CN100562534C - A kind of method of grafting polymer on inorganic material surface - Google Patents
A kind of method of grafting polymer on inorganic material surface Download PDFInfo
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- CN100562534C CN100562534C CNB2007100712843A CN200710071284A CN100562534C CN 100562534 C CN100562534 C CN 100562534C CN B2007100712843 A CNB2007100712843 A CN B2007100712843A CN 200710071284 A CN200710071284 A CN 200710071284A CN 100562534 C CN100562534 C CN 100562534C
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- inorganic material
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- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention discloses a kind of method of grafting polymer on inorganic material surface.At first, adopt by covalence key or ionic linkage the end of the chain is had the polyoxyethylene or the polyoxyethylene glycol of amino or hydroxyl, the compound that perhaps contains glucose unit is fixed on the surface of inorganic materials, makes its surface have reductibility organic chemistry group; Then, add high price cerium salt and polymerisable monomer, utilize the reductibility organic group of high price cerium salt and inorganic material surface to constitute oxidation-reduction initiating system, the polymerization of trigger monomer under acidic conditions, thus make polymer graft to inorganic material surface.The inventive method can arrive inorganic material surface with polymer graft easily, has the advantage that reaction process is easy, reaction conditions is gentle and percentage of grafting is high, is particularly suitable at inorganic material surface grafting water-soluble polymers or polyalcohol hydrogel thin layer.
Description
Technical field
The present invention relates to the method for grafting polymer on inorganic material surface.
Background technology
Grafting polymer on inorganic material surface promptly is incorporated into inorganic material surface by chemical action with polymer bonds, can give new surface physics of inorganic materials and chemical property, all has great importance for scientific research and many industrial application.For example, it is one of research focus that nanoparticle surface is carried out polymer graft, and the nanoparticle surface graftomer has important meaning to designing new functional organic/inorganic hybridization material.This hybrid material both can have thermotolerance, the chemical resistant properties of inorganics, can have dispersiveness, stability, biological activity, biocompatibility and the environmental response characteristic etc. of graftomer again.In addition, the material that is used for implant into body or contacts with blood, protein chip, gene chip etc. all need to improve consistency by chemical conversion treatment usually.
Usually need two steps at grafting polymer on inorganic material surface: the first step is that the small molecules organic compound that will have the particular chemical group is grafted to inorganic material surface, promptly realizes organising of inorganic material surface; Second step was only polymer graft on the inorganic materials of surface organic.
In the first step, the method that inorganic material surface organises is normally handled with silane coupling agent, utilize the reactive behavior of silane coupling agent further to react then, for example, when using amino silicane coupling agent, can add vinylformic acid polyoxyethylene ester or Methylacrylic Acid Polyoxyethylene Ester,, make polyoxyethylene graft on inorganic material surface by covalent linkage by Michael reactions amino and two keys; Perhaps add compounds such as aldehyde, acyl chlorides and amino reaction.But these class methods can only be introduced low-molecular-weight organic compound at inorganic material surface.
In second step, the method for grafting polymer on inorganic material surface can be divided into " surperficial coupling (graft to) " and " (graft from) caused on the surface " dual mode.Wherein, the former is first synthetic polymer, then by the active group on polymkeric substance and inorganic material surface reaction, with the macromolecular chain coupling at inorganic material surface; The latter be with the initiation center fixation at inorganic material surface, trigger monomer polymerization then, like this macromolecular chain just can be directly in the inorganic material surface growth and form polymer layer.In these two kinds of grafting modes, the percentage of grafting of " surperficial coupling " is lower, the residual more homopolymer of meeting in the reaction system; And " cause on the surface " mode has the percentage of grafting height, and therefore the advantage that transformation efficiency is high is extensively paid close attention to.
In " cause on the surface " mode, transition metal atoms transferring free-radical polymerization (ATRP) of greatest concern.Yet the shortcoming of ATRP is that the residual quantity of transition metal complex is big, and for fear of coupling termination, the concentration ratio of general living radical is lower, so polymerization velocity is slow.
On the other hand, cerium ion (Ce (IV)) can be formed redox system with alcohol, aldehyde, ketone, amine, acid amides etc., in acidic aqueous solution, show very high reactive behavior, compare with other initiator systems and to have lot of advantages, low as temperature of reaction, side reaction is few, aqueous polymerization, percentage of grafting height, not with an organic solvent and speed of reaction fast, thereby be widely used in the preparation of graft polymerization and block polymer.For example, Chinese patent application CN1557849 discloses the method that a kind of W-Gum and cerium salt cause methyl acrylate and acrylate graft copolymer; Chinese patent application CN1186082 discloses a kind of ceric ammonium nitrate to be caused, the preparation method of preparation polyvinyl alcohol graft copolymerized 4-vinyl pyridine in acidic aqueous solution; Chinese patent application CN1978501 discloses a kind of acidic aqueous solution of cerous salt as catalyst/initiator system, under ultraviolet light irradiation, by causing saturated polyfunctional compound reacts or cause the surface light graft polymerization of unsaturated monomer at the optical coupling of polymer surfaces method.Gu Lixia etc. (Sui Kunyan, Gu Lixia, University Of Qingdao's journal, 15,4,2002,10-17) with Ce (IV)/PEO-NH
2Redox initiation system prepares polyacrylonitrile-polyoxyethylene block copolymer; Qian Jinwen etc. report (Qian Jinwen, Wang Meng, the poplar duck is far away, polymer material science and engineering, 2003,19,6,58-61) redox initiation system of ceric ammonium nitrate and poly-hydroxy organism (glycerol, tetramethylolmethane, sucrose) composition is initiator acrylamide triggered (AM) radical polymerization, can prepare the star polyacrylamide; These methods all are polymkeric substance being carried out graft modification or the synthesizing new multipolymer is a purpose, rather than are used for grafting polymer on inorganic material surface.
Talk (what is said or talked about jade pendant jade pendants such as jade pendant jade pendant, Guan Mingyun, Sun Yimin, Ye Xinyu, Ma Zhisen, synthetic chemistry, 2005,13 (1), 61-63) nano titanium oxide is carried out the surface and coat with water miscible hydroxypropylcellulose, obtain nano titanium oxide/hydroxypropylcellulose composite particles, again with ammonium cerous sulfate as initiator, carry out the graft polymerization of hydroxypropylcellulose and methyl methacrylate on nano titanium oxide/hydroxypropylcellulose composite particles surface, finally obtain nano titanium oxide/hydroxypropylcellulose composite particles that the nanometer polymethylmethacrylate coats, realized the organic modification of nano titanium oxide.Its weak point is: in this system, hydroxypropylcellulose is a kind of polyhydric compound, be attached together by weak interaction of hydrogen bond with the lip-deep hydroxyl of nano titanium oxide, therefore, can't guarantee hydroxypropylcellulose clad nano titanium dioxide in good condition, so just cause nanoparticle to coat not exclusively easily, and the hydroxypropylcellulose that comes off can induce reaction and form more homopolymer in the solution, thereby the reduction percentage of grafting, and cause cohesion between the particle easily.
(Ma Z.Y. such as Ma, Guan Y.P., Liu X.Q., and Liu H.Z., Langmuir 2005,21,6987-6994) the ferrite nano particles of handling with the Vinyl Acetate Copolymer oleic acid-coated of divinylbenzene crosslink, having obtained mean diameter after the hydrolysis of sodium alkoxide solution is the magnetic hybrid microballoon of 5 microns surface hydroxylation, in the salpeter solution of ceric ammonium nitrate, cause the polymerization of soluble anionic monomers then, obtain the magnetic hybrid microballoon that the surface grafting anionic polyelectrolyte coats, can be used for absorption of proteins, separation.Inorganic particulate is that the polymkeric substance that is crosslinked by hydrophobic interaction after handling with tensio-active agent coats in this method, its shortcoming is that inorganic particulate content is low, the microballoon size is big, reactions steps is many, and is difficult to obtain monodispersed nanoparticle with nucleocapsid structure.
(Tsubokawa N. such as Tsubokawa, Maruyama K., Sone Y.and Shimomura M., Polymer Journal, 1989,21,6,475-481) respectively with γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan as silane coupling agent grafting silicon-dioxide.Wherein, the glycol that hydrolysis generates under acidic conditions of the epoxy group(ing) in γ-glycidyl ether oxygen propyl trimethoxy silicane.Utilize terminal hydroxy group in the above-mentioned silane coupling agent, end is amino or the end sulfydryl with ceric ammonium nitrate formation redox initiation system with Polyacrylamide Grafted in silica sphere.But, the surface active groups reactive behavior that above-mentioned silane coupling agent is introduced is lower, cause percentage of grafting lower, the γ-Qiu Jibingjisanjiayangjiguiwan modified system percentage of grafting that for example percentage of grafting is the highest is also less than 25%, but the system of γ-glycidyl ether oxygen propyl trimethoxy silicane modification, percentage of grafting has only 10.5%, and wherein, percentage of grafting is defined as (weight of polymers grafted)/(weight of inorganic nanoparticles) * 100.
United States Patent (USP) (US005777001A) discloses a kind of utilization high price cerium salt and metal oxide particle (is representative with titanium dioxide) reacts in the aqueous solution, make the reactive metal oxide surface be with hydroxyl radical free radical, add the polymerization of vinyl monomer initiation grafting then, obtain the metal oxide particle of polymer graft.But, metal oxide particle does not carry out any chemically modified, and the hydroxyl radical free radical in the reaction system is to be adsorbed in the metal oxide particle surface by physisorption, can not suppress the generation of homopolymer, the percentage of grafting that provides in the embodiment generally all＜20% is up to 58%.
Summary of the invention
The objective of the invention is in order to overcome the defective that above-mentioned prior art exists, a kind of method of easy, grafting polymer on inorganic material surface with high percentage of grafting is provided.
The objective of the invention is to be achieved through the following technical solutions: at first inorganic material surface is handled, interact and to be fixed at inorganic material surface with the reductibility compound of high price cerium salt formation active oxidation-reduction free radical initiator system by covalent linkage or ionic linkage, add high price cerium salt and monomer then, under acidic conditions, carry out graft polymerization, obtain the inorganic materials of surface grafting polymerization thing.
Concrete steps are as follows:
1) hydroxyl or amino organic compound are grafted on the surface of inorganic materials by covalent linkage or ionic linkage;
2) the resulting product of step 1) is carried out purifying through washing, filtration or dialysis, flood then or be scattered in the water, add high price cerium salt and monomer, monomer is 20: 1～10000: 1 with the mol ratio of high price cerium salt, regulate pH to acid, deoxygenation is carried out graft reaction in 0～50 ℃;
3) purifying is carried out in step 2) resulting product process washing, filtration or dialysis, removes surface residues.
Among the present invention, said inorganic materials comprises inorganic, metal oxide, oxyhydroxide and inorganic metal salt, can be selected from one or more matrix materials in silicon-dioxide, titanium dioxide, aluminum oxide, Z 250, ferric oxide, zirconium white, zirconium phosphate, manganese oxide, magnesium oxide, magnesium hydroxide, aluminium hydroxide, zinc oxide, hydroxyapatite, osteoid apatite, bio-vitric, biological ceramics, forging bone, barium sulfate, antimonous oxide, hydrotalcite, polynite, attapulgite clay, sepiolite and the kaolin.
Among the present invention, said hydroxyl or amino organic compound are end amino or terminal hydroxy group polyoxyethylene, end amino or terminal hydroxy group polyoxyethylene glycol, perhaps contain the compound of glucose unit.
The above-mentioned compound that contains glucose unit can be one or several the mixture in glucosamine, glycosaminoglycan, oligochitosan, chitosan, hyaluronic acid, glyconic acid, Lalgine or their sodium salt.
Among the present invention, said high price cerium salt can be ceric ammonium nitrate or ammonium cerous sulfate.
Among the present invention, said monomer can be the N-N-isopropylacrylamide, vinyl pyrrolidone, caprolactam, the methylacryoyloxyethyl phosphorylcholine, the acrylyl oxy-ethyl phosphorylcholine, methacrylic acid, vinylformic acid, acrylamide, vinyl pyridine, Dimethylaminoethyl Methacrylate, the methylacryoyloxyethyl trimethyl ammonium chloride, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido dodecyl sodium sulfonate, allyl amine, N, N '-methylene-bisacrylamide, Vinylstyrene, maleic acid, methylene-succinic acid, vinyl cyanide, acrylate, vinyl acetate, vinylbenzene, styrene sulfonic acid, the vinylbenzene benzyl ammonium chloride, methacrylic ester, the vinylformic acid polyoxyethylene ester, Methylacrylic Acid Polyoxyethylene Ester, hydroxyethyl methylacrylate, Rocryl 410, the methacrylic acid hydroxy butyl ester, Hydroxyethyl acrylate, one or more mixtures in the vinylformic acid hydroxy butyl ester.
Inorganic material surface is handled in the inventive method step 1) can use conventional methods, and be specific as follows:
For inorganic, metal oxide, oxyhydroxide, handle inorganic materials with the end amino silicane coupling agent, make the inorganic material surface amination, add single epoxy group(ing) polyoxyethylene then, make epoxy group(ing) and amino reaction, make polyoxyethylene graft on inorganic material surface and terminal hydroxy group outwardly; Perhaps, add end epoxy group(ing) polyoxyethylene glycol in surface amination inorganic materials system, make end epoxy group(ing) polyoxyethylene glycol graft on inorganic material surface, end group becomes the 1 structure after the epoxide group hydrolysis; Perhaps, in surface amination inorganic materials system, add vinylformic acid polyoxyethylene ester or Methylacrylic Acid Polyoxyethylene Ester,, make polyoxyethylene graft on inorganic material surface by covalent linkage by Michael reactions amino and two keys;
Perhaps, the use side epoxy silane coupling is handled inorganic materials, make inorganic material surface have epoxide group, add the amino polyoxyethylene glycol of end, glycosaminoglycan, glucosamine, oligochitosan or chitosan then, make epoxy group(ing) and amino reaction, make these aminocompounds graft on inorganic material surface;
For inorganic metal salt, handle inorganic materials with grape acid, Lalgine, hyaluronic acid or polyoxyethylene glycol maleic acid monoesters or their sodium salt, make above-claimed cpd be fixed in inorganic material surface by ionization.
Beneficial effect of the present invention is: because inorganic materials has been passed through surface chemical modification, connected polyoxyethylene, polyoxyethylene glycol or contain the compound of glucose unit, these compounds have than high reaction activity and high and higher percentage of grafting with the redox initiation system that high price cerium salt constitutes, for example, when using diameter to be the nano SiO 2 particle of 60 nanometers, the percentage of grafting of polymkeric substance can reach more than 60%, and can find that with transmission electron microscope observation resulting microballoon has tangible nucleocapsid structure, the thickness of graft polymer layer is about 20nm.This method is particularly suitable at inorganic material surface grafting water-soluble polymers or polyalcohol hydrogel thin layer.
Description of drawings
The transmission electron microscope of Fig. 1 silicon dioxide microsphere (TEM) photo;
The TEM photo of the silicon dioxide microsphere of Fig. 2 surface grafting polymethylmethacrylate;
The TEM photo of the silicon dioxide microsphere of Fig. 3 surface grafting poly N-isopropyl acrylamide;
The thermogravimetric curve of the silicon dioxide microsphere of the silicon dioxide microsphere of Fig. 4 (a) silicon dioxide microsphere, (b) surface grafting polymethylmethacrylate, (c) surface grafting poly N-isopropyl acrylamide.
Embodiment
Further specify the present invention below in conjunction with embodiment, but summary of the invention is not limited only to given example.
Embodiment 1
Silicon dioxide microsphere is handled with silane coupling agent KH550; make amino group on the titanium dioxide silicon ribbon; in single epoxy group(ing) polyoxyethylene, soaked 24 hours; temperature of reaction 40 degree; polyoxyethylene ester is grafted on the silica sphere by covalent linkage; wash then; be scattered in the water by stirring or sonic oscillation; add 0.001 molar nitric acid cerium ammonium and 1 mole of methyl methacrylate; with nitric acid with pH regulator to 2 about; deoxygenation is also carried out 24 hours graft reactions under nitrogen protection; washing; filter, remove the remaining redox initiation system that constitutes by high price cerium salt and inorganic material surface treatment agent; monomer or homopolymer obtain the silicon dioxide microsphere (Fig. 2) of surface grafting polymethylmethacrylate; thermogravimetric curve is seen Fig. 4 (b), and percentage of grafting is 25.6%.
Silicon dioxide microsphere TEM photo before the grafting is seen Fig. 1, and thermogravimetric curve is seen Fig. 4 (a).
Embodiment 2
The preparation method is with embodiment 1; difference is that the silicon dioxide microsphere of the surface grafting vinylformic acid polyoxyethylene ester that will obtain is scattered in the water; add 0.0005 molar nitric acid cerium ammonium and 2 moles of N-N-isopropylacrylamide; with nitric acid with pH regulator to 1 about; deoxygenation is also carried out 48 hours graft reactions under nitrogen protection, remove surface residues, obtains the silicon dioxide microsphere (Fig. 3) of surface grafting poly N-isopropyl acrylamide; percentage of grafting is 63.7%, and thermogravimetric curve is seen Fig. 4 (c).
Embodiment 3
Hydroxyapatite is scattered in the water, adds sodium alginate, suction filtration, purifying remove unnecessary sodium alginate repeatedly.Add 0.0001 molar nitric acid cerium ammonium and 1 mole of N-N-isopropylacrylamide then; with nitric acid with pH regulator to 2 about; deoxygenation is also carried out 24 hours graft reactions under nitrogen protection; remove surface residues; obtain the hydroxyapatite of surface grafting poly N-isopropyl acrylamide, percentage of grafting is 72.5%.
Embodiment 4
Hydroxyapatite is scattered in the water, adds sodium alginate, suction filtration, purifying remove unnecessary sodium alginate repeatedly.Add 0.05 molar nitric acid cerium ammonium and 1 mole of hydroxyethyl methylacrylate then; with nitric acid with pH regulator to 3 about; deoxygenation is also carried out 12 hours graft reactions under nitrogen protection; remove surface residues; obtain the hydroxyapatite of surface grafting poly hydroxy ethyl acrylate, percentage of grafting is 46.2%.
Embodiment 5
Hydrotalcite is scattered in the water, adds glyconic acid, suction filtration, purifying remove unnecessary glyconic acid repeatedly.Add 0.0001 molar nitric acid cerium ammonium and 1 mol propylene acid amides then, with nitric acid with pH regulator to 2 about, deoxygenation is also carried out 24 hours graft reactions under nitrogen protection, remove surface residues, obtains the nano hydrotalcite of surface grafting polyacrylamide.
Embodiment 6
With the quartz plate surface cleaning, handle with silane coupling agent KH550, make the quartz plate surface amination, be to soak 24 hours in 10% the vinylformic acid polyoxyethylene ester methanol solution in concentration then, temperature of reaction 40 degree, Michael reaction takes place, and makes the terminal hydroxy group polyoxyethylene graft on the quartz plate surface by covalent linkage; Unnecessary coupling agent and vinylformic acid polyoxyethylene ester are removed in the quartz plate washing; impregnated in the water then; add 0.001 molar nitric acid cerium ammonium and 0.1 mole of N-N-isopropylacrylamide; with nitric acid with pH regulator to 2 about; deoxygenation is also carried out 12 hours graft reactions under nitrogen protection; remove surface residues, obtain poly N-isopropyl acrylamide grafted quartz plate.
Embodiment 7
Fiberglass surfacing is cleaned; handle with silane coupling agent KH560; make epoxide group on the fiberglass surfacing band; in the amino polyoxyethylene of end, soaked 12 hours then; temperature of reaction 60 degree; make the amino polyoxyethylene of end graft on fiberglass surfacing by covalent linkage; wash then; remove unnecessary coupling agent and the amino polyoxyethylene of end, impregnated in then in the water, add 0.01 molar nitric acid cerium ammonium and 10 mol propylene acid amides; with nitric acid with pH regulator to 3 about; deoxygenation is also carried out 24 hours graft reactions under nitrogen protection, remove surface residues, obtains the glass fibre of Polyacrylamide Grafted.
Embodiment 8
Glass tubing is cleaned; handle with silane coupling agent KH550; make amino group on the Glass tubing inner wall belt; concentration is to soak 36 hours in 5% the terminal hydroxy group polyoxyethylene acrylic monoester methanol solution; temperature of reaction 30 degree; Michael reaction takes place; the terminal hydroxy group polyoxyethylene is grafted on the Glass tubing inwall by covalent linkage; wash then, impregnated in the water, add 0.001 molar nitric acid cerium ammonium and 10 mol propylene acid; with nitric acid with pH regulator to 4 about; deoxygenation is also carried out 48 hours graft reactions under nitrogen protection, remove surface residues, obtains the Glass tubing of inwall grafted polyacrylic acid.
Embodiment 9
With diameter is the silicon dioxide microsphere silane coupling agent KH550 processing of 20nm; make amino group on the titanium dioxide silicon ribbon; concentration is to soak 24 hours under the room temperature in the methanol solution of 5% Hydroxyethyl acrylate; Michael reaction takes place; Hydroxyethyl acrylate is grafted on the silicon dioxide microsphere by covalent linkage; dialyse then behind the purifying; impregnated in the water; add 0.001 molar nitric acid cerium ammonium and 10 moles of methacrylic acids; with nitric acid with pH regulator to 1 about, deoxygenation is also carried out 48 hours graft reactions under nitrogen protection, remove surface residues; obtain the silicon-dioxide of surface grafting polymethyl acrylic acid, percentage of grafting is 128.4%.
Embodiment 10
The Z 250 microballoon of surperficial coated silica is handled with silane coupling agent KH550; make on the titanium dioxide silicon ribbon amino; concentration is to soak 24 hours under the room temperature in the methanol solution of 10% vinylformic acid polyoxyethylene ester; Michael reaction takes place; the terminal hydroxy group polyoxyethylene is grafted on the Glass tubing inwall by covalent linkage; wash then; again be scattered in the water; add 0.01 molar nitric acid cerium ammonium and 1 mole of methacrylic acid; with nitric acid with pH regulator to 1 about; deoxygenation is also carried out 12 hours graft reactions under nitrogen protection, remove surface residues, obtains the magnetic microsphere of surface grafting polymethyl acrylic acid.
Claims (1)
1. the method for a grafting polymer on inorganic material surface is characterized in that comprising the steps:
1) hydroxyl or amino organic compound are grafted on the surface of inorganic materials by covalent linkage or ionic linkage;
2) the resulting product of step 1) is carried out purifying through washing, filtration or dialysis, flood then or be scattered in the water, add high price cerium salt and monomer, monomer is 20: 1～10000: 1 with the mol ratio of high price cerium salt, regulate pH to acid, deoxygenation is carried out graft reaction in 0～50 ℃;
3) purifying is carried out in step 2) resulting product process washing, filtration or dialysis, removes surface residues;
Above-mentioned hydroxyl or amino organic compound are end amino or terminal hydroxy group polyoxyethylene, glyconic acid or sodium alginate;
Said inorganic materials is selected from silicon-dioxide, Z 250, hydroxyapatite, hydrotalcite, glass fibre, Glass tubing, quartz plate;
Said high price cerium salt is ceric ammonium nitrate or ammonium cerous sulfate;
Said monomer is N-N-isopropylacrylamide, methacrylic acid, vinylformic acid, acrylamide, methyl methacrylate or hydroxyethyl methylacrylate.
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