CN1978553A - Surface grafting organic functional molecular nano silicon dioxide, and its preparing method - Google Patents
Surface grafting organic functional molecular nano silicon dioxide, and its preparing method Download PDFInfo
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Abstract
This invention belongs to the field of nana silicon dioxide modified by organic functioned molecules, especially related to the nano silicon dioxide modified by hindered phenolic antioxygen and its preparation method. The said method is using amino silane coupling agent as a bridge, and chemically grafting the hindered phenolic antioxygen upon the nano silicon dioxide. The amino silane coupling agent accounts for 3%-12% of the total weight of the said processed silicon dioxide and the hindered phenolic antioxygen for 2%-20% by weight. The nano silicon dioxide modified by the said antioxygen molecules can enhance the dispersibility of the nano silicon dioxide the polymer and the comprehensive dynamic performances of the polymer materials, especially the resistance to ageing caused by heat and oxidization during the machining and using processes.
Description
Technical field
The invention belongs to the nano silicon field that organic functional molecular is modified, specially refer to nano silicon of Hinered phenols antioxidant modification and preparation method thereof.
Background technology
In order to reduce macromolecular material cost in use and to improve performance, the interpolation of mineral filler and organic functions auxiliary agent generally is absolutely necessary.Special needs to be pointed out is in order to improve the stability of macromolecular material in processing and use, must add auxiliary agents such as various antiaging agents.
It is the important directions of polymer composites development that nanometer inorganic filler such as nano-calcium carbonate, nanomete talc powder, nano montmorillonite, nano silicon etc. are joined in the polymer materials.Nanoparticle is because of its distinctive small-size effect, surface effects and quantum tunneling effect, add in the polymkeric substance, not only can improve intensity, toughness, the rigidity of polymkeric substance, it is functional also might to obtain excellent light transmission, barrier, thermotolerance, electroconductibility, fungus and mildew resistance, wave absorbtion, anti-ultraviolet radiation etc.The polymer/inorganic nanometer performance of composites depends on chemical structure, surface finishing status and their dispersion situations in polymer materials of inorganic nano material to a great extent.
Nano silicon is applied in the polymkeric substance as a kind of inorganic nano-filler, can improve the over-all properties of polymkeric substance, but because the existence of its surface hydroxyl and unsaturated residual bond shows very strong wetting ability, poor with polymkeric substance compound tense consistency, be difficult to homodisperse.Therefore must carry out surface treatment to nano silicon, as use silane coupling agent to handle (U.S. Pat 6809149B2:functionalizedsilicas), tensio-active agent is handled, surface grafting is handled, oligopolymer and macromole coat processing etc., make its surface show as hydrophobicity, solve compatibility problem with polymkeric substance.
The interpolation of organic functions auxiliary agent such as oxidation inhibitor, UV light absorber, photostabilizer, thermo-stabilizer, static inhibitor etc. can improve the comprehensive use properties of polymkeric substance.Mostly but normally used functional agent is the organic molecule that number molecular weight is lower, and its thermostability is not high, resistant to extraction is relatively poor, has influenced its functioning efficiency in polymkeric substance.Present development trend is the functional agent of preparation desired molecular weight, as functional agent being grafted to (U.S. Pat 6936659 B2:polymer-bondedfunctional agents) on the macromolecular chain, reduces their loss.
Summary of the invention
A purpose of the present invention is the inorganic nano silicon dioxide granule is combined with the organic antioxidant functional agent, the nano silicon of surface grafting organic functional molecular is provided, the inorganic nano-filler of preparation functionalization, this nano material has not only improved dispersiveness and the comprehensive mechanical property of silicon-dioxide in polymkeric substance, improve the thermo oxidative aging of polymkeric substance simultaneously, the more important thing is to have overcome the shortcoming that common organic anti-aging functional agent resistant to extraction is poor, easily move, easily run off.
Another object of the present invention provides has the nano silicon that Hinered phenols antioxidant nontoxic and that resistance of oxidation is strong is modified.
A further object of the present invention provides the preparation method of nano silicon dioxide of surface grafting organic functional molecular.
The nano silicon of surface grafting organic functional molecular of the present invention, it is surface grafting amino silicane coupling agent at nano silicon, and by the amino silicane coupling agent oxidation inhibitor molecule that grafting has the hindered phenol structure as bridging, wherein amino silicane coupling agent accounts for the 3wt%～12wt% of the nano silicon gross weight of surface grafting organic functional molecular, and the oxidation inhibitor molecule accounts for 2wt%～20wt%.
Described oxidation inhibitor molecule with hindered phenol structure is a kind of free radical scavenger, and the thermal-oxidative degradation and the photooxidation droping of polymkeric substance all had stabilization.Nanometer titanium dioxide silicon materials with oxidation inhibitor molecular modification of hindered phenol structure provided by the invention, when being used for macromolecular materials such as polyolefine, polyester, can improve the over-all properties of polymkeric substance, the particularly anti-environmental aging of polymkeric substance, the resistant to extraction of oxidation inhibitor molecule has also obtained solution simultaneously.
The preparation method of nano silicon dioxide of surface grafting organic functional molecular of the present invention is to use amino silicane coupling agent as bridging elder generation and nanometer titanium dioxide pasc reaction, and then organic functions auxiliary agent in the grafting.After the amino silicane coupling agent hydrolysis, at first with nano-silica surface hydroxyl generation condensation reaction, obtain the nano silicon of aminosilane coupling agent modifying, the oxidation inhibitor molecule is grafted on another functional groups amino of coupling agent then, obtains the nano silicon that oxidation inhibitor is modified.
The preparation method of nano silicon dioxide of surface grafting organic functional molecular of the present invention may further comprise the steps:
(1) 1～5 weight part raw material nano silicon-dioxide is joined in the solvent of 50～250 weight parts and stir, form stable silicon-dioxide aaerosol solution;
(2) 1.3～6.5 weight part amino silicane coupling agents are joined in the silica suspension that step (1) obtains, at 100～110 ℃ of following stirring reactions, question response finishes after-filtration, remove reaction solvent, with filter cake for several times with the cleaning solvent washing, remove unreacted coupling agent, obtain the nano silicon of aminosilane coupling agent modifying;
(3) nano silicon of the aminosilane coupling agent modifying that 1～5 weight part step (2) is obtained is dispersed in 50～250 parts by weight solvent again, stirs, and forms steady suspension;
(4) Hinered phenols antioxidant that 0.5～2.5 weight part is had a carboxyl joins in 50～100 weight part acylating reagents, refluxes about 1～2 hour, and the acylating reagent of pressure reducing and steaming surplus obtains the oxidation inhibitor of chloride.
(5) Hinered phenols antioxidant of the chloride that 0.5～2.5 weight part step (4) is obtained and 1.5～7.5 weight part tertiary amine catalysts join in the suspension that step (3) obtains; suspension is under normal temperature and nitrogen protection; stirring reaction; question response finishes after-filtration; remove reaction solvent; filter cake is removed unreacted oxidation inhibitor and tertiary amine catalyst with the cleaning solvent washing for several times.Improved silica after the washing is dried in vacuum drying oven, obtain the nano silicon of surface grafting organic functional molecular.
Nano silicon used in the present invention can be to adopt the vapor phase process preparation, also can adopt the precipitator method or gel method to prepare, and primary particle diameter is at 1～200nm, and specific surface area is at 100～1000m
2/ g, hydroxyl and unsaturated residual bond are contained in the surface, and wetting ability is stronger.
Amino silicane coupling agent used in the present invention is selected from: γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldiethoxysilane, γ-aminopropyl methyldiethoxysilane, γ-aminopropyl methyl dimethoxysilane, a kind of in γ-aminopropyl oxyethyl group dimethylsilane etc.Purpose is for alkoxyl group one end and nano-silica surface hydroxyl generation hydrolysis reaction, and the amino acid chloride groups with oxidation inhibitor of the other end is reacted.
Oxidation inhibitor used in the present invention is the oxidation inhibitor that has response type functional group of Hinered phenols, is selected from 3,5-di-t-butyl-4-hydroxyl-phenylacrylic acid, 3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid, 3, a kind of in 5-di-t-butyl-4-hydroxy-benzoic acid etc.At first change it into corresponding acyl chlorides through acidylate, the amino with silane coupling agent reacts again.
Solvent used in the present invention is the solvent that is primarily aimed at nano silicon, purpose be for nano silicon therein dispersed better, and do not react with reactant amino silicane coupling agent, oxidation inhibitor.Be selected from benzene, toluene, dimethylbenzene, N, a kind of in the dinethylformamide etc.
Acylating reagent used in the present invention is the reagent at carboxyl in the oxidation inhibitor, and purpose is in order to change carboxyl into acyl chlorides, to be selected from thionyl chloride, oxalyl chloride, a kind of in the phosphorus trichloride etc.
Catalyzer used in the present invention is the catalyzer at acylation reaction, is selected from pyridine, triethylamine, Trimethylamine 99, quinoline, picoline, a kind of in the xylidene(s) etc.
Cleaning solvent used in the present invention is at the solvent of excess reactant amino silicane coupling agent, oxidation inhibitor and catalyzer, is selected from benzene, toluene, dimethylbenzene, N, dinethylformamide, ethanol, a kind of in the acetone etc.
Adopt the nano-silica filled polyolefine of the prepared oxidation inhibitor modification of the present invention, and pure nano-silica filled polyolefine adopts following solution method to be prepared into film respectively to be used for thermal-oxidative aging property test: the nano silicon and the pure nano silicon of 0.05～0.5 weight part oxidation inhibitor modification are placed 25～250 weight part dimethylbenzene with 1～10 weight part polyolefine respectively, ultra-sonic dispersion is even, about reheat to 90 ℃, after the stirring and dissolving, add the precipitation agent co-precipitation, remove by filter solvent, with throw out 60 ℃ of oven dry in vacuum drying oven, obtain the nano silicon and the polyolefin silicon dioxide composite material of polyolefine/oxidation inhibitor modification respectively.Thermal-oxidative aging property test result such as Fig. 4 and shown in Figure 6 of being undertaken by this matrix material prepared film.
Description of drawings
Fig. 1. the raw material nano silicon-dioxide of the embodiment of the invention 1, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan and oxidation inhibitor 3, the FT-IR figure of the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified.
A: raw material nano silicon-dioxide; The nano silicon that B:N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan is handled; C: oxidation inhibitor 3, the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified
Fig. 2. the raw material nano silicon-dioxide of the embodiment of the invention 1, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan and oxidation inhibitor 3, the TGA figure of the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified.
A: raw material nano silicon-dioxide; The nano silicon that B:N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan is handled; C: oxidation inhibitor 3, the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified
The XPS figure of the nitrogen of the nano silicon that the N-(β-aminoethyl) of Fig. 3 A. embodiment of the invention 1-γ-An Bingjisanjiayangjiguiwan is modified.
The oxidation inhibitor 3 of Fig. 3 B. embodiment of the invention 1, the XPS figure of the nitrogen of the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified.
Fig. 4. the raw material nano silicon-dioxide of the embodiment of the invention 1, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan and oxidation inhibitor 3, the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified is added in the new LDPE (film grade) oxidation induction time figure of the new LDPE (film grade) that records respectively.
A: new LDPE (film grade)/raw material nano silicon-dioxide; The nano silicon that B: new LDPE (film grade)/N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan is handled; C: new LDPE (film grade)/oxidation inhibitor 3, the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified; D: pure new LDPE (film grade)
The TEM figure of the new LDPE (film grade) of Fig. 5 A. embodiment of the invention 1/raw material nano silicon-dioxide.
The TEM figure of the nano silicon that the new LDPE (film grade)/N-(β-aminoethyl) of Fig. 5 B. embodiment of the invention 1-γ-An Bingjisanjiayangjiguiwan is handled.
New LDPE (film grade)/the oxidation inhibitor 3 of Fig. 5 C. embodiment of the invention 1, the TEM figure of the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified.
Fig. 6. the raw material nano silicon-dioxide of the embodiment of the invention 1, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan and oxidation inhibitor 3, the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified is added in the isotatic polypropylene oxidation induction time figure of the isotatic polypropylene that records respectively.
A: isotatic polypropylene/raw material nano silicon-dioxide; The nano silicon that B: isotatic polypropylene/N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan is handled; C: isotatic polypropylene/oxidation inhibitor 3, the nano silicon that 5-di-t-butyl-4-hydroxyl-phenylacrylic acid is modified; D: pure isotatic polypropylene
Embodiment
Embodiment 1: nano silicon used in the present invention is Degussa A-200, adopts the vapor phase process preparation, primary particle diameter 12nm, specific surface area 200 ± 25m
2/ g.Hydroxyl and unsaturated residual bond are contained in the surface, and wetting ability is stronger.
The amino silicane coupling agent chemical graft is handled nano silicon: take by weighing nano silicon (A-200) 3g and be dispersed in about 150ml toluene, stir, form steady suspension; Add 3.9g N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan then, mixed solution at 24 hours after-filtration of 100～110 ℃ of stirring reactions, and is respectively washed filtrate three times each cleaning solvent consumption 150ml with toluene and ethanol.Nano silicon after the washing is put into vacuum drying oven at 100 ℃, dried by the fire 6 hours.
Oxidation inhibitor molecule chloride: take by weighing 0.5 gram hindered phenol antioxygen 3,5-di-t-butyl-4-hydroxyl-phenylacrylic acid, join in about 40ml thionyl chloride, reflux 1 hour (do not have hydrogenchloride and sulfur dioxide gas substantially emit till) boils off superfluous thionyl chloride then.
Oxidation inhibitor is modified the nano silicon that amino silicane coupling agent is handled: the nano silicon of coupling agent treatment is taken by weighing 1 gram, be dispersed in again in the 50ml toluene, the oxidation inhibitor of chloride is joined in the above-mentioned suspension stir again, drip the 1.5ml pyridine simultaneously; Under nitrogen protection, stirring at normal temperature is reacted 24 hours after-filtration with mixed solution, and filtrate is respectively washed three times with toluene and ethanol, each cleaning solvent consumption 100ml.Nano silicon after the washing is put into vacuum drying oven at 100 ℃, dried by the fire 6 hours.Obtain the nano silicon of oxidation inhibitor molecular modification.
Embodiment 2
With embodiment 1, wherein nano-silica surface is handled with amino silicane coupling agent N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, and the chloride of oxidation inhibitor molecule and oxidation inhibitor molecule are grafted to and adopt the method identical with embodiment 1 on the nano silicon of coupling agent treatment.
Embodiment 3
With embodiment 1, wherein nano-silica surface is handled with 4.5g amino silicane coupling agent γ-An Bingjisanyiyangjiguiwan, and the chloride of oxidation inhibitor molecule and oxidation inhibitor molecule are grafted to and adopt the method identical with embodiment 1 on the nano silicon of coupling agent treatment.
Embodiment 4
With embodiment 1, wherein nano-silica surface is handled with γ-An Bingjisanjiayangjiguiwan.The chloride of oxidation inhibitor molecule: take by weighing 1 gram hindered phenol antioxygen 3,5-di-t-butyl-4-hydroxyl-phenylacrylic acid joins in about 80ml thionyl chloride.The chloride of oxidation inhibitor molecule and oxidation inhibitor molecule are grafted to and adopt the method identical with embodiment 1 on the nano silicon of coupling agent treatment.
Embodiment 5
With embodiment 1, the primary particle diameter 30nm of nano silicon used in the present invention, hydroxyl and unsaturated residual bond are contained in the surface, and wherein oxidation inhibitor is with 3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid.
Embodiment 6
With embodiment 1, wherein oxidation inhibitor is with 3,5-di-t-butyl-4-hydroxy-benzoic acid.
Claims (9)
1. the nano silicon of a surface grafting organic functional molecular, it is characterized in that: at the surface grafting amino silicane coupling agent of nano silicon, and by the amino silicane coupling agent oxidation inhibitor molecule that grafting has the hindered phenol structure as bridging, wherein amino silicane coupling agent accounts for the 3wt%～12wt% of the nano silicon gross weight of surface grafting organic functional molecular, and the oxidation inhibitor molecule accounts for 2wt%～20wt%.
2. nano silicon according to claim 1 is characterized in that: the particle diameter of described nano silicon is 1～200nm, and specific surface area is at 100～1000m2/g, and hydroxyl and unsaturated residual bond are contained in the surface.
3. nano silicon according to claim 1, it is characterized in that: described amino silicane coupling agent is selected from γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldiethoxysilane, γ-aminopropyl methyldiethoxysilane, γ-aminopropyl methyl dimethoxysilane, a kind of in γ-aminopropyl oxyethyl group dimethylsilane.
4. nano silicon according to claim 1 is characterized in that: described oxidation inhibitor is selected from 3,5-di-t-butyl-4-hydroxyl-phenylacrylic acid, 3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid, 3, a kind of in 5-di-t-butyl-4-hydroxy-benzoic acid.
5. one kind according to each described preparation method of nano silicon dioxide of claim 1～4, it is characterized in that described method may further comprise the steps:
(1) 1～5 weight part raw material nano silicon-dioxide is joined in the solvent stirs, form stable silicon-dioxide aaerosol solution;
(2) 1.3～6.5 weight part amino silicane coupling agents are joined in the silica suspension that step (1) obtains, at 100～110 ℃ of following stirring reactions, question response finishes after-filtration, remove reaction solvent, filter cake is washed with cleaning solvent, remove unreacted coupling agent, obtain the nano silicon of aminosilane coupling agent modifying;
(3) nano silicon of the aminosilane coupling agent modifying that 1～5 weight part step (2) is obtained is dispersed in the solvent again, stirs, and forms steady suspension;
(4) Hinered phenols antioxidant that 0.5～2.5 weight part is had a carboxyl joins in the acylating reagent, refluxes, and the acylating reagent of pressure reducing and steaming surplus obtains the oxidation inhibitor of chloride;
(5) Hinered phenols antioxidant of the chloride that 0.5～2.5 weight part step (4) is obtained and 1.5～7.5 weight part tertiary amine catalysts join in the suspension that step (3) obtains, suspension is under normal temperature and nitrogen protection, stirring reaction, question response finishes after-filtration, remove reaction solvent, filter cake washs with cleaning solvent, removes unreacted oxidation inhibitor and tertiary amine catalyst; Improved silica after the washing is dried in vacuum drying oven, obtain the nano silicon of surface grafting organic functional molecular.
6. method according to claim 5 is characterized in that: described solvent is selected from benzene, toluene, dimethylbenzene, N, a kind of in the dinethylformamide.
7. method according to claim 5 is characterized in that: described cleaning solvent is selected from benzene, toluene, dimethylbenzene, N, dinethylformamide, ethanol, a kind of in the acetone.
8. method according to claim 5 is characterized in that: described catalyzer is selected from pyridine, triethylamine, Trimethylamine 99, quinoline, picoline, a kind of in the xylidene(s).
9. method according to claim 5 is characterized in that: described acylating reagent is selected from thionyl chloride, oxalyl chloride, a kind of in the phosphorus trichloride.
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