CN115181397B - 3D printable high-strength high-toughness thermosetting resin composite material and preparation method and application thereof - Google Patents

3D printable high-strength high-toughness thermosetting resin composite material and preparation method and application thereof Download PDF

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CN115181397B
CN115181397B CN202210489323.6A CN202210489323A CN115181397B CN 115181397 B CN115181397 B CN 115181397B CN 202210489323 A CN202210489323 A CN 202210489323A CN 115181397 B CN115181397 B CN 115181397B
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thermosetting resin
composite material
lignocellulose
toughness
resin composite
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CN115181397A (en
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俞娟
马若腾
王志国
范一民
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Nanjing Forestry University
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Nanjing Forestry University
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    • 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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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • B33Y70/00—Materials specially adapted for additive manufacturing
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    • 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
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    • 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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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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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
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

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Abstract

The invention discloses a 3D printable high-strength high-toughness thermosetting resin composite material, and a preparation method and application thereof. And stably dispersing the grafted and modified nano lignocellulose in a thermosetting resin monomer, adding a catalyst, and performing a front-end ring-opening metathesis polymerization reaction to obtain the 3D-printable high-strength high-toughness thermosetting resin composite material. The grafted modified nano lignocellulose can effectively slow down the reaction rate of the thermosetting resin monomer during the front-end ring-opening metathesis polymerization, and simultaneously can realize the simultaneous increase of the tensile stress and the strain of the composite material. The grafted and modified nano lignocellulose is 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 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, packaging boxes and the like.

Description

3D printable high-strength high-toughness thermosetting resin composite material and preparation method and application thereof
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 used for preparing a 3D printable high-strength high-toughness thermosetting resin composite.
Background
Thermosetting resins and their composites currently play an important role in the aerospace, automotive, marine and energy industries due to their excellent stiffness, strength and thermal stability, whereas the manufacture of traditional high performance thermosetting resins often requires stringent conditions such as high temperature and high pressure. In addition, insufficient mechanical properties of thermosetting resins are another factor limiting their wide use. With the development of research, researchers have found that front-end ring-opening metathesis polymerization (FROMP) is a promising strategy to replace traditional curing modes, the self-exothermic reaction of FROMP gradually converts liquid monomers into cured polymers, and only a small amount of energy is needed to start the process without further energy input, thereby reducing the energy required for manufacturing thermosetting resins and reducing the manufacturing requirements.
However, when using FROMP to cure thermoset resins, the rate of polymerization is another issue to be discussed. If the polymerization rate is not limited, the polymerization rate of 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 the too fast polymerization rate makes it difficult to match the 3D printing rate. Meanwhile, too fast polymerization rate can lead to more intense processing time, often the reaction is completed before formal molding is carried out, so that the polymerization is uneven, the final performance is affected, and the processing mode is limited. The current common solution is to use small molecule inhibitors, such as phosphate inhibitors found by Robertson, and the like, and the addition of the inhibitors reduces the rate of FROMP and prolongs the operating time of the liquid monomer at room temperature. However, the addition of the small molecular inhibitor reduces the polymerization rate, but at the same time, the molecular weight of the thermosetting resin is reduced, and the mechanical properties of the whole material are also affected to a certain extent, so that the application scene of the thermosetting resin is limited. Thus, preparing a thermoset resin that can be 3D printed and that has both strength and toughness remains a problem to be solved.
The nano lignocellulose extracted from natural plants has nano-scale size and good mechanical property. They are green fillers with wide application in polymer reinforced functional composites. Many researchers compound the nanofiber with the high molecular polymer, so that the mechanical properties are improved. As in chinese patent CN113004474a, multi-walled carbon nanotubes and polydicyclopentadiene are compounded to obtain a thermosetting resin composite material with excellent properties. Zhang et al compound nanometer lignocellulose with polylactic acid, and when nanometer lignocellulose's addition reached 20%, combined material's bending property has promoted 120.6%. However, the enhancement research of the application of the modified nano lignocellulose to the thermosetting resin prepared by the front-end ring-opening metathesis polymerization reaction is reported recently.
In summary, no effective solution has been proposed at present for the contradiction between the polymerization rate and 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 has been proposed.
Disclosure of Invention
The invention aims to: the small molecular inhibitor adopted in the traditional front-end ring-opening metathesis polymerization has an influence on the mechanical properties of thermosetting resin. In order to solve the problems, the invention provides an inhibitor based on front-end ring-opening metathesis polymerization and a thermosetting resin toughening reinforcing agent, which are used for preparing a 3D printable high-strength high-toughness thermosetting resin composite material. The invention utilizes the excellent dispersion property of the grafted modified nano lignocellulose in the thermosetting resin monomer, plays roles of nano filler and inhibitor, and enhances the mechanical property of the thermosetting resin while weakening the polymerization rate. 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 aim of the invention, the invention adopts the following technical scheme:
the preparation method of the 3D printable high-strength high-toughness thermosetting resin composite material is characterized by comprising the following steps of:
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 obtaining the 3D-printable high-strength high-toughness thermosetting resin composite material after the front-end ring-opening metathesis polymerization reaction.
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 preferably is 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), a Hoveyda-Grubbs catalyst, and preferably a GC2 catalyst.
Further, the source of lignocellulose in the step 1) is any one or a combination of at least two of wood, grass, bamboo cellulose and hemp, preferably wood cellulose.
Further, the modified nano lignocellulose in the step 1) is surface esterification modified or grafting modified nano lignocellulose.
Further, the modified nano lignocellulose is any one 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 is preferably polylactic acid grafted modified nano lignocellulose and polycaprolactone grafted modified nano lignocellulose.
Further, the thermosetting resin monomer in the 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 is preferably endo-dicyclopentadiene or exo-dicyclopentadiene.
Further, the mass ratio of the grafted modified nano lignocellulose to the thermosetting resin monomer in the step 1) is 1:1000-1:10.
Further, the diameter of the nano lignocellulose in the step 1) is 5-1000nm, the length is 0.1-10 mu m, the lignin content is 0% -30%, the diameter is 5-500nm, the length is 0.2-5 mu m, and the lignin content is 0% -25%.
Further, the front-end heating in the step 2) initiates the reaction at a temperature of 10 ℃ to 200 ℃, an ambient temperature of-20 ℃ to 60 ℃, preferably 15 ℃ to 150 ℃, and an ambient temperature of-10 ℃ to 40 ℃.
Furthermore, in the step 2), the rate of the front-end ring-opening metathesis polymerization reaction of the thermosetting resin monomer regulated and controlled by the grafted and modified nano lignocellulose is reduced by 10% -2000%.
According to another aspect of the present invention, there is provided a 3D printable high strength, high toughness thermosetting resin composite material made by a method of making a 3D printable high strength, high toughness thermosetting resin composite material.
Further, the tensile stress enhancement ratio of the composite material is 5% -500%, the tensile strain enhancement ratio is 5% -1000%, and the Young modulus enhancement ratio is 5% -500%.
Further, the composite material can be formed by any one 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, packaging boxes, ship vehicle shells and the like.
The beneficial effects are that: compared with the prior art, the invention has the advantages that:
1) The inhibitor based on front-end ring-opening metathesis polymerization provided by the invention can be stably dispersed in a liquid monomer of thermosetting resin. The heat transfer efficiency of the inhibitor is different from that of the liquid monomer of the thermosetting resin to a certain extent, so that the polymerization rate of the FROMP is slowed down, 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 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, which are provided by the invention, the thermosetting liquid monomer can be processed into the composite material through hot pressing, extrusion molding, injection molding, 3D printing and other processes, 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 high toughness thermosetting resin composite;
FIG. 2 is a transmission electron microscope image of the prepared graft polymerization modified nano lignocellulose;
FIG. 3 is a graph showing the dispersibility of grafted modified nano lignocellulose in dicyclopentadiene liquid monomer; (DCPD is dicyclopentadiene)
FIG. 4 is a photograph of the same FROMP reaction time performed with the addition of 1% and 5% nanocellulose; (CNF-g-PLA is polylactic acid grafted modified nanocellulose, R.T. is room temperature)
FIG. 5 is a graph of mechanical properties of a polydicyclopentadiene composite material after addition of graft polymerization modified nano-lignocellulose;
FIG. 6 is a sample graph of a high strength, high toughness thermoset resin composite material prepared by a 3D printing process;
fig. 7 is an application of the 3D printed high strength high toughness thermosetting resin composite in the engineering protection field. (PDCPD is polydicyclopentadiene for 3D printing, and Composite is polylactic acid grafted modified nanocellulose and polydicyclopentadiene Composite 3D printing material)
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the drawings, technical process steps, specific implementation conditions and materials in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
The lignocellulose raw material used in the present invention may be derived from wood, grass, bamboo, hemp, cotton, etc., and the present invention will be described below using lignocellulose derived from wood as a raw material in examples.
Example 1
The reaction of FROMP was started by adding a GC2 catalyst to the dicyclopentadiene monomer and heating it on a heating table at 65℃for 10 seconds, and the reaction of FROMP was completed within 10 seconds. The resulting polydicyclopentadiene had a tensile stress of 29.56MPa, a tensile strain of 8.21% and a Young's modulus of 623MPa.
Example 2
The reaction rate of FROMP was reduced by 1226% after the completion of the reaction within 150 seconds by adding a GC2 catalyst and tributyl phosphate (TBP) inhibitor to dicyclopentadiene monomer and heating it on a heating table at 65℃for 90 seconds, and the resulting polydicyclopentadiene had a tensile strain increased by 17.84%, a tensile stress reduced by 17.06% and a Young's modulus reduced by 21.33% as compared to that of the pure polydicyclopentadiene in example 10.
Example 3
The reaction of FROMP was started by adding a GC2 catalyst and a triethyl phosphate (TEP) inhibitor to the dicyclopentadiene monomer and heating the mixture for 90s at 65℃on a heating table, and the reaction was completed within 150 s. The reaction rate was reduced by 1314%, and the resulting polydicyclopentadiene had a tensile strain increased by 6.84%, a tensile stress reduced by 26.11%, and a Young's modulus reduced by 29.44% as compared with example 10.
Example 4
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 1:100. The GC2 catalyst was added and heated on a heated table at 65℃for 30 seconds to initiate the FROMP reaction, which was completed within 60 seconds. The reaction rate is reduced by 439%, and compared with pure polydicyclopentadiene, the obtained polydicyclopentadiene nanocellulose composite material has 6.33% of tensile strain, 36.69% of tensile stress and 49.36% of Young modulus.
Example 5
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 2:100. The GC2 catalyst was added and heated on a heated table at 65℃for 45 seconds to initiate the FROMP reaction, which was completed within 60 seconds. The reaction rate is reduced by 564%, and the obtained polydicyclopentadiene nanocellulose composite material has 28.49% of tensile strain, 35.92% of tensile stress and 79.88% of Young modulus compared with pure polydicyclopentadiene.
Example 6
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 3:100. The GC2 catalyst was added and heated on a heated table at 65℃for 60 seconds to initiate the FROMP reaction, which was completed within 90 seconds. The reaction rate is reduced by 768%, and compared with the pure polydicyclopentadiene, the obtained polydicyclopentadiene nanocellulose composite material has 52.37% of tensile strain, 23.15% of tensile stress and 109.88% of Young modulus.
Example 7
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 4:100. The GC2 catalyst was added and heated on a heated table at 65℃for 75 seconds to initiate the FROMP reaction, which was completed within 120 seconds. The reaction rate is reduced by 1105%, and compared with pure polydicyclopentadiene, the obtained polydicyclopentadiene nanocellulose composite material has the tensile strain improved by 111.37%, the tensile stress improved by 21.05% and the Young modulus improved by 263.88%.
Example 8
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 5:100. The GC2 catalyst was added and heated on a heated table at 65℃for 90s to initiate the FROMP reaction, 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% compared with that of pure polydicyclopentadiene, the tensile stress is improved by 22.01%, and the Young modulus is improved by 313.44%.
Example 9
Taking 1g of absolute dry cellulose, wherein the lignin content is 5.69%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polycaprolactone grafted and modified nano lignocellulose is added into dicyclopentadiene monomer, and the ratio of the polycaprolactone grafted and modified nano lignocellulose to the dicyclopentadiene monomer is 1:10. The GC2 catalyst was added and heated on a heated table at 65℃for 90s to initiate the FROMP reaction, 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 improved by 135.75% compared with that of pure polydicyclopentadiene, the tensile stress is improved by 39.05%, and the Young modulus is improved by 493.44%.
Example 10
Taking 1g of absolute dry cellulose, wherein the lignin content is 17.19%, uniformly mixing lignocellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polycaprolactone grafted and modified nano lignocellulose is added into dicyclopentadiene monomer, and the ratio of the polycaprolactone grafted and modified nano lignocellulose to the dicyclopentadiene monomer is 1:10. The GC2 catalyst was added and heated on a heated table at 65℃for 150 seconds to initiate the FROMP reaction, which was completed within 150 seconds. The reaction rate is reduced by 1315%, and the tensile strain of the obtained polydicyclopentadiene nanocellulose composite material is improved by 369.24% compared with that of pure polydicyclopentadiene, the tensile stress is improved by 13.54%, and the Young modulus is improved by 365.19%.
Example 11
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into ethylidene norbornene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the ethylidene norbornene monomer is 1:200. The GC2 catalyst was added and heated on a heated table at 85℃for 150 seconds to initiate the FROMP reaction, which was completed within 150 seconds. The reaction rate is reduced by 1241%, and the tensile strain of the obtained polyethylene norbornene nanocellulose composite material is improved by 89.24%, the tensile stress is improved by 11.54% and the Young modulus is improved by 264.58% compared with that of pure polyethylene norbornene.
Example 12
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 1:20. Adding GC2 catalyst and tributyl phosphate (TBP) inhibitor, heating at 85deg.C for 150s to start FROMP reaction, and finishing the reaction within 150 s. The reaction rate is reduced by 1291%, and compared with pure dicyclopentadiene, the obtained polydicyclopentadiene nanocellulose composite material has the advantages that the tensile strain is improved by 119.24%, the tensile stress is improved by 9.54%, and the Young modulus is improved by 196.58%.
Example 13
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into 5-norbornene-2-methanol monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the 5-norbornene-2-methanol monomer is 0.1:100. Heating at 85deg.C for 150s to start FROMP reaction, and finishing the FROMP reaction within 150 s. The reaction rate is reduced by 1305%, and the tensile strain of the obtained poly-5-norbornene-2-methanol nanocellulose 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 lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted modified nano cellulose to the dicyclopentadiene monomer is 8:100. And (3) placing the monomer dispersion liquid into a 3D printer for 3D printing, setting the temperature of a printing table to 65 ℃ to start FROMP reaction, and obtaining the polydicyclopentadiene nanocellulose composite material with obvious three-dimensional structure through 3D printing.
Example 15
Taking 1g of absolute dry cellulose, wherein the lignin content is 0%, uniformly mixing the cellulose and a lactic acid/choline chloride eutectic solvent according to the 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 a nano cellulose dispersion liquid. Adding stannous octoate catalyst into the dispersion liquid, and heating for 8 hours at 110 ℃ to obtain the grafted modified nano-cellulose. The polylactic acid grafted modified nano cellulose is added into dicyclopentadiene monomer, and the ratio of the polylactic acid grafted 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, FROMP reaction still cannot be started, and the reaction liquid volatilizes under long-time heating, so that the polydicyclopentadiene nanocellulose composite material cannot be prepared.
Example 16
The unmodified nanocellulose dispersion is used as a raw material. Is added to dicyclopentadiene monomer by solvent replacement in a ratio of 1:100. Heating on a heating table at 85 ℃ to start FROMP reaction, and finishing the FROMP reaction within 80 seconds. The reaction rate is reduced by 701%, but the dispersibility of the unmodified nanocellulose in dicyclopentadiene monomer is poor, so that the uniformity of the obtained polydicyclopentadiene nanocellulose 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 be a substitute for the nanocellulose, and since the nanocellulose or nanocellulose is unmodified, the nanocellulose or nanocellulose has poor dispersibility in dicyclopentadiene monomer, which adversely affects the performance of the composite material.
The product of example 9 was subjected to microscopic morphological characterization, and fig. 2 is a TEM image of the modified nanolignocellulose 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 modified nano lignocellulose in the embodiment 7 is subjected to dispersibility characterization, and fig. 3 is a graph showing the effect of the dispersibility of the nano lignocellulose in dicyclopentadiene monomer, and as can be seen from the graph, the modified nano lignocellulose has good dispersibility, so that the thermosetting resin composite material can be constructed through FROMP reaction.
Fig. 4 is a photograph showing the modified nano-lignocellulose prepared in examples 4 and 9, wherein the arrow indicates the parting line between uncured liquid monomer and cured polymer at the same time, and the addition of 5% modified nano-lignocellulose is slower than the addition of 1% to show the advantage of the modified nano-lignocellulose by graft polymerization as an inhibitor of the FROMP reaction. Whereas the polymerization rate was also reduced by adding only 1% of modified nanolignocellulose compared to the commercial inhibitor (no modified nanolignocellulose added). And no bubbles exist in the polymerization process, which indicates that the reaction process is more uniform, the defect of mechanical properties caused by bubbles is avoided, and the improvement of mechanical properties is facilitated.
The modified nano lignocellulose in examples 4 to 8 was compounded with dicyclopentadiene, and the change curves of tensile stress and strain of the obtained composite material are shown in fig. 5. As can be seen from the figure, the stress and strain values of the composite material are improved compared to those without addition. The advantage of the modified nano lignocellulose as a toughening reinforcing agent of thermosetting resin is shown.
The dispersion prepared in example 13 was manufactured by a 3D printing method, and a sample graph obtained is shown in fig. 6, which shows that the high-strength and high-toughness thermosetting resin composite material prepared by the method can be molded by 3D printing.
The dispersions prepared in examples 1 and 13 were manufactured by 3D printing, and the manufactured samples were used as a rail for work Cheng Fanghu. The vehicle crash situation was 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 impact of the vehicle, the vehicle is damaged when the vehicle collides with the sample, and the sample is not deformed. Fig. 7c is a photograph of the sample prepared in example 13 at the moment of impact of the vehicle, when the vehicle collides with the sample, the vehicle is not damaged significantly, and the sample is deformed, indicating that the sample in example 11 has a certain capability of protecting against impact.
The embodiments of the present invention are not limited to the above embodiments, and table 1 provides a simple list of the 3D printable high-strength high-toughness thermosetting resin composite material and the degree of improvement of mechanical properties.
TABLE 1

Claims (7)

1. The preparation method of the 3D printable high-strength high-toughness thermosetting resin composite material is characterized by comprising the following steps of:
s1) adding modified nano lignocellulose into a thermosetting resin monomer to obtain uniform and stable dispersion liquid; the modified nanometer lignocellulose is any one or more than two of lactic acid esterification modified lignocellulose nanofiber, oxalic acid esterification modified lignocellulose nanofiber, acrylic acid esterification modified lignocellulose nanofiber, polylactic acid grafting modified nanometer lignocellulose and polycaprolactone grafting modified nanometer lignocellulose; the thermosetting resin monomer 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;
s2) adding a catalyst into the uniform dispersion liquid obtained in the step 1), and obtaining the 3D-printable high-strength high-toughness thermosetting resin composite material after the front-end ring-opening metathesis polymerization reaction.
2. The method for preparing the 3D printable high-strength high-toughness thermosetting resin composite material according to claim 1, wherein an inhibitor is added in the step 2), and the inhibitor is any one or more than two of trimethylolpropane, triethyl phosphate and tributyl phosphate; the catalyst is any one or more than two of a first generation Grubbs catalyst, a second generation Grubbs catalyst and a Hoveyda-Grubbs catalyst.
3. The method for preparing the 3D printable high-strength high-toughness thermosetting resin composite material 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 is 0.2-5 mu m, and the lignin content is 0% -25%; the mass ratio of the modified nano lignocellulose to the thermosetting resin monomer is as follows: 1:1000-1:10.
4. The method for preparing the 3D printable high-strength high-toughness thermosetting resin composite material according to claim 1 or claim 2, wherein the method comprises the following steps: in the step 2), the front-end heating initiation reaction temperature is 15-150 ℃ and the ambient temperature is-10-40 ℃.
5. A 3D printable high strength, high toughness thermoset resin composite material made by the method of making a 3D printable high strength, high toughness thermoset resin composite material as claimed in any one of claims 1 to 4.
6. The 3D printable high strength, high toughness thermoset resin composite according to claim 5, wherein the composite is formed by any one of hot pressing, injection molding, extrusion molding, and 3D printing processes.
7. The application of the 3D printing high-strength high-toughness thermosetting resin composite material is characterized in that the 3D printing high-strength high-toughness thermosetting resin composite material is applied to the fields of engineering protection, packaging boxes and ship vehicle shells.
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Publication number Priority date Publication date Assignee Title
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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