CN104194011A - Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof - Google Patents
Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof Download PDFInfo
- Publication number
- CN104194011A CN104194011A CN201410421903.7A CN201410421903A CN104194011A CN 104194011 A CN104194011 A CN 104194011A CN 201410421903 A CN201410421903 A CN 201410421903A CN 104194011 A CN104194011 A CN 104194011A
- Authority
- CN
- China
- Prior art keywords
- polysiloxane
- composite membrane
- colloidal sol
- titanium
- preparation
- 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.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polysiloxane/titanium sol photocatalytic composite film and a preparation method thereof. The preparation method comprises the following steps: after mixing terminal hydroxyl silicone oil, polymethylhydrosiloxane, a titanium sol and a solvent methylbenzene in certain amounts, dropwise adding a small amount of Karstedt platinum catalyst; initializing dehydrogenation condensation reaction between two types of silicon oil; after quickly and uniformly stirring, pouring into a polytetrafluoroethylene die; and gradually forming the film along with volatilization and condensation reaction of the solvent. The composite film disclosed by the invention is prepared from easily available raw materials, mild in preparation condition and simple in process and is suitable for large-scale industrialized production. In addition, the composite film is strong in controllability of structural morphology and can give consideration to property of ultraviolet resistance and photocatalytic performance of titanium sol particles, so that the composite film not only has an excellent ultraviolet shielding effect, but also has the functions of generating degraded organic matters, resisting and inhibiting bacteria, self-cleaning and the like due to the photocatalytic effect. The polysiloxane/titanium sol photocatalytic composite film can be used in the fields of textile, cosmetics, coatings, buildings, hygiene, medicines and the like.
Description
Technical field
The present invention relates to organic/inorganic compound film field, be specifically related to a kind of titanium sol particle is evenly distributed in the silicon oil solution that main chain is Si-O key, the volatilization by the condensation reaction between silicone oil and 3 D cross-linked and solvent makes polysiloxane/titanium colloidal sol photocatalysis composite membrane of ageing resistance and preparation method thereof.
Background technology
Due to the development of nanometer material science, functional type nanoparticle has become one of focus of research as additive.Dichloride in anatase type TiO
2as a kind of inorganic functional particle, because it has the advantages such as nonpoisonous and tasteless, stability is strong, uv-shielding capacity good, photo-catalysis capability is excellent, under the effect adhering at tackiness agent, be applied to the fields such as weaving, coating, building, makeup, thereby can make textiles and carrier matrix there is the effects such as continual and steady ultraviolet shielded, bactericidal, degraded dirt, automatically cleaning.
For example, Gao Jianzhong [CN1560353A, nano sunlight screening finishing composition and preparation method and for the afterfinish method of yarn fabric] is mixed with a kind of nano sunlight screening finishing composition by nano titanium oxide, amino silicon, tackiness agent and water and to fabric treating; Liu Fuchun [CN1412258, a kind of nano UV resistant acrylate paint] etc. be take acrylate as organic carrier, plus nano TiO
2prepare a kind of nano UV resistant acrylate paint with dispersion agent.But increasing research shows in recent years, dichloride in anatase type TiO
2can because its strong photocatalysis produces the great high energy OOH of reaction activity and OH free radical, (OOH reaction activity be 431kJmol under illumination
-1, OH reaction activity is 402.7kJmol
-1), these high energy radical pairs are various take C-C key (bond energy is 346kJmol
-1) there is very strong aging infringement for the polymer carrier of main chain and textiles.This has limited dichloride in anatase type TiO to a great extent
2widespread use and large-scale promotion at weaving and other field.
(bond energy is up to 460kJmol with the Si-O key of high energy for polysiloxane
-1) be the main chain backbone of its dimensional network structure, and above-mentioned high energy free radical and strong UV-light are had to very strong defensive ability/resistance ability.While polysiloxane and nano-TiO
2there is good consistency, easily realize effectively compound.Thereby using polysiloxane as novel adhesive carrier, become current dichloride in anatase type TiO
2an important development direction in organic load and adhesion research.Ding Xiaofeng [CN101724342A; CN101962514A; J Mater Chem, 2011,21:6161～6164] etc. take polysiloxane as membrane-forming agent, with a large amount of powder anatase titanium dioxide TiO
2the compound poly-fluorosilicone/TiO of a series of automatically cleanings with super-hydrophobic or super parents' function that made
2nano-composite coating; This seminar application publication number is that the Chinese patent of CN103483607A (a kind of preparation method of titanium dioxide/polysiloxane photocatalysis composite membrane) discloses a kind of method that polysiloxane by vinyl-terminated silicone fluid and containing hydrogen silicone oil addition reaction of silicon with hydrogen and titanium dioxide in-situ polymerization are prepared photocatalysis composite membrane.But there is crosslinked main chain in above-mentioned research, all contain a small amount of C-C key, use can make its ageing-resistant performance variation for a long time.Jiang Mei [polymer journal in addition, 2008,6:594～599], Wang Fang [Journal of Inorganic Materials, 2010,25 (1): 37～40] etc. people to take butyl (tetra) titanate and silane be presoma, by sol-gel and curing of coating process, single stage method has made polysiloxane/titanium colloidal sol hybrid material, the stable and uniform that has not only realized organic/inorganic two-phase is compound, and makes crosslinked main chain be Si-O key.But made titanium sol particle be take undefined structure as main under this system, its photochemical catalysis and ultraviolet shielded ability are poor.
In addition, publication number is that the Chinese patent application of CN101928517A (nano self-cleaning paint and preparation method thereof) discloses a kind of method that anatase titanium dioxide titanium colloidal sol and polysiloxane solution physical blending are prepared nano self-cleaning paint, described in the method, in process, do not relate to the reaction between silicone molecule, there is no constructing of 3 D cross-linked structure yet, thereby the mechanics of manufactured coating itself, optics, photochemical catalysis and the poor-performing such as ageing-resistant.
Summary of the invention
The invention provides the preparation method of a kind of technique high ageing resistance polysiloxane/titanium colloidal sol photocatalysis composite membrane simple, easy to implement.Its core is that to have certain oil loving polymolecularity anatase crystal type titanium sol particle be photocatalyst material, under existing, it carries out the condensation reaction of end hydroxyl silicone oil and polymethyl hydrogen siloxane, make and take completely the polysiloxane cubic network crosslinking structure film that high bond energy Si-O is main chain, realize titanium sol particle evenly firmly the inlaying of film surface half embedding form, thereby give the photocatalytic of composite membrane excellence, ultraviolet shielded property, bacteria resistance and ageing-resistant etc. performance.
A preparation method for polysiloxane/titanium colloidal sol photocatalysis composite membrane, comprises the following steps:
After titanium colloidal sol, end hydroxyl silicone oil, polymethyl hydrogen siloxane and film forming solvent mix, add catalyzer, cause the condensation reaction between silicone oil, after stirring, pour in mould, under the environment of 60 ℃～100 ℃, with the volatilization of solvent and reaction carry out and film forming gradually obtains polysiloxane/titanium colloidal sol photocatalysis composite membrane.
In the present invention, through the condensation reaction between silicone oil, construct and take the 3 D cross-linked structure that siloxane bond is main chain completely, thereby make ageing resistance polysiloxane/titanium colloidal sol photocatalysis composite membrane that titanium sol particle can reach uniform and stable dispersion in polysiloxane matrix.
Titanium sol particle in described titanium colloidal sol is anatase crystal type, a large amount of Si-OH and Si-OR isoreactivity group are contained in surface, particle diameter is 20～50nm, and in described titanium colloidal sol, titanium sol particle consumption is 1%～5% of end hydroxyl silicone oil and polymethyl hydrogen siloxane total mass.
Titanium sol particle, because having typical anatase crystal type, can guarantee that particle itself has good photocatalysis, thereby can be composite membrane, provides photocatalysis effect and the automatically cleaning effects such as excellent antibacterial bacteriostatic, degradation of organic substances.Titanium sol particle particle diameter is chosen as 20～50nm.Particle diameter is less than 20nm, and the crystal formation of particle is very unstable, and its photo-catalysis capability can be weakened.Be greater than 50nm, particle is dispersion stabilization meeting variation in sol system, and its photo-catalysis capability also can the corresponding reduction because of the reduction of specific surface area.
1%～5% of the quality that titanium colloidal sol consumption is end hydroxyl silicone oil.Titanium sol particle particle diameter is little, even thereby also can be at the numerous titanium sol particles of composite membrane surface inserting under lower consumption, thereby give the photochemical catalysis effect that composite membrane is good.Too much can increase cost adding not only of titanium sol particle in addition, also can cause that particle is assembled in the inner part occurring of composite membrane and reunion is separated out, thereby affect the transparency, mechanical property and the corresponding photocatalysis performance of composite membrane.
Anatase crystal type titanium colloidal sol is by the katalysis of concentrated hydrochloric acid, comparatively high temps (for example 70 ℃) lower adopt sol-gel process prepare (can be referring to Shen Xingcong, Xu Jie, Zhang Rui, Chen Zhijie, Qi Dongming. nano-TiO
2sol-gel method preparation and characterize Institutes Of Technology Of Zhejiang's journal, 2012,29 (2): 249-253).Above-mentioned colloidal sol can change by carry out the mode of medium displacement in Rotary Evaporators the medium of its dispersion.These titanium sol particle surfaces often remain some and do not remove clean-OC
4h
9etc. oil loving alkoxy grp, this can strengthen itself and organic consistency, and then improves its dispersiveness and dispersion stabilization in organic medium and polysiloxane matrix.In addition, as nano particle, can there is a large amount of Ti-OH groups in titanium sol particle surface, its can with polymethyl hydrogen siloxane in the anti-raw condensation reaction of Si-H key, thereby improve the compound fastness of titanium sol particle in composite membrane.
The molecular formula of described end hydroxyl silicone oil is as follows:
Wherein, 160≤a≤350, and a is integer, end hydroxyl silicone oil molecular weight is (1.2～2.6) * 10
4.
The hydroxyl at molecular formula two ends has very high reactive behavior, can under strong acidic condition, dehydration condensation occur, thereby expands the length of molecular chain.Select the end hydroxyl silicone oil that contains 160～350 repeating unit dimethyl silscone in molecule, molecular weight is (1.2～2.6) * 10
4.Molecular weight is less than this scope, and condensation reaction is too violent, and system stability is poor, and easily local excessive is crosslinked and reunite, and makes the final quality of composite membrane all can variation; Molecular weight is greater than this scope, condensation reaction probability occurs in unit reaction volume and decline, and the crosslinking degree of system can be not, and composite membrane film formation time mechanical property of a specified duration and corresponding is not good.
The molecular formula of described polymethyl hydrogen siloxane is as follows:
Wherein, 6≤m≤18,250≤n≤460, and m, n be integer, polymethyl hydrogen siloxane molecular weight is (1.8～3.4) * 10
4, and in molecule Si-H with the content of H, be 0.017～0.092% of polymethyl hydrogen siloxane molecular mass.
Repeating unit in polymethyl hydrogen siloxane molecular formula is comprised of two kinds of methyl silicone and dimethyl silscone.In methyl silicone unit wherein, contain a si-h bond, under the condition that this reactive group can exist at platinum catalyst with Si-OH, carry out condensation reaction and deviate from H
2.In polymethyl hydrogen siloxane molecule, the quantity of methyl silicone unit is 6～18, thereby a polymethyl hydrogen siloxane molecule can react with a plurality of end hydroxyl silicone oil molecules.Its functionality is greater than 2, thereby can play therein the effect of linking agent.In molecular formula, dimethyl silscone unit is inertia unit, its Main Function is the concentration of si-h bond in diluent molecules, thereby weaken the severe degree of condensation reaction and the crosslinking degree of final product, also can increase on the other hand the molecular weight of polymethyl hydrogen siloxane, thereby improve the mechanical property of composite membrane.Preferably dimethyl silscone element number is 250～460, and polymethyl hydrogen siloxane molecular weight is (1.8～3.4) * 10
4, and in molecule Si-H with the content of H, be 0.017%～0.092% of polymethyl hydrogen siloxane molecule.In the case, system reaction process is stable, composite membrane mechanical strength is better.Be less than this scope, Si-H too high levels, condensation reaction is too violent, and easily local excessive is cross-linked and reunites, and the H generating
2can not get rid of in time, easily make to be full of bubble in composite membrane, finally cause the quality variation of composite membrane; Be greater than this scope, the crosslinking degree of composite membrane is inadequate, and film forming properties is poor.
Described end hydroxyl silicone oil and the mol ratio of polymethyl hydrogen siloxane are 3～9:1.This mainly determines according to the quantity m of silicon hydrogen group in polymethyl hydrogen siloxane molecule, because there be m silicon hydrogen base can participate in condensation reaction in a polymethyl hydrogen siloxane, and in an end hydroxyl silicone oil molecule, has two terminal hydroxy group can participate in condensation reaction.Thereby using the input mol ratio of m/2 as both.
Described catalyzer is karstedt catalyzer, karstedt catalyzer is a kind of commercially available high reactivity platinum catalyst, condensation reaction between hydroxy silicon oil and polymethyl hydrogen siloxane is had to good katalysis, contribute to more stably to construct the 3 D cross-linked structure of polysiloxane in drying and forming-film process, thereby promote the performance of composite membrane.The consumption of described karstedt catalyzer is (5～15) * 10 of end hydroxyl silicone oil and polymethyl hydrogen siloxane total mass
-4%, is greater than this scope, and it is fiercer that condensation reaction is carried out, and easily local generation, produces a large amount of bubbles and make film uniformity poor at excessively crosslinked reunion; Be less than this scope, react slower, crosslinking structure is more incomplete, can reduce equally the mechanical property of film material.
Described film forming solvent is toluene, because itself and titanium colloidal sol and polysiloxane have good consistency, contributes to dissolving, the dispersion of above-mentioned substance in system and flows.Toluene in system consists of titanium sol medium and filming medium two portions, the medium of described titanium colloidal sol is toluene, described titanium colloidal sol is comprised of titanium sol particle and toluene, and total consumption of the toluene in described titanium colloidal sol and the film forming solvent toluene adding is end hydroxyl silicone oil and polymethyl hydrogen siloxane total mass 0.3～2 times.Consumption is less than 0.3 times of silicone oil total mass, and the mobility of film forming system is too poor, is unfavorable for the carrying out of crosslinking reaction between Different Silicon oil molecule, makes homogeneity, the transparency and the mechanical strength of composite membrane all can be relative poor.With being greater than 2 times of silicone oil total mass, can make the titanium sol particle in composite membrane because consistency is bad, separate out and reunite, extend film formation time, and can increase tooling cost.Thereby, the solvent medium in described titanium colloidal sol and add total consumption of film forming solvent to be preferably end hydroxyl silicone oil and polymethyl hydrogen siloxane total mass 0.3～2 times.
End hydroxyl silicone oil is close with polymethyl hydrogen siloxane backbone structure, and consistency is better, very easily mixes.Some dehydration generations-OH is contained on titanium sol particle surface, can react with Si-OH and Si-H, thereby easily mix with silicone oil, and can reach therein firmly even, stable dispersion, and this dispersion state is very important to the effect of final composite membrane.
Karstedt platinum catalyst is a kind of effective catalyst, and Si-OH and Si-H all have higher reactive behavior, at room temperature adds a small amount of catalyzer can cause the condensation reaction between end hydroxyl silicone oil and polymethyl hydrogen siloxane in above-mentioned system, sloughs a H
2.Its reaction equation is as follows:
Said mixture is poured in tetrafluoroethylene mould, and under 80 ℃ of dry environment, along with the carrying out of volatilization and the condensation reaction of solvent, system viscosity and density raise, and film-forming gradually.In process, contain a plurality of silicon hydrogen bases polymethyl hydrogen siloxane molecule can with a plurality of end hydroxyl silicone oil molecule generation condensation reactions, and can connect different polymethyl hydrogen siloxane molecules containing the end hydroxyl silicone oil molecule of two hydroxyls, thereby can in system, build cubic network crosslinking structure.And in this crosslinking structure, the Si-O key that its main chain is high energy forms, and this contributes to improve mechanical property and the ageing-resistant performance of film material.Titanium sol particle can disperse uniformly in cross-linking system simultaneously, thereby gives the good photocatalytic of composite membrane and uv-shielding capacity.
The described photocatalysis composite membrane that contains titanium sol particle has good ageing-resistant performance, composite membrane is placed in ultraviolet ageing instrument and is irradiated, the accelerated deterioration that ultraviolet lighting-clear water flushing of take is cycling element (under 60 ℃ of environment, predominant wavelength 340nm, irradiation intensity 0.68Wm
-2ultraluminescence light irradiation 10h; Cold water spray 2h under 50 ℃ of dark conditions), after illumination 300h, the rate of weight loss of composite membrane is only in 5%.
The standard thickness of the described polysiloxane/titanium colloidal sol photocatalysis composite membrane that contains titanium sol particle is 300 μ m, has efficient photocatalysis.In dye liquor, adding diameter is the composite membrane of 5.0cm, and dye liquor is placed under the 50w ultraviolet mercury lamp (predominant wavelength 365nm) at liquid level 50cm place and is degraded.After 6h irradiates, the composite membrane that titanium sol particle effective content is 5% can reach more than 95% the palliating degradation degree of rhodamine B.This can guarantee that composite membrane has good photocatalytic Degradation.In addition, this composite membrane also can be used for the organic compound such as PARA FORMALDEHYDE PRILLS(91,95) and residual tensio-active agent and carries out photocatalytic degradation.
The described composite membrane that contains titanium sol particle has excellent photocatalysis antibacterial effect, in the substratum of streptococcus aureus, place the composite membrane that titanium colloidal sol effective content is 5%, after the UV illumination 24h of 15w, can produce ring degree wide is the inhibition zone of 0.45cm.
In the present invention, described be uniformly mixed, medium displacement, the molten film etc. cast be the typical unit operation in chemical process, can adopt existing conventional equipment to realize.
Compared with prior art, the present invention has following beneficial effect:
(1) using polysiloxane that full Si-O key is main chain as anatase titanium dioxide TiO
2organic carrier, not only uvioresistant performance is good, also has excellent ageing resistance.Also can avoid TiO simultaneously
2photocatalysis is to take the organic carrier embrittlement damage that the low bond energys such as C-C key are main chain, thereby effectively improves the ageing-resistant performance of organic carrier.And polysiloxane itself is soft, has good weathering resistance and organic/inorganic both sexes, can give the good feel of composite membrane and sticking power.
(2) polymethyl hydrogen siloxane and end hydroxyl silicone oil are carried out to crosslinking reaction, because the polymethyl hydrogen siloxane molecule that contains a plurality of silicon hydrogen bases can react with a plurality of end hydroxyl silicone oil molecule generation dehydrogenative condensations, end hydroxyl silicone oil molecule containing two hydroxyls can connect different polymethyl hydrogen siloxane molecular chains simultaneously, thereby can in system, build cubic network crosslinking structure.This contributes to improve mechanical property and the ageing-resistant performance of film material.
(3) as inorganic functional particle anatase crystal type titanium sol particle surface used, contain a small amount of alcoxyl residue, can there is certain consistency with polysiloxane, in film process, can effectively avoid conventional inorganic particle to have serious problem of assembling, thereby realize the dispersing uniformity of titanium sol particle in composite membrane, and keep the photocatalysis that sol particle is good.
(4) in film process, anatase crystal type titanium sol particle surface used is contained and is not removed on a small quantity clean alcoxyl residue, this make titanium sol particle and polyoxy alkane consistency better.But because titanium colloidal sol nano grain surface still can be take hydroxyl as main generally, thereby titanium sol particle is not completely compatible with polysiloxane.So titanium sol particle can be subject to repulsion to a certain extent in film process, thereby have many titanium sol particles meeting enrichments and be embedded in composite membrane surface, the exposed complex form of this photocatalytic particle half can give composite membrane better photocatalysis.
(5) the titanium sol particle surface as nano particle inevitably still can remain with many hydroxyls, and these groups with certain reactive behavior can react with the Si-H group generation dehydrogenative condensation in polymethyl hydrogen siloxane equally in condensation reaction film process.This not only can improve the dispersing uniformity of titanium sol particle in composite membrane, also will contribute to reinforce the compound fastness of titanium sol particle and poly-silica silicon matrix, makes it can be embedded in more firmly film surface, thus improve composite membrane can reusing.And also can be used as the cross-linking set of macrobead form, in system, play certain crosslinked strengthening action.
(6) raw material involved in the present invention is easy to get, and preparation condition is gentle, and technique is simple, can be suitable for large-scale industrial production.In addition, the controllability of this structure of composite membrane form is strong, can take into account uvioresistant performance and the photocatalysis performance of titanium sol particle in film simultaneously, make the ultraviolet shielded effect of the existing excellence of composite membrane, because of photocatalysis, produce again the effects such as degradation of organic substances, antibacterial bacteriostatic, automatically cleaning, can be used for the fields such as weaving, makeup, coating, building, health, medical science.
Accompanying drawing explanation
Fig. 1 is the infrared spectra spectrogram of end hydroxyl silicone oil in comparative example 1, polymethyl hydrogen siloxane and the prepared polysiloxane film of condensation reaction;
Fig. 2 is the surface topography (FE-SEM photo) of embodiment 1 made composite membrane;
Fig. 3 is the ultraviolet ageing rate of weight loss curve of comparative example 1 and the made polysiloxane film of embodiment 1 and polypropylene sorrel;
Fig. 4 is the antibacterial effect comparison diagram of the made polysiloxane composite membrane of comparative example 1 (left side) and the made polysiloxane/titanium of embodiment 10 colloidal sol composite membrane (the right);
Fig. 5 is that in the made polysiloxane composite membrane of comparative example 1 and the experiment of the made polysiloxane/titanium colloidal sol of embodiment 8,10 and 1 photocatalysis composite membrane degradation of dye, dye liquor concentration is with the change curve of light application time;
Fig. 6 is that in the experiment of the made polysiloxane/titanium of embodiment 1 colloidal sol photocatalysis composite membrane circulation degradation of dye, dye liquor concentration is with the change curve of light application time.
Embodiment
Embodiment 1～12
By a certain amount of end hydroxyl silicone oil, polymethyl hydrogen siloxane, titanium colloidal sol (wherein, toluene is 100g) put into beaker and stir, then add in a small amount of film forming solvent toluene (28g), in system, amount to toluene 128g, after mixing (wherein, the weight of end hydroxyl silicone oil and polymethyl hydrogen siloxane adds up to 100g, adds the benchmark of quality as other material), drip Karstedt platinum catalyst and cause the condensation reaction between silicone oil, and pour in tetrafluoroethylene mould.Under the environment of 80 ℃, with the volatilization of solvent and carrying out gradually of condensation reaction, construct 3 D cross-linked structure further film, after 24h, can obtain the dispersed and part of titanium sol particle and be embedded in the multi-functional composite membrane on polysiloxane matrix surface, be polysiloxane/titanium colloidal sol photocatalysis composite membrane, control thickness in 300 μ m left and right.
Concrete technology formula and composite membrane performance are in Table 1.
Table 1
Comparative example 1～4
The same comparative example of operating process, concrete technology formula and composite membrane performance are in Table 2, and wherein, the toluene in titanium colloidal sol is 128g with total consumption of the film forming solvent toluene adding.
Table 2
The characterizing method explanation relating in embodiment 1～12 and comparative example 1～4:
Adopt Fourier transform infrared spectrograph (FT-IR, the Nicolet of U.S. power & light company 5700) to carry out analysis of the molecular structure to polysiloxane film and each component;
Adopt field emission scanning electron microscope (FE-SEM, the German Zeiss Ultra of company 55 types) to observe the surface topography of polysiloxane/titanium colloidal sol photocatalysis composite membrane;
The illumination weightless test of composite membrane: in ultraviolet accelerated deterioration instrument, adopt illumination-spray reciprocation cycle process carry out accelerated deterioration experiment (under 60 ℃ of environment, predominant wavelength 340nm, irradiation intensity 0.68Wm
-2ultraluminescence light irradiation 10h; Cold water spray 2h under 50 ℃ of dark conditions), and interval sampling during the course, after being dried, weigh, utilize the weightless degree of film to assess the photocatalytic Degradation of titanium sol particle to membrane matrix.
The photocatalysis antibacterial experiment of composite membrane: add 20 μ L bacteriums respectively in centrifuge tube with 10 μ L liquid-transfering guns, after mixing, be coated in respectively on substratum, all processes all realize on disinfecting action platform.The onesize polysiloxane film through sterilising treatment and polysiloxane/titanium colloidal sol photocatalysis composite membrane disk are placed on above-mentioned substratum, substratum is positioned in the climatic chamber of built-in 15W ultraviolet lamp (predominant wavelength 254nm), lamp is apart from substratum 30cm, (37 ℃ of bacterium optimum growh environment, 50% relative humidity) under, cultivate after 24h, observe the formational situation of the outer inhibition zone of composite membrane disk.
Press GB/T528-1998 standard, the tensile property of test compound film in electronic universal material testing machine (American I nstron Corporation2345 type), draw speed 100mmmin
-1.
The photocatalytic degradation of dye molecule experiment of composite membrane: water-soluble dye rhodamine B is made into the dye liquor of 20ppm, puts into polysiloxane film or polysiloxane/titanium colloidal sol composite membrane wherein flat screen, controlling diaphragm material add-on is 20gL
-1.Etc. standing 30min absorption saturated after, with 50W ultraviolet mercury lamp (predominant wavelength 365nm) irradiation dye liquor in 50cm place above liquid level.Interval certain hour shakes up sampling, measures the absorbancy of dye liquor at the main absorption peak 540nm of dyestuff place and changes, to assess degradation of dye effect in ultraviolet/visible spectrophotometer (UV/Vis, the Perkin Elmer Lambda of company 900 types).
It is as shown in table 1 that embodiment 1～12 surveys the results such as the width, tensile property of inhibition zone endless belt.
It is as shown in table 2 that comparative example 1～4 is surveyed the results such as the width, tensile property of inhibition zone endless belt.
Fig. 1 is the infrared spectra spectrogram of end hydroxyl silicone oil in comparative example 1, polymethyl hydrogen siloxane and the prepared polysiloxane film of condensation reaction.As shown in Figure 1, in figure 1000 and 2960cm
-1the two strong absorption peaks in place belong to respectively organosilicon main chain backbone Si-O-Si and side group-CH
3stretching vibration peak, in three samples, above-mentioned two peaks do not have notable difference, illustrate that material basic structure is similar before and after condensation reaction.In polymethyl hydrogen siloxane 2157 and 911cm
-1two place's absorption peaks are very obvious, and two absorption peaks belong to respectively the flexible and anti-stretching vibration of Si-H.3300cm in end hydroxyl silicone oil
-1place's absorption peak is very obvious, the stretching vibration of belong to-OH.And not obvious at the characteristic peak at above-mentioned three places in gained polysiloxane, illustrate contain a plurality of Si-H bases polymethyl hydrogen siloxane fully and end hydroxyl silicone oil-there is condensation reaction, thereby can obtain having the polysiloxane film of certain crosslinking structure in OH.
Fig. 2 is the surface topography (FE-SEM photo) of embodiment 1 made composite membrane, and as shown in Figure 2, composite membrane surface is without obvious outstanding coacervate, and whole film surface is flooded with the TiO of a large amount of exquisitenesses
2particle, these particles are about 20-50nm in unordered its size of loose stacking states.These TiO
2particle is mainly partly embedded in polysiloxane film surface with the form of inlaying, and this will make composite membrane show better photo-catalysis capability.
Fig. 3 is the ultraviolet ageing rate of weight loss curve of comparative example 1 and the made polysiloxane film of embodiment 1 and polypropylene sorrel.As shown in Figure 3, under uv irradiating, the quality of polyacrylic ester basement membrane all has obvious decline.And after composite titanium sol particle, the aging tendency of film is obviously strengthened.Polysiloxane basement membrane shows good ageing resistance, (probably comes from volatilization gradually and the escape of original small molecules and oligopolymer in film) except having in starting 25h certain weightlessness, and quality remains unchanged substantially afterwards.Polysiloxane that Si-O key is main chain is take in explanation, and not only self uvioresistant ability is strong, and resistance to TiO
2the strong oxidation-reduction of the high energy free radical that produces.
Fig. 4 is the antibacterial effect comparison diagram of the made polysiloxane film of comparative example 1 (left side) and the made polysiloxane/titanium of embodiment 10 colloidal sol composite membrane (the right).As shown in Figure 4, polysiloxane film itself does not have anti-microbial effect; Polysiloxane/titanium colloidal sol composite membrane disk there will be an obvious inhibition zone around, and the width of this ring band is 0.38cm, illustrates that it has good antibacterial and bacteriostasis.
Fig. 5 is that in the made polysiloxane/titanium dioxide photocatalysis composite membrane degradation of dye experiment of the made polysiloxane film of comparative example 1 and embodiment 8,10 and 1, dye liquor concentration is with the change curve of light application time.Ordinate zou (C/C
0) be the ratio of the concentration after the degraded of water-soluble dye rhodamine B with its starting point concentration.As shown in Figure 5: by above-mentioned film in dye liquor, adsorb saturated after, under UV-irradiation, polysiloxane film itself does not have degradation effect substantially to rhdamine B molecule.And polysiloxane/titanium colloidal sol photocatalysis composite membrane has good photocatalytic degradation effect, and degradation effect and titanium sol content closely related.When titanium sol content is silicone oil quality 1.0%, photocatalysis effect is more general.And when titanium sol content increases to 3.0%, irradiate after 4.5h, there is the dye molecule of half left and right effectively to be decomposed.When content further increases to 5.0%, dyestuff decomposes half required time and is reduced to about 2h.
Fig. 6 is that in the experiment of the made polysiloxane/titanium dioxide photocatalysis composite membrane of embodiment 1 circulation degradation of dye, dye liquor concentration is with the change curve of light application time.Ordinate zou (C/C
0) be the ratio of the concentration after the degraded of water-soluble dye rhodamine B with its starting point concentration.As shown in Figure 6, under UV-light, after polysiloxane/titanium colloidal sol photocatalysis composite membrane recycles for three times, to the degradation efficiency of dyestuff, still can reach more than 80%, and degradation rate is almost constant.Illustrate that thus polysiloxane/titanium colloidal sol photocatalysis composite membrane not only has the effect of efficient photocatalytic degradation of dye, and can recycled for multiple times, the utilising efficiency of material improved.
Claims (10)
1. a preparation method for polysiloxane/titanium colloidal sol photocatalysis composite membrane, is characterized in that, comprises the following steps:
After titanium colloidal sol, end hydroxyl silicone oil, polymethyl hydrogen siloxane and film forming solvent mix, add catalyzer, cause the condensation reaction between silicone oil, after stirring, pour in mould, under the environment of 60 ℃～100 ℃, with the volatilization of solvent and reaction carry out and film forming gradually obtains polysiloxane/titanium colloidal sol photocatalysis composite membrane.
2. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, the titanium sol particle in described titanium colloidal sol is anatase crystal type, and particle diameter is 20～50nm.
3. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, in described titanium colloidal sol, titanium sol particle consumption is 1%～5% of end hydroxyl silicone oil and polymethyl hydrogen siloxane total mass.
4. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, the molecular formula of described end hydroxyl silicone oil is as follows:
Wherein, 160≤a≤350, and a is integer.
5. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, the molecular formula of described polymethyl hydrogen siloxane is as follows:
Wherein, 6≤m≤18,250≤n≤460, and m, n are integer.
6. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, described end hydroxyl silicone oil and the mol ratio of polymethyl hydrogen siloxane are 3～9:1.
7. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, described catalyzer is karstedt catalyzer.
8. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 1, is characterized in that, described film forming solvent is toluene, and described titanium colloidal sol is comprised of titanium sol particle and toluene.
9. the preparation method of polysiloxane/titanium colloidal sol photocatalysis composite membrane according to claim 8, it is characterized in that, total consumption of the toluene in described titanium colloidal sol and the film forming solvent toluene adding is end hydroxyl silicone oil and polymethyl hydrogen siloxane total mass 0.3～2 times.
10. polysiloxane/titanium colloidal sol photocatalysis composite membrane of preparing according to the preparation method described in claim 1～9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410421903.7A CN104194011B (en) | 2014-08-25 | 2014-08-25 | Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410421903.7A CN104194011B (en) | 2014-08-25 | 2014-08-25 | Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104194011A true CN104194011A (en) | 2014-12-10 |
| CN104194011B CN104194011B (en) | 2017-02-22 |
Family
ID=52079399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410421903.7A Active CN104194011B (en) | 2014-08-25 | 2014-08-25 | Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104194011B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835936A (en) * | 2022-05-05 | 2022-08-02 | 江苏盈泰新材料科技有限公司 | Photocatalytic self-cleaning PVC (polyvinyl chloride) film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185854A (en) * | 2007-08-29 | 2008-05-28 | 江南大学 | Silicon rubber oxygen-enriched film doped silicon dioxide and preparation method thereof |
| CN103483607A (en) * | 2013-09-04 | 2014-01-01 | 浙江理工大学 | Preparation method of titanium dioxide/polysiloxane photocatalytic composite film |
| CN104263238A (en) * | 2014-09-11 | 2015-01-07 | 天津大学 | Fluoridated POSS (polysilsesquioxane) composite organic silicon coating as well as preparation method and anti-icing application thereof |
-
2014
- 2014-08-25 CN CN201410421903.7A patent/CN104194011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185854A (en) * | 2007-08-29 | 2008-05-28 | 江南大学 | Silicon rubber oxygen-enriched film doped silicon dioxide and preparation method thereof |
| CN103483607A (en) * | 2013-09-04 | 2014-01-01 | 浙江理工大学 | Preparation method of titanium dioxide/polysiloxane photocatalytic composite film |
| CN104263238A (en) * | 2014-09-11 | 2015-01-07 | 天津大学 | Fluoridated POSS (polysilsesquioxane) composite organic silicon coating as well as preparation method and anti-icing application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835936A (en) * | 2022-05-05 | 2022-08-02 | 江苏盈泰新材料科技有限公司 | Photocatalytic self-cleaning PVC (polyvinyl chloride) film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104194011B (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103483607B (en) | A kind of preparation method of titanium dioxide/polysiloxane photocatalytic composite film | |
| CN107022279A (en) | A kind of preparation method of the wear-resisting super hydrophobic composite coating of high transparency | |
| CN104556072B (en) | A kind of in-situ modified method preparing monodisperse nano silicon dioxide | |
| CN105670500B (en) | A kind of preparation method of zinc oxide/Cellulose nanocrystal bluk recombination super-hydrophobic coat | |
| CN108084494A (en) | Functionalized nano titanium dioxide of surface grafting antioxygen agent molecule and preparation method thereof | |
| CN101481874A (en) | Nano metal titanium dioxide sol negative oxygen ion finishing method for fabric | |
| CN110205025A (en) | It is a kind of using organopolysilazane as super-hydrophilic coating of anchor molecule and preparation method thereof | |
| CN103835133B (en) | A kind of method preparing floride-free super-hydrophobic fabric face | |
| CN105289457B (en) | A kind of hollow structure TiO2The preparation method and applications of nano material | |
| CN108855234A (en) | A kind of method that energy light degradation dyestuff microfluid prepares Ag-carried nanometer titanium dioxide PVP fiber | |
| CN114685907B (en) | Preparation method and application of adjustable amphiphobic fluorescent polystyrene microsphere filler | |
| CN110885592A (en) | Super-hydrophobic antibacterial cationic fluoropolymer nano-coating | |
| CN106914266B (en) | g-C for fast degrading pollutant3N4Composite photocatalyst and preparation method thereof | |
| CN104194011A (en) | Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof | |
| CN1838993A (en) | Nano composite photocatalytic coating | |
| Chen et al. | In-situ immobilization of titanium dioxide on poly (ether ether ketone) hollow fiber membranes and the effect of pH level on the photo-removal process of dyes | |
| CN109880500A (en) | The preparation method of nano boron carbide modified aqueous polyurethane high wear resistance coatings | |
| Moafi et al. | The comparative study of photocatalytic self‐cleaning properties of synthesized nanoscale titania and zirconia onto polyacrylonitrile fibers | |
| WO2012074419A2 (en) | Process of manufacturing textile barrier materials | |
| CN104327279A (en) | Photosensitive nanosilicon dioxide and preparation method thereof | |
| CN110128739A (en) | A kind of EVA foamed material of area load modified titanium dioxide photocatalyst and preparation method thereof | |
| CN109369882A (en) | A kind of titanium deoxid film preparation method based on nano-fluid | |
| CN106582590B (en) | Glass mat-nano-TiO2Coating structure and its preparation method and application | |
| CN107376885A (en) | A kind of photocatalysis artificial flowers and its preparation method and application | |
| CN107434434A (en) | A kind of photocatalysis stone material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |