CN116496629B - Hydrophobic oleophobic bio-based thermosetting polysiloxane and preparation method and application thereof - Google Patents
Hydrophobic oleophobic bio-based thermosetting polysiloxane and preparation method and application thereof Download PDFInfo
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- -1 polysiloxane Polymers 0.000 title claims abstract description 44
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 43
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 38
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002028 Biomass Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 14
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- 239000012312 sodium hydride Substances 0.000 claims description 10
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FBUZNPORDKVYFD-AATRIKPKSA-N (e)-1-bromohex-1-ene Chemical compound CCCC\C=C\Br FBUZNPORDKVYFD-AATRIKPKSA-N 0.000 claims description 2
- NNQDMQVWOWCVEM-NSCUHMNNSA-N (e)-1-bromoprop-1-ene Chemical compound C\C=C\Br NNQDMQVWOWCVEM-NSCUHMNNSA-N 0.000 claims description 2
- WSXIDSNEEOYBFA-UHFFFAOYSA-N 1-bromopent-1-ene Chemical compound CCCC=CBr WSXIDSNEEOYBFA-UHFFFAOYSA-N 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 5
- 235000010290 biphenyl Nutrition 0.000 abstract description 3
- 239000004305 biphenyl Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000011161 development Methods 0.000 description 8
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 244000271437 Bambusa arundinacea Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 235000010792 Phyllostachys aurea Nutrition 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/05—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the field of new bio-based materials, and discloses a hydrophobic and oleophobic bio-based thermosetting polysiloxane, and a preparation method and application thereof. The method comprises the following operation steps: under the nitrogen atmosphere, the renewable biomass magnolol is dissolved in a solvent, a dehydrogenation agent is added, dehydrogenation reaction is carried out at room temperature, then monosubstituted bromoolefin is added at 55-65 ℃ for reaction for 5-8 hours; obtaining biomass magnolol derivative containing four carbon-carbon double bond structures; and uniformly stirring the obtained biomass magnolol derivative, polymethyl hydrosiloxane and a catalyst, and solidifying to obtain the hydrophobic oleophobic bio-based thermosetting polysiloxane. The biomass magnolol derivative containing four carbon-carbon double bond structures can improve the crosslinking density of polysiloxane and form a network structure. And a large number of biphenyl structures are introduced into the polysiloxane, so that the hydrophobic and oleophobic properties and the mechanical properties of the polysiloxane can be greatly improved.
Description
Technical Field
The invention belongs to the field of new bio-based materials, and particularly relates to a hydrophobic and oleophobic bio-based thermosetting polysiloxane, and a preparation method and application thereof.
Background
In recent years, sustainable development has become one of the topics of global heat. In various fields, environmentally friendly alternatives are actively sought. Among them, the demands for hydrophobic and oleophobic materials are increasing, because these materials can effectively prevent the diffusion and infiltration of pollutants, while improving the service life of the product. It is therefore very urgent to develop hydrophobic and oleophobic materials with sustainable development characteristics.
The polysiloxane is an organosilicon compound taking Si-O-Si bond as a main chain, and has high bond energy (422.5 KJ/mol) between siloxanes, so that compared with a common polymer, the polysiloxane has better heat stability, oxidation resistance, high and low temperature resistance, radiation resistance and the like. In addition, because of the special arrangement mode of the main chain and the side chain, the polysiloxane has lower surface energy and certain hydrophobicity and oleophobicity.
But with the continuous development of industry, the requirements on performance are also higher and higher, the hydrophobic and oleophobic properties of the self-cleaning agent cannot meet the requirements of the industry. Thus, a large number of researchers have improved this property of polysiloxanes by introducing special structures. Wherein, the introduction of fluorine atoms is an effective method, which can effectively improve the hydrophobicity and oleophobicity of the fluorine-containing polysiloxane/PP hydrophobic material (golden bamboo, shoushun, zhou Changlin, etc. the preparation and the performance of the IPN-type fluorine-containing polysiloxane/PP hydrophobic material [ J ]. Fine chemical industry, 2022,39 (04): 712-718.). However, the introduction of fluorine-containing atoms into the polysiloxane is relatively complicated, is not suitable for mass industrial production, and generates corrosive hydrogen fluoride gas under heating conditions, thereby causing harm to human bodies and the environment. Moreover, most of the current hydrophobic and oleophobic polysiloxane materials are produced by petrochemical raw materials, which is unfavorable for long-term sustainable development.
Therefore, in order to meet the requirements of social demands and sustainable development, development and preparation of the polysiloxane hydrophobic and oleophobic material with easy and excellent performance and sustainable development are urgently needed.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the primary purpose of the invention is to provide a preparation method of hydrophobic oleophobic bio-based thermosetting polysiloxane; the method comprises the steps of preparing a biomass magnolol derivative containing four carbon-carbon double bond structures through the reaction of renewable biomass magnolol and bromopropene, and curing polymethylhydrosiloxane by utilizing the biomass magnolol derivative to obtain the bio-based thermosetting polysiloxane with hydrophobic and oleophobic properties, so that the hydrophobic and oleophobic properties, sustainable development and good mechanical properties of the polysiloxane are realized.
The invention also aims to provide the hydrophobic oleophobic bio-based thermosetting polysiloxane prepared by the preparation method.
It is another object of the present invention to provide the use of the above-described hydrophobic oleophobic bio-based thermoset polysiloxanes.
The aim of the invention is achieved by the following technical scheme:
a preparation method of hydrophobic oleophobic bio-based thermosetting polysiloxane, which comprises the following operation steps:
(1) Under the nitrogen atmosphere, dissolving renewable biomass magnolol in a solvent, adding a dehydrogenation agent, performing dehydrogenation reaction at room temperature, then adding monosubstituted bromoolefin at 55-65 ℃ and reacting for 5-8 hours to obtain a biomass magnolol derivative containing four carbon-carbon double bond structures;
(2) Uniformly stirring the biomass magnolol derivative obtained in the step (1) together with polymethylhydrosiloxane and a catalyst, and solidifying to obtain the hydrophobic and oleophobic bio-based thermosetting polysiloxane.
The solvent in the step (1) is any one or two of tetrahydrofuran, toluene and N, N-dimethylformamide; the dehydrogenation agent is any one of sodium hydride and potassium carbonate; the monosubstituted bromoolefin is any one of 1-bromopropene, 1-bromopentene and 1-bromohexene.
The dehydrogenation agent in the step (1) is sodium hydride; the dehydrogenation reaction time is 5-15min.
The molar ratio of the renewable biomass magnolol, the dehydrogenation agent and the monosubstituted bromoolefin in the step (1) is 1:2.1:2.2.
the hydrogen content of the polymethylhydrosiloxane in the step (2) is 0.3%, 0.5% or 0.75% by mass; the catalyst is at least one of a Karster catalyst and a Speier catalyst;
the mass ratio of the polymethylhydrosiloxane to the biomass magnolol derivative in the step (2) is 1 (0.17-0.4).
The catalyst in the step (2) is used in an amount of 10-30ppm; the concrete operation of the curing is as follows: pre-curing for 10min-30min at 60-80deg.C, curing for 2-4 hr at 80-100deg.C, curing for 1-3 hr at 100-120deg.C, and curing for 10-30min at 120-140deg.C.
Preferably, the catalyst is used in an amount of 20ppm; the concrete operation of the curing is as follows: pre-curing for 15min at 70 ℃, then curing for 3h at 80-100 ℃, then curing for 1h at 110 ℃, and finally curing for 20min at 130 ℃.
The hydrophobic oleophobic bio-based thermosetting polysiloxane prepared by the preparation method is prepared.
The application of the hydrophobic oleophobic bio-based thermosetting polysiloxane in the fields of antifouling, corrosion prevention and self-cleaning.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts the renewable magnolol with obvious abundance, is modified by etherification reaction, is used for curing the polymethylhydrosiloxane, is environment-friendly, does not involve complicated processing technology, and can reduce petroleum resources and fluorine-containing substances used in the production process of the hydrophobic oleophobic polysiloxane.
(2) The biomass magnolol derivative containing four carbon-carbon double bond structures can improve the crosslinking density of polysiloxane and form a network structure; and a large number of biphenyl structures are introduced into the polysiloxane, so that the hydrophobic and oleophobic properties and the mechanical properties of the polysiloxane can be greatly improved.
(3) The invention provides a method for removing and solidifying polymethylhydrosiloxane from biomass magnolol derivative for the first time. The method can not only efficiently convert natural products into high value-added products, but also remarkably improve the comprehensive performance of polysiloxane; the bio-based curing mode is expected to replace the petroleum-based curing mode, and provides a new way for the high-value utilization of biomass resources and the sustainable replacement of petroleum-based materials.
Drawings
FIG. 1 is a schematic representation of the synthetic route of the hydrophobic oleophobic bio-based thermoset polysiloxane (M-PSO-X) prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic spectrum of allylated magnolol derivative (A-M) prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market, and the process parameters which are not specially noted can be carried out by referring to the conventional technology.
Example 1:
under nitrogen atmosphere, 5.32g of magnolol is dissolved in 40mL of tetrahydrofuran, 1.008g of sodium hydride is added, the reaction is carried out for 5min at room temperature, then 5.28g of bromopropene is added, the reaction is carried out for 6h at 60 ℃, after the reaction is completed, the mixture is filtered in vacuum, filtrate is collected and distilled under reduced pressure rapidly, yellow oily liquid is obtained, the yellow oily liquid is washed three times by deionized water, and the allylated magnolol derivative is obtained by drying in a vacuum oven at 60 ℃, and is named as A-M. 3g of polymethylhydrosilane (hydrogen content 0.3% by mass), 0.51. 0.51g A-M and 20ppm of Karster catalyst were uniformly mixed, pre-cured at 60℃for 10min, cured at 85℃for 3h, cured at 110℃for 1h and cured at 125℃for 20min, and the hydrophobic oleophobic bio-based thermosetting polysiloxane product after curing was designated as M-PSO-A. The synthetic route for the preparation of the hydrophobic oleophobic bio-based thermoset polysiloxane (M-PSO-X) of this example is shown in FIG. 1.
The nuclear magnetic spectrum of the allylated magnolol derivative A-M obtained in the preparation process is shown in figure 2, and signals (a, b, c) in the range of 6.73-7.11ppm can be attributed to proton hydrogen on biphenyl aromatic rings. For the four double bonds, the signal of the terminal proton hydrogen was observed in the range of 4.87-5.25ppm (i, g) and the signal of the other terminal proton was also observed in the range of 5.73-5.96ppm (h, f). Proton signals in the range of 4.29 to 4.47ppm (d) are caused by O-CH 2-methylenehydrogen produced by the etherification reaction. Taken together, the allylated magnolol derivative A-M was shown to be successfully synthesized.
Example 2:
under nitrogen atmosphere, 5.32g of magnolol is dissolved in 40mL of tetrahydrofuran, 1.008g of sodium hydride is added, the reaction is carried out for 5min at room temperature, then 5.28g of bromopropene is added, the reaction is carried out for 6h at 60 ℃, after the reaction is completed, the mixture is filtered in vacuum, filtrate is collected and distilled under reduced pressure rapidly, yellow oily liquid is obtained, the yellow oily liquid is washed three times by deionized water, and the allylated magnolol derivative is obtained by drying in a vacuum oven at 60 ℃, and is named as A-M. 3g of polymethylhydrosilane (hydrogen content 0.5% by mass), 0.81. 0.81g A-M and 20ppm of Karster catalyst were uniformly mixed, pre-cured at 60℃for 10min, cured at 85℃for 3h, cured at 110℃for 1h and cured at 125℃for 20min, and the hydrophobic oleophobic bio-based thermosetting polysiloxane product after curing was designated as M-PSO-B.
Example 3:
under nitrogen atmosphere, 5.32g of magnolol is dissolved in 40mL of tetrahydrofuran, 1.008g of sodium hydride is added, the reaction is carried out for 5min at room temperature, then 5.28g of bromopropene is added, the reaction is carried out for 6h at 60 ℃, after the reaction is completed, the mixture is filtered in vacuum, filtrate is collected and distilled under reduced pressure rapidly, yellow oily liquid is obtained, the yellow oily liquid is washed three times by deionized water, and the allylated magnolol derivative is obtained by drying in a vacuum oven at 60 ℃, and is named as A-M. 3g of polymethylhydrosilane (hydrogen content 0.75% by mass), 1.14. 1.14g A-M and 20ppm of Karster's catalyst were uniformly mixed, pre-cured at 60℃for 10min, cured at 85℃for 3h, cured at 110℃for 1h and cured at 125℃for 20min, and the resulting hydrophobic oleophobic bio-based thermosetting polysiloxane product was designated as M-PSO-C.
Example 4:
under nitrogen atmosphere, 5.32g of magnolol is dissolved in 40mL of tetrahydrofuran, 1.008g of sodium hydride is added, the reaction is carried out for 5min at room temperature, then 5.28g of bromopropene is added, the reaction is carried out for 6h at 60 ℃, after the reaction is completed, the mixture is filtered in vacuum, filtrate is collected and distilled under reduced pressure rapidly, yellow oily liquid is obtained, the yellow oily liquid is washed three times by deionized water, and the allylated magnolol derivative is obtained by drying in a vacuum oven at 60 ℃, and is named as A-M. 3g of polymethylhydrosilane (hydrogen content 0.3% by mass), 0.51. 0.51g A-M and 20ppm of Karster catalyst were uniformly mixed, pre-cured at 70℃for 10min, cured at 90℃for 3h, cured at 110℃for 1h and cured at 130℃for 20min, and the hydrophobic oleophobic bio-based thermosetting polysiloxane product after curing was designated as M-PSO-1.
Example 5:
under nitrogen atmosphere, 5.32g of magnolol is dissolved in 40mL of tetrahydrofuran, 1.008g of sodium hydride is added, the reaction is carried out for 5min at room temperature, then 5.28g of bromopropene is added, the reaction is carried out for 6h at 60 ℃, after the reaction is completed, the mixture is filtered in vacuum, filtrate is collected and distilled under reduced pressure rapidly, yellow oily liquid is obtained, the yellow oily liquid is washed three times by deionized water, and the allylated magnolol derivative is obtained by drying in a vacuum oven at 60 ℃, and is named as A-M. 3g of polymethylhydrosilane (hydrogen content 0.5% by mass), 0.81. 0.81g A-M and 20ppm of Karster catalyst were uniformly mixed, pre-cured at 70℃for 10min, cured at 90℃for 3h, cured at 110℃for 1h and cured at 130℃for 20min, and the hydrophobic oleophobic bio-based thermosetting polysiloxane product after curing was designated as M-PSO-2.
Example 6:
under nitrogen atmosphere, 5.32g of magnolol is dissolved in 40mL of tetrahydrofuran, 1.008g of sodium hydride is added, the reaction is carried out for 5min at room temperature, then 5.28g of bromopropene is added, the reaction is carried out for 6h at 60 ℃, after the reaction is completed, the mixture is filtered in vacuum, filtrate is collected and distilled under reduced pressure rapidly, yellow oily liquid is obtained, the yellow oily liquid is washed three times by deionized water, and the allylated magnolol derivative is obtained by drying in a vacuum oven at 60 ℃, and is named as A-M. 3g of polymethylhydrosilane (hydrogen content 0.75% by mass), 1.14. 1.14g A-M and 20ppm of Karster catalyst were uniformly mixed, pre-cured at 70℃for 10min, cured at 90℃for 3h, cured at 110℃for 1h and cured at 130℃for 20min, and the resulting hydrophobic oleophobic bio-based thermosetting polysiloxane product was designated as M-PSO-3.
Comparative example 1:
3g of polymethylhydrosiloxane (hydrogen content 0.3% by mass), 0.51g of tetravinylcyclotetrasiloxane, 20ppm of Kadster catalyst were homogeneously mixed, pre-cured at 60℃for 10min, cured at 85℃for 3h, cured at 110℃for 1h, and cured at 125℃for 20min, and the cured product was designated PSO.
The products prepared in comparative example 1 and examples 4, 5 and 6 were subjected to mechanical properties and hydrophobic and oleophobic properties characterization, and the characterization means and results are as follows:
1. mechanical properties
Tensile properties of the cured materials were tested according to the GB/T1447-2005 test method using a CMT4303SANS Universal tester (MTS System, shenzhen, china). Tensile strength and elongation at break were measured according to GB/T2568-1995 standard.
2. Hydrophobic Properties
The water contact angle measurement was performed by a contact angle goniometer (JC 2000D1, shanghai digital technical equipment limited).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the hydrophobic oleophobic bio-based thermosetting polysiloxane is characterized by comprising the following operation steps:
(1) Under the nitrogen atmosphere, the renewable biomass magnolol is dissolved in a solvent, a dehydrogenation agent is added, dehydrogenation reaction is carried out at room temperature, then monosubstituted bromoolefin is added at 55-65 ℃ for reaction for 5-8 hours; obtaining biomass magnolol derivative containing four carbon-carbon double bond structures;
(2) Uniformly stirring the biomass magnolol derivative obtained in the step (1) together with polymethylhydrosiloxane and a catalyst, and solidifying to obtain the hydrophobic and oleophobic bio-based thermosetting polysiloxane.
2. The method of manufacturing according to claim 1, characterized in that: the solvent in the step (1) is any one or two of tetrahydrofuran, toluene and N, N-dimethylformamide; the dehydrogenation agent is any one of sodium hydride and potassium carbonate; the monosubstituted bromoolefin is any one of 1-bromopropene, 1-bromopentene and 1-bromohexene.
3. The method of manufacturing according to claim 1, characterized in that: the dehydrogenation agent in the step (1) is sodium hydride; the dehydrogenation reaction time is 5-15min.
4. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the renewable biomass magnolol, the dehydrogenation agent and the monosubstituted bromoolefin in the step (1) is 1:2.1:2.2.
5. the method of manufacturing according to claim 1, characterized in that: the hydrogen content of the polymethylhydrosiloxane in the step (2) is 0.3%, 0.5% or 0.75% by mass; the catalyst is at least one of a Karster catalyst and a Speier catalyst.
6. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the polymethylhydrosiloxane to the biomass magnolol derivative in the step (2) is 1 (0.17-0.4).
7. The method of manufacturing according to claim 1, characterized in that: the catalyst in the step (2) is used in an amount of 10-30ppm; the concrete operation of the curing is as follows: pre-curing for 10min-30min at 60-80deg.C, curing for 2-4 hr at 80-100deg.C, curing for 1-3 hr at 100-120deg.C, and curing for 10-30min at 120-140deg.C.
8. The method of manufacturing according to claim 1, characterized in that: the catalyst in step (2) was used in an amount of 20ppm; the concrete operation of the curing is as follows: pre-curing for 15min at 70 ℃, then curing for 3h at 80-100 ℃, then curing for 1h at 110 ℃, and finally curing for 20min at 130 ℃.
9. The hydrophobic oleophobic bio-based thermoset polysiloxane prepared by the method of any one of claims 1-8.
10. Use of the hydrophobic oleophobic bio-based thermoset polysiloxane according to claim 9 in the fields of anti-fouling, anti-corrosion, self-cleaning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310475895.3A CN116496629B (en) | 2023-04-28 | 2023-04-28 | Hydrophobic oleophobic bio-based thermosetting polysiloxane and preparation method and application thereof |
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