11 g of N,N'-carbonyldiimidazole and 30 ml of chloroform were placed in 100 mL round bottom flask and stirred at room temperature for 12 hours. Wash with 20 ml of 5% NaHCO 3 aqueous solution and saturated brine, and dry over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to remove the solvent, and recrystallized three times with a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:3 to obtain white crystals of 2-imidazolecarbonyl-2-methyltrimethylene carbonate with a yield of 34%. Its infrared (FT-IR), nuclear magnetic resonance ( 1 H NMR and 13 C NMR) and elemental analysis (EA) data are the same as in Example 1.
实施例3Example 3
本实施例中所采用的合成步骤如下：The synthetic steps adopted in the present embodiment are as follows:
2-咪唑羰基-2-甲基三亚甲基碳酸酯的制备：将2.68克2，2-二羟甲基丙酸、8.11克N，N’-羰基二咪唑和30毫升二氯甲烷置于100毫升圆底烧瓶中，在室温下搅拌12小时。用20毫升5％NaHCO3水溶液和饱和盐水各洗一次，无水硫酸镁干燥。过滤，滤液浓缩除溶剂，并用四氢呋喃和乙醚体积比为1比2的混合溶剂重结晶三次，得到白色晶体2-咪唑羰基-2-甲基三亚甲基碳酸酯，产率为27％。其红外(FT-IR)、核磁共振谱(1H NMR和13C NMR)和元素分析(EA)数据同实施例1。Preparation of 2-imidazolecarbonyl-2-methyltrimethylene carbonate: 2.68 g of 2,2-dimethylolpropionic acid, 8.11 g of N,N'-carbonyldiimidazole and 30 ml of dichloromethane were placed in 100 mL round bottom flask and stirred at room temperature for 12 hours. Wash with 20 ml of 5% NaHCO 3 aqueous solution and saturated brine, and dry over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to remove the solvent, and recrystallized three times with a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:2 to obtain white crystals of 2-imidazolecarbonyl-2-methyltrimethylene carbonate with a yield of 27%. Its infrared (FT-IR), nuclear magnetic resonance ( 1 H NMR and 13 C NMR) and elemental analysis (EA) data are the same as in Example 1.
实施例4Example 4
本实施例中所采用的合成步骤如下：The synthetic steps adopted in the present embodiment are as follows:
2-咪唑羰基-2-甲基三亚甲基碳酸酯的制备：将2.68克2，2-二羟甲基丙酸、8.11克N，N’-羰基二咪唑和30毫升二氯甲烷置于100毫升圆底烧瓶中，在室温下搅拌12小时。用20毫升5％NaHCO3水溶液和饱和盐水各洗一次，无水硫酸镁干燥。过滤，滤液浓缩除溶剂，并用四氢呋喃和乙醚体积比为1比4的混合溶剂重结晶三次，得到白色晶体2-咪唑羰基-2-甲基三亚甲基碳酸酯，产率为32％。其红外(FT-IR)、核磁共振谱(1H NMR和13C NMR)和元素分析(EA)数据同实施例1。Preparation of 2-imidazolecarbonyl-2-methyltrimethylene carbonate: 2.68 g of 2,2-dimethylolpropionic acid, 8.11 g of N,N'-carbonyldiimidazole and 30 ml of dichloromethane were placed in 100 mL round bottom flask and stirred at room temperature for 12 hours. Wash with 20 ml of 5% NaHCO 3 aqueous solution and saturated brine, and dry over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to remove the solvent, and recrystallized three times with a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:4 to obtain white crystals of 2-imidazolecarbonyl-2-methyltrimethylene carbonate with a yield of 32%. Its infrared (FT-IR), nuclear magnetic resonance ( 1 H NMR and 13 C NMR) and elemental analysis (EA) data are the same as in Example 1.
实施例5Example 5
本实施例中将上述所制备的2-咪唑羰基-2-甲基三亚甲基碳酸酯进行置换反应，合成其他六元环状碳酸酯单体，并进一步将该单体合成具有良好生物相容性的功能化聚碳酸酯。具体步骤如下：In this example, the 2-imidazolecarbonyl-2-methyltrimethylene carbonate prepared above was subjected to a displacement reaction to synthesize other six-membered cyclic carbonate monomers, and the monomers were further synthesized to have good biocompatibility Highly functionalized polycarbonate. Specific steps are as follows:
(1)、2-乙氧羰基-2-甲基三亚甲基碳酸酯的制备：将0.21克2-咪唑羰基-2-甲基三亚甲基碳酸酯、0.06克无水乙醇和10毫升二氯甲烷置于50毫升圆底烧瓶中，在室温下搅拌12小时。用20毫升5％NaHCO3水溶液和饱和盐水各洗一次，无水硫酸镁干燥。过滤，滤液浓缩除溶剂，并用四氢呋喃和乙醚体积比为1比3的混合溶剂重结晶三次，得到白色晶体，产率为64％。通过红外(FT-IR)和核磁共振谱(1H NMR和13C NMR)表征分析，证实该白色晶体为2-乙氧羰基-2-甲基三亚甲基碳酸酯。FT-IR：v＝1753cm-1(C＝O)。1H NMR(CDCl3，ppm)：4.66(d，2H，CH2OCOO)，4.23(q，1H，OCH2CH3)，4.18(d，2H，CH2OCOO)，1.33(s，3H，CH3)，1.28(t，3H，OCH2CH3)。13C NMR(CDCl3，ppm)：171.2，147.3，137.3，73.1，62.4，39.8，17.1，13.6。(1), the preparation of 2-ethoxycarbonyl-2-methyltrimethylene carbonate: 0.21 gram of 2-imidazolecarbonyl-2-methyltrimethylene carbonate, 0.06 gram of absolute ethanol and 10 milliliters of dichloromethylene Methane was placed in a 50 mL round bottom flask and stirred at room temperature for 12 hours. Wash with 20 ml of 5% NaHCO 3 aqueous solution and saturated brine, and dry over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to remove the solvent, and recrystallized three times with a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:3 to obtain white crystals with a yield of 64%. Through infrared (FT-IR) and nuclear magnetic resonance spectrum ( 1 H NMR and 13 C NMR) characterization analysis, it was confirmed that the white crystal was 2-ethoxycarbonyl-2-methyltrimethylene carbonate. FT-IR: v = 1753 cm -1 (C = O). 1 H NMR (CDCl 3 , ppm): 4.66 (d, 2H, CH 2 OCOO), 4.23 (q, 1H, OCH 2 CH 3 ), 4.18 (d, 2H, CH 2 OCOO), 1.33 (s, 3H, CH3 ), 1.28 (t, 3H , OCH2CH3 ). 13 C NMR (CDCl 3 , ppm): 171.2, 147.3, 137.3, 73.1, 62.4, 39.8, 17.1, 13.6.
(2)、聚(2-乙氧羰基-2-甲基三亚甲基碳酸酯)的制备：将0.2克2-乙氧羰基-2-甲基三亚甲基碳酸酯和4毫克二氮杂二环溶于2毫升二氯甲烷中，室温下反应5小时。用50毫升正己烷沉淀，所得聚合物在40℃下真空干燥24小时，产率为87％。数均分子量为8200，多分散指数为1.21。FT-IR：v＝1752cm-1(C＝O)。1H NMR(CDCl3，ppm)：4.44-4.12(m，6H，CH2O)，1.33-1.15(m，6H，CH3)。(2), preparation of poly(2-ethoxycarbonyl-2-methyltrimethylene carbonate): 0.2 gram of 2-ethoxycarbonyl-2-methyltrimethylene carbonate and 4 mg of diazabis The ring was dissolved in 2 ml of dichloromethane and reacted at room temperature for 5 hours. Precipitate with 50 ml of n-hexane, and vacuum-dry the obtained polymer at 40° C. for 24 hours, with a yield of 87%. The number average molecular weight is 8200, and the polydispersity index is 1.21. FT-IR: v = 1752 cm -1 (C = O). 1 H NMR (CDCl 3 , ppm): 4.44-4.12 (m, 6H, CH 2 O), 1.33-1.15 (m, 6H, CH 3 ).
实施例6Example 6
本实施例中将上述所制备的2-咪唑羰基-2-甲基三亚甲基碳酸酯进行置换反应，合成其他六元环状碳酸酯单体，并进一步将该单体合成具有良好生物相容性的功能化聚碳酸酯。具体步骤如下：In this example, the 2-imidazolecarbonyl-2-methyltrimethylene carbonate prepared above was subjected to a displacement reaction to synthesize other six-membered cyclic carbonate monomers, and the monomers were further synthesized to have good biocompatibility Highly functionalized polycarbonate. Specific steps are as follows:
(1)、2-二甲基酰胺基-2-甲基三亚甲基碳酸酯的制备：将0.21克2-咪唑羰基-2-甲基三亚甲基碳酸酯、0.06克二甲胺和10毫升二氯甲烷置于50毫升圆底烧瓶中，在室温下搅拌12小时。用20毫升5％NaHCO3水溶液和饱和盐水各洗一次，无水硫酸镁干燥。过滤，滤液浓缩除溶剂，并用四氢呋喃和乙醚体积比为1比3的混合溶剂重结晶三次，得到白色晶体，产率为78％。通过红外(FT-IR)和核磁共振谱(1H NMR和13C NMR)表征分析，证实该白色晶体为2-二甲基酰胺基-2-甲基三亚甲基碳酸酯。FT-IR：v＝1752cm-1(C＝O)，v＝1659cm-1(CONH I)，v＝1532cm-1(CONH II)。1H NMR(CDCl3，ppm)：4.65(d，2H，CH2O)，4.34(d，2H，CH2O)，3.02(s，6H，NCH3)，1.52(s，3H，CH3)。13C NMR(CDCl3，ppm)：170.2，147.9，73.3，39.6，17.6。(1), preparation of 2-dimethylamido-2-methyltrimethylene carbonate: 0.21 gram of 2-imidazolecarbonyl-2-methyltrimethylene carbonate, 0.06 gram of dimethylamine and 10 ml Dichloromethane was placed in a 50 ml round bottom flask and stirred at room temperature for 12 hours. Wash with 20 ml of 5% NaHCO 3 aqueous solution and saturated brine, and dry over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to remove the solvent, and recrystallized three times with a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:3 to obtain white crystals with a yield of 78%. Through infrared (FT-IR) and nuclear magnetic resonance spectrum ( 1 H NMR and 13 C NMR) characterization analysis, it was confirmed that the white crystal was 2-dimethylamido-2-methyltrimethylene carbonate. FT-IR: v=1752cm -1 (C=O), v=1659cm -1 (CONH I), v=1532cm -1 (CONH II). 1 H NMR (CDCl 3 , ppm): 4.65 (d, 2H, CH 2 O), 4.34 (d, 2H, CH 2 O), 3.02 (s, 6H, NCH 3 ), 1.52 (s, 3H, CH 3 ). 13 C NMR (CDCl 3 , ppm): 170.2, 147.9, 73.3, 39.6, 17.6.
(2)、聚(2-二甲基酰胺基-2-甲基三亚甲基碳酸酯)的制备：将0.2克2-二甲基酰胺基-2-甲基三亚甲基碳酸酯和4毫克二氮杂二环溶于2毫升二氯甲烷中，室温下反应5小时。用50毫升正己烷沉淀，所得聚合物在40℃下真空干燥24小时，产率为77％。数均分子量为7800，多分散指数为1.28。FT-IR：v＝1753cm-1(C＝O)，v＝1657cm-1(CONH I)，v＝1531cm-1(CONH II)。1H NMR(CDCl3，ppm)：4.56-4.22(m，4H，CH2O)，3.04-2.93(br，6H，NCH3)，1.43-1.30(m，3H，CH3)。(2), preparation of poly(2-dimethylamido-2-methyltrimethylene carbonate): 0.2 gram of 2-dimethylamido-2-methyltrimethylene carbonate and 4 mg The diazabicyclo was dissolved in 2 ml of dichloromethane and reacted at room temperature for 5 hours. Precipitate with 50 ml of n-hexane, and vacuum-dry the obtained polymer at 40° C. for 24 hours, with a yield of 77%. The number average molecular weight is 7800, and the polydispersity index is 1.28. FT-IR: v=1753cm -1 (C=O), v=1657cm -1 (CONH I), v=1531cm -1 (CONH II). 1 H NMR (CDCl 3 , ppm): 4.56-4.22 (m, 4H, CH 2 O), 3.04-2.93 (br, 6H, NCH 3 ), 1.43-1.30 (m, 3H, CH 3 ).
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