CN109912952A

CN109912952A - The unsaturated polyester resin and preparation method thereof of the hybridization porous material containing hyperbranched type

Info

Publication number: CN109912952A
Application number: CN201811527122.0A
Authority: CN
Inventors: 孙宾; 曾婷; 朱美芳; 江晓泽; 相恒学; 陈珈; 胡余宗
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2018-12-13
Filing date: 2018-12-13
Publication date: 2019-06-21
Anticipated expiration: 2038-12-13
Also published as: CN109912952B

Abstract

The present invention relates to unsaturated polyester resins of a kind of hybridization porous material containing hyperbranched type and preparation method thereof, the preparation method comprises the following steps: solidifying the unsaturated polyester resin that the hybridization porous material containing hyperbranched type is made after multifunctional modification agent, unsaturated polyester resin and curing agent are mixed, multifunctional modification agent is the hybridization porous material of hyperbranched type of metal ion, for porous microsphere, it is nucleated by hyperbranched type hybrid and carries out pore-creating again after growth forms microballoon and be made；Its molecular structural formula is mainly by molecule A, molecule B and metal ions Mⁿ⁺It constitutes, molecule A is the carboxylic hyperbranched polymer molecule of end group, and molecule B is the chain molecule with amido, the carboxyl in molecule A, amido and metal ions M in molecule Bⁿ⁺Between by the way that ionic bond and coordinate bond are bonded form following triangle bonding structure:

Description

The unsaturated polyester resin and preparation method thereof of the hybridization porous material containing hyperbranched type

Technical field

The invention belongs to unsaturated polyester modified resin art, the unsaturation for being related to the hybridization porous material containing hyperbranched type is poly- Ester resin and preparation method thereof, more particularly to a kind of method by adding flame-proof antibiotic agent modified unsaturated polyester resin.

Background technique

Unsaturated polyester resin (UPR) is as binary acid and dihydric alcohol through made from polycondensation reaction, being thermosetting resin One of principal item.Due to unsaturated polyester composite have excellent electric property, mechanical performance, hot-working character and The features such as high production efficiency, is now widely used for rail traffic, construction material, automotive material, hull material and electrical equipment Equal fields.With the continuous development of society, more stringent requirements are proposed for functionality of the people to unsaturated polyester resin material.It is right Unsaturated polyester resin, which carries out functional modification, becomes the research direction of current hot spot.

But phase is easy to happen using unsaturated polyester resin material made from modified (inorganic modified) method of existing capabilityization Separation, this is because the physico-chemical property of inorganic modifier differs greatly with macromolecule organic matrix, is easy to cause its generation mutually to separate. The flame retardant property of unsaturated polyester resin itself is poor, generally requires to enhance its flame retardant property, and mostly at present is inorganic by adding What fire-retardant filler was realized, this kind of method be easy to operate, Halogen and at low cost, but its additive amount is larger, is easy to cause composition Specific gravity and viscosity increase, and influence fire-retardant filler in the dispersing uniformity of material, the final mechanical performance for influencing product.The prior art In organic fire-resisting filler be mostly small molecule type or oligomeric species, not only thermal stability is bad, but also volatile, additive amount Height, with matrix poor compatibility, this greatly affected the flame retardant property and processing performance of modified obtained unsaturated polyester resin.It is existing There is antibiotic functional material similar with fire-retardant filler, there is problem above.

Therefore, the unsaturated polyester resin that flame retardant property, anti-microbial property and mechanical performance can be taken into account by studying one kind has Highly important realistic meaning.

Summary of the invention

The technical problem to be solved by the present invention is to overcome the defect of the prior art, provide one kind can take into account flame retardant property, The unsaturated polyester resin of anti-microbial property and mechanical performance.

In order to achieve the above object, present invention employs the following technical solutions:

The unsaturated polyester resin of the hybridization porous material containing hyperbranched type, mainly by unsaturated polyester resin matrix and The even multifunctional modification agent composition being dispersed in unsaturated polyester resin matrix；

The multifunctional modification agent is the hybridization porous material of hyperbranched type of metal ion, is porous microsphere, by overspending Pore-creating is carried out after change type hybrid is nucleated and growth forms microballoon again to 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 of n Range 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 the bonded formation triangle bonding structure of coordinate bond, molecule B, which can reach, changes molecule A The effect of property, improves its hydrophilicity, so that being nucleated and being grown the microballoon of the formation energy in water phase by hyperbranched type hybrid It is enough to be dispersed with nanoscale, and aqueous dispersion particle is less likely to occur to reunite during preparing porous microsphere, to guarantee The size of the porous microsphere generated, and the good dispersibility in polyester matrix, make the hybridization porous material containing hyperbranched type Polyester resin can have both absorption, deodorization, fire-retardant and antibacterial functions.

The mechanism that stable triangle bonding structure is formed in structural formula signal is as follows: in the carboxyl and molecule B in molecule A Amido combine and form complex, complex ionizes generation-COO^-With-NH₃ ⁺,-COO^-With-NH₃ ⁺Because of the suction of positive and negative charge Draw, generates electrostatic attraction, that is, form ionic bond；Due to-COO^-In oxygen on have lone pair electrons, therefore lone pair electrons enter metal The unoccupied orbital of ion forms coordinate bond, due to-NH in conjunction with metal ion generation covalent coordinate₃ ⁺In N atom there is also lonely right Electronics is equally capable of providing lone pair electrons and is formed in conjunction with coordinate bond with metal ion, therefore forms stable triangle bonding Structure.

Stable triangle bonding structure on the one hand by means of the catalytic action of metal ion improve the fire-retardant of product and Anti-microbial property greatly improves the thermal stability of carboxylate, significantly improves it and add on the other hand by introducing metal ion Work performance.Processing is blended with unsaturated polyester resin in the hybridization porous material of hyperbranched type of metal ion to be made containing hyperbranched The unsaturated polyester resin of the hybridization porous material of type, the fire-retardant of product, antibacterial and processing performance are excellent.

As a preferred technical scheme:

The unsaturated polyester resin of the hybridization porous material containing hyperbranched type as described above, the hybridization porous material containing hyperbranched type The content of multifunctional modification agent is 8~12wt% in the unsaturated polyester resin of material；

The tensile strength of the unsaturated polyester resin of the hybridization porous material containing hyperbranched type is 32.3~45.4MPa, fracture Elongation is 11.3%~13.3%, and temperature of initial decomposition is 290~340 DEG C, and limit oxygen index is 31%~38%, UL-94 Reach V-0 grades, through before and after 50 washings to the bacteriostasis rate of staphylococcus aureus be respectively 75%~93% and 68%~ 89%, through being respectively 83%~98% and 71%~95% to the bacteriostasis rate of Escherichia coli before and after 50 washings；This field skill Art personnel can adjust the content of multifunctional modification agent according to the actual situation, and the various performance parameters of product also will be with the variation of content And change；The unsaturated polyester resin of the hybridization porous material containing hyperbranched type of the invention combines compared with the prior art Good mechanical, fire-retardant and anti-microbial property, great application prospect；

The load capacity of metal ion is 70~1700mg/g in the hybridization porous material of hyperbranched type of metal ion；

The aperture of the hybridization porous material of hyperbranched type of metal ion be 40~100nm, porosity be 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 load capacity of the metal ion of the hyperbranched porous material of the prior art be 50~200mg/g, 600 Carbon yield is 30~45wt% at DEG C.The metal ion of the hybridization porous material of hyperbranched type of metal ion of the invention is born Carbon yield is much higher than the prior art at carrying capacity and 600 DEG C.The hybridization porous material of hyperbranched type of metal ion of the invention The above parameter be not limited to that those skilled in the art can the above parameter of appropriate adjustment according to actual needs.

The unsaturated polyester resin of the hybridization porous material containing hyperbranched type as described above, Mⁿ⁺For Ag⁺、Fe²⁺、 Fe³⁺、Au³ ⁺、Cr³⁺、Zn²⁺、Pt²⁺、Pd²⁺、Cu²⁺、Ni²⁺、Cd²⁺Or be trivalent rare earth ion, species of metal ion of the invention is not It is 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, it is metal-modified Cross carboxylate is easily dissolved in water, can not be separated；

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 unsaturated polyester resin of the hybridization porous material containing hyperbranched type as described above, the trivalent rare earth ion For 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 is also wrapped Hydroxyl or carboxyl, the molecular backbone of the molecule B further include element O or N, and the molecule A further includes element P, O or N.Molecule The element species and group that A and molecule B include are not limited to that, also may include other elements or other groups, as long as energy Enough guarantee the carboxyl in molecule A, amido and metal ions M in molecule Bⁿ⁺Between to form triangle bonding structure firm；

The present invention also provides a kind of unsaturated polyester resins for preparing the hybridization porous material containing hyperbranched type as described above Method, will multifunctional modification agent, unsaturated polyester resin and curing agent mix after solidify be made containing hyperbranched type it is hybridization porous The unsaturated polyester resin of material.

As a preferred technical scheme:

Method as described above, according to parts by weight, the unsaturated polyester resin master of the hybridization porous material containing hyperbranched type It to be made of 100 parts of unsaturated polyester resins, 20~40 parts of multifunctional modification agent and 1~3 part of curing agent；The curing agent was Aoxidize one or more of methyl ethyl ketone, cyclohexanone peroxide and dibenzoyl peroxide.

Method as described above, the specific steps are as follows:

(1) by after multifunctional modification agent and unsaturated polyester resin in a mixer 20~30min of mechanical stirring, to mixing Curing agent is added in device, and 1~5min of mechanical stirring obtains mixture again, wherein all churned mechanically revolving speeds be 500~ 600r/min；

(2) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is gone by way of vacuumizing Except the bubble in mixture, negative pressure is -0.085~-0.120MPa in vacuum drying oven；

(3) it pours the mixture into Teflon mould, again 80~100 after solidifying 1.5~2 hours at normal temperature DEG C temperature under the conditions of solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 6~10 hours.

Method as described above, the preparation process of the multifunctional modification agent are as follows: by the substance of A containing molecule in the form of powder It is mixed with the aqueous solution of the B substance containing molecule, when mixing accompanies by stirring, then metal salt solution is added dropwise into mixed system, when dropwise addition Stirring is accompanied by, hyperbranched type hybrid microballoon is made, hyperbranched type hybrid microballoon is made through 140~230 DEG C of heat treatments containing gold Belong to the hybridization porous material of hyperbranched type of ion, wherein the metal ion in metal salt solution is Mⁿ⁺.Molecule B's is hydrophilic Aqueous dispersion particle can be prepared in short molecular chain in conjunction with molecule A and metal ion, ensure that and prepare hyperbranched type hybrid Particle is not reunited (including prepare and dry) when porous microsphere, this ensure that the size of final porous microsphere；

The prior art for preparing triangle bonding structure at present is mostly the natural polymer matrix body with good aqueous solubility System, it is organic solvent (tetrahydrofuran and ethyl alcohol etc.) that dissaving polymer system, which takes long time and can be used solvent in the presence of dissolution, The problem of, the present invention, which forms the main difficulty of triangle bonding structure, two: an one, suitable dicyandiamide solution, two, molecule B and point Structure after sub- A reaction is still needed to metal coordination ability.The present invention selects environmentally protective water as solvent, selects and contains carboxyl Molecule A and amino-contained molecule B as reactant, the substance of the B containing molecule contains a large amount of amidos, and dissolubility is preferable, can be compared with Fast to dissolve, the amido reaction in molecule A in carboxyl and molecule B generates the intermediate with the ability of metal coordination, is then added Metal salt solution carries out metal coordination, forms triangle bonding structure.The substance of A containing molecule is carboxylate, poor water resistance, exposure Its ester bond is easily degraded when in wet environment, therefore it is saved mostly in the form of powder, the substance of A containing molecule in the present invention Addition form is also not limited to powder, and the form that other do not influence its performance is also applicable.The substance of A containing molecule is difficult to directly molten Solution in water, is only dissolve in the organic solvents such as DMSO, DMF, when the dissolution of the substance of A containing molecule forms solution in organic solvent It is mixed again with the solution of the B substance containing molecule afterwards, since high forces can be generated between organic solvent and molecule B, thus it is unfavorable Ionic bond is formed in molecule A and molecule B, and then is unfavorable for forming triangle bonding structure.The present invention passes through miscellaneous to hyperbranched type Compound microballoon carries out the porous hybrid material that nanoscale has been made in heat treatment, changes its aggregated structure, substantially increases Its dispersion performance in polyester matrix, while the functions such as the distinctive absorption of product porous material and deodorization are imparted, it widens Material application and be able to achieve in water phase nanoscale dispersion.Heat treatment temperature of the invention is excessively high, and it is organic to destroy other The bonding of covalent bond, to reduce the flame retardant property of functional material, heat treatment temperature is too low, it is difficult to destroy the short chain with amido point Son is to obtain porous hybrid material.

Method as described above, the concentration of the aqueous solution of the B substance containing molecule are 0.3~0.58mol/L；B containing molecule The concentration of the aqueous solution of substance can carry out appropriate adjustment, but should not too, excessive concentration, it is difficult to accurate control B substance containing molecule Aqueous solution additive amount, be easy to cause the excessive addition of B substance containing molecule, and coordination to occur with metal salt solution anti-by molecule B Precipitating should be generated, to influence the separation of substance, concentration is too low, and excessively slow with bit rate, yield in unit time is too low, greatly shadow Economic benefit is rung；

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 Appropriate adjustment can be carried out with the molar ratio of the B substance containing molecule, but should not too, molar ratio is excessively high, be easy to cause B substance containing molecule Excessive addition, and complexation reaction can occur with metal salt solution and generate precipitating to influence the separation of substance, molar ratio mistake by molecule B So that the amount deficiency that carboxyl is reacted with amido, the water-soluble of system reduce, dispersibility is deteriorated for low 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 that 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 the base 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, filters separation Obtained 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 before the heat treatment Rate is 15~20 DEG C/min；It is heat-treated under air atmosphere, short chain molecule is easier that the fracture of molecular link occurs.At heat Manage overlong time or heating rate it is excessively slow, may part other organic covalent bonds bonding, to reduce the resistance of functional material Fire performance；Heat treatment time is too short or heating rate is too fast is difficult to destroy the short chain molecule with amido to obtain porous hybrid material Material.

The B substance containing molecule is selected from chain length less than the alkyl streptamine of 6 carbon, polyetheramine D230, polyetheramine D400, poly- Ether amines 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 For AgNO₃、FeCl₂、FeCl₃、HAuCl₄、 Cr₂(SO₄)₃、ZnCl₂、PtCl₂、PdCl₂、CuSO₄、Ni(NO₃)₂Or CdCl₂Water Solution is rare earth metal salt solutions；The present invention only enumerates moieties, and the substance that other meet structural formula is applicable In the present invention.

Method as described above, the chain length are positive propylamine, n-butylamine, n-amylamine or just less than the alkyl streptamine of 6 carbon Hexylamine；The rare earth metal salt solutions are LaCl₃、Ce₂(SO₄)₃、Eu(NO₃)₃、ErCl₃、YbCl₃、 Tm(NO₃)₃、Ho(NO₃)₃ Or 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 its In one be carboxyl monomer, B₃For the monomer containing three reactive hydroxyl groups；A feasible technical side is only enumerated herein Case, the preparation method and its raw material of the substance of the A of the invention containing molecule are not limited to that, as long as its product, which has, meets structure The molecule A that formula requires；

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 Phenyl propyl ketone, 2,3,4- trihydroxy-acetophenone or 1,2,4- trihydroxy benzene.A is only enumerated herein₂And B₃The possible substance in part, this hair Bright A₂And B₃It is not limited to that, other substances that the substance of A containing molecule can be made may be applicable to the present invention.

Invention mechanism:

The present invention by being modified the hybridization porous material of hyperbranched type of obtained metal ion to dissaving polymer, And as multifunctional modification agent, solidification is carried out after mixing with unsaturated polyester resin and curing agent and is made miscellaneous containing hyperbranched type Change the unsaturated polyester resin of porous material, multifunctional modification agent of the invention can be dispersed in unsaturated polyester resin base In body, improve processing performance, and have the function of fire-retardant and antibacterial etc..

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, on the one hand due to introducing hydrophilic radical-amido, the water solubility of dissaving polymer is improved, is had Conducive to the progress of next step reaction, another aspect molecule B is the small molecule of low pole, low pole molecule B is grafted to hyperbranched On polymer molecule, followed by the coordination of carboxyl and amido and metal ion, metal ion is introduced into hyperbranched polymerization Form stable triangle bonding structure in object and obtain the hyperbranched type hybrid material of metal ion, by introduce metal from Son greatly improves the thermal stability of dissaving polymer, so that dissaving polymer of the invention, which has, does not influence traditional base The characteristic of the melt-processed of body significantly improves its processing performance, overcomes when prior art dissaving polymer is blended and adds The problem of work difficult forming, the hybridization porous material of hyperbranched type of metal ion is made finally by heat treatment pore-creating, simultaneously Due in flame-retardant system the metallic compounds such as metal ion or metal oxide to fire retardant itself in macromolecular thermal degradation process And the physical reaction between fire retardant and macromolecule matrix is specially that dehydrogenation and deoxidation in macromolecular thermal degradation process etc. is chemical Reaction is that chain degradation and cross-linking process have catalytic action, and it is anti-can to play the carbon yield for improving material, reduction combustion process heat The effect of feedback and flue gas release, the catalysis that stable triangle bonding structure of the invention can further improve metal ion are made With improving the flame retardant property of product, be finally heat-treated to obtain the hybridization porous material of hyperbranched type of metal ion to material Expect, in heat treatment process, since the thermal stability of the strand of the small molecule of amino-contained is esterified than unmodified preceding hyperbranched type Object is poor, and gaseous material volatilization is degraded under heated, so that hybrid material is porous microsphere, the present invention by solid microsphere variation By being heat-treated the pore-creating on the hyperbranched type hybrid material of metal ion, its aggregated structure is changed, product is imparted The good characteristic of the distinctive absorption property of porous material, while having both fire-retardant, antibacterial and deodoriging properties, widened the application of material and The generation for effectively preventing its agglomeration in process is conducive to the size for the porous microsphere that control generates, and guarantees more Dispersibility of the hole microballoon in polyester matrix.

The mechanism that wherein stable triangle bonding structure is formed is as follows: the amido knot in carboxyl and molecule B in molecule A Conjunction forms complex, and complex ionizes generation-COO^-With-NH₃ ⁺,-COO^-With-NH₃ ⁺Because of the attraction of positive and negative charge, generate quiet Electric attraction forms ionic bond, due to-COO^-In oxygen on have lone pair electrons, therefore lone pair electrons enter the sky of metal ion Track forms coordinate bond, due to-NH in conjunction with metal ion generation covalent coordinate₃ ⁺In N atom there is also lone pair electrons, together Sample is capable of providing lone pair electrons and is formed in conjunction with coordinate bond with metal ion, therefore forms the stable triangle key in structural formula Close structure.

The utility model has the advantages that

A, the unsaturated polyester resin of the hybridization porous material of the invention containing hyperbranched type has been taken into account fire-retardant, anti-well Bacterium and mechanical performance, market prospects are good；

B, the preparation method of the unsaturated polyester resin of the hybridization porous material of the invention containing hyperbranched type, using water conduct Reaction dissolvent, it is nontoxic, it is environmentally protective；

C, the preparation method of the unsaturated polyester resin of the hybridization porous material of the invention containing hyperbranched type, equipment investment compared with Few, operating process is simply easy to implement, and experiment condition is mild, low in cost, great market prospects；

D, the preparation method of the unsaturated polyester resin of the hybridization porous material of the invention containing hyperbranched type, in preparation containing super The hydrophilic short molecular chain of molecule B makes the hyperbranched type hybrid without pore-creating micro- in the hybridization porous materials process of branching type Ball can be dispersed in water phase with nanoscale, avoid preparing the generation of agglomeration in the process of porous microsphere, to protect The size of porous microsphere obtained is demonstrate,proved, so that porous microsphere good dispersion in polyester matrix.

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 carboxyl, molecule B in the molecule A in the dissaving polymer of the easily distributed loaded metal ion of water phase In amido 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, quaternary ammonium group, 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；

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；

Embodiment 1

The preparation method of the unsaturated polyester resin of the hybridization porous material containing hyperbranched type, the specific steps are as follows:

(1) the hybridization porous material of hyperbranched type of multifunctional modification agent namely metal ion is prepared；

(a) 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；

(b) substance of A containing molecule made from step (a) (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；

(c) 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 in molecule A, the amido in molecule B and metal ion Ag⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 70mg/g, the aperture of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material For 90~100nm, porosity 40%, initial decomposition temperature is that carbon yield is 50wt% at 340 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 40 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 30min of 500r/min after, into mixer be added 3 parts of peroxides Change methyl ethyl ketone and mixture is obtained with the revolving speed mechanical stirring 1min of 600r/min again；

(3) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is gone by way of vacuumizing Except the bubble in mixture, negative pressure is -0.085MPa in vacuum drying oven；

(4) it pours the mixture into Teflon mould, again in 80 DEG C of temperature strip after solidifying at normal temperature 1.5 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 6 hours under part.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 12wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 45.4MPa, elongation at break 13.3%, temperature of initial decomposition It is 300 DEG C, limit oxygen index 38%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 93% and 89%, through being respectively 98% and 95% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 2

(a) 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, under nitrogen protection carry out esterification 2h, then temperature be 180 DEG C, pressure be -0.1MPa under conditions of vacuumize into The substance of A containing molecule is made in row polycondensation reaction 3h, wherein needs to be stirred during esterification and polycondensation reaction, the speed of stirring Rate is 300rpm；

(b) substance of A containing molecule made from step (a) (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；

(c) 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.Carboxyl in molecule A, the amido in molecule B and metal cations Fe²⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 1700mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 40~50nm, and porosity 60%, initial decomposition temperature is that carbon yield is 65wt% at 380 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 20 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 20min of 600r/min after, into mixer be added 1 part of peroxide Change cyclohexanone and mixture is obtained with the revolving speed mechanical stirring 5min of 500r/min again；

(3) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is gone by way of vacuumizing Except the bubble in mixture, negative pressure is -0.120MPa in vacuum drying oven；

(4) it pours the mixture into Teflon mould, again in 100 DEG C of temperature strip after solidifying at normal temperature 2 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 10 hours under part.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 8wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 32.3MPa, elongation at break 11.3%, temperature of initial decomposition It is 308 DEG C, limit oxygen index 31%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 75% and 68%, through being respectively 83% and 71% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 3

(a) 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；

(b) by the substance of A containing molecule made from step (a) 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；

(c) 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；Carboxyl in molecule A, the amido in molecule B and metal cations Fe³⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 700mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 60~70nm, and porosity 45%, initial decomposition temperature is that carbon yield is 56wt% at 365 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 30 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 25min of 550r/min after, into mixer be added 2 parts of peroxides Change dibenzoyl and mixture is obtained with the revolving speed mechanical stirring 3min of 550r/min again；

(3) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is gone by way of vacuumizing Except the bubble in mixture, negative pressure is -0.100MPa in vacuum drying oven；

(4) it pours the mixture into Teflon mould, again in 90 DEG C of temperature strip after solidifying at normal temperature 1.6 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 8 hours under part.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 10wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 38.3MPa, elongation at break 12.3%, temperature of initial decomposition It is 330 DEG C, limit oxygen index 35%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 83% and 74%, through being respectively 90% and 86% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 4

(a) 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；

(b) by the substance of A containing molecule made from step (a) 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；

(c) 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 in molecule A, the amido in molecule B and metal ion Cu²⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 510mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 60~80nm, and porosity 49%, initial decomposition temperature is that carbon yield is 56wt% at 350 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 25 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 22min of 500r/min after, into mixer be added 2 parts of peroxides Change methyl ethyl ketone/cyclohexanone peroxide (mixture that mass ratio is 1:1) again with the revolving speed mechanical stirring 2min of 600r/min Obtain mixture；

(3) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is gone by way of vacuumizing Except the bubble in mixture, negative pressure is -0.095MPa in vacuum drying oven；

(4) it pours the mixture into Teflon mould, again in 85 DEG C of temperature strip after solidifying at normal temperature 1.5 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 7 hours under part.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 9wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 40.4MPa, elongation at break 11.8%, temperature of initial decomposition It is 290 DEG C, limit oxygen index 33%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 79% and 72%, through being respectively 86% and 79% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 5

(a) 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；

(b) by the substance of A containing molecule made from step (a) 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；

(c) 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 in molecule A, the amido in molecule B and metal ion Pd²⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 400mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 45~55nm, and porosity 44%, initial decomposition temperature is that carbon yield is 53wt% at 360 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 40 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 20min of 500r/min after, into mixer be added 3 parts of peroxides Change cyclohexanone/dibenzoyl peroxide (mixture of mass ratio 1:2) to obtain again with the revolving speed mechanical stirring 1min of 500r/min Mixture；

(4) it pours the mixture into Teflon mould, again in 95 DEG C of temperature condition after solidifying at normal temperature 2 hours It is lower to solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 8 hours.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 11wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 42.4MPa, elongation at break 13.0%, temperature of initial decomposition It is 320 DEG C, limit oxygen index 36%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 88% and 80%, through being respectively 92% and 89% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 6

(a) 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；

(b) by the substance of A containing molecule made from step (a) 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；

(c) 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 in molecule A, the amido in molecule B and metal ion Ni²⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 1320mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 45~60nm, and porosity 56%, initial decomposition temperature is that carbon yield is 60wt% at 380 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 30 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 25min of 600r/min after, into mixer be added 1 part of peroxide Change dibenzoyl and mixture is obtained with the revolving speed mechanical stirring 5min of 550r/min again；

(4) it pours the mixture into Teflon mould, again in 85 DEG C of temperature strip after solidifying at normal temperature 1.6 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 9 hours under part.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 10wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 39.5MPa, elongation at break 13.0%, temperature of initial decomposition It is 327 DEG C, limit oxygen index 35%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 86% and 80%, through being respectively 90% and 84% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 7

(a) 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；

(b) by the substance of A containing molecule made from step (a) 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；

(c) 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 in molecule A, the amido in molecule B and metal ion Tm³⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 900mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 86~95nm, and porosity 43%, initial decomposition temperature is that carbon yield is 58wt% at 355 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 20 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 20min of 500r/min after, into mixer be added 1 part of peroxide Change cyclohexanone and mixture is obtained with the revolving speed mechanical stirring 3min of 550r/min again；

(3) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is gone by way of vacuumizing Except the bubble in mixture, negative pressure is -0.110MPa in vacuum drying oven；

(4) it pours the mixture into Teflon mould, again in 80 DEG C of temperature condition after solidifying at normal temperature 2 hours It is lower to solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 6 hours.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 8wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 32.8MPa, elongation at break 11.8%, temperature of initial decomposition It is 340 DEG C, limit oxygen index 37%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 85% and 80%, through being respectively 93% and 85% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 8

(a) 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 under conditions of being -0.1MPa It carries out polycondensation reaction 4h and the substance of A containing molecule is made, wherein need to be stirred during esterification and polycondensation reaction, stirring Rate is 200rpm；

(b) by the substance of A containing molecule made from step (a) 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, it is micro- that hyperbranched type hybrid is made Ball, wherein in mixed system, the molar ratio of the substance of A containing molecule and aliphatic amine polyoxyethylene ether AC-1812 are 1:2, addition Metal 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；

(c) 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 in molecule A, the amido in molecule B and metal ion Eu³⁺Between pass through Ionic bond and the bonded formation triangle bonding structure as shown in formula (I) of coordinate bond；The hyperbranched type of metal ion obtained The load capacity of metal ion is 1410mg/g, the hole of the hybridization porous material of hyperbranched type of metal ion in hybridization porous material Diameter is 60~70nm, and porosity 50%, initial decomposition temperature is that carbon yield is 55wt% at 355 DEG C, 600 DEG C；

(2) according to parts by weight, by the cross carboxylate of the easily distributed loaded metal ion of 35 parts of water phases and 100 parts Unsaturated polyester resin in a mixer with the revolving speed mechanical stirring 25min of 500r/min after, into mixer be added 1 part of peroxide Change methyl ethyl ketone and mixture is obtained with the revolving speed mechanical stirring 2min of 550r/min again；

(4) it pours the mixture into Teflon mould, again in 80 DEG C of temperature strip after solidifying at normal temperature 1.5 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 9 hours under part.

The unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type is mainly by unsaturated polyester resin The cross esterification of matrix and the easily distributed loaded metal ion of the water phase being dispersed in unsaturated polyester resin matrix Object composition, wherein the content of the cross carboxylate of the easily distributed loaded metal ion of water phase is 11wt%, miscellaneous containing hyperbranched type The tensile strength for changing the unsaturated polyester resin of porous material is 42.4MPa, elongation at break 13.2%, temperature of initial decomposition It is 300 DEG C, limit oxygen index 37%, UL-94 reaches V-0 grades, through the suppression before and after 50 washings to staphylococcus aureus Bacterium rate is respectively 88% and 85%, through being respectively 84% and 89% to the bacteriostasis rate of Escherichia coli before and after 50 washings.

Embodiment 9~20

The preparation method of the unsaturated polyester resin of the hybridization porous material containing hyperbranched type, specific steps and 1 base of embodiment This is consistent, and difference is to prepare the type of the B substance containing molecule in multifunctional modification agent, the type of metal salt solution and multi-functional changes The various performance parameters of property agent, are specifically shown in Table 1, the metal ion in multifunctional modification agent molecule structural formula is mentioned by metal salt solution For X is the relative molecular weight of molecule B in table, and unit g/mol, Z are by the bonded carboxyl of ionic bond and coordinate bond and to lead to The ratio of the sum of ionic bond and the bonded amine groups content of coordinate bond with the sum of carboxyl in molecule A and molecule B and amido mole is crossed, Unit is %, and load capacity is the load capacity of metal ion in product, unit mg/g, and aperture is the aperture of product, unit nm, Porosity be product porosity, unit %, temperature be product initial decomposition temperature, unit be DEG C, carbon yield is product The carbon yield at 600 DEG C, unit wt%.

The content I of multifunctional modification agent in the unsaturated polyester resin of the final hybridization porous material obtained containing hyperbranched type (wt%), tensile strength J (MPa), elongation at break K (%), temperature of initial decomposition L (DEG C), limit oxygen index M (%), UL-94 Grade N, bacteriostasis rate O (to the bacteriostasis rate of staphylococcus aureus), bacteriostasis rate P are (to staphylococcus aureus after 50 washings Bacteriostasis rate), bacteriostasis rate Q (to the bacteriostasis rate of Escherichia coli) and bacteriostasis rate S be (to the antibacterial of Escherichia coli after 50 washings Rate) specifically it is shown in Table 2.

Table 1

Table 2

Claims

1. the unsaturated polyester resin of the hybridization porous material containing hyperbranched type, it is characterized in that: mainly by unsaturated polyester resin base Body and the multifunctional modification agent being dispersed in unsaturated polyester resin matrix composition；

The multifunctional modification agent is the hybridization porous material of hyperbranched type of metal ion, is porous microsphere, by hyperbranched type Pore-creating is carried out after hybrid is nucleated and growth forms microballoon again to 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 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 unsaturated polyester resin of the hybridization porous material according to claim 1 containing hyperbranched type, which is characterized in that contain The content of multifunctional modification agent is 8~12wt% in the unsaturated polyester resin of the hyperbranched hybridization porous material of type；

The tensile strength of the unsaturated polyester resin of the hybridization porous material containing hyperbranched type is 32.3~45.4MPa, extension at break Rate is 11.3%~13.3%, and temperature of initial decomposition is 290~340 DEG C, and limit oxygen index is that 31%~38%, UL-94 reaches V-0 grades, through being respectively 75%~93% and 68%~89%, warp to the bacteriostasis rate of staphylococcus aureus before and after 50 washings It is respectively 83%~98% and 71%~95% to the bacteriostasis rate of Escherichia coli before and after 50 washings；

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%.

3. the unsaturated polyester resin of the hybridization porous material according to claim 2 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；

4. the unsaturated polyester resin of the hybridization porous material according to claim 3 containing hyperbranched type, which is characterized in that institute Stating trivalent 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 further includes element P, O or N.

5. preparing the unsaturated polyester resin of the hybridization porous material as described in any one of claims 1 to 4 containing hyperbranched type Method, it is characterized in that: will multifunctional modification agent, unsaturated polyester resin and curing agent mix after solidify be made contain hyperbranched type The unsaturated polyester resin of hybridization porous material.

6. according to the method described in claim 5, it is characterized in that, according to parts by weight, the hybridization porous material containing hyperbranched type Unsaturated polyester resin mainly by 100 parts of unsaturated polyester resins, 20~40 parts of multifunctional modification agent and 1~3 part of curing agent Composition；The curing agent is one or more of methyl ethyl ketone peroxide, cyclohexanone peroxide and dibenzoyl peroxide.

7. according to the method described in claim 5, it is characterized in that, specific step is as follows:

(1) by after multifunctional modification agent and unsaturated polyester resin in a mixer 20~30min of mechanical stirring, into mixer Curing agent is added, and 1~5min of mechanical stirring obtains mixture again, wherein all churned mechanically revolving speeds are 500~600r/ min；

(2) mixture is placed in vacuum drying oven, keeping temperature in vacuum drying oven is room temperature, is removed by way of vacuumizing mixed The bubble in object is closed, negative pressure is -0.085~-0.120MPa in vacuum drying oven；

(3) it pours the mixture into Teflon mould, again in 80~100 DEG C of temperature after solidifying at normal temperature 1.5~2 hours Solidify the unsaturated polyester resin for obtaining the hybridization porous material containing hyperbranched type for 6~10 hours under the conditions of degree.

8. according to the method described in claim 5, it is characterized in that, the preparation process of the multifunctional modification agent are as follows: will contain point Sub- A substance is mixed in the form of powder with the aqueous solution of the B substance containing molecule, and when mixing accompanies by stirring, then drips into mixed system Add metal salt solution, when dropwise addition, accompanies by stirring, be made hyperbranched type hybrid microballoon, hyperbranched type hybrid microballoon through 140~ 230 DEG C are heat-treated the hybridization porous material of hyperbranched type that metal ion is made, wherein the metal ion in metal salt solution is Mⁿ⁺。

9. according to the method described in claim 8, it is characterized in that, the concentration of the aqueous solution of the B substance containing molecule be 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, and suction filtration separation is carried out after the completion of dropwise addition, is filtered isolated 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 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.

10. according to the method described in claim 9, it is characterized in that, the chain length is positive third less than the alkyl streptamine of 6 carbon Amine, 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- trihydroxybutyrophenone, 2,3,4- trihydroxy-acetophenone or 1,2,4- trihydroxy benzene.