CN113308077B - Self-repairing circular processing formed poly (ampholyte-triazine)/quartz sand composite material and preparation method thereof - Google Patents
Self-repairing circular processing formed poly (ampholyte-triazine)/quartz sand composite material and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种可自修复循环加工成型的聚(两性电解质‑三嗪)/石英砂复合材料的制备方法，采用一锅法将带正电荷单元DAC、带负电荷单元NaSS、三嗪单元VDT、化学交联剂和光引发剂均匀混合，在紫外光照条件下引发聚合得到P(NaSS‑co‑DAC‑co‑VDT)复合凝胶，与石英砂共混后得到可自修复循环加工成型的聚(两性电解质‑三嗪)/石英砂复合材料。该聚(两性电解质‑三嗪)/石英砂复合材料在吸水和固化的循环过程中，其压缩强度和模量可跨越几个数量级的变化，固化后的复合材料具有自修复性，并且可以循环加工成型多次。
The invention discloses a preparation method of a poly(ampholyte-triazine)/quartz sand composite material capable of self-healing and cyclic processing. A one-pot method is used to combine a positively charged unit DAC, a negatively charged unit NaSS, and a triazine unit VDT, chemical cross-linking agent and photoinitiator are evenly mixed, and polymerization is initiated under ultraviolet light to obtain P(NaSS‑co‑DAC‑co‑VDT) composite gel, which is blended with quartz sand to obtain a self-healing cyclic processing and molding Poly(ampholyte-triazine)/quartz sand composites. The compressive strength and modulus of the poly(ampholyte-triazine)/quartz sand composite can vary across several orders of magnitude during the cycling process of water absorption and curing, and the cured composite is self-healing and can be cycled Processed many times.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a self-repairing cycle processing and molding poly (ampholyte-triazine)/quartz sand composite material.
Background
In general, a strong bond requires both strong non-covalent interactions at the interface and high toughness of the host material. The thermosetting adhesive material has high bonding strength, but is mostly formed in one step, and the thermosetting adhesive material is generally poor in water resistance, so that the application range is extremely limited. It is known that water molecules greatly weaken the interaction between interface molecules, and for adhesive materials, it is a great challenge to achieve a firm adhesive effect in water.
Hydrogel is an ideal adhesive material. Gong topic group [ H Fan, Wang J, Gong J P. barnacle center Proteins-injected medicaments with Robust, Long-testing, and Repeatable Underwater addition [ J].Advanced Functional Materials,2020,2009334.]A hydrogel with aromatic components, cations and aromatic ring units is designed. The electrostatic repulsion and hydrophobic interaction between polymer chains and cation-aromatic ring pi interaction are balanced by optimizing the ratio of monomers, and the prepared hydrogel shows excellent performance. The toughness and cohesive strength of the gel are enhanced by the pi-pi interaction of the interchain aromatic ring and the pi interaction of the cation-aromatic ring (high sigma)c). Aromatic groups can break up the hydrated layer of the surface, thereby providing an interior region of lower dielectric constant, enhancing electrostatic interaction between adjacent cationic groups. In water, the hydrogel is strongly adhered by interfacial electrostatic and hydrophobic interactions (adhesion strength of 180kPa), but inorganic substrates such as various types of quartz sand are somewhat electronegative, and adhesion relying only on electrostatic interactions limits the application of this gel. Zeng et al [ Zhang J W, Xiaoing L, Yan B, Zeng H B. nanomechanics of Anion-pi Interaction in Aqueous Solution ] [ J].Journal of the American Chemical Society,2020,142,1710-1714.]A surface force device with complementary calculation simulation is designed, and first experimental identification and direct quantification are carried out on the nanomechanics of anion-aromatic ring pi interaction in the aqueous solution. The method uses anionic phosphate ester and a small ring part with aromatic ring pi-conjugation which are abundantly present in marine organism adhesives as a model system. In this system, strong and reversible wet adhesion was detected, the anionic-aromatic ring pi interaction between the anionic phosphate and the aromatic ring pi-conjugated poly (catechol) moiety being the predominant oneA contributor. The strength of the anion-aromatic ring pi interaction follows that of phosphate>HPO4 2->SO4 2->NO3 -The tendency of (a) is influenced by charge density, polarity and hydration effects, but such anion-carrying aromatic ring pi interactions do not provide a contribution to bonding inorganic substrates such as various types of quartz sand.
During the research process, the inventor of the present application unexpectedly found that an adhesive system can produce good adhesion effect with quartz materials, and the compressive strength and modulus can change over several orders of magnitude during the cycle of water absorption and curing. The composite material is compounded with quartz sand material, has special performance and can be used for technical materials such as soft ceramics and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a poly (ampholyte-triazine)/quartz sand composite material which has the advantages of simple process, easy operation, easily obtained raw materials, lower cost and excellent self-repairing cycle processing and forming.
The technical scheme comprises the following specific steps:
a preparation method of a self-repairing cycle processing formed poly (ampholyte-triazine)/quartz sand composite material comprises the following specific steps:
1) adding sodium p-styrenesulfonate NaSS, acryloyloxyethyl trimethyl ammonium chloride DAC, 2-vinyl-4-6-diamino-1, 3, 5-triazine VDT, a cross-linking agent and a photoinitiator into dimethyl sulfoxide DMSO, and stirring and dissolving under a shading condition to obtain a uniform mixed solution;
2) carrying out ultraviolet curing on the mixed solution obtained in the step 1) to obtain the gel with strong hydrogen bonds and polyampholyte high bonding.
3) Adding quantitative water into the strong hydrogen bonds and the polyampholyte high-bonding gel obtained in the step 2), and blending with quartz sand to obtain the poly (ampholyte-triazine)/quartz sand composite material capable of being processed and molded in a self-repairing and circulating manner.
Preferably, the cross-linking agent is N, N' -methylenebisacrylamide MBAA, and the photoinitiator is a radical polymerization initiator, preferably 2-oxoglutarate KA.
Preferably, in the mixed solution obtained in the step 1), the concentration of NaSS is 196-263 mg/mL, the concentration of DAC is 218-296 mg/mL, and the concentration of VDT is 26-41 mg/mL. The total molar concentration of NaSS, DAC and VDT monomers is 2.30-2.38 mol/L.
Preferably, in the mixed solution obtained in step 1), the percentage of the cross-linking agent in the total molar amount of the monomers is 0.1%.
Preferably, in the mixed solution obtained in step 1), the photoinitiator accounts for 0.25% of the total molar amount of the monomers, and the photoinitiator is used for initiating the free radical copolymerization reaction of the monomers NaSS, DAC and VDT to generate the polymer P (NaSS-co-DAC-co-VDT), wherein too much concentration of the photoinitiator causes too many free radicals to quench, the molecular weight of the polymerization product is low, too little the polymerization speed is too slow, and insufficient polymerization causes gel to be incapable of forming.
Preferably, the temperature during stirring in the step 1) is controlled to be 70-80 ℃, and the stirring time is 30-40 min.
Preferably, in the step 2), the conditions of the illumination under the ultraviolet lamp are as follows: the illumination time is 10-12 h under an ultraviolet lamp with the wavelength of 365nm and the power of 300W.
Preferably, in the step 3), the mass ratio of the water to the gel to the quartz sand is (0.07-0.11): (0.16-0.24): (0.76-0.84), more preferably (0.07-0.11): 0.19: 0.81.
the invention also provides a self-repairing cycle processing and molding poly (ampholyte-triazine)/quartz sand composite material which is prepared by adopting the method.
The invention also provides application of the poly (ampholyte-triazine)/quartz sand composite material capable of being self-repaired and molded by circular processing in the field of repeated molding materials, wherein the composite quartz material is subjected to molding after absorbing water, is dried and cured to obtain a product with a specific shape, and can be subjected to water absorption molding-drying curing in a circular manner.
The preparation method comprises the steps of uniformly mixing acryloyl oxyethyl trimethyl ammonium chloride (DAC) with a positive charge unit, sodium styrene sulfonate (NaSS) with a negative charge unit, triazine unit 2-vinyl-4-6-diamino-1, 3, 5-triazine (VDT), a chemical cross-linking agent and a photoinitiator, initiating polymerization under the condition of ultraviolet illumination to obtain P (NaSS-co-DAC-co-VDT) composite gel, and blending the P (NaSS-co-DAC-co-VDT) composite gel with quartz sand to obtain the poly (ampholyte-triazine)/quartz sand composite material capable of being processed and molded in a self-repairing and circulating mode. FIG. 1 is a diagram showing the intermolecular structure and interaction force of the resulting P (NaSS-co-DAC-co-VDT) gel. Cation-anion and triazine unit pi bond structures are formed in the gel to interact with each other, so that the gel has strong bonding capacity; the positive ion unit in the gel and the negative electricity unit on the surface of the quartz sand form strong electrostatic interaction, the VDT unit in the gel has certain hydrophobicity, and the multiple hydrogen bond structure of the VDT unit and the hydroxyl on the surface of the quartz sand form strong hydrogen bond interaction, so that the gel and the quartz sand are easily compounded in water to obtain the poly (ampholyte-triazine)/quartz sand composite material. The above dynamic physical interaction also imparts self-healing properties to the composite material, thereby achieving its reworkable nature. In addition, the compressive strength and modulus of the poly (ampholyte-triazine)/quartz sand composite material can change over several orders of magnitude in the water absorption and curing circulation process, because water molecules can form hydrogen bonds with partial peripheral triazine functional groups and also can form hydrogen bonds with partial quartz sand with hydroxyl groups before curing, the water molecules surround the quartz sand to reduce entanglement of polymer chains to the quartz sand, the interference of water after curing is eliminated, the triazine functional groups and the quartz sand with the hydroxyl groups can form hydrogen bonds, negative charge units on the surface of the quartz sand can form strong electrostatic interaction with cationic units in gel, the sand is more tightly entangled by the polymer chains, a relatively contracted 'compact composite material' is formed, and the circulation process can be repeated for many times. The self-repairing cycle processing formed poly (ampholyte-triazine)/quartz sand composite material is prepared by adopting a one-pot method, the process is simple and easy to control, the prepared gel has a uniform structure, and the gel has the advantages of free forming, self-repairing and cycle processing after being blended with quartz sand, so that the method becomes a general method for preparing the composite material by the synergistic combination of a strong hydrogen bond and ampholyte cation-anion-pi.
Compared with the prior art, the invention has the following advantages and remarkable progress:
1) the invention adopts a simple one-pot method, has simple preparation process, short production period, simple and convenient process conditions, easily obtained raw materials and low production cost.
2) The invention has simple and convenient shaping and curing, can be repeatedly used, is used as a preferred material of artistic soft ceramics, and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the preparation of the P (NaSS-co-DAC-co-VDT) gel of the present invention;
FIG. 2 is a schematic diagram showing the changes of the macro and micro structures of the quartz sand composite material obtained in the present invention during the cycle processing and molding process.
Detailed Description
Example 1
Step 1): NaSS 2.1367g, DAC 2.8585g, VDT 0.2558g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solutions, the DMSO solutions are stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain uniform mixed solutions, the concentration of NaSS is 214mg/mL, the concentration of DAC is 286mg/mL, the concentration of VDT is 26mg/mL, the molar weight of MBAA accounts for 0.1% of the total molar weight of the monomers, and the molar weight of KA accounts for 0.25% of the total molar weight of the monomers in the obtained mixed solutions.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 12g of quartz sand (the mass ratio of the quartz sand to the gel is 5: 1) then, 1.6mL of water was added (so that the mass ratio of water to "gel + quartz sand" was 0.11: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 4.8kPa, the elastic modulus is 20.4kPa, the compression strength before the secondary molding and curing is 25.6kPa, and the elastic modulus is 115.5kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 3.3MPa, the elastic modulus is 92.8MPa, the compression strength after the secondary molding and curing is 5.8MPa, and the elastic modulus is 417.0MPa, which are measured by a compression test at the speed of 1 mm/min.
Example 2
Step 1): respectively weighing NaSS 2.1739g, DAC 2.9082g, VDT 0.2603g, MBAA 0.0037g and KA0.0192g to prepare 10mL DMSO solution, stirring the solution in a water bath at 70 ℃ for 30min under the shading condition to obtain a uniform mixed solution, wherein in the obtained mixed solution, the concentration of NaSS is 217mg/mL, the concentration of DAC is 291mg/mL, the concentration of VDT is 26mg/mL, the molar amount of MBAA accounts for 0.1 percent of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25 percent of the total molar amount of the monomers.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 10g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.08: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 4.2kPa, the elastic modulus is 17.9kPa, the compression strength before the secondary molding and curing is 40.1kPa, and the elastic modulus is 53.0kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 5.6MPa, the elastic modulus is 446.3MPa, the compression strength after the secondary molding and curing is 7.3MPa, and the elastic modulus is 506.2MPa, which are measured by a compression test at the speed of 1 mm/min.
Example 3
Step 1): NaSS 2.2110g, DAC 2.9579g, VDT 0.2647g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solutions, the DMSO solutions are stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain uniform mixed solutions, the concentration of NaSS is 221mg/mL, the concentration of DAC is 296mg/mL, the concentration of VDT is 26mg/mL, the molar amount of MBAA accounts for 0.1% of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25% of the total molar amount of the monomers in the obtained mixed solutions.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 8g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 3.3: 1) then, 0.7mL of water was added (so that the mass ratio of water to "gel + quartz sand" was 0.07: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 4.6kPa, the elastic modulus is 9.5kPa, the compression strength before the secondary molding and curing is 36.1kPa, and the elastic modulus is 84.0kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 3.7MPa, the elastic modulus is 339.1MPa, the compression strength after the secondary molding and curing is 5.1MPa, and the elastic modulus is 283.7MPa, which are measured by a compression test at a speed of 1 mm/min.
Example 4
Step 1): NaSS 2.0869g, DAC 2.9082g, VDT 0.3123g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solutions, the DMSO solutions are stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain uniform mixed solutions, the concentration of NaSS is 209mg/mL, the concentration of DAC is 291mg/mL, the concentration of VDT is 31mg/mL, the molar amount of MBAA accounts for 0.1% of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25% of the total molar amount of the monomers in the obtained mixed solutions.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 10g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.08: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 4.2kPa, the elastic modulus is 14.2kPa, the compression strength before the secondary molding and curing is 18.3kPa, and the elastic modulus is 44.0kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 5.9MPa, the elastic modulus is 432.0MPa, the compression strength after the secondary molding and curing is 7.4MPa, and the elastic modulus is 370.6MPa, which are measured by a compression test at the speed of 1 mm/min.
Example 5
Step 1): respectively weighing NaSS 1.9565g, DAC 2.9082g, VDT 0.3904g, MBAA 0.0037g and KA0.0192g to prepare 10mL DMSO solution, stirring the solution in a water bath at 70 ℃ for 30min under the shading condition to obtain a uniform mixed solution, wherein in the obtained mixed solution, the concentration of NaSS is 196mg/mL, the concentration of DAC is 291mg/mL, the concentration of VDT is 39mg/mL, the molar amount of MBAA accounts for 0.1 percent of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25 percent of the total molar amount of the monomers.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 10g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1.1mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.09: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 4.2kPa, the elastic modulus is 13.8kPa, the compression strength before the secondary molding and curing is 15.1kPa, and the elastic modulus is 37.2kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 3.7MPa, the elastic modulus is 300.3MPa, the compression strength after the secondary molding and curing is 7.1MPa, and the elastic modulus is 312.5MPa, which are measured by a compression test at the speed of 1 mm/min.
Example 6
Step 1): NaSS 2.5640g, DAC 2.3821g, VDT 0.2698g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solutions, the DMSO solutions are stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain uniform mixed solutions, the concentration of NaSS is 256mg/mL, the concentration of DAC is 238mg/mL, the concentration of VDT is 27mg/mL, the molar amount of MBAA accounts for 0.1% of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25% of the total molar amount of the monomers in the obtained mixed solutions.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 12g of quartz sand (the mass ratio of the quartz sand to the gel is 5: 1) then, 1.6mL of water was added (so that the mass ratio of water to "gel + quartz sand" was 0.11: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 8.5kPa, the elastic modulus is 25.1kPa, the compression strength before the secondary molding and curing is 28.7kPa, and the elastic modulus is 64.9kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 4.3MPa, the elastic modulus is 356.0MPa, the compression strength after the secondary molding and curing is 4.5MPa, and the elastic modulus is 586.9MPa, which are measured by a compression test at a speed of 1 mm/min.
Example 7
Step 1): NaSS 2.6060g, DAC 2.4210g, VDT 0.2742g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solutions, the DMSO solutions are stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain uniform mixed solutions, the concentration of NaSS is 261mg/mL, the concentration of DAC is 242mg/mL, the concentration of VDT is 27mg/mL, the molar amount of MBAA accounts for 0.1% of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25% of the total molar amount of the monomers in the obtained mixed solutions.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 10g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1.1mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.09: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 5.2kPa, the elastic modulus is 8.6kPa, the compression strength before the secondary molding and curing is 11.7kPa, and the elastic modulus is 18.9kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 6.3MPa, the elastic modulus is 421.7MPa, the compression strength after the secondary molding and curing is 7.9MPa, and the elastic modulus is 610.2MPa, which are measured by a compression test at the speed of 1 mm/min.
Example 8
Step 1): NaSS 2.6320g, DAC 2.4649g, VDT 0.2792g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solutions, the DMSO solutions are stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain uniform mixed solutions, the concentration of NaSS is 263mg/mL, the concentration of DAC is 246mg/mL, the concentration of VDT is 28mg/mL, the molar amount of MBAA accounts for 0.1% of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25% of the total molar amount of the monomers in the obtained mixed solutions.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 8g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 3.3: 1) then, 0.7mL of water was added (so that the mass ratio of water to "gel + quartz sand" was 0.07: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 9.8kPa, the elastic modulus is 13.4kPa, the compression strength before the secondary molding and curing is 14.1kPa, and the elastic modulus is 43.3kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 5.7MPa, the elastic modulus is 280.5MPa, the compression strength after the secondary molding and curing is 5.4MPa, and the elastic modulus is 425.1MPa, which are measured by a compression test at a speed of 1 mm/min.
Example 9
Step 1): NaSS 2.6060g, DAC 2.3242g, VDT 0.3292g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solution, the DMSO solution is stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain a uniform mixed solution, the concentration of NaSS is 261mg/mL, the concentration of DAC is 232mg/mL, the concentration of VDT is 33mg/mL, the molar weight of MBAA accounts for 0.1% of the total molar weight of the monomers, and the molar weight of KA accounts for 0.25% of the total molar weight of the monomers in the obtained mixed solution.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 10g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.08: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 6.1kPa, the elastic modulus is 14.2kPa, the compression strength before the secondary molding and curing is 12.6kPa, and the elastic modulus is 28.7kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 4.9MPa, the elastic modulus is 348.9MPa, the compression strength after the secondary molding and curing is 6.6MPa, and the elastic modulus is 416.2MPa, which are measured by a compression test at the speed of 1 mm/min.
Example 10
Step 1): NaSS 2.6060g, DAC 2.1789g, VDT 0.4114g, MBAA 0.0037g and KA0.0192g are respectively weighed and prepared into 10mL DMSO solution, the DMSO solution is stirred for 30min in a water bath at 70 ℃ under the shading condition to obtain a uniform mixed solution, the concentration of NaSS is 261mg/mL, the concentration of DAC is 218mg/mL, the concentration of VDT is 41mg/mL, the molar amount of MBAA accounts for 0.1% of the total molar amount of the monomers, and the molar amount of KA accounts for 0.25% of the total molar amount of the monomers in the obtained mixed solution.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the high-bonding gel of the strong hydrogen bond and the polyampholyte.
Step 3): taking 2.4g and 10g of quartz sand from the high-bonding gel of the strong hydrogen bond and the polyampholyte obtained in the step 2) (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.08: 1) blending to obtain the poly (ampholyte-triazine)/quartz sand composite material which can be self-repaired and molded by circular processing.
The poly (ampholyte-triazine)/quartz sand composite material obtained in this example was tested for its compressive properties before and after primary molding and secondary molding curing using an electronic universal tester; the compression strength before the primary molding and curing is 10.7kPa, the elastic modulus is 36.4kPa, the compression strength before the secondary molding and curing is 16.6kPa, and the elastic modulus is 41.5kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 4.5MPa, the elastic modulus is 276.8MPa, the compression strength after the secondary molding and curing is 5.1MPa, and the elastic modulus is 254.1MPa, which are measured by a compression test at the speed of 1 mm/min.
Comparative example 1
Step 1): 2.9052g of DAC, 1.5596g of VDT, 0.0037g of MBAA and 0.0192g of KA are respectively weighed and prepared into 10mL of DMSO solution, the DMSO solution is stirred for 30min in a water bath at 70 ℃ under a shading condition to obtain a uniform mixed solution, the concentration of DAC is 291mg/mL, the concentration of VDT is 156mg/mL, the molar weight of MBAA accounts for 0.1% of the total molar weight of monomers, and the molar weight of KA accounts for 0.25% of the total molar weight of monomers in the obtained mixed solution.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the strong hydrogen bond and cation pi synergistic composite gel.
Step 3): taking 2.4g and 10g of quartz sand (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1.2mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.1: 1) and blending to obtain the strong hydrogen bond and cation pi synergistic composite quartz sand material.
The quartz sand composite material obtained by the comparative example is tested for the compression performance before and after one-time forming and secondary forming curing by using an electronic universal testing machine; the compression strength before the primary molding and curing is 7.3kPa, the elastic modulus is 10.8kPa, the compression strength before the secondary molding and curing is 10.7kPa, and the elastic modulus is 20.6kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 1.2MPa, the elastic modulus is 80.4MPa, the compression strength after the secondary molding and curing is 0.9MPa, and the elastic modulus is 90.3MPa, which are measured by a compression test at the speed of 1 mm/min.
Comparative example 2
Step 1): respectively weighing NaSS 2.6060g, VDT 1.6456g, MBAA 0.0037g and KA0.0192g to prepare 10mL DMSO solution, stirring in a water bath at 70 ℃ for 30min under a shading condition to obtain a uniform mixed solution, wherein in the obtained mixed solution, the concentration of NaSS is 261mg/mL, the concentration of VDT is 165mg/mL, the molar weight of MBAA accounts for 0.1% of the total molar weight of the monomers, and the molar weight of KA accounts for 0.25% of the total molar weight of the monomers.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the strong hydrogen bond and anion pi synergistic composite gel.
Step 3): taking 2.4g and 10g of quartz sand (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 0.9mL of water was added (so that the mass ratio of water to "gel + quartz sand" was 0.07: 1) and blending to obtain the strong hydrogen bond and anion pi synergistic composite quartz sand material.
The quartz sand composite material obtained by the comparative example has the advantages that the gel and the sand are scattered and cannot be freely formed, and the specific compression strength cannot be measured by an electronic universal testing machine.
Comparative example 3
Step 1): respectively weighing NaSS 2.1367g, DAC 2.8585g, MBAA 0.0037g and KA0.0192g to prepare 10mL DMSO solution, stirring in a water bath at 70 ℃ for 30min under a shading condition to obtain a uniform mixed solution, and enabling the concentration of NaSS to be 214mg/mL, the concentration of DAC to be 286mg/mL, the molar weight of MBAA to be 0.1% of the total molar weight of monomers and the molar weight of KA to be 0.25% of the total molar weight of monomers in the obtained mixed solution.
Step 2): and (2) injecting the mixed solution obtained in the step 1) into a glass mold under a shading condition, and placing under an ultraviolet lamp for illumination for 10 hours to obtain the polyampholyte gel.
Step 3): taking 2.4g and 10g of quartz sand (the mass ratio of the quartz sand to the gel is 4.2: 1) then, 1.2mL of water was added (the mass ratio of water to "gel + quartz sand" was made 0.1: 1) and blending to obtain the polyampholyte quartz sand composite material.
The quartz sand composite material obtained by the comparative example is tested for the compression performance before and after one-time forming and secondary forming curing by using an electronic universal testing machine; the compression strength before the primary molding and curing is 8.4kPa, the elastic modulus is 9.7kPa, the compression strength before the secondary molding and curing is 11.2kPa, and the elastic modulus is 17.8kPa, which are measured by a compression test at a speed of 2 mm/min; the compression strength after the primary molding and curing is 1.4MPa, the elastic modulus is 117.5MPa, the compression strength after the secondary molding and curing is 1.0MPa, and the elastic modulus is 123.7 MPa.
The compressive strength of the quartz sand composite materials obtained in the above examples and comparative examples is shown in the following table 1:
table 1: compression performance of poly (ampholyte-triazine)/quartz sand composite material before and after one-step molding and secondary molding curing
As can be seen from the data in table 1:
examples 1 to 3 are poly (ampholyte-triazine)/silica sand composite materials prepared by changing the silica sand content under the condition that the DAC concentration is constant and the molar concentration and the mass percentage content of NaSS and VDT are constant, examples 2, 4, and 5 are poly (ampholyte-triazine)/silica sand composite materials prepared by changing the molar concentration and the mass percentage of NaSS and VDT under the condition that the DAC and the silica sand content are constant, examples 6 to 8 are poly (ampholyte-triazine)/silica sand composite materials prepared by changing the silica sand content under the condition that the NaSS concentration is constant and the molar concentration and the mass percentage content of DAC and VDT are constant, examples 7, 9, and 10 are poly (ampholyte-triazine)/silica sand composite materials prepared by changing the molar concentration and the mass percentage of NaSS and VDT under the condition that the NaSS and the silica sand content are constant, comparative examples 1 to 3 are silica sand composite materials prepared without NaSS, DAC and VDT, and the content of silica sand is consistent with that of examples 2, 4, 5, 7, 9 and 10. From examples 1 to 3, it can be seen that the compressive strength of the quartz sand composite material after once forming and curing is increased from 3.3MPa to 5.6MPa and then decreased to 3.7MPa, and the compressive strength of the quartz sand composite material is increased and then decreased with the increase of the content of the quartz sand, and similarly, examples 6 to 8 show the same trend. As can be seen from the examples 2, 4 and 5 in the table, the compressive strength of the quartz sand composite material after once-forming and curing is reduced from 5.6MPa to 3.7MPa along with the reduction of the monomer molar ratio n (NaSS): n (VDT), which is mainly the excessive amount of the monomer VDT with aromaticity in the examples 4 and 5, and the strength of the quartz sand composite material is reduced, and similarly, the examples 7, 9 and 10 show the same trend along with the reduction of the monomer molar ratio n (DAC): n (VDT). As can be seen from the compressive strengths of examples 2, 4, 5, 7, 9, 10 and comparative examples 1, 2, 3 after the primary molding curing, the compressive strength of comparative example 1 without NaSS was lower than that of the other examples, comparative example 2 without DAC could not be molded after blending with silica sand, the specific compressive strength could not be measured by the instrument, and comparative example 3 without VDT was also lower than that of the other examples. In the comparative example 1, electrostatic interaction between DAC and quartz sand and hydrogen bond interaction between VDT and quartz sand exist, the hydration effect of gel is reduced due to the existence of a large amount of VDT, and the coating effect of a polymer chain on quartz sand is reduced, so that the compression strength of the quartz sand composite material is reduced; in the comparative example 2, only hydrogen bond interaction between VDT and quartz sand exists, and the gel and the quartz sand cannot be molded after being blended; in comparative example 3, only the electrostatic interaction between DAC and quartz sand exists, but because the molecular chains in the zwitterionic gel have strong affinity and hydrophilicity with water, a compact hydration layer can be formed on the surface of the zwitterionic gel, the coating effect of the polymer chains on the quartz sand is enhanced, the compressive strength is slightly increased compared with that of comparative example 1, but the compressive strength is still lower compared with that of examples 1-10. As can be seen from examples 1-10 and comparative examples 1-3 in the table, the cation unit DAC and the negative electricity unit on the surface of the quartz sand form strong electrostatic interaction, the multiple hydrogen bond structure of the VDT unit and the hydroxyl on the surface of the quartz sand form strong hydrogen bond interaction, the two interactions are synergistic to greatly improve the strength of the cured quartz sand composite material, the DAC and the NaSS zwitterionic unit enable the molecular chain in the gel and water to have stronger hydrophilicity, a compact hydration layer can be formed on the surface of the polar quartz sand, the coating effect of the polymer chain on the quartz sand is obviously enhanced, the synergistic effect of the above effects enables the compressive strength and modulus of the poly (ampholyte-triazine)/quartz sand composite material before and after curing to span several orders of magnitude changes, and the performance change is not large after multiple forming, thus showing excellent repeated processing characteristics. FIG. 2 is a schematic view of the macro and micro structure of the obtained composite material in the cycle processing and forming process.
Self-repairing performance test of the poly (ampholyte-triazine)/quartz sand composite material:
taking the poly (ampholyte-triazine)/quartz sand composite material obtained in the example 2 as an example, drying and curing the composite material to obtain a hard quartz sand composite material, cutting the hard quartz sand composite material into two halves, coating the two halves of the hard quartz sand composite material to distinguish a cut interface, dripping a small amount of deionized water on the cross section of a sample, re-bonding the two halves of the sample after water is infiltrated, drying and curing the sample to obtain the repaired poly (ampholyte-triazine)/quartz sand composite material.
Testing the compression performance of the cured product by using an electronic universal testing machine; it has a compressive strength after curing of 6.7MPa and an elastic modulus of 456.2MPa as measured by a compression test at a speed of 1 mm/min.
Table 2: compressive properties of poly (ampholyte-triazine)/quartz sand composite material before and after self-repair
As can be seen from the data in table 2, the compressive strength after the repair can be recovered to 91.2% of the original strength, and the elastic modulus can be recovered to 91.9% of the original strength, which shows excellent self-repairing performance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of a poly (ampholyte-triazine)/quartz sand composite material capable of self-repairing and processing and forming in a circulating way is characterized by comprising the following steps:
1) adding sodium p-styrenesulfonate NaSS, acryloyloxyethyl trimethyl ammonium chloride DAC, 2-vinyl-4-6-diamino-1, 3, 5-triazine VDT, a cross-linking agent and a photoinitiator into dimethyl sulfoxide DMSO, and stirring and dissolving under a shading condition to obtain a uniform mixed solution;
2) carrying out ultraviolet curing on the mixed solution obtained in the step 1) to obtain strong hydrogen bond and polyampholyte high-bonding gel;
3) adding quantitative water into the strong hydrogen bonds and the polyampholyte high-bonding gel obtained in the step 2), and blending with quartz sand to obtain the poly (ampholyte-triazine)/quartz sand composite material capable of being processed and molded in a self-repairing and circulating manner.
2. The method of making a self-healing rotomolding poly (ampholyte-triazine)/silica sand composite as recited in claim 1, wherein: the cross-linking agent is N, N' -methylene bisacrylamide MBAA, and the photoinitiator is 2-oxoglutaric acid KA.
3. The method of making a self-healing rotomolding poly (ampholyte-triazine)/silica sand composite as recited in claim 1, wherein: in the mixed solution obtained in the step 1), the concentration of NaSS is 196-263 mg/mL, the concentration of DAC is 218-296 mg/mL, and the concentration of VDT is 26-41 mg/mL; the cross-linking agent accounts for 0.1 percent of the total mole amount of the monomers; the photoinitiator accounted for 0.25% of the total molar amount of the monomers.
4. The method of making a self-healing rotomolding poly (ampholyte-triazine)/silica sand composite as recited in claim 1, wherein: in the mixed solution obtained in the step 1), the total molar concentration of NaSS, DAC and VDT monomers is 2.30-2.38 mol/L.
5. The method of making a self-healing rotomolding poly (ampholyte-triazine)/silica sand composite as recited in claim 1, wherein: the temperature during stirring in the step 1) is controlled to be 70-80 ℃, and the stirring time is 30-40 min.
6. The method of making a self-healing rotomolding poly (ampholyte-triazine)/silica sand composite as recited in claim 1, wherein: in the step 2), the illumination condition under the ultraviolet lamp is as follows: and (3) irradiating for 10-12 h under an ultraviolet lamp with the wavelength of 365nm and the power of 300W.
7. The method of making a self-healing rotomolding poly (ampholyte-triazine)/silica sand composite as recited in claim 1, wherein: in the step 3), the mass ratio of water to gel to quartz sand is (0.07-0.11): (0.16-0.24): (0.76-0.84).
8. A self-repairing cycle processing formed poly (ampholyte-triazine)/quartz sand composite material is characterized in that: prepared by the method of any one of claims 1 to 7.
9. The application of the self-repairable poly (ampholyte-triazine)/quartz sand composite material capable of being molded by cyclic processing as claimed in claim 8, wherein the composite material is used for repeated molding, the composite quartz material is molded after absorbing water, dried and cured to obtain a product with a specific shape, and the water absorption molding-drying curing can be carried out in a cyclic manner.
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