CN107640913B - A kind of preparation method and applications of Basalt fiber surface modification coating - Google Patents
A kind of preparation method and applications of Basalt fiber surface modification coating Download PDFInfo
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- CN107640913B CN107640913B CN201710724783.1A CN201710724783A CN107640913B CN 107640913 B CN107640913 B CN 107640913B CN 201710724783 A CN201710724783 A CN 201710724783A CN 107640913 B CN107640913 B CN 107640913B
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Abstract
The invention belongs to inorfil technical field of modification, are related to the preparation method of Basalt fiber surface modification more particularly to Basalt fiber surface modification coating.First in proper amount of nano silica dispersions be added silane coupling agent, surfactant solution, polyacrylamide solution and 1/3 aqueous epoxy resins, back flow reaction；Then it heats up while remaining aqueous epoxy resins and initiator solution is added dropwise, be made after alkaline system sustained response.The invention also discloses obtained Basalt fiber surface modification coating applications, first with dense H2SO4/H2O2Mixed solution to basalt fibre surface group activate, then use hydrochloric acid, then infiltrated and be grafted in the coating, finally drying to constant weight.Coating emulsion prepared by the present invention is free of any organic solvent, and environmentally protective, operating technology is convenient and simple, strong applicability, performance are stablized, can fast and effeciently treated basalt fiber, its surface roughness is obviously increased, can be applied to microbial membrane carrier Material Field.
Description
Technical field
The invention belongs to inorfil technical field of modification, are related to the method for Basalt fiber surface modification, more particularly to
A kind of preparation method and applications of Basalt fiber surface modification coating.
Background technique
It China's shortage of water resources and water pollution problems and deposits at present, surface water pollution situation remains unchanged sternness, water conservation,
Improve water environment, it is very urgent to improve sewage/wastewater treatment effeciency.The common process of sewage/wastewater processing covers physics, chemistry and life
Object space method, the most sewage/wastewater processing in China is based on bioanalysis.In the technique of Biochemical method sewage/wastewater, biomembrane
Technique is most widely used technology.Biomembrane wastewater processing technology is that microorganism is fixed on to formation biomembrane on carrier to make to give up
The technology that pollutant in water is degraded, by carrier material as place, carrier material is for the growth and breeding of biomembrane
The core of biofilm water treatment technology, performance quality influence the type, quantity, activity of microorganism and metabolism in biological tank and produce
The mass transfer of object, the also efficiency of direct shadow biofilm water treatment technology.Therefore, the correct selection of carrier is to raising wastewater treatment
Effect is extremely important.
The requirement of biofilm carrier material are as follows: easily film forming, nonhazardous effect；Big specific surface area can be provided, to increase life
Object adhesion amount；Cheap, easy materials.Biofilm carrier material can be divided into organic carrier and inorganic carrier at present.Have
Machine class carrier such as PVC, PE, PS, PP, various types of resins, plastics, soft or semi-soft fiber etc., production process not environmentally, pollutant
Discharge is more, and phenomena such as aging, fracture of wire is easy to appear in waste water, influences service life, secondly, regeneration is difficult, easily to environment
Cause secondary pollution.
Basalt fibre (BF) is a kind of high performance inorganic silicate fibrous, by basalt ore at 1450~1500 DEG C
It is formed after lower melting by the quick wire drawing of platinum-rhodium alloy bushing, mainly by SiO2、Al2O3、CaO、FexOy、MgO、TiO2、
Na2O、K2The composition such as O, diameter are generally 7~13 μm.There is no the discharge of boron or alkali metal oxide in BF generating process, and not
Needing to introduce any new component can be obtained, therefore the preparation process of basalt fibre will not cause bad shadow to environment and the mankind
It rings, is a kind of 100% fully natural green industrial materials.This also avoids traditional material in production, use and waste procedures
The disadvantages of consuming a large amount of energy and resource, causing environmental pollution.
Basalt fibre has excellent mechanical property, and tensile strength and elasticity modulus are all higher, even higher than glass
Fiber and aramid fiber, tensile strength are also suitable with carbon fiber.In addition, basalt fibre has chemical stability outstanding,
Basalt ore belongs to silicate ore, and basalt fibre can have natural compatibility with silicate, have very high acidproof
Alkalinity.Therefore, intensity and resistance to acid and alkali possessed by basalt fibre can satisfy the requirement of biofilm carrier material, be a kind of
More satisfactory biofilm carrier material；But basalt fibre surface is smooth, and general commercially available basalt fibre surface hydrophilic
Property it is poor, influence microorganism attachment, reduce biomembrane mass-transfer efficiency, so before being applied to biofilm carrier material
It needs to handle basalt fibre surface, improves its surface property.
Fiber surface modification method mainly has Surface Oxidation Modification method, soda acid etching method, plasma modification method and surface
Coating modified method etc..The scholar of countries in the world carries out grinding for fiber surface modification technical aspect with great enthusiasm at this stage
Study carefully work, the main achievement obtained at present has:
[1]Surface modification and characterizations of basalt fibers with
Non-thermal plasma, Surface&Coatings Technology, 2007,201 (15): 6565-6568. is reported
A kind of plasma surface modification technology, by the mixed gas of plasma and nitrogen and hydrogen to basalt fibre surface into
Row is modified, the results showed that modified basalt fiber surface introduces many active ion and group (NH2, OH etc.).But wait from
Equipment Requirement needed for daughter modification technology is high, at high cost, and the dynamics of plasma modification is little, and research work also compares zero
It dissipates, therefore limits its application.
[2] acid etch is to basalt fibre surface coupling agent adsorbance and fiber/epoxy resin composite material mechanical property
Influence, composite material journal, 2014,31 (4): 888-894. reports a kind of salt acid etch and carries out to basalt fibre surface
The method of processing, the results showed that the monofilament tensile strength of fiber is as the raising of concentration of hydrochloric acid is in acceleration downward trend, 1mol/L
Fiber surface after HCl treatment is maximum to the adsorbance of silane resin acceptor kh-550, and there is optimal tensile property and interlayer to cut
Shearing stress.
[3]Strengthening of basalt fibers with nano-SiO2-epoxy composite
Coating, Materials and Design, 2011, (32): 4180-4186. reports a kind of modified basalt of surface covering
The technology of fiber, text in use Epoxy/nano SiO2Composite material is as basalt fibre coating, the results showed that modified
Basalt fibre can effectively improve its mechanical property and surface roughness.
In the research of above-mentioned Basalt fiber surface modification technology, stress the mechanics of basalt fibre after research before modified
Performance at present has not been reported the hydrophilic linguistic term on basalt fibre surface.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the invention discloses a kind of sides of Basalt fiber surface modification
Method, by preparing polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Surface covering of the multiple emulsion as basalt fibre,
The processes such as activated, etching, infiltration, grafting, dry obtain modified basalt fibre, change its surface hydrophilicity
Kind, fiber surface biological affinity improves, and meets its requirement as biofilm carrier material.
It is an object of the present invention to a kind of preparation method of Basalt fiber surface modification coating is disclosed, including
Following steps:
A, tetraethyl orthosilicate (TEOS), deionized water, dehydrated alcohol are stirred according to mass ratio 1.18:4.00:6.31
Mixing, with salt acid for adjusting pH to 3~4 or so, 30 DEG C are persistently stirred 3h and obtain nano silicon dioxide dispersion；
B, proper amount of nano silica dispersions are added to the reaction for being furnished with mechanical agitator, reflux condensing tube, thermometer
In container, by silane coupling agent, surfactant solution, polyacrylamide solution and 1/3 aqueous epoxy resins be added mixing
It in liquid, is stirred until homogeneous, back flow reaction temperature is 40~50 DEG C, preferably 45 DEG C；
C, reaction temperature is risen to 65~80 DEG C, while remaining aqueous epoxy resins and initiator solution is added dropwise, with pH
Buffer tune pH persistently stirs 3~5h between 12~14, wherein and preferably 75 DEG C of reaction temperature, preferable ph 13, reaction
Time preferred 4h, pH buffer are one of potassium hydroxide or sodium hydroxide, preferably potassium hydroxide；
D, to fully reacting, it is down to room temperature, hydrochloric acid tune pH value 7~8 is added dropwise, filtering obtains polyacrylamide/water-base epoxy
Resin/Nano-meter SiO_22Multiple emulsion, i.e. Basalt fiber surface modification coating.
Wherein, each material mass percentage of reaction is participated in are as follows:
Nano silicon dioxide dispersion 1.17~5.88%, preferably 3.52%；
Silane coupling agent 0.09~0.47%, preferably 0.28%；
Surfactant 0.06~0.2%, preferably 0.15%；
Polyacrylamide 0.12~0.59%, preferably 0.35%；
Aqueous epoxy resins 2.18~31.57%, preferably 19.14%；
Initiator 0.07~0.12%, preferably 0.09%；
Deionized water 61.17~96.31%, preferably 76.47%.
Further, silane coupling agent of the present invention is gamma-aminopropyl-triethoxy-silane (KH-550), γ-shrink
In glycerol ether oxygen propyl trimethoxy silicane (KH-560) and γ-methacryloxypropyl trimethoxy silane (KH-570)
One kind or two kinds any, preferred gamma-aminopropyl-triethoxy-silane (KH-550)；
The aqueous epoxy resins are bisphenol A type epoxy resin, preferably E-51；
The surfactant is quaternary surfactant, hexadecyltrimethylammonium chloride (HTMAC) and octadecane
One of base trimethyl ammonium chloride (ODAC), preferably hexadecyltrimethylammonium chloride (HTMAC)；
The initiator is one of potassium peroxydisulfate (KPS) and ammonium persulfate (APS), preferably potassium peroxydisulfate (KPS).
Another object of the present invention is that the application of prepared Basalt fiber surface modification coating is disclosed,
Include the following steps:
A, basalt fibre surface group activates: using dense H2SO4/H2O2Mixed solution (H2SO4/H2O2Volume ratio is 7:3)
Fiber surface is activated, its surface is made to generate more silanol groups.Concrete operations are that basalt fibre is soaked in H2SO4/
H2O2In mixed solution, being placed in temperature is in 80~120 DEG C of hydrothermal synthesis reaction kettles, and activation time is 0.5~2h, wherein it is preferred that
Temperature is 90 DEG C, the preferred 1h of activation time；
B, the etching of basalt fibre: the basalt fibre after activation is immersed in hydrochloric acid solution, and concentration of hydrochloric acid solution is
0.5~2M, preferably 1M, etching temperature are 30~50 DEG C, and preferably 40 DEG C, etch period is 30~90min, preferably 60min；
C, infiltration and grafting process: a large amount of silanol group is contained on pretreated basalt fibre surface, and surface is passed through
Acid etch surface roughness increases, and is immersed in polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Multiple emulsion, i.e. institute
It is infiltrated in the Basalt fiber surface modification coating of preparation, the silanol group of fiber surface is easily reacted with size, to make
Organic polymer chain in multiple emulsion is grafted on fiber surface, further, since the presence of silane coupling agent, the one of coupling agent
End can be reacted with the organic principle in size, the other end can in nano silica in size or basalt fibre
Silica generate Si-O-Si structure, to obtain modified basalt fibre, infiltrating time is 60~150min, excellent
120min is selected, infiltration temperature is 25~60 DEG C, and preferable temperature is 40 DEG C；
D, drying process: basalt fibre after infiltration take out after 100 DEG C drying to constant weight.
Tetraethyl orthosilicate used in the present invention, dehydrated alcohol, concentrated hydrochloric acid, potassium hydroxide, silane coupling agent (KH-
550, KH-560 or KH-570) and polyacrylamide, analyze pure, Sinopharm Chemical Reagent Co., Ltd.；Epoxy resin (E-
51), hexadecyltrimethylammonium chloride (HTMAC) and octadecyltrimethylammonium chloride (ODAC) analyze pure, the excellent rope in Shandong
Work Science and Technology Ltd.；Potassium peroxydisulfate and ammonium persulfate, excellent pure grade, Tianjin Kermel Chemical Reagent Co., Ltd.；Basalt
Fiber is commercially available, Jiangsu Lvcaigu New Materials Technology Development Co., Ltd..
The basic demand of microbial membrane carrier material first is that carrier material must have certain bioaffinity, the present invention
Measurement can be carried out to the Static water contact angles and surface of the basalt fibre monofilament after before modified.Due to the structure of epoxy resin
In contain amino, ehter bond and other polar groups, have more excellent adhesive property.In addition, polyacrylamide is a kind of
Linear macromolecule soluble easily in water can react with epoxy group under strongly alkaline conditions, be also easy to containing a large amount of amide groups
Hydrogen bond action occurs for other materials, and the addition of polyacrylamide can significantly decrease the hydrophily of aqueous epoxy resins, and doping is received
The roughness on basalt fibre surface can be improved in rice silica.Statistics indicate that polyacrylamide prepared by the present invention/aqueous
Epoxy/nano SiO2Multiple emulsion treated basalt fiber does not destroy the mechanical property of basalt fibre itself, and can change
The surface hydrophilicity of kind basalt fibre, hence it is evident that drop low-fiber water contact angle, improve the affinity between fiber and microorganism.
Beneficial effect
The method of modifying of basalt fibre disclosed in this invention, polyacrylamide/aqueous ring easy to operate, obtained
Oxygen resin/Nano-meter SiO_22Multiple emulsion and fiber have good compatibility, and modified material used is environmentally protective raw material,
Epoxy resin is also aqueous epoxy resins, is free of organic solvent in size, will not environment and the mankind be polluted and be injured.
In addition, organic size with inorfil is connect by silane coupling agent in the present invention, wrapped up on basalt fibre surface
One layer of organic coating, reduces the hydrophily of fiber, improves its dispersibility in water, and modified basalt fibre has one
Fixed pliability meets its requirement as microbial carrier material.
Detailed description of the invention
Fig. 1 basalt fibre before modified after SEM figure, wherein a be basalt fibre (BF) microscopic appearance, b are before modified
Modified basalt fibre (MBF) microscopic appearance.
Fig. 2 basalt fibre before modified after FTIR figure.
Fig. 3 basalt fibre before modified after water contact angle variation diagram.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Embodiment 1
(1) 1.18g TEOS, 40g deionized water and 63.12g dehydrated alcohol are added in 250ml three-necked flask, are stirred
It is uniformly mixed, is 3 or so with salt acid for adjusting pH, temperature is stirred to react 3h under the conditions of being 30 DEG C, obtains nano silica dispersion
Liquid.
(2) in the 250mL four-hole bottle equipped with blender, reflux condensing tube, the dispersion of 1g nano silica is sequentially added
Liquid, 0.077g silane resin acceptor kh-550,0.1g polyacrylamide (PAM), 0.051g hexadecyltrimethylammonium chloride
(HTMAC), 0.62g epoxy resin and 5g deionized water, stir, and back flow reaction temperature is 40 DEG C.
(3) reaction temperature is warming up to 65 DEG C, while 1.24g epoxy resin is added dropwise and 0.06g APS initiator solution is (molten
In 10g deionized water), NaOH buffer solution is added, adjusting pH value is 12 or so, persistently stirs 3h, to fully reacting, is down to
Room temperature adjusts pH value to 7~8, can get polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Multiple emulsion (Emulsion-
1).Wherein, in the present embodiment, all deionization dosages are 81.86g (mass ratio 96.31%, relative to institute in size
There is ratio shared by the quality summation of monomer component).
(4) basalt fibre is placed in H2SO4/H2O2Mixed solution (H2SO4/H2O2=7:3, volume ratio) in, it is placed in temperature
For in 80 DEG C of hydrothermal synthesis reaction kettle, activation time 30min.Basalt fibre after activation is immersed in the hydrochloric acid of 0.5M
In, etching temperature is 30 DEG C, and etch period 30min obtains pretreated basalt fibre.
(5) basalt fibre after pretreatment is immersed in Emulsion-1 multiple emulsion, soaking time 60min, is soaked
Steeping temperature is 25 DEG C.After 1 hour, the basalt fibre taking-up after immersion is placed in thermostatic drying chamber and is dried to perseverance for 100 DEG C
Weight, obtains modified basalt fibre (MBF-1).
Embodiment 2
(1) 1.18g TEOS, 40g deionized water and 63.12g dehydrated alcohol are added in 250ml three-necked flask, are stirred
It is uniformly mixed, is 3 or so with salt acid for adjusting pH, temperature is stirred to react 3h under the conditions of being 30 DEG C, obtains nano silica dispersion
Liquid.
(2) in the 250mL four-hole bottle equipped with blender, reflux condensing tube, the dispersion of 2g nano silica is sequentially added
Liquid, 0.2g silane coupling agent (KH-560), 0.3g polyacrylamide (PAM), 0.1g hexadecyltrimethylammonium chloride
(HTMAC), 4.53g epoxy resin and 10g deionized water, stir, and back flow reaction temperature is 45 DEG C.
(3) reaction temperature is warming up to 70 DEG C, while 9.06g epoxy resin and 0.085g KPS initiator solution is added dropwise
(being dissolved in 10g deionized water), it is 13 or so that KOH buffer solution, which is added, and adjusts pH value, 4h is persistently stirred, to fully reacting, drop
To room temperature, pH value is adjusted to 7~8, can get polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Multiple emulsion
(Emulsion-2).Wherein, in the present embodiment, all deionization dosages be 68.72g, (mass ratio 80.85%, relative to
Ratio shared by the quality summation of all monomer components in size).
(4) basalt fibre is placed in H2SO4/H2O2Mixed solution (H2SO4/H2O2=7:3, volume ratio) in, it is placed in temperature
For in 90 DEG C of hydrothermal synthesis reaction kettle, activation time 1h.Basalt fibre after activation is immersed in the hydrochloric acid of 2M, is carved
Losing temperature is 40 DEG C, and etch period 60min obtains pretreated basalt fibre.
(5) basalt fibre after pretreatment is immersed in Emulsion-2 multiple emulsion, soaking time 120min, is soaked
Steeping temperature is 40 DEG C.After 2 hours, the basalt fibre taking-up after immersion is placed in thermostatic drying chamber and is dried to perseverance for 100 DEG C
Weight, obtains modified basalt fibre (MBF-2).
Embodiment 3
(1) 1.18g TEOS, 40g deionized water and 63.12g dehydrated alcohol are added in 250ml three-necked flask, are stirred
It is uniformly mixed, is 3 or so with salt acid for adjusting pH, temperature is stirred to react 3h under the conditions of being 30 DEG C, obtains nano silica dispersion
Liquid.
(2) in the 250mL four-hole bottle equipped with blender, reflux condensing tube, the dispersion of 3g nano silica is sequentially added
Liquid, 0.24g silane coupling agent (KH-550), 0.3g polyacrylamide (PAM), 0.128g hexadecyltrimethylammonium chloride
(HTMAC), 5.42g epoxy resin and 10g deionized water, stir, and back flow reaction temperature is 45 DEG C.
(3) reaction temperature is warming up to 75 DEG C, while 10.85g epoxy resin is added dropwise and 0.077g initiator solution (is dissolved in
In 10g deionized water), it is 13 or so that KOH buffer solution, which is added, and adjusts pH value, persistently stirs 4h, to fully reacting, is down to room
Temperature adjusts pH value to 7~8, can get polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Multiple emulsion (Emulsion-3).
Wherein, in the present embodiment, all deionization dosages are 64.99g, and (mass ratio 76.47% owns relative in size
Ratio shared by the quality summation of monomer component).
(4) basalt fibre is placed in H2SO4/H2O2Mixed solution (H2SO4/H2O2=7:3, volume ratio) in, it is placed in temperature
For in 90 DEG C of hydrothermal synthesis reaction kettle, activation time 1h.Basalt fibre after activation is immersed in the hydrochloric acid of 1M, is carved
Losing temperature is 40 DEG C, and etch period 60min obtains pretreated basalt fibre.
(5) basalt fibre after pretreatment is immersed in Emulsion-3 multiple emulsion, soaking time 120min, is soaked
Steeping temperature is 40 DEG C.After 2 hours, the basalt fibre taking-up after immersion is placed in thermostatic drying chamber and is dried to perseverance for 100 DEG C
Weight, obtains modified basalt fibre (MBF-3).
Embodiment 4
(1) 1.18g TEOS, 40g deionized water and 63.12g dehydrated alcohol are added in 250ml three-necked flask, are stirred
It is uniformly mixed, is 3 or so with salt acid for adjusting pH, temperature is stirred to react 3h under the conditions of being 30 DEG C, obtains nano silica dispersion
Liquid.
(2) in the 250mL four-hole bottle equipped with blender, reflux condensing tube, the dispersion of 4g nano silica is sequentially added
Liquid, 0.3g silane coupling agent (KH-550), 0.4g polyacrylamide (PAM), 0.15g octadecyltrimethylammonium chloride
(ODAC), 7.15g epoxy resin and 15g deionized water, stir, and back flow reaction temperature is 50 DEG C.
(3) reaction temperature is warming up to 80 DEG C, while 14.31g epoxy resin and 0.085g APS initiator solution is added dropwise
(being dissolved in 15g deionized water), it is 14 or so that NaOH buffer solution, which is added, and adjusts pH value, 5h is persistently stirred, to fully reacting, drop
To room temperature, pH value is adjusted to 7~8, can get polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Multiple emulsion
(Emulsion-4).Wherein, in the present embodiment, all deionization dosages be 58.6g, (mass ratio 68.94%, relative to
Ratio shared by the quality summation of all monomer components in size).
(4) basalt fibre is placed in H2SO4/H2O2Mixed solution (H2SO4/H2O2=7:3, volume ratio) in, it is placed in temperature
For in 120 DEG C of hydrothermal synthesis reaction kettle, activation time 1.5h.Basalt fibre after activation is immersed in the hydrochloric acid of 2M
In, etching temperature is 50 DEG C, and etch period 90min obtains pretreated basalt fibre.
(5) basalt fibre after pretreatment is immersed in Emulsion-4 multiple emulsion, soaking time 120min, is soaked
Steeping temperature is 50 DEG C.After 2 hours, the basalt fibre taking-up after immersion is placed in thermostatic drying chamber and is dried to perseverance for 100 DEG C
Weight, obtains modified basalt fibre (MBF-4).
Obtained by above-described embodiment before modified after basalt fiber performance test result be shown in Table 1.
Table 1. before modified after basalt fiber performance test result
Embodiment 5
(1) 1.18g TEOS, 40g deionized water and 63.12g dehydrated alcohol are added in 250ml three-necked flask, are stirred
It is uniformly mixed, is 3 or so with salt acid for adjusting pH, temperature is stirred to react 3h under the conditions of being 30 DEG C, obtains nano silica dispersion
Liquid.
(2) in the 250mL four-hole bottle equipped with blender, reflux condensing tube, the dispersion of 5g nano silica is sequentially added
Liquid, 0.4g silane coupling agent (KH-570), 0.5g polyacrylamide (PAM), 0.17g octadecyltrimethylammonium chloride
(ODAC), 8.94g epoxy resin and 15g deionized water, stir, and back flow reaction temperature is 50 DEG C.
(3) reaction temperature is warming up to 80 DEG C, while 17.89g epoxy resin and 0.102g APS initiator solution is added dropwise
(being dissolved in 15g deionized water), it is 14 or so that KOH buffer solution, which is added, and adjusts pH value, 5h is persistently stirred, to fully reacting, drop
To room temperature, pH value is adjusted to 7~8, can get polyacrylamide/aqueous epoxy resins/Nano-meter SiO_22Multiple emulsion
(Emulsion-5).Wherein, in the present embodiment, all deionization dosages be 51.99g, (mass ratio 61.17%, relative to
Ratio shared by the quality summation of all monomer components in size).
(4) basalt fibre is placed in H2SO4/H2O2Mixed solution (H2SO4/H2O2=7:3, volume ratio) in, it is placed in temperature
For in 120 DEG C of hydrothermal synthesis reaction kettle, activation time 2h.Basalt fibre after activation is immersed in the hydrochloric acid of 1M,
Etching temperature is 50 DEG C, and etch period 90min obtains pretreated basalt fibre.
(5) basalt fibre after pretreatment is immersed in Emulsion-5 multiple emulsion, soaking time 150min, is soaked
Steeping temperature is 60 DEG C.After 2.5 hours, the basalt fibre taking-up after immersion is placed in thermostatic drying chamber and is dried to for 100 DEG C
Constant weight obtains modified basalt fibre (MBF-5).
Surface roughness using the modified basalt fibre of the present invention increases, and surface microcellular structure occurs, is conducive to
The attachment of microorganism, modified basalt fibre is in 1276cm in infrared spectrum-1Locate the flexural vibrations peak of appearance-CONH-,
3300cm-1Locate appearance-NH2There is a large amount of hydrophilic radical in stretching vibration peak, and contact angle test result also indicates that hydrophily obtains
To being obviously improved, surface can be improved significantly, and improve the affinity of the microorganism of fiber surface, modified basalt
Fiber can be applied in microbial membrane carrier Material Field.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (16)
1. a kind of preparation method of Basalt fiber surface modification coating, which comprises the steps of:
A, tetraethyl orthosilicate TEOS, deionized water, dehydrated alcohol are stirred according to mass ratio 1.18:4.00:6.31, are used
Salt acid for adjusting pH persistently stirs 3h to 3~4,30 DEG C and obtains nano silicon dioxide dispersion；
B, proper amount of nano silica dispersions are added to the reaction vessel for being furnished with mechanical agitator, reflux condensing tube, thermometer
In, by silane coupling agent, surfactant solution, polyacrylamide solution and 1/3 aqueous epoxy resins be added mixed liquor in,
It is stirred until homogeneous, back flow reaction temperature is 40 ~ 50 DEG C；
C, reaction temperature is risen to 65~80 DEG C, while remaining aqueous epoxy resins and initiator solution is added dropwise, buffered with pH
Agent tune pH persistently stirs 3~5 h between 12 ~ 14, wherein pH buffer is one of potassium hydroxide or sodium hydroxide；
D, to fully reacting, it is down to room temperature, hydrochloric acid tune pH value 7~8 is added dropwise, filtering obtains polyacrylamide/water-base epoxy tree
Rouge/Nano-meter SiO_22Multiple emulsion, i.e. Basalt fiber surface modification coating.
2. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: institute in step B
Stating back flow reaction temperature is 45 DEG C.
3. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: institute in step C
75 DEG C of reaction temperature are stated, pH value 13, pH buffer is potassium hydroxide.
4. the preparation method of Basalt fiber surface modification coating according to claim 1, which is characterized in that participate in reaction
Each material mass percentage are as follows: nano silicon dioxide dispersion 1.17~5.88%；Silane coupling agent 0.09~0.47%；Surface is living
Property agent 0.06~0.2%；Polyacrylamide 0.12~0.59%；Aqueous epoxy resins 2.18 ~ 31.57%；Initiator 0.07~
0.12%；Deionized water 61.17~96.31%.
5. the preparation method of Basalt fiber surface modification coating according to claim 1, which is characterized in that participate in reaction
Each material mass percentage are as follows: nano silicon dioxide dispersion 3.52%, silane coupling agent 0.28%, surfactant 0.15% gather
Acrylamide 0.35%, aqueous epoxy resins 19.14%, initiator 0.09%；Deionized water 76.47%.
6. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: the silane is even
Connection agent is gamma-aminopropyl-triethoxy-silane KH-550, γ-glycidyl ether oxygen propyl trimethoxy silicane KH-560 and γ-
Two kinds of one of methacryloxypropyl trimethoxy silane KH-570 or any；
The aqueous epoxy resins are bisphenol A type epoxy resin；
The surfactant is quaternary surfactant；
The initiator is one of potassium peroxydisulfate KPS and ammonium persulfate APS.
7. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: the silane is even
Connection agent is gamma-aminopropyl-triethoxy-silane KH-550.
8. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: the aqueous ring
Oxygen resin is E-51.
9. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: the surface is living
Property agent be one of hexadecyltrimethylammonium chloride HTMAC and octadecyltrimethylammonium chloride ODAC.
10. the preparation method of Basalt fiber surface modification coating according to claim 1, it is characterised in that: the initiation
Agent is potassium peroxydisulfate KPS.
11. Basalt fiber surface modification coating made from -10 any the methods according to claim 1.
12. a kind of application of Basalt fiber surface modification coating as claimed in claim 11, which is characterized in that including walking as follows
It is rapid:
A, basalt fibre is soaked in H2SO4/H2O2In mixed solution, being placed in temperature is 80~120 DEG C of hydrothermal synthesis reaction kettles
Interior, activation time is 0.5~2h, the H2SO4/H2O2H in mixed solution2SO4/H2O2Volume ratio is 7:3；
B, the basalt fibre after activation is immersed in hydrochloric acid solution, concentration of hydrochloric acid solution be 0.5~2M, etching temperature be 30~
50 DEG C, etch period is 30~90 min；
C, 60~150 min of infiltration in Basalt fiber surface modification coating described in claim 11, infiltration temperature are immersed in
25~60 DEG C of degree；
D, after basalt fibre after infiltration takes out 100 DEG C drying to constant weight.
13. the application of Basalt fiber surface modification coating according to claim 12, it is characterised in that: be placed in step A
Temperature is activation time 1h in 90 DEG C of hydrothermal synthesis reaction kettles.
14. the application of Basalt fiber surface modification coating according to claim 12, it is characterised in that: described in step B
Concentration of hydrochloric acid solution is 1M.
15. the application of Basalt fiber surface modification coating according to claim 12, it is characterised in that: described in step B
Etching temperature is 40 DEG C, etch period 60min.
16. the application of Basalt fiber surface modification coating according to claim 12, it is characterised in that: described in step C
Infiltrate 120min, 40 DEG C of infiltration temperature.
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