CN114702419A - Preparation method of aliphatic monomer containing disulfide bond - Google Patents
Preparation method of aliphatic monomer containing disulfide bond Download PDFInfo
- Publication number
- CN114702419A CN114702419A CN202210220281.6A CN202210220281A CN114702419A CN 114702419 A CN114702419 A CN 114702419A CN 202210220281 A CN202210220281 A CN 202210220281A CN 114702419 A CN114702419 A CN 114702419A
- Authority
- CN
- China
- Prior art keywords
- formula
- disulfide bond
- compound
- aliphatic monomer
- preparation
- 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.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 41
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 description 17
- 239000004814 polyurethane Substances 0.000 description 17
- 239000004970 Chain extender Substances 0.000 description 14
- NGDIAZZSCVVCEW-UHFFFAOYSA-M sodium;butyl sulfate Chemical compound [Na+].CCCCOS([O-])(=O)=O NGDIAZZSCVVCEW-UHFFFAOYSA-M 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 8
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 6
- -1 4,4 '-dithiodiphenyl Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012029 structural testing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of aliphatic monomers containing disulfide bonds, which comprises the following steps: mixing an alkaline catalyst, acrylate with a structure shown in a formula (I) and an organic solution containing a compound with a structure shown in a formula (II), stirring and reacting for 6-24 h at the reaction temperature of 20-45 ℃, washing, and drying to obtain the aliphatic monomer containing the disulfide bond. The aliphatic monomer containing the disulfide bond has the advantages of simple preparation method, wide raw material source and low cost, and the aliphatic monomer containing the disulfide bond prepared by the method can improve the mechanical property and the self-healing property of the polyurethane elastomer.
Description
Technical Field
The invention relates to a preparation method of aliphatic monomers containing disulfide bonds.
Background
The structure and the performance of the polyurethane elastomer can be regulated and controlled by changing the formula, so that various requirements of people are met. For example, a dynamic reversible chemical bond is introduced into the structure of the polyurethane elastomer, and the self-repairing polyurethane elastomer can be prepared by endowing the elastomer with the characteristic of reversible dynamic.
Disulfide bonds (i.e., disulfide bonds) are an important dynamic reversible chemical bond. The disulfide bond has low bond energy, can generate exchange reaction under various external stimuli, has mild condition and is easy to regulate and control. In the design of the disulfide bond-based self-repairing polyurethane elastomer, most of the disulfide bond-containing monomers are used as chain extenders to prepare the polyurethane elastomer containing dynamic disulfide bonds in a molecular structure, and the polyurethane elastomer realizes the recombination and self-repairing of the elastomer through exchange reaction among the disulfide bonds.
At present, the literature reports that 2-hydroxyethyl disulfide or 4,4 '-dithiodiphenyl is mostly adopted as a chain extender to prepare a disulfide bond self-repairing polyurethane elastomer, and although the research achieves good effects, the 2-hydroxyethyl disulfide or 4,4' -dithiodiphenyl is adopted as the chain extender containing the disulfide bond, so that the price is high, and the mass preparation of the self-repairing polyurethane elastomer is difficult. Therefore, it is highly desirable to develop a disulfide bond-containing monomer with a wide source of raw materials and low cost.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing an aliphatic monomer containing a disulfide bond, which is simple, has a wide raw material source and a low cost, and can be used as a chain extender.
The invention provides a preparation method of an aliphatic monomer containing a disulfide bond, which comprises the following steps:
mixing an alkaline catalyst, acrylate with a structure shown in a formula (I) and an organic solution containing a compound with a structure shown in a formula (II), stirring and reacting for 6-24 hours at a reaction temperature of 20-45 ℃, washing, and drying to obtain an aliphatic monomer containing a disulfide bond;
wherein R1 and R2 are independently selected from C1-C6 alkylene, and R3 is selected from C6-C20 alkyl.
In the present invention, R1 and R2 may be independently selected from linear or branched C1 to C6 alkylene groups, respectively. Preferably, R1 and R2 are each independently selected from C2 to C4 alkylene groups. More preferably, R1 and R2 are each C2 alkylene groups. In the present invention, R3 may be selected from C6-C20 alkyl groups. Preferably, R3 is selected from C10-C18 alkyl. More preferably, R3 is selected from C12-C18. The aliphatic monomer containing the disulfide bond prepared in the way can be used as a chain extender and used for preparing a self-repairing polyurethane elastomer.
According to the preparation method of the invention, preferably, R1 and R2 are respectively and independently selected from C2-C4 alkylene, and R3 is selected from C10-C18 alkyl.
According to some embodiments of the invention, R1 and R2 are each C2 alkylene, and R3 is C12, C14, C16, or C18 alkyl. Therefore, the cost is low, and the mechanical property and the self-healing property of the polyurethane elastomer can be improved. According to some preferred embodiments of the invention, R1 and R2 are each C2 alkylene groups and R3 is C18 alkyl groups. Namely, the acrylate with the structure shown in the formula (I) is octadecyl acrylate, and the compound with the structure shown in the formula (II) is cystamine dihydrochloride. Cystamine dihydrochloride is a common intermediate, and the raw material is simple and has wide sources. The cystamine dihydrochloride is adopted to prepare the aliphatic monomer containing the disulfide bond, so that the cost is low, and the cystamine dihydrochloride serving as a chain extender of polyurethane can remarkably improve the mechanical property and the self-healing property of the polyurethane elastomer.
According to the preparation method of the present invention, preferably, the basic catalyst is selected from one or more of sodium amide, sodium ethoxide, sodium hydroxide, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine and triethylamine.
According to the preparation method of the present invention, preferably, the basic catalyst is selected from methylamine, ethylamine, dimethylamine or triethylamine.
According to some embodiments of the invention, the basic catalyst is triethylamine. According to other embodiments of the invention, the basic catalyst is triethylamine; the compound containing the structure shown in the formula (II) is cystamine dihydrochloride.
According to some preferred embodiments of the invention, the basic catalyst is triethylamine; the compound with the structure shown in the formula (I) is octadecyl acrylate, and the compound with the structure shown in the formula (II) is cystamine dihydrochloride. The cost price of the aliphatic monomer containing the disulfide bond is 1/3-1/2 of the price of the traditional chain extender; the self-repairing polyurethane prepared by using the self-repairing polyurethane as a chain extender has good mechanical property and high self-healing rate which can reach more than 90%.
The preparation method according to the present invention preferably further comprises the steps of: adding a compound with a structure shown in a formula (II) into a mixed solvent to obtain an organic solution containing the compound with the structure shown in the formula (II); the mixed solvent is a mixed solution of ethanol and tetrahydrofuran in a mass ratio of (1-2) to (1-2).
According to the preparation method of the invention, preferably, the mixed solvent is a mixed solution of ethanol and tetrahydrofuran in a mass ratio of 1 (1-2).
In the invention, the solvent is a mixed solution of ethanol and tetrahydrofuran. The mass ratio of the ethanol to the tetrahydrofuran can be (1-2) to (1-2); preferably 1 (1-2); more preferably 1: 1. The aliphatic monomer containing the disulfide bond prepared in the way can obviously improve the mechanical property and the self-healing property of the self-healing polyurethane.
According to the production method of the present invention, it is preferable that the mass concentration of the compound having the structure represented by formula (II) in the organic solution containing the compound having the structure represented by formula (II) is 5 to 30 wt%.
In the invention, in the organic solution containing the compound with the structure shown in the formula (II), the mass concentration of the compound with the structure shown in the formula (II) can be 5-30 wt%; preferably 10 to 25 wt%; more preferably 15 to 20 wt%. This contributes further to the improvement in the yield of the aliphatic monomer having a disulfide bond.
According to the preparation method of the invention, the molar ratio of the basic catalyst, the compound with the structure shown in the formula (II) and the compound with the structure shown in the formula (II) is preferably (1-2): (2-4): 1-2.
According to the preparation method of the invention, the molar ratio of the basic catalyst, the acrylate with the structure shown in the formula (I) and the compound with the structure shown in the formula (II) is preferably (1-2): 2-4): 1.
According to some preferred embodiments of the present invention, the molar ratio of the basic catalyst, the compound having the structure represented by formula (I), and the compound having the structure represented by formula (II) is 2:2: 1. This can increase the yield of aliphatic monomers containing disulfide bonds while keeping the cost low.
According to the preparation method of the invention, the reaction temperature is preferably 25-40 ℃.
In the invention, the reaction temperature is 20-45 ℃, preferably 25-40 ℃, and more preferably 30-35 ℃. This reduces side reactions while ensuring a faster reaction rate.
In the present invention, the stirring speed under the "stirring condition" may be 100 to 1000rpm, preferably 200 to 800rpm, and more preferably 300 to 600 rpm. Stirring can make the reaction more complete.
In the invention, the reaction time is 6-24 h, preferably 10-18 h, and more preferably 12-16 h. Therefore, the full reaction can be ensured, and the production efficiency can be improved.
According to some preferred embodiments of the present invention, the reaction temperature is 30 to 35 ℃ and the reaction time is 12 to 16 hours. Thus being beneficial to simultaneously improving the mechanical property and the self-healing property of the self-repairing polyurethane.
In the invention, after the reaction is finished, the reaction product is washed by water to obtain a precipitate. According to some embodiments of the present invention, deionized water is used for washing, which allows better washing of aliphatic monomers containing disulfide bonds, resulting in a higher purity product.
In the present invention, the aliphatic monomer having a disulfide bond after washing is dried. The drying temperature can be 50-70 ℃, and is preferably 55-65 ℃. The drying time is not particularly limited, and it is only necessary to make the moisture in the aliphatic monomer having a disulfide bond sufficiently small to avoid agglomeration. In certain embodiments, the washed aliphatic monomer containing a disulfide bond is dried in a vacuum oven at 50 ℃ for 24 hours.
The preparation method of the aliphatic monomer containing the disulfide bond is simple, wide in raw material source and low in cost. The aliphatic monomer containing the disulfide bond prepared by the method can be used as a chain extender and is used for improving the mechanical property and the self-healing property of the polyurethane elastomer.
Drawings
FIG. 1 is an infrared spectrum of stearyl acrylate, cystamine dihydrochloride, and an aliphatic monomer having a disulfide bond in example 1.
FIG. 2 is a Raman spectrum of the aliphatic monomer having a disulfide bond of example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
The test method is described below:
(1) structural determination of aliphatic monomers containing disulfide bonds:
the structure determination was carried out using a Fourier Infrared spectrometer (TENSOR II, Bruker Spectroscopy, Germany) with a scanning range: 4000-400 cm-1。
Performing structure determination by using a Raman spectrometer (HORIBA Scientific LabRAM HR Evolution) with a scanning range of 200-4000 cm-1The excitation wavelength was 633 nm.
(2) And (3) measuring the mechanical properties of the self-repairing polyurethane:
the self-repairing polyurethane was cut into a dumbbell shape having a size of 35mm × 2mm × 0.5mm, and the tensile strength of the test pieces was measured at a tensile rate of 100mm/min using a universal tester (WDW-2, Shanghanistan instruments manufacturing Co., Ltd. in China), and the final result was expressed as an average value of three test pieces.
(3) And (3) measuring the self-healing rate of the self-repairing polyurethane:
the self-repairing polyurethane is cut into a dumbbell shape with the size of 35mm multiplied by 2mm multiplied by 0.5mm, and the self-healing rate is measured.
Firstly, the mechanical properties of the self-repairing polyurethane are tested, and the original tensile strength of the self-repairing polyurethane sample is recorded. Then, the pulled-out sample was spliced and self-healed at 150 ℃ (electric heating constant temperature air-blast drying oven, model LDO-101-2, shanghai dragon leaping instruments ltd). And after the sample is completely spliced and the surface of the sample has no cracks, measuring the mechanical property of the healed sample, and recording the tensile strength of the self-healed sample.
Self-healing rate (%) (tensile strength of sample after self-healing/original tensile strength of sample) × 100%.
In the examples, the comparative examples, the application examples and the comparative examples of the present invention, all the chemical reagents used were Analytical Reagents (AR) available from shanghai alading biochem-scientific and technology ltd.
Examples 1 to 4 and comparative examples 1 to 3
Weighing raw materials according to the formula in table 1, and then adding cystamine dihydrochloride into a mixed solution of ethanol and tetrahydrofuran to obtain an organic solution of cystamine dihydrochloride; adding triethylamine and octadecyl acrylate into an organic solution of cystamine dihydrochloride to react; after the reaction is finished, washing with deionized water to obtain a light yellow precipitate; and (3) drying the light yellow precipitate in a vacuum oven to obtain the aliphatic monomer containing the disulfide bond.
The resulting product of example 1 was subjected to structural testing, and the results are shown in fig. 1 and 2.
In FIG. 1, curve a is the IR spectrum of octadecyl acrylate, curve b is the IR spectrum of cystamine dihydrochloride, and curve c is the IR spectrum of aliphatic monomer containing disulfide bond. From the IR spectrum of FIG. 1, it can be observed that the IR spectrum of aliphatic monomers containing disulfide bonds differs from the IR spectrum of octadecyl acrylate, cystamine dihydrochloride. Some of the characteristic groups of octadecyl acrylate appear to contain bis2930cm in infrared spectrum of aliphatic monomer with sulfur bond-1And 2850cm-1Has a C-H stretching peak at 1734cm-1The peak is the stretching vibration peak of the ester group.
FIG. 2 is a Raman spectrum of an aliphatic monomer having a disulfide bond. As can be observed from FIG. 2, 508cm-1Nearby S-S bond and 640cm-1The characteristic peak of C-S bond indicates that S-S bond exists in aliphatic monomer containing disulfide bond. The results show that the aliphatic monomer containing the disulfide bond is successfully synthesized by the method.
The reaction principle of example 1 is as follows:
TABLE 1
Application examples 1 to 4 and application comparative examples 1 to 5
According to the formula shown in table 2, the aliphatic monomers containing disulfide bonds prepared in examples 1 to 4 and comparative examples 1 to 3, the commercially available 2-hydroxyethyl disulfide and 4,4' -dithio-diphenyl are respectively used as chain extenders, and self-repairing polyurethanes with different disulfide bond contents in the main chain are prepared by a prepolymer mixing method, and the specific steps are as follows:
(1) PPG (polypropylene glycol 2000), N330 (polyether polyol) and DBTDL (dibutyl tin dilaurate) were added sequentially to a 250ml three-necked flask connected to a mechanical stirrer, and the mixture was dehydrated at 120 ℃ for 1h to give a first reactant.
(2) To the first reaction was added DMPA (dimethylolpropionic acid) and stirred for 5 minutes. The temperature was lowered to 90 ℃ and IPDI (isophorone diisocyanate) was added and the reaction was continued for 1 h. BDO (1, 4-butanediol) was then added and reacted for 2 h. Then cooled to 70 ℃, TEA (triethylamine) was added dropwise to completely neutralize the acid groups of DMPA, and reacted for 10 min. The chain extender was added and the reaction was continued for 2 hours and then cooled to ambient temperature. If the viscosity is high during the reaction, acetone is dropped into the reaction system. And then emulsifying the prepolymer for 30min by using deionized water at the rotating speed of 1000rpm, and removing acetone by decompressing to obtain the waterborne polyurethane emulsion.
(3) Pouring the aqueous polyurethane emulsion into a polytetrafluoroethylene mold, and drying at room temperature for 24 hours to evaporate water to obtain the self-repairing polyurethane.
The self-repairing polyurethane prepared in the above steps was subjected to mechanical property and self-healing rate tests, and the results are shown in table 3.
The aliphatic monomer having a disulfide bond of example 1 and a commercially available chain extender were compared in price, and the results are shown in table 4.
TABLE 2
TABLE 3
TABLE 4
| Number of | Cost price (thousand yuan/kg) |
| Aliphatic monomers containing disulfide bonds | 4～8 |
| 2-hydroxyethyl disulfide | 10～20 |
| 4,4' -dithiodiphenyl | 15～25 |
As can be seen from Table 3, the self-repairing polyurethane prepared by using the aliphatic monomer containing the disulfide bond as the chain extender has good mechanical properties and high self-healing rate which can reach more than 90%.
As can be seen from Table 4, the aliphatic monomer having a disulfide bond of the present invention is inexpensive, and the cost thereof is 1/3 to 1/2, which is equivalent to the cost of a commercially available chain extender.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A preparation method of aliphatic monomer containing disulfide bond is characterized by comprising the following steps:
mixing an alkaline catalyst, acrylate with a structure shown in a formula (I) and an organic solution containing a compound with a structure shown in a formula (II), stirring and reacting for 6-24 hours at a reaction temperature of 20-45 ℃, washing, and drying to obtain an aliphatic monomer containing a disulfide bond;
wherein R1 and R2 are independently selected from C1-C6 alkylene, and R3 is selected from C6-C20 alkyl.
2. The method according to claim 1, wherein R1 and R2 are each independently selected from C2-C4 alkylene groups, and R3 is selected from C10-C18 alkyl groups.
3. The preparation method of claim 1, wherein the basic catalyst is selected from one or more of sodium amide, sodium ethoxide, sodium hydroxide, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine and triethylamine.
4. The method according to claim 3, wherein the basic catalyst is selected from methylamine, ethylamine, dimethylamine or triethylamine.
5. The method of claim 1, further comprising the steps of: adding a compound with a structure shown in a formula (II) into a mixed solvent to obtain an organic solution containing the compound with the structure shown in the formula (II); the mixed solvent is a mixed solution of ethanol and tetrahydrofuran in a mass ratio of (1-2) to (1-2).
6. The preparation method according to claim 5, wherein the mixed solvent is a mixed solution of ethanol and tetrahydrofuran in a mass ratio of 1 (1-2).
7. The method according to claim 1, wherein the mass concentration of the compound having the structure represented by formula (II) in the organic solution containing the compound having the structure represented by formula (II) is 5 to 30 wt%.
8. The method according to claim 1, wherein the molar ratio of the basic catalyst, the acrylate having the structure represented by formula (I), and the compound having the structure represented by formula (II) is (1-2): (2-4): (1-2).
9. The method according to claim 8, wherein the molar ratio of the basic catalyst, the acrylate having the structure represented by formula (I), and the compound having the structure represented by formula (II) is (1-2): (2-4): 1.
10. The method according to claim 1, wherein the reaction temperature is 25 to 40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210220281.6A CN114702419B (en) | 2022-03-08 | 2022-03-08 | Preparation method of aliphatic monomer containing disulfide bond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210220281.6A CN114702419B (en) | 2022-03-08 | 2022-03-08 | Preparation method of aliphatic monomer containing disulfide bond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114702419A true CN114702419A (en) | 2022-07-05 |
| CN114702419B CN114702419B (en) | 2024-03-01 |
Family
ID=82168102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210220281.6A Active CN114702419B (en) | 2022-03-08 | 2022-03-08 | Preparation method of aliphatic monomer containing disulfide bond |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114702419B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756571A (en) * | 2002-12-30 | 2006-04-05 | 血管技术国际股份公司 | Tissue reactive compounds and compositions and uses thereof |
| CN112239530A (en) * | 2020-08-31 | 2021-01-19 | 济南大学 | Novel method for preparing hydrophobic self-healing super-elastic polyurethane elastomer |
| CN113736125A (en) * | 2021-09-07 | 2021-12-03 | 天津理工大学 | Preparation method of antibacterial polyurethane film |
| CN115926113A (en) * | 2023-01-10 | 2023-04-07 | 重庆市智翔铺道技术工程有限公司 | Curing agent, preparation method and application thereof |
-
2022
- 2022-03-08 CN CN202210220281.6A patent/CN114702419B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756571A (en) * | 2002-12-30 | 2006-04-05 | 血管技术国际股份公司 | Tissue reactive compounds and compositions and uses thereof |
| CN112239530A (en) * | 2020-08-31 | 2021-01-19 | 济南大学 | Novel method for preparing hydrophobic self-healing super-elastic polyurethane elastomer |
| CN113736125A (en) * | 2021-09-07 | 2021-12-03 | 天津理工大学 | Preparation method of antibacterial polyurethane film |
| CN115926113A (en) * | 2023-01-10 | 2023-04-07 | 重庆市智翔铺道技术工程有限公司 | Curing agent, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| DAVID J. FORTMAN，等: "Rapidly Reprocessable Cross-Linked Polyhydroxyurethanes Based on Disulfide Exchange", ACS MACRO LETT., vol. 07, no. 10, 20 September 2018 (2018-09-20), pages 1226 * |
| FELGUEIRAS, HELENA P., 等: "Octadecyl Chains Immobilized onto Hyaluronic Acid Coatings by Thiol-ene "Click Chemistry" Increase the Surface Antimicrobial Properties and Prevent Platelet Adhesion and Activation to Polyurethane", ACS APPLIED MATERIALS & INTERFACES, vol. 09, no. 09, 6 February 2017 (2017-02-06), pages 7979 - 7989 * |
| SHAN, BAILIN，等: "Self-healing and malleable waterborne polyurethane bearing aliphatic disulfide linkages with hydrophobic branching chains", POLYMER, no. 285, 20 October 2023 (2023-10-20), pages 1 - 9 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114702419B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107556452B (en) | Castor oil-based hydrophilic chain extender and preparation method and application thereof | |
| CN103881049B (en) | The preparation method of eleostearic acid monoglyceride modified aqueous polyurethane emulsion | |
| CN108912296B (en) | Crosslinking type waterborne polyurethane and preparation method thereof | |
| CN103709363A (en) | Sulfonate polyurethane emulsion with high solid content as well as preparation method and application thereof | |
| CN103030770A (en) | Environment-friendly flame-retardant polyurethane emulsion and preparation method thereof | |
| CN103497301B (en) | The preparation method of a kind of leatheroid, use for synthetic leather hyperbranched aqueous polyurethane | |
| CN106700021A (en) | Chitosan modified cationic waterborne polyurethane resin and preparation method and application thereof | |
| CN112028801B (en) | Chain extender and preparation method and application thereof | |
| CN113444221A (en) | Preparation method of epoxy resin modified waterborne polyurethane | |
| CN115521437A (en) | Preparation method of water-soluble ultraviolet-curing hyperbranched polyurethane acrylic resin | |
| CN114149565B (en) | Preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate | |
| CN113321780B (en) | Preparation method of organosilicon modified polyurethane | |
| CN115433338A (en) | Preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin | |
| CN108467471B (en) | Comb-shaped multi-branched aqueous polyurethane dispersion and preparation and application thereof | |
| CN114702419A (en) | Preparation method of aliphatic monomer containing disulfide bond | |
| CN112062934B (en) | Anionic water-based isocyanate curing agent and preparation method and application thereof | |
| CN117362588A (en) | Controllably crosslinked waterborne polyurethane and synthetic method thereof | |
| CN107955123A (en) | The preparation method of the polyurethane-modified silicone oil of carbon fiber finish | |
| CN112225877A (en) | Tri-functionality isocyanate modified polyurethane thickener and preparation method thereof | |
| CN112341593A (en) | Water-based surface layer polyurethane resin for automobile leather and preparation method thereof | |
| CN114853972B (en) | Vegetable oil-based polyol and preparation method thereof, and thermosetting vegetable oil-based polyurethane and preparation method and application thereof | |
| CN115044003B (en) | Preparation method of fluorine-containing self-healing aqueous polyurethane artificial skin material | |
| CN112159509B (en) | Waterborne polyurethane and preparation method and application thereof | |
| CN113024601B (en) | Reactive photocuring halogen-free flame retardant, bio-based flame retardant material, and preparation method and application thereof | |
| KR101102867B1 (en) | Composition of Water-dispersive Re-emulsifiable Polyurethane/Arcrylate Copolymer Hybrid and Method of Producing the Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |