CN114213754B - MOFs particle doped composite material and preparation method thereof - Google Patents
MOFs particle doped composite material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a MOFs particle doped composite material and a preparation method thereof. The method comprises the following steps: preparing stone powder into aqueous phase solution; adding the mixture into an oily organic solution to prepare an amphiphilic block copolymer as a pre-solution; adding tetraethoxysilane and aqueous phase solution into the pre-solution, and performing reaction treatment to obtain turbid liquid; MOFs modification is carried out on particles in the turbid liquid to obtain precursor liquid; adding oil-soluble phenolic resin and polydimethylsiloxane-polycarbonate block copolymer into precursor liquid, uniformly mixing, adding water, dispersing, and separating oil phase to obtain a coating liquid; coating and drying the coating liquid to constant weight, collecting the product, and drying after the reaction of the product, polydimethoxyl siloxane and dibutyltin dilaurate is completed to obtain doped particles; the doped particles are added to the molten pipe plastic for strengthening. The invention has obvious improvement effect from the aspects of mechanical property, temperature resistance and antifouling property of the pipeline plastic.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a MOFs particle doped composite material and a preparation method thereof.
Background
The plastic pipe is a polymer material specially used for preparing water guiding and draining pipes, and compared with the traditional pipes such as cast iron pipes, galvanized steel pipes, cement pipes and the like, the plastic pipe has the problems of low preparation cost, low difficulty, small cold and hot shrinkage rate and the like, and generally has better weather resistance and is not easy to generate oxidation corrosion.
However, plastic tubing also suffers from certain drawbacks compared to conventional non-plastic tubing. The plastic of the pipeline is usually PPR, PVC, PP, PE, PE-RT, PE/HDPE and other materials, and the problems that the plastic material is not low-temperature resistant, poor in thermal shock resistance, easy to scale in the pipeline and the like are commonly existed. In a specific use process, the pipeline plastic is easy to be brittle broken at a lower use temperature due to low-temperature resistance and poor thermal shock resistance. In addition, most of the existing plastics have no good hydrophobicity, and the preparation of the hydrophobic anti-fouling coating can not be realized through effective surface treatment, so that the actual anti-fouling performance is poor, the pipeline decontamination process is complicated, especially the decontamination of the embedded pipeline can not be effectively carried out, and the auxiliary decontamination can be carried out only through specific chemical auxiliary agents.
Therefore, how to improve the temperature resistance and the anti-fouling capability of the plastic pipeline is a great development center of gravity in the field of pipeline plastics.
Disclosure of Invention
The invention provides a MOFs particle doped composite material and a preparation method thereof, and aims to solve the problems that the existing pipeline plastic has poor temperature resistance, is easy to generate brittle failure in a cold environment, is easy to generate thermal cracking when hot water is conveyed, has poor mechanical property, is easy to crack after being impacted, is easy to generate cracking when hot steam is conveyed when hot water is conveyed, and the like.
The invention aims at:
1. the heat resistance of the existing pipeline plastic can be effectively enhanced, so that the pipeline plastic is more cold-resistant, heat-resistant and heat-shock-resistant;
2. the static load resistance of the pipeline plastic is greatly improved;
3. the impact resistance of the pipeline plastic is enhanced;
4. the strengthening leads the pipeline plastic to form certain antifouling and antifouling capacity.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A preparation method of MOFs particle doped composite material,
the method comprises the following steps:
1) Dispersing ultrafine stone powder serving as an aluminum silicate component in a water system to prepare an aqueous phase solution;
2) Adding the amphiphilic block copolymer into an oily organic solution to prepare a pre-solution;
3) Adding ethyl orthosilicate into the pre-solution obtained in the step 2), uniformly mixing, adding the aqueous phase solution obtained in the step 1), performing ultrasonic treatment, standing, filtering, separating the solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained in the separation, and performing ultrasonic dispersion to obtain turbid liquid;
4) Adding a zinc salt alcohol solution into the turbid liquid obtained in the step 3), and mixing to obtain a prefabricated liquid;
5) Adding a ligand imidazole alcohol solution into the prefabricated liquid obtained in the step 4), filtering a solid substance after mixing reaction, carrying out low-temperature treatment on the solid substance to obtain a precursor, and adding the precursor into the filtrate again to obtain a precursor liquid;
6) Adding oil-soluble phenolic resin and polydimethylsiloxane-polycarbonate segmented copolymer into the precursor liquid obtained in the step 5), uniformly mixing, adding water, performing dispersion treatment, and separating an oil phase to obtain a coating liquid;
7) Coating and drying the coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into an organic solvent, uniformly dispersing, adding polydimethoxyl siloxane at least twice, controlling the adding amount of the polydimethoxyl siloxane for the first time to be less than or equal to 5wt% of the total adding amount, carrying out the reaction again, dispersing again until the polydimethoxyl siloxane and the dibutyl tin dilaurate are added after the uniform dispersion, and drying after the stirring reaction is completed to obtain doped particles;
8) Adding the doped particles into molten pipeline plastic for strengthening, and thus completing the preparation of the composite material.
Stone powders of aluminum silicate compositions are a more common type of stone powders used for plastic reinforcement. However, the strengthening effect is limited, and the wear resistance of the plastic can be effectively improved, but the temperature resistance of the plastic is often further weakened.
According to the technical scheme, stone powder of aluminum silicate components is used as a carrier, the preparation of a hollow cladding structure is carried out on the surface of the stone powder through block copolymerization, specifically in the processes of 1) to 3), a pre-solution is added after the stone powder is dispersed, an oil-water mixed liquid is formed through a stirring mode, and in the oil-water mixed liquid, on one hand, oil-water droplet separation can promote the dispersion of the stone powder, and on the other hand, soft agglomerated stone powder is captured and separated through amphipathy of a block copolymer, so that the dispersibility of the stone powder is further improved, and then tetraethoxysilane and hydrolysis of tetraethoxysilane at an oil-water interface are captured through the amphipathy block copolymer, the stone powder is encapsulated, and particles of the silica-coated stone powder are formed. The use of amphiphilic block copolymers is particularly critical in this series of processes. Therefore, if the stone powder is simply dispersed in the oil liquid, the preparation of the silica coated stone powder can be realized by adding the tetraethoxysilane and slowly dispersing the tetraethoxysilane, but the dispersibility of the stone powder cannot be ensured in the process, although the dispersion effect of the stone powder in the oily liquid is slightly better than that of the aqueous phase liquid through the test, the secondary dispersion is difficult to realize in the oil phase liquid, and then the tetraethoxysilane is hydrolyzed by adding the water, so that the silica cannot be ensured to effectively grow and be coated on the surface of the stone powder, and on the other hand, even if the stone powder is coated, the stone powder is coated in a relatively tight coating mode, a solid core-shell structure is formed, and compared with an empty core-shell structure, which is not in direct contact with the shell and the inner core of the invention, the thermal shock resistance of the plastic is still easy to be weakened, the specific surface area is relatively small, and the subsequent MOFs modification is unfavorable. And then step 4) and step 5), carrying out ZIF-8 modification, namely MOFs modification, through zinc salt and ligand imidazole, wherein ZIF-8 modification is a MOFs modification mode of common plastics, but is usually used for hydrophobic modification of membrane materials because of good hydrophobicity. However, simply modifying such MOFs does not effectively increase the hydrophobicity of the pipe plastic, and simply surface treating the pipe with the modified particles is more inconvenient, and therefore further processing is required thereafter. In the step 6), a structure similar to a branch structure is formed by a self-assembly mode of the segmented copolymer, the formed branch structure is a key for enabling doped particles to improve the hydrophobicity of the pipeline plastic, the branch structure can be connected with a pipeline plastic matrix, the doped particles can be highly dispersed and dispersed under the expansion effect of the segmented copolymer, so that the modified particles supported in the extrusion molding process of the molten master batch can at least partially float up to the surface of the formed plastic pipeline for hydrophobic modification, and meanwhile, the surface hardness and the wear resistance of the pipeline are enhanced. And step 7) is to carry out final modification treatment, so that the affinity of the doped particles with the pipeline plastic is stronger.
Specifically, the pipeline plastic disclosed by the invention comprises but is not limited to any one or more of PP and/or PE, and has the best matching effect with the PP and the PE through experiments, so that the PP or PE composite material modified by MOFs (ZIF-8) particles with relatively better performance can be formed.
As a preferred alternative to this,
the aluminum silicate component superfine stone powder in the step 1) is mullite powder and/or halloysite powder;
the mesh number of the mullite powder and/or halloysite powder is more than or equal to 2000 meshes;
the content of the superfine stone powder of the aluminum silicate component in the aqueous phase solution is 15-30 g/L.
Mullite powder and halloysite powder have wide sources and relatively high aluminum silicate content, and the preparation of ultrafine stone powder is easy to realize through a ball mill, and can be simply and quickly finished through a 2000-mesh ball mill in the actual preparation process. On the one hand, soft agglomeration is easy to occur in the dispersing process due to the fact that the content of mullite powder and halloysite powder is too high, so that the uniformity of the particle size of the prepared doped particles is poor, on the other hand, when the content is too high, the amphiphilic block copolymer is matched with the amphiphilic block copolymer in a follow-up mode, a block copolymer pre-solution with higher concentration is needed, the amphiphilic block copolymer is easy to undergo netlike assembly, and spherical assembly cannot be effectively achieved.
As a preferred alternative to this,
step 2) the amphiphilic block copolymer is a polyethylene glycol-polycaprolactone block copolymer or a polyethylene glycol-polycaprolactone-polyethylene glycol triblock copolymer;
the concentration of the amphiphilic block copolymer in the pre-solution is 12-18 mmol/L.
The amphiphilic block copolymers selected for use as described above are relatively common and readily available block copolymer types. The concentration of the block copolymer is mainly controlled to realize the capturing and dispersing of the stone powder and the tetraethoxysilane respectively, and the effective capturing and dispersing cannot be realized when the dosage is too small, but the dosage is too large to easily cause the formation of a hollow shell structure, so that the proper control of the dosage is one of key factors for ensuring the quality of doped particles and the quality of finally formed plastics. The optimal concentration of about 12-30 mmol/L can be selected by the actual concentration through the test, but the invention considers that the relatively low concentration is selected in the actual production process, so that the amphiphilic block copolymer can be completely consumed in single preparation, the oil solvent can be recovered for secondary use in the subsequent process, and the influence on the subsequent reaction is avoided.
In addition, for the selection of the two block copolymers, the polyethylene glycol-polycaprolactone block copolymer can finally ensure that the plastic has relatively better mechanical properties, and the polyethylene glycol-polycaprolactone-polyethylene glycol triblock copolymer can ensure that the plastic has relatively better temperature resistance.
As a preferred alternative to this,
step 3) the ethyl orthosilicate is 4-8% VOL of the pre-liquid;
the dosage of the aqueous phase solution is 2-5% of VOL of the pre-solution.
The amount of ethyl orthosilicate can have a significant effect on shell assembly. However, when the dosage is too large, the addition of the ethyl orthosilicate is excessive, and residues of the ethyl orthosilicate are generated in the solution, so that the material waste is caused. The invention controls the relative dosage of the ethyl orthosilicate and the aqueous phase solution, ensures that the stone powder is effectively dispersed to form an empty core-shell structure, and simultaneously ensures that the ethyl orthosilicate can be basically and completely consumed, thereby being convenient for recycling the oily organic solvent and reducing the influence on subsequent reactions.
As a preferred alternative to this,
the zinc salt alcohol solution in the step 4) is a methanol and/or ethanol solution of zinc nitrate and/or zinc chloride;
the total concentration of the zinc nitrate and/or the zinc chloride is 20-50 g/L.
The zinc salts have good alcohol solubility and are commonly and easily obtained.
As a preferred alternative to this,
the dosage of the zinc salt alcohol solution is 3-5 times of the volume of the turbid liquid.
The use of a larger amount of zinc salt alcohol solution can carry out secondary dispersion of turbid liquid, and meanwhile, the alcohol has the function of well promoting the dispersion of silicon dioxide. In practice, MOFs modification can be realized by adopting zinc salt aqueous solution, but in the aqueous solution, the formed hollow core-shell structure particles have a silicon dioxide shell, so that the dispersibility is poor, soft agglomeration is easy to form again, and therefore, the adoption of alcohol solution is a key factor for guaranteeing MOFs modification effect.
As a preferred alternative to this,
step 5) 2-methylimidazole alcohol solution with the concentration of the ligand imidazole alcohol solution of 0.5-2.0 g/L;
the dosage of the ligand imidazole alcohol solution is 0.5-2 times of the volume of the prefabricated liquid.
The ligand imidazole can be matched with zinc salt to effectively form MOFs modification, so that the hydrophobic property of the particles is greatly enhanced.
As a preferred alternative to this,
and 6) in the coating plate liquid obtained in the step 6):
the concentration of the oil-soluble phenolic resin is 0.8-1.2 mol/L;
the concentration of the polydimethylsiloxane-polycarbonate segmented copolymer is 8-13 mmol/L.
The oil-soluble phenolic resin and the polydimethylsiloxane-polycarbonate segmented copolymer can form net-shaped self-assembly in the technical scheme of the invention, wherein the polydimethylsiloxane-polycarbonate segmented copolymer is commonly used for flame retardant reinforcement, but in the technical scheme of the invention, the oil-soluble phenolic resin is matched with the oil-soluble phenolic resin to form non-closed net-shaped assembly, so that the connection strength and the dispersibility of MOFs particles formed by MOFs modified doped particles and a pipeline plastic matrix are reinforced, and the MOFs particles can at least partially float up to the surface of a formed plastic pipeline.
As a preferred alternative to this,
the dosage of the polydimethoxyl siloxane in the step 7) is 4-7 times of the weight of the solid product, and the dibutyl tin dilaurate is 1-6 times of the weight of the solid product.
The two common and common cross-linking agents and catalysts can improve the compatibility of the doped particles and the plastic matrix of the pipeline.
MOFs particle doped composite materials.
The composite material prepared by the invention has good hydrophobic and antifouling properties, and has good mechanical properties such as wear resistance, bending strength, impact toughness and the like, is not easy to generate brittle failure or cracking when facing temperature change, and has very remarkable beneficial effects when being used for preparing and using pipelines.
The beneficial effects of the invention are as follows:
1) The hydrophobic and antifouling properties of the pipeline plastic are greatly improved, so that the inner wall of the pipeline is not easy to be fouled;
2) The surface wear resistance and impact toughness of the pipeline plastic are improved, and the pipeline plastic has better chemical weather resistance, so that the damage of a dredging agent to the pipeline is reduced when the pipeline is dredged, and the damage to the pipeline in the physical dredging process can be effectively avoided;
3) The PP matrix composite material has good thermal shock resistance, and the PP matrix composite material has good performance in a thermal shock test at-30 ℃ to 140 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall under the protection of the present invention
The raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art unless specifically stated otherwise; the methods used in the examples of the present invention are those known to those skilled in the art unless specifically stated otherwise.
Example 1
A MOFs particle modified composite material prepared by the method of:
1) Dispersing 2000 mesh mullite powder in deionized water to prepare 25g/L aqueous phase solution;
2) Adding the polyethylene glycol-polycaprolactone block copolymer into n-heptane to prepare a 15mmol/L pre-solution;
3) Adding 60mL of ethyl orthosilicate into each 1L of the pre-solution obtained in the step 2), uniformly mixing, adding 45mL of the aqueous phase solution obtained in the step 1), performing ultrasonic treatment for 15min, standing for 20min, filtering, separating to obtain a precipitate and an oil phase solution, washing the precipitate, adding the precipitate into the oil phase solution obtained in the step, and performing ultrasonic dispersion for 15min to obtain turbid liquid;
4) Adding 4L of zinc nitrate ethanol solution with the concentration of 35g/L into each 1L of turbid liquid obtained in the step 3) according to a proportion, and mixing to obtain a prefabricated liquid;
5) Adding 1.5L of 2-methylimidazole ethanol solution with the concentration of 1.5g/L into each 1L of prefabricated liquid obtained in the step 4) in an equal amount for five times in proportion, mixing and reacting for 6 hours after each addition, filtering out solid matters after the addition and the reaction are completed, carrying out heat treatment on the solid matters at 60 ℃ for 12 hours to obtain a precursor, and adding the precursor into filtrate again to obtain precursor liquid;
6) Adding (commercially available) 100% oil-soluble phenolic resin into the precursor liquid obtained in the step 5) according to the proportion of 1.15mol/L, adding deionized water with the volume of 2 times of the precursor liquid after uniformly mixing, dispersing uniformly, separating liquid, separating and removing oil phase to obtain a coating liquid;
7) Coating the plate coating liquid obtained in the step 6) at 60 ℃ to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, uniformly dispersing, adding polydimethoxyl siloxane with 5 times of the mass of the solid product twice, wherein the addition of the polydimethoxyl siloxane for the first time is 3.5 weight percent of the total mass of the polydimethoxyl silane, reacting for 15min, dispersing again, adding the rest polydimethoxyl siloxane and dibutyltin dilaurate with 3 times of the mass of the solid product after uniform dispersion, stirring, and drying the plate coating at 60 ℃ after the reaction is completed to obtain doped particles;
8) And melting the commercially available PP pipeline plastic master batch (PP master batch), adding doping particles for strengthening, wherein the adding amount of the doping particles is 3.75wt% of the total mass of the PP master batch, and thus the preparation of the composite material is completed.
The composite material can be pelletized to prepare reinforced master batch or directly used for extrusion molding. The present example was directly extruded to prepare a DN90 x en8.2mm standard tube conforming to the GB/T13663-2000 standard, the standard tube prepared in the present example being labeled BG1.
Example 2
A MOFs particle modified composite material prepared by the method of:
1) Dispersing 2000 mesh mullite powder in deionized water to prepare a 20g/L aqueous phase solution;
2) Adding the polyethylene glycol-polycaprolactone block copolymer into n-heptane to prepare 14mmol/L pre-solution;
3) Adding 55mL of ethyl orthosilicate into each 1L of the pre-solution obtained in the step 2), uniformly mixing, adding 38mL of the aqueous phase solution obtained in the step 1), performing ultrasonic treatment for 15min, standing for 20min, filtering, separating to obtain a precipitate and an oil phase solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained in the step, and performing ultrasonic dispersion for 15min to obtain turbid liquid;
4) Adding 4L of zinc nitrate ethanol solution with the concentration of 25g/L into each 1L of turbid liquid obtained in the step 3) according to a proportion, and mixing to obtain a prefabricated liquid;
5) Adding 1.25L of 2-methylimidazole ethanol solution with the concentration of 1.2g/L into each 1L of prefabricated liquid obtained in the step 4) in an equal amount for five times in proportion, mixing and reacting for 6 hours after each addition, filtering out solid matters after the addition and the reaction are completed, carrying out heat treatment on the solid matters at 60 ℃ for 12 hours to obtain a precursor, and adding the precursor into filtrate again to obtain precursor liquid;
6) Adding (commercially available) 100% oil-soluble phenolic resin into the precursor liquid obtained in the step 5) according to the proportion of 1.0mol/L, adding deionized water with the volume of 2 times of the precursor liquid after uniformly mixing, dispersing uniformly, separating liquid, separating and removing oil phase to obtain a coating liquid;
7) Coating the plate coating liquid obtained in the step 6) at 60 ℃ to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, uniformly dispersing, adding polydimethoxyl siloxane with 6 times of mass of the solid product twice, wherein the addition of the polydimethoxyl siloxane for the first time is 5wt% of the total mass of the polydimethoxyl silane, reacting for 15min, dispersing again, adding the rest polydimethoxyl siloxane and dibutyl tin dilaurate with 4.5 times of mass of the solid product after uniform dispersion, stirring, and drying the plate coating at 60 ℃ after the reaction is completed to obtain doped particles;
8) And melting the commercially available PP pipeline plastic master batch (PP master batch), adding doping particles for strengthening, wherein the addition amount of the doping particles is 5.15wt% of the total mass of the PP master batch, and thus the preparation of the composite material is completed.
The composite material can be pelletized to prepare reinforced master batch or directly used for extrusion molding. The present example was directly extruded to prepare a DN90 x en8.2mm standard tube conforming to the GB/T13663-2000 standard, the standard tube prepared in the present example being labeled BG2.
Example 3
A MOFs particle modified composite material prepared by the method of:
1) Dispersing 2000 mesh mullite powder in deionized water to prepare 15g/L aqueous phase solution;
2) Adding the polyethylene glycol-polycaprolactone block copolymer into n-heptane to prepare a pre-solution with the concentration of 12 mmol/L;
3) Adding 40mL of ethyl orthosilicate into each 1L of the pre-solution obtained in the step 2), uniformly mixing, adding 20mL of the aqueous phase solution obtained in the step 1), performing ultrasonic treatment for 15min, standing for 20min, filtering, separating to obtain a precipitate and an oil phase solution, washing the precipitate, adding the precipitate into the oil phase solution obtained in the step, and performing ultrasonic dispersion for 15min to obtain turbid liquid;
4) Adding 3L of zinc nitrate ethanol solution with the concentration of 20g/L into each 1L of turbid liquid obtained in the step 3) according to a proportion, and mixing to obtain a prefabricated liquid;
5) Adding 0.5L of 2-methylimidazole ethanol solution with the concentration of 2.0g/L into each 1L of prefabricated liquid obtained in the step 4) in an equal amount for five times in proportion, mixing and reacting for 6 hours after each addition, filtering out solid matters after the addition and the reaction are completed, carrying out heat treatment on the solid matters at 60 ℃ for 12 hours to obtain a precursor, and adding the precursor into filtrate again to obtain precursor liquid;
6) Adding (commercially available) 100% oil-soluble phenolic resin into the precursor liquid obtained in the step 5) according to the proportion of 1.2mol/L, adding deionized water with the volume of 2 times of the precursor liquid after uniformly mixing, dispersing uniformly, separating liquid, separating and removing oil phase to obtain a coating liquid;
7) Coating the coating solution obtained in the step 6) at 60 ℃ to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, uniformly dispersing, adding 4 times of polydimethoxyl siloxane with the mass of the solid product, wherein the addition of the polydimethoxyl siloxane for the first time is 3wt% of the total polydimethoxyl silane, reacting for 15min, dispersing again, adding the rest polydimethoxyl siloxane and 1 time of dibutyltin dilaurate with the mass of the solid product after uniform dispersion, stirring, and coating at 60 ℃ to dry to obtain doped particles;
8) And melting the commercially available PP pipeline plastic master batch (PP master batch), adding doping particles for strengthening, wherein the adding amount of the doping particles is 3wt% of the total mass of the PP master batch, and thus the preparation of the composite material is completed.
The composite material can be pelletized to prepare reinforced master batch or directly used for extrusion molding. The present example was directly extruded to prepare a DN90 x en8.2mm standard tube conforming to the GB/T13663-2000 standard, the standard tube prepared in the present example being labeled BG3.
Example 4
A MOFs particle modified composite material prepared by the method of:
1) Dispersing 2000 mesh mullite powder in deionized water to prepare 30g/L aqueous phase solution;
2) Adding the polyethylene glycol-polycaprolactone block copolymer into n-heptane to prepare 18mmol/L pre-solution;
3) Adding 80mL of ethyl orthosilicate into each 1L of the pre-solution obtained in the step 2), uniformly mixing, adding 50mL of the aqueous phase solution obtained in the step 1), performing ultrasonic treatment for 15min, standing for 20min, filtering, separating to obtain a precipitate and an oil phase solution, washing the precipitate, adding the precipitate into the oil phase solution obtained in the step, and performing ultrasonic dispersion for 15min to obtain turbid liquid;
4) Adding 5L of zinc nitrate ethanol solution with the concentration of 50g/L into each 1L of turbid liquid obtained in the step 3) according to a proportion, and mixing to obtain a prefabricated liquid;
5) Adding 2L of 2-methylimidazole ethanol solution with the concentration of 0.75g/L into each 1L of prefabricated liquid obtained in the step 4) in an equal amount for five times in proportion, mixing and reacting for 6 hours after each addition, filtering out solid matters after the addition and the reaction are completed, carrying out heat treatment on the solid matters at the temperature of 60 ℃ for 12 hours to obtain a precursor, and adding the precursor into the filtrate again to obtain precursor liquid;
6) Adding (commercially available) 100% oil-soluble phenolic resin into the precursor liquid obtained in the step 5) according to the proportion of 0.8mol/L, adding deionized water with the volume of 2 times of the precursor liquid after uniformly mixing, dispersing uniformly, separating liquid, separating and removing oil phase to obtain a coating liquid;
7) Coating the coating solution obtained in the step 6) at 60 ℃ to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, uniformly dispersing, adding 7 times of polydimethoxyl siloxane with the mass of 7 times of the solid product, reacting for 15min, dispersing again, adding the rest polydimethoxyl siloxane and the dibutyl tin dilaurate with 6 times of the mass of the solid product after uniform dispersion, stirring, and coating at 60 ℃ to dry to obtain doped particles;
8) And melting the commercially available PP pipeline plastic master batch (PP master batch), adding doped particles for strengthening, wherein the addition amount of the doped particles is 6wt% of the total mass of the PP master batch, and thus the preparation of the composite material is completed.
The composite material can be pelletized to prepare reinforced master batch or directly used for extrusion molding. The present example was directly extruded to prepare a DN90 x en8.2mm standard tube conforming to the GB/T13663-2000 standard, the standard tube prepared in the present example being labeled BG4.
Example 5
The specific preparation process of MOFs particle-modified composite material is the same as in example 1, except that:
the polyethylene glycol-polycaprolactone block copolymer used in step 2) was replaced with a polyethylene glycol-polycaprolactone-polyethylene glycol block copolymer, and the other process operating parameters were the same as in example 1. DN 90X EN8.2mm standard tube conforming to GB/T13663-2000 standard was prepared in the same manner, and the standard tube prepared in this example was labeled BG5.
Comparative example 1
A composite material is prepared by the same process as in example 1, except that:
step 2) was not performed and the remaining process operating parameters were the same as in example 1. DN 90X EN8.2mm standard tubes conforming to the GB/T13663-2000 standard were prepared in the same manner, and the standard tube prepared in this comparative example was designated DBG1.
Comparative example 2
A composite material is prepared by the same process as in example 1, except that:
step 6) was not performed and the remaining process operating parameters were the same as in example 1. DN 90X EN8.2mm standard tubes conforming to the GB/T13663-2000 standard were prepared in the same manner, and the standard tube prepared in this comparative example was designated DBG2.
Comparative example 3
The commercial DN 90X EN8.2mm standard tube conforming to the GB/T13663-2000 standard is made of PP. The standard tube of this comparative example is labeled DBG3.
Test I
And (3) carrying out mechanical property detection on the standard pipe according to GB/T19278-2018. The mechanical property detection comprises tensile strength, bending strength, inner wall hardness (D Shore hardness), impact strength and the like. Specific test results are shown in table 1 below. All assays were averaged over ten effective tests.
Table 1: and (5) detecting mechanical properties.
As can be seen from the detection results of the table, the standard pipe prepared from the composite material has excellent mechanical properties, and compared with the PP pipe with the same specification and size on the market, the mechanical properties of the standard pipe are obviously improved, and particularly, the standard pipe has extremely obvious improvement effect on the aspects of bending strength and impact strength. The working pressure of the pipeline can be effectively improved, and the pipeline is less prone to cracking and damage when being impacted. In addition, as can be seen from comparing the results of BG1 and BG5, although the mechanical properties of BG5 are slightly inferior to those of BG1, the notched impact strength of BG under low temperature condition is significantly higher than that of BG1, and the change of BG1 and BG5 is only that the replacement of the block copolymer, which indicates that the selection of the block copolymer in step 2) has a significant influence on the temperature resistance of the composite material, and the selected diblock copolymer and triblock copolymer can form different microstructures, so that the reaction of the doped particles in the composite material when influenced by temperature is influenced. The comparison of DBG1 and BG1 can also find that the mechanical properties are almost the same under the normal temperature detection condition, but the mechanical properties have more remarkable influence under the low temperature condition. In addition, comparing BG1 and DBG2, it can be seen that the process of step 6) has a relatively significant impact on the mechanical properties of the composite material. Under microscopic observation, the doped particles in DBG2 are partially agglomerated to generate a small amount of banded structures, so that the mechanical properties of the composite material pipe are actually influenced, the mechanical properties are uneven, and the doped particles in BG1 are uniformly dispersed, and the mechanical properties are uniform.
Test II
And further detecting the temperature resistance and the hydrophobic property of the pipe prepared from the composite material.
Wherein, the temperature resistance adopts the inspection standard of the factory, and the specific inspection process is as follows: pouring 92% pure water with full volume into the pipe, cooling and freezing to-40 ℃, naturally deicing at 10 ℃ after keeping for 2 hours, placing the water in a hot drying chamber at 135+/-5 ℃ for standing for 2 hours, repeatedly performing 12 times, detecting cracks on the surface of the composite pipe, and detecting the impact strength (22 ℃) without gaps. The detection result shows that the surfaces of the BG 1-BG 5 pipes are free of cracks, the high-low temperature resistance is good, the reduction rate of the notch-free impact strength of the BG 1-BG 4 pipes is less than or equal to 10%, the reduction rate of the notch-free impact strength of the BG5 pipes is less than or equal to 6%, and the high-temperature resistance is very excellent. However, the surface of DBG1 forms severe cracks in the form of spider web, which cannot be effectively detected for unnotched impact strength. But the surface cracks of the DBG2 pipe are not obvious, but the impact strength without the notch is reduced to 13-16%, and the reduction is obvious. While commercial PP pipe DBG3 is claimed to work at-40-130 ℃ and theoretical PP can withstand the working conditions of-40-130 ℃, relatively severe temperature changes also cause cracking of the surface of the PP pipe DBG3, cracking fragments exist on the outer surface part of the PP pipe DBG, and effective detection of the unnotched impact strength cannot be performed even if the PP pipe DBG is severely damaged.
The test shows that the addition of the composite material has very obvious effect of strengthening the temperature resistance of the PP pipe. Can effectively bear the environment of extreme cold and hot alternation, and has excellent use effect when being used for hot water supply in the northern area.
The hydrophobic performance detection is measured by a contact angle tester, the contact angles of the inner walls of the BG 1-BG 5 and DBG1 pipes are more than or equal to 152 degrees, the super-hydrophobic performance is achieved, the contact angle of the inner wall of the DBG2 pipe is about 131-133, the hydrophobic performance is lower than that of the BG 1-BG 5 and DBG1 pipes, the doped particles cannot be effectively dispersed and diffused to the surface layer in extrusion molding, the hydrophobic performance of the doped particles cannot be effectively exerted, the contact angle of the DBG3 pipe is about 119-122, the contact angle is between the hydrophobic performance and the super-hydrophobic performance, the effect of the DBG3 pipe on the anti-fouling performance is very limited, dirt is still easy to be accumulated in the use process, and the pipe is blocked after long-term use.
The embodiment, the comparative example and the test show that the technical scheme of the invention obviously improves the existing pipeline plastic, has obvious improvement effects from the aspects of mechanical property, temperature resistance and antifouling property of the pipe, and has obvious beneficial effects.
Claims (10)
1. A preparation method of MOFs particle doped composite material is characterized in that,
the method comprises the following steps:
1) Dispersing ultrafine stone powder serving as an aluminum silicate component in a water system to prepare an aqueous phase solution;
2) Adding the amphiphilic block copolymer into an oily organic solution to prepare a pre-solution;
3) Adding ethyl orthosilicate into the pre-solution obtained in the step 2), uniformly mixing, adding the aqueous phase solution obtained in the step 1), performing ultrasonic treatment, standing, filtering, separating the solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained in the separation, and performing ultrasonic dispersion to obtain turbid liquid;
4) Adding a zinc salt alcohol solution into the turbid liquid obtained in the step 3), and mixing to obtain a prefabricated liquid;
5) Adding a ligand imidazole alcohol solution into the prefabricated liquid obtained in the step 4), filtering a solid substance after mixing reaction, carrying out low-temperature treatment on the solid substance to obtain a precursor, and adding the precursor into the filtrate again to obtain a precursor liquid;
6) Adding oil-soluble phenolic resin and polydimethylsiloxane-polycarbonate segmented copolymer into the precursor liquid obtained in the step 5), uniformly mixing, adding water, performing dispersion treatment, and separating an oil phase to obtain a coating liquid;
7) Coating and drying the coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into an organic solvent, uniformly dispersing, adding polydimethoxyl siloxane twice, controlling the adding amount of the polydimethoxyl siloxane for the first time to be less than or equal to 5wt percent of the total adding amount, carrying out the reaction again, dispersing again until the polydimethoxyl siloxane and the dibutyl tin dilaurate are added after the uniform dispersion, and drying after the stirring reaction is completed to obtain doped particles;
8) Adding the doped particles into molten pipeline plastic for reinforcement, and thus completing the preparation of the composite material;
wherein:
the amphiphilic block copolymer in the step 2) is a polyethylene glycol-polycaprolactone block copolymer or a polyethylene glycol-polycaprolactone-polyethylene glycol triblock copolymer.
2. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
the aluminum silicate component superfine stone powder in the step 1) is mullite powder and/or halloysite powder;
the mesh number of the mullite powder and/or halloysite powder is more than or equal to 2000 meshes;
the content of the superfine stone powder of the aluminum silicate component in the aqueous phase solution is 15-30 g/L.
3. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
the concentration of the amphiphilic block copolymer in the pre-solution is 12-18 mmol/L.
4. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
step 3) the ethyl orthosilicate is 4-8% VOL of the pre-liquid;
the dosage of the aqueous phase solution is 2-5% of VOL of the pre-solution.
5. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
the zinc salt alcohol solution in the step 4) is a methanol and/or ethanol solution of zinc nitrate and/or zinc chloride;
the total concentration of the zinc nitrate and/or the zinc chloride is 20-50 g/L.
6. The method for preparing MOFs particle-doped composite material according to claim 1 or 5, wherein,
the dosage of the zinc salt alcohol solution is 3-5 times of the volume of the turbid liquid.
7. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
step 5) 2-methylimidazole alcohol solution with the concentration of the ligand imidazole alcohol solution of 0.5-2.0 g/L;
the dosage of the ligand imidazole alcohol solution is 0.5-2 times of the volume of the prefabricated liquid.
8. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
and 6) in the coating plate liquid obtained in the step 6):
the concentration of the oil-soluble phenolic resin is 0.8-1.2 mol/L;
the concentration of the polydimethylsiloxane-polycarbonate segmented copolymer is 8-13 mmol/L.
9. The method for preparing MOFs particle-doped composite material according to claim 1, wherein,
the dosage of the polydimethoxyl siloxane in the step 7) is 4-7 times of the weight of the solid product, and the dibutyl tin dilaurate is 1-6 times of the weight of the solid product.
10. A MOFs particle doped composite material obtainable by the process of any one of claims 1 to 9.
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