CN102399376B - Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof - Google Patents
Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof Download PDFInfo
- Publication number
- CN102399376B CN102399376B CN201010276979.7A CN201010276979A CN102399376B CN 102399376 B CN102399376 B CN 102399376B CN 201010276979 A CN201010276979 A CN 201010276979A CN 102399376 B CN102399376 B CN 102399376B
- Authority
- CN
- China
- Prior art keywords
- dioxide
- silicon
- mass fraction
- surface grafting
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention belongs to the field of silicon dioxide modified with organic functional molecules, and especially relates to silicon dioxide with organic phosphorus heterocyclic compounds grafted on the surface, a preparation method thereof, and a purpose thereof. According to the invention, a silane coupling agent is adopted for bridging; and the organic phosphorus heterocyclic compounds are chemically grafted onto the surface of silicon dioxide. The silicon dioxide with the organic functional molecules grafted on the surface comprises components of, by weight: 0.1 to 50% of the silane coupling agent, 0.1 to 50% of the organic phosphorus heterocyclic compounds, and balance of silicon dioxide. The silicon dioxide with the organic functional molecules grafted on the surface can be used as a functional auxiliary agent, and can be added to high-molecular materials such as polyolefin, polyester, epoxy resin, agglomerants, paints, rubber, or fiber, for improving properties such as thermal-aging resistance, photo-aging resistance, heat resistance, transparency and flame retardance of the materials.
Description
Technical field
The invention belongs to the silicon-dioxide field that organic functional molecular is modified, specially refer to silicon-dioxide of surface grafting organic phosphates heterogeneous ring compound and its production and use.
Background technology
In order to reduce the cost of macromolecular material and to improve its over-all properties, often in polymkeric substance, add a large amount of mineral fillers and organic functions auxiliary agent, but these fillers and organic functions auxiliary agent are joined to the over-all properties that can reduce material in macromolecule matrix by conventional physical admixture, and mineral filler and organic functions auxiliary agent are passed through to chemical bonding, can greatly reduce the usage quantity of filler, improve the over-all properties of material.
When the mineral filler of some scale is joined in polymeric matrix as calcium carbonate, talcum powder, montmorillonite, vermiculite, silicon-dioxide, zinc oxide, titanium dioxide, ferric oxide etc., can give the performance of polymer materials excellence, be the important directions of polymer composites development.When the yardstick of filler reaches nanoscale, in the time of in nanoparticulate fillers is joined to polymkeric substance, because of the distinctive small-size effect of filler grain, surface effects and quantum tunneling effect, not only can improve intensity, toughness, the rigidity of polymkeric substance, polymkeric substance also likely obtains the functions such as excellent light transmission, barrier, flame retardant resistance, thermotolerance, electroconductibility, fungus and mildew resistance, wave absorbtion, anti-radiation.
Silicon-dioxide is applied in polymkeric substance as a kind of mineral filler, can improve the over-all properties of polymkeric substance, but due to its surface hydroxyl and the existence of unsaturated residual bond, show very strong wetting ability, poor with polymkeric substance compound tense consistency, be difficult to dispersed, therefore must carry out surface treatment to silicon-dioxide, as use silane coupling agent to process (US Patent No. 6809149B2:functionalized silicas), tensio-active agent is processed, surface grafting is processed, the coated processing of oligopolymer and macromole etc., make its surface show as hydrophobicity, solve the compatibility problem with polymkeric substance.
Organic functions auxiliary agent can improve the Integrated using performance of polymkeric substance as the interpolation of fire retardant, oxidation inhibitor, UV light absorber, photostabilizer, thermo-stabilizer, static inhibitor etc., and normally used functional agent mostly is the compound that molecular weight is lower, its thermostability is low, resistant to extraction is poor, has affected its functioning efficiency in polymkeric substance.Current development trend is the functional agent of preparation desired molecular weight, as functional agent being grafted to (US Patent No. 6936659B2:polymer-bonded functional agents) on macromolecular chain, reduces the loss of functional agent; Organic phosphates heterogeneous ring compound is grafted on silane coupling agent, by the polymerization of silane coupling agent, the fire retardant of generation (Chinese patent 200610117894.8: the flame retardant properties that a kind of organic silicon compound containing phosphorus and preparation method thereof) can improve material; By the method for chemical graft, can greatly improve the effectiveness (Chinese patent 200510125662.2: nano silicon of surface grafting organic functional molecular and preparation method thereof) of filler and auxiliary agent, bring into play organic additive and the chemical cooperated effect of mineral filler, can realize functionalization and the high performance of macromolecular material.
Summary of the invention
The object of the invention is to by silicon dioxide granule with there is higher thermostability, oxidation-resistance and good water tolerance and nontoxic organic phosphates heterogeneous ring compound and pass through chemical bonds, the silicon-dioxide of surface grafting organic functional molecular is provided, the Application Areas that expands organic phosphates heterogeneous ring compound is widely used it in polyolefine, polyester, epoxy resin, binding agent, coating, rubber, fiber.
Another object of the present invention is to provide the preparation method of the silicon-dioxide of surface grafting organic functional molecular.
A further object of the present invention is to provide the purposes of the silicon-dioxide of surface grafting organic functional molecular, and the silicon-dioxide of surface grafting organic functional molecular is applied in polymkeric substance.
The silicon-dioxide of surface grafting organic functional molecular of the present invention, that surface grafting at silicon-dioxide has silane coupling agent, and by silane coupling agent as bridging, grafting organic phosphates heterogeneous ring compound, wherein silane coupling agent accounts for the 0.1wt%～50wt% of the silicon-dioxide total amount of surface grafting organic functional molecular, organic phosphates heterogeneous ring compound accounts for the 0.1wt%～50wt% of the silicon-dioxide total amount of surface grafting organic functional molecular, and surplus is silicon-dioxide.
The particle diameter of described silicon-dioxide is 0.001～100 μ m.
The preparation method of the silicon-dioxide of surface grafting organic functional molecular of the present invention (connecing the organic phosphates heterogeneous ring compound of skill by silane coupling agent as bridging) comprising: (1) is used silane coupling agent as bridging, elder generation and silicon dioxde reaction, and then organic phosphates heterogeneous ring compound in grafting.Silane coupling agent elder generation and silica sphere hydroxyl generation condensation reaction under certain condition, obtain silane coupler modified silicon-dioxide, then organic phosphates heterogeneous ring compound is grafted in another functional group of silane coupling agent, obtains the silicon-dioxide of surface grafting organic functional molecular; Or (2) first react organic phosphates heterogeneous ring compound after certain hour in reactor with silane coupling agent, then add a certain amount of silicon-dioxide in reactor, obtain the silicon-dioxide of surface grafting organic functional molecular; Or (3) together join silicon-dioxide, organic phosphates heterogeneous ring compound in reactor and react with silane coupling agent, obtain the silicon-dioxide of surface grafting organic functional molecular.In the method for the invention, by regulating feed ratio or reaction times can control silane coupling agent and organic phosphates heterogeneous ring compound in the grafting amount of silica sphere.
The preparation method of the silicon-dioxide of surface grafting organic functional molecular of the present invention comprises following several:
Method one: the mass fraction of raw material silicon-dioxide of take is benchmark
A. the raw material silicon-dioxide of 1～20 mass fraction is distributed in the organic solvent of 100 mass fractions and forms suspension;
B. the silane coupling agent of 0.1～2.5 mass fraction is joined in the silica suspension that step a obtains, stirring reaction, filters, and washing is dry, obtains silane coupler modified silicon-dioxide;
The silane coupler modified silicon-dioxide of 1～5 mass fraction c. step b being obtained is dispersed in and in organic solvent, forms suspension;
D. the catalyzer of the organic phosphates heterogeneous ring compound of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction is joined in the suspension that step c obtains, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular.
Method two: the mass fraction of raw material silicon-dioxide of take is benchmark
E. the raw material silicon-dioxide of 1～20 mass fraction is distributed in the organic solvent of 100 mass fractions and forms suspension;
F. the silane coupling agent of 0.1～2.5 mass fraction is joined in the silica suspension that step e obtains to stirring reaction;
G. the catalyzer of the organic phosphates heterogeneous ring compound of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction is joined in the suspension that step f obtains, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular.
Method three: the mass fraction of raw material silicon-dioxide of take is benchmark
H. together with the organic solvent of the catalyzer of the organic phosphates heterogeneous ring compound of the silane coupling agent of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor, after reaction, remove unreacted silane coupling agent and organic phosphates heterogeneous ring compound, obtain the product of organic phosphates heterogeneous ring compound grafted silane coupling agent;
The product of the organic phosphates heterogeneous ring compound grafted silane coupling agent i. step h being obtained is dispersed in organic solvent, adds the silicon-dioxide of 1～5 part of massfraction, stirring reaction, filter, washing, dry, the silicon-dioxide of the surface grafting organic functional molecular described in obtaining.
Method four: the mass fraction of raw material silicon-dioxide of take is benchmark
J. together with the organic solvent of the catalyzer of the organic phosphates heterogeneous ring compound of the silane coupling agent of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor stirring reaction;
K. to the silicon-dioxide that adds 1～5 part of massfraction in the reactor of step j, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular.
Method five: the mass fraction of raw material silicon-dioxide of take is benchmark:
Together with the organic solvent of the catalyzer of the organic phosphates heterogeneous ring compound of the silane coupling agent of the silicon-dioxide of 1～5 part of massfraction, 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor, stirring reaction, washing, dry, the silicon-dioxide of the surface grafting organic functional molecular described in obtaining.
Silicon-dioxide used in the present invention can be to adopt vapor phase process or arc process to be prepared, and can be also to adopt microemulsion method or the precipitator method or sol-gel method to be prepared to obtain, and the particle diameter of primary silicon-dioxide is 0.001～100 μ m.
In silane coupled agent molecule used in the present invention, at least contain a reactable group, described reactable group is selected from vinyl, ethynyl, isocyanate group, amino, carboxyl or halogen atom etc.; Described halogen atom is chlorine, bromine or iodine.
Organic phosphates heterogeneous ring compound molecule used in the present invention has one of following structural formula:
Organic solvent used in the present invention is the organic solvent mainly for silicon-dioxide, and object is for silicon-dioxide has good dispersiveness therein, and does not react with reactant silane coupling agent, organic phosphates heterogeneous ring compound.Be selected from benzene,toluene,xylene, methyl alcohol, ethanol, chloroform, methylene dichloride, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dioxane, acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, aniline, methyl trioctylammonium nitrate ion liquid [C
25h
54n] [NO
3], methyl trioctylammonium secondary octyl phenylium ionic liquid [C
25h
54n] [C
15h
23oCOO], the secondary nonylphenoxyacetic acid ionic liquid of methyl trioctylammonium [C
25h
54n] [C
16h
25oCOO], methyl trioctylammonium two (2-ethylhexyl) phosphonic acids ionic liquid [C
25h
54n] [C
16h
34pOO], methyl trioctylammonium 2-ethylhexyl single 2-ethyl hexyl phosphonic acids ionic liquid [C
25h
54n] [C
16h
34o
2pOO], methyl trioctylammonium two (2,4,4-tri-methyl-amyl) phosphonic acids ionic liquid [C
25h
54n] [C
16h
34pOO] and the single phosphonothionic acid ionic liquid [C of methyl trioctylammonium two (2,4,4-tri-methyl-amyl)
25h
54n] [C
16h
34pSO] in a kind of.
The present invention when washing cleaning solvent used be for excessive reactant and the selected organic solvent of catalyzer, be selected from a kind of in benzene,toluene,xylene, methyl alcohol, ethanol, chloroform, methylene dichloride, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dioxane, acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile and aniline.
Catalyzer used in the present invention is the catalyzer for reaction, is selected from a kind of in pyridine, sodium hydroxide, potassium hydroxide, tertiary butyl alcohol potassium, sodium amide, level Four ammonium alkali, triethylamine, Trimethylamine 99, quinoline, picoline, xylidene(s), sodium methylate and sodium ethylate.
The effect that organic phosphates heterogeneous ring compound used in the present invention is all improved the thermal destruction of polymkeric substance and flame retardant properties, therefore, the earth silicon material of surface grafting organic phosphates heterogeneous ring compound provided by the invention, as functional agent, adding polyolefine to, polyester, epoxy resin, binding agent, coating, rubber, in the time of in the macromolecular materials such as fiber, can improve the over-all properties of preparing gained above-mentioned materials, particularly improve the resistance to heat aging of preparing gained above-mentioned materials, anti-light aging, thermotolerance, the transparency and flame retardant properties, the resistant to extraction of organic phosphates heterogeneous ring compound is also resolved simultaneously.
The silicon-dioxide of surface grafting organic functional molecular of the present invention, expanded the Application Areas of organic phosphates heterogeneous ring compound, the silicon-dioxide of surface grafting organic functional molecular is applied in polymkeric substance, it has not only improved dispersiveness and the comprehensive mechanical property of silicon-dioxide in polymkeric substance, improved the transparency of polymkeric substance, improve the resistance to heat aging, anti-light aging, flame retardant properties of polymkeric substance etc. simultaneously, the more important thing is the shortcoming that has overcome poor, the easy migration of common organic functions auxiliary agent resistant to extraction, easily run off.After the silicon-dioxide of surface grafting organic functional molecular of the present invention and other additive compound, join again in polymkeric substance, the performance of material is improved to degree larger.
Accompanying drawing explanation
Fig. 1. infrared spectra (FT-IR) figure of the raw material nano silicon-dioxide of the embodiment of the present invention 1, the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification and the nano silicon of surface grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO); Wherein:
A: raw material nano silicon-dioxide; The nano silicon of B: γ-(methacryloxypropyl) propyl trimethoxy silicane modification; C: the nano silicon of surface grafting DOPO.
Fig. 2. the nano silicon of the raw material nano silicon-dioxide of the embodiment of the present invention 1, the modification of γ-(methacryloxypropyl) propyl trimethoxy silicane, the nano silicon of surface grafting DOPO and the thermal weight loss of DOPO (TGA) figure; Wherein:
A: raw material nano silicon-dioxide; The nano silicon of B: γ-(methacryloxypropyl) propyl trimethoxy silicane modification; C: the silicon-dioxide of surface grafting DOPO; D:DOPO.
Fig. 3. the solid state nmr figure spectrogram of the nano silicon of the DOPO of the embodiment of the present invention 1 and surface grafting DOPO; Wherein:
The solid state nmr collection of illustrative plates of A:DOPO; B: the solid state nmr figure spectrogram of the nano silicon of surface grafting DOPO.
Fig. 4. the embodiment of the present invention 9 raw material nano silicon-dioxide, the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification, the nano silicon of surface grafting DOPO are added on respectively in polypropylene, the polyacrylic TGA figure recording; Wherein:
A: pure polypropylene; B: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material); The nano silicon of C: polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification (wherein the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification); D: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO).
Fig. 5. the embodiment of the present invention 9 raw material nano silicon-dioxide, the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification, the nano silicon of surface grafting DOPO are added on respectively in polypropylene, the ultraviolet-visible absorption spectroscopy recording; Wherein:
A: pure polypropylene; B: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material); The nano silicon of C: polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification (wherein the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification); D: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO).
Fig. 6. the nano silicon by raw material nano silicon-dioxide and surface grafting DOPO of the embodiment of the present invention 9 is added on respectively in polypropylene, records the transmission electron microscope picture of material; Wherein:
A: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material, and magnification is 10000 times of polypropylene/raw material nano silicon dioxide composite material); B: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material, and magnification is 30000 times of polypropylene/raw material nano silicon dioxide composite material); C: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO, and magnification is 10000 times of polypropylene/raw material nano silicon dioxide composite material); D: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO, and magnification is 30000 times of polypropylene/raw material nano silicon dioxide composite material).
Embodiment
The present invention will be described in more details technical scheme of the present invention by the following specific embodiments, but the present invention is not limited to following embodiment.
Embodiment 1:
The nano silicon that the present embodiment is used is (the J Colloid Interf Sci 2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface, and wetting ability is stronger that adopts vapor phase process to prepare.
Silane coupling agent chemical graft is processed nano silicon: take 5 grams of above-mentioned nano silicons (FT-IR is as shown in accompanying drawing 1A), and be dispersed in 100ml toluene, stir, form suspension; Add 2.5 grams of γ-(methacryloxypropyl) propyl trimethoxy silicane, suspension is filtered after 24 hours at 100～110 ℃ of stirring reactions, and filtrate is respectively washed three times with toluene and ethanol, each cleaning solvent consumption 100ml, obtains the nano silicon (FT-IR is as shown in accompanying drawing 1B) of γ-(methacryloxypropyl) propyl trimethoxy silicane modification.The nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification after washing is put into baking oven, under 100 ℃ of conditions, dry 12 hours.
The nano silicon of surface grafting DOPO: the nano silicon that takes the modification of 1 gram of above-mentioned γ-(methacryloxypropyl) propyl trimethoxy silicane; again be dispersed in 50ml toluene and form suspension; again 1 gram of DOPO is joined in above-mentioned suspension and stirred; add 0.5 gram of triethylamine simultaneously; by mixed solution under nitrogen atmosphere protection; 110 ℃ of stirring reactions filtered after 24 hours; and filtrate is respectively washed three times with toluene and ethanol; each cleaning solvent consumption 100ml, obtains the nano silicon (FT-IR is as shown in accompanying drawing 1C) of surface grafting DOPO.The nano silicon of surface grafting DOPO after washing is put into 100 ℃ of baking ovens, dry 12 hours.The nano silicon of nano silicon, the modification of γ-(methacryloxypropyl) propyl trimethoxy silicane, the nano silicon of surface grafting DOPO, the TGA of DOPO figure are respectively as shown in A, B, C, D in accompanying drawing 2; The solid state nmr spectrogram of the nano silicon of DOPO and surface grafting DOPO is respectively as shown in A and B in accompanying drawing 3.
Wherein γ-(methacryloxypropyl) propyl trimethoxy silicane accounts for the 4wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane and DOPO, DOPO accounts for the 2wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane and DOPO, and surplus is silicon-dioxide.
Embodiment 2
Adopt and the essentially identical method of embodiment 1, but the primary particle diameter of the silicon-dioxide using in the present embodiment is 100 μ m, hydroxyl and unsaturated residual bond are contained in surface, wetting ability is stronger, the silane coupling agent using is γ-(methacryloxypropyl) propyl group mono methoxy silane, can obtain the silane-modified nano silicon of γ-(methacryloxypropyl) propyl group mono methoxy, with the nano silicon of surface grafting DOPO.Wherein γ-(methacryloxypropyl) propyl group mono methoxy silane accounts for the 0.1wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl group mono methoxy silane and DOPO, DOPO accounts for the 0.1wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl group mono methoxy silane and DOPO, and surplus is silicon-dioxide.
Embodiment 3
Adopt and the essentially identical method of embodiment 1, but the silicon-dioxide using in the present embodiment adopts sol-gel method preparation, particle diameter is 1nm, hydroxyl and unsaturated residual bond are contained in surface, wetting ability is stronger, the silane coupling agent using is γ-r-chloropropyl trimethoxyl silane, obtains the nano silicon of γ-r-chloropropyl trimethoxyl silane modification, with the nano silicon of surface grafting DOPO.Wherein γ-r-chloropropyl trimethoxyl silane accounts for the 50wt% of the nano silicon total amount of surface grafting γ-r-chloropropyl trimethoxyl silane and DOPO, DOPO accounts for the 20wt% of the nano silicon total amount of surface grafting γ-r-chloropropyl trimethoxyl silane and DOPO, and surplus is silicon-dioxide.
Embodiment 4
Adopt and the essentially identical method of embodiment 1, but the silicon-dioxide using in the present embodiment adopts sol-gel method preparation, particle diameter is 1nm, hydroxyl and unsaturated residual bond are contained in surface, wetting ability is stronger, the silane coupling agent using is vinyltrimethoxy silane, can obtain the silicon-dioxide of vinyltrimethoxy silane modification, the nano silicon of surface grafting DOPO.Therein ethylene base Trimethoxy silane accounts for the 30wt% of the nano silicon total amount of surface grafting vinyltrimethoxy silane and DOPO, DOPO accounts for the 50wt% of the nano silicon total amount of surface grafting vinyltrimethoxy silane and DOPO, and surplus is silicon-dioxide.
Embodiment 5
The nano silicon that the present embodiment is used is (the J Colloid Interf Sci 2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface that adopts vapor phase process to prepare.
Taking 1 gram of above-mentioned raw materials silicon-dioxide is distributed in 100ml methylene dichloride and forms suspension, the γ-aminopropyl triethoxysilane of 1.5 grams is joined in above-mentioned silica suspension, 40 ℃ of stirring reactions are after 24 hours, by [6-oxygen-(the 6H)-dibenzo-(CE) (1 of 2.5 grams, 2) the own ring-6-ketone of-oxygen phospha] methyl)-succinic acid, 0.2 gram of sodium methylate joins in the suspension of above-mentioned reaction, stir after 24 hours, filter, and filtrate is respectively washed three times with toluene and ethanol, each cleaning solvent consumption 100ml, sample after washing is put into 100 ℃ of baking ovens, dry 12 hours, obtain surface grafting [6-oxygen-(6H)-dibenzo-(CE) (1, 2) oneself ring-6-ketone of-oxygen phospha] methyl) silicon-dioxide of-succinic acid.Wherein γ-aminopropyl triethoxysilane accounts for surface grafting γ-aminopropyl triethoxysilane and [6-oxygen-(6H)-dibenzo-(CE) (1,2) oneself ring-6-ketone of-oxygen phospha] methyl] 20wt% of nano silicon total amount of-succinic acid, [6-oxygen-(6H)-dibenzo-(CE) (1,2) oneself ring-6-ketone of-oxygen phospha] methyl]-succinic acid accounts for surface grafting γ-aminopropyl triethoxysilane and [6-oxygen-(6H)-dibenzo-(CE) (1,2) oneself ring-6-ketone of-oxygen phospha] methyl] 50wt% of nano silicon total amount of-succinic acid, surplus is silicon-dioxide.
Embodiment 6
The nano silicon that the present embodiment is used is (the J Colloid Interf Sci 2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface, and wetting ability is stronger that adopts vapor phase process to prepare.
Take 5 grams of above-mentioned nano silicons, 2.5 grams of γ-(methacryloxypropyl) propyl trimethoxy silicanes, 2.5 grams of DOPO, 0.5 gram of sodium ethylate and join in reactor together with 100ml toluene, stirring reaction, washing.Sample after washing is put into 100 ℃ of baking ovens, dry 12 hours, obtain the nano silicon of surface grafting DOPO.Wherein γ-(methacryloxypropyl) propyl trimethoxy silicane accounts for the 2wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane and DOPO, DOPO accounts for the 1wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane and DOPO, and surplus is silicon-dioxide.
Embodiment 7
The nano silicon that the present embodiment is used is (the J Colloid Interf Sci 2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface, and wetting ability is stronger that adopts vapor phase process to prepare.
Silane coupling agent grafting DOPO product: take 2.5 grams of DOPO and be dispersed in 100ml methylene dichloride, stir, in solution, add 2.5 grams of γ-(methacryloxypropyl) propyl trimethoxy silicane, add 0.5 gram of triethylamine simultaneously, by reaction solution at 40 ℃ of stirring reactions after 24 hours, after unreacted DOPO being removed by liquid chromatography, obtain silane coupling agent grafting DOPO product.
The nano silicon of surface grafting DOPO: take 2 grams of above-mentioned silane coupling agent grafting DOPO products, again be dispersed in 100ml methylene dichloride, again 1 gram of nano silicon is joined in above-mentioned suspension and stirred, 40 ℃ of stirring reactions filtered after 24 hours, and by filtrate washing with acetone five times, each cleaning solvent consumption 100ml.Sample after washing is put into 100 ℃ of baking ovens and dry 12 hours, obtain the nano silicon of surface grafting DOPO.Wherein γ-(methacryloxypropyl) propyl trimethoxy silicane accounts for the 3wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane and DOPO, DOPO accounts for the 2wt% of the nano silicon total amount of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane and DOPO, and surplus is silicon-dioxide.
Embodiment 8
The nano silicon that the present embodiment is used is (the J Colloid Interf Sci 2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface, and wetting ability is stronger that adopts vapor phase process to prepare.
Taking 2.5 grams of DOPO is dispersed in 100ml dimethyl sulfoxide (DMSO), stir, in solution, add 2.5 grams of γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane adds 0.5 gram of triethylamine simultaneously, by reaction solution at 100 ℃ of stirring reactions after 24 hours, in reactor, add 1 gram of nano silicon, 100 ℃ of stirring reactions filtered after 24 hours, and by filtrate washing with acetone five times, each cleaning solvent consumption 100ml.Sample after washing is put into 100 ℃ of baking ovens and heat 12 hours, obtain the nano silicon of surface grafting DOPO.γ-(2 wherein, 3-epoxy the third oxygen) propyl trimethoxy silicane accounts for surface grafting γ-(2,3-epoxy the third oxygen) 3wt% of the nano silicon total amount of propyl trimethoxy silicane and DOPO, DOPO accounts for surface grafting γ-(2,3-epoxy the third oxygen) 2wt% of the nano silicon total amount of propyl trimethoxy silicane and DOPO, surplus is silicon-dioxide.
Embodiment 9
The product that adopts embodiment 1 to prepare, and pure nano silicon (particle diameter is 12nm) is respectively as functional stuffing, adopts respectively following melt-blending process to add to and prepares in polypropylene, and be prepared into the sample of definite shape, for performance characterization:
Described pure nano silicon is (the J Colloid Interf Sci2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface, and wetting ability is stronger that adopts vapor phase process to prepare.
The nano silicon of the γ respectively 5 grams of embodiment 1 being prepared-(methacryloxypropyl) propyl trimethoxy silicane modification, the nano silicon of 5 grams of surface grafting DOPO, and 5 grams of unmodified nano silicons (particle diameter is 12nm) join respectively in the polypropylene of 95 grams, by above-mentioned 3 kinds of mixtures and 100 grams of pure polypropylene, in temperature, be melt blending 5 minutes in the Banbury mixer of 190 ℃ respectively respectively, by gained sample press mold, obtain respectively the nanometer silicon dioxide composite material of polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification, the matrix material of the nano silicon of polypropylene/surface grafting DOPO, the matrix material of PP/Nano silicon-dioxide and virgin pp.The prepared film of above-mentioned four kinds of materials is carried out to thermal stability and characterize, as shown in Figure 4: A: pure polypropylene; B: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material); The nano silicon of C: polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification (wherein the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification); D: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO).Above-mentioned four kinds of prepared films of material are characterized with uv-vis spectra, the result obtaining as shown in Figure 5: A: pure polypropylene; B: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material); The nano silicon of C: polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification (wherein the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/γ-(methacryloxypropyl) propyl trimethoxy silicane modification); D: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO).Dispersion to nano silicon in the matrix material (5wt%) of the matrix material (5wt%) of the nano silicon of polypropylene/surface grafting DOPO and PP/Nano silicon-dioxide in matrix characterizes with transmission electron microscope, result is as shown in Figure 6: A: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material, and magnification is 10000 times of polypropylene/raw material nano silicon dioxide composite material); B: polypropylene/raw material nano silicon-dioxide (wherein raw material nano silicon-dioxide accounts for the 5wt% of polypropylene/raw material nano silicon dioxide composite material, and magnification is 30000 times of polypropylene/raw material nano silicon dioxide composite material); C: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO, and magnification is 10000 times of polypropylene/raw material nano silicon dioxide composite material); D: the nano silicon of polypropylene/surface grafting DOPO (wherein the nano silicon of surface grafting DOPO accounts for the 5wt% of the nanometer silicon dioxide composite material of polypropylene/surface grafting DOPO, and magnification is 30000 times of polypropylene/raw material nano silicon dioxide composite material).
The nano silicon of the surface grafting DOPO that employing embodiment 1 prepares, and pure nano silicon (particle diameter is 12nm) is respectively as functional stuffing, adopt respectively following melt-blending process to add to and prepare in polypropylene, and be prepared into the sample of definite shape, for performance characterization:
Described pure nano silicon is (the J Colloid Interf Sci2007:312 (2): 326-332), primary particle diameter is 12nm, and hydroxyl and unsaturated residual bond are contained in surface, and wetting ability is stronger that adopts vapor phase process to prepare.
Respectively by 5 grams, 10 grams, 15 grams, 20 grams, the nano silicon of the surface grafting DOPO that the embodiment 1 of 30 grams prepares, and 5 grams, 10 grams, 15 grams, 20 grams, 30 grams of pure nano silicons (particle diameter is 12nm) join respectively in the polypropylene of 100 grams, in temperature, it is blend granulation in the twin screw extruder of 200 ℃, obtain respectively the matrix material of nano silicon and the matrix material of PP/Nano silicon-dioxide of polypropylene/surface grafting DOPO, the above-mentioned six kinds of matrix materials of gained are injected into standard batten, according to GB/T 2406, carry out oxygen index combustionproperty test (JF-3, Jiangning county analytical instrument factory).The limiting oxygen index(LOI) of above-mentioned matrix material is as shown in table 1.
The limiting oxygen index(LOI) of the behavior of polypropylene composites of table 1 different content
*polypropylene: the ratio of filler be massfraction than (gram)
Claims (8)
1. the silicon-dioxide of a surface grafting organic functional molecular, it is characterized in that: the surface grafting at silicon-dioxide has silane coupling agent, and by silane coupling agent as bridging, the organic phosphorous heterocylic compound of grafting, wherein silane coupling agent accounts for the 0.1wt%～50wt% of the silicon-dioxide total amount of surface grafting organic functional molecular, organophosphorus heterogeneous ring compound accounts for the 0.1wt%～50wt% of the silicon-dioxide total amount of surface grafting organic functional molecular, and surplus is silicon-dioxide;
Described organophosphorus heterogeneous ring compound has one of following structural formula:
The silicon-dioxide of described surface grafting organic functional molecular is to be prepared by following methods, and the mass fraction of raw material silicon-dioxide of take is benchmark;
A. the raw material silicon-dioxide of 1～20 mass fraction is distributed in the organic solvent of 100 mass fractions and forms suspension;
B. the silane coupling agent of 0.1～2.5 mass fraction is joined in the silica suspension that step a obtains, stirring reaction, filters, and washing is dry, obtains silane coupler modified silicon-dioxide;
The silane coupler modified silicon-dioxide of 1～5 mass fraction c. step b being obtained is dispersed in and in organic solvent, forms suspension;
D. the catalyzer of the organophosphorus heterogeneous ring compound of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction is joined in the suspension that step c obtains, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular;
Or
E. the raw material silicon-dioxide of 1～20 mass fraction is distributed in the organic solvent of 100 mass fractions and forms suspension;
F. the silane coupling agent of 0.1～2.5 mass fraction is joined in the silica suspension that step e obtains to stirring reaction;
G. the catalyzer of the organophosphorus heterogeneous ring compound of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction is joined in the suspension that step f obtains, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular;
Or
H. together with the organic solvent of the catalyzer of the organophosphorus heterogeneous ring compound of the silane coupling agent of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor, after stirring reaction, remove unreacted silane coupling agent and organophosphorus heterogeneous ring compound, obtain the product of organophosphorus heterogeneous ring compound grafted silane coupling agent;
The product of the organophosphorus heterogeneous ring compound grafted silane coupling agent i. step h being obtained is dispersed in organic solvent, adds the silicon-dioxide of 1～5 part of mass fraction, stirring reaction, filter, washing, dry, the silicon-dioxide of the surface grafting organic functional molecular described in obtaining;
Or
J. together with the organic solvent of the catalyzer of the organophosphorus heterogeneous ring compound of the silane coupling agent of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor stirring reaction;
K. to the silicon-dioxide that adds 1～5 part of mass fraction in the reactor of step j, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular;
Or
Together with the organic solvent of the catalyzer of the organophosphorus heterogeneous ring compound of the silane coupling agent of the silicon-dioxide of 1～5 part of mass fraction, 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor, stirring reaction, washing, dry, the silicon-dioxide of the surface grafting organic functional molecular described in obtaining.
2. the silicon-dioxide of surface grafting organic functional molecular according to claim 1, is characterized in that: the particle diameter of described silicon-dioxide is 0.001～100 μ m.
3. the silicon-dioxide of surface grafting organic functional molecular according to claim 1, it is characterized in that: in described silane coupled agent molecule, at least contain a reactable group, described reactable group is selected from vinyl, ethynyl, isocyanate group, epoxy group(ing), amino, carboxyl or halogen atom.
4. a preparation method for the silicon-dioxide of surface grafting organic functional molecular, is characterized in that: the mass fraction of raw material silicon-dioxide of take is benchmark;
A. the raw material silicon-dioxide of 1～20 mass fraction is distributed in the organic solvent of 100 mass fractions and forms suspension;
B. the silane coupling agent of 0.1～2.5 mass fraction is joined in the silica suspension that step a obtains, stirring reaction, filters, and washing is dry, obtains silane coupler modified silicon-dioxide;
The silane coupler modified silicon-dioxide of 1～5 mass fraction c. step b being obtained is dispersed in and in organic solvent, forms suspension;
D. the catalyzer of the organophosphorus heterogeneous ring compound of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction is joined in the suspension that step c obtains, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular;
Or
E. the raw material silicon-dioxide of 1～20 mass fraction is distributed in the organic solvent of 100 mass fractions and forms suspension;
F. the silane coupling agent of 0.1～2.5 mass fraction is joined in the silica suspension that step e obtains to stirring reaction;
G. the catalyzer of the organophosphorus heterogeneous ring compound of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction is joined in the suspension that step f obtains, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular;
Or
H. together with the organic solvent of the catalyzer of the organophosphorus heterogeneous ring compound of the silane coupling agent of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor, after stirring reaction, remove unreacted silane coupling agent and organophosphorus heterogeneous ring compound, obtain the product of organophosphorus heterogeneous ring compound grafted silane coupling agent;
The product of the organophosphorus heterogeneous ring compound grafted silane coupling agent i. step h being obtained is dispersed in organic solvent, adds the silicon-dioxide of 1～5 part of mass fraction, stirring reaction, filter, washing, dry, the silicon-dioxide of the surface grafting organic functional molecular described in obtaining;
Or
J. together with the organic solvent of the catalyzer of the organophosphorus heterogeneous ring compound of the silane coupling agent of 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor stirring reaction;
K. to the silicon-dioxide that adds 1～5 part of mass fraction in the reactor of step j, stirring reaction, filters, and washing is dry, obtains the silicon-dioxide of described surface grafting organic functional molecular;
Or
Together with the organic solvent of the catalyzer of the organophosphorus heterogeneous ring compound of the silane coupling agent of the silicon-dioxide of 1～5 part of mass fraction, 0.1～2.5 mass fraction, 0.1～2.5 mass fraction, 0.5～2.5 mass fraction and 100 mass fractions, join in reactor, stirring reaction, washing, dry, the silicon-dioxide of the surface grafting organic functional molecular described in obtaining;
Described organic solvent is selected from benzene, toluene, dimethylbenzene, methyl alcohol, ethanol, chloroform, methylene dichloride, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dioxane, acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, aniline, methyl trioctylammonium nitrate ion liquid, methyl trioctylammonium secondary octyl phenylium ionic liquid, the secondary nonylphenoxyacetic acid ionic liquid of methyl trioctylammonium, methyl trioctylammonium two (2-ethylhexyl) phosphonic acids ionic liquid, methyl trioctylammonium 2-ethylhexyl single 2-ethyl hexyl phosphonic acids ionic liquid, methyl trioctylammonium two (2, 4, 4-tri-methyl-amyl) phosphonic acids ionic liquid and methyl trioctylammonium two (2, 4, 4-tri-methyl-amyl) a kind of in single phosphonothionic acid ionic liquid,
Described organophosphorus heterogeneous ring compound has one of following structural formula:
Described catalyzer is selected from a kind of in pyridine, sodium hydroxide, potassium hydroxide, tertiary butyl alcohol potassium, sodium amide, level Four ammonium alkali, triethylamine, Trimethylamine 99, quinoline, picoline, xylidene(s), sodium methylate and sodium ethylate.
5. method according to claim 4, is characterized in that: the particle diameter of described raw material silicon-dioxide is 0.001～100 μ m.
6. method according to claim 4, is characterized in that: in described silane coupled agent molecule, at least contain a reactable group, described reactable group is selected from vinyl, ethynyl, isocyanate group, amino, carboxyl or halogen atom.
7. method according to claim 4, is characterized in that: during described washing, organic solvent used is selected from a kind of in benzene,toluene,xylene, methyl alcohol, ethanol, chloroform, methylene dichloride, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dioxane, acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile and aniline.
8. one kind according to the purposes of the silicon-dioxide of the surface grafting organic functional molecular described in claim 1～3 any one, it is characterized in that, the silicon-dioxide of described surface grafting organic functional molecular as functional agent, add to prepare polyolefine, polyester, epoxy resin, binding agent, coating, rubber or polymeric fibrous material in time, for improving, prepare resistance to heat aging, anti-light aging, thermotolerance, the transparency and the flame retardant properties of gained above-mentioned materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010276979.7A CN102399376B (en) | 2010-09-09 | 2010-09-09 | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010276979.7A CN102399376B (en) | 2010-09-09 | 2010-09-09 | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102399376A CN102399376A (en) | 2012-04-04 |
| CN102399376B true CN102399376B (en) | 2014-03-12 |
Family
ID=45882064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010276979.7A Active CN102399376B (en) | 2010-09-09 | 2010-09-09 | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102399376B (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8961831B2 (en) * | 2011-05-31 | 2015-02-24 | E Ink California, Llc | Silane-containing pigment particles for electrophoretic display |
| CN102993782B (en) * | 2012-12-12 | 2014-04-16 | 江南大学 | Preparation method of polyurethane acrylate oligomer surface modified silica |
| CN103173056B (en) * | 2012-12-14 | 2015-02-11 | 北京康拓科技有限公司 | Preparation method of Fe/SiO2 nano-multilayer film electromagnetic-wave absorbing material |
| CN103788408B (en) * | 2014-01-22 | 2016-09-28 | 广州辰东新材料有限公司 | DOPO modified inorganic fire retardant and preparation method thereof |
| CN103804858B (en) * | 2014-01-22 | 2018-06-15 | 广州辰东新材料有限公司 | A kind of polyester composite and preparation method thereof |
| CN103980736A (en) * | 2014-04-13 | 2014-08-13 | 北京化工大学 | Phosphaphenanthrene compound 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) grafted and modified sepiolite fibers and preparation method thereof |
| CN104891512B (en) * | 2015-06-05 | 2017-10-17 | 厦门大学 | A kind of phosphorous polymer modified Nano particle and preparation method thereof |
| CN106893442B (en) * | 2015-12-17 | 2019-08-16 | 中国科学院金属研究所 | A kind of transparent nano silica-anti-corrosive paint of epoxy resin and preparation method |
| CN106009038B (en) * | 2016-07-18 | 2019-05-24 | 江林（贵州）高科发展股份有限公司 | Halogen-free phosphorus-containing silicon fire retardant, anti-flaming transparent makrolon material and preparation and application |
| CN108097306B (en) * | 2016-11-24 | 2020-07-21 | 中国科学院大连化学物理研究所 | Dual-functionalized silicon oxide catalytic material and preparation and application thereof |
| CN108623844A (en) * | 2017-03-15 | 2018-10-09 | 中国石油化工股份有限公司 | DOPO-LDH composite fire retardants and preparation method thereof and halogen-free flame retardant ethylene propylene diene monomer (EPDM) material and its application |
| CN108084494A (en) * | 2017-12-08 | 2018-05-29 | 中国科学院化学研究所 | Functionalized nano titanium dioxide of surface grafting antioxygen agent molecule and preparation method thereof |
| CN108440817B (en) * | 2018-03-08 | 2021-03-02 | 日丰企业集团有限公司 | Hydrophobic and oleophobic polyolefin material and preparation method thereof |
| KR101986583B1 (en) * | 2018-03-19 | 2019-06-10 | 한국신발피혁연구원 | Functional thermosetting resin composition for ship deck coating |
| CN108641365A (en) * | 2018-05-11 | 2018-10-12 | 中国科学院化学研究所 | Have both modified white carbon black of damping and flame retardant property and preparation method thereof, silicon rubber |
| CN109181097A (en) * | 2018-07-13 | 2019-01-11 | 安徽义林塑业有限公司 | A kind of anti-pollution polypropylene packaging material |
| CN109135345A (en) * | 2018-08-01 | 2019-01-04 | 安徽锦华氧化锌有限公司 | A kind of method of the rubber product anti-old coupling agent modified Nano carbon white of ionic liquid- |
| CN111040471B (en) * | 2018-10-12 | 2021-02-26 | 中国科学院化学研究所 | Organic functional molecule grafted silicon dioxide nano particle and preparation method and application thereof |
| CN111960960B (en) * | 2019-05-20 | 2022-12-30 | 广东生益科技股份有限公司 | Diamine compound, method for producing same, thermosetting resin composition, and use thereof |
| CN110746917A (en) * | 2019-10-18 | 2020-02-04 | 李志兴 | Preparation method of high-temperature-resistant epoxy resin adhesive |
| CN110818953A (en) * | 2019-11-18 | 2020-02-21 | 福州大学 | Preparation method and application of modified fly ash floating bead loaded DOPO |
| CN111073348A (en) * | 2019-12-11 | 2020-04-28 | 江苏联瑞新材料股份有限公司 | Preparation method of flame-retardant modified silica micropowder for halogen-free copper-clad plate |
| CN111087652A (en) * | 2019-12-20 | 2020-05-01 | 佛山科学技术学院 | Silicone rubber heat-resistant additive and preparation method thereof |
| CN113234324B (en) * | 2021-06-03 | 2022-06-10 | 山东弗克新材料有限公司 | Flame-retardant ceramizable organic silicon material and preparation method thereof |
| CN113522243B (en) * | 2021-07-07 | 2022-09-23 | 北京科技大学 | Preparation method of organic phosphinic acid functional group modified silicon-based adsorption material |
| CN113717443B (en) * | 2021-09-28 | 2023-05-23 | 四川轻化工大学 | Modified beta-cyclodextrin-DOPO composite material and preparation method thereof |
| CN113903994B (en) * | 2021-11-20 | 2023-06-30 | 郑州中科新兴产业技术研究院 | High-safety electrolyte and preparation method thereof |
| CN116004035A (en) * | 2022-12-20 | 2023-04-25 | 烟台大学 | Inorganic calcium carbonate surface modification method and application thereof |
| CN116120575A (en) * | 2023-01-09 | 2023-05-16 | 汕头大学 | Silicon dioxide graft polymer and preparation method and application thereof |
| CN116215023B (en) * | 2023-01-10 | 2023-11-28 | 南京绿力新材料有限公司 | High-temperature-resistant flame-retardant aluminum foil bag and preparation method thereof |
| CN116285888A (en) * | 2023-03-24 | 2023-06-23 | 哈尔滨工业大学（威海） | Preparation method and application of silicon dioxide-based conductive composite material with nitrogen atoms grafted on surface |
| CN116685050B (en) * | 2023-05-31 | 2024-01-23 | 江苏耀鸿电子有限公司 | Manufacturing method of PCB |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460472C (en) * | 2005-12-02 | 2009-02-11 | 中国科学院化学研究所 | Surface grafting organic functional molecular nano silicon dioxide, and its preparing method |
| CN100410262C (en) * | 2006-11-02 | 2008-08-13 | 上海交通大学 | Organic silicon compound containing phosphorus and its preparing method |
| CN101792537A (en) * | 2010-03-17 | 2010-08-04 | 北京理工大学 | Silane coupling agent containing DOPO group and preparation method thereof |
-
2010
- 2010-09-09 CN CN201010276979.7A patent/CN102399376B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102399376A (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102399376B (en) | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof | |
| CN103849165B (en) | Functionalized nanometer silica with ultraviolet ray absorption function group grafted on surface, and preparation method thereof | |
| CN100460472C (en) | Surface grafting organic functional molecular nano silicon dioxide, and its preparing method | |
| CN103387757B (en) | A kind of preparation method of overcritical middle hydrotalcite grafting fire retardant | |
| CN103911021B (en) | A kind of transparent magnesium hydroxide liquid dispersion and preparation method and application | |
| Gao et al. | Synthesis and characterization of polyurethane/SiO2 nanocomposites | |
| Gao et al. | Synthesis and characterization of well-dispersed polyurethane/CaCO3 nanocomposites | |
| WO2021109993A1 (en) | Preparation method for organic phosphine grafted hollow metal organic framework material and use thereof | |
| CN107057322B (en) | A kind of PC alloy material and preparation method thereof | |
| Jung et al. | Keratinous fiber based intumescent flame retardant with controllable functional compound loading | |
| CN103402914B (en) | The manufacture method of oxidation sheet graphite derivative, its resin composite materials and this resin composite materials | |
| CN105418971B (en) | The preparation method of phosphorus nitrogen high load Graphene fire retardant | |
| CN103396459A (en) | Method for preparing phosphorus silicate hybridization flame retardant from organic silicon waste liquid | |
| TW201345934A (en) | Polymers, polymer blends, and flame retardant materials | |
| CN1333035C (en) | Single component mildew-proof flame retarded organic silicon sealing agent for machinery and preparation process thereof | |
| CN110615915A (en) | Composite polypropylene nucleating agent and preparation method and application thereof | |
| CN106928490B (en) | A kind of inorganic-organic hybridization nano compound, preparation method and its flame-proof polylactic acid with the fire-retardant synergistic effect of chain extension- | |
| CN109384959B (en) | Preparation method of phosphorus-nitrogen high-load hydrotalcite flame retardant | |
| CN113150386A (en) | Modified ammonium polyphosphate intumescent flame retardant and preparation method and application thereof | |
| CN103360798A (en) | Method for preparing hydrophobic white carbon black | |
| CN111303616B (en) | Graphene oxide grafted phosphorus-containing maleic acid flame-retardant auxiliary agent and preparation method and application thereof | |
| CN101704953B (en) | Synthesis method of organic silicon resin containing OH groups | |
| CN109988411A (en) | Flame-retardant smoke inhibition thermoplastic polyurethane anti-static composite material and preparation method thereof | |
| CN105985525A (en) | Modified cellulose and composite material using same | |
| WO2003097652A1 (en) | Nanofiller, production, and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221123 Address after: 523591 Room 201, Building 4, No. 68, Xiegang Zhenxing Avenue, Xiegang Town, Dongguan City, Guangdong Province Patentee after: Guangdong Zhongke Huatong new Mstar Technology Ltd. Address before: 100190 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee before: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |