CN118240194A - Application of (thio) urea/phosphazene alkali mixture, polyester and preparation method thereof - Google Patents
Application of (thio) urea/phosphazene alkali mixture, polyester and preparation method thereof Download PDFInfo
- Publication number
- CN118240194A CN118240194A CN202410503211.0A CN202410503211A CN118240194A CN 118240194 A CN118240194 A CN 118240194A CN 202410503211 A CN202410503211 A CN 202410503211A CN 118240194 A CN118240194 A CN 118240194A
- Authority
- CN
- China
- Prior art keywords
- polyester
- urea
- thio
- phosphazene
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229920000728 polyester Polymers 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- SSGGNFYQMRDXFH-UHFFFAOYSA-N sulfanylurea Chemical compound NC(=O)NS SSGGNFYQMRDXFH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003513 alkali Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002585 base Substances 0.000 claims abstract description 30
- -1 cyclic anhydride Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 25
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 239000011541 reaction mixture Substances 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 13
- 238000010790 dilution Methods 0.000 description 13
- 239000012895 dilution Substances 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000010183 spectrum analysis Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FXOSSGVJGGNASE-UHFFFAOYSA-N 1-isothiocyanato-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(N=C=S)=CC(C(F)(F)F)=C1 FXOSSGVJGGNASE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000003585 thioureas Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- PZSMLGOAJXSDMK-UHFFFAOYSA-N (1-methylimidazol-2-yl)methanamine Chemical compound CN1C=CN=C1CN PZSMLGOAJXSDMK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- NRSSOFNMWSJECS-UHFFFAOYSA-N 1-isocyanato-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(N=C=O)=CC(C(F)(F)F)=C1 NRSSOFNMWSJECS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000006978 adaptation Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
An application of (sulfur) urea/phosphazene alkali mixture and polyester and a preparation method thereof relate to the technical field of polyester synthesis, in particular to an application of (sulfur) urea/phosphazene alkali mixture and polyester and a preparation method thereof, which solve the problems of metal residue and low molecular weight of the existing polyester synthesis method. (thio) urea/phosphazene base mixtures are used for catalyzing polyester synthesis; adding (sulfur) urea, phosphazene base, cyclic anhydride and styrene oxide into a reaction container under anhydrous and anaerobic conditions to perform a reaction; after the reaction was completed, the obtained mixture was diluted with methylene chloride, and then slowly dropped into excess ethanol to precipitate a polymer, followed by filtration and drying to obtain a polyester. The invention can realize the controllable synthesis of high molecular weight polyester by the (thio) urea/phosphazene base catalyst catalyzed ring-opening copolymerization of styrene oxide and cyclic anhydride.
Description
Technical Field
The invention relates to the technical field of polyester synthesis, in particular to application of a (thio) urea/phosphazene alkali mixture, polyester and a preparation method thereof.
Background
In order to alleviate the problem of serious environmental pollution caused by difficult degradation of high molecular materials (polyolefin, etc.), development of degradable materials with low price and excellent performance has gradually become a hot spot of research. Wherein the polyester is a polymer material with degradable potential, and can be widely applied to the fields of fiber products, food packaging, biomedical devices and the like. The synthesis of degradable polyester by using cheap monomer to gradually replace refractory polymer material is a very promising strategy.
Styrene oxide is an epoxy monomer produced by the epoxidation of inexpensive raw material styrene. The polyester material with various structures and adjustable performance can be obtained through the copolymerization reaction of the polyester material and the cyclic anhydride. In addition, the existence of benzene ring side groups in the styrene oxide ensures the mechanical property and thermal property of the copolymer. However, this also results in a poor structural stability during polymerization, easy isomerization to phenylacetaldehyde and only low molecular weight (number average molecular weight: 1 to 20 kDa) polyesters. As in 2019, lv Xiaobing et al (J.Am. Chem. Soc.2019,141, 8937-8942) used a binuclear aluminum catalyst, and only low molecular weight (18.3 kDa, 1.18) copolymers could be obtained by copolymerization of styrene oxide with phthalic anhydride at room temperature. And after the polymer is synthesized by using the metal catalyst, metal residues exist in the polymer, which is unfavorable for subsequent utilization.
Disclosure of Invention
In order to solve the problems of metal residue and low molecular weight of the existing polyester synthesis method, the invention provides application of a (thio) urea/phosphazene alkali mixture, polyester and a preparation method thereof.
The invention firstly provides an application of a (sulfur) urea/phosphazene alkali mixture for catalyzing polyester synthesis;
the structural general formula of the (thio) urea is as follows:
The phosphazene base has the following structural general formula:
preferably, the (thio) urea is selected from the following structural formulas:
Preferably, the phosphazene base is selected from the following structural formulas:
the invention also provides a polyester which is prepared by taking the (sulfur) urea/phosphazene alkali mixture as a catalyst;
The number average molecular weight of the polyester is 1.12-7.67 ten thousand, and the molecular weight distribution is 1.13-1.82.
Preferably, the (thio) urea has the structural formula:
The phosphazene base has the structural formula:
The number average molecular weight of the polyester is 5.09 ten thousand to 7.67 ten thousand.
The invention also provides a preparation method of the polyester, which specifically comprises the following steps:
S1, adding (thio) urea, phosphazene base, cyclic anhydride and styrene oxide into a reaction container under anhydrous and anaerobic conditions to perform a reaction;
S2, after the reaction is finished, diluting the obtained mixture with dichloromethane, slowly dripping the diluted mixture into excessive ethanol to precipitate a polymer, and then filtering and drying to obtain the polyester.
Preferably, the cyclic anhydride is one or a mixture of at least two of phthalic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, and norbornene dianhydride.
Preferably, the mass ratio of the (thio) urea, phosphazene base, cyclic anhydride and styrene oxide is 1: 1-20: 50-10000: 100 to 20000.
Preferably, the reaction temperature of the reaction in step S1 is from 40 ℃ to 150 ℃, more preferably from 80 ℃ to 120 ℃; the reaction time is 1 to 200 hours, more preferably 2 to 60 hours.
Preferably, the drying in step S2 is preferably heating vacuum drying, and the drying time is 24 h-48 h, more preferably 36h; the drying temperature is 30 to 80 ℃, more preferably 45 ℃.
Compared with the prior art, the invention has the following specific beneficial effects:
1. The (thio) urea/phosphazene alkali mixture provided by the invention has the functions of an initiator and a catalyst, can initiate and catalyze the ring-opening copolymerization of styrene oxide and cyclic anhydride, solves the problem of poor structural stability of styrene oxide in the polymerization process, improves the reaction selectivity of styrene oxide, and can realize the controllable synthesis of high molecular weight polyester by catalyzing the ring-opening copolymerization of styrene oxide and cyclic anhydride through the (thio) urea/phosphazene alkali catalyst.
2. Compared with the use of a metal catalyst, the method provided by the invention has the advantage of no metal residue due to the use of an organic catalyst, and is beneficial to subsequent utilization.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the polyester synthesized in example 11;
FIG. 2 is a gel permeation chromatogram of the polyester synthesized in example 11.
Detailed Description
In order to make the technical solution of the present invention clearer, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention, and it should be noted that the following embodiments are only used for better understanding of the technical solution of the present invention, and should not be construed as limiting the present invention.
The sources of the styrene oxide and the cyclic anhydride are not particularly limited, and commercially available products may be used, and the present invention preferably purifies the commercially available products of styrene oxide and cyclic anhydride and then performs polymerization. In the present invention, styrene oxide serves as both the reactive monomer and the solvent in which the monomer and polymer are dissolved. The amount of the dichloromethane is not particularly limited, and the obtained polymerization reaction mixture can be fully dissolved; the amount of the ethanol is not particularly limited, and the diluted polymerization reaction mixture can be precipitated with a high yield; the method of filtration and drying is not particularly limited, and filtration and drying techniques well known to those skilled in the art may be employed.
Example 1.
1-Methyl-2-imidazolemethanamine (0.61 g,5.5 mmol), 3, 5-bis (trifluoromethyl) phenyl isocyanate (1.28 g,5 mmol) and methylene chloride (8 mL) were added to a schlenk flask under anhydrous and anaerobic conditions and stirred at room temperature for 24h. After the reaction was completed, the reaction mixture was concentrated, filtered, and recrystallized twice from ethanol/diethyl ether in 76% yield.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum analysis and test, and the result is as follows:
1H NMR(500MHz,DMSO-d6 TMS):δ9.44(s,1H),8.07(d,J＝1.6Hz,2H),7.56(s,1H),7.09(d,J＝1.3Hz,1H),6.96(t,J＝5.3Hz,1H),6.81(d,J＝1.2Hz,1H),4.37(d,J＝5.3Hz,2H),3.63(s,3H).
Successful synthesis of urea derivative C1 can be demonstrated:
Example 2.
1-Methyl-2-imidazolylmethylamine (0.61 g,5.5 mmol), 3, 5-bis (trifluoromethyl) phenyl isothiocyanate (1.36 g,5 mmol) and methylene chloride (8 mL) were added to a schlenk flask under anhydrous and anaerobic conditions and stirred at room temperature for 24h. After the reaction was completed, the reaction mixture was concentrated, filtered, and recrystallized twice from methylene chloride/diethyl ether in 83% yield.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum analysis and test, and the result is as follows:
1H NMR(500MHz,DMSO-d6,TMS):δ10.39(s,1H),8.62(s,1H),8.33(d,J＝1.7Hz,2H),7.75(s,1H),7.14(d,J＝1.2Hz,1H),6.86(s,1H),4.74(s,2H),3.65(s,3H).
It can be demonstrated that the thiourea derivative C2 was successfully synthesized:
Example 3.
Cyclohexylamine (0.55 g,5.5 mmol), 3, 5-bis (trifluoromethyl) phenyl isothiocyanate (1.36 g,5 mmol) and methylene chloride (8 mL) were added to a schlenk flask under anhydrous and anaerobic conditions and stirred at room temperature for 24h. After the reaction was completed, the reaction mixture was concentrated, filtered, and recrystallized twice from methylene chloride/diethyl ether in 89% yield.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum analysis and test, and the result is as follows:
1H NMR(500MHz,CDCl3,TMS):δ7.75(s,2H),7.72(s,1H),5.98(s,1H),4.20(s,1H),2.12-2.07(m,2H),1.74-1.70(m,2H),1.67-1.62(m,1H),1.47-1.39(m,2H),1.26-1.18(m,4H).
it can be demonstrated that the thiourea derivative C3 was successfully synthesized:
Example 4.
O-phenylenediamine (0.27 g,2.5 mmol), 3, 5-bis (trifluoromethyl) phenyl isothiocyanate (1.49 g,5.5 mmol) and tetrahydrofuran (4 mL) were added to a schlenk flask under anhydrous and anaerobic conditions and stirred at room temperature for 24h. After the reaction was completed, the reaction mixture was concentrated, filtered, and recrystallized twice from tetrahydrofuran/dichloromethane in 77% yield.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum analysis and test, and the result is as follows:
1H NMR(500MHz,DMSO-d6,TMS):δ10.02(s,2H),9.90(s,2H),8.10(s,4H),7.70(s,2H),7.49(dd,J＝5.9,3.6Hz,2H),7.39(dd,J＝6.0,3.5Hz,2H).
it can be demonstrated that the thiourea derivative C4 was successfully synthesized:
Example 5.
Cis-cyclohexanediamine (0.29 g,2.5 mmol), 3, 5-bis (trifluoromethyl) phenylisothiocyanate (1.49 g,5.5 mmol) and tetrahydrofuran (4 mL) were added to a schlenk flask under anhydrous and anaerobic conditions and stirred at room temperature for 24h. After the reaction was completed, the reaction mixture was concentrated, filtered, and recrystallized twice from tetrahydrofuran/dichloromethane in 81% yield.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum analysis and test, and the result is as follows:
1H NMR(500MHz,DMSO-d6,TMS):δ10.09(s,2H),8.28(s,4H),7.98(d,J＝6.0Hz,2H),7.72(s,2H),4.68(s,2H),1.84-1.39(m,8H).
It can be demonstrated that thiourea derivative C5 was successfully synthesized:
Example 6.
Under the anhydrous and anaerobic condition, C1 (0.02 mmol), phosphazene base P1 (0.1 mmol), phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle to react for 12 hours at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to obtain 2.52g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 1.72 ten thousand, and the molecular weight distribution was 1.13.
The catalyst C1 was changed to an equimolar amount of C2, the reaction time was changed from 12 hours to 15.5 hours, the balance was unchanged, the conversion was 99%, 2.46g of a polymer was obtained by settling, the number average molecular weight was 2.44 ten thousand, and the molecular weight distribution was 1.14.
Example 7.
Under the anhydrous and anaerobic condition, C2 (0.02 mmol), phosphazene base P1' (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle to react for 12 hours at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 2.48g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 2.21 ten thousand, and the molecular weight distribution was 1.13.
Example 8.
Under the anhydrous and anaerobic condition, C2 (0.02 mmol), phosphazene base P2 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle to react for 15.5h at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 2.55g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 3.12 ten thousand and the molecular weight distribution was 1.37.
Example 9.
Under the anhydrous and anaerobic condition, C2 (0.02 mmol), phosphazene base P2 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle to react for 60 hours at the temperature of 60 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 2.43g of polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 2.81 ten thousand, and the molecular weight distribution was 1.29.
Example 10.
C3 (0.02 mmol), phosphazene base P2 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle under the anhydrous and anaerobic condition, and the reaction is carried out for 18.5h at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 2.38g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 5.09 ten thousand and the molecular weight distribution was 1.37.
Example 11.
C3 (0.02 mmol), phosphazene base P4 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle under the anhydrous and anaerobic condition, and the reaction is carried out for 15 hours at 80 ℃; adding 5mL of dichloromethane for dilution, and taking about 0.2mL of mixed solution for 1 H NMR analysis, wherein the obtained nuclear magnetic resonance hydrogen spectrum is shown in figure 1; phthalic anhydride conversion was 99%; the reaction mixture was settled with 100mL of ethanol to give 2.45g of polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, the gel permeation chromatography is shown in fig. 2, the number average molecular weight of the copolymer is 7.67 ten thousand, and the molecular weight distribution is 1.82.
Example 12.
Under the anhydrous and anaerobic condition, C4 (0.02 mmol), phosphazene base P4 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle to react for 12 hours at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to obtain 2.53g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 3.11 ten thousand and the molecular weight distribution was 1.50.
Example 13.
C5 (0.02 mmol), phosphazene base P4 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle under the anhydrous and anaerobic condition, and the reaction is carried out for 13 hours at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to obtain 2.39g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 6.61 ten thousand and the molecular weight distribution was 1.69.
Example 14.
In the anhydrous and anaerobic condition, adding C3 (0.01 mmol), phosphazene base P4 (0.1 mmol) phthalic anhydride (10 mmol) and styrene oxide (18 mmol) into a reaction bottle for reaction at 80 ℃ for 17h; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to obtain 2.32g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 7.02 ten thousand, and the molecular weight distribution was 1.63.
Example 15.
C3 (0.01 mmol), phosphazene base P4 (0.1 mmol) succinic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle under the anhydrous and anaerobic condition, and the mixture is reacted for 30 hours at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 2.01g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 1.21 ten thousand, and the molecular weight distribution was 1.64.
Example 16.
C3 (0.01 mmol), phosphazene base P4 (0.1 mmol) maleic anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle under the anhydrous and anaerobic condition, and the mixture is reacted for 25 hours at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 1.87g of polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 1.12 ten thousand, and the molecular weight distribution was 1.68.
Example 17.
C3 (0.01 mmol), phosphazene base P4 (0.1 mmol) glutaric anhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle under the anhydrous and anaerobic condition, and the reaction is carried out for 32h at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to obtain 2.13g of a polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 1.79 ten thousand, and the molecular weight distribution was 1.70.
Example 18.
In the anhydrous and anaerobic condition, C3 (0.01 mmol), phosphazene base P4 (0.1 mmol) norbornene dianhydride (10 mmol) and styrene oxide (18 mmol) are added into a reaction bottle to react for 32h at 80 ℃; 5mL of methylene dichloride is added for dilution, about 0.2mL of mixed solution is taken for carrying out 1 H NMR analysis, and the phthalic anhydride conversion rate is 99%; the reaction mixture was settled with 100mL of ethanol to give 2.66g of polymer; the polymer obtained in this example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the obtained copolymer was 2.14 ten thousand, and the molecular weight distribution was 1.75.
From the above examples, the invention adopts (thio) urea/phosphazene base as catalyst, solves the instability problem of styrene oxide in the polymerization process, and can realize the controllable ring-opening copolymerization of low-cost monomer styrene oxide and cyclic anhydride to synthesize high molecular weight polyester.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. Use of a (thio) urea/phosphazene base mixture for catalyzing the synthesis of polyesters;
the structural general formula of the (thio) urea is as follows:
The phosphazene base has the following structural general formula:
2. Use of a (thio) urea/phosphazene base mixture according to claim 1, characterized in that the (thio) urea is selected from the following structural formulas:
3. Use of a (thio) urea/phosphazene base mixture according to claim 1, characterized in that the phosphazene base is selected from the following structural formulas:
4. a polyester, characterized in that the polyester is prepared by using a (thio) urea/phosphazene alkali mixture as a catalyst;
The number average molecular weight of the polyester is 1.12-7.67 ten thousand, and the molecular weight distribution is 1.13-1.82.
5. The polyester of claim 4, wherein the (thio) urea has the formula:
The phosphazene base has the structural formula:
The number average molecular weight of the polyester is 5.09 ten thousand to 7.67 ten thousand.
6. A process for the preparation of a polyester as claimed in claim 4 or 5, characterized in that it comprises in particular the following steps:
S1, adding (thio) urea, phosphazene base, cyclic anhydride and styrene oxide into a reaction container under anhydrous and anaerobic conditions to perform a reaction;
S2, after the reaction is finished, diluting the obtained mixture with dichloromethane, slowly dripping the diluted mixture into excessive ethanol to precipitate a polymer, and then filtering and drying to obtain the polyester.
7. The method for producing a polyester according to claim 6, wherein the cyclic anhydride is one or a mixture of at least two of phthalic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, and norbornene dianhydride.
8. The method for producing a polyester according to claim 6, wherein the mass ratio of the (thio) urea, phosphazene base, cyclic anhydride and styrene oxide is 1: 1-20: 50-10000: 100 to 20000.
9. The process for producing a polyester according to claim 6, wherein the reaction temperature in the step S1 is 40℃to 150℃and the reaction time is 1h to 200h.
10. The method for producing a polyester according to claim 6, wherein the drying time in step S2 is 24 to 48 hours and the drying temperature is 30 to 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410503211.0A CN118240194A (en) | 2024-04-25 | 2024-04-25 | Application of (thio) urea/phosphazene alkali mixture, polyester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410503211.0A CN118240194A (en) | 2024-04-25 | 2024-04-25 | Application of (thio) urea/phosphazene alkali mixture, polyester and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118240194A true CN118240194A (en) | 2024-06-25 |
Family
ID=91562345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410503211.0A Pending CN118240194A (en) | 2024-04-25 | 2024-04-25 | Application of (thio) urea/phosphazene alkali mixture, polyester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118240194A (en) |
-
2024
- 2024-04-25 CN CN202410503211.0A patent/CN118240194A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109879992B (en) | Application of para-phenyl-containing alpha-diimine nickel (II) complex in catalyzing 3-heptene chain walking polymerization | |
| CN114478635A (en) | Chromium compound, preparation method thereof and preparation method of multi-block polyester material | |
| US11905378B2 (en) | High-grafting density cyclic comb shaped polymer and preparation method therefor | |
| CN112812230B (en) | Catalytic load polymer and preparation method and application thereof | |
| CN118240194A (en) | Application of (thio) urea/phosphazene alkali mixture, polyester and preparation method thereof | |
| CN110938164B (en) | One-pot method for tandem catalytic copolymerization of ethylene and 1, 2-disubstituted polar internal olefin and product thereof | |
| CN109651955B (en) | Preparation method of acetoacetate-based modified castor oil cured coating | |
| CN111233755A (en) | Pyridine imine ligand, pyridine imine palladium complex based on pyridine imine ligand and catalytic application of pyridine imine palladium complex | |
| CN107057047B (en) | The brush polymer of method and preparation based on poly- (N- heterocycle carbine) structure self-catalysis self-initiating open loop synthesis brush polymer | |
| CN113527190B (en) | Pyridine imine ligand, pyridine imine nickel palladium complex based on ligand and application of pyridine imine nickel palladium complex in catalyzing ethylene polymerization reaction | |
| CN112876665B (en) | Method for synthesizing polyester or polyether ester containing polyunsaturated side group by using rare earth catalyst and post-modification method thereof | |
| CN108570143A (en) | A method of it is polymerize using the aluminium compound catalysis glycolide containing chiral cyclohexanediamine base | |
| CN113087659B (en) | DMAP-thiourea catalyst and preparation method thereof, and high molecular weight biodegradable polyester and preparation method thereof | |
| CN105399760B (en) | A kind of rare earth metal complex, carbon monoxide-olefin polymeric and application | |
| CN114736356A (en) | Dibenzo-dense dinaphthyl polymer photocatalyst for preparing hydrogen by photocatalytic decomposition of water and preparation method thereof | |
| CN110396207B (en) | Liquid crystal polymer organogel and preparation method thereof | |
| CN108395536B (en) | Preparation method of episulfide monomer and single-chiral polythioether with skeleton structure | |
| CN109956978B (en) | Phenanthrenequinone-based asymmetric alpha-diimine nickel catalyst and preparation method and application thereof | |
| CN104497280A (en) | Preparation method of polyglycolide | |
| Lohr et al. | Polyimidines, 7. Synthesis and the polymerization of 3‐(p‐Aminophenyl)‐3‐phenylphthalide | |
| CN115894884B (en) | Trifunctional organic catalyst and preparation method and application thereof | |
| CN116023632A (en) | Furanyl polyester compound containing olefin structure, and preparation method and application thereof | |
| CN114560829B (en) | Preparation method of macrocyclic monomer and ring-opening polymerization reaction thereof | |
| CN112876514A (en) | Complex for preparing highly branched polyethylene material and preparation method thereof | |
| CN115710284A (en) | Catalyst for synthesizing lactide from lactic acid and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication |