CN109721968B - Functional master batch containing hyperbranched hybrid porous material and preparation method thereof - Google Patents
Functional master batch containing hyperbranched hybrid porous material and preparation method thereof Download PDFInfo
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- CN109721968B CN109721968B CN201811527106.1A CN201811527106A CN109721968B CN 109721968 B CN109721968 B CN 109721968B CN 201811527106 A CN201811527106 A CN 201811527106A CN 109721968 B CN109721968 B CN 109721968B
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Abstract
The invention relates to a functional master batch containing hyperbranched hybrid porous material and a preparation method thereof, wherein a polymer matrix material, the hyperbranched hybrid porous material containing metal ions and other components are uniformly mixed and then melted and extruded to prepare the functional master batch containing the hyperbranched hybrid porous material, the hyperbranched hybrid porous material containing the metal ions is porous microspheres, and the functional master batch is prepared by nucleating and growing hyperbranched hybrids to form microspheres and then carrying out pore-forming; the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Mn+The value range of n is 1-3, carboxyl in the molecule A, amido in the molecule B and metal ion Mn+The bonding between the two groups is realized through ionic bonding and coordinate bonding to form a triangular bonding structure, and the structural formula is as follows:
Description
Technical Field
The invention belongs to the technical field of functional master batches, and relates to a functional master batch containing a hyperbranched hybrid porous material and a preparation method thereof.
Background
The masterbatch, also known as masterbatch, is a processing aid, and is a concentrate in which a functional aid is carried in a resin in an excessive amount. When preparing multifunctional polymer products, people usually do not need to add corresponding functional additives, but only need to add corresponding multifunctional master batches containing the functional additives. Therefore, the method is one of the most important forms of the application of the functional additives and the modification of the polymer in the world at present, and has the characteristics of simple process, convenient use, convenient realization of production automation and high productivity.
Hyperbranched polymers such as hyperbranched polyester and the like have good compatibility due to similar matrix structures with polymers such as polyester and the like, and in addition, the hyperbranched polymers have a highly branched molecular structure, are ideal functional modified carriers and are widely applied to the field of high-molecular blending at present, such as blending of hyperbranched polyester and flame retardant and the like, but the hyperbranched polymers serving as low-molecular-weight polymers generally have the problems of easy migration, low hot melting temperature, easy flowing and difficulty in matching with a thermoplastic polymer melt processing temperature range, and greatly influence the processing performance of products. Therefore, it is important to improve the processability of the hyperbranched polymer by lowering the flowability thereof and increasing the heat-melting temperature thereof.
The metal ion load is a common hyperbranched polymer modification means, and particularly refers to a hyperbranched metal hybrid material prepared by bonding metal ions to carrier molecules through the action of chemical bonds or physical bonds. However, although the organic-inorganic hybrid material obtained by coordinating the hyperbranched polymer with the metal ion is similar to inorganic particles to a certain extent, most of the solvents used for preparing the hyperbranched polymer loaded with the metal ion at present are organic solvents which are not friendly to the environment, and in addition, the synthesized hyperbranched polymer loaded with the metal ion is difficult to achieve nanoscale dispersion in a low-polarity high polymer matrix, which greatly limits the application of the hyperbranched polymer in fiber modification of aqueous phase polymer material molding such as solution spinning molding.
In addition, the existing hyperbranched metal hybrid materials are few in types and forms, most of which only have one function such as flame retardance or antibiosis, and cannot simultaneously have multiple functions such as flame retardance, antibiosis, deodorization and adsorption. When in use, a plurality of materials are needed to be added, which increases the cost.
Therefore, the development of the functional master batch with multiple functions and the preparation method thereof have very important significance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a flame-retardant, antibacterial and deodorant functional master batch containing hyperbranched hybrid porous material and a preparation method thereof
In order to achieve the purpose, the invention adopts the technical scheme that:
the functional master batch containing the hyperbranched hybrid porous material mainly comprises a polymer matrix and the hyperbranched hybrid porous material containing metal ions, which is uniformly dispersed in the polymer matrix, wherein the hyperbranched hybrid porous material containing the metal ions is porous microspheres, and is prepared by nucleating and growing hyperbranched hybrids to form the microspheres and then carrying out pore-forming;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Mn+The value range of n is 1-3;
the molecule A is a hyperbranched polymer molecule with an end group containing carboxyl;
the molecule B is a chain molecule with amino;
carboxyl in molecule A, amino in molecule B and metal ion Mn+The bonding between the two groups is realized through ionic bonding and coordinate bonding to form a triangular bonding structure, and the structural formula is as follows:
wherein R is a cationic group, an anionic group or a polar nonionic group.
The hyperbranched hybrid porous material containing metal ions has carboxyl in a molecule A, amido in a molecule B and metal ions Mn+The hyperbranched type porous microsphere is characterized in that a triangular bonding structure is formed by bonding through ionic bonds and coordination bonds, the molecule B can achieve the effect of modifying the molecule A, the hydrophilic performance of the hyperbranched type porous microsphere is improved, and water-based dispersed particles are not easy to agglomerate in the process of forming the microsphere by nucleating and growing hyperbranched type hybrid, so that the size of the generated porous microsphere is ensured, and the hyperbranched type porous microsphere can simultaneously have the functions of adsorption, deodorization, flame retardance and antibiosis, and can be uniformly dispersed in a polymer matrix to prepare flame-retardant, antibacterial and deodorant functional master batches.
As a preferred technical scheme:
the functional master batch containing the hyperbranched hybrid porous material has the advantages that the content of the hyperbranched hybrid porous material containing metal ions, which is prepared from the functional master batch containing the hyperbranched hybrid porous material, is 0.5-10 wt% of fiber, the limiting oxygen index is 30-33%, the bacteriostatic rates on staphylococcus aureus before and after 50 times of water washing are 85-90% and 80-87%, the bacteriostatic rates on escherichia coli before and after 50 times of water washing are 90-95% and 80-85%, and the adsorption rates on ammonia gas, acetic acid and isovaleric acid are 85-95%, 90-92% and 92-98%, respectively.
The functional master batch containing the hyperbranched hybrid porous material, Mn+Is Ag+、Fe2+、Fe3+、Au3+、Cr3+、Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+Or 3-valent rare earth metal ions; the metal ion species of the present invention are not limited thereto, and only some of the possible metal ion species are listed herein;
in the molecule A and the molecule B, the sum of the carboxyl content, the amino content and the hydroxyl content is 130 to 170 percent of the sum of the molar weights of the molecule A and the molecule B;
the sum of the contents of carboxyl groups bonded by ionic bonds and coordinate bonds and the contents of amino groups bonded by ionic bonds and coordinate bonds is more than or equal to 20 percent of the sum of the molar amounts of the carboxyl groups and the amino groups in the molecules A and B;
in the molecule A and the molecule B, carboxyl, amino and hydroxyl are all hydrophilic groups, the carboxyl and amino are groups participating in forming a triangular bonding structure, in the molecule A and the molecule B, the sum of the carboxyl content, the amino content and the hydroxyl content is too small to form the triangular bonding structure, the carboxyl and amino are combined to overcome a plurality of obstacles, such as entanglement acting force between molecular chains, repulsive force between molecules and the like, only when the quantity reaches a certain degree, the carboxyl and amino can be ensured to be combined to overcome the obstacles, and then the triangular bonding structure is formed by being combined with metal ions, in the molecule A and the molecule B, the sum of the carboxyl content, the amino content and the hydroxyl content is too large, the difficulty in production and processing is easily brought, when the hydrophilic groups reach a certain degree, the proportion of the hydrophilic groups participating in forming the triangular bonding structure to the whole is small, namely, the proportion of the carboxyl groups bonded through ionic bonds and coordinate bonds and the amino content bonded through the ionic bonds and and less than 20% of the sum of the molar weights of carboxyl and amino groups in the molecule A and the molecule B, the hyperbranched type hybrid is easy to dissolve in water and cannot be separated;
the sum of the contents of carboxyl groups bonded by ionic bonds and coordinate bonds and the contents of amino groups bonded by ionic bonds and coordinate bonds is more than or equal to 20 percent of the sum of the molar amounts of the carboxyl groups and the amino groups in the molecules A and B;
the number of terminal carboxyl groups in the molecule A accounts for 25-100% of the total amount of the terminal groups, the branching degree of the molecule A is 30-100%, the relative molecular weight is 1100-50000 g/mol, and the molecule A mainly comprises C and H except for O of the carboxyl groups;
the molecular weight of the molecule B is less than or equal to 5000g/mol, and the molecular main chain is mainly composed of C and H except N of amine groups.
The functional master batch containing the hyperbranched hybrid porous material is characterized in that the 3-valent rare earth metal ions are La3+、Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+；
The cationic group is a tertiary ammonium group or a quaternary ammonium group, the anionic group is a carboxylic acid group, and the polar nonionic group is a hydroxyl group, an ether group, an amine group, an amide group, a mercapto group or halogen;
the amine group bonded through an ionic bond and a coordinate bond is located in a main chain or a branch chain of the molecule B, the molecule B further comprises a hydroxyl group or a carboxyl group, the main chain of the molecule B further comprises an element O or N, and the molecule A further comprises an element P, O or N. The types and groups of the elements contained in the molecule A and the molecule B are not limited thereto, and they may contain other elements or other groups as long as they can ensure the carboxyl group in the molecule A, the amine group in the molecule B and the metal ion Mn+The triangular bonding structure is formed between the two parts to be stable. The load capacity and the carbon residue rate at 600 ℃ of the metal ions of the hyperbranched hybrid porous material containing the metal ions are far higher than those of the prior art.
According to the functional master batch containing the hyperbranched hybrid porous material, the loading capacity of metal ions in the hyperbranched hybrid porous material containing the metal ions is 70-1700 mg/g;
the aperture of the hyperbranched hybrid porous material containing the metal ions is 40-100 nm, and the porosity is 40% -60%;
the initial decomposition temperature of the hyperbranched hybrid porous material containing the metal ions is 340-380 ℃, and the carbon residue rate at 600 ℃ is 50-65 wt%.
The functional master batch containing the hyperbranched hybrid porous material consists of 51-81 wt% of a polymer matrix, 10-40 wt% of a hyperbranched hybrid porous material containing metal ions, 2-6 wt% of a dispersant and 1-3 wt% of an antioxidant;
the polymer matrix is made of PET, PA6 or PLA;
the dispersing agent is more than one of polyethylene wax, calcium stearate and zinc stearate;
the antioxidant is 2, 4-di- (n-octyl sulfur methylene) -6-methylphenol or 2, 4-di (dodecyl sulfur methyl).
The preparation method of the hyperbranched hybrid porous material containing metal ions comprises the following steps: mixing a substance containing molecules A with an aqueous solution containing a substance containing molecules B in a powder form, stirring while mixing, then dropwise adding a metal salt solution into the mixed system, stirring while dropwise adding to prepare hyperbranched hybrid microspheres, and performing heat treatment on the hyperbranched hybrid microspheres at 140-230 ℃ to prepare the hyperbranched hybrid porous material containing metal ions, wherein the metal ions in the metal salt solution are Mn+(ii) a At present, most of the existing technologies for preparing the triangular bonding structure are natural polymer matrix systems with good water solubility, and hyperbranched polymer systems all have the problems of too long dissolution time and all available solvents are organic solvents (tetrahydrofuran, ethanol and the like), and the main difficulties of forming the triangular bonding structure are two: the structure of the first, proper solvent system, the second, molecule B and molecule A after reaction still needs to have metal coordination ability. The invention selects green and environment-friendly water as a solvent, selects a molecule A containing carboxyl and a molecule B containing amido as reactants, the substance containing the molecule B contains a large amount of amido, has good solubility and can be dissolved quickly, the carboxyl in the molecule A and the amido in the molecule B react to generate an intermediate with metal coordination capability, and then a metal salt solution is added for metal coordination to form a triangular bonding structure. The substance containing the molecule A is an esterified substance, the water resistance is poor, and ester bonds are easy to degrade when the substance is exposed to a humid environment, so the substance is mostly stored in a powder form. The substance containing the molecule A is difficult to be directly dissolved in water and only can be dissolved in organic solvents such as DMSO, DMF and the like, when the substance containing the molecule A is dissolved in the organic solvent to form a solution and then is mixed with the solution containing the substance containing the molecule B, strong acting force can be generated between the organic solvent and the molecule B, so that the formation of ionic bonds between the molecule A and the molecule B is not facilitated, and a triangular bonding structure is further not facilitated. The invention prepares the nano-scale porous hybrid material by carrying out heat treatment on the hyperbranched hybrid microsphere, and changes the polymerization of the nano-scale porous hybrid materialThe aggregate structure endows the product with the special functions of adsorption, deodorization and the like of the porous material, and widens the application of the material. The bonding of other organic covalent bonds can be destroyed due to overhigh heat treatment temperature, so that the flame retardant property of the functional material is reduced, and the short-chain molecules with amino groups are difficult to destroy due to overlow heat treatment temperature, so that the porous hybrid material is obtained;
the concentration of the aqueous solution containing the molecular B substance is 0.3-0.58 mol/L; the concentration of the aqueous solution containing the molecular B substance can be properly adjusted, but the concentration is not too high, the addition amount of the aqueous solution containing the molecular B substance is difficult to accurately control, the addition amount of the molecular B substance is easy to cause excessive addition, the molecular B and a metal salt solution generate a coordination reaction to generate a precipitate, so that the separation of substances is influenced, the concentration is too low, the coordination speed is too slow, the yield per unit time is too low, and the economic benefit is greatly influenced;
in the mixed system, the molar ratio of the substance containing the molecules A to the substance containing the molecules B is 1: 2-7; the molar ratio of the substance containing the molecule A to the substance containing the molecule B can be properly adjusted, but is not too high, the molar ratio is too high, the substance containing the molecule B is easily added in an excessive amount, the molecule B and a metal salt solution generate a coordination reaction to generate precipitation so as to influence the separation of the substances, and the excessive molar ratio can cause the reaction amount of carboxyl and amino groups to be insufficient, the water solubility of a system is reduced, and the dispersibility is poor;
the concentration of the metal salt solution is 0.4-1.2 mol/L, and the molar ratio of the total amount of the added metal salt to the substance containing the molecules A is 1: 2-6; the concentration of the metal salt solution and the molar ratio of the total amount of the metal salt added to the molecule A-containing substance can be adjusted appropriately, but it is not preferable that the molar ratio is too high, for example, the dispersibility of the metal salt in the polymer matrix is affected (the dispersibility is deteriorated);
stirring at the stirring speed of 300-400 rpm, performing suction filtration separation after the dropwise addition is finished, and performing vacuum drying on a filter cake obtained by the suction filtration separation for 8-12 h under the conditions that the temperature is 25-30 ℃ and the vacuum degree is-0.09-0.1 MPa;
the atmosphere of the heat treatment is air, the time of the heat treatment is 40-50 min, and the temperature rise rate before the heat treatment is 15-20 ℃/min; when the heat treatment is performed in an oxygen-containing atmosphere, the short-chain molecules are more likely to be broken in molecular bonds. If the heat treatment time is too long or the temperature rise rate is too slow, part of other organic covalent bonds can be bonded, so that the flame retardant property of the functional material is reduced; the short-chain molecules with amino groups are difficult to damage due to too short heat treatment time or too high temperature rise rate, so that the porous hybrid material is obtained;
the substance containing the molecule B is selected from one of alkyl chain amine with the chain length of less than 6 carbons, polyether amine D230, polyether amine D400, polyether amine D2000, polyether amine D4000, polyether amine T403, polyether amine T3000, polyether amine T5000, fatty amine polyoxyethylene ether AC-1810, fatty amine polyoxyethylene ether AC-1812, fatty amine polyoxyethylene ether AC-1815, fatty amine polyoxyethylene ether AC-1205, fatty amine polyoxyethylene ether AC-1210 and fatty amine polyoxyethylene ether AC-1215; the metal salt solution is AgNO3、FeCl2、FeCl3、HAuCl4、Cr2(SO4)3、ZnCl2、PtCl2、PdCl2、CuSO4、Ni(NO3)2Or CdCl2Or a rare earth metal salt solution. The hydrophilic short molecular chain of the molecule B is combined with the molecule A and the metal ions to prepare the water-based dispersed particles, so that the particles are prevented from agglomerating (including preparation, drying and the like) when the hyperbranched hybrid porous microspheres are prepared, and the size of the final porous microspheres is ensured;
the functional master batch containing the hyperbranched hybrid porous material has the advantages that the alkyl chain amine with the chain length of less than 6 carbons is n-propylamine, n-butylamine, n-pentylamine or n-hexylamine; the rare earth metal salt solution is LaCl3、Ce2(SO4)3、Eu(NO3)3、ErCl3、YbCl3、Tm(NO3)3、Ho(NO3)3Or Pr (NO)3)3An aqueous solution of (a);
the substance containing molecule A is a2+B3Prepared by a synthetic method, A2Is a monomer containing two reactive groups, at least one of which is a carboxyl group, B3Is a monomer containing three reactive hydroxyl groups;
a is described2Is pyrazine-2, 3-dicarboxylic acid, 2-carboxyethylphenylphosphinic acid, 5-tert-butyl-1, 3-benzenedicarboxylic acid or 2-carboxyethylphosphoric acid, B3Is 1,1, 1-tri (hydroxymethyl) propane, tri (2-hydroxyethyl) isocyanurate, 2,4, 5-trihydroxybenzene butanone, 2,3, 4-trihydroxyacetophenone or 1,2, 4-trihydroxybenzene. The method for producing the substance containing the molecule A and the raw material thereof of the present invention are not limited thereto as long as the product thereof has the molecule A satisfying the structural formula. Here, only A is mentioned2And B3Part of the possible substances, A of the invention2And B3Without being limited thereto, other substances capable of producing the substance containing the molecule A can be applied to the present invention.
The invention also provides a method for preparing the functional master batch containing the hyperbranched hybrid porous material, which is to uniformly mix the polymer matrix material, the hyperbranched hybrid porous material containing metal ions and other components and then melt and extrude the mixture to prepare the functional master batch containing the hyperbranched hybrid porous material.
As a preferred technical scheme:
according to the method, the polymer matrix material is dried for 1-2 hours at 100-120 ℃ before being uniformly mixed, and the uniform mixing is realized by mixing in a high-speed mixer for 30-40 min;
the polymer matrix is made of polyester, polyamide and polylactic acid, and the melt extrusion temperature is 220-290 ℃, 230-290 ℃ and 150-180 ℃ respectively.
The invention mechanism is as follows:
the invention firstly uses substance containing molecule B (molecule B is micromolecule containing amido group) to modify hyperbranched polymer (substance containing molecule A), on one hand, because hydrophilic group-amido group is introduced to improve the water solubility of the hyperbranched polymer, which is beneficial to the next reaction, on the other hand, the molecule B is micromolecule with weak polarity, the molecule B with weak polarity is grafted on the hyperbranched polymer molecule, then, the coordination of carboxyl and amido group and metal ion is utilized to introduce the metal ion into the hyperbranched polymer to form stable triangle bonding structure to obtain hyperbranched type hybrid material containing metal ion, and by introducing the metal ion, the thermal stability of the hyperbranched polymer is greatly improved, so that the hyperbranched polymer of the invention has the characteristic of not influencing the melt processing of the traditional matrix, the processing performance is greatly improved, and the problem of difficult processing and forming when the hyperbranched polymer is blended in the prior art is overcome, finally, the hyperbranched hybrid porous material containing the metal ions is prepared by heat treatment and pore-forming, in the heat treatment process, because the heat stability of the molecular chain of the micromolecule containing the amido is poorer than that of the hyperbranched polymer before being modified, the micromolecule is degraded into gaseous substances to volatilize under heating, so that the hybrid material is changed from the solid microspheres into the porous microspheres.
In addition, the metal ions contained in the hyperbranched hybrid porous material containing the metal ions have a catalytic effect on chemical reactions such as dehydrogenation and deoxidation in the macromolecular thermal degradation process, namely, the chain degradation and crosslinking process, and can play a role in improving the carbon residue rate of the material and reducing the thermal feedback and smoke release in the combustion process.
The mechanism of formation of the stable triangular bonding structure of the present invention is as follows: carboxyl in the molecule A is combined with amino in the molecule B to form a complex, and the complex is ionized to generate-COO-and-NH3 +，-COO-and-NH3 +Because of the attraction of positive and negative charges, electrostatic attraction is generated, i.e. ionic bonds are formed, due to-COO-The oxygen in the metal ion has a lone pair electron, so that the lone pair electron enters the empty orbit of the metal ion to be covalently coordinated with the metal ion to form a coordination bond due to-NH3 +The N atom in (A) also has a lone pair of electrons, and the lone pair of electrons can be provided to form a coordination with the metal ionThe position bonds are combined, so that a stable triangular bonding structure in the structural formula is formed.
When the functional master batch is prepared by using the hyperbranched hybrid porous material containing the metal ions, the high porosity of the hyperbranched hybrid porous material containing the metal ions can endow the master batch with excellent deodorization function, the metal ions contained in the hyperbranched hybrid porous material containing the metal ions and functional elements such as P, N and the like can endow the master batch with excellent flame retardant property, and meanwhile, the metal ions can endow the master batch with excellent sterilization property, so that the finally prepared master batch has excellent flame retardant, antibacterial and deodorization functions.
Has the advantages that:
(1) the functional master batch containing the hyperbranched hybrid porous material and the hyperbranched hybrid porous material containing the metal ions can realize nanoscale dispersion in a polyester matrix, have adjustable metal ion loading capacity, good thermal stability, good processability and good adsorption performance, and simultaneously have flame retardant, antibacterial and deodorizing functions, so that the prepared master batch has excellent flame retardant, antibacterial and deodorizing functions;
(2) the preparation method of the functional master batch containing the hyperbranched hybrid porous material adopts water as a reaction solvent, and is non-toxic, harmless, green and environment-friendly;
(3) the preparation method of the functional master batch containing the hyperbranched hybrid porous material has the advantages of less equipment investment, simple and easily implemented operation process, mild experimental conditions, low cost and great market prospect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The formula (I) is carboxyl in a molecule A, amido in a molecule B and metal ions M in the hyperbranched hybrid porous material containing the metal ionsn+A triangular bonding structure formed by bonding through ionic bonds and coordination bonds, wherein R is a tertiary ammonium group, a quaternary ammonium group, a carboxylic acid group, a hydroxyl group, an ether group, an amino group, an amide group, a mercapto group or halogen, and the group represented by R corresponds to the molecule B;
the molecule A is a hyperbranched polymer molecule with an end group containing carboxyl;
the molecule B is a chain molecule with amino;
in the molecule A and the molecule B, the sum of the carboxyl content, the amino content and the hydroxyl content is 130 to 170 percent of the sum of the molar weights of the molecule A and the molecule B;
in the following examples, the number of terminal carboxyl groups in the molecule A accounts for 25-100% of the total amount of the terminal groups, the branching degree of the molecule A is 30-100%, the relative molecular weight is 1100-50000 g/mol, and the molecule A mainly comprises C and H except for the O of the carboxyl groups;
the molecular weight of the molecule B is less than or equal to 5000g/mol, and the molecular main chain is mainly composed of C and H except N of amine groups.
Example 1
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
performing esterification reaction on pyrazine-2, 3-dicarboxylic acid and 1,1, 1-tris (hydroxymethyl) propane at a molar ratio of 1:1 at 150 ℃ under the protection of nitrogen for 1h, and then performing vacuum pumping at 200 ℃ under the pressure of 0MPa for polycondensation reaction for 4h to obtain a substance containing molecules A, wherein stirring is required in the esterification reaction and polycondensation reaction processes, and the stirring speed is 200 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with an aqueous solution of n-propylamine (substance containing the molecules B) with the concentration of 0.3mol/L, stirring the mixture, and dropwise adding AgNO with the concentration of 0.4mol/L into the mixed system3Stirring the aqueous solution during dripping, performing suction filtration separation after dripping, and allowing the filter cake obtained by suction filtration separation to react at 25 ℃,Vacuum drying for 8h under the condition that the vacuum degree is-0.09 MPa to prepare the hyperbranched hybrid microsphere, wherein in the mixed system, the molar ratio of the substance containing the molecule A to the n-propylamine is 1:2, and AgNO is added3The molar ratio of the total amount to the substance containing the molecule A is 1:2, and the stirring speed during mixing and dripping is 300 rpm;
(3) carrying out heat treatment on the hyperbranched hybrid microspheres at 140 ℃ in an air atmosphere for 40min to obtain a hyperbranched hybrid porous material containing metal ions, wherein the heating rate before the heat treatment is 20 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Ag+A composition wherein the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and of amino groups bonded through ionic bonds and coordinate bonds is equal to 20% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and a metal ion Ag+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the load capacity of metal ions in the finally prepared hyperbranched hybrid porous material containing the metal ions is 70mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 90-100 nm, the porosity is 40%, the initial decomposition temperature is 340 ℃, and the carbon residue rate is 50 wt% at 600 ℃;
(4) firstly, drying PET powder for 1.5h at 110 ℃, then mixing the PET powder, the hyperbranched hybrid porous material containing metal ions, polyethylene wax and 2, 4-di- (n-octylthiomethylene) -6-methylphenol in a high-speed mixer for 35min to realize uniform mixing of all components, wherein the content of each component is as follows when preparing the functional master batch: 75 wt% of PET powder, 20 wt% of hyperbranched type hybrid porous material containing metal ions, 2 wt% of polyethylene wax and 3wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol, and finally melting and extruding the mixed components at the temperature of 250 ℃ to obtain the functional master batch containing the hyperbranched type hybrid porous material.
The PET fiber containing 5wt% of metal ion and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 32%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are 87% and 84% respectively, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are 93% and 83% respectively, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are 90%, 91% and 95% respectively.
Example 2
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
2-carboxyethyl phenyl phosphinic acid and tris (2-hydroxyethyl) isocyanurate in a molar ratio of 1:2 are subjected to esterification reaction for 2 hours at the temperature of 180 ℃ under the protection of nitrogen, and then are subjected to vacuum pumping for polycondensation reaction for 3 hours at the temperature of 180 ℃ and the pressure of-0.1 MPa to obtain a substance containing the molecule A, wherein stirring is required in the esterification reaction and polycondensation reaction processes, and the stirring speed is 300 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with an aqueous solution of n-butylamine (substance containing the molecules B) with the concentration of 0.58mol/L, stirring the mixture, and dropwise adding FeCl with the concentration of 1.2mol/L into the mixed system2Stirring the aqueous solution during dropwise adding, performing suction filtration separation after dropwise adding, and performing vacuum drying on a filter cake obtained by suction filtration separation for 12 hours at the temperature of 30 ℃ and the vacuum degree of-0.1 MPa to obtain the hyperbranched hybrid microsphere, wherein the molar ratio of the substance containing the molecules A to the n-butylamine in a mixed system is 1:7, and FeCl is added2The molar ratio of the total amount to the substance containing the molecule A is 1:6, and the stirring speed during mixing and dripping is 400 rpm;
(3) carrying out heat treatment on the hyperbranched hybrid microspheres in the air atmosphere at 230 ℃ for 50min to obtain a hyperbranched hybrid porous material containing metal ions, wherein the heating rate before the heat treatment is 15 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Fe2+A constitution in which the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and of amino groups bonded through ionic bonds and coordinate bonds is equal to 25% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, the sum of carboxyl groups and amino groups in molecule A beingCarboxyl, amino in molecule B and metal ion Fe2+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the load capacity of metal ions in the finally prepared hyperbranched hybrid porous material containing the metal ions is 1700mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 40-50 nm, the porosity is 60%, the initial decomposition temperature is 380 ℃, and the carbon residue rate at 600 ℃ is 65 wt%;
(4) firstly, drying PET powder for 1h at 100 ℃, then mixing the PET powder, a hyperbranched hybrid porous material containing metal ions, calcium stearate and 2, 4-di- (n-octylthiomethylene) -6-methylphenol in a high-speed mixer for 30min to realize the uniform mixing of all components, wherein the content of each component is as follows when preparing the functional master batch: 81wt% of PET powder, 10wt% of hyperbranched type hybrid porous material containing metal ions, 6wt% of calcium stearate and 3wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol, and finally melting and extruding the mixed components at 220 ℃ to obtain the functional master batch containing the hyperbranched type hybrid porous material.
The PET fiber containing 0.5 wt% of metal ion and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 30%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are 85% and 80% respectively, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are 90% and 80% respectively, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are 85%, 92% and 92% respectively.
Example 3
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
5-tert-butyl-1, 3-benzene dicarboxylic acid and 2,4, 5-trihydroxybenzene butanone with the molar ratio of 1:3 are subjected to esterification reaction for 1.5h at the temperature of 160 ℃ under the protection of nitrogen, and then the mixture is subjected to vacuum pumping for polycondensation reaction for 2h at the temperature of 190 ℃ and the pressure of-0.05 MPa to obtain a substance containing molecules A, wherein stirring is required in the esterification reaction and the polycondensation reaction, and the stirring speed is 400 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with the aqueous solution of polyetheramine D230 (substance containing the molecules B) with the concentration of 0.49mol/L, stirring the mixture, and then dropwise adding FeCl with the concentration of 0.8mol/L into the mixed system3Stirring the aqueous solution during dropwise adding, performing suction filtration separation after dropwise adding, and performing vacuum drying on a filter cake obtained by suction filtration separation for 10 hours at the temperature of 27 ℃ and the vacuum degree of-0.095 MPa to obtain the hyperbranched hybrid microsphere, wherein in a mixed system, the molar ratio of a substance containing the molecule A to the polyetheramine D230 is 1:5, and FeCl is added3The molar ratio of the total amount to the substance containing the molecule A is 1:4, and the stirring speed during mixing and dripping is 350 rpm;
(3) carrying out heat treatment on the hyperbranched hybrid microspheres in the air atmosphere at 200 ℃ for 45min to obtain a hyperbranched hybrid porous material containing metal ions, wherein the heating rate before the heat treatment is 18 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Fe3+A composition wherein the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and amino groups bonded through ionic bonds and coordinate bonds is 22% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and metal ion Fe3+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the loading capacity of metal ions in the finally prepared hyperbranched hybrid porous material containing the metal ions is 700mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 60-70 nm, the porosity is 45%, the initial decomposition temperature is 365 ℃, and the carbon residue rate at 600 ℃ is 56 wt%;
(4) firstly, drying PET powder at 120 ℃ for 2h, then mixing the PET powder, a hyperbranched hybrid porous material containing metal ions, zinc stearate and 2, 4-di- (n-octylthiomethylene) -6-methylphenol in a high-speed mixer for 40min to realize uniform mixing of all components, wherein the content of each component is as follows when preparing the functional master batch: 57 wt% of PET powder, 40wt% of hyperbranched type hybrid porous material containing metal ions, 2 wt% of zinc stearate and 1wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol, and finally melting and extruding the mixed components at 290 ℃ to prepare the functional master batch containing the hyperbranched type hybrid porous material.
The PET fiber containing 10wt% of metal ion and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 33%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are respectively 90% and 87%, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are respectively 95% and 85%, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are respectively 95%, 92% and 98%.
Example 4
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
2-carboxyethyl phosphoric acid and 2,3, 4-trihydroxyacetophenone in a molar ratio of 1:1.5 are subjected to esterification reaction for 3 hours at the temperature of 200 ℃ under the protection of nitrogen, and then are subjected to polycondensation reaction for 2.5 hours under the conditions of the temperature of 210 ℃ and the pressure of-0.1 MPa by vacuumizing to obtain a substance containing molecules A, wherein stirring is required in the esterification reaction and the polycondensation reaction, and the stirring speed is 500 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with the aqueous solution of polyetheramine T403 (substance containing the molecules B) with the concentration of 0.4mol/L, stirring the mixture, and then dropwise adding CuSO with the concentration of 0.6mol/L into the mixed system4Stirring the aqueous solution during dropwise adding, performing suction filtration separation after dropwise adding, and performing vacuum drying on a filter cake obtained by suction filtration separation for 8 hours at the temperature of 28 ℃ and the vacuum degree of-0.09 MPa to obtain the hyperbranched hybrid microsphere, wherein the molar ratio of the substance containing the molecule A to the polyetheramine T403 in the mixed system is 1:7, and CuSO is added4The molar ratio of the total amount to the substance containing the molecule A is 1:2, and the stirring speed during mixing and dripping is 300 rpm;
(3) carrying out heat treatment on the hyperbranched hybrid microspheres in the air atmosphere at 150 ℃ for 48min to obtain a hyperbranched hybrid porous material containing metal ions, wherein the heating rate before the heat treatment is 15 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and metal ions Cu2+A constitution in which the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and amino groups bonded through ionic bonds and coordinate bonds is 21% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and metal ion Cu2+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the finally prepared hyperbranched hybrid porous material containing the metal ions has the metal ion loading capacity of 510mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 60-80 nm, the porosity is 49%, the initial decomposition temperature is 350 ℃, and the carbon residue rate is 56 wt% at 600 ℃;
(4) firstly, drying PA6 powder at 100 ℃ for 2h, then mixing PA6 powder, a hyperbranched hybrid porous material containing metal ions, a dispersing agent (a mixture of polyethylene wax and calcium stearate in a mass ratio of 1: 1) and 2, 4-di- (n-octylthiomethylene) -6-methylphenol in a high-speed mixer for 35min to realize uniform mixing of all components, wherein the content of each component is as follows when the functional master batch is prepared: 51 wt% of PA6 powder, 40wt% of hyperbranched type hybrid porous material containing metal ions, 6wt% of dispersant and 3wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol, and finally melting and extruding the mixed components at 290 ℃ to prepare the functional master batch containing the hyperbranched type hybrid porous material.
The PA6 fiber containing 2 wt% of metal ion and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 31%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are 85% and 80% respectively, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are 90% and 80% respectively, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are 85.5%, 90.5% and 92% respectively.
Example 5
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
2-carboxyethyl phenyl phosphinic acid and 1,2, 4-trihydroxybenzene with the molar ratio of 1:2.5 are subjected to esterification reaction for 1h at the temperature of 220 ℃ under the protection of nitrogen, and then are subjected to polycondensation reaction for 1.5h under the conditions of the temperature of 220 ℃ and the pressure of 0MPa to obtain a substance containing the molecule A, wherein stirring is required in the esterification reaction and the polycondensation reaction, and the stirring speed is 250 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with an aqueous solution of 0.5mol/L fatty amine polyoxyethylene ether AC-1810 (substance containing the molecules B), stirring while mixing, and then dropwise adding 1.2mol/L PdCl into the mixed system2Stirring the aqueous solution during dropwise adding, performing suction filtration separation after dropwise adding, and performing vacuum drying on a filter cake obtained by suction filtration separation for 8 hours at the temperature of 30 ℃ and the vacuum degree of-0.1 MPa to prepare the hyperbranched hybrid microsphere, wherein in a mixed system, the molar ratio of a substance containing the molecular A to the fatty amine polyoxyethylene ether AC-1810 is 1:3, the molar ratio of the total amount of the added metal salt to the substance containing the molecular A is 1:6, and the stirring speed during mixing and dropwise adding is 300 rpm;
(3) the hyperbranched hybrid microspheres are subjected to heat treatment for 50min at 160 ℃ in the air atmosphere to prepare a hyperbranched hybrid porous material containing metal ions, and the heating rate before the heat treatment is 18 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and metal ions Pd2+A constitution in which the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and amino groups bonded through ionic bonds and coordinate bonds is 23% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and metal ion Pd2+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the load capacity of metal ions in the finally prepared hyperbranched hybrid porous material containing the metal ions is 400mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 45-55 nm, the porosity is 44%, the initial decomposition temperature is 360 ℃, and the carbon residue rate is 53 wt% at 600 ℃;
(4) firstly, drying PA6 powder at 120 ℃ for 2h, then mixing PA6 powder, a hyperbranched hybrid porous material containing metal ions, a dispersing agent (a mixture of polyethylene wax, calcium stearate and zinc stearate in a mass ratio of 1:1: 1) and 2, 4-bis (dodecyl sulfur methyl) in a high-speed mixer for 35min to realize uniform mixing of all components, wherein the content of each component is as follows when the functional master batch is prepared: 70 wt% of PA6 powder, 24 wt% of hyperbranched hybrid porous material containing metal ions, 4 wt% of dispersant and 2 wt% of 2, 4-bis (dodecyl sulfur methyl), and finally melting and extruding the mixed components at 230 ℃ to prepare the functional master batch containing the hyperbranched hybrid porous material.
The PA6 fiber containing 4 wt% of metal ion and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 32%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are 87% and 83% respectively, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are 92% and 82% respectively, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are 87%, 91% and 93% respectively.
Example 6
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
5-tert-butyl-1, 3-benzene dicarboxylic acid and 1,1, 1-tri (hydroxymethyl) propane in a molar ratio of 1:1 are subjected to esterification reaction for 2.5h at the temperature of 210 ℃ under the protection of nitrogen, and then are subjected to vacuum pumping for polycondensation reaction for 2h under the conditions of the temperature of 230 ℃ and the pressure of-0.05 MPa to obtain a substance containing molecules A, wherein stirring is required in the esterification reaction and polycondensation reaction processes, and the stirring speed is 350 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with the aqueous solution of polyetheramine D400 (substance containing the molecules B) with the concentration of 0.3mol/L, stirring the mixture, and dropwise adding Ni (NO) with the concentration of 0.5mol/L into the mixed system3)2Stirring the aqueous solution during dropwise adding, performing suction filtration separation after dropwise adding, and vacuum drying the filter cake obtained by suction filtration separation for 11h at the temperature of 25 ℃ and the vacuum degree of-0.09 MPa to obtain the hyperbranched hybrid microsphere, wherein in the mixed system, the molar ratio of the substance containing the molecule A to the polyetheramine D400 is 1:5, and Ni (NO) is added3)2The molar ratio of the total amount to the substance containing the molecule A is 1:5, and the stirring speed during mixing and dripping is 400 rpm;
(3) carrying out heat treatment on the hyperbranched hybrid microspheres in the air atmosphere at 140 ℃ for 50min to obtain a hyperbranched hybrid porous material containing metal ions, wherein the heating rate before the heat treatment is 15 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and metal ions Ni2+A constitution in which the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and amino groups bonded through ionic bonds and coordinate bonds is 24% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and metal ion Ni2+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the finally prepared hyperbranched hybrid porous material containing the metal ions has the metal ion loading capacity of 1320mg/g, the aperture of 45-60 nm, the porosity of 56 percent, the initial decomposition temperature of 380 ℃ and the carbon residue rate of 60 percent by weight at 600 ℃;
(4) firstly, drying PLA powder for 2 hours at 110 ℃, then mixing the PLA powder, hyperbranched hybrid porous material containing metal ions, polyethylene wax and 2, 4-bis (dodecyl sulfur methyl) in a high-speed mixer for 40min to realize the uniform mixing of all components, wherein the content of each component is as follows when preparing the functional master batch: 65wt% of PLA powder, 30 wt% of hyperbranched type hybrid porous material containing metal ions, 3wt% of polyethylene wax and 2 wt% of 2, 4-bis (dodecyl sulfur methyl), and finally melting and extruding the mixed components at the temperature of 150 ℃ to obtain the functional master batch containing the hyperbranched type hybrid porous material.
The PLA fiber containing 5.5 wt% of metal ions and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 32%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are respectively 87.5% and 83%, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are respectively 92.5% and 83%, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are respectively 89%, 91.5% and 95%.
Example 7
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
performing esterification reaction on pyrazine-2, 3-dicarboxylic acid and tris (2-hydroxyethyl) isocyanurate in a molar ratio of 1:3 at 155 ℃ for 3h under the protection of nitrogen, and then performing polycondensation reaction for 3.5h under the conditions of 250 ℃ and-0.08 MPa by vacuumizing to obtain a substance containing molecules A, wherein stirring is required in the esterification reaction and the polycondensation reaction, and the stirring speed is 450 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with an aqueous solution of polyetheramine T3000 (substance containing the molecules B) with the concentration of 0.48mol/L, stirring the mixture, and dropwise adding Tm (NO) with the concentration of 0.9mol/L into the mixed system3)3Stirring the aqueous solution during dropwise adding, performing suction filtration separation after dropwise adding, and vacuum drying the filter cake obtained by suction filtration separation for 8h at the temperature of 28 ℃ and the vacuum degree of-0.09 MPa to obtain the hyperbranched hybrid microsphere, wherein in the mixed system, the molar ratio of the substance containing the molecule A to the polyetheramine T3000 is 1:2, and Tm (NO) is added3)3The molar ratio of the total amount to the substance containing the molecule A is 1:6, and the stirring speed during mixing and dripping is 350 rpm;
(3) the hyperbranched hybrid microspheres are subjected to heat treatment for 40min at 180 ℃ in the air atmosphere to prepare a hyperbranched hybrid porous material containing metal ions, and the heating rate before the heat treatment is 20 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Tm3+In which the ionic bond and the coordinate bond are bondedThe sum of the contents of bonded carboxyl groups and amino groups bonded by ionic and coordinate bonds is equal to 20% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and metal ions Tm3+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the load capacity of metal ions in the finally prepared hyperbranched hybrid porous material containing the metal ions is 900mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 86-95 nm, the porosity is 43 percent, the initial decomposition temperature is 355 ℃, and the carbon residue rate at 600 ℃ is 58wt percent;
(4) firstly, drying PLA powder for 2 hours at 120 ℃, then mixing the PLA powder, hyperbranched hybrid porous material containing metal ions, polyethylene wax and 2, 4-bis (dodecyl sulfur methyl) in a high-speed mixer for 30 minutes to realize the uniform mixing of all components, wherein the content of each component is as follows when preparing the functional master batch: 70 wt% of PLA powder, 27 wt% of hyperbranched type hybrid porous material containing metal ions, 2 wt% of polyethylene wax and 1wt% of 2, 4-bis (dodecyl sulfur methyl), and finally melting and extruding the mixed components at the temperature of 180 ℃ to prepare the functional master batch containing the hyperbranched type hybrid porous material.
The PLA fiber containing 7.5 wt% of metal ions and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 32.5%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are respectively 88% and 84%, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are respectively 93% and 84%, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are respectively 91%, 91% and 96%.
Example 8
The preparation method of the functional master batch containing the hyperbranched hybrid porous material comprises the following specific steps:
(1) preparing a substance containing molecule A;
5-tert-butyl-1, 3-benzene dicarboxylic acid and 2,3, 4-trihydroxyacetophenone in a molar ratio of 1:1.5 are subjected to esterification reaction for 1h at the temperature of 150 ℃ under the protection of nitrogen, and then are subjected to vacuum pumping for polycondensation reaction for 4h at the temperature of 240 ℃ and the pressure of-0.1 MPa to prepare a substance containing molecules A, wherein stirring is required in the esterification reaction and polycondensation reaction processes, and the stirring speed is 200 rpm;
(2) mixing the substance containing the molecules A prepared in the step (1) in the form of powder with an aqueous solution of 0.4mol/L fatty amine polyoxyethylene ether AC-1812 (substance containing the molecules B), stirring while mixing, and then dropwise adding Eu (NO) with the concentration of 0.6mol/L into the mixed system3)3Stirring the aqueous solution during dripping, performing suction filtration separation after dripping is finished, and performing vacuum drying on a filter cake obtained by suction filtration separation for 12 hours at the temperature of 25 ℃ and the vacuum degree of-0.1 MPa to obtain the hyperbranched hybrid microsphere, wherein in a mixed system, the molar ratio of a substance containing the molecule A to the fatty amine polyoxyethylene ether AC-1812 is 1:2, and a metal salt Eu (NO) is added3)3The molar ratio of the total amount to the substance containing the molecule A is 1:5, and the stirring speed during mixing and dripping is 300 rpm;
(3) carrying out heat treatment on the hyperbranched hybrid microspheres in the air atmosphere at 170 ℃ for 50min to obtain a hyperbranched hybrid porous material containing metal ions, wherein the heating rate before the heat treatment is 15 ℃/min;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Eu3+A composition wherein the sum of the contents of carboxyl groups bonded through ionic bonds and coordinate bonds and of amino groups bonded through ionic bonds and coordinate bonds is 21% of the sum of the molar amounts of carboxyl groups and amino groups in molecule A and molecule B, carboxyl groups in molecule A, amino groups in molecule B and metal ion Eu3+The bonding is carried out through ionic bonds and coordinate bonds to form a triangular bonding structure shown in a formula (I);
the loading capacity of metal ions in the finally prepared hyperbranched hybrid porous material containing the metal ions is 1410mg/g, the aperture of the hyperbranched hybrid porous material containing the metal ions is 60-70 nm, the porosity is 50%, the initial decomposition temperature is 355 ℃, and the carbon residue rate at 600 ℃ is 55 wt%;
(4) firstly, drying PLA powder for 2h at 100 ℃, then mixing the PLA powder, the hyperbranched hybrid porous material containing metal ions, calcium stearate and 2, 4-bis (dodecyl sulfur methyl) in a high-speed mixer for 40min to realize the uniform mixing of all the components, wherein the content of each component is as follows when preparing the functional master batch: 55 wt% of PLA powder, 40wt% of hyperbranched type hybrid porous material containing metal ions, 2 wt% of calcium stearate and 3wt% of 2, 4-bis (dodecyl sulfur methyl), and finally melting and extruding the mixed components at the temperature of 170 ℃ to prepare the functional master batch containing the hyperbranched type hybrid porous material.
The PLA fiber containing 9 wt% of metal ions and prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 33%, the bacteriostasis rates to staphylococcus aureus before and after 50 times of water washing are 89% and 86% respectively, the bacteriostasis rates to escherichia coli before and after 50 times of water washing are 94% and 84% respectively, and the adsorption rates to ammonia gas, acetic acid and isovaleric acid are 94%, 92% and 96% respectively.
Examples 9 to 20
The steps of the preparation method of the functional master batch containing the hyperbranched hybrid porous material are basically the same as that of the embodiment 8, and the differences are that the type of the substance containing the molecule B, the type of the metal salt solution, the hyperbranched hybrid porous material containing the metal ions, the content of the hyperbranched hybrid porous material containing the metal ions in the finally prepared fiber and various parameters of the fiber, and are specifically shown in the table 1 and the table 2, wherein the metal ions in the structural formula of the hyperbranched hybrid porous material containing the metal ions are provided by the metal salt solution, Z in the table is the ratio of the sum of the contents of carboxyl bonded by ionic bonds and coordinate bonds and the amino bonded by ionic bonds and coordinate bonds to the sum of the molar weights of the carboxyl and the amino in the molecule A and the molecule B, the unit is%, the load amount is the load amount of the metal ions in the hyperbranched hybrid porous material containing the metal ions, and the unit is mg/g, the pore diameter is the pore diameter of the hyperbranched hybrid porous material containing the metal ions and is measured in nm, the porosity is the porosity of the hyperbranched hybrid porous material containing the metal ions, the temperature is the initial decomposition temperature of the hyperbranched hybrid porous material containing the metal ions and is measured in wt%, and the carbon residue rate is the carbon residue rate of the hyperbranched hybrid porous material containing the metal ions at 600 ℃.
The content of the hyperbranched hybrid porous material containing the metal ions, which is finally prepared from the functional master batch containing the hyperbranched hybrid porous material containing the metal ions and the hyperbranched hybrid porous material containing the hyperbranched hybrid porous material, is Awt% fiber, the limiting oxygen index is B, the bacteriostatic rates on staphylococcus aureus before and after 50 times of water washing are C% and D% respectively, the bacteriostatic rates on escherichia coli before and after 50 times of water washing are E% and F% respectively, the adsorption rates on ammonia gas, acetic acid and isovaleric acid are G%, H% and J% respectively, and the values of A, B, C, D, E, F, G, H and J are detailed in Table 2.
TABLE 1
TABLE 2
Claims (10)
1. Functional master batch containing hyperbranched hybrid porous material is characterized in that: the hyperbranched hybrid porous material containing the metal ions is porous microspheres, and is prepared by nucleating and growing hyperbranched hybrids to form microspheres and then carrying out pore-forming;
the molecular structural formula of the hyperbranched hybrid mainly comprises a molecule A, a molecule B and a metal ion Mn+The value range of n is 1-3;
the molecule A is a hyperbranched polymer molecule with an end group containing carboxyl;
the molecule B is a chain molecule with amino;
carboxyl in molecule A, amino in molecule B and metal ion Mn+The bonding between the two groups of the compound is realized through ionic bonding and coordinate bonding to form a triangular bonding structure, and the structural formula is as follows：
Wherein R is a cationic group, an anionic group or a polar nonionic group;
the preparation method of the hyperbranched hybrid porous material containing the metal ions comprises the following steps: mixing a substance containing molecules A with an aqueous solution containing a substance containing molecules B in a powder form, stirring while mixing, then dropwise adding a metal salt solution into the mixed system, stirring while dropwise adding to prepare hyperbranched hybrid microspheres, and performing heat treatment on the hyperbranched hybrid microspheres at 140-230 ℃ to prepare the hyperbranched hybrid porous material containing metal ions, wherein the metal ions in the metal salt solution are Mn+。
2. The functional master batch containing the hyperbranched hybrid porous material as claimed in claim 1, wherein the hyperbranched hybrid porous material containing metal ions prepared from the functional master batch containing the hyperbranched hybrid porous material has a limiting oxygen index of 30-33% for fibers with a content of 0.5-10 wt%, has an inhibition rate of 85-90% and 80-87% for Staphylococcus aureus before and after 50 times of water washing, has an inhibition rate of 90-95% and 80-85% for Escherichia coli before and after 50 times of water washing, and has an adsorption rate of 85-95%, 90-92% and 92-98% for ammonia, acetic acid and isovaleric acid.
3. The functional masterbatch containing hyperbranched hybrid porous material according to claim 1, wherein M is Mn+Is Ag+、Fe2+、Fe3+、Au3+、Cr3+、Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+Or 3-valent rare earth metal ions;
in the molecule A and the molecule B, the sum of the carboxyl content, the amino content and the hydroxyl content is 130-170% of the sum of the molar weights of the molecule A and the molecule B;
the sum of the contents of carboxyl groups bonded by ionic bonds and coordinate bonds and the contents of amino groups bonded by ionic bonds and coordinate bonds is more than or equal to 20 percent of the sum of the molar amounts of the carboxyl groups and the amino groups in the molecules A and B;
the number of terminal carboxyl groups in the molecule A accounts for 25-100% of the total amount of the terminal groups, the branching degree of the molecule A is 30-100%, the relative molecular weight is 1100-50000 g/mol, and the molecule A mainly comprises C and H except for O of the carboxyl groups;
the molecular weight of the molecule B is less than or equal to 5000g/mol, and the molecular main chain is mainly composed of C and H except N of amine groups.
4. The functional masterbatch containing hyperbranched hybrid porous material of claim 3, wherein the rare earth metal ion with valence of 3 is La3+、Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+；
The cationic group is a tertiary ammonium group or a quaternary ammonium group, the anionic group is a carboxylic acid group, and the polar nonionic group is a hydroxyl group, an ether group, an amine group, an amide group, a mercapto group or halogen;
the amine group bonded through an ionic bond and a coordinate bond is located in a main chain or a branch chain of the molecule B, the molecule B further comprises a hydroxyl group or a carboxyl group, the main chain of the molecule B further comprises an element O or N, and the molecule A further comprises an element P, O or N.
5. The functional master batch containing the hyperbranched hybrid porous material according to claim 1, wherein the metal ion loading amount in the hyperbranched hybrid porous material containing the metal ion is 70-1700 mg/g;
the aperture of the hyperbranched hybrid porous material containing the metal ions is 40-100 nm, and the porosity is 40% -60%;
the initial decomposition temperature of the hyperbranched hybrid porous material containing the metal ions is 340-380 ℃, and the carbon residue rate at 600 ℃ is 50-65 wt%.
6. The functional master batch containing the hyperbranched hybrid porous material according to claim 1, wherein the functional master batch containing the hyperbranched hybrid porous material consists of 51-81 wt% of a polymer matrix, 10-40 wt% of the hyperbranched hybrid porous material containing metal ions, 2-6 wt% of a dispersant and 1-3 wt% of an antioxidant;
the polymer matrix is made of PET, PA6 or PLA;
the dispersing agent is more than one of polyethylene wax, calcium stearate and zinc stearate;
the antioxidant is 2, 4-di- (n-octyl sulfur methylene) -6-methylphenol or 2, 4-di (dodecyl sulfur methyl).
7. The functional master batch containing the hyperbranched hybrid porous material according to claim 1, wherein the concentration of the aqueous solution containing the molecular B substance is 0.3-0.58 mol/L;
in the mixed system, the molar ratio of the substance containing the molecules A to the substance containing the molecules B is 1: 2-7;
the concentration of the metal salt solution is 0.4-1.2 mol/L, and the molar ratio of the total amount of the added metal salt to the substance containing the molecules A is 1: 2-6;
stirring at the stirring speed of 300-400 rpm, performing suction filtration separation after the dropwise addition is finished, and performing vacuum drying on a filter cake obtained by the suction filtration separation for 8-12 h under the conditions that the temperature is 25-30 ℃ and the vacuum degree is-0.09 to-0.1 MPa;
the atmosphere of the heat treatment is air, the time of the heat treatment is 40-50 min, and the temperature rise rate before the heat treatment is 15-20 ℃/min;
the substance containing the molecule B is selected from one of alkyl chain amine with the chain length of less than 6 carbons, polyether amine D230, polyether amine D400, polyether amine D2000, polyether amine D4000, polyether amine T403, polyether amine T3000, polyether amine T5000, fatty amine polyoxyethylene ether AC-1810, fatty amine polyoxyethylene ether AC-1812, fatty amine polyoxyethylene ether AC-1815, fatty amine polyoxyethylene ether AC-1205, fatty amine polyoxyethylene ether AC-1210 and fatty amine polyoxyethylene ether AC-1215; the metal salt solution is AgNO3、FeCl2、FeCl3、HAuCl4、Cr2(SO4)3、ZnCl2、PtCl2、PdCl2、CuSO4、Ni(NO3)2Or CdCl2Or a rare earth metal salt solution.
8. The functional masterbatch containing hyperbranched hybrid porous material according to claim 7, wherein the alkyl chain amine with a chain length of less than 6 carbons is n-propylamine, n-butylamine, or n-pentylamine; the rare earth metal salt solution is LaCl3、Ce2(SO4)3、Eu(NO3)3、ErCl3、YbCl3、Tm(NO3)3、Ho(NO3)3Or Pr (NO)3)3An aqueous solution of (a);
the substance containing molecule A is a2+B3Prepared by a synthetic method, A2Is a monomer containing two reactive groups, at least one of which is a carboxyl group, B3Is a monomer containing three reactive hydroxyl groups;
a is described2Is pyrazine-2, 3-dicarboxylic acid, 2-carboxyethylphenylphosphinic acid, 5-tert-butyl-1, 3-benzenedicarboxylic acid or 2-carboxyethylphosphoric acid, B3Is 1,1, 1-tri (hydroxymethyl) propane, tri (2-hydroxyethyl) isocyanurate, 2,4, 5-trihydroxybenzene butanone, 2,3, 4-trihydroxyacetophenone or 1,2, 4-trihydroxybenzene.
9. The method for preparing the functional master batch containing the hyperbranched hybrid porous material as claimed in any one of claims 1 to 8, which is characterized in that: the polymer matrix material, the hyperbranched hybrid porous material containing metal ions and other components are uniformly mixed and then melted and extruded to prepare the functional master batch containing the hyperbranched hybrid porous material.
10. The method according to claim 9, wherein the polymer matrix material is dried for 1 to 2 hours at 100 to 120 ℃ before being uniformly mixed, wherein the uniform mixing is realized by mixing in a high-speed mixer for 30 to 40 min;
when the polymer matrix is made of PET, PA6 and PLA, the corresponding melt extrusion temperatures are 220-290 ℃, 230-290 ℃ and 150-180 ℃.
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| "超支化Boltorn聚酯对Co离子的封装研究";唐鹏飞等;《南华大学学报（自然科学版）》;20140630;第28卷(第2期);第94-98、108页 * |
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