CN106229444A - A kind of pressure three-layer composite structure microporous polypropylene membrane - Google Patents

A kind of pressure three-layer composite structure microporous polypropylene membrane Download PDF

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Publication number
CN106229444A
CN106229444A CN201610577492.XA CN201610577492A CN106229444A CN 106229444 A CN106229444 A CN 106229444A CN 201610577492 A CN201610577492 A CN 201610577492A CN 106229444 A CN106229444 A CN 106229444A
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hopp
composite structure
described
type beta
layer composite
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CN201610577492.XA
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丁大欢
马骁
谢新春
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昆明云天化纽米科技有限公司
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/14Separators; Membranes; Diaphragms; Spacing elements
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/14Separators; Membranes; Diaphragms; Spacing elements
    • H01M2/16Separators; Membranes; Diaphragms; Spacing elements characterised by the material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/14Separators; Membranes; Diaphragms; Spacing elements
    • H01M2/16Separators; Membranes; Diaphragms; Spacing elements characterised by the material
    • H01M2/164Separators; Membranes; Diaphragms; Spacing elements characterised by the material comprising non-fibrous material
    • H01M2/1653Organic non-fibrous material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/14Separators; Membranes; Diaphragms; Spacing elements
    • H01M2/16Separators; Membranes; Diaphragms; Spacing elements characterised by the material
    • H01M2/1686Separators having two or more layers of either fibrous or non-fibrous materials

Abstract

A kind of pressure three-layer composite structure microporous polypropylene membrane of the present invention, belong to Material Field, three-layer composite structure microporous polypropylene membrane is A/B/C three-decker, the raw material of A/B/C three-decker consists of: the raw material of surface layer A and surface layer C is addition type beta nucleater and the HOPP of antioxidant, and the raw material of sandwich layer B is addition type beta nucleater and the HOPP of antioxidant.In the HOPP of described addition type beta nucleater, beta crystal content is more than 80%, and in the HOPP of described addition type beta nucleater, beta crystal content is more than 80%.Three-layer composite structure polypropylene microporous membrane porosity is high, permeability is good, mechanical strength is high, has high imbibition concurrently, protects liquid rate, the feature that air permeability change is little and morphotropism is excellent during pressurization.

Description

A kind of pressure three-layer composite structure microporous polypropylene membrane

Technical field

The invention belongs to Material Field, particularly relate to a kind of pressure three-layer composite structure microporous polypropylene membrane.

Background technology

In lithium ion battery structure, barrier film is one of crucial interior layer assembly, plays and is separated by the positive and negative electrode of battery Come, prevent battery short circuit, additionally there is the function that electrolyte ion can be made to pass through.Microporous polyolefin film is being used as lithium electricity In the case of the separator of pond, its performance and microstructure greatly affect the characteristic of battery, productivity ratio and safety.Cause This, need to have excellent breathability, mechanical performance, thermal contraction performance, micropore closing property, high temperature stability in the large etc..

In known technology, using pulling method to prepare polypropylene micropore diaphragm mainly has two kinds of modes of production.One is By melt extrusion film forming, annealing increases content and the size of platelet, and accurately stretching forms it into the microcellular structure of dense regular. Another kind is to use melt polypropylene film extrusion, under certain temperature conditions, formed have certain content β brilliant sheet Material, by stretching sheet material, forms micropore.Publication number CN101245150A proposes, and uses polypropylene beta nucleator with equal Poly-polypropylene fusion is extruded, by controlling specific crystalline texture and the crystallization shape of two crystal surfaces of sheet in crystallization process The asymmetry of the micropore being adjusted on film, the polypropylene porous film of preparation asymmetry, the wherein content of polypropylene beta nucleator For polypropylene beta nucleator and the 0.05 ~ 5% of HOPP gross weight.But, this asymmetry polypropylene porous membrane surface hole Footpath is excessive, and intensity is insufficient, and the polypropylene porous film compression property of this asymmetry is poor simultaneously, when as lithium battery separator The probability causing off-capacity (cycle performance change) is high.

Publication number CN103990388A proposes a kind of three-layer composite structure microporous polypropylene membrane and preparation method thereof, surface layer The raw material of A and surface layer C is beta-crystalline homopolymerization polypropylene, and the raw material of sandwich layer B is beta crystal COPP;Or, surface layer A and surface layer The raw material of C is beta crystal COPP, and the raw material forming B is beta-crystalline homopolymerization polypropylene.By brilliant to beta-crystalline homopolymerization polypropylene and β Go out through three layers of compound die coextrusion head after type COPP melting mixing respectively, form three-layer composite structure crystalline p p sheet, Three-layer composite structure microporous polypropylene membrane is prepared after drawn.This microporous polypropylene membrane has high temperature fusing performance and low temperature closed pore Performance, but this microporous polypropylene membrane compression property is poor, and (cycle performance becomes to cause off-capacity when as lithium battery separator Change) probability high.

The patent of publication number CN101253232A discloses employing matter average molecular weight 7 × 105Above supra polymer More than ratio 1 mass % of weight northylen and prepared by the polyvinyl resin that ratio is 5 ~ 300 of matter average molecular weight relative number average molecular weight Have and at least form micropore size more than the thick structure sheaf of 0.04 μm and micropore size densification below 0.04 μm in one side The polyethene microporous membrane of structure sheaf.But owing to this polyethene microporous membrane micropore more than 120 DEG C is closed, polyethylene high-temperature stable Property is poor.

The patent documentation of publication number CN1034375A and CN1062357A individually disclose two kinds of microporous polypropylene membranes and Preparation method, although both microporous polypropylene membrane porositys are high, good permeability, but its electrolysis when lithium battery separator The absorbent of liquid is poor, and this microporous membrane compression property is poor simultaneously, causes off-capacity (cyclicity when as lithium battery separator Can change) probability high.

Recently, along with high-power, high-rate lithium battery are gradually favored by market, the high-temperature stability of barrier film is proposed Higher requirement, in the patent documentation of above-mentioned polyethene microporous membrane, due to the characteristic of polyethylene self, reaches in temperature More than 120 DEG C, micropore is closed, and simultaneously along with the rising of temperature, its high temperature stability performance is poor.

For the characteristic of barrier film, not only breathability or mechanical strength but also cycle characteristics etc. are relevant to service life of lithium battery Characteristic, the spy such as the microstructure of the characteristic relevant to lithium battery productivity ratio such as electrolyte injection or barrier film and lithium battery performance Property the most gradually comes into one's own.Especially the electrode of lithium battery charging time expand due to the insertion of lithium ion, electric discharge time by Shrink in the desorbing of lithium ion, and along with the high capacity of recent battery, coefficient of expansion during charging exists big the becoming of change Gesture.Due to barrier film when electrode expansion oppressed, so breathability change when needing barrier film to have oppressed is little and can inhale Receive the morphotropism of electrode expansion so that barrier film has excellent guarantor's liquid rate.But, in described every microporous polypropylene membrane patent The resistance against compression of the microporous polypropylene membrane described in document is the most insufficient.If the compression property of microporous membrane is poor, as lithium electricity The probability causing off-capacity (cycle performance change) during the separator of pond is high.

If the absorbent of electrolyte is poor, then production performance when manufacturing battery is poor.For improving the imbibition of electrolyte The effective ways of performance are the large apertures of the small-boreization on microporous polypropylene membrane top layer and sandwich layer, surface micropore " capillary is existing As " imbibition ability of microporous polypropylene membrane can be effectively improved.In order to ensure mechanical strength, microporous polypropylene membrane needs have densification The layer of structure.Meanwhile, the large apertureization of sandwich layer can effectively reduce the internal resistance of lithium battery, improves the capacity of lithium battery.Therefore, exist In lithium battery microporous membrane, it is desirable to there are two surface layers with compact texture, and also containing having the thick of relatively large micropore aperture Macrotectonics layer.

Summary of the invention

In place of overcoming the deficiencies in the prior art, propose to improve the physical property of microporous polyolefin film and the side of microstructure Method, by the optimized technical scheme such as raw material composition, slab condition, stretching condition, heat treatment condition, invents as follows.

A kind of pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that: described three-layer composite structure polypropylene Microporous membrane is A/B/C three-decker, and the raw material of A/B/C three-decker consists of: the raw material of surface layer A and surface layer C is addition type β Nucleator and the HOPP of antioxidant, the raw material of sandwich layer B is addition type beta nucleater and the HOPP of antioxidant. In the HOPP of described addition type beta nucleater, beta crystal content is more than 80%, described addition type beta nucleater equal In poly-polypropylene, beta crystal content is more than 80%.Described HOPP, wherein HOPP melt index is 1~10g/ 10min.Described antioxidant is phenolic antioxidant;Described antioxidant content is antioxidant, type or type beta nucleater and all The 0.1 ~ 5% of poly-polypropylene gross weight;The content of described type beta nucleater is HOPP and type beta nucleater gross weight 0.01~5%;The content of described type beta nucleater is HOPP and the 0.01 ~ 5% of type beta nucleater gross weight;Described Type beta nucleater is one or more the mixture in aromatic series diamide nucleator and/or terres rares;Described Type beta nucleater is one or more the mixing in 1,5-pentanedicarboxylic acid., suberic acid and/or its calcium salt, and/or calcium stearate Thing;Described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester.Described type β nucleation Agent content is type beta nucleater, antioxidant and the 0.01 ~ 5% of HOPP gross weight;Described type beta nucleater content is Type beta nucleater, antioxidant and the 0.01 ~ 5% of HOPP gross weight;

Described have surface layer A and surface layer C two sides is formed, compact texture layer that mean pore aperture is less than 40nm and sandwich layer B The mean pore aperture thick structure sheaf more than 40nm;The area ratio of the compact texture layer that described thick structure sheaf is relatively described Film section is 0.1 ~ 0.8.

A kind of preparation method of pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that: comprise the following steps:

1) by addition type beta crystal-type nucleater and the HOPP of antioxidant and addition type beta nucleater and the homopolymerization of antioxidant Through three-layer composite structure die head coextrusion after polypropylene is melted respectively, its medium-sized beta crystal-type nucleater content is type beta crystal nucleation Agent, antioxidant and the 0.01 ~ 5% of HOPP gross weight;Type beta crystal-type nucleater content is type beta crystal-type nucleater, resists Oxygen agent and the 0.01 ~ 5% of HOPP gross weight;Antioxidant content is type or type beta crystal-type nucleater, antioxidant and homopolymerization The 0.1 ~ 5% of polypropylene gross weight;Melt stretches, and obtains three layers of composite beta crystal-type crystalline p p sheet, and beta crystal content is more than 80%, Control the crystallization temperature on two surfaces of sheet material in crystallization process when melt is stretched and keep consistent, two surfaces of sheet material Temperature is 110 ~ 130 DEG C so that sheet material carries out crystallisation by cooling, it is thus achieved that the crystalline texture on two surfaces and pattern basically identical three Layer composite beta crystal-type crystalline p p sheet;

2) Beta-crystalline polyacrylic sheet material stretching step 1) obtained, obtains a kind of three-layer composite structure polypropylene micropore diaphragm.

In described step 1), melting mixing temperature is 180~250 DEG C, and the hauling speed of melt extrusion sheet material is 1~15 M/min, traction multiplying power is 2~15 times, and melt extrusion sheet material chilling temperature is 110~130 DEG C, and cool time is 0.5~5 point Clock.

Described step 2) in, drawing process is the substep biaxial tension of cross directional stretch after first longitudinal stretching, or synchronizes double To stretching;Step by step during biaxial tension, longitudinal drawing temperature is 70~120 DEG C, and stretching ratio is 2~6 times;Transverse drawing temperature is 100~160 DEG C, stretching ratio is 2~6 times, and controlling total extension area ratio is 4~30 times;During synchronous bidirectional stretching, draft temperature Being 100~140 DEG C, all directions stretching ratio is 2~6 times, and controlling total extension area ratio is 4~30 times.

A kind of three-layer composite structure polypropylene micropore diaphragm obtained is carried out thermal finalization process, and heat setting temperature is 150 DEG C~170 DEG C, heat-setting time is 0.5~3 minute.

The compact texture layer of the present invention refers to that the beta crystal formed by aromatic series diamide and/or terres rares nucleator is equal Poly-crystalline p p sheet, stretched formation afterwards.

The thick structure sheaf of the present invention refers to by 1,5-pentanedicarboxylic acid., suberic acid and/or its calcium salt, and/or calcium stearate nucleator The beta-crystalline homopolymerization polypropylene sheet material formed, stretched formation afterwards.

A kind of pressure three-layer composite structure microporous polypropylene membrane of the present invention, technological progress and distinguishing feature be: these three layers multiple Closing structure microporous polypropylene membrane technology path is a kind of surface layer with two dense construction layers and a relatively large micropore aperture The sandwich layer of thick techonosphere, it is achieved have the technical effect that this three-layer composite structure polypropylene microporous membrane porosity is high, permeability is good, Mechanical strength is high, it is achieved technical purpose be to have high imbibition concurrently, protect liquid rate, air permeability change during pressurization is little and morphotropism is excellent Feature.

Accompanying drawing explanation

Fig. 1. film surface microstructure figure.

Fig. 2. film section micro-structure diagram.

Detailed description of the invention

Embodiment 1

1) by the N of 0.5% weight, N '-dicyclohexyl terephthalamide, four [β-(3,5-di-t-butyl-4-hydroxyls of 1% weight Phenyl) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 98.5% weight, obtain type beta-crystalline homopolymerization poly-third Alkene, its beta crystal content is 82%, and melt index is 3.0g/10min, and degree of crystallinity is 63%, and fusing point is 165 DEG C.

2) by the calcium pimelate of 0.5% weight, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] seasons of 1% weight The HOPP mixing extruding pelletization of Doutrate and 98.5% weight, obtains type beta-crystalline homopolymerization polypropylene, its beta crystal content Being 80%, melt index is 3.2g/10min, and degree of crystallinity is 60%, and fusing point is 165 DEG C.

3) using above-mentioned type beta-crystalline homopolymerization polypropylene as surface layer A and the raw material of surface layer C, by above-mentioned type beta-crystalline homopolymerization Polypropylene, as the raw material of sandwich layer B, goes out through three layers of compound die coextrusion head after melting mixing, melt extrusion sheet at 240 DEG C respectively The hauling speed of material is 5m/min, and traction multiplying power is 8 times, and melt extrusion sheet material obtains A/B/ after cooling down 1.5 minutes at 120 DEG C The three-layer composite structure Beta-crystalline polyacrylic sheet material of C-structure.

4) three layers of composite beta crystal-type crystalline p p sheet being carried out step drawing, first carry out longitudinal stretching, draft temperature is 100 DEG C, stretching ratio is 5 times;Carrying out cross directional stretch again, stretching ratio is 4 times.Carrying out thermal finalization process again, heat setting temperature is 160 DEG C, heat-setting time is 1min, obtains a kind of pressure three-layer composite structure polypropylene micropore diaphragm.

5) or by three layers of composite beta crystal-type crystalline p p sheet carrying out synchro-draw, longitudinal stretching multiplying power is 5 times, cross directional stretch Multiplying power is 4 times, and draft temperature is 125 DEG C, then carries out thermal finalization process, and heat setting temperature is 160 DEG C, and heat-setting time is 1min, obtains a kind of pressure three-layer composite structure polypropylene micropore diaphragm.

Embodiment 2

1) by the N of 1.5% weight, N '-dicyclohexyl aphthalimide, four [β-(3,5-di-t-butyl-4-hydroxyls of 1.5% weight Phenyl) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 97% weight, obtain beta-crystalline homopolymerization polypropylene 1., Recording its beta crystal content is 90%, and melt index is 5g/10min, and degree of crystallinity is 68%, and fusing point is 166 DEG C.Benzene by 1.5% weight Dicarboximide, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol esters of 1.5% weight and 97% weight 2. HOPP mixing extruding pelletization, obtain beta-crystalline homopolymerization polypropylene, and recording its beta crystal content is 88%, and melt index is 4.5g/10min, degree of crystallinity is 66%, and fusing point is 165 DEG C.

2) by the suberic acid of 1.5% weight, the calcium carbonate of 2% weight, four [β-(3,5-di-t-butyl-4-hydroxyls of 1.5% weight Base phenyl) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 95% weight, obtain beta-crystalline homopolymerization polypropylene 3., recording its beta crystal content is 83%, and melt index is 4.8g/10min, and degree of crystallinity is 60%, and fusing point is 162 DEG C.

3) using above-mentioned beta-crystalline homopolymerization polypropylene 1. as the raw material of surface layer A, using above-mentioned beta-crystalline homopolymerization polypropylene 2. as The raw material of surface layer C, using above-mentioned beta-crystalline homopolymerization polypropylene 3. as the raw material of sandwich layer B, warp after difference melting mixing at 230 DEG C Three layers of compound die coextrusion head go out, and the hauling speed of melt extrusion sheet material is 12m/min, and traction multiplying power is 13 times, melt extrusion sheet Material obtains three layers of composite beta crystal-type crystalline p p sheet of A/B/C structure after cooling down 2min at 125 DEG C.

3) three layers of composite beta crystal-type crystalline p p sheet being carried out step drawing, first carry out longitudinal stretching, draft temperature is 115 DEG C, stretching ratio is 5.5 times;Carrying out cross directional stretch again, draft temperature is 135 DEG C, and stretching ratio is 4 times.Carry out thermal finalization again Process, heat setting temperature is 158 DEG C, and heat-setting time is 1min, obtain a kind of pressure three-layer composite structure polypropylene microporous every Film.

4) or by three layers of composite beta crystal-type crystalline p p sheet carrying out synchro-draw, longitudinal stretching multiplying power is 5.5 times, laterally draws Stretching multiplying power is 4 times, and draft temperature is 130 DEG C, then carries out thermal finalization process, and heat setting temperature is 158 DEG C, and heat-setting time is 1min, obtains a kind of pressure three-layer composite structure polypropylene micropore diaphragm.

Embodiment 3

1) by the Phthalimide of 1.5% weight, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] seasons of 1% weight The HOPP mixing extruding pelletization of Doutrate and 97.5% weight, obtains beta-crystalline homopolymerization polypropylene, records its β crystalline substance and contains Amount is 82%, and melt index is 5g/10min, and degree of crystallinity is 62%, and fusing point is 165 DEG C.By the WBG-II of 2% weight, 1% weight The HOPP mixing extrusion of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol esters and 97% weight is made Grain, obtains beta-crystalline homopolymerization polypropylene, and recording its beta crystal content is 85%, and melt index is 4.8g/10min, and degree of crystallinity is 63%, Fusing point is 163 DEG C.

2) by the suberic acid of 2% weight, the calcium carbonate of 2% weight, four [β-(3,5-di-t-butyl-4-hydroxyls of 1.5% weight Phenyl) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 95% weight, obtain beta-crystalline homopolymerization polypropylene, Recording its beta crystal content is 82%, and melt index is 6g/10min, and degree of crystallinity is 60%, and fusing point is 162 DEG C.

3) using above-mentioned beta-crystalline homopolymerization polypropylene as the raw material of surface layer A, using above-mentioned beta-crystalline homopolymerization polypropylene as face The raw material of layer C, using above-mentioned beta-crystalline homopolymerization polypropylene as the raw material of sandwich layer B, at 225 DEG C respectively after melting mixing through three Layer compound die coextrusion head goes out, and melt extrusion sheet material hauling speed is 10m/min, and traction multiplying power is 12 times, and melt extrusion sheet material exists Three layers of compound beta-crystal polypropylene sheet material of A/B/C structure are obtained after cooling down 1.5min at 115 DEG C.

4) three layers of compound beta-crystal polypropylene sheet material being carried out step drawing, first carry out longitudinal stretching, draft temperature is 100 DEG C, Stretching ratio is 5.8 times;Carrying out cross directional stretch again, draft temperature is 135 DEG C, and stretching ratio is 4.5 times, then carries out at thermal finalization Reason, heat setting temperature is 163 DEG C, and heat-setting time is 1min, obtains a kind of pressure three-layer composite structure polypropylene micropore diaphragm.

5) or by three layers of compound beta-crystal polypropylene sheet material carrying out synchro-draw, longitudinal stretching multiplying power is 4.5 times, cross directional stretch Multiplying power is 5 times, and draft temperature is 135 DEG C, then carries out thermal finalization process, and heat setting temperature is 163 DEG C, and heat-setting time is 1min, obtains a kind of pressure three-layer composite structure polypropylene micropore diaphragm.

Comparative example 1

1) by the N of 1% weight, N '-dicyclohexyl aphthalimide, four [β-(3,5-di-t-butyl-4-hydroxy benzeness of 1% weight Base) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 98% weight, obtain type beta-crystalline homopolymerization polypropylene, survey Obtaining its beta crystal content 85%, melt index is 4g/10min, and degree of crystallinity is 63%, and fusing point is 165 DEG C.

2) by the calcium pimelate of 1% weight, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] seasons penta of 1% weight The HOPP mixing extruding pelletization of four alcohol esters and 98% weight, obtains type beta-crystalline homopolymerization polypropylene, records its beta crystal content 84%, melt index is 4.5g/10min, and degree of crystallinity is 62%, and fusing point is 165 DEG C.

3) using above-mentioned type beta-crystalline homopolymerization polypropylene as surface layer A and the raw material of surface layer C, by above-mentioned type beta-crystalline homopolymerization Polypropylene, as the raw material of sandwich layer B, goes out through three layers of compound die coextrusion head after melting mixing, melt extrusion sheet at 235 DEG C respectively The hauling speed of material is 8m/min, and traction multiplying power is 10 times, and melt extrusion sheet material cools down 1.5min at 115 DEG C and obtains A/B/C Three layers of compound beta-crystal polypropylene sheet material of structure.

4) three layers of compound beta-crystal polypropylene sheet material being carried out step drawing, first carry out longitudinal stretching, draft temperature is 110 DEG C, Stretching ratio is 5 times;Carrying out cross directional stretch again, draft temperature is 125 DEG C, and stretching ratio is 4 times.Carry out thermal finalization process again, Heat setting temperature is 155 DEG C, and heat-setting time is 1min, obtains a kind of micro-pore septum.

Comparative example 2

1) by the N of 2% weight, N '-dicyclohexyl aphthalimide, four [β-(3,5-di-t-butyl-4-hydroxy benzeness of 1.5% weight Base) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 96.5% weight, obtain beta-crystalline homopolymerization polypropylene, survey Obtaining its beta crystal content is 92%, and melt index is 5g/10min, and degree of crystallinity is 65%, and fusing point is 165 DEG C.

2) beta-crystalline homopolymerization polypropylene is extruded through flat-mould head after melting mixing at 230 DEG C, the traction of melt extrusion sheet material Speed is 10m/min, and traction multiplying power is 12 times, and melt extrusion sheet material obtains beta crystal poly-third after cooling down 1.5min at 110 DEG C Alkene sheet material.

3) Beta-crystalline polyacrylic sheet material carrying out step drawing, first carry out longitudinal stretching, draft temperature is 90 DEG C, stretching times Rate is 5 times;Carrying out cross directional stretch again, draft temperature is 120 DEG C, and stretching ratio is 3.5 times.Carrying out thermal finalization process again, heat is fixed Type temperature is 158 DEG C, and heat-setting time is 1min, obtains single-layer polypropylene micro-pore septum.

Comparative example 3

1) by the suberic acid of 1.5% weight, the calcium carbonate of 2% weight, four [β-(3,5-di-t-butyl-4-hydroxy benzeness of 1.5% weight Base) propanoic acid] pentaerythritol ester and the HOPP mixing extruding pelletization of 95% weight, obtain beta-crystalline homopolymerization polypropylene, record Its beta crystal content is 83%, and melt index is 7.5g/10min, and degree of crystallinity is 55%, and fusing point is 160 DEG C.

2) beta-crystalline homopolymerization polypropylene is extruded through flat-mould head after melting mixing at 220 DEG C, the traction of melt extrusion sheet material Speed is 12m/min, and traction multiplying power is 13 times, and melt extrusion sheet material obtains beta crystal poly-third after cooling down 1.5min at 120 DEG C Alkene sheet material.

3) Beta-crystalline polyacrylic sheet material carrying out step drawing, first carry out longitudinal stretching, draft temperature is 105 DEG C, stretching times Rate is 6 times;Carrying out cross directional stretch again, draft temperature is 135 DEG C, and stretching ratio is 4 times.Carry out thermal finalization process, thermal finalization again Temperature is 161 DEG C, and heat-setting time is 1min, obtains single-layer polypropylene micro-pore septum.

The performance of polypropylene micropore diaphragm prepared by each embodiment above-mentioned is as shown in the table:

Example Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2 Comparative example 3 Thickness (μm) 20 20 20 20 20 20 Porosity (%) 44 43 45 49 39 48 Air permeability (s) 290 250 275 200 500 185 Puncture strength (g/20 μm) 680 700 720 500 600 330 Longitudinal tensile strength (MPa) 148 165 150 105 130 91 Transverse tensile strength (MPa) 80 88 85 50 69 32

Claims (9)

1. a pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that: described three-layer composite structure polypropylene is micro- Pore membrane is A/B/C three-decker, and the raw material of A/B/C three-decker consists of: the raw material of surface layer A and surface layer C is that addition type β becomes Core agent and the HOPP of antioxidant, the raw material of sandwich layer B is addition type beta nucleater and the HOPP of antioxidant.
One the most according to claim 1 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that: described adds Enter in the HOPP of type beta nucleater beta crystal content more than 80%, the HOPP of described addition type beta nucleater Middle beta crystal content is more than 80%.
Three-layer composite structure polypropylene micropore diaphragm that one the most according to claim 1 is pressure, it is characterised in that described HOPP, wherein HOPP melt index is 1~10g/10min.
One the most according to claim 1 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that described is anti- Oxygen agent is phenolic antioxidant;Described antioxidant content is antioxidant, type or type beta nucleater and HOPP gross weight 0.1 ~ 5%.
One the most according to claim 1 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that described The content of type beta nucleater is HOPP and the 0.01 ~ 5% of type beta nucleater gross weight;Containing of described type beta nucleater Amount is HOPP and the 0.01 ~ 5% of type beta nucleater gross weight.
One the most according to claim 1 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that described Type beta nucleater is one or more the mixture in aromatic series diamide nucleator and/or terres rares;Described Type beta nucleater is one or more the mixture in 1,5-pentanedicarboxylic acid., suberic acid and/or its calcium salt, and/or calcium stearate; Described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester.
One the most according to claim 1 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that described Type beta nucleater content is type beta nucleater, antioxidant and the 0.01 ~ 5% of HOPP gross weight;Described type beta nucleater Content is type beta nucleater, antioxidant and the 0.01 ~ 5% of HOPP gross weight.
One the most according to claim 1 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that described tool There are compact texture layer that surface layer A and surface layer C two sides are formed, that mean pore aperture is less than 40nm and sandwich layer B mean pore aperture Thick structure sheaf more than 40nm.
One the most according to claim 8 is pressure three-layer composite structure microporous polypropylene membrane, it is characterised in that described is thick The area ratio of the compact texture layer that big structure sheaf is relatively described is 0.1 ~ 0.8 in film section.
CN201610577492.XA 2016-07-21 2016-07-21 A kind of pressure three-layer composite structure microporous polypropylene membrane CN106229444A (en)

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