CN106750743A - The film forming formulation of UHMWPE/PVDF blend films and the method using the film forming formulation masking - Google Patents
The film forming formulation of UHMWPE/PVDF blend films and the method using the film forming formulation masking Download PDFInfo
- Publication number
- CN106750743A CN106750743A CN201611064825.5A CN201611064825A CN106750743A CN 106750743 A CN106750743 A CN 106750743A CN 201611064825 A CN201611064825 A CN 201611064825A CN 106750743 A CN106750743 A CN 106750743A
- Authority
- CN
- China
- Prior art keywords
- uhmwpe
- pvdf
- film forming
- molecular weight
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of film forming formulation the invention discloses UHMWPE/PVDF blend films and the method using the film forming formulation masking, the film forming formulation include following components in parts by weight：1~15 part of UHMWPE, 1~10 part of PVDF, 60~98 parts of paraffin oils and 0.2~0.5 part of antioxidant.Method using the film forming formulation masking comprises the following steps：The powder in formula is dried first, then each component and antioxidant are mixed, stirred, be warming up to blend solution presentation transparence, obtain casting solution；Knifing, room temperature cooling, obtains primary membrane；By extraction, freeze-drying obtains UHMWPE/PVDF blend films.Micropore membrane pore structure obtained in the method enriches, and aperture is controllable, flux is big, and mechanical strength is obviously improved.
Description
Technical field
The present invention relates to polymeric membrane preparation field, more particularly to a kind of film forming formulation of UHMWPE/PVDF blend films
And using the method for the film forming formulation masking.
Background technology
With continuing to develop for industrialization and urbanization, water consumption and wastewater discharge increase sharply, and cause many areas
The serious nervous and environmental pollution of water resource.Membrane Materials are that a kind of liquid that Conventional espresso technique and UF membrane are combined separates skill
Art, in the presence of the side steam pressure difference of film two, volatile component realizes separate through fenestra in vapour form in feed liquid for it
Membrane process.Membrane Materials can be operated under Room-temperature low-pressure, and equipment is simple and convenient to operate, easily amplifies and using low-quality heat
Source, therefore had a wide range of applications in the field such as seawater and brackish water desalination, the extraction of volatile component, waste water high enrichment.
Membrane Materials need to meet two requirements of aspect of low-surface-energy and porous, in addition to having porosity higher and enough
Mechanical strength, good heat endurance and chemical stability.In recent years, the research about Membrane Materials membrane material is concentrated mainly on
On polytetrafluoroethylene (PTFE) (PTFE), three kinds of materials of polypropylene (PP) and Kynoar (PVDF).
Ultra-high molecular weight polyethylene is polyethylene of the molecular weight more than 1,000,000, it have high-strength and high-modulus, UV resistant,
The characteristic such as seawater corrosion resistance, self-lubricating, hydrophobic, but its heat distortion temperature is 85 DEG C, is not suitable for long-term use at high temperature, is passed through
Blending and modifying is just hopeful to be applied to Membrane Materials field.At present, ultra high molecular weight polyethylene films most common method is thermic phase
Hair method (TIPS), it is that in high-temperature diluent disentanglement and UHMWPE macromolecule chains are formed into uniform frozen glue, high-viscosity
Frozen glue makes the strand unfolded remain behind well, and UHMWPE chain-folded lamellaes are formed during temperature drop causes frozen glue body, this
When by the induction mode such as stretching, realize rearranging for molecule segment in frozen glue body and other additives, extraction washes diluent
UHMWPE microporous barriers are then obtained afterwards.But there is larger shrinkage factor during cooling due to UHMWPE, cause solvent extraction
The interface cavity that leaves afterwards reduces or disappears, therefore the interstitial hole of microporous barrier obtained in this method is connective poor, while hole
Generation type it is also relatively simple.
PVDF is a kind of spherical particle of molecular weight more than 500,000, with good chemical resistance, heat-resisting quantity,
Oxidative resistance and radiation resistance, and hydrophobicity is also especially good, but short texture, intensity is not good enough, is not suitable for being used alone, TIPS methods
It is the most frequently used most one of method of current PVDF micropores film preparation.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention provides film forming formulation and the utilization of a kind of UHMWPE/PVDF blend films
The method of the film forming formulation masking, is enriched using the pore structure of UHMWPE/PVDF blend films obtained in the film forming formulation, and aperture can
Control, flux are big, and mechanical strength is obviously improved.
Therefore, technical program of the present invention lies in：
A kind of film forming formulation of UHMWPE/PVDF blend films, including following components in parts by weight：
1~15 part of ultra-high molecular weight polyethylene (UHMWPE)；
1~10 part of Kynoar (PVDF)；
60~98 parts of paraffin oil (LP).
It is preferred that, also including 0.2~0.5 part of antioxidant.It is further preferred that the antioxidant is：Antioxidant 1076, i.e., [β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid] positive octadecanol ester；Antioxidant 1010, i.e., four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol ester；Irgasfos 168, i.e., three [2.4- di-tert-butyl-phenyls] phosphite esters.
A kind of UHMWPE/PVDF blend films, it is by 1~15 portion of ultra-high molecular weight polyethylene, 1~30 part of Kynoar group
Into it is continuous phase to form a kind of UHMWPE, and PVDF is the network looping structure of dispersed phase.It is preferred that, also including 0.2~0.5 part
Antioxidant, antioxidant is dispersed in film.
It is preferred that, the molecular weight of the ultra-high molecular weight polyethylene is higher than 1,000,000.
The molecular weight of Kynoar used in the present invention is 50~520,000；Paraffin oil is carbon number in the short of 8-12
Alkane.
The method that UHMWPE/PVDF blend films are prepared using above-mentioned film forming formulation, is comprised the following steps：
1) ultra-high molecular weight polyethylene, Kynoar are respectively dried standby；
2) ultra-high molecular weight polyethylene, Kynoar, paraffin oil are to slowly warm up to 80 DEG C to 100 under agitation
DEG C and keep 20min to 40min, be then warming up to again 130 DEG C to 150 DEG C holding 30min to 50min, it is finally heated to 180 DEG C
80min to 120min or so is kept to 200 DEG C, until blend solution is presented transparence, casting solution is obtained；
Preferred steps 2) be, by ultra-high molecular weight polyethylene, Kynoar, paraffin oil and antioxidant under agitation
It is to slowly warm up to 80 DEG C to 100 DEG C and keeps 20min to 40min, 130 DEG C to 150 DEG C is then warming up to again and keeps 30min to arrive
50min, finally heated to 180 DEG C to 200 DEG C keep 80min to 120min or so, until blend solution is presented transparence, obtain
Casting solution；
3) the striking film forming on lamina membranacea of scraping by the casting solution at 100 DEG C to 150 DEG C, room temperature cooling, obtains primary membrane；
4) primary membrane is extracted into 24h to 48h in the oil, removes paraffin oil, then be placed in freeze drier
12h to 24h is dried, ultra-high molecular weight polyethylene/Kynoar binary blend film is obtained.
Step 4 of the present invention) gasoline that uses is No. 120 gasoline, is No. 120 industrial napthas, white gas or rubber solvents
Gasoline, main component is aliphatic compound.
This film-forming method that the present invention is provided is will be a kind of new associated with Thermal inactive method and melt-mixing method
Film-forming method, the method cause two kinds of polymer be blended heating process in one kind be dissolved in solvent formed network structure, it is another
It is that spherocrystal aggregation is formed after melting that polymer is planted insoluble in solvent, then two kinds of polymer is formed networks by high-speed stirred
Looping structure, used as reinforcement, one kind is used as dispersion for a kind of polymer.
Compared with the prior art compared with the present invention mixes UHMWPE and PVDF by a certain percentage, then adds in the mixture
Enter a certain amount of paraffin oil (LP) (paraffin oil is the good diluent of UHMWPE, is but the non-diluted agent of PVDF), be heated slowly to
180 DEG C and it is sufficiently stirred for obtaining the UHMWPE/PVDF/LP tertiary blending solution of homogeneous transparent.Additionally, adding in the mixture few
The antioxidant of amount, prevents the degraded of UHMWPE in heating process.Then tertiary blending transparent liquid is put into and is scraped on lamina membranacea, with 120
DEG C knifing rod onboard carry out knifing, obtain certain thickness film sample；Film sample is placed on and is cooled down at room temperature, consolidated
Change；The film after cooling is put into extractant gasoline again extracts LP；Finally the film after extraction is put into freeze drier and is done
It is dry, obtain final product UHMWPE/PVDF binary blending microporous membranes.
Brief description of the drawings
Fig. 1 a scheme for the FSEM for not having the microporous barrier surface for adding PVDF in comparative example 1；
Fig. 1 b, 1c, 1d, 1e are the blending microporous membrane surface FSEM figures after 4 components addition PVDF in embodiment 1~4；
Fig. 2 a are the electron microscope in the circle band interface hole on the blend film surface that embodiment 1 is obtained；
Fig. 2 b are the network structure electron microscope of the blend film section that embodiment 1 is obtained；
The surface interface hole that the blend film solid- liquid separation that Fig. 2 c embodiments 1 are obtained is formed；
Fig. 3 is the film cross section (a1, b1, c1, d1, a2, b2, c2, d2) and crust that the embodiment 9~11 of comparative example 2 is obtained
The influence of layer (a3, b3, c3, d3) SEM results；A1-a3 represents comparative example 1；B1-b3 represents embodiment 9；C1-c3 is represented and implemented
Example 10；D1-d3 represents embodiment 11.
Fig. 4 is the influence of the blend film hydrophobic properties of the surface that embodiment 1~4 is obtained；
Fig. 5 is the influence of the blend film hydrophobic properties of the surface that embodiment 1~4 is obtained；
Fig. 6 is the influence of the blend film crystallinity that embodiment 1~4 is obtained；
Fig. 7 is the influence of the blending film-strength that embodiment 1~4 is obtained；
Fig. 8 is influence of the PVDF contents to porosity in the blend film that embodiment 1~4 is obtained；
Fig. 9 is influence of the PVDF contents to blend film air flux in the blend film that embodiment 1~4 is obtained；
Figure 10 is influence of the PVDF contents to blending membrane porosity in the blend film that embodiment 1~4 is obtained；
PVDF contents are to blend film pure water flux and the shadow of bubble point diameter in the blend film that Figure 11 is obtained for embodiment 1~4
Ring.
Specific embodiment
Technical scheme is described in detail below in conjunction with drawings and Examples.
Comparative example 1
(1) ultra-high molecular weight polyethylene powder is placed on preliminary drying 3-5h in 90 DEG C of baking oven, weighs superhigh molecular weight polyethylene
2 parts of alkene, 97.7 parts of saxol, 0.3 part of antioxidant；
(2) ultra-high molecular weight polyethylene and paraffin oil are to slowly warm up to 90 DEG C of holding 30min under agitation, then
145 ± 10 DEG C of holding 45min are warming up to again, 180 DEG C is finally warmed up to untill solution becomes transparent, obtain casting solution；
(3) casting solution that step (2) is obtained is poured on immediately and is scraped on lamina membranacea, immediately with the knifing for having been heated to 120 DEG C
Rod carries out scraping membrane operations, is placed on sample after the completion of knifing and cools down at room temperature, solidifies；
(4) film after solidifying extracts 24h in being first put into one gasoline, after to place into and extract 12h in two road gasoline, then will
Film after extraction dries 12h in being put into -50 DEG C of freeze drier, obtains ultra-high molecular mass polyethylene micropore film.
Comparative example 2
(1) polymer UHMWPE is placed in 90 DEG C of baking oven and fools 3-5h in advance, weigh 15 parts of ultra-high molecular weight polyethylene, resisted
84.7 parts of 0.3 part of oxygen agent and paraffin oil.
(2) after 15 parts of polymer, 0.3 part of antioxidant and mineral oil being made into suspension, prepared with double screw extruder
UHMWPE/PVDF binary blend hollow fiber membranes, wherein cooling medium are 20 DEG C of air.
(3) solvent, the ultrafiltration water logging of the film after extraction are fallen in extraction in the hollow-fibre membrane after cooling being put into No. 120 gasoline
Bubble 30min, is placed in fixed length heat treatment 30min in 100 DEG C of water, is finally immersed in 24h in 60% glycerine water solution, take out after
Air-dry at room temperature standby.
Embodiment 1~4
(1) ultra-high molecular weight polyethylene and Kynoar powder are placed on preliminary drying 3-5h in 90 DEG C of baking oven, are pressed respectively
Following table weighs ultra-high molecular weight polyethylene, Kynoar part, saxol and antioxidant.
(2) ultra-high molecular weight polyethylene, Kynoar and paraffin oil are to slowly warm up to 90 DEG C of guarantors under agitation
30min is held, 145 ± 10 DEG C of holding 45min are then warming up to again, be finally warmed up to 180 DEG C untill solution becomes transparent, obtained
To casting solution；
(3) casting solution is immediately placed in and is scraped on lamina membranacea, carry out knifing with the knifing rod for having been heated to 120 DEG C immediately
, be placed on for sample after the completion of knifing cool down at room temperature, solidify by operation；
(4) film after solidification is first put into one gasoline and extracts 24h, after to place into and extract 12h in two road gasoline, then
Film after extraction is put into -50 DEG C of freeze drier and dries 12h, obtain that ultra-high molecular weight polyethylene is micro- and Kynoar
Binary hybrid microporous barrier, namely UHMWPE/PVDF blend films.
The electron microscope of contrast comparative example 1 and embodiment 1~4, from Fig. 1 a and Fig. 1 b, because the presence of PVDF microballoons makes
Obtain UHMWPE/PVDF binary hybrid microporous barriers surface substantially more coarse than UHMWPE microporous barrier, the enhancing of hybridized film hydrophobicity.
As shown in Fig. 2 the formation of blending membrane micropore, the micropore that only UHMWPE and LP solid- liquid separations are not formed, such as Fig. 2 a
With shown in Fig. 2 b, also UHMWPE and PVDF solid-solid separations formed interface cavity, as shown in Figure 2 c so that blend film micropore
Formation more enrich；
Known by Fig. 4, act also as the effect of nucleator in system due to PVDF microballoons so that the knot of UHMWPE in hybridized film
Brilliant degree has within the specific limits and has obvious increase, and mechanical property is relative to be remarkably reinforced；Due to UHMWPE and PVDF hybrid systems
The change of middle macroscopic property causes that the heat resistance of UHMWPE components in hybridized film has an obvious improvement, aqueous increase, more
Membrane Materials film is met to hydrophobic requirement.As shown in Figure 10,11, in hollow-fibre membrane the porosity and pure water flux of film and
Bubble point aperture increases all as PVDF contents increase, and main cause is the increase in the generation of UHMWPE and PVDF interface cavities.Make
Obtain being more widely applied for film.
The crystallinity of UHMWPE is calculated in the microporous barrier that comparative example 1 and embodiment 1~4 are made, and specific data are painted
Into figure such as Fig. 6.The crystallinity of UHMWPE is substantially reduced after PVDF is added as seen from the figure, but when PVDF contents are in certain model
The crystallinity of UHMWPE increases with the increase of PVDF when enclosing interior, and main cause is process of a part of PVDF spherocrystals in cooling
Middle preferential crystallization serves as the effect of nucleator so that the crystallinity of UHMWPE increases.Although the crystallinity increase of UHMWPE is still
Film strength does not increase, as shown in figure 3, the amount for being primarily due to UHMWPE is that certain can only to strengthen limited PVDF micro-
Ball, so as the increase film-strength of PVDF microspheres amounts is in reduction, and the increase of UHMWPE crystallinity can only delay film-strength
Reduction, film-strength can not be lifted.
The air flux change of comparative example 1 and embodiment 1-4 is totally carried as shown in figure 9, being added in PVDF with the flux of caudacoria
Height, because the addition of PVDF causes that the generation type of micropore is more enriched, and increased the connectedness of film interstitial hole.Excessive
PVDF causes that the main cause that flux declines is the porosity reduction of the solid content increase film of film.
Fig. 4 and Fig. 5 show either in PVDF/UHMWPE binary blend flat sheet membrane or hollow-fibre membrane, due to
PVDF content increases increase the surface roughness of film, so cause the hydrophobicity of film strengthening.Fig. 6 shows, a part of PVDF balls
It is brilliant to induce UHMWPE crystallizations as nucleator in temperature-fall period.Fig. 7 and Fig. 8 show the increase of PVDF contents so that Flat Membrane
Intensity and porosity decline, and Fig. 9 and Figure 11 show that PVDF enhances the flux that the connectedness of film interstitial hole causes and increases.Figure
Under 10 show identical solid content, the porosity of film increases with the increase of PVDF contents.
Embodiment 5~8
(1) preliminary drying 3-5h is pressed respectively in ultra-high molecular weight polyethylene and Kynoar powder being placed on into 90 DEG C of baking oven
Table weighs ultra-high molecular weight polyethylene, Kynoar part and saxol.
(2) ultra-high molecular weight polyethylene, Kynoar and paraffin oil are to slowly warm up to 90 DEG C of guarantors under agitation
30min is held, 145 ± 10 DEG C of holding 45min are then warming up to again, be finally warmed up to 180 DEG C untill solution becomes transparent, obtained
To casting solution；
(3) casting solution is immediately placed in and is scraped on lamina membranacea, solution uniformly spreads over and scrapes on lamina membranacea, be not required to knifing rod and enter
Row scrapes membrane operations, is then placed on and cools down at room temperature, solidifies,
(4) film after solidification is first put into one gasoline and extracts 24h, after to place into and extract 12h in two road gasoline, then
Film after extraction is put into -50 DEG C of freeze drier and dries 12h, obtain that ultra-high molecular weight polyethylene is micro- and Kynoar
Binary hybrid microporous barrier, namely UHMWPE/PVDF blend films.
In embodiment 5~8, because antioxidant is not added, and ultra-high molecular weight polyethylene is easily degraded at high temperature, plus
Strict temperature control is needed when hot, once temperature is too high, the ultra-high molecular weight polyethylene for obtaining occurs a large amount of degradeds, it is difficult to
Form polymer macromolecule chain, it is impossible to play a part of to strengthen PVDF spherocrystals, cannot be formed with mechanical strength after knifing
Film.
Embodiment 9~11
(1) polymer UHMWPE and PVDF are placed in 90 DEG C of baking oven and fool 3-5h in advance.According to the form below weighs superelevation point respectively
Sub- weight northylen, Kynoar part, saxol and antioxidant.
(2) after 15wt% polymer, 0.3wt% antioxidant and mineral oil being made into suspension, twin-screw extrusion mechanism is used
Standby UHMWPE/PVDF binary blend hollow fiber membranes, wherein cooling medium are 20 DEG C of air.
(3) solvent, the ultrafiltration water logging of the film after extraction are fallen in extraction in the hollow-fibre membrane after cooling being put into No. 120 gasoline
Bubble 30min, is placed in fixed length heat treatment 30min in 100 DEG C of water, is finally immersed in 24h in 60% glycerine water solution, take out after
Air-dry at room temperature standby.
By the contrast of comparative example 2 and embodiment 9~11, from the figure 3, it may be seen that with the increase film of PVDF contents in polymer
Hydrophobicity be remarkably reinforced, the roughness for being primarily due to film surface increases so that the hydrophobicity of film increases, and more meets film steaming
Film is evaporated to hydrophobic requirement.As shown in Figure 10,11, the porosity and pure water flux of film and bubble point aperture in hollow-fibre membrane
Increase all as PVDF contents increase, main cause is the increase in the generation of UHMWPE and PVDF interface cavities.
The microporous barrier prepared by thermic phase method after UHMWPE and PVDF blendings is increased by the network-like structure of UHMWPE
Strong PVDF spherocrystals so that the compact conformation intensity between PVDF spherocrystals increases, simultaneously because two kinds of polymer are incompatible and cooling is received
Shrinkage is different to cause that solid-solid phase separating interface hole occurs during cooling in blend film.Because the presence of interface cavity is enriched
Membrane pore structure, increased the connectedness of microporous barrier interstitial hole, and the size in aperture is controlled.But because PVDF is in Blending Processes
In be insoluble in solvent, it is dispersed in casting solution with molten form, and enhancing network structure by UHMWPE is mutually interconnected
Connect, two kinds of polymer blend contents all have a direct impact to membrane pore structure, intensity etc., therefore processing compound is prepared for the method
Film is extremely important.
The present invention proposes the complete incompatible polymers blendings of UHMWPE and bis- kinds of PVDF using the network fibril of UHMWPE
The connectivity of discrete PVDF microballoons high, makes the aperture of microporous barrier easily controllable, and film strength increases.Wherein PVDF is whole
Not only served as nucleator in film system but also served as pore former, and film agent structure.In the system, PVDF microballoon conducts
UHMWPE nucleators increased grain density, reduce crystalline size so that the pore structure of microporous barrier is smaller, and pore-size distribution is more equal
It is even；In phase separation, UHMWPE is continuous phase, PVDF is dispersed phase, can obtain circle band interface hole so that microporous barrier
Pore structure is more enriched, connective more preferable, aperture is easier to precise control.The microporous barrier for preparing in this way can be caused
Pore-size distribution, such as bubble point pore diameter distribution figure in Figure 11 hollow-fibre membranes, can reach at 0.1~0.4 μm during Membrane Materials
More preferable effect.
Claims (7)
1. a kind of film forming formulation of UHMWPE/PVDF blend films, it is characterised in that including following components in parts by weight：
1~15 part of ultra-high molecular weight polyethylene (UHMWPE)；
1~10 part of Kynoar (PVDF)；
60~98 parts of paraffin oil (LP).
2. the film forming formulation of UHMWPE/PVDF blend films as claimed in claim 1, it is characterised in that：Also include 0.2~0.5 part
Antioxidant.
3. the film forming formulation of UHMWPE/PVDF blend films as claimed in claim 2, it is characterised in that：The antioxidant is：Antioxygen
Agent 1076, antioxidant 1010, or irgasfos 168.
4. the method for preparing UHMWPE/PVDF blend films using the film forming formulation as described in any one in claims 1 to 3, its
It is characterised by comprising the following steps：
1) ultra-high molecular weight polyethylene, Kynoar are respectively dried standby；
2) ultra-high molecular weight polyethylene, Kynoar and paraffin oil are mixed, 80~100 is to slowly warm up under agitation
DEG C and keep 20~40min, be then warming up to again 130~150 DEG C holding 30~50min, finally heated to 180~200 DEG C guarantor
80~120min or so is held, until blend solution is presented transparence, casting solution is obtained；
Or ultra-high molecular weight polyethylene, Kynoar, paraffin oil and the antioxidant mixing that 2) will be counted by weight, stirring
Be to slowly warm up under the conditions of mixing 80~100 DEG C and keep 20~40min, be then warming up to again 130~150 DEG C keep 30~
50min, finally heated to 180~200 DEG C keep 80~120min or so, until blend solution is presented transparence, obtain casting film
Liquid；
3) the striking film forming on lamina membranacea of scraping by the casting solution at 100~150 DEG C, room temperature cooling, obtains primary membrane；
4) primary membrane is extracted in the oil, removes paraffin oil, then be placed on drying in freeze drier, obtained
UHMWPE/PVDF blend films.
5. preparation method as claimed in claim 4, it is characterised in that：Step 4) gasoline that uses is No. 120 gasoline.
6. preparation method as claimed in claim 4, it is characterised in that：The molecular weight of the ultra-high molecular weight polyethylene is higher than 100
Ten thousand；The molecular weight of the Kynoar is 50~520,000；Paraffin oil is short chain alkanes of the carbon number in 8-12.
7. the method for preparing UHMWPE/PVDF blend hollow fiber membranes using the film forming formulation as described in Claims 2 or 3, its
It is characterised by comprising the following steps：
1) ultra-high molecular weight polyethylene, Kynoar are respectively dried standby；
2) ultra-high molecular weight polyethylene, Kynoar, paraffin oil and antioxidant are mixed through mechanical agitation, obtains suspension；
3) suspension is extruded through double screw extruder, nascent doughnut is obtained after air bath, water-bath solidification cooling
Film；
4) the nascent hollow-fibre membrane is extracted in the oil, removes paraffin oil, then through the immersion of ultrafiltration water, then in the hot water
Nervous thermal finalization is carried out, the UHMWPE/PVDF blend hollow fiber membranes are obtained after most being processed through glycerine water solution afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611064825.5A CN106750743A (en) | 2016-11-28 | 2016-11-28 | The film forming formulation of UHMWPE/PVDF blend films and the method using the film forming formulation masking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611064825.5A CN106750743A (en) | 2016-11-28 | 2016-11-28 | The film forming formulation of UHMWPE/PVDF blend films and the method using the film forming formulation masking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106750743A true CN106750743A (en) | 2017-05-31 |
Family
ID=58902014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611064825.5A Pending CN106750743A (en) | 2016-11-28 | 2016-11-28 | The film forming formulation of UHMWPE/PVDF blend films and the method using the film forming formulation masking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106750743A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554190A (en) * | 2018-03-05 | 2018-09-21 | 北京清源洁华膜技术有限公司 | A kind of seperation film and preparation method thereof for detaching bavin gasoline gas and air |
| CN108939947A (en) * | 2018-08-06 | 2018-12-07 | 天津工业大学 | Kynoar and ultra-high molecular weight polyethylene blending microporous membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090080785A (en) * | 2008-01-22 | 2009-07-27 | 도레이새한 주식회사 | Method of manufacturing a multi-component separator film with ultra high molecule weight polyethylene for lithium secondary battery and a multi-component separator film for lithium secondary battery therefrom |
| CN101695634A (en) * | 2009-10-30 | 2010-04-21 | 天津工业大学 | Preparation method of hybrid hollow fiber film of ultrahigh molecular weight polyethylene/inorganic particles |
| CN102863642A (en) * | 2012-09-17 | 2013-01-09 | 中国科学院化学研究所 | High-performance diaphragm and preparation method thereof |
| CN103143272A (en) * | 2013-03-08 | 2013-06-12 | 北京德源通环保科技有限公司 | Method for preparing polyethylene microporous film |
-
2016
- 2016-11-28 CN CN201611064825.5A patent/CN106750743A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090080785A (en) * | 2008-01-22 | 2009-07-27 | 도레이새한 주식회사 | Method of manufacturing a multi-component separator film with ultra high molecule weight polyethylene for lithium secondary battery and a multi-component separator film for lithium secondary battery therefrom |
| CN101695634A (en) * | 2009-10-30 | 2010-04-21 | 天津工业大学 | Preparation method of hybrid hollow fiber film of ultrahigh molecular weight polyethylene/inorganic particles |
| CN102863642A (en) * | 2012-09-17 | 2013-01-09 | 中国科学院化学研究所 | High-performance diaphragm and preparation method thereof |
| CN103143272A (en) * | 2013-03-08 | 2013-06-12 | 北京德源通环保科技有限公司 | Method for preparing polyethylene microporous film |
Non-Patent Citations (1)
| Title |
|---|
| NANA LI ET AL.: "The preparation and study of poly(vinylidene fluoride)/ultrahigh-molecular-weight polyethylene/SiO2 hollow fiber membrane with network enhanced structure", 《REACTIVE AND FUNCTIONAL POLYMERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554190A (en) * | 2018-03-05 | 2018-09-21 | 北京清源洁华膜技术有限公司 | A kind of seperation film and preparation method thereof for detaching bavin gasoline gas and air |
| CN108554190B (en) * | 2018-03-05 | 2021-03-02 | 北京清源洁华膜技术有限公司 | Separation membrane for separating diesel and gasoline gas and air and preparation method thereof |
| CN108939947A (en) * | 2018-08-06 | 2018-12-07 | 天津工业大学 | Kynoar and ultra-high molecular weight polyethylene blending microporous membrane and preparation method thereof |
| CN108939947B (en) * | 2018-08-06 | 2020-12-04 | 天津工业大学 | Polyvinylidene fluoride and ultra-high molecular weight polyethylene blended microporous membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Poly (vinylidene fluoride)/polyethersulfone blend membranes: effects of solvent sort, polyethersulfone and polyvinylpyrrolidone concentration on their properties and morphology | |
| US11077487B2 (en) | Metal form containing dispersed aerogel particles impregnated with polymers and a method of producing the same | |
| Wang et al. | Porous PVDF asymmetric hollow fiber membranes prepared with the use of small molecular additives | |
| DE69637390T2 (en) | POROUS FILM | |
| Yeow et al. | Preparation of porous PVDF hollow fibre membrane via a phase inversion method using lithium perchlorate (LiClO4) as an additive | |
| CN101695634B (en) | Preparation method of hybrid hollow fiber film of ultrahigh molecular weight polyethylene/inorganic particles | |
| CN101223217B (en) | Microporous polyethylene film through liquid-liquid phase separation mechanism and preparing method thereof | |
| CN101342465B (en) | Hollow fiber porous film and process for producing same | |
| WO2009097745A1 (en) | A polyvinylidene fluoride porous membrane and a method for producing the same | |
| CN100389861C (en) | Porous film made of polyunsymfluoroethylene, and its prepn. method | |
| CN102580571B (en) | Method for preparing ultra high molecular weight polyethylene micro-filtration membrane | |
| Chen et al. | Effect of poly (ethylene glycol) on the properties and foaming behavior of macroporous poly (lactic acid)/sodium chloride scaffold | |
| CN103111190B (en) | Method for preparing hollow fiber membranes by melt extrusion process | |
| CN106750743A (en) | The film forming formulation of UHMWPE/PVDF blend films and the method using the film forming formulation masking | |
| CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
| CN101234304A (en) | Polyether-ether-ketone porous film and preparation thereof | |
| CN113413775A (en) | Preparation method of polytetrafluoroethylene nano microporous membrane | |
| EP2557111A1 (en) | Process for production of porous membrane | |
| CN106492645A (en) | Enhancement ultra-high molecular weight polyethylene and Kynoar binary blend film and preparation method thereof | |
| CN104987580B (en) | High density polyethylene (HDPE) micro-porous film and preparation method thereof | |
| CN107353426A (en) | A kind of preparation method and open-cell material of polymer open-cell material | |
| CN106268356B (en) | Method for preparing ultrahigh molecular weight polyethylene composite hollow fiber by thermally induced phase separation | |
| CN101912739B (en) | Preparation method of polyvinyl chloride hollow-fiber membrane | |
| CN104607061A (en) | A method of preparing a poly(ethene-co-tetrafluoroethene) film | |
| CN105749765A (en) | Preparation method of high-performance cellulose triacetate forward osmosis membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170531 |