CN115181397A - High-strength high-toughness thermosetting resin composite material capable of being printed in 3D mode and preparation method and application thereof - Google Patents
High-strength high-toughness thermosetting resin composite material capable of being printed in 3D mode and preparation method and application thereof Download PDFInfo
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- CN115181397A CN115181397A CN202210489323.6A CN202210489323A CN115181397A CN 115181397 A CN115181397 A CN 115181397A CN 202210489323 A CN202210489323 A CN 202210489323A CN 115181397 A CN115181397 A CN 115181397A
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- thermosetting resin
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- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 16
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims description 2
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims description 2
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 12
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- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 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
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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Abstract
The invention discloses a high-strength high-toughness thermosetting resin composite material capable of being printed in a 3D mode and a preparation method and application thereof. The grafting modified nano lignocellulose is stably dispersed in thermosetting resin monomers, a catalyst is added, and the high-strength high-toughness thermosetting resin composite material capable of being printed in 3D is obtained after ring-opening metathesis polymerization reaction at the front end. The grafted and modified nano lignocellulose can effectively slow down the reaction rate of thermosetting resin monomers during ring-opening metathesis polymerization at the front end, and can simultaneously increase the tensile stress and strain of the composite material. The grafted and modified nano lignocellulose can be simultaneously used as an inhibitor of front-end ring-opening metathesis polymerization and a toughening reinforcing agent of a thermosetting material, can be widely applied to the preparation of 3D printing thermosetting resin materials, and the prepared 3D printing composite material can be widely applied to the fields of engineering protection, automobile and ship shells, packing cases and the like.
Description
Technical Field
The invention belongs to the field of thermosetting resin nanocomposite polymerization, and particularly relates to modified nano lignocellulose which can be used as an inhibitor of front-end ring-opening metathesis polymerization and a toughening reinforcing agent of thermosetting resin and is used for preparing a high-strength high-toughness thermosetting resin composite material capable of being printed in a 3D mode.
Background
Thermosetting resins and their composites play an important role in aerospace, automotive, marine and energy industries due to their excellent stiffness, strength and thermal stability, however, the manufacture of traditional high performance thermosetting resins often requires strict conditions such as high temperature and high pressure. Besides, the insufficient mechanical properties of thermosetting resins are another factor limiting their wide application. With the development of research, researchers have found that front-end ring-opening metathesis polymerization (FROMP) is a promising strategy to replace traditional curing methods, and that the self-exothermic reaction of FROMP gradually converts liquid monomers into cured polymers, and only a small amount of energy is required to start the process without further energy input, reducing the energy required for thermoset resin manufacture and reducing the manufacturing requirements.
However, the rate of polymerization becomes another issue to be discussed when using FROMP to cure thermoset resins. If no limitation is placed on the polymerization rate, the polymerization rate of the FROMP is too fast under the action of the catalyst, so that the thermosetting resin suitable for the reaction is limited in 3D printing, and too fast a polymerization rate makes it difficult for the thermosetting resin to match the 3D printing rate. At the same time, too fast a polymerization rate also leads to a more stressed processing time, often the reaction is completed before the formal molding is carried out, resulting in non-uniform polymerization, affecting the final properties and limiting the processing mode. The current solution is to use small molecule inhibitors such as phosphate inhibitors found by Robertson, which reduce the FROMP rate and extend the operating time of the liquid monomer at room temperature. However, although the addition of the small-molecule inhibitor reduces the polymerization rate, the molecular weight is reduced because the polymerization of the thermosetting resin is inhibited, and the mechanical properties of the whole material are influenced to a certain extent, so that the application scene is limited. Therefore, preparing a thermosetting resin that can be 3D printed and has both strength and toughness remains a problem to be solved.
The nano lignocellulose extracted from natural plants has nano size and good mechanical properties. They are green fillers and have wide application in polymer reinforced functional composite materials. Many researchers have improved the mechanical properties of the composite of the nanofiber and the high molecular polymer. For example, in chinese patent CN113004474a, a multi-walled carbon nanotube is compounded with polydicyclopentadiene to obtain a thermosetting resin composite material with excellent performance. Zhang et al compounds nano lignocellulose with polylactic acid, and when the addition of nano lignocellulose reaches 20%, the bending property of the composite material is improved by 120.6%. However, the reinforcement research of applying the modified nano lignocellulose to the thermosetting resin prepared by the front-end ring-opening metathesis polymerization reaction is rarely reported at present.
In summary, no effective solution has been proposed at present for the contradiction between the polymerization rate and the mechanical properties of the thermosetting resin prepared by the front-end ring-opening metathesis polymerization and the problems in the related art.
In view of this, the present invention is proposed.
Disclosure of Invention
The purpose of the invention is as follows: the small molecule inhibitor adopted in the traditional front-end ring-opening metathesis polymerization has influence on the mechanical property of the thermosetting resin. Aiming at the problems, the invention provides an inhibitor and a thermosetting resin toughening reinforcing agent which can be based on front-end ring-opening metathesis polymerization at the same time, and the inhibitor and the thermosetting resin toughening reinforcing agent are used for preparing a high-strength high-toughness thermosetting resin composite material capable of being printed in a 3D mode. The invention utilizes the excellent dispersion performance of the grafted and modified nano lignocellulose in the thermosetting resin monomer, and simultaneously plays the roles of the nano filler and the inhibitor, thereby realizing the purposes of weakening the polymerization rate and enhancing the mechanical property of the thermosetting resin. The inhibitor and the toughening reinforcing agent are used as bio-based products, and have the characteristics of environmental friendliness, high production efficiency, strong operability and the like.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of a high-strength high-toughness thermosetting resin composite material capable of being printed in a 3D mode is characterized by comprising the following steps:
s1) adding modified nano lignocellulose into a thermosetting resin monomer to obtain uniform and stable dispersion liquid;
s2) adding a catalyst into the uniform dispersion liquid obtained in the step 1), and carrying out ring-opening metathesis polymerization reaction on the front end to obtain the high-strength high-toughness thermosetting resin composite material capable of being printed in 3D.
Further, an inhibitor is added in the step 2), wherein the inhibitor is any one or a combination of at least two of trimethylolpropane, triethyl phosphate and tributyl phosphate, and is preferably triethyl phosphate.
Further, the catalyst in the step 2) is at least one of a first-generation Grubbs catalyst (GC 1), a second-generation Grubbs catalyst (GC 2) and a Hoveyda-Grubbs catalyst, and is preferably a GC2 catalyst.
Further, the lignocellulose source in the step 1) is any one or a combination of at least two of wood, grass, bamboo cellulose and hemp, and is preferably wood cellulose.
Further, the modified nano lignocellulose obtained in the step 1) is surface esterification modified or grafting modified nano lignocellulose.
Further, the modified nano lignocellulose is any one of or a combination of at least two of lactic acid-esterified nano lignocellulose, oxalic acid-esterified nano lignocellulose, acrylic acid-esterified nano lignocellulose, polylactic acid-grafted modified nano lignocellulose and polycaprolactone-grafted modified nano lignocellulose, and preferably is polylactic acid-grafted modified nano lignocellulose and polycaprolactone-grafted modified nano lignocellulose.
Further, the thermosetting resin monomer in step 1) includes: any one or a combination of at least two of endo-dicyclopentadiene, exo-dicyclopentadiene, ethylidene norbornene, exo-5-norbornene carboxylic acid, and 5-norbornene-2-methanol, preferably endo-dicyclopentadiene or exo-dicyclopentadiene.
Further, the mass ratio of the grafting modified nano lignocellulose in the step 1) to the thermosetting resin monomer is 1: 1000-1: 10.
Further, the diameter of the nano lignocellulose in the step 1) is 5-1000nm, the length of the nano lignocellulose is 0.1-10 microns, the content of the lignin is 0-30%, preferably, the diameter of the nano lignocellulose is 5-500nm, the length of the nano lignocellulose is 0.2-5 microns, and the content of the lignin is 0-25%.
Further, the front-end heating initiation reaction temperature in the step 2) is 10-200 ℃, the ambient temperature is-20-60 ℃, and the preferable reaction temperature is 15-150 ℃, and the ambient temperature is-10-40 ℃.
Further, the rate of the front-end ring-opening metathesis polymerization reaction of the grafted and modified nano lignocellulose regulated thermosetting resin monomer in the step 2) is reduced by 10-2000%.
According to another aspect of the invention, a high-strength high-toughness thermosetting resin composite material capable of being 3D printed is provided, and the high-strength high-toughness thermosetting resin composite material capable of being 3D printed is prepared by the preparation method.
Furthermore, the tensile stress reinforcement ratio of the composite material is 5-500%, the tensile strain reinforcement ratio is 5-1000%, and the Young modulus improvement ratio is 5-500%.
Furthermore, the composite material can be processed and formed in any mode of hot pressing, injection molding, extrusion molding and 3D printing processes. Injection molding and 3D printing processes are preferred.
Furthermore, the composite material can be applied to the fields of engineering protection, packing boxes, ship and vehicle shells and the like.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1) The inhibitor based on the ring-opening metathesis polymerization of the front end can be stably dispersed in the liquid monomer of the thermosetting resin. The heat transfer efficiency of the inhibitor is different from that of the liquid monomer of the thermosetting resin, so that the polymerization rate of the FROMP is reduced, and the polymerization rate can be controlled according to the addition amount of the inhibitor.
2) Compared with the traditional small molecule inhibitor, the toughening reinforcing agent based on the front-end ring-opening metathesis polymerization provided by the invention can improve the tensile stress and tensile strain of the thermosetting polymer.
3) According to the inhibitor and the toughening reinforcing agent based on the front-end ring-opening metathesis polymerization, the thermosetting liquid monomer can be processed into the composite material through the processes of hot pressing, extrusion molding, injection molding, 3D printing and the like, the reaction rate is controllable, the method is simple, and the obtained material has good performance.
Drawings
FIG. 1 is a flow chart of the preparation of a 3D printable high strength and high toughness thermoset resin composite;
FIG. 2 is a transmission electron microscope image of the prepared graft polymerization modified nano-sized lignocellulose;
FIG. 3 is a graph showing the dispersibility of the grafted and modified nano-lignocellulose in dicyclopentadiene liquid monomer; (DCPD is dicyclopentadiene)
FIG. 4 is a photograph of the same FROMP reaction time with the addition of 1% and 5% nanocellulose; (CNF-g-PLA is polylactic acid graft modified nano-cellulose, R.T. is room temperature)
FIG. 5 is a graph of the mechanical properties of polydicyclopentadiene composite after addition of graft polymerized modified nano-lignocellulose;
FIG. 6 is a sample diagram of a high strength and high toughness thermoset resin composite prepared by a 3D printing process;
FIG. 7 is a 3D printed application of high strength and high toughness thermosetting resin composite material in the field of engineering protection. (PDCPD is 3D printing polydicyclopentadiene, composite is polylactic acid graft modified nano-cellulose and polydicyclopentadiene Composite 3D printing material)
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings, technical process steps, specific implementation conditions and materials in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The lignocellulosic raw material used in the present invention may be derived from wood, grasses, bamboo, hemp, cotton, etc., and the present invention will be described below in examples using lignocellulose derived from wood as a raw material.
Example 1
The FROMP reaction was initiated by adding GC2 catalyst to the dicyclopentadiene monomer and heating on a 65 ℃ heat block for 10s, which was less than 10s complete. The tensile stress of the polydicyclopentadiene was 29.56MPa, the tensile strain was 8.21%, and the Young's modulus was 623MPa.
Example 2
The reaction rate is reduced by 1226% after the reaction of the FROMP within 150s, the tensile strain of the obtained polydicyclopentadiene is increased by 17.84% compared with that of pure polydicyclopentadiene, the tensile stress is reduced by 17.06% and the Young modulus is reduced by 21.33% compared with example 10.
Example 3
The FROMP reaction was initiated by adding GC2 catalyst and triethyl phosphate (TEP) inhibitor to the dicyclopentadiene monomer and heating on a heating table at 65 ℃ for 90s, with the FROMP reacting to completion within 150 s. The reaction rate is reduced by 1314%, and compared with the polydicyclopentadiene prepared in example 10, the tensile strain is increased by 6.84%, the tensile stress is reduced by 26.11%, and the Young modulus is reduced by 29.44%.
Example 4
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating the dispersion liquid for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into a dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 1: 100. The FROMP reaction was started by adding GC2 catalyst and heating on a heating table at 65 ℃ for 30s, which was completed within 60 s. The reaction rate is reduced by 439 percent, and the tensile strain of the obtained polydicyclopentadiene nano-cellulose composite material is improved by 6.33 percent compared with that of pure polydicyclopentadiene, the tensile stress is improved by 36.69 percent, and the Young modulus is improved by 49.36 percent.
Example 5
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 2: 100. The FROMP reaction was initiated by addition of GC2 catalyst and heating on a 65 ℃ heating block for 45s, which was completed within 60 s. The reaction rate is reduced by 564%, and the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is improved by 28.49%, the tensile stress is improved by 35.92%, and the Young modulus is improved by 79.88% compared with that of pure polydicyclopentadiene.
Example 6
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 3: 100. The FROMP reaction was started by adding GC2 catalyst and heating on a heating table at 65 ℃ for 60s, which was completed within 90 s. The reaction rate is reduced by 768%, and compared with the pure dicyclopentadiene, the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is increased by 52.37%, the tensile stress is increased by 23.15%, and the Young modulus is increased by 109.88%.
Example 7
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/m 1), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 4: 100. The FROMP reaction was started by adding GC2 catalyst and heating on a heating table at 65 ℃ for 75s, which was completed within 120 s. The reaction rate is reduced by 1105%, and the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is increased by 111.37%, the tensile stress is increased by 21.05% and the Young modulus is increased by 263.88% compared with that of pure polydicyclopentadiene.
Example 8
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/m 1), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 5: 100. The FROMP reaction was initiated by addition of GC2 catalyst and heating on a 65 ℃ heating block for 90s, which was completed within 150 s. The reaction rate is reduced by 1221%, and the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is improved by 303.88%, the tensile stress is improved by 22.01%, and the Young modulus is improved by 313.44% compared with that of pure polydicyclopentadiene.
Example 9
Taking 1g of absolute dry cellulose, wherein the content of lignin is 5.69%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano-cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating the dispersion liquid for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polycaprolactone grafted and modified nano lignocellulose into a dicyclopentadiene monomer in a ratio of 1: 10. The FROMP reaction was initiated by addition of GC2 catalyst and heating on a 65 ℃ heating block for 90s, which was completed within 150 s. The reaction rate is reduced by 1198%, and the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is increased by 135.75%, the tensile stress is increased by 39.05% and the Young modulus is increased by 493.44% compared with that of pure polydicyclopentadiene.
Example 10
Taking 1g of absolute dry cellulose, wherein the content of lignin is 17.19%, uniformly mixing lignocellulose and lactic acid/choline chloride eutectic solvent in a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating in a colloid mill for 40min to obtain the nano-cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polycaprolactone grafted and modified nano lignocellulose into a dicyclopentadiene monomer in a ratio of 1: 10. The FROMP reaction was initiated by addition of GC2 catalyst and heating on a 65 ℃ heating block for 150s, which was completed within 150 s. The reaction rate is reduced by 1315%, and the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is improved by 369.24%, the tensile stress is improved by 13.54%, and the Young modulus is improved by 365.19% compared with that of pure polydicyclopentadiene.
Example 11
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into an ethylidene norbornene monomer in a ratio of 1: 200. The FROMP reaction was initiated by heating the reaction mixture with GC2 catalyst on a heating table at 85 ℃ for 150 seconds, and the FROMP reaction was completed within 150 seconds. The reaction rate is reduced by 1241%, and the tensile strain of the obtained poly ethylidene norbornene nano cellulose composite material is increased by 89.24% compared with that of pure poly ethylidene norbornene, the tensile stress is increased by 11.54%, and the Young modulus is increased by 264.58%.
Example 12
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/m 1), heating and swelling at 100 ℃ for 3h, and then circulating in a colloid mill for 40min to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 1: 20. The FROMP reaction was initiated by adding GC2 catalyst and tributyl phosphate (TBP) inhibitor and heating at 85 deg.C for 150 seconds, which was less than 150 seconds. The reaction rate is reduced by 1291%, and compared with pure dicyclopentadiene, the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is increased by 119.24%, the tensile stress is increased by 9.54%, and the Young modulus is increased by 196.58%.
Example 13
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling at 100 ℃ for 3h, and then circulating in a colloid mill for 40min to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into a 5-norbornene-2-methanol monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the 5-norbornene-2-methanol monomer is 0.1: 100. The FROMP reaction was initiated by heating on a heating block at 85 ℃ for 150s, and the FROMP reaction was completed within 150 s. The reaction rate is reduced by 1305%, and the tensile strain of the obtained poly-5-norbornene-2-methanol nano-cellulose composite material is improved by 299.53%, the tensile stress is improved by 38.69% and the Young modulus is improved by 234.58% compared with that of pure poly-5-norbornene-2-methanol.
Example 14
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 8: 100. And (3) putting the monomer dispersion liquid into a 3D printer for 3D printing, setting the temperature of a printing table to 65 ℃ to start a FROMP reaction, wherein the polydicyclopentadiene nanocellulose composite material obtained by 3D printing has an obvious three-dimensional structure.
Example 15
Taking 1g of absolute dry cellulose, wherein the content of lignin is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to a solid-to-liquid ratio of 1: 10 (g/ml), heating and swelling for 3h at 100 ℃, and then circulating for 40min in a colloid mill to obtain the nano cellulose dispersion liquid. Adding a stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the graft modified nano-cellulose. Adding the polylactic acid graft modified nano-cellulose into dicyclopentadiene monomer, wherein the ratio of the polylactic acid graft modified nano-cellulose to the dicyclopentadiene monomer is 1: 8. Adding a GC2 catalyst and heating on a heating table at 65 ℃, wherein after long-time heating, the FROMP reaction can not be started, the reaction solution volatilizes under long-time heating, and the polydicyclopentadiene nanocellulose composite material can not be prepared.
Example 16
The unmodified nano-cellulose dispersion is used as a raw material. Adding into dicyclopentadiene monomer by solvent replacement method, wherein the ratio is 1: 100. Heating at 85 deg.C on a heating table to start the FROMP reaction, and the FROMP reaction is completed within 80 s. The reaction rate is reduced by 701%, but the dispersibility of the unmodified nano-cellulose in the dicyclopentadiene monomer is poor, so that the uniformity of the obtained polydicyclopentadiene nano-cellulose composite material is reduced, the tensile strain is reduced by 33.53% compared with that of pure polydicyclopentadiene, the tensile stress is reduced by 38.69%, and the Young modulus is reduced by 19.58%.
In this embodiment, the nanocellulose may also be a substitute for the nanocellulose, and as the nanocellulose or the nanocellulose is not modified, the dispersion performance of the nanocellulose or the nanocellulose in the dicyclopentadiene monomer is poor, and the performance of the composite material is adversely affected.
Microscopic morphological characterization of the product of example 9 was performed, and fig. 2 is a TEM image of the modified nano-lignocellulose prepared. As can be seen from fig. 2, the diameter of the nano lignocellulose is less than 100nm, and the length is several micrometers.
The dispersibility characterization of the modified nano-lignocellulose in example 7 is performed, and fig. 3 is a dispersion effect diagram of the nano-lignocellulose in the dicyclopentadiene monomer, which can be seen from the figure that the modified nano-lignocellulose has good dispersibility and is beneficial to the construction of the thermosetting resin composite material through the FROMP reaction.
Fig. 4 is a photograph showing that the modified nano-lignocellulose prepared in examples 4 and 9 was added to dicyclopentadiene to perform FROMP reaction, wherein the arrows indicate the boundary between the uncured liquid monomer and the cured polymer at the same time, and it can be seen that the addition of 5% of the modified nano-lignocellulose resulted in a slower polymerization rate than the addition of 1%, indicating the advantage of the graft polymerization modified nano-lignocellulose as an inhibitor of the FROMP reaction. Compared with the commercial inhibitor (without adding the modified nano lignocellulose), the polymerization rate of the modified nano lignocellulose is reduced by only adding 1 percent. And no bubble exists in the polymerization process, which shows that the reaction process is more uniform, avoids the mechanical property defect caused by the bubble, and is beneficial to the improvement of the mechanical property.
The modified nano lignocellulose obtained in examples 4 to 8 is compounded with dicyclopentadiene, and fig. 5 is a change curve of tensile stress and strain of the obtained composite material. As can be seen from the figure, the stress and strain values of the composite material are improved compared to the non-added condition. The advantages of the modified nano lignocellulose as the toughening reinforcing agent of the thermosetting resin are shown.
The dispersion prepared in example 13 was manufactured by a 3D printing method, and the manufactured sample graph is shown in fig. 6, which shows that the high-strength and high-toughness thermosetting resin composite material prepared by the method can be formed by 3D printing.
The dispersions prepared in examples 1 and 13 were manufactured by 3D printing, and the manufactured samples were used as engineering protective fences. The vehicle crash situation is simulated by a simple experimental setup in fig. 7 a. Fig. 7b is a photograph of the sample prepared in example 1 at the moment of vehicle impact, when the vehicle collides with the sample, the vehicle is damaged, and the sample is not deformed. Fig. 7c is a photograph of the sample prepared in example 13 at the moment of impact with a vehicle, when the vehicle collides with the sample, the vehicle is not significantly damaged, and the sample is deformed, indicating that the sample in example 11 has a certain impact resistance.
The embodiments related to the present invention are not limited to the above embodiments, and table 1 briefly lists the 3D printable high-strength high-toughness thermosetting resin composite material and the degree of improvement in mechanical properties.
TABLE 1
Claims (10)
1. A preparation method of a high-strength high-toughness thermosetting resin composite material capable of being printed in a 3D mode is characterized by comprising the following steps:
s1) adding modified nano lignocellulose into a thermosetting resin monomer to obtain uniform and stable dispersion liquid;
s2) adding a catalyst into the uniform dispersion liquid obtained in the step 1), and carrying out ring-opening metathesis polymerization reaction on the front end to obtain the high-strength high-toughness thermosetting resin composite material capable of being printed in 3D.
2. The preparation method of the 3D printable high-strength high-toughness thermosetting resin composite material according to the claim 1, characterized in that an inhibitor is further added in the step 2), wherein the inhibitor is any one or a combination of more than two of trimethylolpropane, triethyl phosphate and tributyl phosphate; the catalyst is any one or more of a first-generation Grubbs catalyst (GC 1), a second-generation Grubbs catalyst (GC 2) and a Hoveyda-Grubbs catalyst.
3. The method for preparing a high-strength high-toughness thermosetting resin composite material capable of being 3D printed according to claim 1 or claim 2, wherein the method comprises the following steps: in the step 1), the modified nano lignocellulose is any one or a combination of more than two of lactic acid esterification modified lignocellulose nano fiber, oxalic acid esterification modified lignocellulose nano fiber, acrylic acid esterification modified lignocellulose nano fiber, polylactic acid grafting modified nano lignocellulose and polycaprolactone grafting modified nano lignocellulose.
4. The method for preparing a high-strength high-toughness thermosetting resin composite material capable of being 3D printed according to claim 1 or claim 2, wherein the method comprises the following steps: in the step 1), the diameter of the nano lignocellulose is 5-500nm, the length of the nano lignocellulose is 0.2-5 microns, and the content of lignin is 0% -25%; the mass ratio of the grafted modified nano lignocellulose to the thermosetting resin monomer is as follows: 1: 1000-1: 10.
5. The method for preparing a high-strength high-toughness thermosetting resin composite material capable of being 3D printed according to claim 1 or claim 2, wherein the method comprises the following steps: in step 1), the thermosetting resin monomer comprises: any one or a combination of at least two of endo-dicyclopentadiene, exo-dicyclopentadiene, ethylidene norbornene, exo-5-norbornene carboxylic acid, and 5-norbornene-2-methanol.
6. The method for preparing a high strength and high toughness thermosetting resin composite material capable of being 3D printed according to claim 1 or claim 2, wherein: in the step 2), the reaction temperature of the front end heating initiation is 15-150 ℃, and the ambient temperature is-10-40 ℃.
7. The method for preparing a high-strength high-toughness thermosetting resin composite material capable of being 3D printed according to claim 1 or claim 2, wherein the method comprises the following steps: in the step 2), the rate of the front-end ring-opening metathesis polymerization reaction of the grafted and modified nano lignocellulose regulated thermosetting resin monomer is reduced by 10-2000%.
8. A 3D printable high strength and toughness thermosetting resin composite material, which is prepared by the preparation method of the 3D printable high strength and toughness thermosetting resin composite material according to any one of claims 1 to 7; the tensile stress reinforcement proportion of the high-strength high-toughness thermosetting resin composite material is 5-500%, the tensile strain reinforcement proportion is 5-1000%, and the Young modulus improvement proportion is 5-500%.
9. The 3D printable high strength and toughness thermosetting resin composite material as claimed in claim 8, wherein the composite material can be formed by any one of hot pressing, injection molding, extrusion molding and 3D printing process.
10. The application of the 3D-printable high-strength high-toughness thermosetting resin composite material is characterized in that the 3D-printable high-strength high-toughness thermosetting resin composite material disclosed by claim 8 is applied to the fields of engineering protection, packing cases, ship and vehicle shells and the like.
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| US6040363A (en) * | 1997-09-05 | 2000-03-21 | A. O. Smith Corporation | Metathesis polymerizered olefin composites including sized reinforcement material |
| CN108727565A (en) * | 2018-05-31 | 2018-11-02 | 上海化工研究院有限公司 | A kind of high purity carbon fiberreinforced Polydicyclopentadiencomposite composite material |
| CN110938175A (en) * | 2019-10-30 | 2020-03-31 | 杭州乐一新材料科技有限公司 | Light-heat dual-curing 3D printing method utilizing ring-opening metathesis polymerization and product thereof |
| WO2021222086A1 (en) * | 2020-04-28 | 2021-11-04 | Carbon, Inc. | Methods of making a three-dimensional object |
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| US6040363A (en) * | 1997-09-05 | 2000-03-21 | A. O. Smith Corporation | Metathesis polymerizered olefin composites including sized reinforcement material |
| CN108727565A (en) * | 2018-05-31 | 2018-11-02 | 上海化工研究院有限公司 | A kind of high purity carbon fiberreinforced Polydicyclopentadiencomposite composite material |
| CN110938175A (en) * | 2019-10-30 | 2020-03-31 | 杭州乐一新材料科技有限公司 | Light-heat dual-curing 3D printing method utilizing ring-opening metathesis polymerization and product thereof |
| WO2021222086A1 (en) * | 2020-04-28 | 2021-11-04 | Carbon, Inc. | Methods of making a three-dimensional object |
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