CN111704714B - Benzo five-membered and six-membered cyclic (thio) urea catalyst and application thereof in ring-opening polymerization - Google Patents
Benzo five-membered and six-membered cyclic (thio) urea catalyst and application thereof in ring-opening polymerization Download PDFInfo
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Abstract
The invention discloses a series of benzo five-membered and six-membered ring (sulfur) urea-containing catalysts and application thereof in ring-opening polymerization of lactone monomers. The (thio) urea catalyst prepared by the invention has synergistic effect with alkali, and catalyzes ring-opening polymerization of lactone monomers in the presence of initiator alcohol to obtain polyesters with different topological structures; without the addition of an alcohol initiator, a cyclic polyester can be obtained. According to different polymerization conditions, polyester products with adjustable structure, controllable molecular weight and narrow molecular weight distribution can be obtained. The catalyst has high catalytic efficiency, less consumption, simple synthesis, mild reaction condition and no metal residue in the product. The ring-opening polymerization method has the characteristics of simple and convenient process, low cost, high reaction rate, controllable process, narrow molecular weight distribution of the product and the like, and the bulk polymerization solution polymerization can be implemented.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a benzo five-membered and six-membered cyclic (thio) urea catalyst and application thereof in lactone ring-opening polymerization.
Background
Along with the development of economy and society and the consumption of energy sources, the development and popularization of biodegradable materials are particularly important. The environment-friendly high polymer material is mainly degradable aliphatic polyester, such as polycaprolactone, valerolactone, lactide and the like. Because of good biocompatibility, the composite material can be widely applied to various fields such as biological medicine, packaging mulching films and the like.
Polyesters are generally prepared by polycondensation of diols with diacids or ring-opening polymerization of lactone monomers. Although the application of the condensation polymerization technology has higher accessibility than the ring-opening polymerization, the ring-opening polymerization of the lactone monomer uses mild reaction conditions, the formation of small molecule byproducts can be effectively avoided, and the thermodynamic driving force of the ring-opening polymerization technology is the release of ring stress, which can overcome the unfavorable entropy in the polymerization reaction. In recent years researchers have synthesized polyesters with different topologies including linear, cyclic, star-shaped, comb-shaped, etc. In these structures, cyclic polyesters have unique properties such as higher glass transition temperatures, smaller hydrodynamic volumes, lower intrinsic viscosities, and different crystallization rates than their linear counterparts; whereas star polymers generally have lower viscosity, different thermal and mechanical properties and improved physical processability, they have unique advantages in the field of drug release.
In the last decades, ring-opening polymerization catalysts have evolved tremendously. Conventional catalysts are classified into organic catalysts and metal complex catalysts. Organic catalysts are of a wide variety and mainly comprise organic nucleophiles and organic superalkalines. The monomers are activated mainly by their nucleophilicity and basicity. The nonmetal organic catalyst has the characteristics of low cost, easy preparation, low toxicity and the like, and has good research prospect.
In recent decades, (thio) urea catalysts have been widely studied for the preparation of polyesters by ring opening polymerization, such as Macromolecules 2006,39,8574-8583; nat. Commun.2016,8,1047-1053; J.am.chem.Soc.2017,139,1645-1652; ACS Macro lett.2017,6,421-425; macromolecules 2017,50,22,8948-8954; j.am.chem.soc.2015,137,39,12506-12509; polym.chem.2016,7,6843-6853; european Polymer Journal 2019,121; macromolecules 2018,51,24,10121-10126, and the like. These systems, while having a relatively high activity, have difficulty achieving both high molecular weight and narrow distribution. Therefore, it is necessary to find a catalyst with high activity and controllable molecular weight.
Disclosure of Invention
One of the purposes of the invention is to provide a benzo five-membered and six-membered ring (sulfur) urea catalyst, which has the following structure:
among them, X, Y, A, Z may be the same or different, and is preferably a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and X-Y, Y-A, A-Z is a single bond or a double bond. R is R 1 –R 8 Is hydrogen, an electron withdrawing group, an alkyl group, or an alkoxy group; the electron withdrawing group comprises a halogen atom, trifluoromethyl and nitro; alkyl includes any C 1 –C 10 A linear or branched alkyl group of the structure; alkoxy includes any C 1 –C 10 Straight-chain alkoxy or branched alkoxy of the structure; e is oxygen or sulfur.
Preferably, R 1 、R 4 、R 5 Is a hydrogen atom; r is R 2 、R 3 Is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl, methyl, isopropyl, tert-butyl; r is R 6 、R 7 、R 8 Is trifluoromethyl, fluorine atom, chlorine atom, bromine atom, or nitro group.
Preferably, in the formula I, X, Y and A are NCC, NCN, NNN, CNN, NCO, CNC, NCS, OCO, CCC, CNC, CCO, COC or OCC respectively; x, Y, A and Z in the formula II are CCCC, CNNC, CCNN, CNCN, CCCN, OCCO or NCCN respectively.
Further, the catalyst is preferably 1- (benzo [ d ] oxazol-6-yl) -3- (3, 5-bis (trifluoromethyl) phenyl) urea, 1- (benzo [ d ] thiazol-6-yl) -3- (3, 5-bis (trifluoromethyl) phenyl) urea, 1- (1H-benzo [ d ] imidazol-6-yl) -3- (3, 5-bis (trifluoromethyl) phenyl) urea, 1- (3, 5-bis (trifluoromethyl) phenyl) -3- (1-methyl-1H-indol-5-yl) urea, 1- (3, 5-bis (trifluoromethyl) phenyl) -3- (1H-indol-5-yl) urea, 1- (benzo [ d ] [1,3] dioxa-5-yl) -3- (3, 5-bis (trifluoromethyl) phenyl) urea, 1- (3, 5-bis (trifluoromethyl) phenyl) -3- (naphthalen-2-yl) urea, 1- (3, 4-difluoro-phenyl) -3- (1-methyl-1H-indol-5-yl) urea, 1- (3, 5-bis (trifluoromethyl) phenyl) -3- (1H-indol-5-yl) urea or the like.
The invention provides a preparation method of a benzo five-membered and six-membered cyclic (thio) urea catalyst, which comprises the following steps: dissolving aminopyridine or aminopyridine containing substituent groups in purified dichloromethane, adding 3, 5-bis (trifluoromethyl) phenyl isocyanate or phenyl isocyanate containing other substituent groups, mixing with aniline containing benzo five-membered and six-membered rings in dichloromethane, tetrahydrofuran or toluene, reacting at 0-90 ℃ for 0.5-12h, separating to obtain corresponding benzo five-membered and six-membered ring (sulfur) urea catalyst, and drying to constant weight.
It is a further object of the present invention to provide the use of the above-described benzo five-membered and six-membered ring (thio) urea catalysts for catalyzing the ring opening polymerization of lactone monomers, including glycolide, lactide, butyrolactone, valerolactone, caprolactone, heptolactone, octanolide, trimethylene carbonate, pentadecanolide, preferably valerolactone, caprolactone, lactide, trimethylene carbonate.
The benzo five-membered and six-membered cyclic (thio) urea catalyst is matched with alkali to be used as a catalytic system for catalyzing the ring-opening polymerization of lactone monomers, and the specific steps are as follows:
mixing benzo five-membered and six-membered ring (sulfur) urea catalysts with 0.1-10 molar equivalents of alkali, adding monomers to carry out polymerization reaction under the condition of adding alcohol as an initiator or adding no initiator, wherein no solvent is added in the polymerization, or one or more of toluene, benzene, tetrahydrofuran and methylene dichloride are added as solvents; the molar ratio of the polymerization catalyst system, alcohol and lactone is 1:10-1:1000, the polymerization reaction temperature is 0-100 ℃, the polymerization time is 5 minutes to 10 hours, and the benzoic acid can be adopted for stopping.
The benzo five-membered and six-membered cyclic (thio) urea catalyst is matched with alkali as a catalytic system, and the alkali comprises 1,5, 7-triazidine bicyclo (4.4.0) dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD), 4-Dimethylaminopyridine (DMAP), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), chickpea alkali, potassium alkoxide and sodium alkoxide, preferably TBD, MTBD, DBU, potassium alkoxide and sodium alkoxide.
The initiator is monohydric alcohol, dihydric alcohol, trihydric alcohol and polyhydric alcohol with a C1-C10 straight chain, branched chain or cyclic structure, or benzyl alcohol and terephthalyl alcohol, and the molar ratio of the polymerization catalytic system to the alcohol is 1:0.1-1:50. The reaction is preferably toluene, tetrahydrofuran without adding solvent or solvent, and the polymerization temperature is preferably 25 ℃ or 100 ℃ (when the alcohol is a solid alcohol).
The (thio) urea catalyst prepared by the invention has synergistic effect with alkali, and catalyzes ring-opening polymerization of lactone monomers in the presence of initiator alcohol to obtain polyesters with different topological structures; without the addition of an alcohol initiator, a cyclic polyester can be obtained. According to different polymerization conditions, polyester products with adjustable structure, controllable molecular weight and narrow molecular weight distribution can be obtained. The cyclic polyester product obtained without adding the alcohol initiator has larger molecular weight, slightly wide molecular weight distribution, more difference from the theoretical molecular weight obtained by calculating the ratio of the monomer to the catalyst, the molecular weight range is within 1000-200000g & mol < -1 >, and the product structure can be distinguished by nuclear magnetism and other means.
The invention changes the structure of the (sulfur) urea catalyst by introducing benzo five-membered or six-membered rings, achieves the expected good catalytic effect, enriches the types of the urea catalyst and provides a new idea for the development of the catalysts. Meanwhile, compared with the existing urea catalyst, the catalyst dosage can quickly catalyze the valerolactone bulk ring-opening polymerization by only using the catalyst with the molar concentration of 0.25 percent relative to the monomer, has simple synthesis, high catalytic efficiency, milder reaction condition and no metal residue in the product, and the number average molecular weight of the prepared polymer can be in the range of 1000-200000g & mol -1 Within, molecular weight distribution D<1.3, simultaneously realizing the high molecular weight and narrow molecular weight distribution of the polymer, so that the polymer has wide application prospect.
Drawings
FIG. 1 shows a benzoxazolyl urea catalyst 1 H NMR spectrum;
FIG. 2 shows the results of the production of Polycaprolactone (PVL) and Polycaprolactone (PCL) 1 H NMR spectrumThe method comprises the steps of carrying out a first treatment on the surface of the (, represents deuterated chloroform)
FIG. 3 is a GPC chart of linear polyglutlactone of varying molecular weights;
FIG. 4 is a graph of linear PLA and cyclic polylactide (cylic PLA) 1 H NMR spectrum. (, represents deuterated chloroform)
Detailed description of the preferred embodiments
The technical scheme of the invention is described below by using specific examples, and the structure of the benzo five-membered or six-membered cyclic (thio) urea catalyst in the examples is as follows:
example 1
In a 50mL round bottom flask, 6-aminobenzoxazole (534 mg,4 mmol) was dissolved in 5mL purified dichloromethane and 3, 5-bis (trifluoromethyl) phenylisocyanate (0.7 mL,4.04 mmol) was added via syringe and after further reaction at room temperature for 15 minutes, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane, and the precipitate was dried in a vacuum oven to give a pale green powdery product, catalyst 1 (1.34 g, 86% conversion) in the above table, catalyst 1 H NMR is shown in FIG. 1.
FT-IR(KBr disk,cm –1 ):3313,3111,1794,1650,1559,1493,1473,1433,1386,1339,1285,1230,1129,1074,976,943,897,965,817,784,750,735,703,683,627,505,454. 1 H NMR(400MHz,DMSO-d 6 ):δ9.46(s,1H),9.28(s,1H),8.64(s,1H),8.14(s,2H),8.09(d,J＝1.6Hz,1H),7.71(d,J＝8.4Hz,1H),7.64(s,1H),7.33(dd,J 1 ＝8.4Hz,J 2 ＝1.6Hz,1H). 13 C NMR(100MHz,DMSO-d 6 ):δ153.6(N＝C),152.5(C＝O),149.8,141.8,137.2,134.8,130.7(q,J＝33Hz,Ar-C-CF 3 ),123.3(q,J＝272Hz,Ar–CF 3 ),119.9,118.1,116.5,114.5,101.3.Anal.Calcd.for C 16 H 9 F 6 N 3 O 2 (389.26):C,49.37；H,2.33；N,10.80.Found:C,48.28；H,2.36；N,10.61.
Example 2 of the embodiment
In a 50mL round bottom flask, 6-aminobenzothiazole (300 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 5-bis (trifluoromethyl) phenylisocyanate (0.35 mL,2.02 mmol) was added via syringe and after further reaction at room temperature for 20 minutes, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 2 in the table above (569 mg, conversion 70.3%).
FT-IR(KBr disk,cm –1 ):3239,2967,1681,1583,1529,1475,1443,1387,1320,1276,1240,1221,1176,1129,890,862,840,702,680. 1 H NMR(400MHz,DMSO-d 6 ):δ9.49(s,1H),9.28(s,1H),9.24(s,1H),8.41(d,J＝2.0Hz,1H),8.16(s,2H),8.01(d,J＝8.8Hz,1H),7.65(s,1H),7.52(dd,J 1 ＝8.8Hz,J 2 ＝2.4Hz,1H). 13 C NMR(100MHz,DMSO-d 6 ):δ154.4(N＝C),152.6(C＝O),148.8,141.8,136.9,134.5,130.7(q,J＝33Hz,Ar-C-CF 3 ),123.4(q,J＝272Hz,Ar–CF 3 ),123.0,118.7,118.1,114.5,111.3.Anal.Calcd.for C 16 H 9 F 6 N 3 OS(405.32):C,47.41；H,2.24；N,10.37.Found:C,47.38；H,2.27；N,10.67.
Example 3
In a 50mL round bottom flask, 5-aminobenzimidazole (266 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane, 3, 5-bis (trifluoromethyl) phenylisocyanate (0.34 mL,1.97 mmol) was added by syringe, and after continuing the reaction at room temperature for 40 minutes, an orange-red solution was first present in the flask followed by a white precipitate. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 3 in the table above (305 g, 39.3% conversion).
FT-IR(KBr disk,cm –1 ):3311,3107,1675,1570,1476,1444,1388,1348,1281,1178,1049,941,882,703,681. 1 H NMR(400MHz,DMSO-d 6 ):δ12.3(brs,1H),9.36(s,1H),8.97(s,1H),8.15(s,3H),7.86(d,J＝1.6Hz,1H),7.63(s,1H),7.52(d,J＝8.4Hz,1H),7.14(d,J＝8.4Hz,1H). 13 C NMR(101MHz,DMSO)δ152.7(C＝O),142.1(N＝C),142.0,133.7,131.2(q,J＝97Hz,Ar-C–CF 3 ),130.3,127.5,123.5(q,J＝272Hz,–CF 3 ),119.3,117.9,115.0,114.2.Anal.Calcd.for C 16 H 10 F 6 N 4 O(388.27):C,49.50；H,2.60；N,14.43.Found:C,48.66；H,3.26；N,13.56.
Example 4
In a 50mL round bottom flask, 1-methyl-5-aminoindole (284 mg,4 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 5-bis (trifluoromethyl) phenylisocyanate (0.7 mL,4.04 mmol) was added by syringe and after further reaction at room temperature for 30 minutes, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 4 in the table above (877 mg, 54.8% conversion).
FT-IR(KBr disk,cm –1 ):3312(νNH),3119(NH),1659(C＝O),1577,1475,1423,1389,1337,1275,1234,1180,1130,1056,940,880,750,710,681. 1 H NMR(400MHz,DMSO-d 6 ):δ9.31(s,1H),8.75(s,1H),8.15(s,2H),7.70(d,J＝2.0Hz,1H),7.60(s,1H),7.36(d,J＝8.4Hz,1H),7.28(d,J＝3.2Hz,1H),7.18(dd,J 1 ＝8.8Hz,J 2 ＝2.0Hz,1H),6.36(d,J＝3.2Hz,1H),3.76(s,3H). 13 C NMR(100MHz,DMSO-d 6 ):δ152.8(C＝O),142.3,133.2,130.8,130.5(q,J＝32Hz,Ar-C–CF 3 ),130.2,128.1,123.4(q,J＝272Hz,–CF 3 ),117.8,115.2,113.9,111.2,109.6,100.1,32.5(N-CH 3 ).Anal.Calcd.for C 18 H 13 F 6 N 3 O(401.31):C,53.87；H,3.27；N,10.47.Found:C,53.82；H,3.39；N,10.55.
Example 5
In a 50mL round bottom flask, 5-aminoindole (264 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 5-bis (trifluoromethyl) phenylisocyanate (0.35 mL,2.02 mmol) was added via syringe and after further reaction at room temperature for 30 min, brown precipitate appeared in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 5 in the table above (505.6 g, 65.2% conversion).
FT-IR(KBr disk,cm –1 ):3420,3323,1644,1563,1386,1283,1229,1179,1127,892,760,727,608. 1 H NMR(400MHz,DMSO-d 6 ):δ11.00(s,1H),9.31(s,1H),8.71(s,1H),8.15(s,2H),7.70(d,J＝1.5Hz,1H),7.59(s,1H),7.34(s,1H),7.32(t,J＝6.8Hz,1H),7.11(dd,J 1 ＝8.7,J 2 ＝1.9Hz,1H),6.37(s,1H). 13 C NMR(100MHz,DMSO-d 6 ):δ152.9(C＝O),142.3,130.5(q,J＝33Hz,Ar-C–CF 3 ),127.7,125.9,124.3(q,J＝272Hz,Ar–CF 3 ),117.7,115.4,113.8,111.3,111.1,101.0.Anal.Calcd.forC 17 H 11 F 6 N 3 O(387.08):C,52.72；H,2.86；N,10.85.Found:C,52.42；H,2.96；N,10.91.
Example 6
In a 50mL round bottom flask, 5-aminoindan (53 mg,4 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane, 3, 5-bis (trifluoromethyl) phenylisocyanate (0.7 mL,4.04 mmol) was added by syringe and after further reaction at room temperature for 20 minutes, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 6 (1.33 g, 85.8% conversion) in the above table.
FT-IR(KBr disk,cm –1 ):3308,3125,2959,2846,1656(C＝O),1579,1527,1476,1439,1387,1274,1231,1131,1060,929,883,877,853,832,790,680. 1 H NMR(400MHz,DMSO-d 6 ):δ9.32(s,1H),8.82(s,1H),8.12(s,2H),7.60(s,1H),7.40(s,1H),7.18–7.12(m,2H),2.85–2.78(m,4H),2.04–1.97(m,2H). 13 C NMR(100MHz,DMSO-d 6 ):δ152.5(C＝O),144.2,142.0,137.8,137.1,130.7(q,J＝33Hz,Ar-C-CF 3 ),124.2,123.3(q,J＝272Hz,Ar–CF 3 ),117.8,117.1,115.2,114.1,32.5(CH 2 ),31,7(CH 2 ),25.2(CH 2 ).Anal.Calcd.for C 18 H 14 F 6 N 2 O(388.31):C,55.68；H,3.63；N,7.21.Found:C,55.47；H,3.77；N,7.19.
Example 7
In a 50mL round bottom flask, benzo [ d ] [1,3] dioxol-5 amine (268 mg,4 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 5-bis (trifluoromethyl) phenylisocyanate (0.7 mL,4.04 mmol) was added by syringe and after further reaction at room temperature for 20 minutes, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a earthy yellow powder, catalyst 7 in the table above (1.39 g, 88.6% conversion).
FT-IR(KBr disk,cm –1 ):3290,3093,1653,1569,1502,1494,1469,1449,1389,1346,1284,1221,1177,1127,1038,939,894,857,798,704,681,632,505,404. 1 HNMR(400MHz,DMSO-d 6 ):δ9.33(s,1H,c),8.86(s,1H,d),8.11(s,2H,b),7.61(s,1H,a),7.18(d,J＝2.0Hz,1H,h),6.87–6.81(m,2H,e,f),5.98(s,2H,g). 13 C NMR(100MHz,DMSO-d 6 ):δ152.6(C＝O),147.3,142.7,142.0,133.3,130.6(q,J＝33Hz,Ar-C-CF 3 ),123.3(q,J＝272Hz,Ar–CF 3 ),117.9,114.2,112.0,108.1,101.7,101.0.Anal.Calcd.for C 16 H 10 F 6 N 2 O 3 (392.26):C,48.99；H,2.57；N,7.14.Found:C,48.77；H,2.67；N,7.19.
Example 8
In a 50mL round bottom flask, 4-aminoindole (396 mg,3 mmol) was dissolved in 5mL anhydrous and anaerobic tetrahydrofuran, 3, 5-bis (trifluoromethyl) phenylisocyanate (0.53 mL,3.07 mmol) was added with syringe, after further reaction at room temperature for 3 hours, tetrahydrofuran in the flask was distilled off, and washed three times with anhydrous and anaerobic dichloromethane, and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 8 in the above table (825 mg, conversion 71.0%).
Example 9
In a 50mL round bottom flask, 2-naphthylamine (284 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic tetrahydrofuran, 3, 5-bis (trifluoromethyl) phenyl isocyanate (0.35 mL,2.02 mmol) was added with syringe, after further reaction at room temperature for 30 min, tetrahydrofuran in the flask was distilled off and washed three times with anhydrous and anaerobic dichloromethane, and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 9 in the table above (468 mg, 58.8% conversion).
Example 10
In a 50mL round bottom flask, 7-aminoquinoline (288 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic tetrahydrofuran, 3, 5-bis (trifluoromethyl) phenylisocyanate (0.35 mL,2.02 mmol) was added with syringe, after further reaction at room temperature for 30 min, tetrahydrofuran was distilled off from the flask and washed three times with anhydrous and anaerobic dichloromethane, the precipitate was dried in a vacuum oven to give the product as a pink powder, catalyst 10 in the above table (614 mg, conversion 76.9%).
Example 11
In a 50mL round bottom flask, 1-methyl-5-aminoindole (292 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 4-difluorophenyl isocyanate (0.24 mL,2.05 mmol) was added by syringe and after a further 60 minutes of reaction at room temperature, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 11 in the table above (466 mg, 77.4% conversion).
Example 12
In a 50mL round bottom flask, 1-methyl-5-aminoindole (292 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and then white solid 3, 4-dichlorophenyl isocyanate (380 mg,2.02 mmol) was added and after a further 30 minutes of reaction at room temperature, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 12 in the table above (589 mg, 88.4% conversion).
Example 13
In a 50mL round bottom flask, 1-methyl-5-aminoindole (284 mg,4 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3-trifluoromethylbenzene isocyanate (0.57 mL,4.14 mmol) was added via syringe and the reaction was continued at room temperature for 20 minutes after which time precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 13 in the table above (141 mg, conversion 10.6%).
Example 14
In a 50mL round bottom flask, 1-methyl-5-aminoindole (284 mg,4 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and then 4-chloro-3-trifluoromethylammonium isocyanate (890 mg,4.03 mmol) was added as a yellowish solid and after a further 30 minutes at room temperature, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown gray powder, catalyst 14 in the table above (782 mg, 53.3% conversion).
Example 15
In a 50mL round bottom flask, 5-aminoindole (264 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 4-dichlorophenyl isocyanate (380 mg,2.02 mmol) was added as a white solid and after a further 60 minutes of reaction at room temperature a brown precipitate appeared in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 15 in the table above (392 mg, conversion 61.4%)
Example 16
In a 50mL round bottom flask, 5-aminoindole (264 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 4-chloro-3-trifluoromethylammonium isocyanate (445 mg,2.01 mmol) was added as a yellowish solid and after a further 60 minutes of reaction at room temperature a brown precipitate appeared in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane, and the precipitate was dried in a vacuum oven to give the product as a brown powder, catalyst 16 (567 mg, 80.2% conversion) in the above table
EXAMPLE 17
In a 50mL round bottom flask, 6-aminobenzoxazole (534 mg,4 mmol) was dissolved in 5mL purified dichloromethane and 3, 5-bis (trifluoromethyl) phenyl isothiocyanate (0.75 mL,4.10 mmol) was added via syringe and after further reaction at room temperature for 5 days, precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 17 in the table above (234 mg, 14.4% conversion).
EXAMPLE 18
In a 50mL round bottom flask, 6-aminobenzothiazole (300 mg,2 mmol) was dissolved in 5mL anhydrous and anaerobic dichloromethane and 3, 5-bis (trifluoromethyl) phenyl isothiocyanate (0.38 mL,2.08 mmol) was added via syringe and the reaction was continued at room temperature for 24 hours after which time precipitation occurred in the flask. The crude product was obtained after filtration and washed three times with anhydrous and anaerobic dichloromethane and the precipitate was dried in a vacuum oven to give the product as a white powder, catalyst 18 in the table above (569 mg, 67.6% conversion).
The polymerization reaction in the technical scheme is described with further reference to specific examples, which are given below,
example 19
In a Schlenk flask, 21.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 45.7. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 10 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and vacuum-dried to constant weight to obtain the final product. Of polymers 1 H NMR is shown in the lower black line of FIG. 2, GPC curveAs shown by the solid black line on the right side of fig. 3.
Example 20
In a Schlenk flask, 22.4mg of catalyst 2 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react for 10 minutes at 25℃and complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product.
Example 21
In a Schlenk flask, 21.4mg of catalyst 3 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 40 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product.
Example 22
In a Schlenk flask, 22.1mg of catalyst 4 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to be 25℃for 17 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, and then the mixture was precipitated twice with cold anhydrous methanol and dried under vacuum to constant weight to obtain the final product.
Example 23
In a Schlenk flask, 21.4mg of catalyst 5 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react for 37 minutes at 25℃and complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product.
Example 24
In a Schlenk flask, 21.4mg of catalyst 6 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react for 10 minutes at 25℃and complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product.
Example 25
In a Schlenk flask, 21.6mg of catalyst 7 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 12 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product.
Example 26
In a Schlenk flask, 21.4mg of catalyst 8 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the reaction was carried out at 25℃for 40 minutes, it was observed that complete stirring in the Schlenk flask was stopped, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product.
Example 27
In a Schlenk flask, 21.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 22.8. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react for 10 minutes at 25℃and complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product. GPC curves are shown as the second dashed line on the right side of FIG. 3.
Example 28
In a Schlenk flask, 21.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 11.4. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 12 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and vacuum-dried to constant weight to obtain the final product. (conv=96%,GPC curves are shown as the third dashed line on the right side of FIG. 3.
Example 29
In a Schlenk flask, 21.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD and 7.6. Mu.l of benzyl alcohol were added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 15 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then the mixture was precipitated twice with cold anhydrous methanol, and dried under vacuum to constant weight to obtain the final product. GPC curves are shown as the fourth dashed line on the right side of FIG. 3.
Example 30
In a Schlenk flask, 107.4mg of catalyst 4 was added, nitrogen was replaced three times by vacuum, 39.6. Mu.l of MTBD and 5.7. Mu.l of benzyl alcohol were added, then 5ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 60 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, and then the mixture was precipitated twice with cold anhydrous methanol and dried under vacuum to constant weight to obtain the final product.
Example 31
In a Schlenk flask, 19.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 4.1. Mu.l of benzyl alcohol was added, then 1ml of anhydrous anaerobic toluene and 0.18ml of delta-VL were added by syringe, after stirring well, 7.2. Mu.l of MTBD was added and reacted at 25℃for 1 hour, and the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution. And then precipitating with cold anhydrous methanol twice, and vacuum drying to constant weight to obtain the finished product.
Example 32
In a Schlenk flask, 19.5mg of catalyst 1 is added, nitrogen is replaced by vacuum pumping for three times, 4.1 mu l of benzyl alcohol is added, then 1ml of anhydrous and anaerobic tetrahydrofuran and 0.18ml of delta-VL are added by a syringe, 7.2 mu l of MTBD is added after being stirred uniformly to react for 1 hour at 25 ℃, excessive benzoic acid/methylene dichloride solution is added to terminate the reaction, then cold anhydrous methanol is used for precipitation twice, and vacuum drying is carried out until the weight is constant, thus obtaining the finished product.
Example 33
In a Schlenk flask, 21.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD was added, then 2ml of delta-VL was added by syringe, the temperature was controlled at 25℃for 30 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then precipitated twice with cold anhydrous methanol, and vacuum dried to constant weight to obtain the final product. (conv=97%,
example 34
In a Schlenk flask, 17.2mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 6.3. Mu.l of MTBD was added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 180 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then precipitated twice with cold anhydrous methanol, and vacuum dried to constant weight to obtain the final product.
Example 35
In a Schlenk flask, 21.5mg of catalyst 1 was added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD was added, then 5ml of delta-VL was added by syringe, the temperature was controlled to react at 25℃for 360 minutes, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution, then precipitated twice with cold anhydrous methanol, and vacuum dried to constant weight to obtain the final product.
Example 36
In a Schlenk flask, 21.5mg of catalyst 1 and 30.5mg of terephthalyl alcohol were added, nitrogen was replaced three times by vacuum, 7.92. Mu.l of MTBD was added, then 2ml of delta-VL was added by syringe, the temperature was controlled to react for 10 minutes at 25 ℃, complete agglomeration in the Schlenk flask was observed, the reaction was terminated by adding an excessive amount of benzoic acid/methylene chloride solution, then the reaction was precipitated twice with cold anhydrous methanol, and vacuum-dried to constant weight, thus obtaining a finished product.
Example 37
In a Schlenk flask, 21.5mg of catalyst 1, 30.5mg of 1, 1-trimethylolpropane is added, nitrogen is replaced three times by vacuum pumping, 7.92. Mu.l of MTBD is added, then 2ml of delta-VL is added by a syringe, the temperature is controlled to be 25 ℃ for reaction for 15 minutes, complete agglomeration in the Schlenk flask can be observed, an excessive amount of benzoic acid/dichloromethane solution is added to terminate the reaction, then the reaction is carried out twice by precipitation with cold absolute methanol, and the reaction product is obtained after vacuum drying to constant weight.
Example 38
In a Schlenk flask, 21.5mg of catalyst 1, 33.6mg of xylitol were added and the flask was evacuatedAnd (3) replacing nitrogen three times by air, adding 7.92 mu l of MTBD, adding 2ml of delta-VL by using a syringe, controlling the temperature to react at 100 ℃ for 15 minutes, observing that stirring of the magneton in a Schlenk bottle is stopped, adding an excessive benzoic acid/dichloromethane solution to stop the reaction, then precipitating twice by using cold absolute methanol, and drying in vacuum until the weight is constant, thus obtaining the finished product.
Example 39
In a Schlenk flask, 35.1mg of catalyst 1 was added, nitrogen was purged three times with vacuum, 13.0. Mu.l of MTBD, 37.4. Mu.l of benzyl alcohol was added, then 2ml of ε -CL was added by syringe, the temperature was controlled to 25℃for 40 minutes, complete agglomeration in the Schlenk flask was observed, and the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution.Of polymers 1 H NMR is shown in the upper line of FIG. 2 +.>
Example 40
In a Schlenk flask, 13.5mg of catalyst 1 and 1g of L-LA were added, nitrogen was replaced three times by vacuum, 14.4. Mu.l of benzyl alcohol and 3.5ml of anhydrous anaerobic tetrahydrofuran were added, the temperature was controlled at 25℃and 5.0. Mu.l of MTBD was added to react for 15 minutes, complete agglomeration in the Schlenk flask was observed, and the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution.Of polymers 1 H NMR is shown in the upper line of FIG. 4
Example 41
In a Schlenk flask, 54.0mg of catalyst 1 and 1g of L-LA were added, the nitrogen was purged three times with vacuum, 3.5ml of anhydrous and anaerobic tetrahydrofuran was added, the temperature was controlled at 25℃and 9.95. Mu.l of MTBD was added to react for 10 minutes, and complete agglomeration in the Schlenk flask was observed, and the reaction was terminated by adding an excess of benzoic acid/methylene chloride solution.Of polymers 1 H NMR is shown in the lower line of fig. 4. Therefore, the (thio) urea catalyst prepared by the invention has synergistic effect with alkali, and catalyzes ring-opening polymerization of lactone monomers in the presence of initiator alcohol to obtain polyesters with different topological structures; without the addition of an alcohol initiator, a cyclic polyester can be obtained. />
Claims (5)
1. The application of the benzo five-membered ring urea catalyst is characterized in that the benzo five-membered ring urea catalyst is applied to catalyzing ring opening polymerization of lactone monomers, wherein the lactone monomers comprise glycolide, lactide, butyrolactone, valerolactone, caprolactone, heptolactone, octanol, trimethylene carbonate and pentadecanol;
the method comprises the following steps: mixing the benzo five-membered ring urea catalyst with alkali with the molar ratio of 0.1-10 equivalent, adding lactone monomers to carry out polymerization reaction under the condition of adding alcohol as an initiator or not adding the alcohol initiator, wherein no solvent is added in the polymerization, or one or more solvents of toluene, benzene, tetrahydrofuran and methylene dichloride are added; the temperature range of the polymerization reaction is 0-100 ℃, the polymerization time is 5 minutes to 10 hours, and the polymerization reaction is stopped by adopting benzoic acid;
the structural formula of the benzo five-membered ring urea catalyst is selected from any structural formula shown in formulas 1-8:
2. use according to claim 1, wherein the base is 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, sparteine, potassium or sodium alkoxide.
3. The use according to claim 1, wherein the alcohol is C 1 –C 10 Monohydric, polyhydric, or benzyl, terephthalyl alcohols of linear, branched or cyclic structure.
4. The use according to claim 1, wherein the polymerization process is bulk polymerization, solution polymerization; the bulk polymerization is carried out without adding solvent, and the solvent for solution polymerization is toluene or tetrahydrofuran.
5. The use according to claim 1, wherein the polymerization temperature is 100 ℃ when the alcohol is a solid alcohol.
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| 硫脲亚锡催化δ-戊内酯及ε-己内酯可控开环聚合研究;郭畅;唐定良;陈永福;李健;陶峻;;化学工程与装备(第07期);第32-37页 * |
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