CN102701602B - Method for initiating graft polymer through ultraviolet induction on surface of glass - Google Patents
Method for initiating graft polymer through ultraviolet induction on surface of glass Download PDFInfo
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- CN102701602B CN102701602B CN201210192697.8A CN201210192697A CN102701602B CN 102701602 B CN102701602 B CN 102701602B CN 201210192697 A CN201210192697 A CN 201210192697A CN 102701602 B CN102701602 B CN 102701602B
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Abstract
The invention relates to a method for initiating a graft polymer through ultraviolet induction on the surface of glass, belonging to the technical field of surface modification of the glass. The method comprises the following steps of: uniformly coating a prepared reaction solution on the surface of the glass treated by a silane coupling agent, and placing the glass in an ultraviolet light curing machine to irradiate the glass for 3min, thereby obtaining a sheet glass sample, the surface of which is fixed with a polymer chain. The method has the advantages that an operating technology is simple, the grafting effect is obvious, and raw materials used are commercially available, can be used without needing to be subjected to a complex purification process and are low in cost and easily obtained; graft polymerization is initiated through ultraviolet induction, the operation is simple, the reaction time is short, and the environmental pollution is low; and the method can be used for the reinforcement of adhesive property between resin in a reinforced material and the glass and the modification of the surface character of the glass and has wide industrial application prospect.
Description
Technical field
The invention belongs to Glass Surface Modification technical field, relate to a kind of method of glass surface grafting, particularly at glass surface, pass through the radical polymerization of uv induction redox initiation, the method for grafted polymer.
Background technology
Inorganic material surface is carried out to modification of graft, can produce many new features, as amphipathic, chemically reactive, dispersibility, adsorptivity and consistency etc.Silica-base material, as glass, nanometer SiO
2deng, due to good performance and relatively cheap price, become the first-selected matrix of preparing polymer/inorganic hybrid composite material.
At present, the crosslinking technology of domestic and foreign literature report mainly contains: (1) is with atom transfer radical polymerization (ATRP) grafting.(the Buttcher H such as Bottcher, Hallensleben M L.ATRP grafting from silica surface to create first and second generation of grafts[J] .Polym Bull, 2000,44 (2): 223 ~ 229.) at nanometer SiO
2surface is introduced pre-synthesis coupling agent and is caused atom transfer radical polymerization of styrene as ATRP initiator, as shown in Figure 1.Although the coupling agent structure that this method is used can design on demand, synthesis step is many, and it is also its shortcoming that is difficult to overcome that synthetic coupling agent is difficult to purify.(2) with Reversible Addition Fragmentation Chain-Transfer Polymerization (RAFT) grafting.(the Tsujii Y such as Benicewicz, Ejaz M, Sato K, Goto A, Fukuda T.Mechanism and kinetics of RAFT-mediated graft polymerization of styrene on a solid surface. 1. Experimental evidence of surface radical migration[J] .Macromolecules, 2001,34 (26): 8872 ~ 8878.) first RAFT reagent is bonded in to nanometer SiO
2surface, then carry out graft polymerization, as shown in Figure 2.This method need first be synthesized the coupling agent with RAFT reagent end group, and reaction process is complicated, and purification SiO
2during-RAFT reagent, productive rate is lower.(3) cation graft polymerization.(the Vidal A such as Vidal, Guyot A, Kennedy J P.Silica-grafted polyisobutylene and butyl rubber 1. Synthesis and characterization of silica-grafted polyisobutylene[J] .Polym Bull, 1980,2 (5): 315 ~ 320.) first with silane coupling agent, process nanometer SiO
2introduce Electron Affinities group, then use Lewis acid activation trigger monomer generation cationoid polymerisation, as shown in Figure 3.This method needs the pre-synthesis silane coupling agent containing electrophilic group, and complex disposal process.(4) Anionic Graft Copolymerization.Xuwei arrow etc. (Liu Xi, xuwei arrow, Xiong Yuanqin, Zhou Wei, Zeng little Liang, Hu Shuai. nanometer SiO
2the preparation [J] of surface initiation grafting PA6. synthetic resins and plastics, 2010,27 (3): 11 ~ 14.) utilize SiO
2surface hydroxyl is hexanolactam (CL) monomer fixedly, then take sodium caprolactam(ate) (NaCL) and prepare SiO as initiator causes anionoid polymerization
2grafting nylon 6(SiO
2-PA6).This method complicated operation is loaded down with trivial details, uses the organic solvents such as toluene as reaction medium, and environmental pollution is larger.(5) free yl graft polymerization.Gao Baojiao etc. (Li Ding, Gao Baojiao, position night roc. surperficial Inducing Graft Polymerization legal system meets the grafting particulate SiO of system for height
2-g-PMAA[J]. applied chemistry, 2011,28 (2): 154 ~ 158.) adopt the amino of silica particle surface and ammonium persulphate to form the graft polymerization that redox initiation system causes methymethacrylate (MMA), as shown in Figure 4.Along with the carrying out of polyreaction, not only at SiO
2surface exists by amido causes the graftomer producing, and also will accumulate by HSO more and more in solution
4cause the free homopolymer producing, increased the difficulty of aftertreatment.(the Ribbe A such as R ü he, Prucker O, R ü he J.Imaging of polymer monolayers attached to silica surfaces by element specific transmission electron microscopy[J] .Polymer, 1996,37 (7): 1087 ~ 1093.) utilize silane coupling agent on silica-base material surface, fixedly to contain the unimolecular layer of azo-group, by thermo-cracking, form free radical, the conventional radical polymerization of trigger monomer.But this coupling agent needs special synthetic, in preparation process, also may cause reactive group to decompose, affect graft effect.Li Xiaoxuan etc. (Li Xiaoxuan, left Jian Hua, Wang Jin, Song Enmeng. nanometer SiO
2the research [J] of surface superpolymer graft modification. plastics industry, 2006,34 (z1): 127 ~ 128.) with Silane coupling reagent KH-570 to nanometer SiO
2after processing, utilize suspension polymerization at its surface grafting PMMA.This method utilizes suspension polymerization to prepare the nanometer SiO of surface grafting
2particle is higher to reaction conditions and operational requirement; Yang Wu etc. (Ni Gang, Yang Wu, Bao Lili, Guo Hao, Zhang Wenhao, Gao Jinzhang. surface is caused nitroxyl free radical polyreaction and is prepared polystyrene/SiO
2nano composite material [J]. Science Bulletin, 2006,51 (10): 1234 ~ 1235.) peroxide initiating group is anchored in to nanometer SiO
2surface, by carrying out grafting with the common nitroxyl free radical polymerization causing of oxynitrides.This method reaction process is complicated, and complex operation needs to use a large amount of organic solvents; Father-in-law set the mind on study etc. (Qi Dongming, Bao Yongzhong, Huang Zhiming, father-in-law sets the mind on study. nanometer SiO
2particle anchoring azo initiator and grafting polymethylmethacrylate [J]. polymer journal, 2004, (3): 415 ~ 418.) first at nanometer SiO
2surface anchoring azo initiator causes letex polymerization and prepares nanometer SiO
2-PMMA.This method reaction process is complicated, and needs a large amount of organic solvents, is difficult to realize suitability for industrialized production; (the Wang Weiyong such as Wang Changchun, Gong Tao, Wang Lixin, Wang Changchun, Yang Wuli. mini-emulsion polymerization preparation is loaded with the crosslinked polystyrene fluorescent microsphere [J] of CdTe. chemical journal, 2009,67 (7): 651 ~ 656.) once attempted surface of inorganic particles fixedly Silane coupling reagent KH-570 introduce two keys, subsequently with Potassium Persulphate or Diisopropyl azodicarboxylate Inducing Graft Polymerization.This method is easy and simple to handle, do not form grafted polymer, and therefore just addition in reaction soln produces a large amount of free homopolymer in reaction system, has increased the difficulty of aftertreatment but the elementary free radical of part is added to the two keys of particle surface.(6) light-initiated graft polymerization.(R ü he J, Raghuraman G K, Dhamodharan R, the Prucker O.A robust method for the immobilization of polymer molecules on SiO such as R ü he
2surfaces[J] .Macromolecules, 2008,41:873 ~ 878.) first at nanometer SiO
2the fixing silane coupling agent with benzophenone end group in surface, then by UV photoinitiated grafting polymkeric substance.The method needs pre-synthesis special silane coupling agent, and process is complicated, should not carry out scale operation; (the Yagci Y such as Yagci, Dyer D J, Feng J X, Schmidt R, Wong V N, Zhao T F.Photoinduced polymerization from dimethylamino-terminated self-assembled monolayers on gold[J] .Macromolecules, 2004,37:7072 ~ 7074.) at the fixing coupling agent with Diisopropyl azodicarboxylate (AIBN) end group in nanometer gold surface, then by UV photoinitiated grafting polymkeric substance.The method coupling agent used needs pre-synthesis, cannot meet industrialization production requirements; (the Kim S such as Kim, Kim E, Kim W.Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate[J] .J Colloid Interface Sci, 2005,292:93 ~ 98.) by uv induction BP, directly capture nanometer SiO
2the hydrogen evolution free radical of upper hydroxyl, causes MMA polymerization.This method reaction process is simple, but needs ultraviolet light irradiation 20min to realize, and the reaction times is long.
In existing patent, (the Lee B D such as Lee, Jin Y S, Park H S, Hong J K, Ryu Y S, Kim I J.Method of preparing styrene polymer-silica nanocomposite[P] .United States Patent:US 2008/0255270 A1,2008.10.16.) disclose a kind of use solution polymerization and prepared nanometer SiO
2the method of grafted polystyrene, need to be used a large amount of organic solvents, and operator and environment are all had to disadvantageous effect, and aftertreatment difficulty.(the Yoon T H such as Yoon, Roh J H.Surface modified silica by plasma polymerization, preparation method and apparatus thereof[P] .United States Patent:US 2002/0168480 A1,2002.11.14.) disclose a kind of plasma polymerization that uses and silica-base material has been carried out to the method for surface modification, need to use special plant and instrument, reaction process is complicated.Berkland etc. (Berkland C J, Shi L J.Nanoparticles, nanocapsules and nanogels[P] .United States Patent:US 2008/0075667 A1,2008.3.27.) disclose a kind of at nanometer SiO
2the method of surface grafting polyvinylformamide, reaction need be carried out in organic solvent, and environmental pollution is larger.(the Mitina V such as Mitina, Peter W.Modified silica particles and dirt repellent polymer compositions comprising them[P] .United States Patent:US 2010/0288963 A1,2010.11.18.) disclose a kind of at nanometer SiO
2the method of surface grafting polymerization thing, is used the silane coupling agent with functional group to cause, and need synthesize separately.(the Paganini V such as Paganini, Brocchi V G B.Polymer coating and functionalization of solid surfaces[P] .International Patent:WO 2006/128644,2006.7.12.) a kind of nanometer SiO is disclosed
2surface RAFT Graft Method, its shortcoming is to need the pre-synthesis coupling agent with initiating group.Dong Zhixin etc. (Dong Zhixin, Ji Xiangling, Wei Hua, hair fine horse. a kind of SiO of nucleocapsid structure
2the preparation method [P] of@PDMAEMA nanoparticle. Chinese invention patent: CN 101891867 A, 2010.11.24.) the engrafted nanometer SiO that a kind of ATRP of employing prepares nucleocapsid structure disclosed
2the method of particle.The main drawback of this method is to need the synthetic silane coupling agent with halide end group, has limited its practical application.Zhang Lei etc. (Zhang Lei, Zhang Danfeng. silicane coupled to Nano SiO
2modification method for graft polymerization of acrylic ester [P]. Chinese invention patent: CN 1660917 A, 2005.8.31.) a kind of silicane coupled to Nano SiO disclosed
2modification method for graft polymerization of acrylic ester, adopt Diisopropyl azodicarboxylate to cause radical polymerization grafting as initiator.The main drawback of this method is to use toluene as reaction medium, and environment and operator are all had to disadvantageous effect.Zhou Shibiao etc. (Zhou Shibiao, Xiao Anguo, Chen Zhengan, Zheng Qingyun, Zhang Weiqing, Zhou Huanren, Shen is famous, Li Wenlin, Li Lin, Hao Aiping, Chen Yundao, Zhang Jinping, Zhu Weiguo, Tang Dulin, Xiong Zhifu. nylon 6/ nanometer SiO
2complex fiber material making method [P]. Chinese invention patent: CN 101871138 A, 2010.10.27.) a kind of use modified Nano SiO disclosed
2carry out the method for melt-spinning, wherein nanometer SiO
2surface treatment adopt the method for emulsifier-free emulsion polymerization, the solid content of its system is lower, has limited the industrial applications of this technology.Yu Jian etc. (in building, Liu Wenfang, Guo Chaoxia. olefin polymer/SiO
2nanocomposite Particles and preparation method thereof [P]. Chinese invention patent: CN 1417249 A, 2003.5.14.) a kind of olefin polymer-SiO disclosed
2the preparation method of Nanocomposite Particles, the nanometer SiO in water medium, coupling agent treatment being crossed
2carry out letex polymerization or suspension polymerization grafting, need add emulsifying agent or dispersion agent, last handling process is complicated.Chen Ming wait clearly (Chen Mingqing, Ni Zhongbin, Zhang Ming, Hu Ying, justice is controlled in Feitian, the water paddy south of continuing. a kind of surface modified spherical SiO
2the preparation method of the epoxy resin composite material of particle [P]. Chinese invention patent: CN 101250317 A, 2008.8.27.) a kind of nanometer SiO disclosed
2the preparation method of-epoxy resin composite material, wherein, first uses with the silane coupling agent of unsaturated double-bond and processes nanometer SiO
2surface, then it is carried out to radical polymerization graft modification, make the modified Nano SiO using in matrix material
2particle, the shortcoming of this method is under the condition of acidity and high-speed stirring, to react, and operating process is complicated.
For the grafting method of current announcement, (R ü he J, Raghuraman G K, Dhamodharan R, the Prucker O.A robust method for the immobilization of polymer molecules on SiO such as R ü he
2surfaces[J] .Macromolecules, 2008,41:873 ~ 878.) by silane coupling agent at nanometer SiO
2the method of surperficial fixedly photosensitive group is simple and reliable, but this kind of coupling agent still needs independent synthesizing, and process is loaded down with trivial details.(the Kim S such as Kim, Kim E, Kim W.Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate[J] .J Colloid Interface Sci, 2005,292:93 ~ 98.) by uv induction, directly capture nanometer SiO
2the hydrogen evolution free radical of upper hydroxyl, although the method for trigger monomer polymerization is convenient, the reaction times is long, has limited its application.
The inventor combines the advantage of aforesaid method, utilize silane coupling agent in the fixing primary amine unimolecular layer of glass surface, adopt benzophenone-amine uv induction redox initiation system, by uv irradiation, realized the free yl graft polymerization of glass surface, obtained good effect.Organic primary amine can form uv induction redox initiation system with benzophenone, causes vinyl monomer polymerization.It is generally acknowledged, under benzophenone exists, UV-light can be induced C on primary amine
α-H forms C respectively after charge transfer and prototropy
αfree radical causes the polymerization of short of electricity subclass vinyl monomer.Elicitation procedure as shown in Figure 5.With the additive method being in the news, compare, this method is simply efficient, operate simple and easy, less demanding to reaction conditions; Adopt uv induction Inducing Graft Polymerization, the reaction times is short, and environmental pollution is little; The glass sample of gained surface grafting can be used for improving composite property and other every field.
Summary of the invention
The object of the present invention is to provide a kind of method of glass surface grafted polymer, adopt simple technique, raw material cheap and easy to get, adopt uv induction Inducing Graft Polymerization, obtain good effect, solved existing complex process, pollute and weigh, be difficult to realize the defect of suitability for industrialized production.
The technical solution adopted in the present invention is, a kind of method at glass surface uv induction Inducing Graft Polymerization thing is carried out according to following step:
(1) glass sheet surface is processed
Sheet glass is placed in to polyacrylamide (PAAm) aqueous solution of silane resin acceptor kh-550, after soaking 0.5h, take out, be positioned in 80 ℃ of baking ovens dry, after surface-moisture eliminates completely, oven temperature is risen to 130 ℃, after placement 0.5h, take out, be cooled to after room temperature, be soaked in water, standby after remaining PAAm removes.
(2) preparation of reaction soln
Benzophenone and monomer are dissolved in solvent, make reaction soln.
(3) glass surface grafting
The reaction soln that makes in step (2) is dripped and made on sheet glass in step (1), and irradiation 3min in uv cure machine, can make the glass sheet sample of surface grafting.
Wherein in step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is 1% ~ 5%; The mass percentage concentration of the PAAm aqueous solution is 0.05% ~ 0.2%.As preferred technical scheme, in step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration of 2%, the PAAm aqueous solution is 0.1%.
Wherein in step (2), the solvent that adopts is acetone or acetone/water mixing solutions, and the mass ratio of acetone and water is 1:9.
The monomer wherein adopting in step (2) is DMAA (DMAAm), acrylamide (AAm), N, N-dimethyl-N-methylacryoyloxyethyl-N-propane sulfonic acid inner salt (DMAPS), N, N-dimethyl-N methacrylamide base propyl group-N-propane sulfonic acid inner salt (DMMPPS), sodium acrylate (NaAAc), vinylformic acid (AAc).
Wherein in step (2), the mass ratio of benzophenone and solvent is 1:200, and the mass ratio of monomer and solvent is 1:10.
The present invention adopts benzophenone-amine uv induction redox initiation system, and polymer chain is grafted on to glass surface.Concrete enforcement can be divided into three and walk greatly: the first step is processed sheet glass with KH-550; Second step preparation reaction soln; The 3rd step is evenly coated the glass sheet surface after processing by reaction soln, puts into after uv cure machine irradiation for some time, makes the glass sheet sample of surface grafting.
The invention has the beneficial effects as follows: operating procedure is simple and easy, graft effect is obvious, and the raw material that uses is all commercially available product, do not need can use through complicated purification process, and cheap, easily obtain; Adopt uv induction Inducing Graft Polymerization, simple to operate, the reaction times is short, and environmental pollution is little; Adopt mechanism of free-radical polymerization to carry out grafting, theoretical ripe; The method can be applicable in reinforced composite the adhesive property between resin and glass and changes Properties of Glass Surface by Using, has wide industrial applications prospect.
Accompanying drawing explanation
Fig. 1 is nanometer SiO
2surface A TRP grafted polystyrene schematic diagram.
Fig. 2 is nanometer SiO
2surface RAFT grafting polymethyl methacrylate schematic diagram.
Fig. 3 is nanometer SiO
2isobutylene Initiated cationoid polymerisation schematic diagram after surperficial fixedly Electron Affinities group.
Fig. 4 is persulphate-amine redox initiation nanometer SiO
2surface grafting PMMA schematic diagram.
Fig. 5 is benzophenone-amine uv induction redox initiation mechanism schematic diagram.
Fig. 6 is fixedly primary amine unimolecular layer schematic diagram of glass surface.
Fig. 7 is benzophenone-amine uv induction redox initiation glass surface graft polymerization schematic diagram.
Fig. 8 is that KH-550 processes back glass sheet surface A TR-FTIR spectrogram.
Fig. 9 is the contact angle image of untreated glass sheet surface and water.
Figure 10 is the contact angle image that KH-550 processes back glass sheet surface and water.
Figure 11 is the grafting PDMAAm glass sheet surface ATR-FTIR spectrogram of uv irradiation 5min.
Figure 12 is the contact angle image of grafting PDMAAm glass sheet surface and water.
Figure 13 is the grafting PAAm glass sheet surface ATR-FTIR spectrogram of uv irradiation 5min.
Figure 14 is the contact angle image of grafting PAAm glass sheet surface and water.
Figure 15 is the grafting PDMAPS glass sheet surface ATR-FTIR spectrogram of uv irradiation 5min.
Figure 16 is the contact angle image of grafting PDMAPS glass sheet surface and water.
Figure 17 is the grafting PDMMPPS glass sheet surface ATR-FTIR spectrogram of uv irradiation 5min.
Figure 18 is the contact angle image of grafting PDMMPPS glass sheet surface and water.
Figure 19 is the grafting PNaAAc glass sheet surface ATR-FTIR spectrogram of uv irradiation 5min.
Figure 20 is the contact angle image of grafting PNaAAc glass sheet surface and water.
Figure 21 is the grafting PAAc glass sheet surface ATR-FTIR spectrogram of uv irradiation 5min.
Figure 22 is the contact angle image of grafting PAAc glass sheet surface and water.
specific implementation method
Below in conjunction with specific embodiment, the present invention is elaborated further.
The selected uv cure machine of the present invention is that the Wuxi City special source instrument factory that has a tidal wave of is produced, and model ZX-200, selects fluorescent tube total length 300mm, luminous zone 200mm, spectral range 350 ~ 450nm.
In the present invention, Fig. 1 is nanometer SiO
2surface A TRP grafted polystyrene schematic diagram; Fig. 2 is nanometer SiO
2surface RAFT grafting polymethyl methacrylate schematic diagram; Fig. 3 is nanometer SiO
2isobutylene Initiated cationoid polymerisation schematic diagram after surperficial fixedly Electron Affinities group; Fig. 4 is persulphate-amine redox initiation nanometer SiO
2surface grafting PMMA schematic diagram; Fig. 5 is benzophenone-amine uv induction redox initiation mechanism schematic diagram; Fig. 6 is fixedly primary amine unimolecular layer schematic diagram of glass surface; Fig. 7 is benzophenone-amine uv induction redox initiation glass surface graft polymerization schematic diagram.
The selected PAAm aqueous solution of the present invention is that a certain amount of PAAm is dissolved in to the solution making in distilled water, when being used for dissolving KH-550, KH-550 is uniformly distributed in to glass sheet surface, Fig. 8 is that KH-550 processes back glass sheet surface attenuated total reflectance attenuated total refraction infrared analysis (ATR-FTIR) spectrogram.As can be seen from Figure 8, at 1580 cm
-1with 2930 cm
-1near appearance-NH respectively
2angle vibration and-CH
2-stretching vibration characteristic peak, illustrates that KH-550 has successfully been fixed on glass sheet surface.As shown in Figure 9, untreated glass sheet surface and the contact angle of water are 34.99 °, and as seen from Figure 10, it is 71.95 ° with the contact angle of water that KH-550 processes back glass sheet surface.
Embodiment 1:
0.05g benzophenone and 1g DMAAm are dispersed in 10g acetone, make reaction soln, again reaction soln is evenly coated to the glass sheet surface of processing by the method for step (1), put into uv cure machine irradiation 3min, make the glass sheet sample of surface grafting PDMAAm.In step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration in 1%, the PAAm aqueous solution is 0.05%.Through using infrared spectroscopy analysis, as can be seen from Figure 11, at 2930cm
-1, 1610cm
-1and 1400cm
-1near appearance-CH
3, C=O and C-N characteristic peak, illustrate that PDMAAm is successfully grafted to nanometer SiO
2on.As seen from Figure 12, the glass sheet sample of surface grafting PDMAAm surface is 78.14 ° with the contact angle of water.Recording reaction front glass sheet quality is 0.7865g, and reaction back glass sheet quality is 0.7891g, weightening finish 0.0026g, and rate of body weight gain is 0.3306%.
Embodiment 2:
0.05g benzophenone and 1g AAm are dispersed in 10g acetone, make reaction soln, again reaction soln is evenly coated to the glass sheet surface of processing by the method for step (1), put into uv cure machine irradiation 3min, make the glass sheet sample of surface grafting PAAm.In step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration in 2%, the PAAm aqueous solution is 0.1%.Through using infrared spectroscopy analysis, as can be seen from Figure 13, at 1650cm
-1and 1450cm
-1near there is C=O and C-N characteristic peak, illustrate that PAAm is successfully grafted to nanometer SiO
2on.As seen from Figure 14, the glass sheet sample of surface grafting PAAm surface is 55.78 ° with the contact angle of water.Recording reaction front glass sheet quality is 0.8025g, and reaction back glass sheet quality is 0.8050g, weightening finish 0.0025g, and rate of body weight gain is 0.3115%.
Embodiment 3:
0.05g benzophenone and 1g DMAPS are dispersed in 10g acetone/water mixing solutions, make reaction soln, again reaction soln is evenly coated to the glass sheet surface of processing by the method for step (1), put into uv cure machine irradiation 3min, make the glass sheet sample of surface grafting PDMAPS.In step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration in 3%, the PAAm aqueous solution is 0.15%.Through using infrared spectroscopy analysis, as can be seen from Figure 15, at 1720cm
-1and 1480cm
-1near there is C=O and the ammonium ion characteristic peak on ester group, illustrate that PDMAPS is successfully grafted to nanometer SiO
2on.As seen from Figure 16, the glass sheet sample of surface grafting PDMAPS surface is 45.87 ° with the contact angle of water.Recording reaction front glass sheet quality is 0.6823g, and reaction back glass sheet quality is 0.6863g, weightening finish 0.0040g, and rate of body weight gain is 0.5862%.
Embodiment 4:
0.05g benzophenone and 1g DMMPPS are dispersed in 10g acetone/water mixing solutions, make reaction soln, again reaction soln is evenly coated to the glass sheet surface of processing by the method for step (1), put into uv cure machine irradiation 3min, make the glass sheet sample of surface grafting PDMMPPS.In step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration in 4%, the PAAm aqueous solution is 0.2%.Through using infrared spectroscopy analysis, as can be seen from Figure 17, at 1630cm
-1, 1535cm
-1and 1485 cm
-1near there is C=O, N-H and ammonium ion characteristic peak, illustrate that PDMMPPS is successfully grafted to nanometer SiO
2on.As seen from Figure 18, the glass sheet sample of surface grafting PDMMPPS surface is 38.54 ° with the contact angle of water.Recording reaction front glass sheet quality is 0.6869g, and reaction back glass sheet quality is 0.6891g, weightening finish 0.0022g, and rate of body weight gain is 0.3203%.
Embodiment 5:
0.05g benzophenone and 1g NaAAc are dispersed in 10g acetone/water mixing solutions, make reaction soln, again reaction soln is evenly coated to the glass sheet surface of processing by the method for step (1), put into uv cure machine irradiation 3min, make the glass sheet sample of surface grafting PNaAAc grafting.In step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration in 5%, the PAAm aqueous solution is 0.1%.Through using infrared spectroscopy analysis, as can be seen from Figure 19, at 1545cm
-1and 1405cm
-1near appearance-COO
-with-CH
2-characteristic peak, illustrates that PNaAAc is successfully grafted to nanometer SiO
2on.As seen from Figure 20, the glass sheet sample of surface grafting PNaAAc surface is 51.65 ° with the contact angle of water.Recording reaction front glass sheet quality is 0.6313g, and reaction back glass sheet quality is 0.6320g, weightening finish 0.0007g, and rate of body weight gain is 0.1109%.
Embodiment 6:
0.05g benzophenone and 1g AAc are dispersed in 10g acetone, make reaction soln, again reaction soln is evenly coated to the glass sheet surface of processing by the method for step (1), put into uv cure machine irradiation 3min, make the glass sheet sample of surface grafting PAAc.In step (1), the mass percentage concentration of KH-550 in the PAAm aqueous solution is that the mass percentage concentration in 2%, the PAAm aqueous solution is 0.1%.As can be seen from Figure 21, at 1560cm
-1, 1400cm
-1and 940cm
-1neighbouring appearance-COO ,-CH
2-and C-OH characteristic peak, illustrate that PNaAAc is successfully grafted to nanometer SiO
2on.As seen from Figure 22, the glass sheet sample of surface grafting PAAc surface is 35.49 ° with the contact angle of water.Recording reaction front glass sheet quality is 0.5726g, and reaction back glass sheet quality is 0.5736g, weightening finish 0.0010g, and rate of body weight gain is 0.1746%.
Claims (4)
1. in a method for glass surface uv induction Inducing Graft Polymerization thing, it is characterized in that carrying out according to following step:
(1) glass sheet surface is processed:
Sheet glass is placed in to polyacrylamide (PAAm) aqueous solution of silane resin acceptor kh-550, after soaking 0.5h, take out, be positioned in 80 ℃ of baking ovens dry, after surface-moisture eliminates completely, oven temperature is risen to 130 ℃, after placement 0.5h, take out, be cooled to after room temperature, be soaked in water, standby after remaining PAAm removes;
(2) preparation of reaction soln:
Benzophenone and monomer are dissolved in solvent, make reaction soln;
(3) glass surface grafting:
The reaction soln that makes in step (2) is dripped and made on sheet glass in step (1), and irradiation 3min in uv cure machine, makes the glass sheet sample of surface grafting;
The monomer wherein adopting in step (2) is DMAA, acrylamide, N, N-dimethyl-N-methylacryoyloxyethyl-N-propane sulfonic acid inner salt, N, N-dimethyl-N methacrylamide base propyl group-N-propane sulfonic acid inner salt, sodium acrylate or vinylformic acid.
2. a kind of method at glass surface uv induction Inducing Graft Polymerization thing according to claim 1, is characterized in that wherein the mass percentage concentration of the middle KH-550 of step (1) in the PAAm aqueous solution is 1% ~ 5%; The mass percentage concentration of the PAAm aqueous solution is 0.05% ~ 0.2%.
3. a kind of method at glass surface uv induction Inducing Graft Polymerization thing according to claim 1, is characterized in that wherein the middle solvent that adopts of step (2) is acetone or acetone/water mixing solutions, and the mass ratio of acetone and water is 1:9;
Wherein in step (2), the mass ratio of benzophenone and solvent is 1:200, and the mass ratio of monomer and solvent is 1:10.
4. a kind of method at glass surface uv induction Inducing Graft Polymerization thing according to claim 2, the mass percentage concentration that it is characterized in that KH-550 in step (1) is wherein that the mass percentage concentration of 2%, the PAAm aqueous solution is 0.1%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210192697.8A CN102701602B (en) | 2012-06-12 | 2012-06-12 | Method for initiating graft polymer through ultraviolet induction on surface of glass |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210192697.8A CN102701602B (en) | 2012-06-12 | 2012-06-12 | Method for initiating graft polymer through ultraviolet induction on surface of glass |
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| Publication Number | Publication Date |
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| CN114804651B (en) * | 2022-05-09 | 2024-01-30 | 电子科技大学长三角研究院(湖州) | Method for modifying surface by irradiation grafting of common silicone oil through one-step method and application |
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| JPH10250004A (en) * | 1997-03-10 | 1998-09-22 | Diafoil Co Ltd | Film to be stuck on window |
| WO1999006336A1 (en) * | 1997-08-01 | 1999-02-11 | Revlon Consumer Products Corporation | Glass decorating compositions using bisphenol a epoxies |
| CA2340918A1 (en) * | 1998-08-17 | 2000-02-24 | Revlon Consumer Products Corporation | Glass decorating method using ink compositions containing n-vinyl lactams |
| CN1711309A (en) * | 2002-11-08 | 2005-12-21 | 接枝发展有限责任公司 | Surface treatment method by photopolymerization to obtain biocidal properties |
| CN101560061A (en) * | 2009-05-27 | 2009-10-21 | 上海交通大学 | Method for preparing patterned polymer brush |
| WO2010044668A1 (en) * | 2008-10-17 | 2010-04-22 | Wageningen Universiteit | Photochemical modification of solid materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10250004A (en) * | 1997-03-10 | 1998-09-22 | Diafoil Co Ltd | Film to be stuck on window |
| WO1999006336A1 (en) * | 1997-08-01 | 1999-02-11 | Revlon Consumer Products Corporation | Glass decorating compositions using bisphenol a epoxies |
| CA2340918A1 (en) * | 1998-08-17 | 2000-02-24 | Revlon Consumer Products Corporation | Glass decorating method using ink compositions containing n-vinyl lactams |
| CN1711309A (en) * | 2002-11-08 | 2005-12-21 | 接枝发展有限责任公司 | Surface treatment method by photopolymerization to obtain biocidal properties |
| WO2010044668A1 (en) * | 2008-10-17 | 2010-04-22 | Wageningen Universiteit | Photochemical modification of solid materials |
| CN101560061A (en) * | 2009-05-27 | 2009-10-21 | 上海交通大学 | Method for preparing patterned polymer brush |
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