CN115160589B - MOF-Zn@ZnO composite auxiliary agent for rubber and preparation method thereof - Google Patents

MOF-Zn@ZnO composite auxiliary agent for rubber and preparation method thereof Download PDF

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CN115160589B
CN115160589B CN202210964072.2A CN202210964072A CN115160589B CN 115160589 B CN115160589 B CN 115160589B CN 202210964072 A CN202210964072 A CN 202210964072A CN 115160589 B CN115160589 B CN 115160589B
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zno
auxiliary agent
coo
zno composite
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CN115160589A (en
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陈建
雷智强
伍言康
唐利平
胡茂源
岳晨曦
卿龙
李�瑞
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Sichuan University of Science and Engineering
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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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a MOF-Zn@ZnO composite auxiliary agent for rubber and a preparation method thereof, wherein the MOF-Zn is prepared by a hydrothermal method, and then the MOF-Zn is compounded with ZnO particles; the method for preparing the MOF-Zn material by the hydrothermal method is simple and convenient, can promote the overall activity of the composite material after being compounded with ZnO nano particles, can better promote the performance of the rubber composite material, and has better vulcanization promoting and reinforcing effects compared with the traditional zinc oxide.

Description

MOF-Zn@ZnO composite auxiliary agent for rubber and preparation method thereof
Technical Field
The invention belongs to the technical field of rubber additives, and particularly relates to a MOF-Zn@ZnO composite additive for rubber and a preparation method thereof.
Background
The rubber composite material has been developed for many years, has been put into thousands of households, becomes one of indispensable materials in national economy and daily life production, and has very wide application in the fields of automobile tires, shoes, sealing elements and the like. However, the properties of the raw rubber are poor and cannot be directly used for daily production, so that fillers and auxiliary agents for the rubber are indispensable for obtaining sufficient properties. Various types of fillers or auxiliaries, such as nano filler carbon black, white carbon black or graphene, must be added in the vulcanization process to reinforce the rubber composite material. In the process, zinc oxide filler in the composite material forms accelerator zinc salt with accelerator, then forms polysulfide zinc salt with polysulfide molecules, and finally forms a three-dimensional network structure by bonding with rubber chains. In the subsequent vulcanization process, znO is continuously consumed in the chemical crosslinking process, and vulcanization is completed when sulfur is consumed. In conclusion, the ZnO filler is used as an activator, so that the sulfur consumption in the vulcanization process is reduced, the vulcanization time is shortened, and the mechanical property of the rubber composite material is improved. It is well known that the nano structure can make the ZnO surface have higher activity, promote the reaction of ZnO and the rubber matrix, and maximize the contact between ZnO and the accelerator in the rubber composite material, thereby further improving the crosslinking efficiency. However, zinc oxide nanoparticles are easily agglomerated due to the interfacial effect of the nanoparticles.
The research and application of MOFs materials in the rubber field are also lacking, and the microstructure of MOFs materials prepared by a hydrothermal method is a laminated structure. The structure of the sheet layer increases the specific surface area of the material, is more beneficial to the loading of other materials, and can increase the combination and reaction area between the sheet layer and the rubber matrix. On the other hand, MOFs materials have high surface activity and rich active sites, and are probably a good choice as vulcanization accelerators. Meanwhile, the MOF material is a lamellar porous material, and the MOF material alone is filled into rubber and cannot play a role in promoting vulcanization of the rubber composite material.
ZnO is used as a traditional rubber auxiliary agent, and is widely applied to the rubber field with the advantages of low cost, abundant sources and the like. However, zinc is heavy metal, a large amount of zinc is used to pollute the environment through element enrichment, meanwhile, recycling of tires can be influenced, zinc compounds such as zinc oxide, zinc sulfide and the like are used as main ash in the tire cracking carbon black to cover the surface of the tire cracking carbon black, so that the surface activity of the carbon black is greatly reduced, meanwhile, the utilization cost of the carbon black is increased due to the removal of impurities, the high-value utilization of the tire cracking carbon black is greatly influenced, the activity of the zinc oxide is required to be improved, and the consumption of the zinc oxide is further reduced on the premise that the performance of rubber products is not influenced. Meanwhile, the traditional commercial zinc oxide has low activity, large particle size, more impurities and lower promotion effect on vulcanization reaction compared with nano ZnO.
Here, we propose a MOF-zn@zno composite auxiliary agent for rubber and a preparation method thereof, by preparing a MOF-zn@zno composite material, and using the composite material to replace the conventional (commercial) ZnO to reinforce rubber, thereby making up the defects of the conventional (commercial) ZnO.
Disclosure of Invention
In order to solve the technical problems, the invention provides the MOF-Zn@ZnO composite auxiliary agent for rubber and a preparation method thereof, wherein the MOF-Zn is prepared by a hydrothermal method, and then the MOF-Zn is compounded with ZnO particles; the method for preparing the MOF-Zn material by the hydrothermal method is simple and convenient, can promote the overall activity of the composite material after being compounded with ZnO nano particles, can better promote the performance of the rubber composite material, and has better vulcanization promoting and reinforcing effects compared with the traditional zinc oxide.
In order to achieve the technical purpose, the invention is realized by the following technical scheme:
the preparation method of the MOF-Zn@ZnO composite auxiliary agent for rubber comprises the following steps:
s1: zn (CH) 3 COO) 2 ·2H 2 O and phthalic acid are dissolved in the mixed solution, after ultrasonic treatment, the mixture is poured into the lining of a high-pressure reaction kettle, and then the mixture is cooled to room temperature after high-temperature reaction;
s2: adding N, N-dimethylformamide into the inner lining for soaking, then washing with methanol, mixing, shaking uniformly, filtering, freeze-drying the obtained solid sample, and performing heat treatment to obtain a MOF-Zn sample;
s3: taking MOF-Zn and Zn (CH) 3 COO) 2 ·2H 2 O is dissolved in deionized water, then the solution is poured into MOF-Zn dispersion liquid and is subjected to ultrasonic treatment, heating and stirring are carried out, alkaline solution is taken, and mixed solution is dripped into the mixed solution to raise the PH value to 7-9;
s4: stable at proper temperature for a period of time to form MOF-Zn/Zn (OH) 2 Filtering, washing to neutrality, drying, and heat treating to obtain sample。
Preferably, zn (CH 3 COO) 2 ·2H 2 The mol ratio of O to phthalic acid is 1:1-5:1, the components of the mixed solution are absolute ethyl alcohol, deionized water and N, N-dimethylformamide, the volume ratio of the absolute ethyl alcohol to the deionized water to the N, N-dimethylformamide is 1:1-1:5:5, and the ultrasonic treatment is carried out for 30 min-2 h;
preferably, zn (CH 3 COO) 2 ·2H 2 The solution obtained by mixing O, phthalic acid and mixed solution reacts for 12 to 120 hours at a high temperature of 160 to 200 ℃ in an electrothermal blowing drying oven;
preferably, 5-20 mL of N, N-dimethylformamide in the S2 is soaked for 30 min-2 h, and 5-20 mL of methanol is used for washing;
preferably, the heat treatment of the solid sample in the step S2 is carried out for 3 to 48 hours at 230 to 270 ℃ in a nitrogen or argon atmosphere in a high-temperature tube furnace;
preferably, in S3, the MOF-Zn is mixed with Zn (CH 3 COO) 2 ·2H 2 The content of the mixed solution of O dissolved in deionized water is 1g MOF-Zn, 100-300 mL deionized water, 6.14-24.57 mmole Zn (CH) 3 COO) 2 ·2H 2 O, carrying out ultrasonic treatment for 10 min-2 h;
preferably, in S3, the MOF-Zn is mixed with Zn (CH 3 COO) 2 ·2H 2 Heating the mixed solution of O dissolved in deionized water to 60-150 ℃ and continuously heating and stirring for 2-12 h;
preferably, the alkaline solution in the step S3 is a strong alkali solution such as NaOH, KOH and the like;
preferably, the MOF-Zn/Zn (OH) in S4 2 Stable for 2 to 6 hours at the temperature of 60 to 150 ℃ to form;
preferably, the MOF-Zn/Zn (OH) in S4 2 Drying for 6-72 h at 50-80 ℃ in a blast drying oven, and then carrying out heat treatment for 1-4 h in a nitrogen atmosphere at 155-180 ℃ in a high-temperature tube furnace to obtain a sample.
The beneficial effects of the invention are as follows:
according to the invention, MOF-Zn is prepared by a hydrothermal method, and then the MOF-Zn is compounded with ZnO particles; the method for preparing the MOF-Zn material by the hydrothermal method is simple and convenient, nano ZnO is adopted to replace commercial ZnO, meanwhile, the MOF material is taken as a carrier of ZnO, znO is taken as a load, the contact and combination reaction between the load ZnO and a rubber matrix can be improved by the structure of a sheet layer, the performance of the rubber composite material can be better improved, and the method has better vulcanization promotion and reinforcement effects than the traditional zinc oxide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a standard recipe of the MOF-Zn@ZnO and MOF-Zn and ZnO prepared compound and vulcanized rubber of the invention;
FIG. 2 is an XRD spectrum of MOF-Zn@ZnO, MOF-Zn and ZnO of the invention;
FIG. 3 is a graph of MOF-Zn@ZnO and ZnO of the invention C Raman spectrum of MOF-Zn;
FIG. 4 is a graph of MOF-Zn@ZnO and ZnO of the invention C A comparison graph of the surface morphology of MOF-Zn;
FIG. 5 is a graph of MOF-Zn@ZnO and ZnO of the invention C A stretch-broken section comparison graph of MOF-Zn;
FIG. 6 is a graph of MOF-Zn@ZnO and ZnO of the invention C A morphology diagram and a phase diagram contrast diagram of MOF-Zn;
FIG. 7 is a graph of MOF-Zn@ZnO and ZnO of the invention C A graph comparing the storage modulus (E') and loss tangent (tan delta) of MOF-Zn with temperature;
FIG. 8 is a graph of MOF-Zn@ZnO and ZnO of the invention C MOF-Zn is respectively mixed with SBR and vulcanized to obtain a static mechanical property comparison graph;
FIG. 9 is a graph of MOF-Zn@ZnO and ZnO of the invention C And comparing the cross-linking density of the MOF-Zn and SBR after mixing.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a MOF-Zn@ZnO composite auxiliary agent for rubber and a preparation method thereof, wherein the MOF-Zn is prepared by a hydrothermal method, and then the MOF-Zn is compounded with ZnO particles; the method for preparing the MOF-Zn material by the hydrothermal method is simple and convenient, can well promote the overall activity of the composite material after being compounded with ZnO nano particles, can better promote the performance of the rubber composite material, and has a very large vulcanization promoting and reinforcing effect compared with the traditional zinc oxide.
Example 1
S1: by Zn (CH) 3 COO) 2 ·2H 2 O is a central metal ion source, and terephthalic acid is an organic ligand. Weighing Zn (CH) 3 COO) 2 ·2H 2 O, terephthalic acid (the mol ratio of the O to the terephthalic acid is 2:1) is dissolved in a mixed solution of absolute ethyl alcohol, deionized water and N, N-dimethylformamide (the volume ratio of the O to the terephthalic acid to the N, N-dimethylformamide is 1:2:4), the mixed solution is placed in a beaker for ultrasonic treatment for 1h, and after the raw materials are completely dissolved, the solution is poured into a 100mL high-pressure reaction kettle liner. Then the high-pressure reaction kettle is placed in an electrothermal blowing drying box to react for 24 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature;
s2: adding 10mL of N, N-dimethylformamide into the inner lining, soaking for 1h, washing a sample with 10mL of methanol, uniformly mixing and filtering, repeating twice, putting the obtained solid sample into a vacuum freeze dryer for freeze drying for 24h, finally taking out the solid, and putting the solid into a high-temperature tubular furnace for heat treatment at 250 ℃ for 12h under the nitrogen or argon atmosphere to obtain a MOF-Zn sample;
s3: 1g of MOF-Zn was taken in a three-necked flask, 200mL of deionized water was added thereto, and 12.29 mmole of Zn (CH) 3 COO) 2 ·2H 2 O is dissolved in deionized water, the solution is poured into MOF-Zn dispersion liquid, the mixed solution is subjected to ultrasonic treatment for 30min, and the mixed solution is placed into an oil bath pot after ultrasonic treatment, heated to 120 ℃ and continuously heated and stirred for 6h. Preparing 1wt% NaOH solution, slowly drippingTo the MOF-Zn/Zn (CH) 3 COO) 2 ·2H 2 The rate of the O solution is controlled at 2 drops/s, and the addition amount of NaOH is controlled to control the pH value of the mixed solution to be less than or equal to 9;
s4: stabilizing at 120deg.C for 6h to form MOF-Zn/Zn (OH) 2 . The product is filtered and washed to be neutral, and is dried for 24 hours at 60 ℃ in a blast drying box. Finally, heat treatment is carried out for 2 hours in a high-temperature tube furnace under the atmosphere of 160 ℃ nitrogen, and the sample is taken out and then is put into a drying place for standby.
Example 2
Referring to FIG. 1, the MOF-Zn@ZnO and ZnO of the invention C MOF-Zn in combination with SBR to prepare a mix and a vulcanizate, the standard formulation ratio of which is shown in FIG. 1.
Example 3
Referring to FIG. 2, XRD spectra of MOF-Zn, znO and MOF-Zn@ZnO are shown. Characteristic peaks of 31.5 °, 34.3 °, 36.6 °, 47.5 °, 56.6 °, 62.4 ° and 67.8 ° which can be represented by ZnO curves in the figure indicate that the prepared ZnO structure is hexagonal wurtzite. In the curve MOF-Zn@ZnO, the characteristic peaks of ZnO appear entirely. According to the Debye-Scherrer formula, the grain sizes of ZnO in pure ZnO and MOF-Zn@ZnO were 39.8nm and 28.9nm, respectively. The decrease in grain size indicates that the presence of MOF-Zn inhibits the growth of ZnO grains. Along with the growth of ZnO grains, the ZnO grain size is gradually increased, and the interface effect formed by nano particles is gradually reduced, so that the activity of ZnO is reduced, and atoms reacting on the surfaces of the particles are reduced, so that the vulcanization promotion performance of the ZnO is reduced. And the growth of ZnO grains is inhibited, so that the interface effect of the nano particles can be ensured, and the nano ZnO can keep a higher-activity state.
Example 4
Referring to FIG. 3, znO was obtained C Raman spectrum of MOF-Zn and MOF-zn@zno. ZnO (zinc oxide) C 2E of (2) 2 (M) and E 2 The (high) mode absorption peaks are located at 334cms, respectively -1 And 438cms -1 Where it is located. At 1321cm -1 Dband appears at this point, which is related to the disordered structure of the carbon microsphere, while at 1589cms -1 Gband appears nearby, usually by I D And I G Is the relative ratio of the expression samplesOrder and defect conditions, whereby MOF-Zn I can be obtained D /I G The value was about 1.03. E2 (high) mode of MOF-Zn@ZnO occurs 15cm -1 Since MOF-Zn limits the growth of ZnO crystals in MOF-zn@zno, while the small size of the crystals causes a steric limiting effect. While Dband and Gband of MOF-Zn@ZnO respectively appear at 1319cm -1 And 1586cm -1 At the place, obtain the I of MOF-Zn@ZnO D /I G The value was about 1.20, indicating that the MOF-Zn surface structure was changed due to the surface loading of ZnO and the disruption of the regular structure of the MOF-Zn portion. This suggests that there is some interfacial interaction between ZnO and MOF-Zn.
Example 5
Referring to fig. 4, it can be seen from fig. 4 (a) that ZnO particles are mostly spherical with some agglomeration. FIG. 4 (b) shows an SEM image of MOF-Zn, and it can be seen that MOF-Zn is a sheet material and has a mainly hexagonal shape. In FIG. 4 (c) & (d), znO nanoparticles are supported on the surface of the sheet-shaped MOF-Zn in the MOF-Zn@ZnO, and meanwhile, the distribution of the ZnO nanoparticles can be seen to be relatively uniform.
Example 6
Referring to FIG. 5, the ZnO is observed by FESEM C The stretch-broken sections of/SBR (control, 3/100), MOF-Zn/SBR (control, 6/100) and MOF-Zn@ZnO/SBR (6/100) are shown in FIG. 5. As can be seen from fig. 5 (a) and (c), no larger particles or agglomerates appear in the fracture cross section, indicating that the filler in the composite material is well dispersed in the rubber matrix; also, from FIG. 5 (b), agglomerates of MOF-Zn can be seen at the cross section, indicating poor compatibility with the rubber matrix. Therefore, the dispersibility of MOF-Zn and ZnO nano particles can be well improved by MOF-Zn@ZnO.
Example 7
Referring to FIG. 6, FIG. 6 (a)&(b) Respectively represent ZnO C Topography and phase diagram of SBR (control, 3/100), FIG. 6 (c)&(d) Respectively representing the morphology of MOF-Zn/SBR (control, 6/100) and the phase diagram, FIG. 6 (e)&(f) Representing the morphology and phase diagrams of MOF-Zn@ZnO/SBR (6/100), respectively. In the AFM image, the bright spots in the topography represent protruding carbon black particles, corresponding to the respective positions of the phase diagram,as can be seen from the figure, znO C The filler in the SBR and the MOF-Zn@ZnO/SBR is well dispersed, no obvious agglomeration exists, and the MOF-Zn/SBR is reversely observed, wherein some agglomerates appear, and the experimental result corresponds to the FESEM experimental result. And meanwhile, AFM characterization is carried out on MOF-Zn@ZnO, so that ZnO nanoparticles are attached to the surface of the MOF-Zn, and the result corresponds to the FESEM characterization result.
Example 8
Referring to FIG. 7, in FIG. 7 (a), E' represents the amount of stored energy of the material, reflecting the elastic component in the rubber composite. It can be seen from the graph that the energy storage modulus of the MOF-Zn@ZnO group is higher than that of ZnO C SBR (control, 3/100), wherein the lowest MOF-Zn/SBR group is used to indicate that the composite material can improve the storage energy and rebound resilience of the composite material under the low-temperature environment, compared with the single ZnO C And the MOF-Zn is used, so that safety can be provided for vehicles running under the low-temperature condition, and the MOF-Zn and ZnO nano particles in the MOF-Zn@ZnO hybrid body can be benefited, so that a strong interaction exists between the MOF-Zn and the SBR matrix. Meanwhile, fig. 7 (b) shows the relationship between the loss modulus (E ") of the filler and the temperature, wherein E" reflects the viscosity component in the rubber composite material, and the higher E "is, the larger the viscosity deformation of the composite material is generated when the composite material is subjected to an external force, so that the larger the contact area between the automobile tire and the ground is in the running process, and the running safety of the vehicle can be ensured. From the graph, the MOF-Zn@ZnO can bring more safety to the running process of the vehicle. It can be seen from FIG. 7 (c) that the addition of MOF-Zn@ZnO reduced the peak value of tan delta without significantly affecting the position of tan delta, with the peak value of the MOF-Zn@ZnO/SBR group being the lowest. The rolling resistance of the composite is generally expressed in terms of tan delta values at 60 c, respectively. The tan delta value at 0 ℃ was used to evaluate wet skid resistance, while the tan delta value at 60 ℃ represents rolling resistance. As can be seen from the figures: the rolling resistance (0.1714) of the MOF-Zn@ZnO/SBR is greater than the rolling resistance (0.1588) and ZnO of the MOF-Zn/SBR C Rolling resistance of SBR (0.1568). The MOF-Zn@ZnO is shown to improve the rolling resistance.
Example 9
Referring to FIG. 8, the MOF-Zn@ZnO and ZnO of the invention C Mixing MOF-Zn and SBRAfter vulcanization, the static mechanical properties were measured and 100% tensile stress, 200% tensile stress, 300% tensile stress, tensile strength and tear elongation were recorded, respectively. It can be seen that when MOF-Zn@ZnO is filled into SBR, it is compared with ZnO C for/NR, the MOF-Zn@ZnO/SBR composite material has improved 100% elongation stress, 200% elongation stress, 300% elongation stress and tensile strength by 33.6%, 38.2%, 30.8% and 16.8%, respectively. The elongation at break of the composite material is maintained to a large extent while the tensile property of the composite material is not affected. Meanwhile, MOF-Zn is added into SBR, so that the tensile stress of the composite material can be improved, but the elongation at break of the composite material can be reduced, and the improvement of the tensile strength is not promoted.
Example 10
Referring to FIG. 9, it can be seen that the crosslink density of the MOF-Zn@ZnO/SBR composite material is highest among the three composite materials, and is improved by 25.2% compared with that of the ZnO/SBR composite material. The MOF-Zn@ZnO has a good effect of promoting crosslinking in a composite material system. The reason is that ZnO nano particles in the MOF-Zn@ZnO system have higher activity and are loaded on the surface of the MOF-Zn, which is beneficial to improving the crosslinking performance of the composite material. Meanwhile, when MOF-Zn is singly added into the SBR matrix, the crosslinking density of the MOF-Zn/SBR is larger than that of ZnO/SBR, and the activity of the MOF-Zn is higher than that of ZnO, so that the contribution of the MOF-Zn to the crosslinking in the rubber matrix is larger than that of ZnO. Here, the crosslinking density of the MOF-Zn/SBR and the MOF-Zn@ZnO/SBR is greater than that of the ZnO/SBR, and the test result of the DMA is just proved. It can thus be concluded that MOF-zn@zno contributes to an increase in vulcanization speed, promoting cross-linking between rubber composites.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.

Claims (10)

1. The preparation method of the MOF-Zn@ZnO composite auxiliary agent for rubber is characterized by comprising the following steps of:
s1: zn (CH) 3 COO) 2 ·2H 2 O and phthalic acid are dissolved in the mixed solution, after ultrasonic treatment, the mixture is poured into the lining of a high-pressure reaction kettle, and then the mixture is cooled to room temperature after high-temperature reaction;
s2: adding N, N-dimethylformamide into the inner lining for soaking, then washing with methanol, mixing, shaking uniformly, filtering, freeze-drying the obtained solid sample, and performing heat treatment to obtain a MOF-Zn sample;
s3: taking MOF-Zn and Zn (CH) 3 COO) 2 ·2H 2 O is dissolved in deionized water to form MOF-Zn dispersion liquid and Zn (CH) 3 COO) 2 ·2H 2 O solution, and then Zn (CH) 3 COO) 2 ·2H 2 Pouring the O solution into MOF-Zn dispersion liquid, performing ultrasonic treatment, heating and stirring, dripping alkaline solution into the mixed solution, and lifting the pH value to 7-9;
s4: stable at proper temperature for a period of time to form MOF-Zn/Zn (OH) 2 And filtering, washing to neutrality, drying and heat treating to obtain the sample.
2. The method for preparing MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein Zn (CH 3 COO) 2 ·2H 2 The mol ratio of O to phthalic acid is 1:1-5:1, and the mixed solution comprises absolute ethyl alcohol, deionized water and N, N-dimethylAnd (3) performing ultrasonic treatment on the carbamide for 30min to 2h, wherein the volume ratio of the carbamide to the carbamide is 1:1 to 1:5:5.
3. The method for preparing MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein Zn (CH 3 COO) 2 ·2H 2 And (3) reacting the solution obtained by mixing O, phthalic acid and the mixed solution at a high temperature of 160-200 ℃ in an electrothermal blowing drying oven for 12-120 h.
4. The preparation method of the MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein 5-20 mL of N, N-dimethylformamide in S2 is soaked for 30 min-2 h, and 5-20 mL of methanol is used for washing.
5. The preparation method of the MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein the heat treatment of the solid sample in S2 is carried out for 3-48 hours at 230-270 ℃ in a nitrogen or argon atmosphere in a high-temperature tube furnace.
6. The method for preparing MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein the MOF-Zn and Zn (CH 3 COO) 2 ·2H 2 The content of the mixed solution of O dissolved in deionized water is 1g of MOF-Zn, 100-300 mL of deionized water, 6.14~24.57 mmol Zn (CH) 3 COO) 2 ·2H 2 And O, carrying out ultrasonic treatment for 10 min-2 h.
7. The method for preparing MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein the MOF-Zn and Zn (CH 3 COO) 2 ·2H 2 And heating the mixed solution of O dissolved in deionized water to 60-150 ℃ and continuously heating and stirring for 2-12 h.
8. The preparation method of the MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein the alkaline solution in S3 is a NaOH solution.
9. According to claimThe preparation method of the MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1 is characterized by comprising the step of performing MOF-Zn/Zn (OH) in S4 2 And (3) forming the material stably at the temperature of 60-150 ℃ for 2-6 hours.
10. The process for preparing MOF-Zn@ZnO composite auxiliary agent for rubber according to claim 1, wherein the MOF-Zn/Zn (OH) in S4 2 Drying for 6-72 h at 50-80 ℃ in a forced air drying oven, and then carrying out heat treatment for 1-4 h in a nitrogen atmosphere at 155-180 ℃ in a high-temperature tube furnace to obtain a sample.
CN202210964072.2A 2022-08-11 2022-08-11 MOF-Zn@ZnO composite auxiliary agent for rubber and preparation method thereof Active CN115160589B (en)

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