CN110283314B - Method for preparing hyperbranched polythioether - Google Patents
Method for preparing hyperbranched polythioether Download PDFInfo
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- CN110283314B CN110283314B CN201910538119.7A CN201910538119A CN110283314B CN 110283314 B CN110283314 B CN 110283314B CN 201910538119 A CN201910538119 A CN 201910538119A CN 110283314 B CN110283314 B CN 110283314B
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- 229920006295 polythiol Polymers 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 43
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005580 one pot reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 8
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims description 8
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 7
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KXCKKUIJCYNZAE-UHFFFAOYSA-N benzene-1,3,5-trithiol Chemical compound SC1=CC(S)=CC(S)=C1 KXCKKUIJCYNZAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OPPASAWCZQZMGW-UHFFFAOYSA-N SCCC(=O)O.SCCC(=O)O.SCCC(=O)O.N(CCO)CCO Chemical compound SCCC(=O)O.SCCC(=O)O.SCCC(=O)O.N(CCO)CCO OPPASAWCZQZMGW-UHFFFAOYSA-N 0.000 claims description 2
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 229920000587 hyperbranched polymer Polymers 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000000569 multi-angle light scattering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 239000003643 water by type Substances 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
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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 relates to a method for preparing hyperbranched polythioether based on selective mercapto-alkene and mercapto-epoxy click chemistry. The hyperbranched polythioether with adjustable and controllable framework and end group is synthesized by a one-pot method by taking difunctional glycidyl acrylate monomers and trifunctional mercaptan as raw materials. The preparation method has the advantages of easily obtained raw materials, simple steps, high polymerization rate and good controllability, the prepared hyperbranched polythioether has an adjustable skeleton, and the end group can be effectively controlled to be sulfydryl or epoxy by utilizing the molar ratio of the monomers, and can be further functionally modified, so that the hyperbranched polythioether with specific performance can be prepared.
Description
Technical Field
The invention relates to the field of organic polymers, in particular to a method for preparing hyperbranched polythioether.
Background
The sulfur-containing hyperbranched polymer has special functionality which is not possessed by the conventional hyperbranched polymer (HBP) due to the existence of sulfur atoms, and is increasingly paid more attention. The sulfydryl click chemical reaction gradually becomes a main reaction for preparing the sulfur-containing hyperbranched polymer due to higher reaction activity, mild and efficient reaction and wide monomer applicability. The existing preparation method of hyperbranched polymer mainly comprises AB2And A2+B3Two methods, and the synthesis of the sulfur-containing hyperbranched polymer is performed by AB2Mainly adopts the method. Wherein, the high-grade (Han J, ZHao B, Tang A, et al. Polymer Chemistry,2012,3(7):1918-2Monomers, then AB by mercapto-alkyne click chemistry2Hyperbranched polythioether with alkyne as the end group is prepared by polymerizing monomers, and can be applied to the fields of metal ion adsorption, oil resistance, oxidation resistance resin and the like; gadwal et al (Gadwal I, Binder S, Stuparu M C, et al. macromolecules,2014,47(15):5070-5080.) preparation of AB containing two epoxy groups and one mercapto group by a series of organic syntheses2The hyperbranched polythioether with the end group of epoxy is prepared by using a monomer and a sulfydryl-epoxy click chemical reaction; but due to AB2Few types of monomers, complicated monomer preparation process, and A2+B3The lack of selectivity of the polymerization system and the risk of gelation during the polymerization process severely limit the preparation and application of hyperbranched polythioethers. Furthermore, limited by the monomer structure and polymerization system, the currently reported AB2And A2+B3Most systems can only prepare hyperbranched polythioether with specific framework and terminal group, and the simultaneous regulation and control of the hyperbranched polythioether are difficultSkeleton and end group, thereby limiting the function and application field of the hyperbranched polythioether.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing hyperbranched polythioether, which comprises the following steps:
the hyperbranched polythioether is prepared by using a difunctional glycidyl acrylate monomer and a trifunctional thiol as raw materials through a one-pot method, wherein the molar ratio of the trifunctional thiol monomer to the difunctional glycidyl acrylate monomer is 1: 0.8-2.4, and preferably 1: 2.0-2.4.
Further, mixing a trifunctional trithiol monomer, a difunctional glycidyl acrylate monomer, a catalyst and a solvent, reacting for 2-48 h, and purifying to obtain the hyperbranched polythioether.
Further, the addition amount of the catalyst is 0.5-5 mol% of the monomer amount; the purification comprises rotary evaporation and concentration, dissolution-precipitation operation and vacuum drying of the precipitate.
Further, the concentration of the trifunctional trithiol monomer and the difunctional glycidyl acrylate monomer is 0.1-1.0 g mL-1Within the range.
Further, the solvent includes tetrahydrofuran, dioxane, dimethyl sulfoxide and N, N-dimethylformamide; the catalyst comprises triethylamine, dimethylamino pyridine, 1, 8-bis-azabicyclo [5,4,0] undec-7-ene, 1,5, 7-tris-azabicyclo [4.4.0] dec-5-ene; the reaction temperature is 20-100 ℃.
Further, the tri-functional trithiol monomer includes trimethylolpropane-tris (3-mercaptopropionate), 1,3, 5-benzenetrithiol, tris (2-hydroxyethyl) isocyanurate-tris (3-mercaptopropionate), diethanolamine-tris (3-mercaptopropionate); the difunctional glycidyl acrylate monomer includes glycidyl methacrylate.
Another object of the present invention is to provide a hyperbranched polythioether prepared by any of the methods described above.
Furthermore, the hyperbranched polythioether skeleton contains thioether and hydroxyl, the end group can be effectively controlled to be sulfydryl or epoxy through the monomer molar ratio, the number average molecular weight is 2.5-60 kDa, the polydispersity index is 1.2-2.0, and the Mark-Houwink index alpha is 0.2-0.5.
Further, the hyperbranched polythioether has the following structure:
further, the hyperbranched polythioether has the following structure:
the invention has the advantages that:
the invention takes difunctional glycidyl acrylate compounds as AC monomers (A represents acrylate groups and C represents epoxy groups) and trifunctional mercaptan as B3The monomer is synthesized into the structurally hyperbranched polythioether by a one-pot method. The reaction activity of the acrylate double bond and the sulfydryl in the AC monomer is far higher than that of an epoxy group, and the AC monomer and the B are polymerized in the initial stage by controlling the reaction conditions3Reaction of monomers to CB2Or BC2And (3) further polymerizing the type intermediate to obtain the hyperbranched polythioether with adjustable and controllable framework and end group, wherein the polymerization system is controllable and can effectively avoid gel. The method has the advantages of easily obtained raw materials, simple steps, high polymerization rate and good controllability, and can regulate and control the end group of the hyperbranched polymer to be a sulfydryl group or an epoxy group by controlling the monomer molar ratio, and can further carry out functional modification. Compared with the traditional method, the method has the advantages of difficult gelation, simple and easy operation, high controllability and the like.
Drawings
FIG. 1 is an infrared absorption spectrum of the terminal mercapto hyperbranched polythioether P3 and the monomer Glycidyl Methacrylate (GMA) prepared in example 3.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the terminal mercapto hyperbranched polythioether P3 and the monomer Glycidyl Methacrylate (GMA) prepared in example 3.
FIG. 3 is a GPC outflow time curve of the thiol-terminated hyperbranched polythioether P3 prepared in example 3.
FIG. 4 is a chart of the infrared absorption spectrum of an epoxy-terminated hyperbranched polythioether P7 prepared in example 7.
FIG. 5 is a nuclear magnetic hydrogen spectrum of the epoxy-terminated hyperbranched polythioether P7 prepared in example 7.
FIG. 6 is a GPC outflow time curve for the oxygen-terminated hyperbranched polythioether P7 prepared in example 7.
Detailed Description
The invention is further illustrated below with reference to specific embodiments. It is to be understood that the present invention is not limited to the following embodiments, which are regarded as conventional methods unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
Cases 1-10 are examples of preparation of hyperbranched polythioethers.
Example 1:
9.965g (25mmol) trimethylolpropane-tris (3-mercaptopropionate), 75mL Tetrahydrofuran (THF) and 3.56g (25mmol) glycidyl methacrylate and 0.1012g (1.0mmol) triethylamine were added in one portion to the reactor at room temperature under N2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is dried in vacuum to obtain colorless viscous end-sulfhydryl hyperbranched polythioether P1(9.50g, the yield is 70.4%).
Example 2:
9.965g (25mmol) trimethylolpropane-tris (3-mercaptopropionate), 75mL of N, N-Dimethylformamide (DMF), 3.56g (25mmol) of glycidyl methacrylate and 0.1222g (1.0mmol) of N, N-lutidine were added in one portion to the reactor at room temperature2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is dried in vacuum to obtain colorless viscous end-sulfhydryl hyperbranched polythioether P2(9.26g, the yield is 68.5%).
Example 3:
9.965g (25mmol) trimethylolpropane-tris (3-mercaptopropionate), 75mL DMF and 3.56g (25mmol) glycidyl methacrylate and 0.1522g (1.0mmol)1, 8-diazabicyclo [5,4,0] bicyclo]Adding undec-7-ene (DBU) into the reactor at one time, and adding N at room temperature2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is dried in vacuum to obtain colorless viscous end-sulfhydryl hyperbranched polythioether P3(8.57g, the yield is 63.4%).
FIG. 1 is an infrared absorption spectrum of a mercapto-terminated hyperbranched polythioether P3 and a monomer Glycidyl Methacrylate (GMA) prepared in example 3, wherein 3505cm in the spectrum of P3-1Stretching vibration absorption peak at OH, 2570cm-1Characteristic absorption peak at thiol group of 910cm-1The characteristic peak of epoxy disappears, and the P3 is proved to be mercapto-terminated;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the terminal mercapto hyperbranched polythioether P3 prepared in example 3 and a monomer Glycidyl Methacrylate (GMA), wherein the peak of proton signals of double bonds at 5.58-6.43ppm disappears, the proton signal of mercapto group at 1.65ppm disappears, the characteristic absorption peak of epoxy at 3.28ppm disappears, the proton signal of methylene adjacent to S atom at 2.48-2.85ppm strengthens, and further proves that the end group of P3 is mercapto group;
FIG. 3 is a GPC outflow time curve of a thiol-terminated hyperbranched polythioether P3 prepared in example 3, from which a relative molecular weight M of P3 was fitted with a linear PS as a standardw7.6kDa and PDI 1.57. The absolute molecular weight of P3 was 28.8kDa and the Mark-Houwink index alpha was 0.342 as fitted by using the light scattering-viscosity-GPC triple, combined with a dn/dc value of 0.0580, and was within the range of 0.2-0.5 of the hyperbranched polymer, demonstrating that P3 has a highly branched structure.
Example 4:
4.357g (25mmol) of 1,3, 5-benzenetrithiol, 40mL of DMF, 3.56g (25mmol) of glycidyl methacrylate and 0.1522g (1.0mmol) of 1, 8-diazabicyclo [5,4,0]]Adding undec-7-ene (DBU) into the reactor at one time, adding N into the reactor at room temperature2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is dried in vacuum to obtain colorless viscous end-sulfhydryl hyperbranched polythioether P4(8.57g, the yield is 63.4%).
Example 5:
13.14g (25mmol) tris (2-hydroxyethyl) isocyanurate-tris (3-mercaptopropionate) (THMP), 83mL DMF, 3.56g (25mmol) glycidyl methacrylate and 0.1522g (1.0mmol)1, 8-diazabicyclo [5,4,0]]Adding undec-7-ene (DBU) into the reactor at one time, and adding N at room temperature2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is dried in vacuum to obtain colorless viscous end-sulfhydryl hyperbranched polythioether P6(10.80g, the yield is 64.7%).
Example 6:
9.965g (25mmol) trimethylolpropane-tris (3-mercaptopropionate), 75mL of tetrahydrofuran, 7.11g (50mmol) of glycidyl methacrylate and 0.1012g (1.0mmol) of triethylamine were added in one portion to the reactor at room temperature under N2Protection reaction is carried out for 24 h; after the reaction, the reaction solution was concentrated by rotary evaporation, redissolved with chloroform and precipitated in anhydrous ether, and the dissolution-precipitation procedure was repeated 3 times to obtain colorless viscous epoxy-terminated hyperbranched polythioether P5(9.92g, 58.3% yield) after vacuum drying of the precipitate.
Example 7:
9.965g (25mmol) trimethylolpropane-tris (3-mercaptopropionate), 75mL DMF, 7.11g (50mmol) glycidyl methacrylate and 0.1522g (1.0mmol)1, 8-diazabicyclo [5,4,0] bicyclo]Adding the undec-7-ene into a reactor at one time, and adding N at room temperature2Protection reaction is carried out for 24 h; after the reaction, the reaction solution was concentrated by rotary evaporation, redissolved with chloroform and precipitated in anhydrous ether, and the dissolution-precipitation procedure was repeated 3 times to obtain colorless viscous epoxy-terminated hyperbranched polythioether P7(10.14g, 59.4% yield) after vacuum drying of the precipitate.
FIG. 4 is a chart of the infrared absorption spectrum of an epoxy-terminated hyperbranched polythioether P7 prepared in example 7, wherein3505cm-1910cm of stretching vibration absorption peak at OH-1Is treated as the characteristic peak of epoxy, 2540cm-1The characteristic absorption peak of sulfydryl disappears, and the P7 is proved to be epoxy-terminated;
FIG. 5 is a nuclear magnetic hydrogen spectrum of an epoxy-terminated hyperbranched polythioether P7 prepared in example 7, wherein the peak of a proton signal of a double bond at 5.58-6.43ppm disappears, the peak of a proton signal of a thiol group at 1.65ppm disappears, the characteristic absorption peak of epoxy at 3.28ppm weakens, and the signal of a methylene proton adjacent to an S atom at 2.48-2.85ppm strengthens, further proving that P7 is epoxy-terminated;
FIG. 6 is a GPC outflow time curve of an epoxy-terminated hyperbranched polythioether P7 prepared in example 7, from which a relative molecular weight M of P7 was fitted with a linear PS as a standardw6.0kDa, PDI 1.50; the absolute molecular weights of P7, as fitted by light scattering-viscosity-GPC triplets, combined with a dn/dc value of 0.0580, were each 25.3 kDa; the Mark-Houwink index α was 0.394, in the range of 0.2 to 0.5 for hyperbranched polymers, demonstrating that P7 has the expected highly branched structure.
Example 8:
4.357g (25mmol) of 1,3, 5-benzenetrithiol, 57mL of tetrahydrofuran, 7.11g (50mmol) of glycidyl methacrylate and 0.1522g (1.0mmol) of 1, 8-diazabicyclo [5,4,0]]Adding undec-7-ene (DBU) into the reactor at one time, and adding N at room temperature2Protection reaction is carried out for 24 h; after the reaction, the reaction solution was concentrated by rotary evaporation, redissolved with chloroform and precipitated in anhydrous ether, and the dissolution-precipitation procedure was repeated 3 times to obtain colorless viscous epoxy-terminated hyperbranched polythioether P8(8.52g, 74.3% yield).
Example 9:
13.14g (25mmol) tris (2-hydroxyethyl) isocyanurate-tris (3-mercaptopropionate) (THMP), 100mL tetrahydrofuran, 7.11g (50mmol) glycidyl methacrylate, and 0.1522g (1.0mmol)1, 8-diazabicyclo [5,4,0] bicyclo]Adding the undec-7-ene into a reactor at one time, and adding N at room temperature2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction liquid is evaporated and concentrated, dissolved again by chloroform and then precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is trueAfter air drying, a colorless, viscous epoxy-terminated hyperbranched polythioether P9(12.41g, 61.3% yield) was obtained.
Examples 1-9 various structural parameters of the hyperbranched polythioethers P1-P9 prepared are shown in the following table.
TABLE 1
Note:
the molar ratio is the molar ratio of the trifunctional trithiol monomer to the difunctional glycidyl acrylate monomer.
Mw,GPC(kg/mol) and Mw,GPC/Mn,GPCThe gel permeation chromatography (Waters GPC 486) was followed by linear Polystyrene (PS) as standard and Tetrahydrofuran (THF) as eluent.
Mw,MALLS(kg/mol) and α (mark-houwink index) were measured by a gel permeation chromatography-multi-angle laser light scattering-viscometry triple System (GPC-MALLS, DAWN HELEOS II System) using N, N-Dimethylformamide (DMF) as an eluent, and the specific refractive index increment (dn/dc) of the sample was measured by using a Wyatt Optilab refractive index detector (λ 658 nm); characterizing the intrinsic viscosity of the polymer using a viscosity detector; the raw data were processed with Astra VI software and the absolute weight average molecular weight M of the samples was fitted by dn/dcw,MALLS(kg/mol), the Mark-Houwink index α is fitted using the intrinsic viscosity and the absolute weight average molecular weight.
From the above table, it can be seen that the hyperbranched polythioethers prepared by applying the method of the present invention all have a highly branched structure, and the terminal groups of the hyperbranched polymer can be controlled to be mercapto groups or epoxy groups by changing the molar ratio of the monomers according to the method of the present invention.
Claims (6)
1. A method for preparing hyperbranched polythioether is characterized in that difunctional glycidyl acrylate monomers and trifunctional mercaptan are used as raw materials, the hyperbranched polythioether is prepared by a one-pot method, and the molar ratio of the trifunctional mercaptan monomers to the difunctional glycidyl acrylate monomers is 1: 2.0-2.4;
the trifunctional trithiol monomer comprises trimethylolpropane-tris (3-mercaptopropionate), 1,3, 5-benzenetrithiol, tris (2-hydroxyethyl) isocyanurate-tris (3-mercaptopropionate), diethanolamine-tris (3-mercaptopropionate); the difunctional glycidyl acrylate monomer comprises glycidyl methacrylate;
the hyperbranched polythioether has the number average molecular weight of 2.5-60 kDa, the polydispersity index of 1.2-2.0 and the Mark-Houwink index alpha of 0.2-0.5;
the hyperbranched polythioether has the following structure:
2. the method for preparing hyperbranched polythioether according to claim 1, wherein the method comprises mixing a trifunctional trithiol monomer, a difunctional glycidyl acrylate monomer, a catalyst and a solvent, reacting for 2-48 h, and purifying to obtain the hyperbranched polythioether.
3. The method of claim 2, wherein the catalyst is added in an amount of 0.5 to 5 mol% based on the amount of the monomer; the purification is carried out by dissolving-precipitating after rotary evaporation and concentration, and the precipitate is dried in vacuum.
4. The method of claim 1, wherein the concentration of the trifunctional trithiol monomer and the difunctional glycidyl acrylate monomer is 0.1-1.0 g mL-1Within the range.
5. The method of claim 2, wherein the solvent comprises tetrahydrofuran, dioxane, dimethyl sulfoxide, and N, N-dimethylformamide; the catalyst comprises triethylamine, dimethylamino pyridine, 1, 8-bis-azabicyclo [5,4,0] undec-7-ene, 1,5, 7-tris-azabicyclo [4.4.0] dec-5-ene; the reaction temperature is 20-100 ℃.
6. A hyperbranched polythioether prepared by the method of any one of claims 1 to 5.
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