CN104194011B - Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof - Google Patents
Polysiloxane/titanium sol photocatalytic composite film and preparation method thereof Download PDFInfo
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- CN104194011B CN104194011B CN201410421903.7A CN201410421903A CN104194011B CN 104194011 B CN104194011 B CN 104194011B CN 201410421903 A CN201410421903 A CN 201410421903A CN 104194011 B CN104194011 B CN 104194011B
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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 is and in particular to titanium sol particle is evenly distributed on main chain by one kind
In silicon oil solution for Si-O key, by silicone oil between condensation reaction and the volatilization of 3 D cross-linked and solvent and be obtained ageing-resistant
Polysiloxanes/titanium colloidal sol photocatalysis composite membrane of property and preparation method thereof.
Background technology
Due to the continuous development of nanometer material science, functional type nanoparticle as additive become research focus it
One.Dichloride in anatase type TiO2As a kind of inorganic functional granule, because it has, nonpoisonous and tasteless, stability is strong, uv-shielding capacity
Well, the advantages of photo-catalysis capability is excellent, is applied to the neck such as weaving, coating, building, cosmetics in the presence of binding agent adhesion
Domain, thus can make textile and carrier matrix have continual and steady ultraviolet shielded, bactericidal, degraded dirt, automatically cleaning etc.
Effect.
For example, Gao Jianzhong [CN1560353A, nano sunlight screening finishing agent and preparation method and the Final finishing side for yarn fabric
Method] nano titanium oxide, amino silicone, binding agent and water are mixed with a kind of nano sunlight screening finishing agent and to fabric treating；Liu
Good fortune spring [CN1412258, a kind of nano UV resistant acrylate paint] etc. with acrylate as organic carrier, plus nano TiO2With
Dispersant prepares a kind of nano UV resistant acrylate paint.But increasing research shows in recent years, dichloride in anatase type
TiO2Reaction activity great high energy OOH and OH free radical can be produced because of its strong photocatalysis under light illumination
(OOH reaction activity is 431kJ mol-1, OH reaction activity is 402.7kJ mol-1), these energetic free radical
With C-C key, (bond energy is for 346kJ mol to various-1) it is the macromolecule carrier of main chain and textile has very strong aging infringement.This
Greatly limit dichloride in anatase type TiO2Extensive application and large-scale promotion in weaving and other field.
With the Si-O key of high energy, (bond energy is up to 460kJ mol to polysiloxanes-1) be its dimensional network structure main chain bone
Frame, and to above-mentioned energetic free radical and strong ultraviolet light, there is very strong defensive ability/resistance ability.Polysiloxanes and nano-TiO simultaneously2Tool
There is the good compatibility, easily realize effectively compound.Thus using polysiloxanes as new adhesive carrier, it has also become currently sharp
Titanium-type nano-TiO2One of organic load and adhesion research important development direction.Ding Xiaofeng [CN101724342A；
CN101962514A；J Mater Chem,2011,21:6161～6164] etc. with polysiloxanes as film former, with a large amount of powder body
Anatase titanium dioxide TiO2It is combined and a series of automatically cleaning poly- fluorosilicone/TiOs with super-hydrophobic or super parents function have been obtained2Nanometer is multiple
Close coating；This seminar application publication number be CN103483607A (a kind of titanium dioxide/polysiloxane photocatalytic composite film
Preparation method) Chinese patent disclose a kind of polysiloxanes by vinyl-terminated silicone fluid and containing hydrogen silicone oil hydrosilylation
The method preparing photocatalysis composite membrane with titanium dioxide in-situ polymerization.But the main chain crosslinking in the studies above is all containing a small amount of
C-C key, long use can make its ageing-resistant performance be deteriorated.In addition Jiang Mei [macromolecule journal, 2008,6:594～
599], Wang Fang [Journal of Inorganic Materials, 2010,25 (1):37～40] et al. with butyl titanate and silane as presoma, by molten
Glue-gel and curing of coating process, one-step method has been obtained polysiloxanes/titanium colloidal sol hybrid material, not only achieves organic/inorganic
Biphase stable and uniform is combined, and makes the main chain of crosslinking be Si-O key.But made titanium sol particle is with unformed under this system
Based on structure, its photocatalysis and ultraviolet shielded ability are poor.
Additionally, the Chinese patent application of Publication No. CN101928517A (nano self-cleaning paint and preparation method thereof) is public
Open a kind of method that anatase titanium dioxide titanium colloidal sol prepares nano self-cleaning paint with polysiloxane solution physical blending, described in the method
During be not related between silicone molecule reaction, there is no constructing of 3 D cross-linked structure yet, thus the mechanics of manufactured coating itself,
Optics, photocatalysis and the poor-performing such as ageing-resistant.
Content of the invention
The invention provides a kind of process is simple, high resistance to ag(e)ing polysiloxanes/titanium colloidal sol photocatalysis easy to implement are again
Close the preparation method of film.Its core be with have necessarily oil loving polymolecularity anatase crystal type titanium sol particle for photocatalysis material
Material, carry out the condensation reaction of end hydroxyl silicone oil and polymethyl hydrogen siloxane in the presence, be obtained with high bond energy Si-O be completely
The polysiloxanes cubic network cross-linked structure film of main chain, realizes titanium sol particle and embeds uniformly firmly inlaying of form on film surface half
Embedding, thus giving the excellent photocatalytic of composite membrane, ultraviolet shielded property, bacteria resistance and ageing-resistant etc. performance.
A kind of preparation method of polysiloxanes/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 mixing, add catalyst, cause silicone oil
Between condensation reaction, pour into after stirring in mould, in the environment of 60 DEG C～100 DEG C, with the volatilization of solvent and reaction
Carry out and gradually film forming, obtain polysiloxanes/titanium colloidal sol photocatalysis composite membrane.
In the present invention, condensation reaction through between silicone oil, construct the 3 D cross-linked structure completely with siliconoxygen bond as main chain, from
And titanium sol particle is obtained and can reach uniform and stable scattered resistance to ag(e)ing polysiloxanes/titanium colloidal sol light in polysiloxane matrix
Catalysis composite membrane.
Titanium sol particle in described titanium colloidal sol is anatase crystal type, and a large amount of Si-OH and Si-OR isoreactivity bases are contained on surface
Group, particle diameter is 20～50nm, and in described titanium colloidal sol, titanium sol particle consumption is end hydroxyl silicone oil and polymethyl hydrogen siloxane is total
The 1%～5% of quality.
Titanium sol particle, because having typical anatase crystal type, can guarantee that granule has good photocatalysiss in itself, from
And photocatalysis effect and the automatically cleaning effects such as excellent antibacterial bacteriostatic, degradation of organic substances can be provided for composite membrane.Titanium sol particle
Particle diameter is chosen as 20～50nm.Particle diameter is less than 20nm, then the crystal formation of granule is very unstable, and its photo-catalysis capability can be weakened.
More than 50nm, granule dispersion stabilization in sol system can be deteriorated, and its photo-catalysis capability also can be because of the reduction of specific surface area
And accordingly reduce.
Titanium colloidal sol consumption is the 1%～5% of the quality of end hydroxyl silicone oil.Titanium sol particle particle diameter is little, even if thus relatively
Also numerous titanium sol particles can be inlayed in composite film surface, thus giving composite membrane good photocatalysis effect under low consumption.
In addition the addition of excessive titanium sol particle not only can increase cost, also can cause the localized clusters that granule occurs inside composite membrane
And precipitation of reuniting, thus affect the transparency of composite membrane, mechanical property and corresponding photocatalysis performance.
The catalytic action by concentrated hydrochloric acid for the anatase crystal type titanium colloidal sol, adopts colloidal sol-solidifying under higher temperature (such as 70 DEG C)
Gluing method prepare (can be found in Shen Xingcong, Xu Jie, Zhang Rui, Chen Zhijie, Qi Dongming. nano-TiO2Sol-gel process preparation
And its characterize, Institutes Of Technology Of Zhejiang's journal, 2012,29 (2):249-253).Above-mentioned colloidal sol can be by entering in Rotary Evaporators
The mode of row medium displacement is changing its scattered medium.These titanium sol particle surfaces often remain some and do not remove totally
- OC4H9Etc. oil loving alkoxy grp, this can strengthen the compatibility of itself and Organic substance, and then improves it in organic media and poly-
Dispersibility in siloxane matrix and dispersion stabilization.In addition, as nano-particle, titanium sol particle surface can exist substantial amounts of
Ti-OH group, it instead can give birth to condensation reaction with the Si -- H bond in polymethyl hydrogen siloxane, thus improving titanium sol particle compound
Compound fastness in film.
The molecular formula of described end hydroxyl silicone oil is as follows：
Wherein, 160≤a≤350, and a is integer, that is, end hydroxyl silicone oil molecular weight is (1.2～2.6) * 104.
The hydroxyl at molecular formula two ends has very high reactivity, under strongly acidic conditions dehydration condensation can occur,
Thus expanding the length of strand.Select the end hydroxyl silicone oil containing 160～350 repetitives dimethyl silscones in molecule,
I.e. molecular weight is (1.2～2.6) * 104.Molecular weight is less than this scope, and condensation reaction is excessively violent, and system stability is poor, easily
Local excessive is crosslinked and reunites so that the final quality of composite membrane all can be deteriorated；Molecular weight is more than this scope, then unit reactant
Condensation reaction probability is occurred to decline in long-pending, the crosslinking degree of system can not, the long and corresponding mechanical property of composite membrane film formation time
Can not be good.
The molecular formula of described polymethyl hydrogen siloxane is as follows：
Wherein, 6≤m≤18,250≤n≤460, and m, n be integer, that is, polymethyl hydrogen siloxane molecular weight be (1.8～
3.4)*104, and in molecule, the content of the carried H of Si-H is the 0.017～0.092% of polymethyl hydrogen siloxane molecular mass.
Repetitives in polymethyl hydrogen siloxane molecular formula are made up of methyl silicone and two kinds of dimethyl silscone.Therein
A si-h bond is contained, this reactive group can enter under conditions of platinum catalyst presence with Si-OH in methyl silicone unit
Row condensation reaction deviates from H2.In polymethyl hydrogen siloxane molecule, the quantity of methyl silicone unit is 6～18, thus a poly- methyl
Hydrogen siloxane molecule can be reacted with multiple end hydroxyl silicone oil molecules.Its degree of functionality is more than 2, thus can play crosslinking wherein
The effect of agent.In molecular formula, dimethyl silscone unit is inertia unit, and its Main Function is the concentration of si-h bond in diluent molecules,
Thus weakening the severe degree of condensation reaction and the crosslinking degree of final product, on the other hand polymethyl hydrogen siloxane also can be increased
Molecular weight, thus improving the mechanical property of composite membrane.Preferably dimethyl silscone element number is 250～460, then poly- methyl hydrogen
Siloxane molecule amount is (1.8～3.4) * 104, and in molecule, the content of the carried H of Si-H is polymethyl hydrogen siloxane molecule
0.017%～0.092%.In the case, system course of reaction is preferable compared with stable, composite membrane mechanical strength.Less than this scope,
Si-H too high levels, condensation reaction is excessively violent, and easy local excessive is crosslinked and reunites, and the H generating2Can not exclude in time,
Easily make to be full of bubble in composite membrane, ultimately result in the quality variation of composite membrane；More than this scope, the crosslinking degree of composite membrane is not
Enough, filming performance is poor.
Described end hydroxyl silicone oil is 3～9 with the mol ratio of polymethyl hydrogen siloxane：1.This is mainly according to poly- methyl hydrogen silicon
Depending on quantity m of silicon hydrogen group in oxygen alkane molecule, because there have m silicon hydrogen-based to may participate in condensation in a polymethyl hydrogen siloxane to be anti-
Should, and in an end hydroxyl silicone oil molecule, have two terminal hydroxy groups to may participate in condensation reaction.Thus rubbed using m/2 as both inputs
You compare.
Described catalyst is karstedt catalyst, and karstedt catalyst is a kind of commercially available high activity platinum catalysis
Agent, has good catalytic action to the condensation reaction between hydroxy silicon oil and polymethyl hydrogen siloxane, contributes in drying and forming-film
During more stably construct the 3 D cross-linked structure of polysiloxanes, thus lifting the performance of composite membrane.Described karstedt
The consumption of catalyst is (5～15) * 10 of end hydroxyl silicone oil and polymethyl hydrogen siloxane gross mass-4%, more than this scope, is condensed
It is fiercer that reaction is carried out, and excessively crosslinked reunion easily locally occurs, producing a large amount of bubbles makes film uniformity poor；Less than this model
Enclose, reaction is relatively slow, and cross-linked structure relatively incompletely, equally can reduce the mechanical property of membrane material.
Described film forming solvent is toluene, because it has the good compatibility with titanium colloidal sol and polysiloxanes, contributes to
The dissolving of above-mentioned substance, dispersion and flowing in system.Toluene in system is made up of titanium sol medium and filming medium two parts,
The medium of described titanium colloidal sol is toluene, and that is, described titanium colloidal sol is made up of titanium sol particle and toluene, in described titanium colloidal sol
Toluene and total consumption of the film forming solvent toluene adding be the 0.3～2 of end hydroxyl silicone oil and polymethyl hydrogen siloxane gross mass
Times.Consumption is less than 0.3 times of silicone oil gross mass, then the mobility of film forming system is too poor, is unfavorable between different silicone molecules crosslinked
The carrying out of reaction is so that the uniformity of composite membrane, the transparency and mechanical strength all can be relatively poor.With more than silicone oil gross mass
2 times, then the titanium sol particle in composite membrane can be made to separate out because the compatibility is bad and reunite, extend film formation time, and can increase
Processing cost.Thus, total consumption of the solvent medium in described titanium colloidal sol and addition film forming solvent is preferably end hydroxyl silicone oil
With polymethyl hydrogen siloxane gross mass 0.3～2 times.
End hydroxyl silicone oil and polymethyl hydrogen siloxane backbone structure are close, and the compatibility preferably, easily mixes.Titanium sol particle
- the OH that some dehydrations generate is contained on surface, can react with Si-OH and Si-H, thus easily mix with silicone oil, and can be wherein
Reach firmly uniform, stable dispersion, this dispersity is critically important to effect of final composite membrane.
Karstedt platinum catalyst is a kind of effective catalyst, and Si-OH and Si-H all has higher reactivity, in room
Temperature is lower to add a small amount of catalyst can cause the condensation reaction between end hydroxyl silicone oil and polymethyl hydrogen siloxane in above-mentioned system, takes off
Remove a H2.Its reaction equation is as follows：
Said mixture is poured in Teflon mould, be dried 80 DEG C of environment under, with solvent volatilization and
The carrying out of condensation reaction, system viscosity and density raise, and gradually film-forming.During containing multiple silicon hydrogen-based poly- methyl
Hydrogen siloxane molecule can occur condensation reaction with multiple end hydroxyl silicone oil molecules, and the end hydroxyl silicone oil molecule containing double hydroxyls can join
The different polymethyl hydrogen siloxane molecule of knot, thus cubic network cross-linked structure can be built in system.And in this cross-linked structure
In, its main chain is Si-O key composition, this mechanical property being favorably improved membrane material and the ageing-resistant performance of high energy.Titanium is molten simultaneously
Glue granule uniformly can disperse in cross-linking system, thus giving the excellent photocatalytic of composite membrane and uv-shielding capacity.
The described photocatalysis composite membrane containing titanium sol particle has good ageing-resistant performance, and composite membrane is placed on
Be irradiated in ultraviolet ageing instrument, with ultraviolet lighting-clear water rinse accelerated ageing as cycling element (under 60 DEG C of environment, main ripple
Long 340nm, irradiation intensity 0.68W m-2Ultraluminescence light irradiation 10h；Cold water spray 2h under 50 DEG C of dark conditions), illumination
After 300h, the weight-loss ratio of composite membrane is only within 5%.
The standard thickness of the described polysiloxanes containing titanium sol particle/titanium colloidal sol photocatalysis composite membrane is 300 μm, tool
There are efficient photocatalysiss.Add the composite membrane of a diameter of 5.0cm in dye liquor, dye liquor is placed at liquid level 50cm
Degraded under 50w ultraviolet mercury lamp (dominant wavelength 365nm).After irradiating through 6h, titanium sol particle effective content is 5% composite membrane
More than 95% be can reach to the palliating degradation degree of rhodamine B.This can ensure that composite membrane has good photocatalytic Degradation.This
Outward, this composite membrane can be additionally used in the organic compound such as PARA FORMALDEHYDE PRILLS(91,95) and remaining surface activating agent and carries out photocatalytic degradation.
The described composite membrane containing titanium sol particle has excellent photocatalysis antibacterial effect, in staphylococcus aureuses
Place the composite membrane that titanium colloidal sol effective content is 5% in culture medium, after UV illumination 24h of 15w, ring degree can be produced a width of
The inhibition zone of 0.45cm.
In the present invention, described stirring mixing, medium displacement, molten cast the typical unit behaviour that film etc. is in chemical process
Make, can be realized using existing conventional equipment.
Compared with prior art, the present invention has the advantages that：
(1) polysiloxanes using full Si-O key as main chain are as anatase titanium dioxide TiO2Organic carrier, not only uvioresistant performance
Good, also there is excellent resistance to ag(e)ing.TiO also can be avoided simultaneously2Photocatalysiss are had for main chain to low bond energys such as C-C keys
Airborne body is brittle to be damaged, thus effectively improving the ageing-resistant performance of organic carrier.And, polysiloxanes itself are soft, have excellent
Good weatherability and organic/inorganic both sexes, can give the preferable feel of composite membrane and adhesive force.
(2) polymethyl hydrogen siloxane and end hydroxyl silicone oil are carried out cross-linking reaction, due to the poly- first containing multiple silicon hydrogen-based
Base hydrogen siloxane molecule can occur dehydrogenative condensation reaction with multiple end hydroxyl silicone oil molecules, contain the terminal hydroxy group silicon of double hydroxyls simultaneously
Oil molecule can connect different polymethyl hydrogen siloxane strands, thus cubic network cross-linked structure can be built in system.This has
Help improve mechanical property and the ageing-resistant performance of membrane material.
(3) contain a small amount of alcoxyl residue as the anatase crystal type titanium sol particle surface used by inorganic functional granule, can be with
Polysiloxanes have certain compatibility, can be prevented effectively from conventional inorganic particulates and there is Severe aggregation in film forming procedure,
Thus realizing dispersing uniformity in composite membrane for the titanium sol particle, and keep the good photocatalysiss of sol particle.
(4) anatase crystal type titanium sol particle surface used in film forming procedure contains that on a small quantity not remove clean alcoxyl residual
Base, this makes titanium sol particle preferable with the polyoxy alkane compatibility.But because generally titanium aerosol nanoparticles surface still can be with hydroxyl
Based on, thus titanium sol particle is not fully compatible with polysiloxanes.So titanium sol particle can be subject to one in film forming procedure
Determine the repulsion of degree, thus there being many titanium sol particles can be enriched with and be embedded in composite film surface, this photocatalytic particle is half-naked
The complex form of dew can give composite membrane more preferably photocatalysiss.
(5) the titanium sol particle surface as nano-particle inevitably still can remain with many hydroxyls, and these have
The group of certain reactivity equally can be occurred with the Si -- H in polymethyl hydrogen siloxane in condensation reaction film forming procedure
Dehydrogenative condensation reacts.This not only can improve dispersing uniformity in composite membrane for the titanium sol particle, also will be helpful to reinforcing titanium molten
The compound fastness of glue granule and poly- silica silicon matrix is so as to film surface can be more firmly embedded in, thus improving composite membrane
Repeatable usability.And also can play certain crosslinked strengthening action in system as the crosslinking points of bulky grain form.
(6) raw material involved in the present invention is easy to get, and preparation condition is gentle, and process is simple is suitably adapted for large-scale industry
Metaplasia is produced.In addition, the controllability of this structure of composite membrane form is strong, can take into account in film simultaneously the uvioresistant performance of titanium sol particle and
Photocatalysis performance, makes the existing excellent ultraviolet shielded effect of composite membrane, and because photocatalysiss produce degradation of organic substances, antibacterial suppression
The effects such as bacterium, automatically cleaning, can be used for weaving, the field such as cosmetics, coating, building, health, medical science.
Brief description
Fig. 1 is the red of end hydroxyl silicone oil, polymethyl hydrogen siloxane and polysiloxane film prepared by condensation reaction in comparative example 1
External spectrum spectrogram；
Fig. 2 is the surface topography (FE-SEM photo) of the made composite membrane of embodiment 1；
Fig. 3 is the ultraviolet ageing weight-loss ratio curve of comparative example 1 and the made polysiloxane film of embodiment 1 and polypropylene sorrel；
Fig. 4 is the made polysiloxane composite membrane of comparative example 1 (left side) and the made polysiloxanes of embodiment 10/titanium colloidal sol is combined
The antibacterial effect comparison diagram of film (the right)；
Fig. 5 is the made polysiloxane composite membrane of comparative example 1 and the made polysiloxanes of embodiment 8,10 and 1/titanium colloidal sol light is urged
Change in the experiment of composite membrane degradation of dye, dye liquor concentration is with the change curve of light application time；
Fig. 6 is that in the made polysiloxanes of embodiment 1/titanium colloidal sol photocatalysis composite membrane circulation degraded dye assay, dye liquor is dense
Degree is with the change curve of light application time.
Specific embodiment
Embodiment 1～12
A certain amount of end hydroxyl silicone oil, polymethyl hydrogen siloxane, titanium colloidal sol (wherein, toluene is 100g) are put in beaker
Stirring, is subsequently adding in a small amount of film forming solvent toluene (28g), amounts to toluene 128g in system, (wherein, holds hydroxyl after mix homogeneously
The weight of base silicone oil and polymethyl hydrogen siloxane adds up to 100g, adds the benchmark of quality as other materials), Deca
Karstedt platinum catalyst causes the condensation reaction between silicone oil, and pours in Teflon mould.In the environment of 80 DEG C,
With the volatilization of solvent and gradually carrying out of condensation reaction, construct 3 D cross-linked structure further film, can get titanium after 24h molten
Glue even particulate dispersion the multi-functional composite membrane on polysiloxane matrix surface for the part inlay, i.e. polysiloxanes/titanium colloidal sol
Photocatalysis composite membrane, controls thickness at 300 μm about.
Concrete technology formula and compound film properties are shown in Table 1.
Table 1
Comparative example 1～4
The same comparative example of operating process, concrete technology formula and compound film properties are shown in Table 2, wherein, toluene in titanium colloidal sol and
Total consumption of the film forming solvent toluene adding is 128g.
Table 2
The characterizing method explanation being related in embodiment 1～12 and comparative example 1～4：
Using FTIR technique instrument (FT-IR, power ＆ light company of U.S. Nicolet 5700) to poly- silica
Alkane film and each component carry out analysis of the molecular structure；
Polysiloxanes/titanium colloidal sol is observed using field emission scanning electron microscope (FE-SEM, German Zeiss company Ultra 55 type)
The surface topography of photocatalysis composite membrane；
The illumination weightless test of composite membrane：In ultraviolet accelerated ageing instrument, carried out using illumination-spray reciprocation cycle process
Accelerated aging tests (under 60 DEG C of environment, dominant wavelength 340nm, irradiation intensity 0.68W m-2Ultraluminescence light irradiation 10h；50℃
Under dark condition cold water spray 2h), and during interval sampling, be dried after weigh, the weightless scale evaluation titanium using film is molten
The photocatalytic Degradation to membrane matrix for the glue granule.
The photocatalysis antibacterial experiment of composite membrane：Add 20 μ L antibacterials with 10 μ L liquid-transfering guns respectively in centrifuge tube, mixing is all
After even, it is coated in respectively in culture medium, all processes are realized all on disinfecting action platform.An equal amount of sterilized process is poly-
Silicone film and polysiloxanes/titanium colloidal sol photocatalysis composite membrane disk are placed on the above medium, culture medium are positioned over interior
Put in the climatic chamber of 15W uviol lamp (dominant wavelength 254nm), lamp away from culture medium 30cm, in antibacterial optimum growh environment (37
DEG C, 50% relative humidity) under, after culture 24h, observe the formational situation of the outer inhibition zone of composite membrane disk.
By GB/T528-1998 standard, in electronic universal material testing machine (U.S. Instron Corporation2345
Type) in test compound film tensile property, draw speed 100mm min-1.
The photocatalytic degradation of dye molecule experiments of composite membrane：Water-soluble dye rhodamine B is made into the dye liquor of 20ppm, to
Put into polysiloxane film or polysiloxanes/titanium colloidal sol composite membrane, control membrane material addition is 20g L wherein flat screen-1.Etc. quiet
After putting 30min adsorption saturation, irradiate dye liquor at ullage 50cm with 50W ultraviolet mercury lamp (dominant wavelength 365nm).Interval is certain
Time shakes up sampling, measurement in ultraviolet/visible spectrophotometer (UV/Vis, Perkin Elmer company Lambda 900 type)
Absorbance change at dyestuff main absworption peak 540nm for the dye liquor, to assess degradation of dye effect.
The results such as the width of the surveyed inhibition zone annulus of embodiment 1～12, tensile property are as shown in table 1.
The results such as the width of the surveyed inhibition zone annulus of comparative example 1～4, tensile property are as shown in table 2.
Fig. 1 is the red of end hydroxyl silicone oil, polymethyl hydrogen siloxane and polysiloxane film prepared by condensation reaction in comparative example 1
External spectrum spectrogram.As shown in figure 1, in figure 1000 and 2960cm-1At two, strong absworption peak is respectively belonging to silicone backbone skeleton Si-
O-Si and side base-CH3Stretching vibration peak, in three samples, above-mentioned two peaks do not have notable difference, and material before and after condensation reaction is described
Basic structure is similar.2157 and 911cm in polymethyl hydrogen siloxane-1At two, clearly, two absworption peaks belong to absworption peak respectively
In the flexible of Si-H and anti-stretching vibration.3300cm in end hydroxyl silicone oil-1Place's absworption peak clearly, belongs to the flexible of-OH and shakes
Dynamic.And the characteristic peak at above-mentioned three is inconspicuous in gained polysiloxanes, the poly- methyl hydrogen silica containing multiple Si-H bases is described
The relatively abundant and end hydroxyl silicone oil-OH of alkane there occurs condensation reaction, thus the poly- silica with certain cross-linked structure can be obtained
Alkane film.
Fig. 2 is the surface topography (FE-SEM photo) of the made composite membrane of embodiment 1, as shown in Fig. 2 composite film surface is no bright
Aobvious prominent aggregate, and whole film surface is flooded with TiO fine and smooth in a large number2Granule, these granules are in unordered loose heap
Its size of cumuliformis state is about 20-50nm.These TiO2Granule is mainly partly embedded in polysiloxane film surface with the form of inlaying, this
Composite membrane will be made to show more preferably photo-catalysis capability.
Fig. 3 is the ultraviolet ageing weight-loss ratio curve of comparative example 1 and the made polysiloxane film of embodiment 1 and polypropylene sorrel.
As shown in figure 3, under ultra-vioket radiation, the quality of polyacrylate basement membrane is all decreased obviously.And after composite titanium sol particle, film
Aging tendency substantially strengthen.And polysiloxanes basement membrane then shows preferable ageing resistace, certain except having in beginning 25h
Weightlessness outside (likely originate from the gradually volatilization of original small molecule and oligomer and escape in film), quality keeps substantially afterwards
Constant.Polysiloxanes with Si-O key as main chain are described, and not only itself uvioresistant ability is strong, and resistance to TiO2Produced high energy is certainly
Strong oxdiative-reduction by base.
Fig. 4 is the made polysiloxane film of comparative example 1 (left side) and the made polysiloxanes of embodiment 10/titanium colloidal sol composite membrane
The antibacterial effect comparison diagram on (the right).As shown in figure 4, polysiloxane film does not have antibacterial action in itself；And polysiloxanes/titanium colloidal sol
An obvious inhibition zone then occurs, the width of this ring band is 0.38cm, illustrates that it has well around composite membrane disk
Antibacterial and bacteriostasis.
Fig. 5 is the made polysiloxane film of comparative example 1 and the made polysiloxanes/optically catalytic TiO 2 of embodiment 8,10 and 1
In the experiment of composite membrane degradation of dye, dye liquor concentration is with the change curve of light application time.Vertical coordinate (C/C0) it is water-soluble dye sieve
The ratio of the concentration after red bright B degraded and its initial concentration.As shown in Figure 5：After the adsorption saturation in dye liquor of above-mentioned film, in ultraviolet
Under light irradiation, polysiloxane film itself does not have degradation effect substantially to rhdamine B molecule.And polysiloxanes/titanium colloidal sol light
Catalysis composite membrane has preferable photocatalytic degradation effect, and degradation effect is closely related with titanium sol content.When titanium colloidal sol contains
When measuring as silicone oil quality 1.0%, photocatalysis effect is more general.And when titanium sol content increases to 3.0%, after irradiating 4.5h,
The dye molecule about half is had can effectively to be decomposed.When content increases to 5.0% further, then dyestuff decomposes half and is taken
Between be reduced to 2h.
Fig. 6 is dye liquor in the made polysiloxanes of embodiment 1/titanium dioxide photocatalysis composite membrane circulation degraded dye assay
Concentration is with the change curve of light application time.Vertical coordinate (C/C0) initial with it for the concentration after the degraded of water-soluble dye rhodamine B
The ratio of concentration.As shown in fig. 6, under ultraviolet light, after polysiloxanes/titanium colloidal sol photocatalysis composite membrane three times recycles, to dye
The degradation efficiency of material remains to reach more than 80%, and degradation rate is almost unchanged.Polysiloxanes/titanium colloidal sol photocatalysis are thus described
Composite membrane only have efficient photocatalytic degradation of dye effect, and can recycled for multiple times, improve material utilization ratio.
Claims (5)
1. a kind of preparation method of polysiloxanes/titanium colloidal sol photocatalysis composite membrane is it is characterised in that comprise the following steps：
After titanium colloidal sol, end hydroxyl silicone oil, polymethyl hydrogen siloxane and film forming solvent mixing, add catalyst, cause between silicone oil
Condensation reaction, pours into after stirring in mould, in the environment of 60 DEG C～100 DEG C, with the volatilization of solvent and the carrying out of reaction
And gradually film forming, obtain polysiloxanes/titanium colloidal sol photocatalysis composite membrane；
Titanium sol particle in described titanium colloidal sol is anatase crystal type, and particle diameter is 20～50nm；
In described titanium colloidal sol, titanium sol particle consumption is the 1%～5% of end hydroxyl silicone oil and polymethyl hydrogen siloxane gross mass；
The molecular formula of described end hydroxyl silicone oil is as follows：
Wherein, 160≤a≤350, and a is integer；
The molecular formula of described polymethyl hydrogen siloxane is as follows：
Wherein, 6≤m≤18,250≤n≤460, and m, n are integer；
Described catalyst is karstedt catalyst, and the consumption of described karstedt catalyst is end hydroxyl silicone oil and poly- first
(5～15) * 10 of base hydrogen siloxane gross mass-4%.
2. the preparation method of polysiloxanes according to claim 1/titanium colloidal sol photocatalysis composite membrane is it is characterised in that institute
The end hydroxyl silicone oil stated is 3～9 with the mol ratio of polymethyl hydrogen siloxane：1.
3. the preparation method of polysiloxanes according to claim 1/titanium colloidal sol photocatalysis composite membrane is it is characterised in that institute
The film forming solvent stated is toluene, and described titanium colloidal sol is made up of titanium sol particle and toluene.
4. the preparation method of polysiloxanes according to claim 3/titanium colloidal sol photocatalysis composite membrane is it is characterised in that institute
Total consumption of the toluene in the titanium colloidal sol stated and the film forming solvent toluene adding is end hydroxyl silicone oil and polymethyl hydrogen siloxane is total
0.3～2 times of quality.
5. polysiloxanes/titanium colloidal sol the photocatalysis composite membrane of the preparation method preparation according to any one of Claims 1 to 4.
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| CN101185854A (en) * | 2007-08-29 | 2008-05-28 | 江南大学 | Silicon rubber oxygen-enriched film doped silicon dioxide and preparation method thereof |
| 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 |
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| CN101185854A (en) * | 2007-08-29 | 2008-05-28 | 江南大学 | Silicon rubber oxygen-enriched film doped silicon dioxide and preparation method thereof |
| 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 |
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