CN105169965A - Ultra-high molecular weight polyethylene micro-porous membrane and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene micro-porous membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ultra-high molecular weight polyethylene micro-porous membrane and a preparation method thereof. The thickness of the micro-porous membrane is smaller than or equal to 40 microns, the porosity is 35-70%, the average pore size is 20-100 nanometers, the longitudinal/transverse tensile strength is greater than or equal to 160 Ma, and longitudinal/transverse elongation at break is greater than or equal to 50%. After the micro-porous membrane is arranged in a drying oven at the temperature of 120 DEG C for 1 hour, the longitudinal/transverse thermal shrinkage of the micro-porous membrane is smaller than or equal to 5. The ultra-high molecular weight polyethylene micro-porous membrane prepared by means of the preparation method is of a multi-layer structure, the anti-compression capacity and heat-resisting deformation temperature of the ultra-high molecular weight polyethylene micro-porous membrane can be effectively improved, the strength of the micro-porous membrane is improved, and the microstructure consistency of the micro-porous membrane is improved. In addition, the speed of a production line can be effectively improved, and the requirement for production speed can be met by normal-temperature soft water replacing chilled water.
Description
Technical field
The present invention relates to microporous film products, especially relate to a kind of composite micro porous film with features such as heat-resistant deforming temperature is high, even structure, and there is the preparation method of higher line speed.
Background technology
The effect of lithium ion battery isolates both positive and negative polarity in battery use procedure, prevents the two poles of the earth from contacting and short circuit, simultaneously for the ion in electrolyte provides passage.Lithium ion battery requires more to barrier film, as chemical resistance, inhales and protects fluidity, good mechanical properties, uniform thickness and high uniformity porosity and aperture.
Polyolefin has good chemical stability and excellent physical property, and its microporous barrier barrier film is widely used in battery, capacitor, water treatment, water desalination and bio-medical and the field such as medical, is used as lithium ion battery separator especially in a large number.Thermally induced phase separation prepares one of MIcroporous polyolefin film common method.
Thermally induced phase separation (thermallyinducedphaseseparation, be called for short TIPS) mainly utilize the thermodynamic property of polymer solution to prepare polymer microporous film, its principle is: polymer macromolecule and the micromolecular diluent of higher boiling are mixed to form homogeneous phase solution at a certain temperature, then reduces system temperature and causes polymer macromolecule and diluent Small molecular to be separated.After being separated, diluent Small molecular is dispersed between polymer solid, and diluent Small molecular is fallen in finally extraction, between polymer molecule, just leave microcellular structure.
Temperature controls there is considerable influence to the microporous barrier aperture structure prepared by thermally induced phase separation.Ultra-high molecular weight polyethylene molecular entanglement point is many and cause crystalline rate slow, has a strong impact on the size that is separated.Meanwhile, casting films thickness is thicker, is difficult to the uniformity ensureing melt cooling on horizontal direction and thickness direction, thus easily causes the aperture structure of microporous barrier to there is larger difference at horizontal direction and thickness direction, greatly have impact on battery production and battery performance.Usually, in order to ensure that melt cools fast, during supra polymer molecular weight polyethylene microporous barrier industrial production, curtain coating speed is low, and chilling roll temperature is low, this greatly reduces production efficiency, low temperature cold roller easily causes roll surface form condensed water and affect normally carrying out of production simultaneously.How to improve the processability of UHMWPE microporous barrier, uniformity and safety in utilization etc. and become the important topic further developing UHMWPE microporous barrier.
Summary of the invention
For overcoming above-mentioned shortcoming, the invention provides a kind of ultra-high molecular mass polyethylene micropore film and preparation method thereof, make the microporous barrier obtained have multilayered structure, effectively can improve resistance to compression and the heat-resistant deforming temperature of ultra high molecular polyethylene microporous barrier, improve micropore film strength; And effectively can improve line speed, just can meet the requirement of speed of production with the soft water of normal temperature without the need to chilled water.
Technical scheme of the present invention:
A ultra-high molecular mass polyethylene micropore film prepared by thermally induced phase separation, it is characterized in that, comprise ultra-high molecular weight polyethylene, nucleator, antioxidant and aid anti-oxidants, and described microporous barrier is at least two-layer, wherein:
Wherein, above-mentioned nucleator comprises one or more in metal oxide nucleator, inorganic silicate nucleator, polymeric nucleating agent, organic acid nucleator, acylate nucleator, organic phosphate nucleating agent, D-sorbite or derivatives thereof nucleator, tricarballylic acid type acid amides nucleator.
In TIPS method, for crystalline polymer, often consider to add nano inorganic nucleator, its effect has be the crystalline rate of accelerating polymer at three: one, thus controls to be separated, and then affects the dynamic process of film forming; Two is improve the degree of crystallinity of polymer, contributes to improving the mechanical strength of material and heat resistance etc.; Three is improve porosity.Conventional nucleator has: nano-calcium carbonate particles, titanium dioxide nanoparticle, nanometer silicon dioxide particle, CNT etc.As everyone knows, nano inorganic particle is very easily reunited, and is generally difficult to the dispersion realizing primary particle rank, is thus difficult to the property embodying nano particle; Moreover the surface hydrophilic not oleophylic of nano inorganic particle, has higher polarity and surface energy, very poor with polymer compatibility.Therefore, mix nano inorganic particle and polymer simply, not only cannot realize good nano-scale dispersion, and the incompatible boundary existed also can cause the deterioration of film article mechanical property.Therefore select a kind of nucleation efficiencies high, be TIPS legal system with the good nucleator of polymeric system compatibility for one of the key technology of microporous barrier.So the present invention preferably selects organic nucleating agent, compared with inorganic nucleator, beneficial effect is more remarkable.
Preferably, the molecular weight M of described supermolecule weight northylen
w=0.5 × 10
6~ 5 × 10
6.More preferably, the molecular weight M of described supermolecule weight northylen
w=2 × 10
6~ 4 × 10
6.
Preferably, organic nucleating agent of the present invention is spherocrystal shape, because spherocrystal shape organic nucleating agent has obvious advantage as the modifier improving UHMWPE microporous barrier selected by the present invention.Usually, when semi-crystalline polymer is cooled to solid-state form from molten condition, the effect of nucleator in given interval, forms nucleus quantity under increasing predetermined temperature, final growth rate and the degree of crystallinity controlling polymer spherocrystal.As mentioned above, spherocrystal is formed relative to a center or nucleus growth, a large amount of sites for growing when therefore nucleator can provide melt cooling.In TIPS method, add spherocrystal shape organic nucleating agent as follows for ultra-high molecular weight polyethylene effect: one is reduce crystallization induction time, accelerates the crystalline rate of polymer, thus controls the degree that is separated, and then affect the dynamic process of film forming; Two is improve the degree of crystallinity of polymer, is conducive to improving the mechanical strength of microporous barrier and heat resistance etc.; Three is improve grain density, thus controls the aperture of microporous barrier.Therefore, the TIPS technique of ultra-high molecular mass polyethylene micropore film, the organic nucleating agent that the present invention selects also can select difformity, such as bar-shaped and fibrous, the advantage of comprehensive in the preparation difformity organic nucleating agent, the preparation of spherocrystal shape has the micro-pore septum of interlayer performance complementation.
As a kind of mode of priority, described antioxidant is the conventional antioxidant of this area, preferred β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester.
As a kind of mode of priority, described aid anti-oxidants is the conventional aid anti-oxidants of this area, the hard ester alcohol ester of preferred diphosphorous acid pentaerythrite two.
For ensureing the original excellent properties of ultra-high molecular mass polyethylene micropore film, improve its processability, uniformity and safety in utilization etc. better, its preparation method is very crucial, and the invention provides a kind of ultra-high molecular mass polyethylene micropore film and preparation method thereof, the method comprises the steps:
(1) add thermal diluent to technological temperature, under supersonic generator effect, by a certain percentage by organic nucleating agent, diluent and antioxidant, aid anti-oxidants Homogeneous phase mixing, form mixture A;
(2) by mixture A and ultra-high molecular weight polyethylene according to ratio according to claim 1 add First double screw extruder carry out plastifying, blended;
(3) add thermal diluent to technological temperature, under supersonic generator effect, by a certain percentage by organic nucleating agent, diluent and antioxidant, aid anti-oxidants Homogeneous phase mixing, form mixture B;
(4) by mixture A and B respectively with ultra-high molecular weight polyethylene according to ratio according to claim 1 add second double screw extruder carry out plastifying, blended;
(5) melt formed by double screw extruder forms oil film through Multi-layer coextruding die head, chilling roller, oil film is carried out biaxial tension, ultra-high molecular mass polyethylene micropore film that extraction, thermal finalization obtain sandwich construction.
The double screw extruder of multiple stage can be had, more preferably 2 extruders in above-mentioned production line.
Preferably, the nucleator added in described different mixture melts can be same, also can be not identical type.
Preferably, described ultra-high molecular mass polyethylene micropore film has sandwich construction, and architectural feature comprises ABA, ABCBA and similar more multi-layered, AB, ABC and similar more multi-layered; And microporous barrier rolling speed is not less than 30m/min.
Wherein, the diluent used by thermally induced phase separation mainly contain in decahydronaphthalene, kerosene, paraffin oil, paraffin one or more; Preferably, described diluent is paraffin oil or paraffin.
Used extractant mainly contains alcohol, alkenyl halide or halogenated alkane, such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, a vinyl chloride, dichloroethylene, chloroform, carbon tetrachloride, carrene etc.
The technological difficulties of this area are the impact that nucleator is separated on ultra-high molecular weight polyethylene/paraffin oil, invention has been ratio optimization and cooldown rate optimization.
As a kind of mode of priority, described processing and forming is extrusion molding, and extrusion temperature is 150 DEG C ~ 250 DEG C, and slab cooldown rate is 50 ~ 100 DEG C/min.
The present invention only need improve a little and can directly produce on original UHMWPE microporous barrier production equipment; Microporous barrier film thickness of the present invention is less than or equal to 40 μm, and porosity is 35 ~ 70%, and average pore size is 20 ~ 100 nanometers, and MD/TD hot strength is more than or equal to 160MPa, and MD/TD elongation at break is more than or equal to 50%; Under 120 DEG C/1h condition, its MD/TD thermal contraction is less than or equal to 5.
Wherein MD is MachineDirection, i.e. longitudinal stretching direction.TD is TransverseDirection, i.e. cross directional stretch direction.
Relative with prior art, the present invention is medium with diluent, and organic nucleating agent is added polymeric system, and then under high temperature, high shear field effect, dispersion forms different mixed system, under TIPS dynamics and Thermodynamic effect, form different phase separation structure.Composite micro porous film prepared by the present invention has multilayered structure, effectively can improve resistance to compression and the heat-resistant deforming temperature of ultra high molecular polyethylene microporous barrier, improve micropore film strength; And effectively can improve line speed, just can meet the requirement of speed of production with the soft water of normal temperature without the need to chilled water, effectively can ensure production efficiency, improve production stability.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
By 0.3 part of nucleator DBS (1,3:2,4-dibenzylidene sorbitol) with 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) with 233 parts of paraffin oils in the blended formation mixed liquor A of supersonic generator effect.Above-mentioned mixed liquor A and dry UHMWPE powder are added in First extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
By 0.3 part of nucleator CNT (CNT) and 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) with 233 parts of paraffin oils in the blended formation mixed liquid B of supersonic generator effect.Above-mentioned mixed liquid B and dry UHMWPE powder are added in second extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
The melt formed by double screw extruder forms oil film through die head, chilling roller, oil film is carried out biaxial tension, extraction, thermal finalization obtains ultra-high molecular weight polyethylene/thermotropic liquid crystal composite micro porous film, can obtain the microporous barrier of ABA structure of the present invention.The performance test results is as table 1.
Comparative example 1
Except not adding any nucleator, the preparation process of embodiment 1 all as described above, prepares ultra-high molecular weight polyethylene/thermotropic liquid crystal composite micro porous film.The performance test results is as table 1.
Embodiment 2
By 0.3 part of nucleator DBS (1,3:2,4-dibenzylidene sorbitol) with 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) with 233 parts of paraffin oils in the blended formation mixed liquor A of supersonic generator effect.Above-mentioned mixed liquor A and dry UHMWPE powder are added in First extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
By 0.3 part of nucleator HPN-68 (1,3:2,4-dibenzylidene sorbitol) with 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) with 233 parts of paraffin oils in the blended formation mixed liquid B of supersonic generator effect.Above-mentioned mixed liquid B and dry UHMWPE powder are added in second extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
The melt formed by double screw extruder forms oil film through die head, chilling roller, oil film is carried out biaxial tension, extraction, thermal finalization obtains ultra-high molecular weight polyethylene/thermotropic liquid crystal composite micro porous film, can obtain the microporous barrier of AB structure of the present invention.
Embodiment 3
By 1 part of nucleator SiO
2(silica) and 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) and 233 parts of paraffin oils are in the blended formation mixed liquor A of supersonic generator effect.Above-mentioned mixed liquor A and dry UHMWPE powder are added in First extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
By 1 part of nucleant agent N A-11 (1,3:2,4-dibenzylidene sorbitol) with 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) with 233 parts of paraffin oils in the blended formation mixed liquid B of supersonic generator effect.Above-mentioned mixed liquid B and dry UHMWPE powder are added in second extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
The melt formed by double screw extruder forms oil film through die head, chilling roller, oil film is carried out biaxial tension, extraction, thermal finalization obtains ultra-high molecular weight polyethylene/thermotropic liquid crystal composite micro porous film, can obtain ABA microporous barrier of the present invention.The performance test results is as table 1.
Table 1
From table 1, add the ultra-high molecular mass polyethylene micropore film of nucleator, because nucleator can the dynamic process of effective control TIPS, control hole gauge structure.Meanwhile, nucleator can improve the crystallization temperature of ultra-high molecular weight polyethylene, increases the degree of crystallinity of microporous barrier, improves the heat resistance of microporous barrier, also to have some improvement effect to the hot strength of microporous barrier.
Embodiment 4
By 0.3 part of nucleator DBS (1,3:2,4-dibenzylidene sorbitol) with 1 part of antioxidant (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester), 0.05 part of aid anti-oxidants (the hard ester alcohol ester of diphosphorous acid pentaerythrite two) with 233 parts of paraffin oils in the blended formation mixed liquor A of supersonic generator effect.Above-mentioned mixed liquor A and dry UHMWPE powder are added in extruder by 235 parts: 100 parts of proportionings, blended in high temperature, Strong shear even action.
First, the melt formed by double screw extruder forms oil film through die head, chilling roller, and wherein, extrusion temperature is 200 DEG C, and slab cooldown rate is 60 DEG C/min.Then, oil film is carried out biaxial tension, extraction, thermal finalization obtains ultra-high molecular weight polyethylene/thermotropic liquid crystal composite micro porous film, microporous barrier of the present invention can be obtained.
Further, with reference to above-mentioned preparation method, adopt difform organic nucleating agent respectively, test result is specifically as shown in table 2.
Table 2
From table 2, wherein, spherical organic nucleator is compared with threadiness with bar-shaped, has degree of crystallinity high, and hot strength is large, and average pore size evenly waits marked improvement, especially preferred 2% ~ 4% scope of the present invention, and beneficial effect is more remarkable.
More than that ultra-high molecular mass polyethylene micropore film of the present invention and preparation method thereof is set forth; the present invention is understood for helping; but embodiments of the present invention are not restricted to the described embodiments; any do not deviate from the principle of the invention under do change, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a ultra-high molecular mass polyethylene micropore film, is characterized in that, described microporous barrier comprises ultra-high molecular weight polyethylene, nucleator, antioxidant and aid anti-oxidants, and described microporous barrier is at least two-layer, wherein:
2. ultra-high molecular mass polyethylene micropore film according to claim 1, is characterized in that: described nucleator be selected from metal oxide nucleator, inorganic silicate nucleator, organic acid nucleator, acylate nucleator, organic phosphate nucleating agent, D-sorbite or derivatives thereof nucleator, tricarballylic acid type acid amides nucleator one or more.
3. ultra-high molecular mass polyethylene micropore film according to claim 1 and 2, is characterized in that: described antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester.
4. ultra-high molecular mass polyethylene micropore film according to claim 1 and 2, is characterized in that: described aid anti-oxidants is the hard ester alcohol ester of diphosphorous acid pentaerythrite two.
5. ultra-high molecular mass polyethylene micropore film according to claim 1 and 2, it is characterized in that, described microporous barrier film thickness is less than or equal to 40 μm, porosity is 35 ~ 70%, average pore size is 20 ~ 100 nanometers, longitudinal direction/transverse tensile strength is more than or equal to 160MPa, and longitudinal direction/transverse breakage percentage elongation is more than or equal to 50%; Under 120 DEG C/1h condition, its longitudinal direction/horizontal thermal contraction is less than or equal to 5.
6. the preparation method containing ultra-high molecular mass polyethylene micropore film described in the arbitrary claim of claim 1-5, is characterized in that, comprise the steps:
(1) under supersonic generator effect, by a certain percentage by nucleator, diluent and antioxidant, aid anti-oxidants Homogeneous phase mixing, mixture A is formed;
(2) by mixture A and ultra-high molecular weight polyethylene according to ratio according to claim 1 add First double screw extruder carry out plastifying, blended;
(3) under supersonic generator effect, by a certain percentage by nucleator, diluent and antioxidant, aid anti-oxidants Homogeneous phase mixing, mixture B is formed;
(4) by mixture B and ultra-high molecular weight polyethylene according to ratio according to claim 1 add second double screw extruder carry out plastifying, blended;
(5) melt A, B that double screw extruder is formed are extruded through multilayer die head, chilling roller is formed has the oil film of sandwich construction, oil film is carried out biaxial tension, extraction, thermal finalization obtains ultra-high molecular mass polyethylene micropore film.
7. preparation method according to claim 6, is characterized in that, described processing and forming is extrusion molding, and extrusion temperature is 150 DEG C ~ 250 DEG C, and slab cooldown rate is 50 ~ 100 DEG C/min.
8. preparation method according to claim 6, is characterized in that, the double screw extruder in described production line is more than 2, is preferably 2.
9. preparation method according to claim 6, is characterized in that, the nucleator added in described different mixture melts can be same, also can be not identical type.
10. preparation method according to claim 6, is characterized in that, described ultra-high molecular mass polyethylene micropore film has sandwich construction, comprises ABA, ABCBA, AB, or ABC and similar sandwich construction thereof.
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Application publication date: 20151223 |