CN106518836A - Benzylethanolamine trimethylene carbonate and preparation method and application thereof - Google Patents

Abstract

The present invention provides a monomer material benzyl ethanolamine trimethylene carbonate capable of synthesizing biodegradable polycarbonate. The benzyl ethanolamine trimethylene carbonate is a white crystal with C ₁₅ H ₁₉ NO ₅ and a molecular weight of 293 . The synthetic route of the substance is as follows: starting from 2,2-dimethylolpropionic acid, through condensation reaction and ring-closing reaction, a new six-membered cyclic carbonate monomer, benzyl ethanolamine trimethylene carbonate, is prepared. This substance can be used to synthesize functionalized polycarbonate materials, because its side chain contains benzyl ethanolamine, it can be used to prepare polycarbonate with hydroxyl groups in the side chains, and further combine with a series of compounds with carboxyl groups, acid chloride groups and isocyanate groups The reaction is carried out to realize the modification of the physical, chemical and biological properties of polycarbonate. Moreover, the raw material of the invention is cheap, has wide sources, simple preparation method and high application value.

Description

Benzyl ethanolamine trimethylene carbonate and its preparation method and use

technical field

The invention provides a biodegradable polycarbonate compound and its preparation method and application, especially relates to benzyl ethanolamine trimethylene carbonate and belongs to the field of biomedical materials.

Background technique

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.

Contents of the invention

The invention provides a monomer material benzyl ethanolamine trimethylene carbonate capable of synthesizing biodegradable polycarbonate, the structural formula of which is:

The above-mentioned benzyl ethanolamine trimethylene carbonate is a white crystal with a molecular formula of C ₁₅ H ₁₉ NO ₅ and a molecular weight of 293.

The present invention also provides a preparation method of the material, comprising the following steps: (1) dissolving 2,2-dimethylolpropionic acid and benzyl ethanolamine in tetrahydrofuran, adding a condensation reagent, and reacting at room temperature for 10 to 14 hours , to obtain benzyl ethanolamine modified 1,3-propanediol; (2) then benzyl ethanolamine modified 1,3-propanediol and ethyl chloroformate take triethylamine as catalyst, and take tetrahydrofuran as solvent, react at room temperature for 1～ After 3 hours, benzyl ethanolamine trimethylene carbonate was obtained after recrystallization and purification.

The condensation reagent described in step (1) is N, N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, or 1-ethyl-(3-dimethylaminopropyl) carbodiimide Amine hydrochloride and 1-hydroxybenzotriazole.

The solvent used for recrystallization in step (2) is a mixed solution of tetrahydrofuran and ether.

The solvent used for recrystallization in step (2) is a solution of tetrahydrofuran and diethyl ether mixed in a volume ratio of 1:3.

The benzyl ethanolamine trimethylene carbonate provided by the present invention can be used for synthesizing functionalized polycarbonate material, because benzyl ethanolamine is contained on its side chain, can be used for preparing the polycarbonate of side chain band hydroxyl, and further and A series of compounds with carboxyl group, acid chloride group and isocyanate group react to realize the modification of physical, chemical and biological properties of polycarbonate. Moreover, the raw material of the invention is cheap, has wide sources, simple preparation method and high application value.

Description of drawings

Fig. 1 is the structural formula of benzyl ethanolamine trimethylene carbonate provided by the present invention;

Figure 2 is a synthetic route diagram of benzyl ethanolamine trimethylene carbonate provided by the present invention.

detailed description

The benzyl ethanolamine trimethylene carbonate provided in the examples of the present invention has a structural formula as shown in Figure 1, and the synthetic route of the substance is shown in Figure 2: starting from 2,2-dimethylolpropionic acid, through A new six-membered cyclic carbonate monomer, benzyl ethanolamine trimethylene carbonate, was prepared through condensation reaction and ring closure reaction. Below in conjunction with specific embodiment this above-mentioned synthesis method is described in detail:

Example 1

The synthetic steps adopted in the present embodiment are as follows:

(1), preparation of 1,3-propanediol modified by benzyl ethanolamine: 9.78 grams of 2,2-dimethylolpropionic acid, 11.02 grams of benzyl ethanolamine, 15.04 grams of N,N'-dicyclohexylcarbodiethylene Amine, 0.89 g of 4-dimethylaminopyridine and 40 ml of anhydrous tetrahydrofuran were placed in a 100 ml round bottom flask and stirred at room temperature for 12 hours. Concentrate to remove the solvent, add 40 ml of ethyl acetate, wash with 40 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 ethyl acetate and petroleum ether at a volume ratio of 1:1 to obtain a white solid with a yield of 78%. Infrared (FT-IR): v=1748cm ^-1 (OH), v=1655cm ^-1 (CONH I), v=1533cm ^-1 (CONH II). Proton nuclear magnetic resonance spectrum ( ¹ H NMR) (CDCl ₃ , ppm): 7.33 (s, 5H, Ph), 4.77 (s, 2H, PhCH ₂ ), 3.66 (s, 4H, CH ₂ OH), 3.56 (t, 2H, CH2O), 3.24 (t, 2H, _CH2N ), 1.27 (s, 3H, _{CH3 )} .

(2), preparation of benzyl ethanolamine trimethylene carbonate: 2.7 grams of benzyl ethanolamine modified 1,3-propylene glycol, 2.4 grams of ethyl chloroformate and 30 milliliters of anhydrous tetrahydrofuran were placed in a 50 milliliter round bottom flask, After stirring in an ice bath, 1.2 g of triethylamine was added dropwise, and the addition was completed in about 10 minutes. Remove the ice bath and react at room temperature for 2 hours. After filtration, the filtrate was concentrated and excess anhydrous ether was added to precipitate white crystals, which were recrystallized three times with a mixed solvent of tetrahydrofuran and anhydrous ether at a volume ratio of 1:2 to obtain white crystals with a yield of 48%. Characterization and analysis by infrared (FT-IR), nuclear magnetic resonance ( ¹ H NMR and ¹³ C NMR) and elemental analysis (EA) confirmed that the white crystal was benzyl ethanolamine trimethylene carbonate. FT-IR: v=1752cm ^-1 (C=O), v=1664cm ^-1 (CONH I), v=1525cm ^-1 (CONH II). ¹ H NMR (CDCl ₃ , ppm): 7.33 (s, 5H, Ph), 4.75 (s, 2H, PhCH ₂ ), 4.51 (d, 2H, CH ₂ O), 4.26 (d, 2H, CH ₂ O) , 3.61 (t, 2H, CH2O), 3.25 (t, 2H, _CH2N ), 1.26 (s, 3H, _{CH3 )} . ¹³ C NMR (CDCl ₃ , ppm): 177.4, 152.3, 137.6, 128.4, 127.6, 80.2, 72.3, 69.3, 41.3, 33.8, 21.2. C ₁₅ H ₁₉ NO ₅ 293.13: Calad. C 61.42, H 6.53, N 4.78; Found C 63.46, H 6.86, N 5.32.

Example 2

The synthetic steps adopted in the present embodiment are as follows:

(1), preparation of 1,3-propanediol modified by benzyl ethanolamine: 9.78 grams of 2,2-dimethylol propionic acid, 11.02 grams of benzyl ethanolamine, 14.04 grams of 1-ethyl-(3-dimethyl Aminopropyl) carbodiimide hydrochloride, 9.92 g of 1-hydroxybenzotriazole and 40 ml of anhydrous tetrahydrofuran were placed in a 100 ml round bottom flask, and stirred at room temperature for 12 hours. Concentrate to remove the solvent, add 40 ml of ethyl acetate, wash with 40 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 ethyl acetate and petroleum ether at a volume ratio of 1:1 to obtain a white solid with a yield of 81%. 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.

(2), preparation of benzyl ethanolamine trimethylene carbonate: 2.7 grams of benzyl ethanolamine modified 1,3-propylene glycol, 2.4 grams of ethyl chloroformate and 30 milliliters of anhydrous tetrahydrofuran were placed in a 50 milliliter round bottom flask, After stirring in an ice bath, 1.2 g of triethylamine was added dropwise, and the addition was completed in about 10 minutes. Remove the ice bath and react at room temperature for 2 hours. After filtration, the filtrate was concentrated and excess anhydrous ether was added to precipitate white crystals, which were recrystallized three times with a mixed solvent of tetrahydrofuran and anhydrous ether at a volume ratio of 1:3 to obtain white crystals with a yield of 64%. 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.

Example 3

Polymerize the benzyl ethanolamine trimethylene carbonate prepared in the above examples to obtain a biodegradable polycarbonate material. The preparation method is as follows: 0.586 g of benzyl ethanolamine trimethylene carbonate and 4.6 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 96.7%. The number average molecular weight is 9500, and the polydispersity index is 1.22. FT-IR: v = 1751 cm ^-1 (C=O), v = 1652 cm ^-1 (CONH I), v = 1535 cm ^-1 (CONH II). ¹ H NMR (CDCl ₃ , ppm): 7.35 (s, 5H, Ph), 4.72 (s, 2H, PhCH ₂ ), 4.48-4.22 (m, 4H, CH ₂ O), 3.58-3.28 (m, 4H, _CH2 ), 1.25 (s, 3H, _CH3 ).

The polycarbonate material with benzyl ethanolamine in the side chain synthesized in this example can further react with a series of compounds with carboxyl, acyl chloride and isocyanate groups because of the hydroxyl group in its side chain, so as to realize the physical properties of polycarbonate. , Modification of chemical and biological properties.

Claims (6)

1. benzyl ethyl alcohol amine trimethylene carbonate, its structural formula is：

2. the preparation method of the benzyl ethyl alcohol amine trimethylene carbonate described in claim 1, it is characterised in that including following step Suddenly：(1) 2,2- dihydromethyl propionic acids and benzyl ethyl alcohol amine are dissolved in tetrahydrofuran, add condensation reagent, react at room temperature 10～14 hours, obtain the amine-modified 1,3-PD of benzyl ethyl alcohol；(2) then the amine-modified 1,3-PD of benzyl ethyl alcohol and Ethyl chloroformate, is reacted 1～3 hour, after recrystallization purifying with triethylamine as catalyst at room temperature with tetrahydrofuran as solvent Obtain benzyl ethyl alcohol amine trimethylene carbonate.

3. the preparation method of benzyl ethyl alcohol amine trimethylene carbonate according to claim 2, it is characterised in that：Step (1) condensation reagent described in is N, N '-dicyclohexylcarbodiimide and DMAP, or 1- ethyls-(3- diformazans Base aminopropyl) carbodiimide hydrochloride and I-hydroxybenzotriazole.

4. the preparation method of benzyl ethyl alcohol amine trimethylene carbonate according to claim 2, it is characterised in that：Step (2) in, recrystallization solvent used is the mixed solution of tetrahydrofuran and ether.

5. the preparation method of benzyl ethyl alcohol amine trimethylene carbonate according to claim 4, it is characterised in that：Step (2) in, recrystallization solvent used is tetrahydrofuran and ether according to 1：The mixed solution of 3 volume ratios.

6. the purposes of the benzyl ethyl alcohol amine trimethylene carbonate described in claim 1, it is characterised in that：For complex functionality Merlon.