CN108043235A - A kind of method for enhancing interfacial adhesion between organic separation membrane and backing material - Google Patents
A kind of method for enhancing interfacial adhesion between organic separation membrane and backing material Download PDFInfo
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- CN108043235A CN108043235A CN201711380529.0A CN201711380529A CN108043235A CN 108043235 A CN108043235 A CN 108043235A CN 201711380529 A CN201711380529 A CN 201711380529A CN 108043235 A CN108043235 A CN 108043235A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
The present invention is a kind of method for enhancing interfacial adhesion between organic separation membrane and backing material.This method comprises the following steps：Backing material is immersed in the aqueous solution of sodium hydroxide, make material surface rich in sufficient hydroxyl and achieve the purpose that be roughened material fiber, then by treated, backing material immerses a period of time in silane coupling agent hydrolyzate, take out drying, using the modified material in surface as backing material during film, casting solution is coated uniformly on thereon, gel in deionized water is immersed and forms a film, you can obtain the enhanced organic separation membrane in interface.The casting solution composition includes membrane material, additive and solvent, and membrane material is Kynoar, polyether sulfone or polysulfones.Treated between organic separation membrane and backing material that interface peel strength can improve about 50% 70% for the method for the present invention.
Description
Technical field
The present invention relates to a kind of method for enhancing interfacial adhesion between organic separation membrane and backing material, be specifically it is a kind of with
Chemical treatment combines silane coupling agent surface modification treatment backing material, so as to promote its interfacial adhesion between organic separation membrane
The process of property and the mechanical property of film.
Background technology
Organic separation membrane is formed by processing of high molecular material, such as Kynoar (PVDF), polysulfones (PSF), polyether sulfone
(PES), polyacrylonitrile (PAN), cellulose acetate (CA) etc..Since organic film has filtering accuracy high, selectivity is big, and materials are wide
General, advantages that per membrane area manufacture is at low cost, and membrane module loading density is big etc. are widely used in recycling of water resource field and industry
Special separation field.But the mechanical performance of most of organic separation membrane is poor, and tensile strength is mostly in 1MPa-3MPa scopes
It is interior.In order to improve the mechanical performance of organic film and service life, film is coated in appropriate branch usually in the manufacturing process of film
Material surface is supportted, it, can be strong by the stretch-proof of film on the basis of the through performance and separating property of seperation film are held essentially constant
Degree is improved to more than 10MPa.Organic separation membrane common backing material such as terylene (PET), polypropylene fibre (PP) etc. in preparation process
With excellent thermal stability, chemical stability and mechanical strength, but since its molecular chain structure is regular, crystallinity is high, surface
Lack highly polar group and hydrophilic radical, cause the adhesiveness between backing material and organic separation membrane poor, in water process etc.
Easily from the surface localized delamination of backing material, the separating property for making film is remarkably decreased film by this in, and then causes film point
It can not be normally carried out from process, add the operating cost of process.
In the interfacial adhesion system of composite material, interfacial adhesion performance depends primarily upon the intrinsic spy on reinforcement surface
Property, such as the surface morphological structure of reinforcement, surface chemistry composition (polar functional group) and surface wettability.Once there are numerous studies
Work is directed to improving the interfacial adhesion characteristic of matrix/enhancing composite material, at chemical etching and grafting, plasma
Reason, surface coating etc., but for the correlative study of interfacial adhesion between organic separation membrane and backing material, there is not been reported, and it is normal
It is such as chemically treated for improving the method for interfacial adhesion, corona treatment, flame treatment, mostly complex process, equipment
Costliness, production cost is higher and is also easy to produce the pollutants such as a large amount of spent acid salkali waste, and later stage treatment cost of waste liquor is huge, is unsuitable for big face
Product industrialization promotion.
The content of the invention
The present invention provides a kind of enhancing organic separation membrane and backing material boundary for deficiency present in current techniques
The method of face adhesiveness.This method will be applied to seperation film field in field of compound material to the surface modifying method of reinforcement,
By that will be chemically treated two kinds of method of modifying optimum organizations are modified with coupling agent surface and in the preparation process of seperation film, selecting
Sodium hydroxide solution is taken to carry out surface preparation, backing material is immersed in the aqueous solution of sodium hydroxide, is rich in material surface
The hydroxyl of abundance simultaneously achievees the purpose that roughening fiber, and then by treated, backing material is immersed one in silane coupling agent hydrolyzate
The section time takes out drying.Using modified material as backing material during film, had using phase separation legal system
Machine seperation film.The interfacial adhesion between organic separation membrane and backing material is characterized by 180 ° of peel strength tests, through the present invention
Treated between organic separation membrane and backing material that interface peel strength can improve about 50%-70% for method.
The technical scheme is that：
A kind of method for enhancing interfacial adhesion between organic separation membrane and backing material, comprises the following steps：
(1) surface clean of backing material and drying：Backing material is immersed in mixed aqueous solution 20-30 minutes, is taken out
It is dried after being rinsed with clear water；
Wherein, mixed aqueous solution is mixed by sodium hydroxide solution and nonionic surfactant solution, and volume ratio is
Sodium hydroxide solution：Nonionic surfactant solution=1:1-1:3；Nonionic surfactant is fatty alcohol polyoxyethylene ether
(AEO), nonionic surfactant water-soluble liquid concentration is 5g/L-10g/L, and the concentration of sodium hydrate aqueous solution is 10g/L-20g/
L；
(2) richness hydroxylating in surface is handled：The sodium hydroxide that backing material obtained by step (1) is immersed to 200-300g/L is water-soluble
30-40 minutes in liquid, taking-up is rinsed well the sodium hydroxide solution of remained on surface with clear water, is placed in 60 DEG C of baking oven dry
When 1-2 is small；
(3) surface modification treatment：According to volume ratio alcohol：Distilled water=7:1-10:1 ratio adds in alcohol in distilled water
Mixing, obtains silane coupling agent hydrolysis medium solution, then instills silane coupling agent thereto, is configured to mass fraction as 1%-
6% silane coupling agent hydrolyzate stands a period of time after stirring evenly at room temperature, backing material obtained by step (2) is immersed
In the hydrolyzate, when reaction 3-5 is small at room temperature；After reaction, backing material from hydrolyzate is taken out, will be supported with alcohol
The remaining silane coupling agent hydrolyzate of material surface is rinsed well, when drying 1-2 is small at 60 DEG C；
(4) the enhanced organic separation membrane in interface is prepared：Casting solution is coated uniformly on obtained by step (3) on backing material,
Casting solution thickness 0.2mm-0.3mm, then when being dipped in that 1-2 is small in 20 DEG C -40 DEG C of deionized water, gel film forming, you can obtain
The enhanced organic separation membrane in interface.
Backing material is non-woven fabrics or hollow tubular fabric (inner support tube) in the step (1).The non-woven fabrics
Material be terylene (PET) or polypropylene fibre (PP) (commercial goods (using hot calendering bonding technique productions))；The hollow tubular is knitted
The material of object is terylene (PET) or polypropylene fibre (PP) (commercial goods (being woven by high tenacity terylene or polypropylene filament)).
Nonionic surfactant is preferably fatty alcohol polyoxyethylene ether (AEO) AEO-6, AEO- in the step (1)
7 or AEO-8.
Silane coupling agent used in the step (3) for gamma-aminopropyl-triethoxy-silane (KH550) or γ-
One kind in glycidyl ether oxygen propyl trimethoxy silicane (KH560).
The volume ratio of alcohol and water is preferably 9 in coupling agent hydrolysis medium solution used in the step (3):1.
The alcoholic solvent in hydrolysis medium solution in the step (3) used in Silane coupling agent KH550 is ethyl alcohol, silane
The alcoholic solvent in hydrolysis medium solution used in coupling agent KH560 is methanol；And when even using silane in the step (3)
When joining agent KH560, glacial acetic acid need to be added dropwise, the PH of KH560 hydrolysis medium solution is adjusted to 3-4.
The time of repose of silane coupling agent hydrolyzate is 30-60 minutes in the step (3).
In the casting solution that the step (4) is related to, casting solution is made of membrane material, additive and solvent, membrane material
For Kynoar (PVDF), polyether sulfone (PES) or polysulfones (PSF), the content of membrane material is 10wt%-20wt%；Additive
For the one or more in polyethylene glycol (PEG), ethylene glycol (EG) and polyvinylpyrrolidone (PVP), the content of additive is
3wt%-20wt%；Remaining is solvent, and solvent is n,N-dimethylacetamide (DMAc) or N-Methyl pyrrolidone (NMP).
The present invention substantive distinguishing features be：
1st, first, UF membrane field is not yet reported to the research of interface problem between film matrix and backing material, and
The interface problem of seperation film (especially hydrophobic membrane) and backing material has seriously affected the service life of film in industrial production
And separating property.The present invention will be applied to seperation film field in field of compound material to the surface modifying method of reinforcement for the first time,
To improve the interface performance between seperation film and backing material, and good result is obtained, the backing material of optimization process effect is with dividing
71% can be improved from intermembranous peel strength.Secondly, it is mostly relatively simple to the surface modifying method of reinforcement at present, the present invention
It will be chemically treated for the first time and coupling agent surface be modified two kinds of method of modifying optimum organizations and in the preparation process of seperation film.One
Aspect, chemical treatment can improve the surface polarity and roughness of backing material fiber, improve the surface wettability of backing material, more
The adverse effect that coupling agent surface treatment generates backing material wetability is mended；On the other hand, coupling agent treatment can repair fibre
Dimension table planar defect improves the intensity of backing material, compensates for the adverse effect that chemical treatment generates backing material intensity.Two kinds
Processing method cooperates, and can not only ensure the mechanical strength of backing material, while can also greatly improve seperation film and support
The interfacial adhesion of storeroom.Finally, for the organic separation membrane made from phase separation method, pass through the method for the present invention
After processing, interfacial adhesion has different degrees of promotion, therefore, for improving the interface between organic separation membrane and backing material
Adhesiveness, the present invention have general applicability.
2nd, the processing step of most critical is sodium hydroxide solution surface preparation in the present invention, and chemical surface treatment can be selected
Chemical reagent it is numerous, but the present invention has selected sodium hydroxide to pre-process, from the aspect of following three：First, hydroxide
Sodium plays the role of roughening to backing material, improves the roughness of backing material fiber surface；Secondly, sodium hydroxide is support
Material surface introduces a large amount of hydrophilic radicals, and fiber surface wetability greatly improved；Finally, what sodium hydroxide was provided is a large amount of
Hydroxyl additionally aids silane coupling agent and dehydration condensation occurs for the hydroxyl on backing material surface.Surface roughness, polar group
Group's (hydrophilic radical) and wetability are to influence three big elements of interfacial adhesion.Therefore, the present invention in sodium hydroxide pretreatment
The promotion contribution acted on to interfacial adhesion is huge, and the concentration of sodium hydroxide solution and processing time are most important in the step.
In addition, the hydrolysis time (time of repose) of silane coupling agent is also required to strictly control (30-60 minutes), hydrolysis time is too short to lead
Hydrolysis is caused to be not thorough, hydrolyzes that the silanol amount of generation is less, and what is mainly played a role during silane coupling agent use is silanol
Key；Hydrolysis time is long, and the silanol of generation occurs, from reuniting, hydrolyzate to be caused to fail.The hydrolysis medium solution of silane coupling agent
Middle alcohol water (volume) is than directly affecting time and hydrolysis effect needed for complete hydrolysis, and KH550 reaches complete water in pure water
Time needed for solution is extremely short, and is easy to that polycondensation reaction occurs between hydrolysate silanol molecule, and modified effect is made to be deteriorated, according to
Hydrolysising balance principle, hydrolytic process generate alcohol, and the addition of alcohol can inhibit hydrolysis and be carried out to positive reaction direction, hinder the water of coupling agent
Solution, therefore, need to add in suitable alcohol to inhibit its hydrolysis rate in system.
3rd, field of compound material is more to the research of storeroom interface problem, but in UF membrane field, seperation film and support
The correlative study of the interface problem of storeroom is rarely reported, and the document that can refer to is less.In Textile Engineering field, flexibility is related to
The research of composite material stripping performance, but single method of modifying is mostly used only, and the interface enhancing effect between different materials is past
Past realized by the third material (adhesive).And other are on reinforcing fiber materials and such as between resin, rubber, metal
Bonding Journal of Sex Research in, reinforcing fiber be typically by dispersiveness it is filametntary in the form of mix in the continuous phase of matrix, with the present invention
The complex form of involved material has fundamental difference.
Beneficial effects of the present invention are：
1st, the interface that the extremely wide organic separation membrane with backing material of practical application is exposed in use
Problem has seriously affected application effect and operating cost of the seperation film in water treatment procedure.Successively useization of the invention
Method and coupling agent surface modification treatment backing material, the pretreatment of sodium hydroxide solution are gone back while material fiber is roughened
The surface polarity and wetability of fiber are improved, silane coupling agent can form plastic deformation layer in fiber surface and repair fiber
Surface defect, reinforcing fiber surface roughness in turn avoid chemical treatment to support while fiber surface activity is improved
The mechanical strength of material adversely affects.After the method for the present invention is handled, the peel strength of optimization process effect is by 71N
m-1It improves to 121.5Nm-1, improve 71.1%.
2nd, good interface performance causes composite material that can preferably transfer tensile stress under plus load effect, and subtracts
The stress raisers phenomenon of few cross-section.Therefore the present invention is improving interface peel strength between seperation film and backing material
Meanwhile also enhance the mechanical property of composite material, the seperation film tensile strength of optimization process effect by 10.3MPa improve to
14.7MPa improves 42.7%.
3rd, present invention process is simple, efficient, and batch processing can be carried out to backing material.In addition, lye (hydrogen in processing procedure
Sodium oxide molybdena) amount need to only cover needed for processing material surface, the sustainable use before alkali lye consumption finishes；When silane is even
The mark that opaque floccule fails as it is formed in connection agent hydrolyzate, interior during this period (when being usually 24 small) is as long as water
The amount of solution liquid can cover the material surface of required processing, reusable.Therefore it is of the invention to lye and silane coupled
The consumption of agent is smaller, meets environment protection requirement, is suitble to large-scale industrial production.Meanwhile it is arrived not involved in embodiment
With separation membrane material after the method for the present invention is handled, interface performance has different degrees of promotion, and therefore, the present invention also has
General applicability.
Description of the drawings
Fig. 1 is 180 ° of peel strength test schematic diagrames
Fig. 2 is the FTIR spectrum figure that KH550 hydrolysis is front and rear in embodiment 1, wherein, before (a) is KH550 hydrolysis
FTIR spectrum, (b) are the FTIR spectrum after KH550 hydrolysis
Fig. 3 is the FTIR spectrum figure of PET nonwoven surfaces before and after modification in embodiment 1, wherein, (a) is
The FTIR spectrum of silane coupler modified before processing PET nonwoven surfaces, (b) is after silane coupler modified processing
The FTIR spectrum of PET nonwoven surfaces
Fig. 4 is PET nonwoven surface energy spectrum diagrams before and after modification in embodiment 1, wherein, Fig. 4 (a) is that KH550 is modified
The pet sheet face energy spectrum diagram of before processing, Fig. 4 (b) are the pet sheet face energy spectrum diagram after KH550 modifications
Fig. 5 is PET nonwoven surface electron microscopes before and after modification in embodiment 1, wherein, Fig. 5 (a) is that KH550 is modified
The PET nonwoven surface electron microscopes of before processing, Fig. 5 (b) are the PET nonwoven surface electron microscopes after KH550 modifications
Fig. 6 is stripping surface (PET nonwoven surfaces) electron microscope of PVDF/PET films before and after modification in embodiment 1,
Wherein, Fig. 6 (a) is the stripping surface electron microscope of PET non-woven fabrics before KH550 modifications, and Fig. 6 (b) is after KH550 modification
The stripping surface electron microscope of PET non-woven fabrics
Fig. 7 is that water contact angle tests (water droplet) figure in embodiment 3, wherein, Fig. 7 (a) is pet sheet before KH550 modifications
The water contact angle test chart in face, Fig. 7 (b) are the water contact angle test chart in pet sheet face after KH550 modifications
Specific embodiment
The present invention relates to silane coupling agent hydrolysis it is as follows：
Silane coupling agent KH550 hydrolysis
Silane coupling agent KH560 hydrolysis
Technical scheme is described further below in conjunction with the accompanying drawings, technical solution of the present invention is not limited to following
Cited specific embodiment further includes any combination between each specific embodiment, every to technical solution of the present invention
It is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention, the guarantor in the present invention should all be covered
It protects in scope.
Embodiment 1
It is specific real present embodiments provide for a kind of method for enhancing interfacial adhesion between organic separation membrane and backing material
Applying step includes the surface clean of backing material (PET (terylene) non-woven fabrics) and drying, the processing of surface richness hydroxylating, surface modification
Processing and preparation enhanced four steps of organic separation membrane in interface, specific implementation step are as follows：
The surface clean of PET non-woven fabrics and drying：It prepares 15g/L sodium hydrate aqueous solutions and 7g/L AEO-8 aqueous solutions is each
Two kinds of solution are uniformly mixed by 500mL.PET non-woven fabrics to be immersed in mixed solution 20 minutes, taking-up is rinsed well with clear water,
It is placed in 70 DEG C of baking ovens and dries.
Surface richness hydroxylating processing：Dried PET nonwovens are arranged in 200g/L sodium hydrate aqueous solutions and impregnate 30
Minute, taking-up rinsed well nonwoven surface with clear water, be placed in 60 DEG C of baking oven dry 1-2 it is small when.
Surface modification treatment：First, measure 180ml ethyl alcohol and 20ml deionized waters are configured to volume ratio as 9:1 coupling
Agent hydrolysis medium solution；Then, the KH550 hydrolysis that KH550 silane coupling agents are configured to 5wt% is added dropwise into hydrolysis medium solution
Liquid stands 40 minutes after stirring evenly at room temperature；Finally, richness hydroxylating treated PET non-woven fabrics in surface is immersed into KH550 water
Solve in liquid, impregnate at room temperature 3 it is small when after take out, nonwoven surface is rinsed well with ethyl alcohol, dry 1-2 is small at 60 DEG C
When.
Prepare the enhanced organic separation membrane in interface：It is respectively Kynoar (PVDF) -12.5% to prepare mass content, is gathered
Vinylpyrrolidone (PVP) -10%, ethylene glycol (EG) -8%, the casting solution of n,N-dimethylacetamide (DMAc) -69.5%,
It is stirred well to and is completely dissolved at 70 DEG C, when then standing and defoaming 48 is small at 35 DEG C.Casting solution is changed on surface with scraper
The equably liquid film of one layer of about 0.25mm thickness of striking on property treated PET non-woven fabrics is then immersed in 35 DEG C of deionization
In water 2 it is small when, its related non-woven fabrics from glass plate is gently removed after liquid film is fully cured, is put into deionized water and impregnates
24 it is small when, when changing water daily 3-6 times, then being placed in that immersion treatment 24 is small in absolute ethyl alcohol, by wet film be placed in it is shady and cool it is dry at dry.
180 ° of peel strength experiments：
Fig. 1 is 180 ° of peel strength test schematic diagrames, is required to set peel strength real according to GB/T 2792-2014 standards
It tests, the bonding force between film and non-woven fabrics backing material is tested using electronics single yarn tester.Peel off film and non-woven fabrics
Adhesive surface, by 180 ° of film free end doubling.Film free end is fixed in strength tester upper grip, and the other end is fixed in lower collet.
Tensiometer is opened, setting peeling rate is 100mm/min, determines stretch value for 10mm.When strip length reaches 10mm, tensiometer
It is stopped, record Average peel force F (N).Interfacial adhesion performance is represented that is, peeling force average peak is with removing by peel strength
The ratio of face width.It is calculated with following formula：
In formula, σTFor peel strength, N/m；F be peeling force average peak, N；B be release surface width, m.
Fig. 2 is the front and rear FTIR spectrum figure of KH550 hydrolysis, in the FTIR spectrum figure before KH550 hydrolysis
2970cm-1、2890cm-1、1458cm-1、1378cm-1、1079cm-1The bands of a spectrum at place are Si-O-C2H5The characteristic peak of group.It stands
(hydrolysis) after forty minutes, 3400cm-1Place's absworption peak broadens, and is to generate silanol after KH550 is hydrolyzed, silicone hydroxyl increases institute in solution
It causes, it is possible thereby to determine that coupling agent KH550 is hydrolyzed.
Hydrolysis method includes positive hydrolysis and solves against the current, and so-called positive hydrolysis is that silane coupling agent is added in hydrolysis medium solution
In, the pH of system is more stable at this time, and the concentration of hydrolysate silanol is smaller, and the glue core of generation is seldom, is unlikely to muddy formation
Flocculent deposit；Solution is then that hydrolysis medium solution is added in silane coupling agent against the current, at this time in system product silanol concentration
It is very big, moment a large amount of glue cores can be generated, silanol condensation is caused to form flocculent deposit, hydrolyzate is made to fail, therefore, the present invention uses
Positive hydrolysis.
Fig. 3 is the FTIR spectrum figure of PET nonwoven surfaces before and after KH550 modifications, 3000cm in figure-1,
1100cm-1And 950cm-1The absorption band at place represents the stretching vibration of PET nonwoven surface silicone hydroxyls respectively, antisymmetry is stretched
Vibration and bending vibration, 1200-1100cm-1Dense band represent the antisymmetric stretching vibration of Si-O-Si, 870cm-1Place occurs
Apparent Si-O stretching vibration peaks, it may be determined that the hydrolysate silanol of K550 coupling agents has been grafted on PET non-woven fabrics.By hydrogen
Sodium oxide molybdena treated non-woven fabrics fiber surface can be bonded rich in great amount of hydroxy group with the silicone hydroxyl in hydrolysate silanol
Reaction, so as to which coupling agent molecule chain is bonded to non-woven fabrics fiber surface, organo-functional group in silanol easily with macromolecule membrane material
Material reacts so that two kinds of storerooms of different nature form " molecular bridge ", and organic film, coupling agent molecule and non-woven fabrics is fine
Dimension is combined into the organism of ternary component, and then improves the interfacial adhesion between film and non-woven fabrics backing material.
Fig. 4 is the energy spectrum diagram of PET nonwoven surfaces before and after KH550 modifications, and table 1 is PET before and after KH550 modifications
The constituent content variation of nonwoven surface, it can be seen that the oxygen of PET nonwoven surfaces, nitrogen, silicon content increase after modification
Add, illustrate that fiber surface has successfully been grafted silane coupling agent and surface polarity enhances, the raising of surface polarity peomotes two
Attraction at material interface between polar molecule once molecule distance reaches 50nm, will generate huge between the polar molecule of interface
Model ylid bloom action power (dipole-dipole force, induction force), wherein, dipole-dipole force to the contribution of interface binding intensity theoretically up to 7.0 ×
102MPa-7.0×103MPa, much larger than the intermolecular cohesive strength of membrane material.It is measured through roughmeter, after KH550 modifications
The roughness parameter Ra of PET nonwoven surfaces is improved by 3.39 μm to 3.97 μm, adds 17.1%；Modification causes nonwoven
Measuring fiber surface roughness increase, specific surface area improve, with film compound tense, can for the two more effective mechanical lock cooperation be provided
With.Through dynamic/static contact angle instrument measurement, the water contact angle of PET nonwoven surfaces is by 90 ° of drops after the coupling agent modified processing of KH550
Down to 67 °, show that nonwoven surface wetability increases, due to the raising of wetability, the contact between casting solution and non-woven fabrics
More close, the machinery be conducive to after film cures between film and non-woven fabrics fiber is sealed, so as to improve membrane material and backing material
Between bond properties.
Fig. 5 is the electron microscope of PET nonwoven surfaces before and after modification, it can be seen that non-woven fabrics fiber surface is wrapped after processing
Coupling agent layer has been covered, has also formed plastic deformation layer on non-woven fabrics fiber surface while fiber surface coarse structure increases, not only
Interfacial stress can be offset, improves the ability of Interface Absorption and scattered impact, and Interface Crack can be prevented to continue to extend, is being changed
The mechanical property of composite material is also improved while the interfacial adhesion of kind composite material.Fig. 6 is by 180 ° of peel strengths
The surface electron microscope of PET non-woven fabrics after test, it can be seen that compared with untreated non-woven fabrics fiber, coupling agent modified processing
The PET of the enhanced PVDF/PET seperation films in interface obtained removes the pvdf membrane showed increased of surface residual after non-woven fabrics, shows
Interfacial adhesion between pvdf membrane and non-woven fabrics is improved.
Measured through electronics single yarn tester, the peel strengths of PVDF/PET seperation films obtained by it is untreated when 71N
m-1It is increased to 121.5Nm-1, add 71.1%；The tensile strength of PVDF/PET seperation films is increased to by 10.31MPa
14.66MPa add 42.2%.The through performance and separating property of film are tested, the pure water flux of film is 1152L
m-2·h-1·bar-1, the rejection of 1g/L BSA solution is 96.1%.
The enhancing of table 1KH550 modification separate front and backs film is changed with PET nonwoven surfaces constituent content (wt%)
Embodiment 2
It is specific real present embodiments provide for a kind of method for enhancing interfacial adhesion between organic separation membrane and backing material
Applying step includes the surface clean of backing material (PET (terylene) non-woven fabrics) and drying, the processing of surface richness hydroxylating, surface modification
Processing and preparation enhanced four steps of organic separation membrane in interface, specific implementation step are as follows：
The surface clean of PET non-woven fabrics and drying：It prepares 15g/L sodium hydrate aqueous solutions and 7g/L AEO-8 aqueous solutions is each
Two kinds of solution are uniformly mixed by 500mL.PET non-woven fabrics to be immersed in mixed solution 20 minutes, taking-up is rinsed well with clear water,
It is placed in 70 DEG C of baking ovens and dries.
Surface richness hydroxylating processing：Dried PET nonwovens are arranged in 200g/L sodium hydrate aqueous solutions and impregnate 30
Minute, taking-up rinsed well nonwoven surface with clear water, be placed in 60 DEG C of baking oven dry 1-2 it is small when.
Surface modification treatment：First, measure 180ml ethyl alcohol and 20ml deionized waters are configured to volume ratio as 9:1 coupling
Agent hydrolysis medium solution；Then, the KH550 hydrolysis that KH550 silane coupling agents are configured to 6wt% is added dropwise into hydrolysis medium solution
Liquid stands 40 minutes after stirring evenly at room temperature；Finally, richness hydroxylating treated PET non-woven fabrics in surface is immersed into KH550 water
Solve in liquid, impregnate at room temperature 3 it is small when after, taking-up is rinsed well nonwoven surface with ethyl alcohol, and dry 1-2 is small at 60 DEG C
When.
Prepare the enhanced organic separation membrane in interface：It is respectively polyether sulfone (PES) -20% to prepare mass content, polyethylene pyrrole
Pyrrolidone (PVP) -8%, the casting solution of N-Methyl pyrrolidone (NMP) -72%, is stirred well at 70 DEG C and is completely dissolved,
When being subsequently placed in that standing and defoaming 48 is small at 35 DEG C.With scraper by casting solution on PET non-woven fabrics after surface modification treatment uniformly
The liquid film of one layer of about 0.25mm thickness of ground striking, be then immersed in 35 DEG C of deionized water 2 it is small when, after liquid film is fully cured
Its related non-woven fabrics is gently removed from glass plate, be put into deionized water impregnate 24 it is small when, change water daily 3-6 times, then put
When immersion treatment 24 is small in absolute ethyl alcohol, wet film is placed at shady and cool drying and is dried.
The method for testing film properties is in the same manner as in Example 1, is measured through roughmeter, PET after KH550 surface modification treatments
The roughness parameter Ra of nonwoven surface is improved by 3.39 μm to 3.74 μm, adds 10.3%；It is surveyed through dynamic/static contact angle instrument
Amount, the water contact angle of PET nonwoven surfaces is reduced to 59 ° by 90 ° after the coupling agent modified processing of KH550；Through electronics single thread force
Instrument measures, the peel strengths of PES/PET seperation films obtained by it is untreated when 81.7Nm-1It is increased to 129Nm-1, increase
57.9%；The tensile strength of PES/PET seperation films is increased to 16.68MPa by 12.63MPa, adds 32.1%；To film
Through performance and separating property are tested, and the pure water flux of film is 150Lm-2·h-1·bar-1, section of 1g/L BSA solution
It is 97.8% to stay rate.
Embodiment 3
It is specific real present embodiments provide for a kind of method for enhancing interfacial adhesion between organic separation membrane and backing material
Applying step includes the surface clean of backing material (PET (terylene) non-woven fabrics) and drying, the processing of surface richness hydroxylating, surface modification
Processing and preparation enhanced four steps of organic separation membrane in interface, specific implementation step are as follows：
The surface clean of PET non-woven fabrics and drying：It prepares 15g/L sodium hydrate aqueous solutions and 7g/L AEO-8 aqueous solutions is each
Two kinds of solution are uniformly mixed by 500mL.PET non-woven fabrics to be immersed in mixed solution 20 minutes, taking-up is rinsed well with clear water,
It is placed in 70 DEG C of baking ovens and dries.
Surface richness hydroxylating processing：Dried PET nonwovens are arranged in 200g/L sodium hydrate aqueous solutions and impregnate 30
Minute, taking-up rinsed well nonwoven surface with clear water, be placed in 60 DEG C of baking oven dry 1-2 it is small when.
Surface modification treatment：First, measure 180ml methanol and 20ml deionized waters are configured to volume ratio as 9:1 coupling
Agent hydrolysis medium solution appropriate glacial acetic acid is added dropwise into solution, solution ph is adjusted to 3；Then KH560 silicon is added dropwise into solution
Alkane coupling agent is configured to the KH560 hydrolyzates of 5wt%, and 40 minutes are stood after stirring evenly at room temperature；Finally, by surface richness hydroxyl
Change treated PET non-woven fabrics to immerse in KH560 hydrolyzates, impregnate at room temperature 5 it is small when, taking-up methanol is by nonwoven surface
It rinses well, when drying 1-2 is small at 60 DEG C.
Prepare the enhanced organic separation membrane in interface：It is respectively Kynoar (PVDF) -12.5% to prepare mass content, is gathered
Vinylpyrrolidone (PVP) -10%, ethylene glycol (EG) -8%, the casting solution of n,N-dimethylacetamide (DMAc) -69.5%,
It is stirred well to and is completely dissolved at 70 DEG C, when then standing and defoaming 48 is small at 35 DEG C.Casting solution is changed on surface with scraper
The equably liquid film of one layer of about 0.25mm thickness of striking on property treated PET non-woven fabrics is then immersed in 35 DEG C of deionization
In water 2 it is small when, its related non-woven fabrics from glass plate is gently removed after liquid film is fully cured, is put into deionized water and impregnates
24 it is small when, when changing water daily 3-6 times, then being placed in that immersion treatment 24 is small in absolute ethyl alcohol, by wet film be placed in it is shady and cool it is dry at dry.
The method for testing film properties is in the same manner as in Example 1, is measured through roughmeter, PET after KH560 surface modification treatments
The surface roughness parameter Ra of non-woven fabrics is improved by 3.39 μm to 4.16 μm, adds 22.7%；Fig. 7 is KH560 modifications
Water contact angle test (water droplet) figure of front and rear PET nonwoven surfaces, measures through dynamic/static contact angle instrument, after KH560 modifications
The water contact angle of PET nonwoven surfaces is reduced to 73 ° by 90 °；It is measured through electronics single yarn tester, PVDF/PET separation obtained
The peel strength of film by it is untreated when 71Nm-1It is increased to 107.2Nm-1, add 51%；PVDF/PET seperation films
Tensile strength is increased to 13.13MPa by 10.31MPa, adds 27.4%；The through performance and separating property of film are surveyed
Examination, the pure water flux 1480Lm of film-2·h-1·bar-1, the rejection of 1g/L BSA solution is 96.5%.
Embodiment 4
For specific implementation step with embodiment 1, difference is that backing material is hollow tubular fabric (commercial goods, material
For terylene (PET)), hollow-fibre membrane is using hollow tubular fabric (inner support tube) as inner support material, utilizes device for spinning
By casting solution coated on a kind of hollow-fibre membrane outside inner support tube, prepared.Its shape is in hollow tubular, using inner support
Mode is made of the film layer of hollow tubular fabric and external cladding.The stripping of hollow-fibre membrane after modification of the present invention
The performances such as the rejection from intensity, pure water flux and BSA solution are close to embodiment 1.
Unaccomplished matter of the present invention is known technology.
Claims (7)
1. a kind of method for enhancing interfacial adhesion between organic separation membrane and backing material, it is characterized in that comprising the following steps：
（1）The surface clean of backing material and drying：Backing material is immersed in mixed aqueous solution 20-30 minutes, is taken out with clear
Water is dried after rinsing；
Wherein, backing material is non-woven fabrics or hollow tubular fabric；Mixed aqueous solution is by sodium hydroxide solution and non-ionic surface
Activator solution mixes, and volume ratio is sodium hydroxide solution：Nonionic surfactant solution=1:1-1:3；Nonionic table
Face activating agent is fatty alcohol polyoxyethylene ether（AEO）, nonionic surfactant water-soluble liquid concentration be 5g/L-10g/L, hydroxide
The concentration of sodium water solution is 10g/L-20g/L；
（2）Surface richness hydroxylating processing：By step（1）Gained backing material is immersed in the sodium hydrate aqueous solution of 200-300g/L
30-40 minutes, the flushing of taking-up clear water be placed in 60 DEG C of baking oven dry 1-2 it is small when；
（3）Surface modification treatment：According to volume ratio alcohol：Distilled water=7:1-10:Alcohol is added in distilled water and mixed by 1 ratio,
Silane coupling agent hydrolysis medium solution is obtained, then instills silane coupling agent thereto, is configured to the silane that mass fraction is 1%-6%
Coupling agent hydrolyzate is stood after stirring evenly at room temperature, then by step（2）Gained backing material is immersed in the hydrolyzate, in room
When the lower reaction 3-5 of temperature is small；After reaction, backing material from hydrolyzate is taken out, backing material is rinsed with alcohol, at 60 DEG C
When drying 1-2 is small；
（4）Prepare the enhanced organic separation membrane in interface：Casting solution is coated uniformly on step（3）On gained backing material, casting film
Liquid thickness 0.2mm-0.3mm, then when being dipped in that 1-2 is small in 20 DEG C -40 DEG C of deionized water, gel film forming, you can obtain interface
Enhanced organic separation membrane；
The casting solution is made of membrane material, additive and solvent, and the content of membrane material is 10wt%-20wt%；Additive
Content is 3wt%-20wt%；Remaining is solvent；Membrane material is Kynoar（PVDF）, polyether sulfone（PES）Or polysulfones（PSF）；
Additive is polyethylene glycol（PEG）, ethylene glycol（EG）And polyvinylpyrrolidone（PVP）In one or more, solvent N,
N- dimethyl acetamides（DMAc）Or N-Methyl pyrrolidone（NMP）.
2. enhance the method for interfacial adhesion between organic separation membrane and backing material as described in claim 1, it is characterized in that institute
The material for the non-woven fabrics stated is terylene（PET）Or polypropylene fibre（PP）；The material of the hollow tubular fabric is terylene（PET）Or third
Synthetic fibre（PP）.
3. enhance the method for interfacial adhesion between organic separation membrane and backing material as described in claim 1, it is characterized in that institute
The step of stating（1）Middle nonionic surfactant is fatty alcohol polyoxyethylene ether（AEO）AEO-6, AEO-7 or AEO-8.
4. enhance the method for interfacial adhesion between organic separation membrane and backing material as described in claim 1, it is characterized in that institute
The step of stating（3）Used in silane coupling agent for γ-Aminopropyl triethoxysilane（KH550）Or γ-glycidol ether
Oxygen propyl trimethoxy silicane（KH560）.
5. enhance the method for interfacial adhesion between organic separation membrane and backing material as described in claim 1, it is characterized in that institute
The step of stating（3）The volume ratio of alcohol and water is 9 in coupling agent hydrolysis medium solution used:1.
6. enhance the method for interfacial adhesion between organic separation membrane and backing material as described in claim 1, it is characterized in that institute
The step of stating（3）The alcoholic solvent in hydrolysis medium solution used in middle Silane coupling agent KH550 is ethyl alcohol, silane coupling agent
The alcoholic solvent in hydrolysis medium solution used in KH560 is methanol；And when the step（3）It is middle to use silane coupling agent
During KH560, glacial acetic acid need to be added dropwise, the PH of KH560 hydrolysis medium solution is adjusted to 3-4.
7. enhance the method for interfacial adhesion between organic separation membrane and backing material as described in claim 1, it is characterized in that institute
The step of stating（3）The time of repose of middle silane coupling agent hydrolyzate is 30-60 minutes.
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| CN110368717A (en) * | 2019-05-30 | 2019-10-25 | 郑州大学 | A kind of polylactic acid non-woven filter cloth material and preparation method thereof for oil/water separation |
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| CN115838572A (en) * | 2021-10-29 | 2023-03-24 | 宁德时代新能源科技股份有限公司 | Method for producing modified adhesive tape, secondary battery, battery module, battery pack, and electric device |
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| CN109012230A (en) * | 2018-09-05 | 2018-12-18 | 常州市超纯环保科技有限公司 | A kind of belt material hollow-fibre membrane |
| CN110038438A (en) * | 2019-04-04 | 2019-07-23 | 三达膜科技（厦门）有限公司 | A kind of preparation method of organo-mineral complexing nanofiltration membrane |
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| CN113831573A (en) * | 2021-10-14 | 2021-12-24 | 吉林大学 | Surface modification method of polyether-ether-ketone hoop |
| CN115838572A (en) * | 2021-10-29 | 2023-03-24 | 宁德时代新能源科技股份有限公司 | Method for producing modified adhesive tape, secondary battery, battery module, battery pack, and electric device |
| CN115838572B (en) * | 2021-10-29 | 2024-03-26 | 宁德时代新能源科技股份有限公司 | Method for producing modified adhesive tape, secondary battery, battery module, battery pack, and electric device |
| CN114259882A (en) * | 2021-11-15 | 2022-04-01 | 南京工业大学 | Lining reinforced hollow fiber solvent-resistant nanofiltration membrane and preparation method thereof |
| CN115318115A (en) * | 2022-07-11 | 2022-11-11 | 华东理工大学 | Micro-channel type hydrophobic membrane, preparation method and application thereof, and prediction method for bromine extraction yield by gas membrane method |
| CN115318115B (en) * | 2022-07-11 | 2023-11-17 | 华东理工大学 | Microchannel type hydrophobic membrane, preparation method, application and prediction method for bromine extraction yield by air film method |
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