CN109438708B - Preparation method of aliphatic polythioester - Google Patents
Preparation method of aliphatic polythioester Download PDFInfo
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- CN109438708B CN109438708B CN201811179125.XA CN201811179125A CN109438708B CN 109438708 B CN109438708 B CN 109438708B CN 201811179125 A CN201811179125 A CN 201811179125A CN 109438708 B CN109438708 B CN 109438708B
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- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 4
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- -1 episulfide alkane Chemical class 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- AAOBUKZEIBZRBI-UHFFFAOYSA-M bis(triphenyl-$l^{5}-phosphanylidene)azanium;acetate Chemical compound CC([O-])=O.C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)=[N+]=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AAOBUKZEIBZRBI-UHFFFAOYSA-M 0.000 claims description 4
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 claims description 4
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 claims description 4
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 claims description 2
- ZLDFDNYLNPWFMC-UHFFFAOYSA-M bis(triphenyl-$l^{5}-phosphanylidene)azanium;bromide Chemical compound [Br-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)=[N+]=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZLDFDNYLNPWFMC-UHFFFAOYSA-M 0.000 claims description 2
- RJUUALNPKZFLIR-UHFFFAOYSA-M bis(triphenyl-$l^{5}-phosphanylidene)azanium;fluoride Chemical compound [F-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)=[N+]=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 RJUUALNPKZFLIR-UHFFFAOYSA-M 0.000 claims description 2
- WGGOEDWXZSTQEE-UHFFFAOYSA-M bis(triphenyl-$l^{5}-phosphanylidene)azanium;iodide Chemical compound [I-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)=[N+]=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WGGOEDWXZSTQEE-UHFFFAOYSA-M 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 28
- 239000012043 crude product Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 238000000746 purification Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- LVRCYPYRKNAAMX-UHFFFAOYSA-M bis(triphenylphosphine)iminium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)N=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LVRCYPYRKNAAMX-UHFFFAOYSA-M 0.000 description 7
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical group [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/26—Polythioesters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of aliphatic polythioester. The cyclic sulfane and aliphatic thioanhydride are used as raw materials, quaternary ammonium salt is used as an initiator, and the cyclic sulfane and aliphatic thioanhydride are subjected to bulk polymerization or solution polymerization reaction at the temperature of 0-120 ℃ for 0.1-24 hours. The method has the advantages of accurately adjustable polymer structure, multiple product types, simple and easily-operated polymerization method and the like, and the generated aliphatic polythioester has good thermal stability and refractive index and has potential application in the field of special optical materials.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of aliphatic polythioester.
Background
Polythioesters are polymers similar in structure to polyesters, i.e., heterochain polymers in which the oxygen atoms of the ester groups in the polyester backbone are replaced by sulfur atoms. The sulfur atoms introduced into the main chain enable the polythioester to show unique properties in the aspects of optical property, chemical resistance and heavy metal ion adsorption while keeping the characteristics of the polyester material. Therefore, the polythioester material has wide application prospect in the aspects of high-performance optical fiber manufacture, adhesives and heavy metal ion-containing wastewater treatment. At present, the synthesis method of polythioester mainly comprises two methods: polycondensation and ring-opening polymerization. The polycondensation method is prepared by reacting dithiol and diacid compound in an organic solvent, and the energy consumption of the synthetic route is larger because the reaction process needs high temperature and high pressure and removes the generated small molecular compound. The ring-opening polymerization method is realized by ring-opening polymerization of six-membered cyclic thio-caprolactone, and is limited by single monomer structure, so that the polythioester prepared by the method has fewer varieties. Neither of these methods is suitable for large-scale production of polythioesters.
The invention contemplates the preparation of polythioesters by alternating polymerization of cycloalkanes with thioanhydrides.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and provides a preparation method of aliphatic polythioester.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of aliphatic polythioester is characterized by that it uses cyclic thioalkane and aliphatic thioanhydride as raw material, uses quaternary ammonium salt as initiator, and makes them undergo the process of bulk polymerization or solution polymerization reaction so as to obtain the invented product.
The number average molecular weight of the aliphatic polythioester is 3000-100000 g/mol, the molecular weight distribution is 1.1-1.6, and the content of the polythioester unit is more than or equal to 99%.
The molar ratio of the cyclic sulfane to the aliphatic thioanhydride is 1: 1-10: 1, preferably 1: 1; the molar ratio of the episulfide alkane to the quaternary ammonium salt is 100: 1-100000: 1, preferably 1000: 1.
The reaction temperature of the polymerization reaction is 0-120 ℃, preferably 25-70 ℃, the reaction time is 0.1-24 h, and the reaction temperature and the reaction time are determined by the conversion rate of the aliphatic thioanhydride.
The quaternary ammonium salt is one or the mixture of more than two of tetramethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium fluoride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, bis (triphenylphosphoranylidene) ammonium acetate, bis (triphenylphosphoranylidene) ammonium nitrate, bis (triphenylphosphoranylidene) ammonium bromide, bis (triphenylphosphoranylidene) ammonium iodide and bis (triphenylphosphoranylidene) ammonium fluoride.
The structural general formula of the episulfide alkane is as follows:
R3＝H、CH3、CH2Cl、CH2Br、CH2OH、CH2(CH2)mCH3or CH2(CH2)mH＝CH2Wherein m is an integer of 0-12;
R4＝CH3、C(CH3)3or CH (CH)3)2；
R5＝CH2Cl、CH2Br、CH2OH or CH2(CH2)mCH3Wherein m is an integer of 0 to 12;
n is an integer of 1 to 4.
The structural formula of the aliphatic thioanhydride is as follows:
when the polymerization reaction is carried out in solution, the adopted solvent is one or more than two of toluene, trichlorobenzene, tetrahydrofuran, xylene, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.
Compared with the prior art, the invention has the following remarkable beneficial effects:
1. the aliphatic polythioester obtained by the invention is polymerized by cyclane and aliphatic thioanhydride, and the two monomers have wide sources, so the prepared polymer has diversity in structure;
2. the reaction condition is mild, and the obtained product has high polythioester unit content;
3. the thermal stability and the optical performance of the product are greatly improved compared with those of the similar products, and the product has potential application in the field of special optical materials;
4. the method has the advantages of accurately adjustable polymer structure, multiple product types, simple polymerization method, easy operation and the like.
Drawings
FIG. 1 is a drawing showing the polymerization product obtained in example 11H NMR chart.
FIG. 2 is a drawing showing the polymerization product obtained in example 113C NMR chart.
FIG. 3 is a drawing showing the polymerization product obtained in example 21H NMR chart.
FIG. 4 is a drawing showing the polymerization product obtained in example 213C NMR chart.
Detailed Description
To describe the present invention in detail, the following detailed description is provided for the purpose of describing the embodiments of the present invention with reference to the accompanying drawings.
The numbers of the cycloalkane and the aliphatic thioanhydride used in the present invention are shown in the following formulae.
Example 1
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1a and aliphatic thioanhydride 2a at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 25 ℃ and magnetic stirring was started. The reaction was carried out for 4h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 23400 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: first, the crude product is dissolved in less solventAdding a large amount of methanol into dichloromethane, stirring vigorously to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying. Preparation of aliphatic polythioester prepared in this example1The H NMR spectrum is shown in FIG. 1, from which it is clear that the polymer segment has no polythioether unit and no cyclic product, indicating that it has a polythioester unit content>99％。13The spectrum C is shown in FIG. 2, from which it is clear that the oxygen-sulfur exchange reaction did not occur.
Example 2
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium acetate, episulfide alkane 1a and aliphatic thioanhydride 2c at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 25 ℃ and magnetic stirring was started. The reaction was carried out for 4h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 31200 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying. Preparation of aliphatic polythioester prepared in this example1The H NMR spectrum is shown in FIG. 3, from which it is clear that the polymer segment has no polythioether unit and no cyclic product, indicating that it has a polythioester unit content>99％。13The spectrum C is shown in FIG. 4, from which it is clear that the oxygen-sulfur exchange reaction did not occur.
Example 3
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphorane) ammonium nitrate, cyclane 1b, aliphatic thioanhydride 2a, cyclane,The molar ratio of the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 40 ℃ and magnetic stirring was started. The reaction was carried out for 2h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymeric molecular weight was 40800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 4
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiators of tetra-n-butyl ammonium chloride, cyclic sulfanilamide 1c and aliphatic thioanhydride 2b at room temperature, wherein the molar ratio of the cyclic sulfanilamide, the aliphatic thioanhydride and the initiators is 2000:1000: 1. Then it was put in an oil bath at 25 ℃ and magnetic stirring was started. The reaction was carried out for 6h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymeric molecular weight was 44800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 5
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator tetra-n-propyl ammonium chloride, cyclic sulfanilamide 1d and aliphatic thioanhydride 2a at room temperature, wherein the molar ratio of the cyclic sulfanilamide, the aliphatic thioanhydride and the initiator is 2000:1000: 1. Then it was put in an oil bath at 40 ℃ and magnetic stirring was started. The reaction was carried out for 2h and the stirring was stopped. Taking out a very small amount of reaction mixtureObject of carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99% and GPC measurement showed that the polymer molecular weight was 35800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 6
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator tetraethylammonium chloride, cyclic sulfanilamide 1e and aliphatic thioanhydride 2b at room temperature, wherein the molar ratio of the cyclic sulfanilamide to the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 80 ℃ and magnetic stirring was started. The reaction was carried out for 2h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1HNMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 49800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 7
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1f and aliphatic thioanhydride 2a at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 1000:1000: 1. Then it was put in an oil bath at 40 ℃ and magnetic stirring was started. The reaction was carried out for 2h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 22500 g/mol. Will be provided withPurification of the remaining reacted polymer, purification of the polymer: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 8
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1a and aliphatic thioanhydride 2a at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 25 ℃ and magnetic stirring was started. The reaction was carried out for 6h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed a polymeric molecular weight of 21800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 9
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1a and aliphatic thioanhydride 2b at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 40 ℃ and magnetic stirring was started. The reaction was carried out for 0.5h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99% and GPC measurement showed that the polymer molecular weight was 28600 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, and vigorously stirring to polymerizeThe precipitate is precipitated out, the process is repeated repeatedly to obtain white polymer, and the white polymer is dried in vacuum for later use.
Example 10
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1f and aliphatic thioanhydride 2b at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 10000:5000: 1. Then it was put in an oil bath at 60 ℃ and magnetic stirring was started. The reaction was carried out for 3h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99% and GPC measurement showed that the polymer molecular weight was 68800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 11
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1b and aliphatic thioanhydride 2a at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 2000:1000: 1. Then it was put in an oil bath at 60 ℃ and magnetic stirring was started. The reaction was carried out for 1h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 19800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 12
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium chloride, episulfide alkane 1d and aliphatic thioanhydride 2a at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 5000:1000: 1. Then it was put in an oil bath at 40 ℃ and magnetic stirring was started. The reaction was carried out for 4h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99% and GPC measurement showed that the polymer molecular weight was 35800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 13
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Under the protection of nitrogen, weighing a certain amount of initiator bis (triphenyl phosphoranylidene) ammonium acetate, episulfide alkane 1a and aliphatic thioanhydride 2d at room temperature, wherein the molar ratio of the episulfide alkane, the aliphatic thioanhydride to the initiator is 2500:500: 1. Then it was put in an oil bath at 25 ℃ and magnetic stirring was started. The reaction was carried out for 8h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 52800 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Example 14
A100 mL pressure-resistant glass bottle with magnetons is dried at 130 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. In thatUnder the protection of nitrogen, weighing a certain amount of initiator benzyltripropylammonium chloride, cyclane 1a and aliphatic thioanhydride 2e at room temperature, wherein the molar ratio of cyclane, aliphatic thioanhydride to initiator is 2500:500: 1. Then it was put in an oil bath at 25 ℃ and magnetic stirring was started. The reaction was carried out for 12h and the stirring was stopped. A very small amount of the reaction mixture is taken off for carrying out1H NMR and GPC testing.1H NMR test shows aliphatic thioanhydride conversion rate>99%, GPC measurement showed that the polymerization molecular weight was 48600 g/mol. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, vigorously stirring to precipitate the polymer, repeating the process to obtain white polymer, and vacuum drying.
Claims (10)
1. The preparation method of the aliphatic polythioester is characterized in that the aliphatic polythioester is a polymer obtained by bulk polymerization or solution polymerization reaction of cycloalkane and aliphatic thioanhydride as raw materials and quaternary ammonium salt as an initiator;
the number average molecular weight of the aliphatic polythioester is 3000-100000 g/mol, the molecular weight distribution is 1.1-1.6, and the content of the polythioester unit is more than or equal to 99 percent;
the molar ratio of the cyclic sulfane to the aliphatic thioanhydride is 1: 1-10: 1; the molar ratio of the episulfide alkane to the quaternary ammonium salt is 100: 1-100000: 1;
the polymerization reaction has the reaction temperature of 0-120 ℃ and the reaction time of 0.1-24 h, and the reaction temperature and the reaction time are determined by the conversion rate of the aliphatic thioanhydride.
2. The method of claim 1, wherein the molar ratio of the episulfide alkane to the quaternary ammonium salt is 1000: 1; the reaction temperature of the polymerization reaction is 25-70 ℃.
3. The method according to claim 1 or 2, wherein the quaternary ammonium salt is one or a mixture of two or more of tetramethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium fluoride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, bis (triphenylphosphoranylidene) ammonium acetate, bis (triphenylphosphoranylidene) ammonium nitrate, bis (triphenylphosphoranylidene) ammonium bromide, bis (triphenylphosphoranylidene) ammonium iodide, and bis (triphenylphosphoranylidene) ammonium fluoride.
4. The method of claim 1 or 2, wherein the cyclic thioalkane has the following general structural formula:
R3＝H、CH3、CH2Cl、CH2Br、CH2OH、CH2(CH2)mCH3or CH2(CH2)mH＝CH2，
Wherein m is an integer of 0-12;
R4＝CH3、C(CH3)3or CH (CH)3)2；
n is an integer of 1 to 4.
5. The method of claim 4, wherein the cyclic thioalkane has the following general structural formula:
R5＝CH2Cl、CH2Br、CH2OH or CH2(CH2)mCH3Wherein m is an integer of 0 to 12And (4) counting.
6. The method of claim 1, 2 or 5, wherein the aliphatic thioanhydride has the formula:
7. the method of claim 3, wherein the aliphatic thioanhydride has the formula:
8. the method of claim 4, wherein the aliphatic thioanhydride has the formula:
9. the method of claim 1, 2, 5, 7 or 8, wherein the polymerization is carried out in solution in the presence of one or more solvents selected from toluene, trichlorobenzene, tetrahydrofuran, xylene, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.
10. The method of claim 6, wherein the polymerization is carried out in solution in the presence of one or more solvents selected from toluene, trichlorobenzene, tetrahydrofuran, xylene, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.
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