CN115536825A - Copolymerization method of anhydride and epoxy catalyzed by fluorine catalyst - Google Patents
Copolymerization method of anhydride and epoxy catalyzed by fluorine catalyst Download PDFInfo
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- CN115536825A CN115536825A CN202211425207.4A CN202211425207A CN115536825A CN 115536825 A CN115536825 A CN 115536825A CN 202211425207 A CN202211425207 A CN 202211425207A CN 115536825 A CN115536825 A CN 115536825A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 37
- 239000004593 Epoxy Substances 0.000 title claims abstract description 35
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 10
- 239000011737 fluorine Substances 0.000 title claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 123
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 5
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims abstract 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 45
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 26
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 26
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 26
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 26
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 15
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- RIIUAPMWDSRBSH-UHFFFAOYSA-N 1,4-oxathiane-2,6-dione Chemical compound O=C1CSCC(=O)O1 RIIUAPMWDSRBSH-UHFFFAOYSA-N 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 6
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 6
- 229940014800 succinic anhydride Drugs 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 2
- -1 epoxide compound Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 74
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 93
- 239000000203 mixture Substances 0.000 description 89
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 60
- 239000004793 Polystyrene Substances 0.000 description 24
- 238000005227 gel permeation chromatography Methods 0.000 description 24
- 229920002223 polystyrene Polymers 0.000 description 24
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- LEMVWTIKPGFBSF-UHFFFAOYSA-N CCCCC1=CC(=C(C(=C1CCCC)CCCC)CCCC)N(C2=CC=CC=C2)C3=C(C(=CC=C3)F)F Chemical compound CCCCC1=CC(=C(C(=C1CCCC)CCCC)CCCC)N(C2=CC=CC=C2)C3=C(C(=CC=C3)F)F LEMVWTIKPGFBSF-UHFFFAOYSA-N 0.000 description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 12
- 238000012648 alternating copolymerization Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- OPYHNLNYCRZOGY-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-iodobenzene Chemical compound FC1=C(F)C(F)=C(I)C(F)=C1F OPYHNLNYCRZOGY-UHFFFAOYSA-N 0.000 description 1
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a copolymerization method of anhydride and epoxy catalyzed by a fluorine catalyst, which comprises the following steps: carrying out alternate copolymerization reaction on anhydride and an epoxy compound under the action of a catalyst to obtain polyester; the catalyst is one or two of tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate. The application provides a synthetic method for polyester polymer by taking a nonmetal catalyst as a catalyst; the yield of the polyester synthesized by the synthesis method can reach 99%.
Description
Technical Field
The invention relates to the technical field of catalyst and polyester synthesis, in particular to a copolymerization method of anhydride and epoxy catalyzed by a fluorine catalyst.
Background
Polyester polymers are biodegradable materials and have wide applications in packaging materials, biomedical and pharmaceutical industries.
The polyester can be obtained by a method of catalyzing ring-opening polymerization of lactone or lactide, and can also be obtained by alternating copolymerization of anhydride and epoxy. Most of common catalysts for catalyzing alternating copolymerization of anhydride and epoxy are metal-containing catalysts, but the residual metal in polyester polymers and the toxicity of part of metal are still problems to be solved urgently, so that the development of non-metallic organic catalysts for catalyzing the reactions has important significance.
Disclosure of Invention
The invention aims to provide a copolymerization method of anhydride and epoxy catalyzed by a fluorine catalyst, which has high polyester yield and no metal residue.
In view of the above, the present application provides a method for copolymerization of anhydride and epoxy catalyzed by a fluorine catalyst, comprising:
carrying out alternate copolymerization reaction on anhydride and an epoxy compound under the action of a catalyst to obtain polyester;
the catalyst is one or two of tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate.
Preferably, the raw materials for the copolymerization reaction further comprise an initiator.
Preferably, the initiator is selected from benzyl alcohol.
Preferably, the anhydride is selected from phthalic anhydride, succinic anhydride, glutaric anhydride or thiodiglycolic anhydride.
Preferably, the epoxy compound is selected from one or more of cyclohexene oxide, propylene oxide, butylene oxide and styrene oxide.
Preferably, the epoxy compound is selected from cyclohexene oxide and styrene oxide, the anhydride is phthalic anhydride, and the catalyst is selected from tetrabutylammonium difluorotriphenylsilicate.
Preferably, the molar ratio of the acid anhydride, the cyclohexene oxide and the styrene oxide is 1: (100-150), and the copolymerization reaction is carried out at 100-120 ℃ for 2-6 h.
Preferably, the molar ratio of the acid anhydride to the epoxy compound is 1: (2-10), wherein the molar ratio of the catalyst to the acid anhydride is 1: (100-10000), the temperature of the copolymerization reaction is 50-150 ℃, and the time is 0.25-24 h.
Preferably, the molar ratio of the initiator to the anhydride is 1: (80 to 120).
The application provides a copolymerization method of anhydride and epoxy catalyzed by a fluorine catalyst, which comprises the steps of carrying out alternate copolymerization reaction on anhydride and an epoxy compound under the action of the catalyst to obtain polyester; the catalyst is selected from tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate. One or two of tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate are used as catalysts for the alternating copolymerization reaction of anhydride and epoxy compound, so that the yield of the polyester is high and can reach 99% at most, and the residue of toxic metal is avoided.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the problem that the catalyst for alternating copolymerization of anhydride and epoxy in the prior art is easy to have metal residue, the method adopts the specific fluorine-containing catalyst to catalyze the alternating polymerization of anhydride and epoxy, so that the yield of the obtained polyester is high, and no metal residue exists. Specifically, the embodiment of the invention discloses a copolymerization method of anhydride and epoxy catalyzed by a fluorine catalyst, which comprises the following steps:
carrying out alternate copolymerization reaction on anhydride and an epoxy compound under the action of a catalyst to obtain polyester;
the catalyst is one or two of tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate.
In the application, the tetrabutylammonium fluoride and/or tetrabutylammonium difluorotriphenylsilicate are both organic catalysts, wherein the tetrabutylammonium fluoride has a structure shown in a formula (I);
the tetrabutyl difluorotriphenylammonium silicate has a structure shown in a formula (II), and the compound can be obtained by reacting tetrabutyl ammonium fluoride with triphenyl silanol and hydrofluoric acid;
the tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate described herein are commercially available products or prepared according to the existing methods, and there is no particular limitation in this application.
In the above process for preparing polyester, an initiator may be further included, and the initiator is specifically selected from one or two of benzyl alcohol and p-xylylene glycol.
In the present application, the anhydride is selected from phthalic anhydride, succinic anhydride, glutaric anhydride or thiodiglycolic anhydride; the epoxy compound is selected from one or more of cyclohexene oxide, propylene oxide, butylene oxide and styrene oxide, and the epoxy compound can be one, two or three. When two epoxy compounds are used, they are in particular chosen from cyclohexene oxide and styrene oxide, the anhydride is phthalic anhydride and the catalyst is chosen from tetrabutylammonium difluorotriphenylsilicate; illustratively, the molar ratio of the anhydride, the cyclohexene oxide, and the styrene oxide is 1.25; the molar ratio of the catalyst to the anhydride is 1: (100-150), wherein the copolymerization reaction is carried out at the temperature of 100-120 ℃ for 2-6 h; more specifically, the molar ratio of the catalyst to the anhydride is 1.
According to the invention, the molar ratio of the acid anhydride to the epoxy compound is 1: (2-10), specifically, the molar ratio of the acid anhydride to the epoxy compound is 1 (3-8), more specifically, the molar ratio of the acid anhydride to the epoxy compound is 1:3, 1:4, 1: 5. 1:6, 1:7, 1:8, 1:9, or 1. The molar ratio of the catalyst to the anhydride is 1: (100 to 10000), specifically, the molar ratio of the catalyst to the acid anhydride is 1: (300 to 8000), more specifically, the molar ratio of the catalyst to the acid anhydride is 1: 4000. 1. The temperature of the copolymerization reaction is 50-150 ℃, and the time is 0.25-24 h; specifically, the temperature of the copolymerization reaction is 60-120 ℃, and the time is 1-18 h. The molar ratio of the initiator to the anhydride is 1: (80-120), more specifically, the molar ratio of the initiator to the acid anhydride is 1: (90-100).
The anhydride should be purified by recrystallization and the epoxy should be purified by distillation. After the alternating copolymerization reaction is finished, the obtained alternating copolymerization reaction product is preferably dissolved by adopting dichloromethane, excessive ethanol is added to precipitate a polymer, and the polymer is filtered and dried to obtain the polyester. The present invention does not specifically limit the amount of dichloromethane used, and the obtained reaction product can be dissolved. The method of filtration and drying is not particularly limited in the present invention, and a technical scheme of filtration and drying well known to those skilled in the art may be adopted. In the present invention, the drying is preferably vacuum drying, and the drying time is preferably 24 hours.
The invention provides tetrabutylammonium fluoride and/or tetrabutylammonium difluorotriphenylsilicate as a catalyst for catalyzing the alternating copolymerization reaction of anhydride and epoxy, and the yield of the synthesized polyester can reach 99%.
For further understanding of the present invention, the copolymerization method of anhydride and epoxy catalyzed by the fluoro catalyst provided by the present invention is described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
The starting materials used in the following examples are all generally commercially available.
Example 1
10.0mmol of recrystallized phthalic anhydride, 100.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutylammonium fluoride are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 1h at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, the polymer is precipitated by excessive ethanol, and the obtained mixture is filtered and dried for 24h in vacuum to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 7.7 kg.
Example 2
10.0mmol of recrystallized phthalic anhydride, 100.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate were mixed under anhydrous and oxygen-free conditions, the obtained mixture was stirred at 120 ℃ for reaction for 1 hour, 10mL of methylene chloride was added to the obtained mixture to dissolve a polymer, and an excessive amount of ethanol was added thereto to precipitate the polymer, which was then filtered and vacuum-dried for 24 hours, to obtain a polyester.
The yield of the polyester weighed by the invention is 99%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 9.9 kg.
Example 3
10.0mmol of recrystallized phthalic anhydride, 100.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutylammonium fluoride are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 1h at 100 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the mixture to precipitate the polymer, and the polymer is filtered and dried for 24h in vacuum to obtain the polyester.
The yield of the polyester weighed by the invention was 45%.
Example 4
10.0mmol of recrystallized phthalic anhydride, 100.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate were mixed under anhydrous and oxygen-free conditions, the obtained mixture was stirred at 100 ℃ for reaction for 1 hour, 10mL of methylene chloride was added to the obtained mixture to dissolve a polymer, and an excessive amount of ethanol was added thereto to precipitate the polymer, which was then filtered and vacuum-dried for 24 hours, to obtain a polyester.
The yield of the polyester weighed by the invention was 87%.
Example 5
10.0mmol of recrystallized phthalic anhydride, 100.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutylammonium fluoride are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 0.5h at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24h to obtain the polyester.
The yield of the polyester weighed by the invention was 68%.
Example 6
10.0mmol of recrystallized phthalic anhydride, 100.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate were mixed under anhydrous and oxygen-free conditions, the obtained mixture was stirred at 120 ℃ for reaction for 0.5h, 10mL of dichloromethane was added to the obtained mixture to dissolve a polymer, an excessive amount of ethanol was added thereto to precipitate the polymer, and the polymer was filtered and vacuum-dried for 24h to obtain a polyester.
The yield of the polyester weighed by the invention was 84%.
Example 7
100.0mmol of recrystallized phthalic anhydride, 1000.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate were mixed under anhydrous and oxygen-free conditions, the resulting mixture was stirred at 120 ℃ for reaction for 24 hours, 10mL of methylene chloride was added to the resulting mixture to dissolve a polymer, and an excess amount of ethanol was added thereto to precipitate the polymer, which was then filtered and vacuum-dried for 24 hours, to obtain a polyester.
The yield of the polyester weighed by the invention is 98 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 2.0 ten thousand.
Example 8
50.0mmol of recrystallized phthalic anhydride, 500.0mmol of distilled cyclohexene oxide and 0.1mmol of ammonium tetrabutylfluoride are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 24 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, the polymer is precipitated by excessive ethanol, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.9 ten thousand.
Example 9
10.0mmol of recrystallized phthalic anhydride, 20.0mmol of distilled cyclohexene oxide and 0.1mmol of ammonium tetrabutyl fluoride are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 1h at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, the polymer is precipitated by excessive ethanol, and the obtained mixture is filtered and dried for 24h in vacuum to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 7.3 kg.
Example 10
10.0mmol of recrystallized phthalic anhydride, 20.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate were mixed under anhydrous and oxygen-free conditions, the obtained mixture was stirred at 120 ℃ for reaction for 1 hour, 10mL of methylene chloride was added to the obtained mixture to dissolve a polymer, and an excessive amount of ethanol was added thereto to precipitate the polymer, which was then filtered and vacuum-dried for 24 hours, to obtain a polyester.
The yield of the polyester weighed by the invention is 98 percent;
the polyester obtained in the embodiment is analyzed by gel permeation chromatography with polystyrene as a standard substance, and the number average molecular weight of the obtained polyester is 1.4 ten thousand.
Example 11
20.0mmol of recrystallized phthalic anhydride, 40.0mmol of distilled cyclohexene oxide and 0.01mmol of tetrabutyl difluorotriphenylammonium silicate are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 16h at 120 ℃, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried for 24h in vacuum to obtain the polyester.
The yield of the polyester weighed by the invention is 98 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 3.9 ten thousand.
Example 12
20.0mmol of recrystallized phthalic anhydride, 40.0mmol of distilled cyclohexene oxide and 0.002mmol of tetrabutyl difluorotriphenylammonium silicate are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the mixture to precipitate the polymer, and the polymer is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.6 ten thousand.
Example 13
20.0mmol of recrystallized phthalic anhydride, 40.0mmol of distilled cyclohexene oxide, 0.2mmol of tetrabutyl difluorotriphenylammonium silicate and 0.01mmol of terephthalyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 120 ℃ for reaction for 24 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 2.2 ten thousand.
Example 14
10.0mmol of recrystallized phthalic anhydride, 50.0mmol of distilled propylene oxide, 0.1mmol of tetrabutyl difluorotriphenylammonium silicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 4 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.5 ten thousand.
Example 15
10.0mmol of recrystallized phthalic anhydride, 50.0mmol of distilled butylene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol were mixed under anhydrous and oxygen-free conditions, the resulting mixture was stirred at 120 ℃ for reaction for 4 hours, 10mL of methylene chloride was added to the resulting mixture to dissolve a polymer, and then an excess amount of ethanol was added thereto to precipitate the polymer, which was filtered and vacuum-dried for 24 hours, to obtain a polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.6 ten thousand.
Example 16
10.0mmol of recrystallized succinic anhydride, 20.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 4h at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24h to obtain the polyester.
The yield of the polyester weighed by the invention is 99%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 2.1 kg.
Example 17
10.0mmol of recrystallized succinic anhydride, 50.0mmol of distilled propylene oxide, 0.1mmol of tetrabutyl difluorotriphenylammonium silicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 4 hours, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the mixture to precipitate the polymer, and the polymer is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 4.6 kg.
Example 18
10.0mmol of recrystallized succinic anhydride, 50.0mmol of distilled butylene oxide, 0.1mmol of tetrabutyl difluorotriphenylammonium silicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 4 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 7.1 kg.
Example 19
10.0mmol of recrystallized glutaric anhydride, 20.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 4h at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24h to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.2 ten thousand.
Example 20
10.0mmol of recrystallized glutaric anhydride, 50.0mmol of distilled propylene oxide, 0.1mmol of tetrabutyl difluorotriphenylammonium silicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 4 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 8.9 kg.
Example 21
10.0mmol of recrystallized glutaric anhydride, 50.0mmol of distilled butylene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 4h, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24h to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 7.9 kg.
Example 22
10.0mmol of recrystallized thiodiglycolic anhydride, 20.0mmol of distilled cyclohexene oxide and 0.1mmol of tetrabutyl difluorotriphenylammonium silicate are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 4 hours at 120 ℃, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried for 24 hours in vacuum to obtain the polyester.
The yield of the polyester weighed by the invention is 99%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 4.1 kg.
Example 23
10.0mmol of recrystallized thiodiglycolic anhydride, 50.0mmol of distilled propylene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 120 ℃ for reaction for 4 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 3.0 kg.
Example 24
10.0mmol of recrystallized thiodiglycolic anhydride, 50.0mmol of distilled butylene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 120 ℃ for reaction for 4 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 5.7 kg.
Example 25
10.0mmol of recrystallized phthalic anhydride, 50.0mmol of distilled styrene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 120 ℃ for reaction for 24 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 91%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a polyester having a number average molecular weight of 4.6 kg.
Example 26
10.0mmol of recrystallized phthalic anhydride, 50.0mmol of distilled styrene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 120 ℃ for reaction for 1h, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24h to obtain the polyester.
The yield of the polyester weighed by the invention was 80%.
Example 27
20.0mmol of recrystallized phthalic anhydride, 40.0mmol of distilled styrene oxide, 0.2mmol of tetrabutylammonium difluorotriphenylsilicate and 0.01mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 170 ℃ for reaction for 12 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 99 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.3 ten thousand.
Example 28
20.0mmol of recrystallized phthalic anhydride, 40.0mmol of distilled styrene oxide, 0.2mmol of tetrabutylammonium difluorotriphenylsilicate and 0.01mmol of terephthalyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 24 hours, 10mL of dichloromethane is added to the obtained mixture to dissolve a polymer, excessive ethanol is added to the obtained mixture to precipitate the polymer, and the obtained mixture is filtered and dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 91%;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 2.0 ten thousand.
Example 29
10.0mmol of recrystallized phthalic anhydride, 12.5mmol of distilled cyclohexene oxide, 12.5mmol of distilled styrene oxide, 0.1mmol of tetrabutylammonium difluorotriphenylsilicate and 0.1mmol of benzyl alcohol are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted at 120 ℃ for 4 hours, 10mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added to precipitate the polymer, the polymer is filtered, and the mixture is dried in vacuum for 24 hours to obtain the polyester.
The yield of the polyester weighed by the invention is 95 percent;
the polyester obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polyester was 1.0 ten thousand.
As can be seen from the above examples, the present invention provides the use of tetrabutylammonium fluoride and/or tetrabutylammonium difluorotriphenylsilicate as a catalyst for catalyzing the alternating copolymerization of an anhydride and an epoxy; tetrabutylammonium fluoride and/or tetrabutylammonium difluorotriphenylsilicate are/is used as a catalyst to catalyze the alternating copolymerization reaction of the acid anhydride and the epoxy. The yield of the synthesized polymer can reach 99%.
Comparative example 1
As in example 1, the only difference is: replacing tetrabutylammonium fluoride with tetrabutylammonium chloride; the results show that the yield of the synthesized polymer is only 9%.
Comparative example 2
As in example 1, the only difference is: replacing tetrabutylammonium fluoride with tetrabutylammonium bromide; the results showed that the yield of the synthesized polymer was only 4%.
Comparative example 3
As in example 1, the only difference is: replacing tetrabutylammonium fluoride with tetrabutylammonium iodide; the results showed that the yield of the synthesized polymer was only 2%.
Comparative example 4
As in example 1, the only difference is: replacing tetrabutylammonium fluoride with pentafluoroiodobenzene; the results showed that the yield of the synthesized polymer was only 4%.
Comparative example 5
As in example 1, the only difference is: replacing tetrabutylammonium fluoride with pentafluorobenzene; the results showed that the yield of the synthesized polymer was only 3%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A method for copolymerization of anhydride and epoxy catalyzed by a fluorine catalyst, comprising:
carrying out alternate copolymerization reaction on anhydride and an epoxy compound under the action of a catalyst to obtain polyester;
the catalyst is selected from one or two of tetrabutylammonium fluoride and tetrabutylammonium difluorotriphenylsilicate.
2. The copolymerization process of claim 1, wherein the starting materials for the copolymerization reaction further comprise an initiator.
3. The copolymerization process of claim 2, wherein the initiator is selected from benzyl alcohol.
4. The copolymerization process according to claim 1 or 2, characterized in that the anhydride is chosen from phthalic anhydride, succinic anhydride, glutaric anhydride or thiodiglycolic anhydride.
5. The copolymerization process of claim 1 or 2, wherein the epoxide compound is selected from one or more of cyclohexene oxide, propylene oxide, butylene oxide and styrene oxide.
6. The copolymerization process of claim 5, wherein the epoxy compound is selected from cyclohexene oxide and styrene oxide, the anhydride is phthalic anhydride, and the catalyst is selected from tetrabutylammonium difluorotriphenylsilicate.
7. The copolymerization process of claim 6, wherein the molar ratio of the anhydride, cyclohexene oxide and styrene oxide is 1.25: (100-150), and the copolymerization reaction is carried out at the temperature of 100-120 ℃ for 2-6 h.
8. The copolymerization process according to claim 1 or 2, wherein the molar ratio of the acid anhydride to the epoxy compound is 1: (2-10), wherein the molar ratio of the catalyst to the acid anhydride is 1: (100-10000), the temperature of the copolymerization reaction is 50-150 ℃, and the time is 0.25-24 h.
9. The copolymerization process according to claim 2 or 3, wherein the molar ratio between the initiator and the anhydride is 1: (80-120).
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