CN109721968A - The functional agglomerate and preparation method thereof of the hybridization porous material containing hyperbranched type - Google Patents
The functional agglomerate and preparation method thereof of the hybridization porous material containing hyperbranched type Download PDFInfo
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- CN109721968A CN109721968A CN201811527106.1A CN201811527106A CN109721968A CN 109721968 A CN109721968 A CN 109721968A CN 201811527106 A CN201811527106 A CN 201811527106A CN 109721968 A CN109721968 A CN 109721968A
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Abstract
The present invention relates to functional agglomerates of the hybridization porous material containing hyperbranched type and preparation method thereof, by the hybridization porous material of the hyperbranched type of polymeric matrix material and metal ion and other components after mixing melting extrusion be made the hybridization porous material containing hyperbranched type functional agglomerate, the hybridization porous material of hyperbranched type of metal ion is porous microsphere, is nucleated by hyperbranched type hybrid and carries out pore-creating again after growth forms microballoon and is made；The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ions Mn+It constitutes, the value range of n is 1~3, the carboxyl in molecule A, amido and metal ions M in molecule Bn+Between by ionic bond and the bonded formation triangle bonding structure of coordinate bond, structural formula it is as follows:
Description
Technical field
The invention belongs to functional agglomerate technical field, it is related to the functional agglomerate and its system of the hybridization porous material containing hyperbranched type
Preparation Method.
Background technique
Master batch, alias masterbatch are a kind of processing aids, be function additive super quantity be attached to it is manufactured dense in resin
Contracting body.People are typically without and corresponding function auxiliary agent are added when preparing multifunctional polymer product, and need to only be added and contain accordingly
The multifunctional concentrate of function additive.Thus, it is that world today's function additive is applied and the most important shape of polymer modification
One of formula, have the characteristics that simple process, it is easy to use, be easy to implement production automation and productivity is high.
For dissaving polymer such as hyper-branched polyester etc. due to similar with the polymeric matrixs structure such as polyester, compatibility is good, this
Outside, with highly branched molecular structure, it is a kind of ideal functional modification carrier, is answered at present in polymer blended field
With extensive, such as hyper-branched polyester is blended with fire retardant, but polymer of the Hyperbranched polymers as low molecular weight, universal
There are easy to migrate, heat fusing temperature is low, Yi Liudong and is difficult to and thermoplastic polymer melt processing temperature section is matched asks
Topic, greatly affected the processing performance of product.Therefore, it reduces the mobility of Hyperbranched polymers while improving its heat fusing
Temperature etc. is of great significance with improving its processing performance.
Metal ion load is a kind of common dissaving polymer modified method, in particular to by chemical bond or object
Metal ion is keyed on carrier molecule hyperbranched type metal hybrid material is made by the effect of reason key, this technology has been now
It is widely applied to metal ion adsorption material, catalysis material, self assembly unit, anti-biotic material and fire proofing etc., is carried
The groups such as hydroxyl, amido and carboxyl in body molecule have good chelation to metal ion, effectively can adsorb or catch
Collect metal ion (functional ion) to realize functional modification.Although however dissaving polymer and metallic ion coordination are obtained
The organic-inorganic hybrid material arrived approximate inorganic particulate, but the current hyperbranched poly for preparing loaded metal ion to a certain extent
Closing the solvent that object uses is mostly organic solvent, unfriendly to environment, in addition, synthesizing the hyperbranched of loaded metal ion obtained
Polymer is difficult to reach nanoscale dispersion in low polar polymer matrix, and this greatly limits it in aqueous polymerization object material
Material molding such as the application in the molding fibre modification of solution-polymerized SBR.
In addition, the type and form of current hyperbranched type metal hybrid material are less, only have the function of mostly one such as
Fire-retardant or antibacterial etc. can not have both multiple functions such as simultaneously while have fire-retardant, antibacterial, deodorization and adsorption function.In application
Multiple material need to be added, cost is increased.
Therefore, a kind of functional agglomerate and preparation method thereof with multiple functions is developed to have a very important significance.
Summary of the invention
The purpose of the invention is to overcome above-mentioned problems of the prior art, a kind of fire-retardant, antibacterial, deodorization are provided
The hybridization porous material containing hyperbranched type functional agglomerate and preparation method thereof
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
The functional agglomerate of the hybridization porous material containing hyperbranched type, mainly by polymeric matrix and being dispersed in polymer matrix
The hybridization porous material composition of the hyperbranched type of metal ion in body, the hybridization porous material of hyperbranched type of metal ion are
Porous microsphere, is nucleated by hyperbranched type hybrid and carries out pore-creating again after growth forms microballoon and be made；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ions Mn+It constitutes, the value model of n
Enclose is 1~3；
Molecule A is the carboxylic hyperbranched polymer molecule of end group；
Molecule B is the chain molecule with amido；
Carboxyl in molecule A, the amido in molecule B and metal ions Mn+Between by ionic bond and coordinate bond it is bonded formed three
Angular bonding structure, structural formula are as follows:
In formula, R is cation group, anionic group or polar nonionic group.
The hybridization porous material of hyperbranched type of metal ion of the invention, the carboxyl in molecule A, the amido in molecule B
And metal ions Mn+Between by ionic bond and bonded the is formationed triangle bonding structure of coordinate bond, molecule B can reach to molecule A modification
Effect, improve its hydrophilicity, be nucleated and grown aqueous dispersion during the microballoon of formation by hyperbranched type hybrid
Particle is less likely to occur to reunite, to ensure that the size of the porous microsphere of generation, while guaranteeing that it can have both absorption, remove
Smelly, fire-retardant and antibacterial functions, therefore fire-retardant, antibacterial, the function of deodorization mother can be made after being dispersed in polymeric matrix
Grain.
As a preferred technical scheme:
The functional agglomerate of the hybridization porous material containing hyperbranched type as described above, by the hybridization porous material containing hyperbranched type
The hybridization porous material content of hyperbranched type of metal ion made from functional agglomerate is that the limit oxygen of 0.5~10wt% fiber refers to
Number is 30~33%, through 50 washings front and rear to the bacteriostasis rate of staphylococcus aureus be respectively 85~90% and 80~
87%, through being respectively 90~95% and 80~85% to the bacteriostasis rate of Escherichia coli before and after 50 washings, to ammonia, acetic acid and
The adsorption rate of isovaleric acid is respectively 85~95%, 90~92% and 92~98%.
The functional agglomerate of the hybridization porous material containing hyperbranched type as described above, Mn+For Ag+、Fe2+、Fe3+、Au3+、Cr3+、
Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+It or is trivalent rare earth ion；Species of metal ion of the invention is not limited to
This, only enumerates the feasible species of metal ion in part herein；
In molecule A and molecule B, the sum of carboxyl-content, amine groups content and hydroxy radical content are the mole of molecule A and molecule B
The sum of 130%~170%；
Greatly by the bonded carboxyl of ionic bond and coordinate bond and by the sum of bonded amine groups content of ionic bond and coordinate bond
In equal to the 20% of the sum of carboxyl in molecule A and molecule B and amido mole；
In molecule A and molecule B, carboxyl, amido and hydroxyl are all hydrophilic radicals, and carboxyl and amido are to participate in forming three again
The group of angular bonding structure, in molecule A and molecule B, the sum of carboxyl-content, amine groups content and hydroxy radical content are too small, are unfavorable for
Triangle bonding structure is formed, carboxyl will overcome many obstacles with amido in conjunction with, such as entanglement effect power between strand, divide
Repulsive force between son etc., only quantity reache a certain level, and just can guarantee that carboxyl and amido can overcome obstacle to combine, into
And triangle bonding structure is formed in conjunction with metal ion, and in molecule A and molecule B, carboxyl-content, amine groups content and hydroxy radical content
The sum of it is excessive, be easy to bring the difficulty of production and processing, when hydrophilic radical reaches a certain level, participation formed triangle bonding
The hydrophilic radical of structure accounts for that overall ratio is smaller, i.e., by the bonded carboxyl of ionic bond and coordinate bond and by ionic bond and
20% of the sum of bonded amine groups content of coordinate bond less than the sum of carboxyl in molecule A and molecule B and amido mole, hyperbranched type
Hybrid is easily dissolved in water, can not be separated；
Greatly by the bonded carboxyl of ionic bond and coordinate bond and by the sum of bonded amine groups content of ionic bond and coordinate bond
In equal to the 20% of the sum of carboxyl in molecule A and molecule B and amido mole；
The quantity of carboxyl end group accounts for the 25%~100% of end group total amount in molecule A, and the degree of branching of molecule A is 30%~
100%, relative molecular weight is 1100~50000g/mol, and other than the O of carboxyl, molecule A is mainly made of C and H；
Relative molecular weight≤5000g/mol of molecule B, other than the N of amido, molecular backbone is mainly made of C and H.
The functional agglomerate of the hybridization porous material containing hyperbranched type as described above, the trivalent rare earth ion are La3+、
Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+；
The cation group is tertiary amine base or quaternary ammonium group, and the anionic group is carboxylic acid group, the polar nonionic
Group is hydroxyl, ether, amido, amide groups, sulfydryl or halogen；
The amido bonded by ionic bond and coordinate bond is located at the main chain or branch of molecule B, and the molecule B also includes
Hydroxy or carboxy, the molecular backbone of the molecule B further include element O or N, and the molecule A also contains element P, O or N.Molecule A
It is not limited to that with the molecule B element species for including and group, also may include other elements or other groups, as long as can
Guarantee the carboxyl in molecule A, amido and metal ions M in molecule Bn+Between to form triangle bonding structure firm.This hair
Carbon yield is much higher than at the load capacity of the metal ion of the hybridization porous material of hyperbranched type of bright metal ion and 600 DEG C
The prior art.
The hyperbranched type of the functional agglomerate of the hybridization porous material containing hyperbranched type as described above, the metal ion is miscellaneous
The load capacity for changing metal ion in porous material is 70~1700mg/g；
The aperture of the hybridization porous material of hyperbranched type of metal ion is 40~100nm, and porosity is 40%~60%；
The initial decomposition temperature of the hybridization porous material of hyperbranched type of metal ion is residual at 340~380 DEG C, 600 DEG C
Charcoal rate is 50~65wt%.
The functional agglomerate of the hybridization porous material containing hyperbranched type as described above, the function of the hybridization porous material containing hyperbranched type
Energy master batch is by the polymeric matrix of 51~81wt%, the hybridization porous material of hyperbranched type of the metal ion of 10~40wt%, 2
The dispersing agent of~6wt% and the antioxidant composition of 1~3wt%；
The material of the polymeric matrix is PET, PA6 or PLA；
The dispersing agent is one or more of polyethylene wax, calcium stearate and zinc stearate；
The antioxidant is 2,4- bis--(n-octylthiomethylene) -6- methylphenol or (the dodecyl sulphur first of 2,4- bis-
Base).
The hyperbranched type of the functional agglomerate of the hybridization porous material containing hyperbranched type as described above, the metal ion is miscellaneous
Change porous material the preparation method comprises the following steps: the substance of A containing molecule is mixed in the form of powder with the aqueous solution of the B substance containing molecule, it is mixed
Stirring is accompanied by when conjunction, then metal salt solution is added dropwise into mixed system, and when dropwise addition accompanies by stirring, and it is micro- that hyperbranched type hybrid is made
Ball, hyperbranched type hybrid microballoon are heat-treated the hybridization porous material of hyperbranched type that metal ion is made through 140~230 DEG C,
Wherein, the metal ion in metal salt solution is Mn+；The prior art for preparing triangle bonding structure at present is mostly to have well
Water-soluble natural polymer matrix system, it is to have that dissaving polymer system, which takes long time and can be used solvent in the presence of dissolution,
The problem of solvent (tetrahydrofuran and ethyl alcohol etc.), the present invention, which forms the main difficulty of triangle bonding structure, to be had two: one, is suitable
Dicyandiamide solution, two, molecule B and molecule A reaction after structure still need to metal coordination ability.The present invention selects environmentally protective
Water as solvent, selecting the molecule B of carboxylic molecule A and amino-contained, the substance of the B containing molecule contains largely as reactant
Amido, dissolubility is preferable, can comparatively fast dissolve, and the amido reaction in molecule A in carboxyl and molecule B, which generates, has metal coordination
Then the intermediate of ability is added metal salt solution and carries out metal coordination, forms triangle bonding structure.The substance of A containing molecule is
Carboxylate, poor water resistance, its ester bond is easily degraded when being exposed in wet environment, therefore it is protected mostly in the form of powder
It deposits, the addition form of the substance of A containing molecule is also not limited to powder in the present invention, other forms for not influencing its performance can also fit
With.The substance of A containing molecule is difficult to be directly dissolved in water, is only dissolve in the organic solvents such as DMSO, DMF, when the substance of A containing molecule
Dissolution is mixed with the solution of the B substance containing molecule again after forming solution in organic solvent, due to energy between organic solvent and molecule B
High forces are enough generated, thus is unfavorable for molecule A and molecule B and forms ionic bond, and then be unfavorable for forming triangle bonding structure.
The present invention changes it by carrying out the porous hybrid material that nanoscale has been made in heat treatment to hyperbranched type hybrid microballoon
Aggregated structure imparts the functions such as the distinctive absorption of product porous material and deodorization, has widened the application of material.Of the invention
Heat treatment temperature is excessively high, can destroy the bonding of other organic covalent bonds, so that the flame retardant property of functional material is reduced, heat treatment temperature
It spends low, it is difficult to destroy the short chain molecule with amido to obtain porous hybrid material；
The concentration of the aqueous solution of the B substance containing molecule is 0.3~0.58mol/L；The aqueous solution of the B substance containing molecule it is dense
Degree can carry out appropriate adjustment, but should not too, excessive concentration, it is difficult to the additive amount of the aqueous solution of accurate control B substance containing molecule,
It is be easy to cause the excessive addition of B substance containing molecule, and complexation reaction can occur with metal salt solution and generate precipitating by molecule B, thus shadow
The separation of substance is rung, concentration is too low, and excessively slow with bit rate, yield in unit time is too low, greatly affected economic benefit；
In the mixed system, the molar ratio of the substance of A containing molecule and the B substance containing molecule is 1:2~7；The substance of A containing molecule with
The molar ratio of the B substance containing molecule can carry out appropriate adjustment, but should not too, and molar ratio is excessively high, and B substance containing molecule is be easy to cause to add
Add excess, and complexation reaction can occur with metal salt solution and generate precipitating to influence the separation of substance by molecule B, molar ratio is too low
So that the amount deficiency that carboxyl is reacted with amido, the water-soluble of system reduce, dispersibility is deteriorated for meeting；
The concentration of the metal salt solution is 0.4~1.2mol/L, the metal salt total amount of addition and rubbing for the substance of A containing molecule
You are than being 1:2~6；Metal salt solution concentration and the metal salt total amount of addition and the molar ratio of the substance of A containing molecule can carry out suitably
Adjustment, but too should not will affect the dispersibility of metal salt in a polymer matrix as molar ratio is too high (dispersibility is deteriorated)；
The stirring rate of all stirrings is 300~400rpm, and suction filtration separation is carried out after the completion of dropwise addition, and suction filtration separates
To filter cake temperature be 25~30 DEG C, vacuum degree be -0.09~-0.1MPa under conditions of be dried in vacuo 8~12h；
The atmosphere of the heat treatment is air, and the time of the heat treatment is 40~50min, the heating before the heat treatment
Rate is 15~20 DEG C/min；It is heat-treated under the atmosphere containing oxygen, short chain molecule is easier that the disconnected of molecular link occurs
It splits.Heat treatment time is too long or heating rate is excessively slow, may part other organic covalent bonds bonding, to reduce function material
The flame retardant property of material；Heat treatment time is too short or heating rate it is too fast be difficult to destroy the short chain molecule with amido it is porous to obtain
Hybrid material；
The B substance containing molecule is selected from alkyl streptamine, polyetheramine D230, polyetheramine D400, polyethers of the chain length less than 6 carbon
Amine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-
1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205,
One of aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；The metal salt solution is
AgNO3、FeCl2、FeCl3、HAuCl4、Cr2(SO4)3、ZnCl2、PtCl2、PdCl2、CuSO4、Ni(NO3)2Or CdCl2Aqueous solution
It or is rare earth metal salt solutions.Water can be prepared in the hydrophilic short molecular chain of molecule B in conjunction with molecule A and metal ion
Property discrete particles, ensure that particle is not reunited when preparing hyperbranched type hybrid porous microsphere (including prepare and dry), this
Sample ensure that the size of final porous microsphere；
The functional agglomerate of the hybridization porous material containing hyperbranched type as described above, alkyl chain of the chain length less than 6 carbon
Amine is n-propylamine, n-butylamine, n-amylamine or n-hexylamine；The rare earth metal salt solutions are LaCl3、Ce2(SO4)3、Eu(NO3)3、
ErCl3、YbCl3、Tm(NO3)3、Ho(NO3)3Or Pr (NO3)3Aqueous solution；
The substance of A containing molecule is to utilize A2+B3Made from synthetic method, A2For containing two reactive groups and at least one of
A monomer for carboxyl, B3For the monomer containing three reactive hydroxyl groups；
The A2For pyrazine -2,3- dicarboxylic acids, 2- carboxyethyl phenyl phosphinic acid, 5- tert-butyl -1,3- benzene dicarboxylic acid or 2-
Carboxyethyl phosphoric acid, the B3For 1,1,1- tri- (methylol) propane, three (2- ethoxy) chlorinated isocyanurates, 2,4,5- trihydroxy benzene
Butanone, 2,3,4- trihydroxy-acetophenone or 1,2,4- trihydroxy benzene.The preparation method and its original of the substance of the A containing molecule of the invention
Material is not limited to that, as long as its product has the molecule A for meeting structural requirements.A is only enumerated herein2And B3Part can
The substance of energy, A of the invention2And B3It is not limited to that, other substances that the substance of A containing molecule can be made may be applicable to this
Invention.
The present invention also provides the methods for preparing the functional agglomerate of the hybridization porous material containing hyperbranched type as described above, will gather
Close the hybridization porous material of hyperbranched type and other components of object basis material and metal ion melting extrusion system after mixing
The functional agglomerate of the hybridization porous material of hyperbranched type must be contained.
As a preferred technical scheme:
Method as described above, the polymeric matrix material before being uniformly mixed first at 100~120 DEG C dry 1h~
2h, described be uniformly mixed is realized by mixing 30~40min in super mixer；
The material of polymeric matrix when being polyester, polyamide and polylactic acid corresponding melting extrusion temperature be 220~
290 DEG C, 230~290 DEG C and 150~180 DEG C.
Invention mechanism:
The present invention is first with B substance containing molecule (small molecule that molecule B is amino-contained) to dissaving polymer (A containing molecule
Substance) it is modified, the water solubility of dissaving polymer is on the one hand improved due to introducing hydrophilic radical-amido, favorably
In the progress of next step reaction, another aspect molecule B is the small molecule of low pole, and low pole molecule B is grafted to hyperbranched poly
On adduct molecule, followed by the coordination of carboxyl and amido and metal ion, metal ion is introduced into dissaving polymer
The stable triangle bonding structure of middle formation obtains the hyperbranched type hybrid material of metal ion, by introducing metal ion,
The thermal stability of dissaving polymer is greatly improved, so that dissaving polymer of the invention, which has, does not influence conventional matrix
The characteristic of melt-processed significantly improves its processing performance, overcomes when prior art dissaving polymer is blended and is processed into
The hybridization porous material of hyperbranched type of metal ion is made finally by heat treatment pore-creating for the problem of type difficulty, heat treated
Cheng Zhong, since the thermal stability of the strand of the small molecule of amino-contained is poorer than unmodified preceding dissaving polymer, heated
Under be degraded to gaseous material volatilization so that hybrid material by solid microsphere variation be porous microsphere, the present invention by heat treatment exists
Pore-creating on the hyperbranched type hybrid material of metal ion, changes its aggregated structure, it is peculiar to impart product porous material
The good characteristic of absorption property, widened the application of material, effectively prevented the generation of its agglomeration in process, have
Conducive to the size for the porous microsphere that control generates, guarantee dispersibility of the porous microsphere in the matrixes such as polyester.
In addition, the metal ion contained in the hybridization porous material of hyperbranched type of metal ion of the invention is to macromolecular
Chemical reactions, that is, the chain degradation such as dehydrogenation and deoxidation in thermal degradation process and cross-linking process have catalytic action, can play raising
The carbon yield of material, the effect for reducing combustion process Thermal feedback and flue gas release, and stable triangle bonding junction of the invention
Structure can further improve the catalytic action of metal ion, improve the flame retardant property of product.
The mechanism that the stable triangle bonding structure of the present invention is formed is as follows: the amido in carboxyl and molecule B in molecule A
In conjunction with complex is formed, complex ionizes generation-COO-With-NH3 +,-COO-With-NH3 +Because of the attraction of positive and negative charge, generate
Electrostatic attraction forms ionic bond, due to-COO-In oxygen on have lone pair electrons, therefore lone pair electrons enter metal ion
Unoccupied orbital forms coordinate bond, due to-NH in conjunction with metal ion generation covalent coordinate3 +In N atom there is also lone pair electrons,
It is equally capable of providing lone pair electrons to be formed in conjunction with coordinate bond with metal ion, therefore forms the stable triangle in structural formula
Bonding structure.
When the present invention prepares functional agglomerate using the hybridization porous material of hyperbranched type of metal ion, metal ion
The high porosity of the hyperbranched hybridization porous material of type can assign master batch excellent deodorization functions, the hyperbranched type of metal ion
The functional elements such as the metal ion and P, N that contain in hybridization porous material can assign master batch excellent flame retardant property, simultaneously
Metal ion can also impart to the excellent bactericidal property of master batch, and therefore, final obtained master batch has excellent fire-retardant, anti-simultaneously
Bacterium, deodorization function.
The utility model has the advantages that
(1) functional agglomerate of the hybridization porous material containing hyperbranched type, the hybridization porous material of hyperbranched type of metal ion,
It is able to achieve nanoscale dispersion in polyester matrix and metal ion load capacity is adjustable, thermal stability is good, and processing performance is good, absorption
Performance is good, while having both fire-retardant, antibacterial and deodorization functions, therefore master batch obtained has excellent fire-retardant, antibacterial and deodorization function
Energy；
(2) preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, it is nontoxic using water as reaction dissolvent
It is harmless, it is environmentally protective；
(3) preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, equipment investment is less, operating process letter
Single easy to implement, experiment condition is mild, low in cost, great market prospects.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Formula (I) is the carboxyl in the molecule A in the hybridization porous material of hyperbranched type of metal ion, the amine in molecule B
Base and metal ions Mn+Between pass through the triangle bonding structure of ionic bond and the bonded formation of coordinate bond, wherein R is tertiary amine base, season
Ammonium, carboxylic acid group, hydroxyl, ether, amido, amide groups, sulfydryl or halogen, the group that R is represented are corresponding with molecule B；
Molecule A is the carboxylic hyperbranched polymer molecule of end group；
Molecule B is the chain molecule with amido；
In molecule A and molecule B, the sum of carboxyl-content, amine groups content and hydroxy radical content are the mole of molecule A and molecule B
The sum of 130%~170%；
The quantity of carboxyl end group accounts for the 25%~100% of end group total amount, the degree of branching of molecule A in molecule A in following embodiment
It is 30%~100%, relative molecular weight is 1100~50000g/mol, and other than the O of carboxyl, molecule A is mainly by C and H structure
At；
Relative molecular weight≤5000g/mol of molecule B, other than the N of amido, molecular backbone is mainly made of C and H.
Embodiment 1
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
Pyrazine -2, the 3- dicarboxylic acids and 1 for being 1:1 by molar ratio, 1,1- tri- (methylol) propane are 150 DEG C in temperature, nitrogen
Esterification 1h is carried out under gas shielded, is then 200 DEG C in temperature, pressure vacuumizes carry out polycondensation reaction under conditions of being 0MPa
The substance of A containing molecule is made in 4h, wherein needs to be stirred during esterification and polycondensation reaction, the rate of stirring is
200rpm；
(2) substance of A containing molecule made from step (1) (is contained with concentration for the n-propylamine of 0.3mol/L in the form of powder
Molecule B substance) aqueous solution mixing, when mixing, accompanies by stirring, then concentration is added dropwise as the AgNO of 0.4mol/L into mixed system3
Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filter isolated filter cake temperature be 25 DEG C,
Vacuum degree is dried in vacuo 8h under conditions of being -0.09MPa, hyperbranched type hybrid microballoon is made, wherein in mixed system, contain
The molar ratio of molecule A substance and n-propylamine is 1:2, the AgNO of addition3Total amount and the molar ratio of the substance of A containing molecule are 1:2, mixing
And stirring rate when being added dropwise is 300rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 140 DEG C 40min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 20 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ion Ag+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 20% of the sum of carboxyl and amido mole in B, carboxyl, the amido in molecule B and metal ion Ag in molecule A+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 70mg/g in the hybridization porous material of hyperbranched type of final metal ion obtained,
The aperture of the hybridization porous material of hyperbranched type of metal ion is 90~100nm, porosity 40%, initial decomposition temperature
It is that carbon yield is 50wt% at 340 DEG C, 600 DEG C；
(4) PET powder is dried to 1.5h at 110 DEG C first, then by PET powder, the hyperbranched type of metal ion
Hybridization porous material, polyethylene wax and 2,4- bis--(n-octylthiomethylene) -6- methylphenol mix in super mixer
35min realizes the uniform mixing of each component, each component content when preparing functional agglomerate are as follows: the PET powder of 75wt%, 20wt%
2,4- bis--(the n-octyl sulphur methylene of the hybridization porous material of hyperbranched type of metal ion, the polyethylene wax of 2wt% and 3wt%
Base) -6- methylphenol, mixed each component is made in 250 DEG C of at a temperature of melting extrusion finally and contains hyperbranched type hydridization
The functional agglomerate of porous material.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PET fiber that material content is 5wt% is 32%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate is respectively 87% and 84%, right through being respectively 93% and 83% to the bacteriostasis rate of Escherichia coli before and after 50 washings
The adsorption rate of ammonia, acetic acid and isovaleric acid is respectively 90%, 91% and 95%.
Embodiment 2
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
It in temperature is 180 by 2- carboxyethyl phenyl phosphinic acid that molar ratio is 1:2 and three (2- ethoxy) chlorinated isocyanurates
DEG C, esterification 2h is carried out under nitrogen protection, is then 180 DEG C in temperature, pressure vacuumizes progress under conditions of being -0.1MPa
The substance of A containing molecule is made in polycondensation reaction 3h, wherein needs to be stirred during esterification and polycondensation reaction, the rate of stirring
For 300rpm；
(2) substance of A containing molecule made from step (1) (is contained with concentration for the n-butylamine of 0.58mol/L in the form of powder
Molecule B substance) aqueous solution mixing, when mixing, accompanies by stirring, then concentration is added dropwise as the FeCl of 1.2mol/L into mixed system2
Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filter isolated filter cake temperature be 30 DEG C,
Vacuum degree is dried in vacuo 12h under conditions of being -0.1MPa, hyperbranched type hybrid microballoon is made, wherein in mixed system, contain
The molar ratio of molecule A substance and n-butylamine is 1:7, the FeCl of addition2Total amount and the molar ratio of the substance of A containing molecule are 1:6, mixing
And stirring rate when being added dropwise is 400rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 230 DEG C 50min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 15 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal cations Fe2+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 25% of the sum of carboxyl and amido mole in B, the carboxyl in molecule A, amido and metal cations Fe in molecule B2+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 1700mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 40~50nm, and porosity 60%, starting is decomposed warm
Degree is that carbon yield is 65wt% at 380 DEG C, 600 DEG C；
(4) PET powder is dried to 1h at 100 DEG C first, it is then that the hyperbranched type of PET powder, metal ion is miscellaneous
Change porous material, calcium stearate and 2,4- bis--(n-octylthiomethylene) -6- methylphenol to mix in super mixer
30min realizes the uniform mixing of each component, each component content when preparing functional agglomerate are as follows: the PET powder of 81wt%, 10wt%
2,4- bis--(the n-octyl sulphur methylene of the hybridization porous material of hyperbranched type of metal ion, the calcium stearate of 6wt% and 3wt%
Base) -6- methylphenol, mixed each component is made in 220 DEG C of at a temperature of melting extrusion finally and contains hyperbranched type hydridization
The functional agglomerate of porous material.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PET fiber that material content is 0.5wt% is 30%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate be respectively 85% and 80%, through being respectively 90% and 80% to the bacteriostasis rate of Escherichia coli before and after 50 washings,
Adsorption rate to ammonia, acetic acid and isovaleric acid is respectively 85%, 92% and 92%.
Embodiment 3
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
By molar ratio be 1:3 5- tert-butyl -1,3- benzene dicarboxylic acid and 2,4,5- trihydroxybutyrophenone in temperature be 160
DEG C, esterification 1.5h is carried out under nitrogen protection, is then 190 DEG C in temperature, pressure vacuumizes under conditions of being -0.05MPa
It carries out polycondensation reaction 2h and the substance of A containing molecule is made, wherein need to be stirred during esterification and polycondensation reaction, stirring
Rate is 400rpm；
(2) by the substance of A containing molecule made from step (1) in the form of powder and concentration for 0.49mol/L polyetheramine
The aqueous solution of D230 (B substance containing molecule) mixes, and when mixing accompanies by stirring, then it is 0.8mol/L that concentration, which is added dropwise, into mixed system
FeCl3Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filter isolated filter cake in temperature
It is dried in vacuo 10h under conditions of being -0.095MPa for 27 DEG C, vacuum degree, hyperbranched type hybrid microballoon is made, wherein mixing
In system, the molar ratio of the substance of A containing molecule and polyetheramine D230 are 1:5, the FeCl of addition3Total amount is rubbed with the substance of A containing molecule
Stirring rate when you are than being 1:4, mixing and dropwise addition is 350rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 200 DEG C 45min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 18 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal cations Fe3+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 22% of the sum of carboxyl and amido mole in B, the carboxyl in molecule A, amido and metal cations Fe in molecule B3+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 700mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 60~70nm, and porosity 45%, starting is decomposed warm
Degree is that carbon yield is 56wt% at 365 DEG C, 600 DEG C；
(4) PET powder is dried to 2h at 120 DEG C first, it is then that the hyperbranched type of PET powder, metal ion is miscellaneous
Change porous material, zinc stearate and 2,4- bis--(n-octylthiomethylene) -6- methylphenol to mix in super mixer
40min realizes the uniform mixing of each component, each component content when preparing functional agglomerate are as follows: the PET powder of 57wt%, 40wt%
2,4- bis--(the n-octyl sulphur methylene of the hybridization porous material of hyperbranched type of metal ion, the zinc stearate of 2wt% and 1wt%
Base) -6- methylphenol, mixed each component is made in 290 DEG C of at a temperature of melting extrusion finally and contains hyperbranched type hydridization
The functional agglomerate of porous material.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PET fiber that material content is 10wt% is 33%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate be respectively 90% and 87%, through being respectively 95% and 85% to the bacteriostasis rate of Escherichia coli before and after 50 washings,
Adsorption rate to ammonia, acetic acid and isovaleric acid is respectively 95%, 92% and 98%.
Embodiment 4
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
The 2- carboxyethyl phosphoric acid and 2 for being 1:1.5 by molar ratio, 3,4- trihydroxy-acetophenones are 200 DEG C in temperature, and nitrogen is protected
Shield is lower to carry out esterification 3h, is then 210 DEG C in temperature, pressure vacuumizes carry out polycondensation reaction under conditions of being -0.1MPa
The substance of A containing molecule is made in 2.5h, wherein needs to be stirred during esterification and polycondensation reaction, the rate of stirring is
500rpm；
(2) by the substance of A containing molecule made from step (1) in the form of powder and concentration for 0.4mol/L polyetheramine T403
The aqueous solution of (B substance containing molecule) mixes, and when mixing accompanies by stirring, then it is 0.6mol/L's that concentration, which is added dropwise, into mixed system
CuSO4Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filtering isolated filter cake in temperature is
28 DEG C, vacuum degree be -0.09MPa under conditions of be dried in vacuo 8h, hyperbranched type hybrid microballoon is made, wherein mixed system
In, the molar ratio of the substance of A containing molecule and polyetheramine T403 are 1:7, the CuSO of addition4The molar ratio of total amount and the substance of A containing molecule
For 1:2, stirring rate when mixing and being added dropwise is 300rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 150 DEG C 48min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 15 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ion Cu2+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 21% of the sum of carboxyl and amido mole in B, carboxyl, the amido in molecule B and metal ion Cu in molecule A2+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 510mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 60~80nm, and porosity 49%, starting is decomposed warm
Degree is that carbon yield is 56wt% at 350 DEG C, 600 DEG C；
(4) PA6 powder is dried to 2h at 100 DEG C first, it is then that the hyperbranched type of PA6 powder, metal ion is miscellaneous
Change porous material, dispersing agent (mixture of polyethylene wax and calcium stearate mass ratio 1:1) and 2,4- bis--(n-octyl sulphur methylene
Base) -6- methylphenol mixed in super mixer 35min realize each component uniform mixing, each group when preparing functional agglomerate
Divide content are as follows: the dispersion of the PA6 powder, hyperbranched the type hybridization porous material, 6wt% of the metal ion of 40wt% of 51wt%
2,4- bis--(n-octylthiomethylene) -6- methylphenol of agent and 3wt%, the finally temperature by mixed each component at 290 DEG C
Spend the functional agglomerate that the hybridization porous material containing hyperbranched type is made in lower melting extrusion.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PA6 fiber that material content is 2wt% is 31%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate is respectively 85% and 80%, right through being respectively 90% and 80% to the bacteriostasis rate of Escherichia coli before and after 50 washings
The adsorption rate of ammonia, acetic acid and isovaleric acid is respectively 85.5%, 90.5% and 92%.
Embodiment 5
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
By molar ratio be 1:2.5 2- carboxyethyl phenyl phosphinic acid and 1,2,4-trihydroxybenzene in temperature be 220 DEG C, nitrogen
Protection is lower to carry out esterification 1h, is then 220 DEG C in temperature, pressure vacuumizes carry out polycondensation reaction under conditions of being 0MPa
The substance of A containing molecule is made in 1.5h, wherein needs to be stirred during esterification and polycondensation reaction, the rate of stirring is
250rpm；
(2) by the substance of A containing molecule made from step (1) in the form of powder and concentration for 0.5mol/L fatty amine polyoxy
The aqueous solution of vinethene AC-1810 (B substance containing molecule) mixes, and when mixing accompanies by stirring, then concentration is added dropwise into mixed system
For the PdCl of 1.2mol/L2Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filter isolated
Filter cake is dried in vacuo 8h under conditions of temperature is 30 DEG C, vacuum degree is -0.1MPa, and hyperbranched type hybrid microballoon is made,
In, in mixed system, the molar ratio of the substance of A containing molecule and aliphatic amine polyoxyethylene ether AC-1810 are 1:3, the metal salt of addition
Stirring rate when total amount and the molar ratio of the substance of A containing molecule are 1:6, mixing and dropwise addition is 300rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 160 DEG C 50min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 18 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ion Pd2+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 23% of the sum of carboxyl and amido mole in B, carboxyl, the amido in molecule B and metal ion Pd in molecule A2+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 400mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 45~55nm, and porosity 44%, starting is decomposed warm
Degree is that carbon yield is 53wt% at 360 DEG C, 600 DEG C；
(4) PA6 powder is dried to 2h at 120 DEG C first, it is then that the hyperbranched type of PA6 powder, metal ion is miscellaneous
Change porous material, dispersing agent (mixture of polyethylene wax, calcium stearate and zinc stearate mass ratio 1:1:1) and 2,4- bis- (ten
Dialkyl group sulfidomethyl) the uniform mixing that 35min realizes each component, each component when preparing functional agglomerate are mixed in super mixer
Content are as follows: the PA6 powder of 70wt%, the hybridization porous material of hyperbranched type of the metal ion of 24wt%, 4wt% dispersing agent
With 2, the 4- bis- (dodecylthiomethyl) of 2wt%, finally the at a temperature of melting extrusion system by mixed each component at 230 DEG C
The functional agglomerate of the hybridization porous material of hyperbranched type must be contained.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PA6 fiber that material content is 4wt% is 32%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate is respectively 87% and 83%, right through being respectively 92% and 82% to the bacteriostasis rate of Escherichia coli before and after 50 washings
The adsorption rate of ammonia, acetic acid and isovaleric acid is respectively 87%, 91% and 93%.
Embodiment 6
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
It in temperature is 210 by 5- tert-butyl -1,3- benzene dicarboxylic acid that molar ratio is 1:1 and (methylol) propane of 1,1,1- tri-
DEG C, esterification 2.5h is carried out under nitrogen protection, is then 230 DEG C in temperature, pressure vacuumizes under conditions of being -0.05MPa
It carries out polycondensation reaction 2h and the substance of A containing molecule is made, wherein need to be stirred during esterification and polycondensation reaction, stirring
Rate is 350rpm；
(2) by the substance of A containing molecule made from step (1) in the form of powder and concentration for 0.3mol/L polyetheramine D400
The aqueous solution of (B substance containing molecule) mixes, and when mixing accompanies by stirring, then concentration is added dropwise as the Ni of 0.5mol/L into mixed system
(NO3)2Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filtering isolated filter cake in temperature is
25 DEG C, vacuum degree be -0.09MPa under conditions of be dried in vacuo 11h, hyperbranched type hybrid microballoon is made, wherein mixed system
In, the molar ratio of the substance of A containing molecule and polyetheramine D400 are 1:5, the Ni (NO of addition3)2Mole of total amount and the substance of A containing molecule
Than for 1:5, mixing and stirring rate when being added dropwise are 400rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 140 DEG C 50min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 15 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ion Ni2+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 24% of the sum of carboxyl and amido mole in B, carboxyl, the amido in molecule B and metal ion Ni in molecule A2+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 1320mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 45~60nm, and porosity 56%, starting is decomposed warm
Degree is that carbon yield is 60wt% at 380 DEG C, 600 DEG C；
(4) PLA powder is dried to 2h at 110 DEG C first, it is then that the hyperbranched type of PLA powder, metal ion is miscellaneous
Change porous material, polyethylene wax and 2,4- bis- (dodecylthiomethyl) and mixes 40min realization each component in super mixer
Uniform mixing, each component content when preparing functional agglomerate are as follows: the PLA powder of 65wt%, the metal ion of 30wt% it is super
2, the 4- bis- (dodecylthiomethyl) of the hybridization porous material of branching type, the polyethylene wax of 3wt% and 2wt%, finally will mixing
The functional agglomerate of the hybridization porous material containing hyperbranched type is made in 150 DEG C of at a temperature of melting extrusion in each component afterwards.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PLA fiber that material content is 5.5wt% is 32%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate be respectively 87.5% and 83%, through being respectively 92.5% He to the bacteriostasis rate of Escherichia coli before and after 50 washings
83%, the adsorption rate to ammonia, acetic acid and isovaleric acid is respectively 89%, 91.5% and 95%.
Embodiment 7
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
It in temperature is 155 DEG C by pyrazine -2,3- dicarboxylic acids that molar ratio is 1:3 and three (2- ethoxy) chlorinated isocyanurates,
Esterification 3h is carried out under nitrogen protection, is then 250 DEG C in temperature, and pressure vacuumizes under conditions of being -0.08MPa to contract
The substance of A containing molecule is made in poly- reaction 3.5h, wherein needs to be stirred during esterification and polycondensation reaction, the rate of stirring
For 450rpm；
(2) by the substance of A containing molecule made from step (1) in the form of powder and concentration for 0.48mol/L polyetheramine
The aqueous solution of T3000 (B substance containing molecule) mixes, and when mixing accompanies by stirring, then it is 0.9mol/ that concentration, which is added dropwise, into mixed system
Tm (the NO of L3)3Aqueous solution, when dropwise addition, accompany by stirring, carry out suction filtration separation after completion of dropwise addition, filter isolated filter cake in temperature
Degree is 28 DEG C, vacuum degree is dried in vacuo 8h under conditions of being -0.09MPa, and hyperbranched type hybrid microballoon is made, wherein mixing
In system, the molar ratio of the substance of A containing molecule and polyetheramine T3000 are 1:2, the Tm (NO of addition3)3Total amount and the substance of A containing molecule
Molar ratio is 1:6, and stirring rate when mixing and being added dropwise is 350rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 180 DEG C 40min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 20 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ion Tm3+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 20% of the sum of carboxyl and amido mole in B, carboxyl, the amido in molecule B and metal ion Tm in molecule A3+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 900mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 86~95nm, and porosity 43%, starting is decomposed warm
Degree is that carbon yield is 58wt% at 355 DEG C, 600 DEG C；
(4) PLA powder is dried to 2h at 120 DEG C first, it is then that the hyperbranched type of PLA powder, metal ion is miscellaneous
Change porous material, polyethylene wax and 2,4- bis- (dodecylthiomethyl) and mixes 30min realization each component in super mixer
Uniform mixing, each component content when preparing functional agglomerate are as follows: the PLA powder of 70wt%, the metal ion of 27wt% it is super
2, the 4- bis- (dodecylthiomethyl) of the hybridization porous material of branching type, the polyethylene wax of 2wt% and 1wt%, finally will mixing
The functional agglomerate of the hybridization porous material containing hyperbranched type is made in 180 DEG C of at a temperature of melting extrusion in each component afterwards.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PLA fiber that material content is 7.5wt% is 32.5%, through 50 washings front and rear to Staphylococcus aureus
The bacteriostasis rate of bacterium is respectively 88% and 84%, through being respectively 93% He to the bacteriostasis rate of Escherichia coli before and after 50 washings
84%, the adsorption rate to ammonia, acetic acid and isovaleric acid is respectively 91%, 91% and 96%.
Embodiment 8
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, the specific steps are as follows:
(1) substance of A containing molecule is prepared；
By molar ratio be 1:1.5 5- tert-butyl -1,3- benzene dicarboxylic acid and 2,3,4- trihydroxy-acetophenone in temperature be 150
DEG C, esterification 1h is carried out under nitrogen protection, is then 240 DEG C in temperature, pressure vacuumizes progress under conditions of being -0.1MPa
The substance of A containing molecule is made in polycondensation reaction 4h, wherein needs to be stirred during esterification and polycondensation reaction, the rate of stirring
For 200rpm；
(2) by the substance of A containing molecule made from step (1) in the form of powder and concentration for 0.4mol/L fatty amine polyoxy
The aqueous solution of vinethene AC-1812 (B substance containing molecule) mixes, and when mixing accompanies by stirring, then concentration is added dropwise into mixed system
For the Eu (NO of 0.6mol/L3)3Aqueous solution, when dropwise addition, accompany by stirring, and suction filtration separation is carried out after completion of dropwise addition, filter isolated
Filter cake temperature be 25 DEG C, vacuum degree be -0.1MPa under conditions of be dried in vacuo 12h, hyperbranched type hybrid microballoon is made,
Wherein, in mixed system, the molar ratio of the substance of A containing molecule and aliphatic amine polyoxyethylene ether AC-1812 are 1:2, the metal of addition
Salt Eu (NO3)3Stirring rate when total amount and the molar ratio of the substance of A containing molecule are 1:5, mixing and dropwise addition is 300rpm；
(3) hyperbranched type hybrid microballoon be heat-treated under conditions of air atmosphere, 170 DEG C 50min be made containing metal from
The hybridization porous material of hyperbranched type of son, the heating rate before heat treatment are 15 DEG C/min；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ion Eu3+It constitutes, wherein passing through
Ionic bond and the bonded carboxyl of coordinate bond and molecule A and molecule are equal to by the sum of bonded amine groups content of ionic bond and coordinate bond
The 21% of the sum of carboxyl and amido mole in B, carboxyl, the amido in molecule B and metal ion Eu in molecule A3+Between pass through
Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；
The load capacity of metal ion is 1410mg/ in the hybridization porous material of hyperbranched type of final metal ion obtained
G, the aperture of the hybridization porous material of hyperbranched type of metal ion are 60~70nm, and porosity 50%, starting is decomposed warm
Degree is that carbon yield is 55wt% at 355 DEG C, 600 DEG C；
(4) PLA powder is dried to 2h at 100 DEG C first, it is then that the hyperbranched type of PLA powder, metal ion is miscellaneous
Change porous material, calcium stearate and 2,4- bis- (dodecylthiomethyl) and mixes 40min realization each component in super mixer
Uniform mixing, each component content when preparing functional agglomerate are as follows: the PLA powder of 55wt%, the metal ion of 40wt% it is super
2, the 4- bis- (dodecylthiomethyl) of the hybridization porous material of branching type, the calcium stearate of 2wt% and 3wt%, finally will mixing
The functional agglomerate of the hybridization porous material containing hyperbranched type is made in 170 DEG C of at a temperature of melting extrusion in each component afterwards.
The hyperbranched type of the metal ion as made from the functional agglomerate of the hybridization porous material containing hyperbranched type is hybridization porous
The limit oxygen index for the PLA fiber that material content is 9wt% is 33%, through 50 washings front and rear to staphylococcus aureus
Bacteriostasis rate is respectively 89% and 86%, right through being respectively 94% and 84% to the bacteriostasis rate of Escherichia coli before and after 50 washings
The adsorption rate of ammonia, acetic acid and isovaleric acid is respectively 94%, 92% and 96%.
Embodiment 9~20
The preparation method of the functional agglomerate of the hybridization porous material containing hyperbranched type, step is substantially the same manner as Example 8, different
It is the type of the B substance containing molecule, the hybridization porous material of hyperbranched type of the type of metal salt solution and metal ion, most
The content of the hybridization porous material of hyperbranched type of metal ion and the various parameters of fiber, are specifically shown in Table in fiber made from end
1 and table 2, wherein the metal ion in the hybridization porous material structure formula of the hyperbranched type of metal ion is mentioned by metal salt solution
For Z is to pass through the bonded carboxyl of ionic bond and coordinate bond and the amine groups content the sum of bonded by ionic bond and coordinate bond in table
With the ratio of the sum of carboxyl in molecule A and molecule B and amido mole, unit %, load capacity is the over-expense of metal ion
The load capacity of metal ion in the hybridization porous material of change type, unit mg/g, aperture are the hyperbranched type hydridization of metal ion
The aperture of porous material, unit nm, porosity are the porosity of the hybridization porous material of hyperbranched type of metal ion, unit
For %, temperature is the initial decomposition temperature of the hybridization porous material of hyperbranched type of metal ion, and unit is DEG C, carbon yield be containing
The hybridization porous material of hyperbranched type of metal ion carbon yield, unit wt% at 600 DEG C.
The finally function of the hybridization porous material containing hyperbranched type of the hybridization porous material of hyperbranched type containing metal ion
The hybridization porous material content of hyperbranched type of metal ion made from energy master batch is that the limit oxygen index of Awt% fiber is B%,
Through being respectively C% and D% to the bacteriostasis rate of staphylococcus aureus before and after 50 washings, through 50 washings front and rear to large intestine
The bacteriostasis rate of bacillus is respectively E% and F%, and the adsorption rate to ammonia, acetic acid and isovaleric acid is respectively G%, H% and J%, A, B,
C, see Table 2 for details for the value of D, E, F, G, H and J.
Table 1
Table 2
Claims (10)
1. the functional agglomerate of the hybridization porous material containing hyperbranched type, it is characterized in that: mainly by polymeric matrix and being dispersed in
The hybridization porous material composition of the hyperbranched type of metal ion in polymeric matrix, the hyperbranched type hydridization of metal ion are more
Porous materials are porous microsphere, are nucleated by hyperbranched type hybrid and carry out pore-creating again after growth forms microballoon and are made；
The molecular structural formula of hyperbranched type hybrid is mainly by molecule A, molecule B and metal ions Mn+It constitutes, the value range of n is
1~3；
Molecule A is the carboxylic hyperbranched polymer molecule of end group；
Molecule B is the chain molecule with amido；
Carboxyl in molecule A, the amido in molecule B and metal ions Mn+Between pass through ionic bond and the bonded formation triangle of coordinate bond
Bonding structure, structural formula are as follows:
In formula, R is cation group, anionic group or polar nonionic group.
2. the functional agglomerate of the hybridization porous material according to claim 1 containing hyperbranched type, which is characterized in that by containing over-expense
The hybridization porous material content of hyperbranched type of metal ion made from the functional agglomerate of the hybridization porous material of change type be 0.5~
The limit oxygen index of the fiber of 10wt% is 30~33%, through dividing before and after 50 washings the bacteriostasis rate of staphylococcus aureus
Not Wei 85~90% and 80~87%, through before and after 50 washings to the bacteriostasis rate of Escherichia coli be respectively 90~95% and 80~
85%, the adsorption rate to ammonia, acetic acid and isovaleric acid is respectively 85~95%, 90~92% and 92~98%.
3. the functional agglomerate of the hybridization porous material according to claim 1 containing hyperbranched type, which is characterized in that Mn+For Ag+、
Fe2+、Fe3+、Au3+、Cr3+、Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+It or is trivalent rare earth ion；
In molecule A and molecule B, the sum of carboxyl-content, amine groups content and hydroxy radical content are the sum of molecule A and the mole of molecule B
130%~170%；
Be greater than by the bonded carboxyl of ionic bond and coordinate bond and by the sum of bonded amine groups content of ionic bond and coordinate bond etc.
The 20% of the sum of carboxyl and amido mole in molecule A and molecule B；
The quantity of carboxyl end group accounts for the 25%~100% of end group total amount in molecule A, and the degree of branching of molecule A is 30%~100%, phase
It is 1100~50000g/mol to molecular weight, other than the O of carboxyl, molecule A is mainly made of C and H；
Relative molecular weight≤5000g/mol of molecule B, other than the N of amido, molecular backbone is mainly made of C and H.
4. the functional agglomerate of the hybridization porous material according to claim 3 containing hyperbranched type, which is characterized in that described 3
Valence rare earth ion is La3+、Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+；
The cation group is tertiary amine base or quaternary ammonium group, and the anionic group is carboxylic acid group, the polar nonionic group
For hydroxyl, ether, amido, amide groups, sulfydryl or halogen；
The amido bonded by ionic bond and coordinate bond is located at the main chain or branch of molecule B, and the molecule B also includes hydroxyl
Or carboxyl, the molecular backbone of the molecule B further include element O or N, the molecule A also contains element P, O or N.
5. the functional agglomerate of the hybridization porous material according to claim 1 containing hyperbranched type, which is characterized in that described containing gold
The load capacity for belonging to metal ion in the hybridization porous material of hyperbranched type of ion is 70~1700mg/g；
The aperture of the hybridization porous material of hyperbranched type of metal ion is 40~100nm, and porosity is 40%~60%；
The initial decomposition temperature of the hybridization porous material of hyperbranched type of metal ion is carbon yield at 340~380 DEG C, 600 DEG C
For 50~65wt%.
6. the functional agglomerate of the hybridization porous material according to claim 1 containing hyperbranched type, which is characterized in that containing hyperbranched
The functional agglomerate of the hybridization porous material of type is by the polymeric matrix of 51~81wt%, the over-expense of the metal ion of 10~40wt%
The antioxidant of the hybridization porous material of change type, the dispersing agent of 2~6wt% and 1~3wt% forms；
The material of the polymeric matrix is PET, PA6 or PLA；
The dispersing agent is one or more of polyethylene wax, calcium stearate and zinc stearate；
The antioxidant is 2,4- bis--(n-octylthiomethylene) -6- methylphenol or 2,4- bis- (dodecylthiomethyl).
7. the functional agglomerate of the hybridization porous material according to claim 1 containing hyperbranched type, which is characterized in that described containing gold
Belong to ion the hybridization porous material of hyperbranched type the preparation method comprises the following steps: by the substance of A containing molecule in the form of powder with the object of B containing molecule
The aqueous solution of matter mixes, and when mixing accompanies by stirring, then metal salt solution is added dropwise into mixed system, and when dropwise addition accompanies by stirring, system
Hyperbranched type hybrid microballoon is obtained, hyperbranched type hybrid microballoon is heat-treated the over-expense that metal ion is made through 140~230 DEG C
The hybridization porous material of change type, wherein the metal ion in metal salt solution is Mn+；
The concentration of the aqueous solution of the B substance containing molecule is 0.3~0.58mol/L；
In the mixed system, the molar ratio of the substance of A containing molecule and the B substance containing molecule is 1:2~7；
The concentration of the metal salt solution is 0.4~1.2mol/L, the metal salt total amount of addition and the molar ratio of the substance of A containing molecule
For 1:2~6；
The stirring rate of all stirrings is 300~400rpm, carries out suction filtration separation after the completion of dropwise addition, filters isolated
Filter cake is dried in vacuo 8~12h under conditions of temperature is 25~30 DEG C, vacuum degree is -0.09~-0.1MPa；
The atmosphere of the heat treatment is air, and the time of the heat treatment is 40~50min, the heating rate before the heat treatment
For 15~20 DEG C/min；
The B substance containing molecule is selected from alkyl streptamine, polyetheramine D230, polyetheramine D400, polyetheramine of the chain length less than 6 carbon
D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-1810,
Aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205, fat
One of amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；The metal salt solution is AgNO3、
FeCl2、FeCl3、HAuCl4、Cr2(SO4)3、ZnCl2、PtCl2、PdCl2、CuSO4、Ni(NO3)2Or CdCl2Aqueous solution or
For rare earth metal salt solutions.
8. the functional agglomerate of the hybridization porous material according to claim 7 containing hyperbranched type, which is characterized in that the chain length
Alkyl streptamine less than 6 carbon is positive propylamine, n-butylamine, n-amylamine or n-hexylamine；The rare earth metal salt solutions are LaCl3、
Ce2(SO4)3、Eu(NO3)3、ErCl3、YbCl3、Tm(NO3)3、Ho(NO3)3Or Pr (NO3)3Aqueous solution；
The substance of A containing molecule is to utilize A2+B3Made from synthetic method, A2For containing two reactive groups and at least one of which is
The monomer of carboxyl, B3For the monomer containing three reactive hydroxyl groups；
The A2For pyrazine -2,3- dicarboxylic acids, 2- carboxyethyl phenyl phosphinic acid, 5- tert-butyl -1,3- benzene dicarboxylic acid or 2- carboxyethyl
Phosphoric acid, the B3For 1,1,1- tri- (methylol) propane, three (2- ethoxy) chlorinated isocyanurates, 2,4,5- trihydroxybutyrophenone,
2,3,4- trihydroxy-acetophenone or 1,2,4- trihydroxy benzene.
9. the method for preparing the functional agglomerate of the hybridization porous material as described in any one of claims 1 to 8 containing hyperbranched type,
It is characterized in: after mixing by the hybridization porous material of the hyperbranched type of polymeric matrix material and metal ion and other components
The functional agglomerate of the hybridization porous material containing hyperbranched type is made in melting extrusion.
10. according to the method described in claim 9, it is characterized in that, the polymeric matrix material first exists before being uniformly mixed
Dry 1h~2h at 100~120 DEG C, described be uniformly mixed is realized by mixing 30~40min in super mixer；
When the material of polymeric matrix is PET, PA6 and PLA, corresponding melting extrusion temperature is respectively 220~290 DEG C, 230~
290 DEG C and 150~180 DEG C.
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| 唐鹏飞等: ""超支化Boltorn聚酯对Co离子的封装研究"", 《南华大学学报（自然科学版）》 * |
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