CN109200834A - A kind of hydrophilic polyolefin microporous barrier and preparation method thereof - Google Patents
A kind of hydrophilic polyolefin microporous barrier and preparation method thereof Download PDFInfo
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- CN109200834A CN109200834A CN201811203460.9A CN201811203460A CN109200834A CN 109200834 A CN109200834 A CN 109200834A CN 201811203460 A CN201811203460 A CN 201811203460A CN 109200834 A CN109200834 A CN 109200834A
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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
- B01D71/26—Polyalkenes
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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
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention provides a kind of hydrophilic polyolefin microporous barrier and preparation method thereof, the microporous barrier includes polymer raw material, hydrophilic filler and antioxidant, the polymer raw material includes at least ultra-high molecular weight polyethylene, and the average molecular weight of the ultra-high molecular weight polyethylene is between 1 × 106~8 × 106Between；The microporous barrier preparation process is based on Thermal inactive principle, passes sequentially through high-temperature blending, extrusion calendaring, cooling split-phase, extraction and separation, stretches orientation and thermocompression forming process, obtains hydrophilic polyolefin microporous barrier.The porosity of prepared microporous barrier is between 30%~70%, and average pore size is between 0.03 μm~3 μm, and average thickness is between 6 μm~30 μm, and contact angle is between 55 °~70 °, and pure water permeation flux is between 150L/m2H bar~600L/m2Between h bar.The features such as present invention has simple process environmental protection, and porosity is high, and highly-hydrophilic, through performance is superior, mechanical strength and good chemical stability can be widely used for medicine, food, biology and water treatment field.
Description
Technical field
The present invention relates to porous membranes separation fields, more particularly to a kind of hydrophilic polyolefin microporous barrier and its system
Preparation Method.
Background technique
Water is the precious resources that the mankind depend on for existence and development, and the seriousness and importance of water problems have become society
The common recognition of all circles.The extremely shortage of China's freshwater resources, and water pollution phenomenon is serious, government agencies at all levels of central and local governments are all water
Problem mentions important position.Therefore, economic, environmental protection, efficient water treatment technology will be the most important development of water treatment field
One of direction.The technology that membrane separation technique is risen as the sixties in last century, energy-efficient with its, environmentally protective, process is simple,
It is easily controllable and in water treatment field by favor.Microfiltration membranes are as the important component in UF membrane industry, in medicine, food
Product, paint, the fields such as biology have been widely applied.Moreover, micro-filtrate membrane filtration is as nanofiltration and the pre-treatment work of reverse osmosis process
Skill, can effective molecular cut off be greater than 0.1 μm of polluter, such as suspended matter in water, bacterium, macromolecular colloid etc.
Grain, plays indispensable role in water treatment field.
High molecule microfilter membrane often passes through Thermal inactive, stretches the methods of pore, non-solvent inversion of phases, electrostatic spinning system
Standby, inorganic micro filtering membrane (such as ceramic membrane) is mainly by sintering process, sol-gal process, the preparation such as anodic oxidation, chemical vapor deposition.It is micro-
Filter sizes are larger, but porosity is usually lower, and film main body is thicker, if surface hydrophobicity, cause water flux relatively low, Wu Faman
The industrial needs of foot.Polythene material is most widely used thermoplastic macromolecule material, and physical and chemical stability is good, machine
Tool intensity is superior, has good resistance to low temperature and acid-proof alkaline, moreover, relative to common membrane material such as polyvinylidene fluoride
Other polymer films such as alkene, polysulfones, polyether sulfone, polyimides, polyethylene has the characteristics that cheap.But polyethylene itself
Strong hydrophobic property causes it not infiltrate in water treatment procedure to liquid, and there is bottlenecks that can not be wetted, thus cannot be straight
It connects and is used in water treatment field.Although the solvent of the low surface tensions such as ethyl alcohol can be in advance polythene material by the way that methanol is added
Wetting then removes solvent again and carries out using but this mode is excessively cumbersome, is not easy to long-term large-scale use.
This invention address that improving the hydrophobic property of conventional polyethylene film, allows to be applied to water treatment procedure, obtain
Flux is high, and thickness is thin, the superior filter membrane of mechanical performance.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of hydrophilic polyolefin microporous barriers
And preparation method thereof, for solving polyethene microporous membrane in the prior art because through performance caused by hydrophobic shows poor ask
Topic.
In order to achieve the above objects and other related objects, the present invention provides a kind of hydrophilic polyolefin microporous barrier, the parent
Water polyolefin microporous barrier includes at least the following component of mass percent:
16%~70% polymer raw material, 23%~81% hydrophilic filling and 0.4%~10% antioxidant；
The polymer raw material includes at least ultra-high molecular weight polyethylene, the mean molecule of the ultra-high molecular weight polyethylene
Amount is between 1 × 106~8 × 106Between.
A kind of scheme of optimization as hydrophilic polyolefin microporous barrier of the present invention, the polymer raw material further include auxiliary
Material, the auxiliary material includes density between 0.940g/cm3~0.976g/cm3Between high density polyethylene (HDPE), density between
0.890g/cm3~0.915g/cm3Between one of low density polyethylene (LDPE), polyphenylene oxide, polytetrafluoroethylene (PTFE) and polypropylene or more
The mixture of kind, using the polymer raw material as total weight, the weight of the ultra-high molecular weight polyethylene accounts for total weight
50%~80%.
A kind of scheme of optimization as hydrophilic polyolefin microporous barrier of the present invention, the hydrophilic filler include hydration
One of silica, hydrated titanium dioxide, polyethylene glycol oxide and polyvinyl alcohol or a variety of mixtures.
A kind of scheme of optimization as hydrophilic polyolefin microporous barrier of the present invention, the antioxidant include phosphite ester,
The double lauryls of thio-2 acid, dibutyl hydroxy toluene, 2,4- dimethyl -6- tert-butyl phenol and N, N'- di-sec-butyl are to benzene
One of diamines or a variety of mixtures.
A kind of scheme of optimization as hydrophilic polyolefin microporous barrier of the present invention, the porosity of the microporous barrier between
Between 30%~70%, average pore size is between 0.03 μm~3 μm, and between 6 μm~30 μm, contact angle is situated between average thickness
Between 55 °~70 °, pure water permeation flux is between 150L/m2H bar~600L/m2Between h bar.
The present invention also provides a kind of preparation method of hydrophilic polyolefin microporous barrier, the preparation method is included at least:
1) by polymer raw material, hydrophilic filler, antioxidant and diluent melt blending, casting solution is obtained, it is described poly-
It closes raw material and includes at least ultra-high molecular weight polyethylene, the average molecular weight of the ultra-high molecular weight polyethylene is between 1 × 106~
8×106Between；
2) after the casting solution being squeezed out using extrusion process, be cast the primary membrane that becomes band；
3) the band-like primary membrane is subjected to asynchronous stretching, forms band-like film；
4) band-like film is obtained described hydrophilic successively by extraction, succeeding stretch, thermal finalization and winding step
Property MIcroporous polyolefin film.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, it is described in step 1)
Between 3:1 between 1:5, the quality of the antioxidant accounts for described poly- the mass ratio of polymer raw material and the hydrophilic filler
Close raw material quality 0.3%~5%, the quality of the diluent account for the quality of the polymer raw material 15%~
65%.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, the hydrophily filling
Agent includes one of hydrated SiO 2, hydrated titanium dioxide, polyethylene glycol oxide and polyvinyl alcohol or a variety of mixtures.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, the antioxidant include
The double lauryls of phosphite ester, thio-2 acid, dibutyl hydroxy toluene, 2,4- dimethyl -6- tert-butyl phenol and N, N'- di-secondary
One of butyl p-phenylenediamine or a variety of mixtures.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, the diluent include
Paraffin oil, C6-15 alkane, C8-15 aliphatic carboxylic acid, C2-6One of halogenated alkane or a variety of mixtures.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, it is described in step 1)
Polymer raw material further includes auxiliary material, and the auxiliary material includes density between 0.940g/cm3~0.976g/cm3Between high density it is poly-
Ethylene, density are between 0.890g/cm3~0.915g/cm3Between low density polyethylene (LDPE), polyphenylene oxide, polytetrafluoroethylene (PTFE) and poly- third
One of alkene or a variety of mixtures, using the polymer raw material as total weight, the weight of the ultra-high molecular weight polyethylene
Amount accounts for the 50%~80% of total weight.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, it is described in step 1)
Melting temperature is between 150 DEG C~220 DEG C.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, it is described in step 2)
The speed of extrusion is between 120 revs/min~300 revs/min, and the temperature of the curtain coating is between 60 DEG C~120 DEG C.
The scheme of a kind of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, in step 3), 110
DEG C~125 DEG C at, carry out cross directional stretch after the band-like primary membrane is first carried out longitudinal stretching, form the band-like film, draw
Multiplying power is stretched between 2 times~4 times.
A kind of scheme of optimization of preparation method as hydrophilic polyolefin microporous barrier of the present invention, it is described in step 4)
Extractant used by extraction step includes one in methylene chloride, perchloroethylene, hexane, chloroform, isopropanol, ether and acetone
Kind or a variety of mixtures；The succeeding stretch includes cross directional stretch, and stretching ratio is between 1.1~1.8 times；The heat is fixed
The temperature of type is between 70 DEG C~110 DEG C, and the time of the thermal finalization is between 1 minute~10 minutes.
As described above, hydrophilic polyolefin microporous barrier and preparation method thereof of the invention, has the advantages that
1, the present invention has carried out hydrophilic modifying to conventional polyethylene microporous barrier, is added to hydrophilic filling, is such as hydrated nothing
Machine nanoparticle or hydrophilic polymer, obtain hydrophilic polyethene microporous membrane.
2, the polyethene microporous membrane of hydrophilic modifying is used for water treatment field by the present invention, compared to other membrane for water treatment, tool
There are excellent comprehensive performance, such as thinner thickness, high through ability and water flux, aperture is uniform, and porosity is high, chemical stability
It is good, high mechanical strength, the strong feature of durability.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method of hydrophilic polyolefin microporous barrier of the present invention.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.Please refer to attached drawing.
The present invention provides a kind of hydrophilic polyolefin microporous barrier, and the hydrophilic polyolefin microporous barrier includes at least quality hundred
Divide than following component:
16%~70% polymer raw material, 23%~81% hydrophilic filling and 0.4%~10% antioxidant；
The polymer raw material includes at least ultra-high molecular weight polyethylene, the mean molecule of the ultra-high molecular weight polyethylene
Amount is between 1 × 106~8 × 106Between.
The High molecular weight polyethylene is major ingredient.As a preferred option, the polymer raw material can also include auxiliary material,
The auxiliary material includes density between 0.940g/cm3~0.976g/cm3Between high density polyethylene (HDPE), density is between 0.890g/
cm3~0.915g/cm3Between one of low density polyethylene (LDPE), polyphenylene oxide, polytetrafluoroethylene (PTFE) and polypropylene or a variety of mixed
Close object, using the polymer raw material as total weight, the weight of the ultra-high molecular weight polyethylene account for total weight 50%~
80%.By the auxiliary material, it can preferably improve mobility of the ultra-high molecular weight polyethylene in double screw extruder and add
Work is conducive to technique and carries out.
As an example, the hydrophilic filler includes hydrated SiO 2, hydrated titanium dioxide, polyethylene glycol oxide and gathers
One of vinyl alcohol or a variety of mixtures.By the way that the hydrophilic filling is added, for example, hydrophilic inorganic is nano-filled
Agent or hydrophilic polymer are modified, and are made it that can form hydrogen bond with hydrone in film surface and inside, are effectively improved film
Surface hydrophilic catches the ability of water, and the through performance of microporous barrier is made to be greatly improved.
As an example, the antioxidant includes phosphite ester, thio-2 acid double lauryl, dibutyl hydroxy toluene, 2,
One of 4- dimethyl -6- tert-butyl phenol and N,N' di sec butyl p phenylene diamine or a variety of mixtures.The antioxidant
It can prevent polymer raw material from aging, degradation occurring within the scope of melt processing temperature.
As an example, the porosity of the microporous barrier, between 30%~70%, average pore size is between 0.03 μm~3 μm
Between, average thickness is between 6 μm~30 μm, and contact angle is between 55 °~70 °, and pure water permeation flux is between 150L/
m2H bar~600L/m2Between h bar.The present invention by hydrophilic filler so that MIcroporous polyolefin film can be very good by
Water infiltration improves water flux, may be implemented preferably to apply in fields such as water process.
As shown in Figure 1, the preparation method is extremely the present invention also provides a kind of preparation method of hydrophilic polyolefin microporous barrier
Include: less
Step S1 is first carried out, polymer raw material, hydrophilic filler, antioxidant and diluent melt blending obtain
Casting solution, the polymer raw material include at least ultra-high molecular weight polyethylene, the mean molecule of the ultra-high molecular weight polyethylene
Amount is between 1 × 106~8 × 106Between；
Then step S2 is executed, after squeezing out the casting solution using extrusion process, is cast the primary membrane that becomes band；
Then step S3 is executed, the band-like primary membrane is subjected to asynchronous stretching, forms band-like film；
Step S4 is finally executed, the band-like film is successively walked by extraction, succeeding stretch, thermal finalization and winding
Suddenly, the hydrophilic polyolefin microporous barrier is obtained.
Wherein, each component additive amount in step S1 needs in suitable range, for the hydrophilic filling, such as
Fruit additional amount is too low, and the effect of hydrophilic modifying is not obvious enough, for example contact angle is only down to 105 ° by 125 °, and modified effect is not
It is good；But if hydrophilic filler additional amount is excessive, will lead to raw material mixed melting unevenness, (hydrophilic filler can be precipitated, nothing
Method is with the complete mixing of polyethylene), homogeneity is poor after film forming, and the defect of film is more, and film mechanical strength is caused to substantially reduce, different
Position hydrophilicity is also irregular.
As an example, the mass ratio of the polymer raw material and the hydrophilic filler is between 3:1 to 1 in step S1:
Between 5, the quality of the antioxidant accounts for the 0.3%~5% of the quality of the polymer raw material, and the quality of the diluent accounts for institute
State the 15%~65% of the quality of polymer raw material.
As an example, the hydrophilic filler includes hydrated SiO 2, hydrated titanium dioxide, polyethylene glycol oxide and gathers
One of vinyl alcohol or a variety of mixtures.By the way that the hydrophilic filling is added, for example, hydrophilic inorganic is nano-filled
Agent or hydrophilic polymer are modified, and are made it that can form hydrogen bond with hydrone in film surface and inside, are effectively improved film
Surface hydrophilic catches the ability of water, and the through performance of microporous barrier is made to be greatly improved.
As an example, the antioxidant includes phosphite ester, thio-2 acid double lauryl, dibutyl hydroxy toluene, 2,
One of 4- dimethyl -6- tert-butyl phenol and N,N' di sec butyl p phenylene diamine or a variety of mixtures.The antioxidant
It can prevent polyethylene from aging, degradation occurring within the scope of melt processing temperature.
As an example, the diluent includes paraffin oil, C6-15 alkane, C8-15 aliphatic carboxylic acid, C2-6In halogenated alkane
One or more mixtures.The diluent is mainly the ingredients such as paraffin oil, crude mineral oils, it is therefore an objective to after thawing
The solvent of polyethylene and other additives such as hydrophilic filler, antioxidant forms casting solution, on the other hand, the diluent
The pore former that can be used as extraction step leaves pore structure by extracting diluent in film.
As an example, the polymer raw material further includes auxiliary material in step S1, the auxiliary material include density between
0.940g/cm3~0.976g/cm3Between high density polyethylene (HDPE), density is between 0.890g/cm3~0.915g/cm3Between
One of low density polyethylene (LDPE), polyphenylene oxide, polytetrafluoroethylene (PTFE) and polypropylene or a variety of mixtures, with the polymer raw material
For total weight, the weight of the ultra-high molecular weight polyethylene accounts for the 50%~80% of total weight.It, can by adding the auxiliary material
Preferably to improve mobility and processability of the ultra-high molecular weight polyethylene in double screw extruder, it is smooth to be conducive to extrusion process
It carries out.
In step S1, the temperature requirement of the melting is higher than melting point polymer, so that polymer raw material melts at high temperature.
As an example, the temperature of the melting is between 150 DEG C~220 DEG C.Preferably, the temperature of the melting between 160 DEG C~
Between 210 DEG C.
In step S2, after the casting solution is squeezed out by double screw extruder, the primary membrane that becomes band is cast through chill roll.As
Example, the speed of the extrusion between 120 revs/min~300 revs/min, the temperature of the curtain coating between 60 DEG C~120 DEG C it
Between.
In step S3, band-like primary membrane is sent into stretching-machine and carries out asynchronous being drawn into band-like film.As an example,
At 110 DEG C~125 DEG C, cross directional stretch is carried out after the band-like primary membrane is first carried out longitudinal stretching, forms the band-like film,
Stretching ratio is between 2 times~4 times.
In step S4, band-like film is placed in extractant and is extracted to remove diluent.As an example, the extraction
Agent includes one of methylene chloride, perchloroethylene, hexane, chloroform, isopropanol, ether and acetone or a variety of mixtures；Institute
Stating succeeding stretch includes cross directional stretch, and stretching ratio is between 1.1~1.8 times；The temperature of the thermal finalization between 70 DEG C~
Between 110 DEG C, the time of the thermal finalization is between 1 minute~10 minutes.
Hydrophilic polyolefin microporous barrier and preparation method thereof of the invention is done furtherly below by specific embodiment
It is bright.
Embodiment 1
By raw material ultra-high molecular weight polyethylene (1.5 × 106) mixed with high density polyethylene (HDPE) according to the ratio of 5.5:4.5,
Using hydrated SiO 2 as filler, filler and polymer raw material are mixed according to the ratio of 1:1, and it is total that addition accounts for polymer raw material
The paraffin oil of 48wt% is measured as diluent, the dibutyl hydroxy toluene of 2wt% is antioxidant, and stirred tank is added in continuous batching,
Form homogeneous mixture.Mixture is melted under the conditions of 180 DEG C, is squeezed out through double screw extruder with 150 revs/min of speed, 100 DEG C
Under be cast to it is cooling mixed.Longitudinal stretching, rear cross directional stretch are first carried out to film, stretching ratio is 3 times.Film is placed in methylene chloride
It is extracted, then carries out cross directional stretch, stretching ratio is respectively 1.2,1.2,1.5 times, and is extracted again with isopropanol.?
Thermal finalization 45 minutes at 80 DEG C, winding obtain hydrophilic polyethene miillpore filter.
12 ± 2 μm of products obtained therefrom thickness, porosity is 55 ± 2%, and opening size test is 0.08 ± 0.025 μm, and contact angle is
62 °, filtration of demineralized water test display, level maintains 300L/m2H bar, and can be reserved for the several months, the only a little decaying of flux.
And if the present embodiment is added without hydrophilic filler, the pure water flux of the microporous barrier of preparation is only in 142~165L/
m2h bar。
Embodiment 2
By raw material ultra-high molecular weight polyethylene (1 × 106) mixed with high density polyethylene (HDPE) according to the ratio of 8:2, with polyoxy
Change ethylene and hydrated SiO 2 be filler, the two is mixed according to the ratio of 1:5, and filler and polymer raw material ratio are 7:
3 (i.e. filler accounts for 49%, 21%) polymer raw material accounts for, rear that the paraffin oil conduct for accounting for polymer raw material total amount 28.5wt% is added
Diluent, the phosphite ester of 1.5wt% are antioxidant, and stirred tank is added in continuous batching, form homogeneous mixture.200 DEG C of conditions
It is lower to melt mixture, it is squeezed out, is cast at 100 DEG C cooling mixed with 150 revs/min of speed through double screw extruder.It is advanced to film
Row longitudinal stretching, rear cross directional stretch, cross directional stretch multiplying power are 5 times.Film is placed in methylene chloride and is extracted, it is rear to carry out laterally
It stretches, stretching ratio is respectively 1.1,1.1,1.3 times, and is extracted again with isopropanol.Thermal finalization 40 minutes at 85 DEG C,
Winding obtains hydrophilic polyethene microporous membrane.
20 ± 2 μm of products obtained therefrom thickness, porosity is 60 ± 2%, and opening size test is 0.082 ± 0.2 μm, and contact angle is
68 °, pure water flux test display, level maintains 450L/m2H bar or so.
And if the present embodiment is added without hydrophilic filler, the pure water flux of the microporous barrier of preparation is only in 180~235L/
m2h bar。
Embodiment 3
2 raw material of example is changed to single ultra-high molecular weight polyethylene (3 × 106), hydrophilic filler is changed to hydration two
Titanium oxide, and increase the ratio of diluent to 39%, single extraction slective extraction agent is chloroform, is stretched at 125 DEG C, is stretched
Multiplying power is 6 times.Thermal finalization at 100 DEG C, winding.
For products obtained therefrom with a thickness of 9 ± 2 μm, porosity is 68 ± 2%, and aperture is 0.12 ± 0.05 μm, and contact angle is 60 °,
Pure water flux is in 530L/m2H bar or so.
And if the present embodiment is added without hydrophilic filler, the pure water flux of the microporous barrier of preparation is only 342L/m2h
bar。
Embodiment 4
By ultra-high molecular weight polyethylene (8 × 106) mixed with low density polyethylene (LDPE) according to the ratio of 7.5:2.5, with hydration
Silica is filler, and filler and mix polyethylene material rate are that (i.e. filler accounts for 61.5% to 3:1, and polymer accounts for
20.5%) paraffin oil for accounting for polymer raw material total amount 17.5wt%, is added as diluent, the N of 0.5wt%, N'- di-sec-butyl
P-phenylenediamine is antioxidant, and 120 DEG C of extrusions are cooled to after melting mixing is uniform at 210 DEG C.Longitudinal stretching is first carried out to film, it is rear horizontal
To stretching, stretching ratio is 2.6 times.Film is placed in methylene chloride and is extracted, carries out cross directional stretch, stretching ratio difference afterwards
It is 1.1,1.1,1.3,1.3 times, and carries out reextraction with hexane.Thermal finalization 30 minutes at 80 DEG C, winding obtain hydrophily
Polyethene microporous membrane.
16 ± 1 μm of products obtained therefrom thickness, porosity is 52 ± 2%, and opening size test is 0.064 ± 0.015 μm, and contact angle is
65 °, filtration of demineralized water test display, flux maintains 225L/m2H bar or so.
And if the present embodiment is added without hydrophilic filler, the pure water flux of the microporous barrier of preparation is only in 115~127L/
m2h bar。
In conclusion the present invention provides a kind of hydrophilic polyolefin microporous barrier and preparation method thereof, the microporous barrier includes
Polymer raw material, hydrophilic filler and antioxidant, the polymer raw material includes at least ultra-high molecular weight polyethylene, described
The average molecular weight of ultra-high molecular weight polyethylene is between 1 × 106~8 × 106Between；The microporous barrier preparation process is based on thermotropic
Phase separation principle passes sequentially through high-temperature blending, extrusion calendaring, cooling split-phase, extraction and separation, stretches orientation and thermocompression forming mistake
Journey obtains hydrophilic polyolefin microporous barrier.Between 30%~70%, average pore size is situated between the porosity of prepared microporous barrier
Between 0.03 μm~3 μm, average thickness is between 6 μm~30 μm, and contact angle is between 55 °~70 °, and pure water is through logical
Amount is between 150L/m2H bar~600L/m2Between h bar.The present invention has simple process environmental protection, and porosity is high, highly-hydrophilic,
The features such as through performance is superior, mechanical strength and good chemical stability can be widely used for medicine, food, biology and water process neck
Domain.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (15)
1. a kind of hydrophilic polyolefin microporous barrier, which is characterized in that the hydrophilic polyolefin microporous barrier includes at least quality hundred
Divide than following component:
16%~70% polymer raw material, 23%~81% hydrophilic filling and 0.4%~10% antioxidant；
The polymer raw material includes at least ultra-high molecular weight polyethylene, and the average molecular weight of the ultra-high molecular weight polyethylene is situated between
In 1 × 106~8 × 106Between.
2. hydrophilic polyolefin microporous barrier according to claim 1, it is characterised in that: the polymer raw material further includes auxiliary
Material, the auxiliary material includes density between 0.940g/cm3~0.976g/cm3Between high density polyethylene (HDPE), density between
0.890g/cm3~0.915g/cm3Between one of low density polyethylene (LDPE), polyphenylene oxide, polytetrafluoroethylene (PTFE) and polypropylene or more
The mixture of kind, using the polymer raw material as total weight, the weight of the ultra-high molecular weight polyethylene accounts for total weight
50%~80%.
3. hydrophilic polyolefin microporous barrier according to claim 1, it is characterised in that: the hydrophilic filler includes water
Close one of silica, hydrated titanium dioxide, polyethylene glycol oxide and polyvinyl alcohol or a variety of mixtures.
4. hydrophilic polyolefin microporous barrier according to claim 1, it is characterised in that: the antioxidant includes phosphorous acid
The double lauryls of ester, thio-2 acid, dibutyl hydroxy toluene, 2,4- dimethyl -6- tert-butyl phenol and N, N'- di-sec-butyl pair
One of phenylenediamine or a variety of mixtures.
5. hydrophilic polyolefin microporous barrier according to claim 1, it is characterised in that: the porosity of the microporous barrier between
Between 30%~70%, average pore size is between 0.03 μm~3 μm, and between 6 μm~30 μm, contact angle is situated between average thickness
Between 55 °~70 °, pure water permeation flux is between 150L/m2H bar~600L/m2Between h bar.
6. a kind of preparation method of hydrophilic polyolefin microporous barrier, which is characterized in that the preparation method includes at least:
1) by polymer raw material, hydrophilic filler, antioxidant and diluent melt blending, casting solution, the polymer are obtained
Raw material includes at least ultra-high molecular weight polyethylene, and the average molecular weight of the ultra-high molecular weight polyethylene is between 1 × 106~8 ×
106Between；
2) after the casting solution being squeezed out using extrusion process, be cast the primary membrane that becomes band；
3) the band-like primary membrane is subjected to asynchronous stretching, forms band-like film；
4) it is poly- to be obtained into the hydrophily successively by extraction, succeeding stretch, thermal finalization and winding step for the band-like film
Alkene microporous barrier.
7. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: in step 1), institute
The mass ratio of polymer raw material and the hydrophilic filler is stated between 3:1 between 1:5, the quality of the antioxidant accounts for described
The 0.3%~5% of the quality of polymer raw material, the quality of the diluent account for the quality of the polymer raw material 15%~
65%.
8. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: the hydrophily is filled out
Filling agent includes one of hydrated SiO 2, hydrated titanium dioxide, polyethylene glycol oxide and polyvinyl alcohol or a variety of mixtures.
9. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: the antioxidant packages
Include the double lauryls of phosphite ester, thio-2 acid, dibutyl hydroxy toluene, 2,4- dimethyl -6- tert-butyl phenol and N, N'- bis-
One of secondary-butyl-p-phenylenediamine or a variety of mixtures.
10. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: the diluent
Including paraffin oil, C6-15 alkane, C8-15 aliphatic carboxylic acid, C2-6One of halogenated alkane or a variety of mixtures.
11. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: in step 1), institute
Stating polymer raw material further includes auxiliary material, and the auxiliary material includes density between 0.940g/cm3~0.976g/cm3Between high density
Polyethylene, density are between 0.890g/cm3~0.915g/cm3Between low density polyethylene (LDPE), polyphenylene oxide, polytetrafluoroethylene (PTFE) and poly-
One of propylene or a variety of mixtures, using the polymer raw material as total weight, the ultra-high molecular weight polyethylene
Weight accounts for the 50%~80% of total weight.
12. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: in step 1), institute
The temperature of melting is stated between 150 DEG C~220 DEG C.
13. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: in step 2), institute
The speed of extrusion is stated between 120 revs/min~300 revs/min, the temperature of the curtain coating is between 60 DEG C~120 DEG C.
14. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: in step 3),
At 110 DEG C~125 DEG C, cross directional stretch is carried out after the band-like primary membrane is first carried out longitudinal stretching, forms the band-like film,
Stretching ratio is between 2 times~4 times.
15. the preparation method of hydrophilic polyolefin microporous barrier according to claim 6, it is characterised in that: in step 4), institute
Stating extractant used by extraction includes one of methylene chloride, perchloroethylene, hexane, chloroform, isopropanol, ether and acetone
Or a variety of mixture；The succeeding stretch includes cross directional stretch, and stretching ratio is between 1.1~1.8 times；The thermal finalization
Temperature between 70 DEG C~110 DEG C, the time of the thermal finalization is between 1 minute~10 minutes.
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