CN118165241A - Method for preparing polyester from alkylene oxide and cyclic anhydride - Google Patents
Method for preparing polyester from alkylene oxide and cyclic anhydride Download PDFInfo
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- CN118165241A CN118165241A CN202410592934.2A CN202410592934A CN118165241A CN 118165241 A CN118165241 A CN 118165241A CN 202410592934 A CN202410592934 A CN 202410592934A CN 118165241 A CN118165241 A CN 118165241A
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- -1 cyclic anhydride Chemical class 0.000 title claims abstract description 81
- 229920000728 polyester Polymers 0.000 title claims abstract description 58
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 12
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 64
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 64
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 55
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 47
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 21
- 239000007983 Tris buffer Substances 0.000 claims description 17
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 7
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229940014800 succinic anhydride Drugs 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 86
- 238000007334 copolymerization reaction Methods 0.000 abstract description 28
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 238000012512 characterization method Methods 0.000 description 35
- 238000001228 spectrum Methods 0.000 description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 34
- 229910052739 hydrogen Inorganic materials 0.000 description 34
- 239000001257 hydrogen Substances 0.000 description 34
- 238000009826 distribution Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 18
- 239000012295 chemical reaction liquid Substances 0.000 description 17
- 238000005227 gel permeation chromatography Methods 0.000 description 17
- 238000010791 quenching Methods 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 14
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 10
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012649 alternating ring-opening copolymerization Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of micromolecular copolymerization, and particularly relates to a method for preparing polyester by taking alkylene oxide and cyclic anhydride as raw materials. The invention discloses a method for preparing polyester from alkylene oxide and cyclic anhydride, which uses triphenol functionalized quaternary ammonium salt as a catalyst to catalyze the copolymerization of the alkylene oxide and the cyclic anhydride to form a polymer in an organic solvent under the heating condition of 80-120 ℃. The quaternary ammonium salts have high catalytic activity, can realize complete conversion of cyclic anhydride in polymerization reaction, and can obtain the polymer with the highest polyester selectivity of more than 99%. The method has the advantages of simple reaction operation, high yield and selectivity of the obtained polymer, and the like, and the obtained polymer avoids the problem of metal residue existing in the prior metal catalyst.
Description
Technical Field
The invention belongs to the technical field of small molecule copolymerization, and particularly relates to a method for preparing polyester from alkylene oxide and cyclic anhydride.
Background
The polyester is a polymer material with biodegradability and has wide application in the fields of daily necessities, medical equipment and the like. In the conventional method for preparing polyester, on one hand, the polyester is prepared by polycondensation reaction of dihydric alcohol and dibasic acid, the reaction conditions are severe, and small molecules are continuously removed in the polymerization process, so that the atom economy is low. On the other hand, the ring-opening polymerization reaction of the lactone is utilized to form the polymer, and the method has the advantages of better atom economy, relatively mild and controllable reaction, relatively higher preparation cost of the reaction monomer, more complex synthesis steps and limited types. In contrast, the polyester prepared by using the alternating ring-opening copolymerization (ROCOP) of the alkylene oxide and the cyclic anhydride has good atom economy, and the reaction monomers are rich in types, low in cost and easy to obtain, and the polyester with different structures can be prepared by combining different anhydrides and alkylene oxides, so that the performance of the obtained polyester can be more flexibly adjusted. Therefore, ring-opening copolymerization of alkylene oxide with a cyclic anhydride has been attracting attention in recent years.
The ring-opening copolymerization of alkylene oxide and cyclic anhydride is divided into two catalytic systems: metal catalyst systems and organic catalyst systems, wherein the metal complex catalyst system starts earlier. It has been reported in the literature that metal complexes of zinc, manganese, aluminum, chromium, cobalt and the like can catalyze ring-opening copolymerization of alkylene oxide with cyclic anhydride and can effectively inhibit isomerization, transesterification, homo-polymerization of alkylene oxide and the like side reactions during polymerization, which promotes production of industrial polyesters (refer to Longo, j.m., sanford, m.j., coatings, g.w., chem. Rev. 2016, 116, 24, 15167-15197.). However, in a system using a metal complex as a catalyst, the problem of metal residue in the obtained polymer is difficult to solve, and the application of polyester in the fields of biological medicine, food and the like is hindered.
In recent years, the application of organic catalytic systems to the copolymerization of cyclic anhydrides with alkylene oxides has been attracting attention in order to avoid the problem of metal residues on the polymers. In 2017, the foreign subject group reported that organic bases such as Dimethylaminopyridine (DMAP), di (triphenylphosphine) ammonium chloride (PPNCl), triphenylphosphine (PPh 3) and the like can catalyze ring-opening copolymerization of Phthalic Anhydride (PA) and cyclohexene oxide (CHO) in toluene solution at 110 ℃ to obtain an alternately copolymerized polyester. The most effective catalyst is di (triphenylphosphine) ammonium chloride (PPNCl), the reaction is carried out at 110 ℃ for 10 h, the conversion rate of the alkylene oxide can reach 90%, and the molecular weight distribution of the obtained polyester is narrowBut 2% of polyether mer is present in the resulting polymer (cf. Eur. Polym. J. 2017, 88, 433-447.).
The group of Wu Anpeng problems in 2021 has screened a series of organoboron compounds for catalyzing the copolymerization of alkylene oxide with cyclic anhydride, and the TOF value can reach 915 h -1 at the highest temperature of 180 ℃. By optimizing the reaction conditions of the ring-opening polymerization, a polyester having a narrow molecular weight distribution (1.10 to 1.40) and an average molecular weight of up to 94.5 kDa can be obtained (refer to : Xie, R., Zhang, Y. Y., Yang, G. W., Zhu, X. F., Li, B., Wu, G. P., Angew. Chem. Int. Ed. 2021, 60, 19253-19261.）.
Therefore, the organic catalyst has great development potential for catalyzing the copolymerization of the cyclic anhydride and the alkylene oxide, has low development cost and can realize the high-efficiency organic catalyst for catalyzing the copolymerization of the alkylene oxide and the cyclic anhydride to form high-selectivity polyester under relatively mild conditions.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing polyester by using an organic compound as a catalyst. The invention adopts N, N, N-trimethyl-N ' -N ' ' - (2-amino ethyl) -1, 2-ethylenediamine bridged tri (2-hydroxy-3, 5-di-tert-butylphenyl) quaternary ammonium salt as a catalyst, and can catalyze the copolymerization of alkylene oxide and cyclic anhydride to form polyester at the temperature of 80-120 ℃. The system has relatively mild reaction condition, high catalytic activity of the catalyst and high selectivity of polyester in the obtained polymer. Toluene is used as a solvent to react for 1 hour at 100 ℃, so that the polymerization of epoxy chloropropane and phthalic anhydride into poly-chloro-propyl phthalate is catalyzed, the conversion rate of the anhydride is up to 91%, and the selectivity of polyester in the obtained product is up to 99%, thus having good potential application value.
In order to solve the technical problems, the application provides the following technical scheme:
The invention discloses a method for preparing polyester (formula I) from alkylene oxide and cyclic anhydride, which takes triphenol functionalized quaternary ammonium salt (formula II) as a catalyst and catalyzes the copolymerization of the alkylene oxide and the cyclic anhydride to form a polymer in an organic solvent under the heating condition of 80-120 ℃. The quaternary ammonium salts have high catalytic activity, can realize complete conversion of cyclic anhydride in polymerization reaction, and can obtain the polymer with the highest polyester selectivity of more than 99%.
；
Wherein R 1 is a hydrogen atom; r 2 is one of methyl, chloromethylene and ethyl; x - is chloride (Cl - ), bromide (Br -), iodide (I -) or methylsulfonate (MeSO 3 -).
The present invention provides a process for preparing polyesters from alkylene oxides and cyclic anhydrides comprising the steps of:
Mixing cyclic anhydride, alkylene oxide and a catalyst in an organic solvent, and heating for reaction to obtain high-selectivity polyester;
The catalyst is selected from the group consisting of triphenol functionalized quaternary ammonium salts.
Preferably, the triphenol functionalized quaternary ammonium salt is selected from N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) quaternary ammonium salt, and the structural formula is shown as (formula III).
；
Wherein X - is selected from one of chloride ion, bromide ion, iodide ion or methylsulfonate ion.
Preferably, the molar ratio of the catalyst to the cyclic anhydride is 1:50-200.
Preferably, the molar ratio of the catalyst to the alkylene oxide is from 1:100 to 400.
Preferably, the organic solvent is toluene, hexane or cyclohexane.
Preferably, the temperature of the heating reaction is 80-120 ℃.
Further, the temperature of the heating reaction is specifically any value between two values.
Preferably, the heating reaction is carried out for a period of time ranging from 1 to 6 h.
Further, the time of the heating reaction is specifically any value between two values.
Preferably, the cyclic anhydride is selected from one of Phthalic Anhydride (PA), maleic Anhydride (MA), succinic Anhydride (SA) and Glutaric Anhydride (GA).
Preferably, the alkylene oxide is one of Epichlorohydrin (ECH), propylene Oxide (PO) and Butylene Oxide (BO).
The invention also provides a high selectivity polyester prepared by the method for preparing polyester from alkylene oxide and cyclic anhydride.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention discloses an application of a simple and easy-to-obtain triphenol functionalized quaternary ammonium salt in catalyzing copolymerization of alkylene oxide and cyclic anhydride into polyester, wherein a catalyst in the system is an organic matter, no metal ion exists, and the residue of metal ion in the obtained polymer is avoided; the activity of the catalyst is high; the reaction condition is mild; high conversion rate of anhydride and high selectivity of polyester in the obtained polymer.
In the invention, under the condition of heating, the catalyst catalyzes the copolymerization of the alkylene oxide and the cyclic anhydride, after the reaction is finished, the reaction is quenched by methylene dichloride, the dissolved product is added with ethanol to settle out the polymer, and the white polymer is obtained after filtration and drying.
Drawings
FIG. 1 is a Mass Spectrometry (MS) spectrum of poly (ECH-alt-PA) MALDI-TOF; wherein the method comprises the steps of m/z = 240.64*n (ECH-alt-PA) + 22.99 (Na+) + 95.13 (MeSO3 -) + 1.01 (H+).
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
This example provides that ammonium N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin (molar ratio catalyst [ Cat. ]: phthalic anhydride [ PA ]: epichlorohydrin [ ECH ] = 1:50:100) at 80 ℃ to form poly (ECH-alt-PA) chlorophthalic acid.
Firstly, 0.20 mL epichlorohydrin (2.5 mmol) and 0.25 toluene (mL) are weighed by a liquid-transferring gun and added into a pressure-resistant bottle, and then 0.185 g (1.25 mmol) phthalic anhydride and 2-diamino-bridged tri (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methane sulfonate (22.4 mg) (0.025 mmol) of the catalyst N, N, N-trimethyl-N ' -N ' ' - (2-amino ethyl) -1, 2-diamino-are weighed by an analytical balance and added into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 80℃for reaction for 4 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 82%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the selectivity of the polyester in the polymer is more than 99%. The number average molecular weight of the polymer was 1.4 kDa and the molecular weight distribution was 1.50 as determined by gel permeation chromatography.
Example 2
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:50:100) at 80℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.20 mL epichlorohydrin (2.5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.185 g phthalic anhydride (1.25 mmol) and a catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate (22.4 mg) (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 80℃for reaction for 5 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is more than 99%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 1.8 kDa and the molecular weight distribution was 1.40 as determined by gel permeation chromatography.
Example 3
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:50:100) at 70℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.20 mL epichlorohydrin (2.5 mmol) and 0.25 mL N-hexane are weighed into a pressure-resistant bottle, then 0.185 g phthalic anhydride (1.25 mmol) and the catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 70℃for reaction for 5 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 68%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 1.5 kDa and the molecular weight distribution was 1.45 as determined by gel permeation chromatography.
Example 4
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:50:100) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.20 mL epichlorohydrin (2.5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.185 g phthalic anhydride (1.25 mmol) and a catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate (22.4 mg) (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for 3 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is more than 99%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 4.7 kDa and the molecular weight distribution was 1.39 as determined by gel permeation chromatography.
Example 5
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:50:100) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.20 mL epichlorohydrin (2.5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.185 g phthalic anhydride (1.25 mmol) and a catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate (22.4 mg) (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 1 hour. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 91%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 4.3 kDa and the molecular weight distribution was 1.26 as determined by gel permeation chromatography.
Example 6
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:100:100) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.39 mL epichlorohydrin (5 mmol) and 0.5mL toluene are weighed into a pressure-resistant bottle, and then 0.74 g phthalic anhydride (5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methanesulfonate 44.8 mg (0.05 mmol) are weighed into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 1 hour. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 63%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 2.3 kDa and the molecular weight distribution was 1.26 as determined by gel permeation chromatography.
Example 7
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium chloride catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:100:100) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.39 mL epichlorohydrin (5 mmol) and 0.5 mL toluene are weighed into a pressure-resistant bottle, and then 0.74 g phthalic anhydride (5 mmol) and a catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-based bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium chloride 41.8 mg (0.05 mmol) are weighed into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 1 hour. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid, and carrying out nuclear magnetic resonance hydrogen spectrum characterization to determine that the phthalic anhydride conversion rate is 29%. Then adding dichloromethane into the reaction system to quench the reaction, and then adding ethanol to precipitate out the polymer. And (5) drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 2.1 kDa and the molecular weight distribution was 1.18 as determined by gel permeation chromatography.
Example 8
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium bromide catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:100:100) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.39 mL epichlorohydrin (5 mmol) and 0.5 toluene mL are weighed into a pressure-resistant bottle, and then 0.74 g phthalic anhydride (5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium bromide 44.0 mg (0.05 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 1 hour. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 60%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 1.8 kDa and the molecular weight distribution was 1.16 as determined by gel permeation chromatography.
Example 9
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium iodide catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:100:100) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.39 mL epichlorohydrin (5 mmol) and 0.5 toluene mL are weighed and added into a pressure-resistant bottle, then 0.74 g phthalic anhydride (5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-amino ethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium iodide 46.4 mg (0.05 mmol) are weighed by an analytical balance and added into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 1 hour. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 39%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 1.9 kDa and the molecular weight distribution was 1.19 as determined by gel permeation chromatography.
Example 10
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:100:200) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.39 mL epichlorohydrin (5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.37 g phthalic anhydride (2.5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 4 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is more than 99%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the selectivity of polyester in the polymer is more than 99%. The number average molecular weight of the polymer was 5.3 kDa as measured by gel permeation chromatography and the molecular weight distribution was 1.35. Characterization of the polymer by matrix assisted laser Desorption ionization time of flight (MALDI-TOF) mass spectrometry (as shown in FIG. 1) shows that the resulting polymers are all polymers in which the two monomers of phthalic anhydride and epichlorohydrin are completely and alternately copolymerized by the methanesulfonic acid anion.
Example 11
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and epichlorohydrin ([ Cat. ]: [ PA ]: [ ECH ] = 1:200:400) at 100℃to form poly (ECH-alt-PA) chloropropionate.
Firstly, 0.78 mL epichlorohydrin (10 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.74 g phthalic anhydride (5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 6 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is more than 99%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 6.1 kDa and the molecular weight distribution was 1.40 as determined by gel permeation chromatography.
Example 12
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and propylene oxide ([ Cat. ]: [ PA ]: [ PO ] = 1:200:200) at 80℃to form poly (PO-alt-PA).
Firstly, 0.31 mL propylene oxide (5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.74 g phthalic anhydride (5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 80℃for reaction for 8 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 78%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. The obtained polymer was subjected to nuclear magnetic hydrogen spectrum characterization, and the polyester selectivity in the polymer was found to be 82%. The number average molecular weight of the polymer was 1.7 kDa and the molecular weight distribution was 1.15 as determined by gel permeation chromatography.
Example 13
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and propylene oxide ([ Cat. ]: [ PA ]: [ PO ] = 1:200:200) at 80℃to form poly (ECH-alt-PA).
Firstly, 0.31 mL propylene oxide (5 mmol) and 0.25 mL cyclohexane are weighed into a pressure-resistant bottle, and then 0.74 g phthalic anhydride (5 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 80℃for reaction for 8 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the phthalic anhydride conversion rate is 80%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. The obtained polymer was subjected to nuclear magnetic hydrogen spectrum characterization, and the polyester selectivity in the polymer was found to be 78%. The number average molecular weight of the polymer was 1.9 kDa and the molecular weight distribution was 1.17 as determined by gel permeation chromatography.
Example 14
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of maleic anhydride and epichlorohydrin ([ Cat. ]: [ MA ]: [ ECH ] = 1:50:100) at 100℃to form poly (ECH-alt-MA) chloropropylmaleate.
Firstly, 0.2 mL epichlorohydrin (2.5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.123 g maleic anhydride (1.25 mmol) and 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate ammonium 22.4 mg (0.025 mmol) which is a catalyst are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 1 hour. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the conversion rate of the maleic anhydride is 70%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 2.1 kDa and the molecular weight distribution was 1.25 as determined by gel permeation chromatography.
Example 15
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of succinic anhydride and epichlorohydrin ([ Cat. ]: [ SA ]: [ ECH ] = 1:50:100) at 100℃to form poly (ECH-alt-SA).
Firstly, 0.2 mL epichlorohydrin (2.5 mmol) and 0.25 toluene (mL) are weighed into a pressure-resistant bottle, then 0.125 g succinic anhydride (1.25 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-amino ethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate (22.4 mg) (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 6 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the succinic anhydride conversion rate is more than 99%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 2.2 kDa and the molecular weight distribution was 1.64 as determined by gel permeation chromatography.
Example 16
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of glutaric anhydride and epichlorohydrin ([ Cat. ]: [ GA ]: [ ECH ] = 1:50:100) at 100℃to form poly (ECH-alt-GA) chloropropyl glutarate.
Firstly, 0.39 mL epichlorohydrin (2.5 mmol) and 0.25 mL toluene are weighed into a pressure-resistant bottle, and then 0.143 g glutaric anhydride (1.25 mmol) and catalyst N, N, N-trimethyl-N ' -N ' ' - (2-amino ethyl) -1, 2-ethylenediamine bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle by an analytical balance. Then, the pressure-resistant bottle was placed in an oil bath at 100℃for reaction for 4 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid for nuclear magnetic hydrogen spectrum characterization, and measuring that the conversion rate of glutaric anhydride is 83%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 3.2 kDa and the molecular weight distribution was 1.53 as determined by gel permeation chromatography.
Example 17
This example provides that N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged ammonium tris (2-hydroxy-3, 5-di-tert-butylphenyl) methylsulfonate catalyzes the copolymerization of phthalic anhydride and butylene oxide ([ Cat. ]: [ PA ]: [ BO ] = 1:200:200) at 120℃to form polybutylphthalate poly (BO-alt-PA).
Firstly, 0.44 mL of butylene oxide (5 mmol) and 0.25 mL of toluene are weighed into a pressure-resistant bottle, and then 0.729 g of phthalic anhydride (5 mmol) and the catalyst N, N, N-trimethyl-N ' -N ' ' - (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) ammonium methylsulfonate 22.4 mg (0.025 mmol) are weighed into the same pressure-resistant bottle. Then, the pressure-resistant bottle was placed in an oil bath at 120℃for reaction for 5 hours. And taking down the pressure-resistant bottle after the reaction is finished, taking a small amount of reaction liquid, and carrying out nuclear magnetic hydrogen spectrum characterization to measure that the phthalic anhydride conversion rate is more than 99%. Then adding dichloromethane into the reaction system to quench the reaction, then adding ethanol to precipitate out polymer, and drying. And (3) carrying out nuclear magnetic hydrogen spectrum characterization on the obtained polymer, and measuring that the polyester selectivity in the polymer is more than 99%. The number average molecular weight of the polymer was 3.5 kDa and the molecular weight distribution was 1.13 as determined by gel permeation chromatography.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A process for preparing a polyester from an alkylene oxide and a cyclic anhydride, comprising the steps of:
Mixing cyclic anhydride, alkylene oxide and a catalyst in an organic solvent, and performing ring-opening polymerization at 80-120 ℃ to obtain high-selectivity polyester; the catalyst is selected from the group consisting of triphenol functionalized quaternary ammonium salts.
2. The method of making a polyester from an alkylene oxide and a cyclic anhydride of claim 1, wherein the triphenolic functionalized quaternary ammonium salt is selected from the group consisting of N, N-trimethyl-N' -N "- (2-aminoethyl) -1, 2-ethylenediamine-bridged tris (2-hydroxy-3, 5-di-tert-butylphenyl) quaternary ammonium salts having the following structural formula:
；
Wherein X - is selected from chloride, bromide, iodide or methylsulfonate ion.
3. The method of producing a polyester from an alkylene oxide and a cyclic anhydride according to claim 1, wherein the molar ratio of catalyst to cyclic anhydride is 1:50-200.
4. The method of producing a polyester from alkylene oxide and cyclic anhydride of claim 1, wherein the molar ratio of catalyst to alkylene oxide is 1:100-400.
5. The method of producing a polyester from an alkylene oxide and a cyclic anhydride according to claim 1, wherein the organic solvent is toluene, n-hexane or cyclohexane.
6. The method of producing a polyester from an alkylene oxide and a cyclic anhydride according to claim 1, wherein the temperature of the ring-opening polymerization reaction is 80 to 120 ℃.
7. The method of producing a polyester from an alkylene oxide and a cyclic anhydride according to claim 1, wherein the ring-opening polymerization reaction is carried out for a period of 1 to 6 h.
8. The method of producing a polyester from an alkylene oxide and a cyclic anhydride according to claim 1, wherein the cyclic anhydride is selected from one of phthalic anhydride, maleic anhydride, succinic anhydride, and glutaric anhydride.
9. The method of producing a polyester from an alkylene oxide and a cyclic anhydride according to claim 1, wherein the alkylene oxide is one of epichlorohydrin, propylene oxide and butylene oxide.
10. A high selectivity polyester prepared according to the process of any one of claims 1-9 from an alkylene oxide and a cyclic anhydride.
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