CN114213754A - 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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- 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
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- 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 an aqueous phase solution; adding the mixture into an oily organic solution to prepare an amphiphilic block copolymer as a pre-solution; adding tetraethoxysilane and a water phase solution into the pre-solution, and reacting to obtain a turbid solution; carrying out MOFs modification on particles in the turbid liquid to obtain precursor liquid; adding oil-soluble phenolic resin and polydimethylsiloxane-polycarbonate segmented copolymer into the precursor liquid, uniformly mixing, adding water, performing dispersion treatment, and separating an oil phase to obtain a coating liquid; coating the plate coating liquid and drying to constant weight, collecting the product, reacting with the polydimethoxysiloxane and dibutyltin dilaurate, and drying to obtain doped particles; the doped particles are added into the molten pipeline plastic for reinforcement. The invention has obvious improvement effect in various 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 pipeline is a special high polymer material for preparing water conducting and draining pipes, and compared with the traditional pipelines such as cast iron pipes, galvanized steel pipes, cement pipes and the like, the plastic pipeline has the problems of low preparation cost, low difficulty, small cold and hot shrinkage rate and the like, generally has better weather resistance and is not easy to generate oxidation corrosion.
However, plastic pipes also have certain drawbacks compared to conventional non-plastic pipes. The pipeline plastic is usually made of materials such as PPR, PVC, PP, PE-RT, PE/HDPE and the like, and the problems that the plastic material is not low temperature resistant, has poor thermal shock resistance, is easy to scale inside the pipeline and the like generally exist. During specific use, the pipeline plastic is easy to be brittle at a lower use temperature due to the low-temperature resistance and poor thermal shock resistance of the pipeline plastic. In addition, most of the existing plastics do not have good hydrophobicity, and the preparation of a hydrophobic antifouling coating cannot be realized through effective surface treatment, so that the actual antifouling performance is poor, the pipeline decontamination process is complicated, especially the decontamination of the embedded pipeline can not be effectively carried out almost, and only the auxiliary decontamination can be carried out through specific chemical additives.
Therefore, how to improve the temperature resistance and the anti-pollution capability of the plastic pipeline is a great development center in the pipeline plastic field.
Disclosure of Invention
The invention provides a MOFs particle doped composite material and a preparation method thereof, aiming at solving the problems that the existing pipeline plastic has poor temperature resistance, is easy to have brittle failure in a cold environment, is easy to generate thermal cracking during hot water conveying, has poor mechanical property, is easy to break after being impacted, and is easy to cause expansion cracking of hot steam during hot water conveying.
The invention aims to:
firstly, the temperature resistance of the existing pipeline plastic can be effectively enhanced, so that the pipeline plastic is more cold-resistant, heat-resistant and thermal shock-resistant;
secondly, the antistatic load capacity of the pipeline plastic is greatly improved;
thirdly, the impact resistance of the pipeline plastic is strengthened;
and fourthly, strengthening to enable the pipeline plastic to form certain antifouling and antifouling capabilities.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for preparing a MOFs particle doped composite material,
the method comprises the following steps:
1) dispersing superfine stone powder of aluminum silicate component in a water system to prepare a water phase solution;
2) adding the amphiphilic block copolymer into an oily organic solution to prepare a pre-solution;
3) adding tetraethoxysilane into the pre-solution obtained in the step 2), uniformly mixing, adding the water phase solution obtained in the step 1), performing ultrasonic treatment, standing, filtering, separating liquid, cleaning the precipitate, adding the cleaned precipitate into the oil phase solution obtained by separating liquid, and performing ultrasonic dispersion to obtain a turbid solution;
4) adding a zinc salt alcohol solution into the turbid solution obtained in the step 3), and mixing to obtain a prefabricated solution;
5) adding ligand imidazole alcohol solution into the prefabricated liquid obtained in the step 4), filtering the solid after mixing and reacting, carrying out low-temperature heat treatment on the solid to obtain a precursor, and adding the precursor into the filtrate again to obtain precursor liquid;
6) adding oil-soluble phenolic resin and polydimethylsiloxane-polycarbonate block 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 the plate coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into an organic solvent, adding the polydimethoxysiloxane at least twice after uniform dispersion, controlling the adding amount of the first polydimethoxysiloxane to be less than or equal to 5 wt% of the total adding amount, dispersing again after reaction, adding the rest polydimethoxysiloxane and dibutyltin dilaurate after uniform dispersion, and drying after stirring reaction to obtain doped particles;
8) and adding the doped particles into the molten pipeline plastic for reinforcement, thus finishing the preparation of the composite material.
The stone powder of aluminum silicate composition is a more common type of stone powder used for plastic reinforcement. However, the strengthening effect is limited, and although the wear resistance of the plastic can be effectively improved, the temperature resistance of the plastic is often further weakened.
In the technical scheme of the invention, stone powder containing aluminum silicate is used as a carrier, a hollow cladding structure is prepared on the surface of the stone powder through block copolymerization, specifically, in the processes 1) to 3), the stone powder is dispersed and then added with a pre-liquid, an oil-water mixed liquid is formed through stirring, in the oil-water mixed liquid, on one hand, oil-water droplet separation can promote the dispersion of the stone powder, on the other hand, soft agglomerated stone powder is captured and separated through the amphipathy of a block copolymer, 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 amphiphilic block copolymer, and the stone powder is encapsulated to form particles of silica coated stone powder. In this series of processes, the use of amphiphilic block copolymers is particularly critical. Therefore, if the stone powder is simply dispersed in oil, tetraethoxysilane is added and water is slowly added for dispersion, the preparation of silica-coated stone powder can be realized, but the dispersibility of the stone powder cannot be ensured in the process, although the dispersing effect of the stone powder in the oil liquid is slightly better than that of the water phase liquid through tests, secondary dispersion cannot be effectively realized in the oil phase liquid, and then water is added for hydrolyzing tetraethoxysilane, so that the effective growth and coating of the silica on the surface of the stone powder cannot be ensured, on the other hand, even if the stone powder is coated, the stone powder is a relatively compact coating mode to form a solid core-shell structure. And then, step 4) and step 5), ZIF-8 modification is carried out through zinc salt and ligand imidazole, namely MOFs modification is carried out, the ZIF-8 modification is a MOFs modification mode of common plastics, but the ZIF-8 modification is usually used for hydrophobic modification of membrane materials because of good hydrophobicity. However, the simple modification of the MOFs cannot effectively improve the hydrophobicity of the pipeline plastic, and the modified particles are inconvenient to simply carry out surface treatment on the pipeline, so that further processing is needed subsequently. In the step 6) of the invention, a structure similar to a branch and vine is formed by self-assembly of the block copolymer, the formed branch and vine structure is a key for enabling the doped particles to improve the hydrophobicity of the pipeline plastic, the formed branch and vine structure can be connected with a pipeline plastic matrix, and the doped particles can be highly dispersed and dispersed under the expansion and expansion effect of the block copolymer, so that the modified particles can be supported to at least partially float up to the surface of the formed plastic pipeline in the extrusion molding process of the molten master batch 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 doping particles and the pipeline plastic is stronger.
Specifically, the pipe plastic provided by the invention comprises but not limited to any one or more of PP and/or PE, and the pipe plastic has the best matching effect with PP and PE through tests, so that a PP or PE composite material modified by MOFs (ZIF-8) particles with relatively better performance can be formed.
As a preference, the first and second liquid crystal compositions are,
step 1), the superfine stone powder of the aluminum silicate component is mullite powder and/or halloysite powder;
the mesh number of the mullite powder and/or the halloysite powder is more than or equal to 2000 meshes;
the content of the aluminum silicate component ultrafine stone powder in the aqueous phase solution is 15-30 g/L.
The mullite powder and the halloysite powder have wide sources and relatively high content of aluminum silicate, and the preparation of the ultrafine stone powder is easily realized by a ball mill, for example, the preparation can be simply and quickly completed by a 2000-mesh ball mill in the actual preparation process. On one hand, the grain diameter uniformity of the prepared doped particles is poor due to the fact that soft agglomeration easily occurs in the dispersing process when the content of the mullite powder and the halloysite powder is too high, and on the other hand, the amphiphilic block copolymer is easy to generate network-like assembly and spherical assembly cannot be effectively achieved due to the fact that block copolymer pre-liquid with higher concentration is needed when the mullite powder and the halloysite powder are subsequently matched with the amphiphilic block copolymer when the content is too high.
As a preference, the first and second liquid crystal compositions are,
the amphiphilic block copolymer in the step 2) 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 above are the more common and readily available types of block copolymers. The control of the concentration of the block copolymer mainly aims at realizing the capture and dispersion of the stone powder and the tetraethoxysilane respectively, when the dosage is too small, the effective capture and dispersion cannot be realized, but when the dosage is too large, a hollow shell structure is easily formed, so that the proper control of the dosage is one of the key factors for ensuring the quality of the doped particles and the quality of finally formed plastics. The actual concentration can be the optimum concentration of about 12-30 mmol/L in the experiment, but the invention considers that the amphiphilic block copolymer is completely consumed in single preparation by selecting relatively low concentration in the actual production process, so that the subsequent recovery of the oily solvent is convenient for secondary utilization, 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 is selected to finally enable the plastic to obtain relatively good mechanical properties, and the polyethylene glycol-polycaprolactone-polyethylene glycol triblock copolymer is selected to enable the plastic to obtain relatively good temperature resistance.
As a preference, the first and second liquid crystal compositions are,
step 3), the ethyl orthosilicate is 4-8% VOL of the pre-solution;
the dosage of the water phase solution is 2-5% VOL of the pre-solution.
The amount of ethyl orthosilicate has a significant effect on the shell assembly. However, when the amount of the tetraethoxysilane is too large, the tetraethoxysilane is excessively added, and the tetraethoxysilane is left 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 to ensure that the mountain flour is effectively dispersed to form an empty core-shell structure and simultaneously ensure that the ethyl orthosilicate can be basically and completely consumed, so that the oily organic solvent can be conveniently recycled and reused and the influence on the subsequent reaction is reduced.
As a preference, the first and second liquid crystal compositions are,
the zinc salt alcoholic 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 all have good alcohol solubility and are commonly and easily available.
As a preference, the first and second liquid crystal compositions are,
the using amount of the zinc salt alcohol solution is 3-5 times of the volume of the turbid solution.
The adoption of a large amount of zinc salt alcohol solution can carry out secondary dispersion on turbid liquid, and simultaneously, the alcohol has a good effect of promoting the dispersion of silicon dioxide. Actually, the MOFs can be modified by adopting a zinc salt aqueous solution, but in the aqueous solution, the formed hollow core-shell structure particles have a silica shell, so that the dispersibility is poor, and soft agglomeration is easily formed again, so that the adoption of an alcoholic solution is a key factor for guaranteeing the MOFs modification effect.
As a preference, the first and second liquid crystal compositions are,
step 5) 2-methylimidazolyl alcohol solution with the ligand imidazolium alcohol solution concentration 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 preference, the first and second liquid crystal compositions are,
in the coating 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 block copolymer is 8-13 mmol/L.
The oil-soluble phenolic resin and the polydimethylsiloxane-polycarbonate block copolymer can form net-shaped self-assembly in the technical scheme of the invention, wherein the polydimethylsiloxane-polycarbonate block copolymer is commonly used for flame-retardant reinforcement, but in the technical scheme of the invention, the use purpose of the oil-soluble phenolic resin is mainly to form non-closed net-shaped assembly by matching with the oil-soluble phenolic resin, and the connection strength and the dispersibility of MOFs particles formed by doping particles modified by MOFs and a plastic matrix of a pipeline are reinforced, so that the MOFs particles can at least partially float upwards to the surface of the molded plastic pipeline.
As a preference, the first and second liquid crystal compositions are,
and 7) the dosage of the polydimethoxysiloxane is 4-7 times of the weight of the solid product, and the dosage of the dibutyltin dilaurate is 1-6 times of the weight of the solid product.
The above are two common and common cross-linking agents and catalysts, which can improve the compatibility of the doped particles with the plastic matrix of the pipeline.
A composite material doped with MOFs particles.
The composite material prepared by the invention has good hydrophobic antifouling performance, good mechanical properties such as wear resistance, bending strength, impact toughness and the like, is not easy to brittle failure or cracking in the face of temperature change, and has very obvious beneficial effects when being used for pipeline preparation and use.
The invention has the beneficial effects that:
1) the hydrophobic antifouling performance of the pipeline plastic is greatly improved, so that the inner wall of the pipeline is not easy to scale;
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 the 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 performance of the PP matrix composite material is good in a thermal shock test at a temperature of between 30 ℃ below zero and 140 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection of the present invention
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
A MOFs particle modified composite material, which is prepared by the following method:
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 15mmol/L of 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 liquid, separating to obtain a precipitate and an oil phase solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained by separating liquid, and performing ultrasonic dispersion for 15min to obtain a turbid solution;
4) adding 4L of 35g/L zinc nitrate ethanol solution into 1L of turbid solution obtained in the step 3) according to the proportion, and mixing to obtain a prefabricated solution;
5) adding 1.5L of 2-methylimidazole ethanol solution with the concentration of 1.5g/L into 1L of the prefabricated liquid obtained in the step 4) in five times in equal amount according to the proportion, mixing and reacting for 6 hours after each addition, filtering out solids after the addition and the reaction are completed, carrying out heat treatment on the solids at 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 1.15mol/L, uniformly mixing with polydimethylsiloxane-polycarbonate block copolymer according to the proportion of 10mmol/L, adding deionized water with the volume of 2 times that of the precursor liquid, uniformly dispersing, separating liquid, and removing an oil phase to obtain a plate coating liquid;
7) carrying out 60 ℃ coating drying on the coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, adding polydimethoxysiloxane with 5 times of solid product mass twice after uniform dispersion, wherein the adding amount of the first polydimethoxysiloxane is 3.5 wt% of the total amount of the polydimethoxysilane, carrying out dispersion again after reacting for 15min, adding the rest polydimethoxysiloxane and dibutyltin dilaurate with 3 times of solid product mass after uniform dispersion, and carrying out 60 ℃ coating drying after stirring reaction to obtain doped particles;
8) melting the commercially available PP pipeline plastic master batch (PP master batch) and adding doping particles for reinforcement, wherein the addition amount of the doping particles is 3.75 wt% of the total mass of the PP master batch, and the preparation of the composite material is completed.
The composite material can be prepared into reinforced master batches by granulation or directly used for extrusion molding. In this example, the standard tube was prepared by direct extrusion molding, and the standard tube was designated as BG1, and was DN90 × EN8.2mm in accordance with GB/T13663-2000 standard.
Example 2
A MOFs particle modified composite material, which is prepared by the following method:
1) dispersing 2000-mesh mullite powder in deionized water to prepare 20g/L aqueous phase solution;
2) adding the polyethylene glycol-polycaprolactone block copolymer into n-heptane to prepare a pre-solution with the concentration of 14 mmol/L;
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 liquid, separating to obtain a precipitate and an oil phase solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained by separating liquid, and performing ultrasonic dispersion for 15min to obtain a turbid solution;
4) adding 4L of zinc nitrate ethanol solution with the concentration of 25g/L into 1L of turbid solution obtained in the step 3) according to the proportion, and mixing to obtain a prefabricated solution;
5) adding 1.25L of 1.2 g/L2-methylimidazole ethanol solution with the concentration of 1.2g/L into 1L of the prefabricated liquid obtained in the step 4) in five times in equal amount according to the proportion, mixing and reacting for 6 hours after each addition, filtering out solids after the addition and the reaction are completed, carrying out heat treatment on the solids at 60 ℃ for 12 hours to obtain a precursor, and adding the precursor into the filtrate again to obtain a 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, uniformly mixing with polydimethylsiloxane-polycarbonate block copolymer according to the proportion of 11mmol/L, adding deionized water with the volume of 2 times that of the precursor liquid, uniformly dispersing, separating liquid, and removing an oil phase to obtain a plate coating liquid;
7) carrying out 60 ℃ coating drying on the coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, adding 6 times of solid product mass of polydimethoxysiloxane twice after uniform dispersion, adding the first polydimethoxysiloxane 5 wt% of the total amount of the polydimethoxysilane, reacting for 15min, dispersing again, adding the rest of polydimethoxysiloxane and 4.5 times of dibutyltin dilaurate with the mass of the solid product after uniform dispersion, and carrying out 60 ℃ coating drying after stirring reaction to obtain doped particles;
8) melting the commercially available PP pipeline plastic master batch (PP master batch) and adding doping particles for reinforcement, wherein the addition amount of the doping particles is 5.15 wt% of the total mass of the PP master batch, and the preparation of the composite material is completed.
The composite material can be prepared into reinforced master batches by granulation or directly used for extrusion molding. In this example, the standard tube was prepared by direct extrusion molding, and the standard tube was designated as BG2, and was DN90 × EN8.2mm in accordance with GB/T13663-2000 standard.
Example 3
A MOFs particle modified composite material, which is prepared by the following method:
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 12mmol/L of pre-solution;
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 liquid, separating to obtain a precipitate and an oil phase solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained by separating liquid, and performing ultrasonic dispersion for 15min to obtain a turbid solution;
4) adding 3L of zinc nitrate ethanol solution with the concentration of 20g/L into 1L of turbid solution obtained in the step 3) according to the proportion, and mixing to obtain a prefabricated solution;
5) adding 0.5L of 2-methylimidazole ethanol solution with the concentration of 2.0g/L into 1L of the prefabricated liquid obtained in the step 4) in five times in equal amount according to the proportion, mixing and reacting for 6 hours after each addition, filtering out solids after the addition and the reaction are completed, carrying out heat treatment on the solids at 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 1.2mol/L, uniformly mixing with polydimethylsiloxane-polycarbonate block copolymer according to the proportion of 13mmol/L, adding deionized water with the volume of 2 times that of the precursor liquid, uniformly dispersing, separating liquid, and removing an oil phase to obtain a plate coating liquid;
7) carrying out 60 ℃ coating drying on the coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, adding polydimethoxysiloxane with 4 times of solid product mass twice after uniform dispersion, adding the polydimethoxysiloxane for the first time in an amount of 3 wt% of the total amount of the polydimethoxysilane, carrying out dispersion again after reacting for 15min, adding the rest polydimethoxysiloxane and dibutyltin dilaurate with 1 time of solid product mass after uniform dispersion, and carrying out 60 ℃ coating drying after stirring reaction is finished to obtain doped particles;
8) melting the pipeline plastic master batch (PP master batch) made of the commercially available PP material, and adding doping particles for strengthening, wherein the addition amount of the doping particles is 3 wt% of the total mass of the PP master batch, so that the preparation of the composite material is completed.
The composite material can be prepared into reinforced master batches by granulation or directly used for extrusion molding. In this example, the standard tube was prepared by direct extrusion molding, and the standard tube was designated as BG3, and was DN90 × EN8.2mm in accordance with GB/T13663-2000 standard.
Example 4
A MOFs particle modified composite material, which is prepared by the following method:
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 a pre-solution with the concentration of 18 mmol/L;
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 liquid, separating to obtain a precipitate and an oil phase solution, cleaning the precipitate, adding the precipitate into the oil phase solution obtained by separating liquid, and performing ultrasonic dispersion for 15min to obtain a turbid solution;
4) adding 5L of zinc nitrate ethanol solution with the concentration of 50g/L into 1L of turbid solution obtained in the step 3) according to the proportion, and mixing to obtain a prefabricated solution;
5) adding 2L of 0.75 g/L2-methylimidazole ethanol solution into 1L of the prefabricated liquid obtained in the step 4) in five times in equal amount according to the proportion, mixing and reacting for 6 hours after each addition, filtering out solids after the addition and the reaction are completed, carrying out heat treatment on the solids at 60 ℃ for 12 hours to obtain a precursor, and adding the precursor into the filtrate again to obtain a 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, uniformly mixing the mixture with the polydimethylsiloxane-polycarbonate block copolymer according to the proportion of 8mmol/L, adding deionized water with the volume of 2 times that of the precursor liquid, uniformly dispersing, separating liquid, and removing an oil phase to obtain a plate coating liquid;
7) carrying out 60 ℃ coating drying on the coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into n-heptane with 8 times of loose volume, adding 7 times of solid product mass of polydimethoxysiloxane twice after uniform dispersion, carrying out dispersion again after 15min of reaction, adding the balance of polydimethoxysiloxane and 6 times of solid product mass of dibutyltin dilaurate after the uniform dispersion is finished, and carrying out 60 ℃ coating drying to obtain doped particles;
8) melting the pipeline plastic master batch (PP master batch) made of the commercially available PP material, and adding doping particles for strengthening, wherein the addition amount of the doping particles is 6 wt% of the total mass of the PP master batch, so that the preparation of the composite material is completed.
The composite material can be prepared into reinforced master batches by granulation or directly used for extrusion molding. In this example, the standard tube was prepared by direct extrusion molding, and the standard tube was designated as BG4, and was DN90 × EN8.2mm in accordance with GB/T13663-2000 standard.
Example 5
The specific preparation process of the MOFs particle modified composite material is the same as that in example 1, except that:
the polyethylene glycol-polycaprolactone block copolymer used in the step 2) is replaced by a polyethylene glycol-polycaprolactone-polyethylene glycol block copolymer, and the other process operation parameters are the same as those in the example 1. A standard tube of DN90 × EN8.2mm, which conforms to GB/T13663-2000 standard, is prepared in the same manner, and the standard tube prepared in the embodiment is marked as BG 5.
Comparative example 1
A composite material, the specific preparation process is the same as example 1, except that:
the operation of step 2) was not performed, and the remaining process operation parameters were the same as in example 1. A standard tube of DN90 × EN8.2mm, which complies with GB/T13663-2000 standard, is prepared in the same manner, and the standard tube prepared in this comparative example is designated DBG 1.
Comparative example 2
A composite material, the specific preparation process is the same as example 1, except that:
step 6) was not performed, and the remaining process operation parameters were the same as in example 1. A standard tube of DN90 × EN8.2mm, which complies with GB/T13663-2000 standard, is prepared in the same manner, and the standard tube prepared in this comparative example is designated DBG 2.
Comparative example 3
The commercial DN90 × EN8.2mm standard tube which conforms to GB/T13663 and 2000 standard is made of PP. The comparative example standard tube is labeled DBG 3.
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 method Shore hardness), impact strength and the like. The specific test results are shown in table 1 below. All measurements were averaged over ten valid tests.
Table 1: and (5) detecting the mechanical property.
From the detection results in the table above, the standard pipe prepared from the composite material has excellent mechanical properties, and compared with the commercially available PP pipe with the same specification and size, the mechanical properties of the standard pipe are remarkably improved, and particularly, the standard pipe has a very remarkable improvement effect on bending strength and impact strength. The working pressure of the pipeline can be effectively improved, and the pipeline is less prone to rupture and damage when being impacted. In addition, the comparison of BG1 and BG5 shows that, although BG5 has slightly inferior mechanical properties to BG1, the notched impact strength of BG at low temperature is significantly higher than BG1, and BG1 and BG5 are changed only by using 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 form different microstructures, so that the reaction of the doped particles in the composite material under the influence of temperature is influenced. Similarly, when DBG1 is compared with BG1, the mechanical performance is almost the same under the normal temperature detection condition, but the mechanical performance has more obvious influence under the low temperature condition. In addition, comparing BG1 and DBG2, it can be seen that the process of step 6) has a significant effect on the mechanical properties of the composite material. Under microscopic observation, the doped particles in the DBG2 are partially agglomerated to generate a small amount of band-shaped structures, so that the mechanical properties of the composite material pipe are actually influenced, the mechanical properties of the composite material pipe are uneven, and the doped particles in the BG1 are uniformly distributed in a dispersed manner and have uniform mechanical properties.
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 factory inspection standard, and the concrete inspection process is: pouring 92% of full volume of pure water into the pipe, cooling and freezing to-40 ℃, keeping for 2h, naturally deicing at 10 ℃, draining, placing in a 135 +/-5 ℃ hot drying chamber for standing for 2h, repeating for 12 times, detecting the surface cracks of the composite pipe, and detecting the unnotched impact strength (22 ℃) of the composite pipe. The detection results show that the surfaces of BG 1-BG 5 pipes are free of cracks, the BG 1-BG 5 pipes have good high and low temperature resistance, the reduction rate of unnotched impact strength of BG 1-BG 4 pipes is less than or equal to 10%, the reduction rate of unnotched impact strength of BG5 pipes is less than or equal to 6%, and the BG5 pipes have very excellent temperature resistance. And serious cracks are formed on the surface of the DBG1, and the cracks are in a cobweb shape, so that the unnotched impact strength detection cannot be effectively carried out. The surface cracks of the DBG2 pipe are not obvious, but the unnotched impact strength is reduced to 13-16%, so that the unnotched impact strength is obviously reduced. While the commercial PP pipe DBG3 is claimed to work under the condition of-40-130 ℃, and theoretical PP can endure the working condition of-40-130 ℃, the relatively severe temperature change causes the surface of the pipe to generate a mouth-shaped crack, the outer surface of the pipe has a chipping fragment, and the pipe can not be effectively tested for the notch-free impact strength even if the pipe is seriously damaged.
The test shows that the addition of the composite material has a very obvious effect on strengthening the temperature resistance of the PP pipe. The hot water supply device can effectively bear an extremely cold and hot alternating environment, and has excellent use effect when being used for supplying hot water in part of northern areas.
The hydrophobic property detection is measured by a contact angle tester, the contact angles of the inner walls of BG 1-BG 5 and DBG1 pipes are more than or equal to 152 degrees and have super-hydrophobic property, the contact angle of the inner wall of DBG2 pipe is about 131-133, which shows that the pipe is not as hydrophobic as BG 1-BG 5 and DBG1 pipes, mainly the doped particles can not be effectively dispersed and diffused to the surface layer during extrusion molding, so that the hydrophobicity of the doped particles can not be effectively exerted, while the contact angle of the DBG3 pipe is about 119-122, which is between hydrophobic and super-hydrophobic, so that the pipe has very limited hydrophobic and antifouling effect, is still easy to accumulate dirt during use, and is blocked after long-term use.
The technical scheme of the invention obviously improves the existing pipeline plastic, has obvious improvement effects in multiple aspects of mechanical property, temperature resistance and antifouling property of the pipe, and generates 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 superfine stone powder of aluminum silicate component in a water system to prepare a water phase solution;
2) adding the amphiphilic block copolymer into an oily organic solution to prepare a pre-solution;
3) adding tetraethoxysilane into the pre-solution obtained in the step 2), uniformly mixing, adding the water phase solution obtained in the step 1), performing ultrasonic treatment, standing, filtering, separating liquid, cleaning the precipitate, adding the cleaned precipitate into the oil phase solution obtained by separating liquid, and performing ultrasonic dispersion to obtain a turbid solution;
4) adding a zinc salt alcohol solution into the turbid solution obtained in the step 3), and mixing to obtain a prefabricated solution;
5) adding ligand imidazole alcohol solution into the prefabricated liquid obtained in the step 4), filtering the solid after mixing and reacting, carrying out low-temperature heat treatment on the solid to obtain a precursor, and adding the precursor into the filtrate again to obtain precursor liquid;
6) adding oil-soluble phenolic resin and polydimethylsiloxane-polycarbonate block 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 the plate coating liquid obtained in the step 6) to constant weight, collecting a solid product, adding the solid product into an organic solvent, adding the polydimethoxysiloxane at least twice after uniform dispersion, controlling the adding amount of the first polydimethoxysiloxane to be less than or equal to 5 wt% of the total adding amount, dispersing again after reaction, adding the rest polydimethoxysiloxane and dibutyltin dilaurate after uniform dispersion, and drying after stirring reaction to obtain doped particles;
8) and adding the doped particles into the molten pipeline plastic for reinforcement, thus finishing the preparation of the composite material.
2. A process for the preparation of a MOFs particle doped composite according to claim 1,
step 1), the superfine stone powder of the aluminum silicate component is mullite powder and/or halloysite powder;
the mesh number of the mullite powder and/or the halloysite powder is more than or equal to 2000 meshes;
the content of the aluminum silicate component ultrafine stone powder in the aqueous phase solution is 15-30 g/L.
3. A process for the preparation of a MOFs particle doped composite according to claim 1,
the amphiphilic block copolymer in the step 2) 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.
4. A process for the preparation of a MOFs particle doped composite according to claim 1,
step 3), the ethyl orthosilicate is 4-8% VOL of the pre-solution;
the dosage of the water phase solution is 2-5% VOL of the pre-solution.
5. A process for the preparation of a MOFs particle doped composite according to claim 1,
the zinc salt alcoholic 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. A process for the preparation of a MOFs particle doped composite according to claim 1 or 5,
the dosage of the zinc salt alcohol solution is 3-5 times of the volume of the turbid solution.
7. A process for the preparation of a MOFs particle doped composite according to claim 1,
step 5) 2-methylimidazolyl alcohol solution with the ligand imidazolium alcohol solution concentration 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. A process for the preparation of a MOFs particle doped composite according to claim 1,
in the coating 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 block copolymer is 8-13 mmol/L.
9. A process for the preparation of a MOFs particle doped composite according to claim 1,
and 7) the dosage of the polydimethoxysiloxane is 4-7 times of the weight of the solid product, and the dosage of the dibutyltin dilaurate is 1-6 times of the weight of the solid product.
10. A MOFs particle doped composite material prepared by the process of any one of claims 1 to 9.
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| JP2662310B2 (en) * | 1989-07-07 | 1997-10-08 | 出光石油化学株式会社 | Polycarbonate-polydimethylsiloxane copolymer and method for producing the same |
| WO2007113118A1 (en) * | 2006-03-29 | 2007-10-11 | Basf Se | Method for commercially obtaining propene |
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| JP2662310B2 (en) * | 1989-07-07 | 1997-10-08 | 出光石油化学株式会社 | Polycarbonate-polydimethylsiloxane copolymer and method for producing the same |
| WO2007113118A1 (en) * | 2006-03-29 | 2007-10-11 | Basf Se | Method for commercially obtaining propene |
| CN103382274A (en) * | 2013-08-05 | 2013-11-06 | 广州赫尔普化工有限公司 | Compound additive for polypropylene block copolymer (PPB) |
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