CN110903606B - Plant oil-based composite material and preparation method thereof - Google Patents
Plant oil-based composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000010773 plant oil Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 80
- 239000008158 vegetable oil Substances 0.000 claims abstract description 80
- 229920002678 cellulose Polymers 0.000 claims abstract description 61
- 239000001913 cellulose Substances 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 239000004593 Epoxy Substances 0.000 claims abstract description 46
- 239000002159 nanocrystal Substances 0.000 claims abstract description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000007112 amidation reaction Methods 0.000 claims abstract description 3
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
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- 238000001291 vacuum drying Methods 0.000 claims description 7
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- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
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- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
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- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
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- 230000008569 process Effects 0.000 abstract description 2
- 239000003623 enhancer Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 28
- 239000000725 suspension Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000007789 sealing Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
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- 239000012744 reinforcing agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000005313 fatty acid group Chemical group 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
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- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 238000013100 final test Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a plant oil-based composite material and a preparation method thereof. The preparation method comprises the following steps: respectively dissolving and dispersing a plant oil epoxy high molecular polymer serving as a matrix material and a cellulose nanocrystal serving as an enhancer material in a DMF (dimethyl formamide) solvent according to the mass ratio of (1-9) to (1), and blending, coating and drying to obtain the composite material; the vegetable oil epoxy high molecular polymer is prepared by sequentially carrying out amidation reaction, esterification reaction, polymerization reaction and epoxidation reaction on vegetable oil; the process is simple and environment-friendly to operate, the defect of insufficient strength of the vegetable oil epoxy polymer is effectively overcome, the rigidity and strength of the vegetable oil polymer are improved, the Young modulus of the reinforced and modified composite material is improved by nearly 9 times, and the tensile strength is improved by nearly 11 times.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a plant oil-based composite material and a preparation method thereof.
Background
With the consumption of various non-renewable resources such as petroleum, natural gas, mineral substances and the like and the increasing increase of environmental pollution, the application of renewable and degradable biomass materials has become a necessary trend of social sustainable development. The vegetable oil has rich source, low cost and good biocompatibility, and the main component is fatty acid triglyceride. The vegetable oil high molecule is finally prepared by modifying double bonds of fatty acid to prepare a multifunctional monomer and then carrying out chain growth type polymerization such as ionic polymerization, ring opening polymerization, free radical polymerization and the like, and becomes a hotspot of academic research and application development at home and abroad in recent years. However, the high molecular soft fatty acid side chain of the vegetable oil limits chain entanglement, and the obtained polymer has low glass transition temperature and poor mechanical property, so that the application of the high molecular material of the vegetable oil is limited. For this reason, the vegetable oil thermoplastic polymer needs to be reinforced and modified.
The cellulose nano-grade refers to ultra-fine fiber with the diameter less than 100nm separated from plant cell walls, and has the advantages of light weight, high specific surface area, high strength, good biocompatibility, ultra-fine structure and the like, the Young modulus of a crystalline region can reach 138GPa, the cellulose nano-grade has good solubility resistance in most solvents, and the cellulose nano-grade is taken as a reinforcing phase to be beneficial to improving the mechanical property and the thermal stability of the vegetable oil polymer.
However, the hydrophilic property of cellulose nanometer makes it difficult to uniformly disperse in a hydrophobic polymer system, and the interfaces of different phase materials are difficult to fuse no matter in a solution system or a melting system, so that defects are easy to occur in the materials. In order to improve the dispersion degree of cellulose nanometer, the cellulose needs to be modified by adjusting the process, such as adding a surfactant or chemically modifying. The Chinese patent publication No. CN 103214623A, entitled "a method for preparing surface graft modified cellulose nanocrystals", discloses such a technical scheme, and solves the problem of poor interfacial compatibility between cellulose nanocrystals and polymer matrix. However, the chemical modification can reduce the crystallinity of the cellulose nanometer at the same time, so that the mechanical property of the material is reduced; the addition of the surfactant does not destroy the crystalline structure of cellulose, but suppresses the formation of hydrogen bonding between fibrils. Moreover, in order to reduce the hydroxyl activity of cellulose, a large amount of chemical agents and organic solvents are required to introduce enough hydrophobic groups or ether groups, which is not environment-friendly.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the plant oil-based composite material which is simple and environment-friendly to prepare and has high mechanical property and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a vegetable oil-based composite material, wherein the matrix material of the composite material is vegetable oil epoxy high molecular polymer, and the reinforcement material is cellulose nanocrystal;
the structural formula of the vegetable oil-based epoxy high molecular polymer is as follows:
wherein R is H or CH3(ii) a M is more than or equal to 20 and less than or equal to 500, and n is more than or equal to 20 and less than or equal to 500; x and y are integers of 1 or more; q is more than or equal to 1 and less than or equal to 6, and q is an integer; in the side chain R1、R2Is a hydrocarbyl group.
Preferably, in the technical scheme, the mass ratio of the vegetable oil epoxy high molecular polymer to the cellulose nanocrystals is (1-9): 1.
Preferably, in the above technical scheme, the hydrocarbon group is one or a combination of a plurality of groups selected from alkyl group, carbonyl group, ester group, aromatic group, amide group, imino group, aldehyde group, ether group, hydroxyl group and carboxyl group.
Preferably, in the above technical scheme, the vegetable oil is one or a mixture of any more of sunflower seed oil, soybean oil, castor oil and palm oil.
Preferably, in the above technical scheme, the vegetable oil epoxy high molecular polymer is a type of vegetable oil epoxy high molecular polymer prepared by sequentially performing amidation reaction, esterification reaction, polymerization reaction and epoxidation reaction on vegetable oil.
Preferably, in the above technical scheme, the cellulose nanocrystal is prepared from type I cellulose by a sulfuric acid hydrolysis method, and the type I cellulose is one or a mixture of any more of absorbent cotton, paper pulp, wood pulp and hemp.
The invention also provides a preparation method of the plant oil-based composite material, which comprises the following steps:
s1, weighing 1-5 parts of cellulose nanocrystals, adding the cellulose nanocrystals into 80-100 parts of N, N-dimethylformamide, and ultrasonically dispersing for 60-90 min under the power condition of 800-1400W to obtain a cellulose nano suspension;
s2, weighing 5-15 parts of vegetable oil epoxy polymer, dissolving the vegetable oil epoxy polymer into 100-500 parts of N, N-dimethylformamide, shaking until the vegetable oil epoxy polymer is completely dissolved, and stirring for 1-2 hours at 25-70 ℃ to obtain a vegetable oil epoxy polymer solution;
s3, weighing 2-20 parts of the cellulose nano suspension prepared in the step S1 and 1-10 parts of the vegetable oil epoxy polymer solution prepared in the step S2, blending the cellulose nano suspension and the vegetable oil epoxy polymer solution, and stirring the mixture at the temperature of 40-60 ℃ for 2-8 hours to obtain a dispersion liquid;
S4, pouring the dispersion liquid obtained in the step S3 into a polytetrafluoroethylene mold for film coating, drying at 45-70 ℃, and then placing in a vacuum drying oven for 24-96 hours to prepare a film with the thickness of 0.21-0.3 mm;
wherein, the sequence of the steps S1 and S2 is not separated in sequence.
Preferably, in the above technical solution, the stirring manner in steps S2 and S3 is magnetic stirring.
The invention has the beneficial effects that:
(1) the invention effectively overcomes the defect of insufficient strength of the vegetable oil thermoplastic polymer by utilizing the uniform dispersion of the cellulose nanocrystals in the vegetable oil epoxy polymer system, and improves the rigidity and strength of the vegetable oil epoxy polymer.
(2) The invention utilizes the special structure of the vegetable oil high molecular polymer to prepare the high-performance composite material simply and quickly through a solution blending system, and the preparation process is simple without modifying cellulose nano-particles, thereby reducing the production cost, being convenient for industrial production and having higher economic value.
(3) The raw materials of the plant oil-based composite material are biomass raw materials, have wide sources and low price, reduce the discharge of polluting chemical reagents, and have better ecological environmental protection benefit and sustainability.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a graph of stress-strain curves for the vegetable oil-based composites prepared in examples 10, 11, 12, 13, 14;
FIG. 2 is a photograph of the mixed solution of the cellulose nanocrystal suspension and the vegetable oil epoxy polymer solution in example 14;
FIG. 3a is a SEM of a cross-section of the vegetable oil-based composite prepared in example 11;
fig. 3b is a scanning electron micrograph of a cross section of the vegetable oil-based composite prepared in example 14.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention are described in more detail below with reference to the embodiments, and the following embodiments are only some embodiments, but not all embodiments, of the present invention.
Example 1 preparation of vegetable oil epoxy Polymer 1
(1) Weighing 10 parts of sunflower seed oil according to parts by weight, purging with nitrogen at 100 ℃ for 30min, cooling to 60 ℃, adding 3 parts of ethanolamine, adding 0.2 part of sodium methoxide methanol solution (5mol/L), sealing at 60 ℃, reacting for 4h, adding 18 parts of Dichloromethane (DCM) for dissolving, washing with brine, and drying with anhydrous magnesium sulfate to obtain a plant oil-based precursor;
(2) Taking 10 parts of the plant oil-based precursor obtained in the step (1), adding 5 parts of methacrylic anhydride and 0.04 part of 4-dimethylaminopyridine, sealing and heating to 60 ℃, reacting for 12 hours, adding 2 parts of deionized water, stirring for 1 hour, pouring into DCM, washing with brine, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to obtain a plant oil-based monomer;
(3) dissolving 10 parts of the plant oil-based monomer obtained in the step (2) in 15 parts of Tetrahydrofuran (THF), adding 0.004 part of azobisisobutyronitrile, sealing and heating to 65 ℃ for reaction for 12 hours, and removing the solvent and unreacted monomers by a tetrahydrofuran-methanol precipitation method to obtain a plant oil-based polymer;
(4) dissolving 10 parts of the vegetable oil-based polymer obtained in the step (3) in 100 parts of Dichloromethane (DCM), adding 4.5 parts of m-chloroperoxybenzoic acid, mixing and stirring uniformly, carrying out sealing reaction at room temperature for 48 hours, carrying out rotary evaporation to remove DCM, adding tetrahydrofuran, and obtaining the vegetable oil epoxy polymer 1 by a tetrahydrofuran-methanol precipitation method, wherein the structural formula is shown in the specification; the relative molecular weights were measured as shown in table 1.
Example 2 preparation of vegetable oil-based epoxy Polymer 2
(1) Weighing 100 parts of palm oil according to parts by mass, purging with nitrogen at 100 ℃ for 1h, cooling to 60 ℃, adding 35 parts of 2-methylaminoethanol, adding 1.5 parts of sodium methoxide methanol solution (5mol/L), sealing at 60 ℃, reacting for 4h, adding 200 parts of Dichloromethane (DCM) for dissolving, washing with brine, and drying with anhydrous magnesium sulfate to obtain a plant oil-based precursor;
(2) Taking 20 parts of the plant oil-based precursor obtained in the step (1), adding 10 parts of methacrylic anhydride and 0.08 part of 4-dimethylamino pyridine, sealing and heating to 60 ℃, reacting for 12 hours, adding 4 parts of deionized water, stirring for 1 hour, pouring into DCM, washing with brine, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to obtain a plant oil-based monomer;
(3) dissolving 20 parts of the plant oil-based monomer obtained in the step (2) in 32 parts of Tetrahydrofuran (THF), adding 0.008 part of azobisisobutyronitrile, sealing and heating to 65 ℃ for reaction for 12 hours, and removing the solvent and unreacted monomers by a tetrahydrofuran-methanol precipitation method to obtain a plant oil-based polymer;
(4) dissolving 20 parts of the plant oil-based polymer obtained in the step (3) in 220 parts of Dichloromethane (DCM), adding 4.5 parts of m-chloroperoxybenzoic acid, mixing and stirring uniformly, carrying out sealing reaction at room temperature for 48 hours, then carrying out rotary evaporation to remove DCM, adding tetrahydrofuran, and obtaining the plant oil-based epoxy polymer 2 by a tetrahydrofuran-methanol precipitation method, wherein the structural formula is shown in the specification; the relative molecular weights and degrees of dispersion were measured as shown in Table 1.
EXAMPLE 3 preparation of vegetable oil epoxy Polymer solution 1
Weighing 12 parts of vegetable oil epoxy polymer 1, dissolving in 100 parts of N, N-dimethylformamide, shaking to dissolve completely, and magnetically stirring at 40 ℃ for 1h to obtain vegetable oil epoxy polymer solution 1.
EXAMPLE 4 preparation of vegetable oil epoxy Polymer solution 2
Weighing 15 parts of the vegetable oil epoxy polymer 2, dissolving in 100 parts of N, N-dimethylformamide, shaking to completely dissolve, and magnetically stirring for 2 hours at 40 ℃ to obtain the vegetable oil epoxy polymer solution 2.
Example 5 preparation of cellulose nanocrystal 1
Weighing 6 parts of absorbent cotton, adding the absorbent cotton into 90 parts of 64 wt% sulfuric acid solution, stirring in a water bath at 45 ℃ for 1 hour, adding 900 parts of deionized water for dilution, carrying out centrifugal separation on the suspension, dialyzing the dispersion to be neutral by using a dialysis membrane, and then carrying out freeze drying to obtain the cellulose nanocrystal 1.
Example 6 preparation of cellulose nanocrystals 2
Weighing 9 parts of paper pulp, adding the paper pulp into 120 parts of 64 wt% sulfuric acid solution, stirring in a water bath at 40 ℃ for 1.5 hours, adding 1200 parts of deionized water for dilution, carrying out centrifugal separation on the suspension, dialyzing the dispersion to be neutral by using a dialysis membrane, and then carrying out freeze drying to obtain the cellulose nanocrystal 2.
Example 7 preparation of cellulose nanocrystal suspension 1
Weighing 4 parts of cellulose nanocrystal 1, adding the cellulose nanocrystal 1 into 100 parts of N, N-dimethylformamide, and performing ultrasonic dispersion for 80 minutes under the power condition of 1000W to obtain a cellulose nanocrystal suspension 1.
EXAMPLE 8 preparation of cellulose nanocrystal suspension 2
Weighing 10 parts of cellulose nanocrystal 2, adding the cellulose nanocrystal 2 into 500 parts of N, N-dimethylformamide, and performing ultrasonic dispersion for 90 minutes under the power condition of 1200W to obtain a cellulose nanocrystal suspension 2.
Example 9 preparation of cellulose nanocrystal suspension 3
Weighing 5 parts of cellulose nanocrystal 1, adding the cellulose nanocrystal 1 into 100 parts of N, N-dimethylformamide, and performing ultrasonic dispersion for 90 minutes under the power condition of 800W to obtain a cellulose nanocrystal suspension 3.
Example 10 preparation of vegetable oil-based composite 1 (control)
Weighing 9 parts of vegetable oil epoxy polymer solution 1, pouring the vegetable oil epoxy polymer solution into a polytetrafluoroethylene mold for coating, drying at 60 ℃, then placing the polytetrafluoroethylene mold in a vacuum drying oven for 48 hours to prepare a film with the thickness of 0.28mm, namely the vegetable oil-based composite material 1, and measuring the mechanical properties of the vegetable oil-based composite material 1, wherein the mechanical properties are shown in figure 1.
Example 11 preparation of vegetable oil-based composite 2
7.5 parts of vegetable oil epoxy polymer solution 1 is weighed and mixed with 2.5 parts of cellulose nanocrystal suspension 1, and the mixture is magnetically stirred for 8 hours at the temperature of 50 ℃. Pouring the uniformly stirred dispersion into a polytetrafluoroethylene mold for coating, drying at 60 ℃, and then placing in a vacuum drying oven for 48 hours to prepare a film with the thickness of 0.25mm, namely the plant oil-based composite material 2. The cross section of the composite film was observed by scanning electron microscopy as shown in FIG. 3. The mechanical properties were measured as shown in FIG. 1.
Example 12 preparation of vegetable oil-based composite 3
Weighing 6.7 parts of the vegetable oil-based epoxy polymer solution 1, magnetically stirring the solution at the temperature of 40-60 ℃ for 2-8 hours, mixing the solution with 10 parts of the cellulose nanocrystal suspension 2, and magnetically stirring the mixture at the temperature of 60 ℃ for 6 hours. Pouring the uniformly stirred dispersion into a polytetrafluoroethylene mold for film coating, drying at 70 ℃, and then placing in a vacuum drying oven for 48 hours to prepare a film with the thickness of 0.24mm, namely the plant oil-based composite material 3. The mechanical properties were measured as shown in FIG. 1.
Example 13 preparation of vegetable oil-based composite 4
4.7 parts of the vegetable oil-based epoxy polymer solution 2 is weighed, mixed with 6 parts of the cellulose nanocrystal suspension 3, and magnetically stirred at 60 ℃ for 6 hours. Pouring the uniformly stirred dispersion into a polytetrafluoroethylene mold for coating, drying at 70 ℃, and then placing in a vacuum drying oven for 48 hours to prepare a film with the thickness of 0.24mm, namely the plant oil-based composite material 4. The mechanical properties were measured as shown in FIG. 1.
Example 14 preparation of vegetable oil-based composite 5
Weighing 4.2 parts of vegetable oil epoxy polymer solution 1, adding 10 parts of cellulose nanocrystal suspension 3, and magnetically stirring at 60 ℃ for 6 hours to obtain a uniform and stable gel-like mixed membrane solution, as shown in fig. 2. Pouring the uniformly stirred dispersion into a polytetrafluoroethylene mold for film coating, drying at 70 ℃, and then placing in a vacuum drying oven for 48 hours to prepare a film with the thickness of 0.21mm, namely the plant oil-based composite material 5. The mechanical properties were measured as shown in FIG. 1. And (3) observing the section morphology of the plant oil-based composite material, as shown in figure 3.
The molecular weights and the distribution degrees of the vegetable oil-based epoxy polymers prepared in examples 1 and 2 are shown in table 1 below:
| relative molecular weight (g/mol) | Degree of molecular weight distribution | |
| Example 1 | 44700 | 3.07 |
| Example 2 | 38200 | 3.1 |
Table 1 illustrates: the performances of the two vegetable oil-based epoxy polymers are not obviously different.
Mechanical tensile property tests are carried out on the plant oil-based composite materials prepared in examples 10-14 according to GB/T1040.3-2006, the final test result is an average value of 5 measurements, and the statistics of test data are shown in the following table 2:
the plant oil-based composite materials prepared in examples 10 to 14 were subjected to a stress-strain test, and the curve is shown in fig. 1.
Combining the data of table 2 with the curves of fig. 1, illustrates: the addition of the cellulose nanocrystals can obviously improve the Young modulus and tensile strength of the vegetable oil-based macromolecules and effectively overcome the defect of insufficient strength of the vegetable oil-based macromolecules. Because of the good interface compatibility between the cellulose nanocrystals and the vegetable oil high molecular in the system, the content of the reinforcing agent can reach 50 wt%, and compared with the vegetable oil-based high molecular material, the Young modulus of the composite material is improved by nearly 9 times, and the tensile strength is improved by nearly 11 times. In addition, with the increase of the content of the cellulose nanocrystals, the tensile strength is almost linearly related therewith, so that the situation that the reinforcing agent is uniformly dispersed in the vegetable oil-based polymer matrix in the composite system is further explained, and a new thought is provided for the further application of the vegetable oil polymer material.
The membrane solution after mixing the cellulose nanocrystal suspension and the vegetable oil epoxy polymer solution in example 14 is shown in fig. 2, and fig. 2 illustrates: the reinforcing agent and the substrate material have good compatibility.
Scanning electron microscopes of sections of the vegetable oil-based composite materials of examples 11 and 14 are shown in fig. 3a and 3b, respectively, and fig. 3a and 3b illustrate: when the addition amounts of the cellulose nanocrystals are 10 wt% and 50 wt%, the cellulose nanocrystals can be uniformly dispersed in the vegetable oil-based polymer matrix, and the nanoscale reinforcing phase does not have obvious aggregation phenomenon, so that a uniform and stable composite network structure can be formed, and the mechanical strength of the vegetable oil-based polymer is improved.
The foregoing is merely illustrative and explanatory of the invention and is not restrictive of the embodiments, as those skilled in the art will be able to make numerous non-essential changes and modifications in light of the above teachings, and fall within the scope of the appended claims.
Claims (8)
1. The plant oil-based composite material is characterized in that a matrix material in the composite material is a plant oil epoxy high molecular polymer, and a reinforcement material is a cellulose nanocrystal; the structural formula of the vegetable oil epoxy high molecular polymer is as follows:
Wherein R is H or CH3(ii) a M is more than or equal to 20 and less than or equal to 500, and n is more than or equal to 20 and less than or equal to 500; x and y are integers greater than or equal to 1; q is more than or equal to 1 and less than or equal to 6, and q is an integer; in the side chain R1、R2Is a hydrocarbyl group.
2. The vegetable oil-based composite of claim 1, wherein: the mass ratio of the vegetable oil epoxy high molecular polymer to the cellulose nanocrystal is (1-9): 1.
3. The vegetable oil-based composite of claim 1, wherein: the alkyl group is one or a combination structure of a plurality of groups of alkyl, carbonyl, ester, aromatic, amide, imino, aldehyde group, ether group, hydroxyl and carboxyl.
4. The plant oil-based composite material according to claim 1 or 2, wherein: the vegetable oil is one or mixture of more of sunflower seed oil, soybean oil, castor oil and palm oil.
5. The plant oil-based composite material according to claim 1 or 2, wherein: the vegetable oil epoxy high molecular polymer is prepared by sequentially carrying out amidation reaction, esterification reaction, polymerization reaction and epoxidation reaction on vegetable oil.
6. The plant oil-based composite of claim 1 or 2, wherein: the cellulose nanocrystal is prepared from I-type cellulose by a sulfuric acid hydrolysis method, wherein the I-type cellulose is one or a mixture of any more of absorbent cotton, paper pulp, wood pulp and hemp.
7. A method of making the plant oil-based composite of any of claims 1 to 6, comprising the steps of:
s1, weighing 1-5 parts of cellulose nanocrystals, adding the cellulose nanocrystals into 80-100 parts of N, N-dimethylformamide, and performing ultrasonic dispersion for 60-90 min under the condition of 800-1400W of power to obtain a cellulose nano suspension;
s2, weighing 5-15 parts of vegetable oil epoxy polymer, dissolving the vegetable oil epoxy polymer into 100-500 parts of N, N-dimethylformamide, shaking until the vegetable oil epoxy polymer is completely dissolved, and stirring for 1-2 hours at 25-70 ℃ to obtain a vegetable oil epoxy polymer solution;
s3, weighing 2-20 parts of the cellulose nano suspension prepared in the step S1 and 1-10 parts of the vegetable oil epoxy polymer solution prepared in the step S2, blending the cellulose nano suspension and the vegetable oil epoxy polymer solution, and stirring the mixture at the temperature of 40-60 ℃ for 2-8 hours to obtain a dispersion liquid;
s4, pouring the dispersion liquid obtained in the step S3 into a polytetrafluoroethylene mold for film coating, drying at 45-70 ℃, and then placing in a vacuum drying oven for 24-96 hours to prepare a film with the thickness of 0.21-0.3 mm;
Wherein, the sequence of the steps S1 and S2 is not separated in sequence.
8. The method of making a plant oil-based composite of claim 7, wherein: the stirring in the steps S2 and S3 is magnetic stirring.
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