CN106947154A - It is a kind of to be used to prepare powder of polyethene microporous membrane and preparation method and application - Google Patents
It is a kind of to be used to prepare powder of polyethene microporous membrane and preparation method and application Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- 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
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2314/02—Ziegler natta catalyst
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Abstract
The present invention relates to a kind of powder for being used to prepare polyethene microporous membrane and preparation method and application, following components is included in every 100 parts by weight of powder：1 99 parts of polyethylene material A, remaining is polyethylene material B；Described polyethylene material A viscosity average molecular weigh is 800,000 500 ten thousand, molecular weight distribution ＞ 3, and branching content is 0 20%；Described polyethylene material B viscosity average molecular weigh is 500,000 200 ten thousand, and molecular weight distribution is 13, and branching content is 0 10%.Compared with prior art, powder of the present invention has the characteristics of molecular chain conformation is adjustable, easy processing, product properties are good, the consumption of solvent can be adjusted according to the molecular chain conformation of powder in process, to ensure that there is higher process velocity, processing benefit is improved, preparation method is simple, greatly improve ultra-high polyethylene and prepare processing characteristics during microporous barrier, reduce solvent load, reduce pollution, cost is reduced, with good application prospect.
Description
Technical field
The invention belongs to polymer material molding processing technique field, it is related to a kind of powder for being used to prepare polyethene microporous membrane
Material and preparation method and application.
Background technology
Polyethene microporous membrane is as a kind of high performance material, because of spacious wealthy, the environment friendly and pollution-free and repeatable profit of its application
The extensive concern of industrial quarters and academia is caused with property.The property of the micropore and material that microporous barrier has using itself in itself
Can, the processes such as exchange, separation, purifying, the concentration of different component can be selectively realized, have been widely used in industrial or agricultural and life
The fields such as sewage disposal living, desalinization, gas-liquid separation membrane and battery diaphragm.During microporous barrier is prepared, most important two
Individual link is exactly selection and the pore-forming process of micropore of material.The selection of material determines the physical property of microporous barrier, enters
And determine processing characteristics and performance；And the pore-forming process of micropore, determine the pore volume of microporous barrier, aperture, insertion
Property, transmitance etc..Ultra-high molecular weight polyethylene has nonpolar, superelevation molecular weight so that it has outstanding performance,
But processing characteristics is very poor.
The method for several raising ultra-high polyethylene processing characteristicies being currently known includes：Addition dilution in process is used
Solvent, low-molecular weight polymer, promote strand unwrapping, increase mobility；Used in ultra-high polyethylene preparation process
Winding of strand etc. in controllable polymerization, reduction polymerization process.Patent such as Application No. 201380065590.X uses decahydro
Naphthalene is used as solvent, Application No. as solvent, the patent of Application No. 200480031794.2 using atoleine
201310498061.0 patent is processed to increase using high density polyethylene (HDPE), linear low density polyethylene (LLDPE) of low molecule amount etc.
Mobility in journey.The patent of Application No. 201510567727.2,201510114917.9 uses FI catalyst preparations low
The ultra-high polyethylene of entanglement.
The patent of Application No. 201380056951.4 is by the ultra-high polyethylene of viscosity average molecular weigh more than 1,000,000 and divides equally again
Son amount is mixed for 1 ten thousand to 80 ten thousand polyethylene by 1 to 99 mass ratio, using solvent that the compound is molten at high temperature
Solution, cool drying, molding obtains the polyethylene film containing micropore.The polyethylene that the patented technology is used is being prepared for homopolymer
Need first to use high boiling solvent during microporous barrier, be completely dissolved polymer, cooled and filtered, drying can use
In punch forming film material.Because ultra-high polyethylene molecular weight is high, being completely dissolved needs high temperature and substantial amounts of solvent, in the patent
Embodiment 1 in only dissolved 5g UHMW-PE and NMW-PE-1 mixtures using 1000ml paraxylene, it can be seen that, should
Method is extremely inefficient, and solvent recovery amount is huge.Different from above-mentioned patent, by the present invention in that with controllable polymerization, being prepared for low twine
The ultra-high polyethylene homopolymerization of knot and copolymer, and material need not be completely dissolved in process, solvent usage amount is reduced,
Simplify procedure.
Application No. 201310080398.X patent by molecular weight be 150 ten thousand to 600 ten thousand ethene and alpha-olefin copolymer
Thing is mixed with diluent, and by heating melting process, microporous barrier is made by biaxial tension in compressing tablet/extrusion, extractant.On
To state mention in patent the polymer and be catalyzed ethene and alpha-olefin copolymer by active polymerizing catalyst and be made.At present, polyolefin work
The polymerization catalyst that industry is used mainly has radical polymerization and coordination polymerization catalysts.Living polymerization due to its molecular weight with
The increase of polymerization time constantly becomes big, and polymerizing condition requires harsh, at present the not value of commercial applications, therefore the patent
Without practical value.Meanwhile, pass through the side chain predominantly short-chain branch introduced with alpha-olefin copolymer, although product can be improved
Extensibility, tensile strength, toughness etc., but crystallinity is also destroyed, fusing point declines substantially, reduces the application of product.
The content of the invention
The purpose of the present invention is exactly the defect in order to overcome above-mentioned prior art presence and provides a kind of for preparing poly- second
Powder of alkene microporous barrier and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
Following components is included in a kind of powder for being used to prepare polyethene microporous membrane, every 100 parts by weight of the powder：Polyethylene
Expect 1-99 parts of A, remaining is polyethylene material B；
Described polyethylene material A viscosity average molecular weigh is 800,000-500 ten thousand, and molecular weight distribution ＞ 3, branching content is 0-
20%；
Described polyethylene material B viscosity average molecular weigh is 500,000-200 ten thousand, and molecular weight distribution is 1-3, and branching content is 0-
10%.
Described polyethylene material A is prepared from by Mg-Ti systems ziegler natta catalyst controllable polymerization, viscosity average molecular weigh
For 1,000,000-500 ten thousand, and side chain in described polyethylene material A is introduced by ethene and alpha-olefin copolymer, and branching content is
0-10%.
Described polyethylene material B is prepared from by single active center's polyethylene catalysts controllable polymerization, and described
Long-chain branch in polyethylene material B eliminates insertion by β-hydrogen and introduced, and short-chain branch is introduced by ethene and alpha-olefin copolymer, side chain
Content is 0-5%.
Few, described alpha-olefin that tangled between strand in described polyethylene material A, polyethylene material B is C3-C20's
Alkene.
As preferred technical scheme, described alpha-olefin is 1- propylene, 1- butylene, 1- hexenes, 1- octenes, cyclohexene or
One kind in ENB.
Described polyethylene material A is prepared by Mg-Ti systems ziegler natta catalyst controllable polymerization, is tangled between strand
Few, the short-chain branch content distribution in polyethylene material A is gradually reduced from low molecular weight part to high molecular weight moieties.
Described polyethylene material B is prepared by single active center's polyethylene catalysts controllable polymerization, is tangled between strand
Few, the short-chain branch content in polyethylene material B is uniformly distributed between HMW and low molecule amount.
A kind of preparation method for being used to prepare the powder of polyethene microporous membrane, this method specifically includes following steps：
Step (1)：Polyethylene material A is mixed by weight with polyethylene material B, diluent is added, is well mixed, is made
Mixed material；
Step (2)：Mixed material is passed sequentially through into extruder or plasticator, make mixed material higher than melting point polymer and
In the range of polymer decomposition temperature, rapidly and uniformly plasticizing mixing completes extrusion/compressing tablet；
Step (3)：The melt of extrusion/compressing tablet is cooled fast to below melting point polymer, produces diluent and polyethylene
It is raw to be separated, micropore is obtained, then carries out extracting and then carrying out again biaxial tension at least one times or proceeds directly to less once
Biaxial tension and then extraction；
Step (4)：By washing and drying, make to remain in the diluent in micropore and wash and evaporate, then drawing
Thermal finalization processing is carried out on width stretching-machine, you can.
Diluent described in step (1) accounts for the 30-90% of mixed material gross mass, and described diluent for C6 and
One or more in more than C6 liquid alkane, arene or esters；
The outlet temperature of extruder or plasticator described in step (2) is 130-240 DEG C；
The temperature of cooling is 30-150 DEG C in step (3), and the solvent that described extraction is used is volatile alkane, C1-
One or more in C6 halogenated alkane, alcohols or ketone；
The used solvent of washing is more than C4 alkane, C1-C6 halogenated alkane, ketone or C1-C5 in step (4)
One or more in alcohols, the temperature of described thermal finalization processing is 90-130 DEG C.
As preferred technical scheme, described diluent is selected from octane, nonane, dodecane, toluene, atoleine, white
One or more in oil, naphthane and decahydronaphthalene, dioctyl phthalate or dibutyl phthalate, described extraction
One or more of the solvent of use in dichloromethane, heptane, hexane, ethanol or acetone.
A kind of application for being used to prepare the powder of polyethene microporous membrane, described powder is used to prepare superhigh molecular weight polyethylene
Alkene microporous barrier, the ultra-high molecular mass polyethylene micropore film is used as battery diaphragm, gas separation membrane or gas liquid separating filtering film.
The thickness of described ultra-high molecular mass polyethylene micropore film is 1-500 μm, and aperture is 0.01-1 μm, and porosity is
20-80%.
In the present invention, the preparation of polyethylene A material：By Mg-Ti systems ziegler natta catalyst in slurry process or gas
Controllable polymerization in phase technique, presence or absence of in the case of co-monomer, carries out ethylene homo or copolymerization, prepares molecular weight
(Mv) it is 800,000-500 ten thousand, molecular weight distribution is more than 3, and branching content is 0-20%, side chain is evenly distributed, tangle between strand
Few polyethylene material A.
Wherein, Mg-Ti systems ziegler natta catalyst reacts to form magnesium compound by magnesium halide and alcohol, magnesium compound with
Silicon compound with least one halogen group reacts to form intermediate product, and intermediate product reacts to form Mg- with titanium compound
Ti systems ziegler natta catalyst or by preparing nascent state magnesium halide, with electron donor haptoreaction, connects with titanium compound
Tactile reaction forms Mg-Ti systems ziegler natta catalyst.The catalyst prepared by both approaches, which can be used alone, also may be used
To be used in mixed way.Specific preparation method referenced patent ZL200610116967.1, ZL200710042467.2.
The polyethylene production process being directed to includes slurry process and gas phase process, when polyethylene material A is without single altogether
Body or co-monomer content are preferred to use slurry process when being less than 10% and produced, when polyethylene material A co-monomer contents are higher than
It is preferred to use gas phase process when 10%.The co-monomer is C3-C20 alpha-olefin, preferably 1- propylene, 1- butylene, 1- hexenes, 1-
Octene.
Wherein the size of viscosity average molecular weigh is by controlling the amount of polymerizing condition Chain transfer agent to realize, branching content passes through
The addition of co-monomer is controlled to realize.Low entanglement by control carrier magnesium chloride formation speed, the Ti content of catalyst and
Polymerization temperature is realized.The chain-transferring agent is alkyl aluminum, hydrogen etc., preferably hydrogen.The catalyst Ti content is not higher than 2%
Wt, polymerization temperature is not higher than 75 DEG C.
Polyethylene material B preparation：Can in slurry process or gas phase process by single active center's polyethylene catalysts
Control polymerization, presence or absence of in the case of co-monomer, carries out ethylene homo or copolymerization, and it is 50 to prepare viscosity average molecular weigh (Mv)
Ten thousand -200 ten thousand, molecular weight distribution is 1-3, and branching content is 0-10%, and side chain is evenly distributed, few poly- second of tangling between strand
Alkene material B.
Wherein single site catalysts by be Zr, Hf or Ti single cyclopentadienyl by metallic atom, single indenyl or single fluorenes
The one or more of the metallocene compounds such as base are supported on modified inorganic carrier and prepared or by that in the course of the polymerization process will may be used
The metallocene compound one or more for occurring β-hydrogen elimination insertion are supported on inorganic carrier and/or organic carrier is compound
Carrier on prepare.Specific preparation method referenced patent ZL201210396049.4, ZL201110355606.3.
The polyethylene production process being directed to includes slurry process and gas phase process, when polyethylene material A is without single altogether
Body or co-monomer content are preferred to use slurry process when being less than 10% and produced.The co-monomer is C3-C20 alpha-olefin,
It is preferred that 1- propylene, 1- butylene, 1- hexenes, 1- octenes, cyclohexene, ENB etc..
Wherein the size of viscosity average molecular weigh is by controlling the amount of polymerizing condition Chain transfer agent to realize, branching content passes through
The type of metallocene compound in the addition and catalyst of co-monomer is controlled to realize.Low entanglement is by controlling in catalyst
Species, load capacity and the polymerization temperature of metallocene compound is realized.The chain-transferring agent is alkyl aluminum, aluminum alkoxide, hydrogen
Deng preferred hydrogen.The species of metallocene compound eliminates insertion so that β-hydrogen can occur in the course of the polymerization process in the catalyst
The how many metallocene compound of reaction (refers to monograph to divide：The organic olefin polymerization catalysis of metal and its olefin polymer, the
Two chapter second sections), load capacity is no more than 1%wt, and polymerization temperature is not higher than 75 DEG C.
Polyethylene material A and polyethylene material B are mixed into addition batch mixer by a certain percentage or mixed again during post-processing
Close can also, wherein A material content be 1-99 parts by weight, B material content be 99-1 parts by weight.Mixed polyethylene material, point
Son amount is between 500,000-500 ten thousand, and preferably 800,000-400 ten thousand, molecular weight distribution is between 1-6, between preferably 3-6, branching content
Between 0-20%, between preferably 0-10%, strand degree of entanglement is low, and mobility of particle is good.
Powder of the present invention is formed by polyethylene material A and polyethylene material B compoundings, poly- by dynamics model catalyst preparation
Feed ethylene A, viscosity average molecular weigh (Mv) is 800,000-500 ten thousand, and molecular weight distribution is more than 3, and branching content is 0-20%, and its side chain leads to
Ethene is crossed to introduce with alpha-olefin copolymer；Polyethylene material B is prepared for by single site catalysts, viscosity average molecular weigh (Mv) is 50
Ten thousand -200 ten thousand, molecular weight distribution is 1-3, and branching content is 0-10%, and its side chain includes short-chain branch and long-chain branch, poly- by catalysis
β-hydrogen during conjunction eliminates insertion, ethene and alpha-olefin copolymer and introduced.The powder includes the polyethylene material A of 1-99 parts by weight,
The polyethylene material B of 99-1 parts by weight.Its specific processing method is as follows：
1) dispensing and batch mixing, just polyethylene material A and B are mixed with 1-99 or 99-1 weight ratio, add diluent, and mixing is equal
It is even.The content of wherein diluent is not higher than 90%, not less than 30%, preferably 90%-60%.It is no longer added in the process
He is used to improve lubricant, plasticizer of ultra-high polyethylene mobility etc., but can add other increase thin film physicses and chemistry
The additive of performance, such as antioxidant, crosslinking agent, nucleator, heat stabilizer, surfactant, modifying agent.Wherein polyethylene
Material A, polyethylene material B, diluent and other addition sequences of additive for needing to add there is no particular requirement that, according to actually making
Determined with situation.The diluent be more than C6 alkane, arene, esters and its mixture, preferably octane, nonane,
Dodecane, toluene, atoleine, white oil, naphthane and decahydronaphthalene, dioctyl phthalate and dibutyl phthalate.
2) mixing and extrusion/compressing tablet, cause material in the temperature higher than melting point polymer, low by extruder/plasticator
At a temperature of polymer is decomposed, quick, uniform plasticizing and mixing extrusion/compressing tablet.Extruder can use common polythene
Processing extruder, calender or superelevation dedicated extruder, including single screw extrusion machine, double screw extruder etc..Plasticator can
Select common polythene processing molding press or high pressure-temperature film laminator etc..Enter extruder/tablet press machine in the material mixed
Before, it can also use or further be well mixed it without using mixer, banbury, kneading machine etc..Extruder/tablet press machine
Outlet temperature preferably 150 DEG C -200 DEG C, is selected between 130 DEG C to 240 DEG C according to the molecular chain conformation of material.
3) cool down and stretch, the melt of extrusion/extrusion is cooled fast to below fusing point so that diluent and polyethylene
Phase separation is produced, micropore is obtained, is then extracted, then biaxial tension or direct biaxial tension extract again.Chilling temperature
For 30 DEG C -150 DEG C, preferably 90 DEG C -150 DEG C, selected according to the molecular chain conformation of material.Extraction solvent is easily to wave
The alkane of hair, C1-C6 halogenated alkane, alcohols and ketone etc., preferably dichloromethane, heptane, hexane, ethanol and acetone etc..
4) washing and thermal finalization processing, cause the diluent remained in microporous barrier to extract and volatilize by washing and drying
Out, thermal finalization processing is then carried out on tentering stretching device.Washer solvent is more than C4 alkane, C1-C6 alkyl halide
Hydrocarbon, C1-C5 alcohols and with volatile ketone and its mixture etc..It can be carried out in thermal finalization processing procedure or without vertical
To stretching, heat setting temperature is less than fusing point, preferably 90 DEG C -130 DEG C.
Compared with prior art, the invention has the characteristics that：
1) powder of the present invention has the characteristics of molecular chain conformation is adjustable, easy processing, product properties are good, in process
In can according to the molecular chain conformation of powder adjust solvent consumption, come ensure have higher process velocity, improve processing effect
Benefit；
2) polymerization catalyst that the present invention is used is Catalysts for Olefin Polymerization, is catalyzed by single site catalysts
Ethylene homo, copolymerization, while introducing short-chain branch and long-chain branch into polymer, due to the presence of short-chain branch and long-chain branch, are improved
The extensibility of product, tensile strength, toughness etc., the fusing point of product will not be also decreased obviously, taken into account processing characteristics and used
Performance；
3) present invention is by the way that low winding, the polyethylene containing side chain between two kinds of strands are mixed, without using low molecule
In the case of weight polymers, the consumption of diluent and pore former when can reduce polyethylene micropore film preparation improves film-making/extrusion
And film forming speed is stretched, processing efficiency is significantly improved, and can effectively solve raw material in existing ultra-high polyethylene microporous barrier process
Be difficult to process, the consumption of solvent and low-molecular weight polymer it is too high, film-making/extrusion and stretching film forming speed are low, and processing efficiency is low
Under technical problem；
4) preparation method is simple, greatly improves ultra-high polyethylene and prepares processing characteristics during microporous barrier, reduces
Solvent load, reduces pollution, reduces cost, with good application prospect.
Embodiment
Illustrate the present invention with reference to embodiments, it, in order to preferably illustrate the present invention, is not to this hair that the embodiment, which is,
The limitation of bright protection domain.
Prepared by all catalyst preparations and polyethylene powder operates in the environment of anhydrous and oxygen-free.Agents useful for same is both needed to essence
Used after system processing.
The viscosity average molecular weigh of polymer uses method as defined in GB/T1633.3-2010 to test, and molecular weight distribution is using solidifying
Glue penetration chromatograph (PL-GPC-220) is characterized, and 1,2,4- trichloro-benzenes is as solvent, and dibutyl hydroxy toluene is antioxidant
(0.05%wt), using polystyrene as standard specimen, dissolves at 150 DEG C and determined at sample preparation, 150 DEG C.Branching content is determined by NMR,
Assay method refers to D.Yan, W.-J.Wang, S.ZhuPolmer40 (1999) 1737-1744.
Embodiment 1-6
Polyethylene material A preparation：
The preparation of Mg-Ti systems ziegler natta catalyst：By preparing nascent state magnesium halide, contacted instead with electron donor
Should, (Ti is contacted with titanium compound:Mg=0.05) reaction forms Mg-Ti systems ziegler natta catalyst Cat1.Specific preparation side
The preparation of catalyst in method referenced patent ZL200610116967.1 embodiments 1.
The preparation of Mg-Ti systems ziegler natta catalyst：React to form magnesium compound by magnesium halide and alcohol, magnesium compound
React to form intermediate product with the silicon compound with least one halogen group, intermediate product reacts (Ti with titanium compound:Mg
=Mg-Ti system ziegler natta catalyst Cat2 0.1) are formed, specific preparation method refers to ZL200710042467.2 embodiments 1
The preparation of middle catalyst.
Polymerisation：2 liters of stainless steel jacket reactors are heated to 100 DEG C, vacuumized 3 hours, 2kg essences are added after cooling
High pure sodium chloride after system, adds catalyst and co-catalyst triethyl aluminum, controls Al：Ti is between 150-200.It is warming up to 60
DEG C, 0.5Mpa ethene is passed through, reacts 4 hours, hydrogen, co-monomer butene-1 can be passed through in polymerization process as needed, is polymerize
After end, filtration drying obtains polyethylene powder, the results are shown in Table 1.
Table 1:Polyethylene powder data
Embodiment 7-12
Polyethylene material B preparation:
Five first class cyclopentadienyl group titanium trichlorides are supported on the chlorination magnesium alcoholate of triethyl aluminum modification and prepare list
First catalyst group in site catalyst Cat3, specific preparation method referenced patent ZL201210396049.4 embodiments 1a
The preparation divided.
Double (1- indenyls) zirconium dichlorides of rac- dimethyl silicon substrate are supported on Styrene-acrylic copolymer and prepare list
Site catalyst Cat4.First catalyst group in specific preparation method referenced patent ZL201110355606.3 embodiments 1a
The preparation divided.
Polymerisation：2 liters of stainless steel jacket reactors are heated to 100 DEG C, vacuumized 3 hours, 1 liter of essence is added after cooling
High-purity n-hexane after system, adds catalyst and co-catalyst MAO, controls Al：Ti is in 100-150.It is warming up to 50
DEG C, 0.5Mpa ethene is passed through, reacts 4 hours, hydrogen, co-monomer hexene -1 can be passed through in polymerization process as needed, is polymerize
After end, filtration drying obtains polyethylene powder, the results are shown in Table 2.
Table 2：Polyethylene powder data
Embodiment 13-23：
A kind of powder for being used to prepare polyethene microporous membrane：
By the polyethylene powder A and polyethylene powder B of preparation, it is mixed to get by a certain percentage a kind of for preparing polyethylene
The powder of microporous barrier.It the results are shown in Table 3.
Table 3:A kind of powder for being used to prepare polyethene microporous membrane
Embodiment 24
The powder that the embodiment 16 of 30 parts by weight is obtained is mixed with the atoleine of 70 parts of weight using multifunctional mini-mixer
Thing mixes 60min at 113 DEG C, is transferred in Small-size Twin-Screw Extruders extruder, keeps outlet of extruder temperature at 160 DEG C, cooling
To below fusing point, 6-8 times is stretched along extrusion direction, vertical direction stretches 2-3 times.Then extracted using dichloromethane, 125
Thermal finalization processing is carried out at DEG C on tentering stretching device, cooling obtains microporous barrier.After tested, the micropore film thickness is 15um, hole
Gap rate is 60%, and average pore size is between 0.05-0.1um, and punctured resistance is more than 400g/20um, and tensile strength is more than
1400kg/cm2.Closed pore temperature is at 135 DEG C, and broken film temperature is at 152 DEG C.Meet requirement of the lithium battery to barrier film.
Embodiment 25
The powder and the white oil mixture of 60 parts of weight for being obtained the embodiment 17 of 40 parts by weight using multifunctional mini-mixer are existed
60min is mixed at 110 DEG C, is transferred in Small-size Twin-Screw Extruders extruder, outlet of extruder temperature is kept at 150 DEG C, along extrusion side
To 6-8 times of stretching, vertical direction stretches 2-3 times.Then extracted using dichloromethane, at 125 DEG C on tentering stretching device
Thermal finalization processing is carried out, cooling obtains microporous barrier.After tested, the micropore film thickness is 20um, and porosity is 54%, average pore size
Between 0.05-0.1um, punctured resistance is more than 350g/20um, and tensile strength is more than 1300kg/cm2.Closed pore temperature is 132
DEG C, broken film temperature is at 150 DEG C.Meet requirement of the lithium battery to barrier film.
Embodiment 26
The powder and the white oil mixture of 80 parts of weight for being obtained the embodiment 18 of 20 parts by weight using multifunctional mini-mixer are existed
60min is mixed at 117 DEG C, is transferred in Small-size Twin-Screw Extruders extruder, keeps outlet of extruder temperature at 180 DEG C, cools to molten
Point is following, stretches 6-8 times along extrusion direction, vertical direction stretches 2-3 times.Then extracted using dichloromethane, at 127 DEG C
Thermal finalization processing is carried out on tentering stretching device, cooling obtains microporous barrier.After tested, the micropore film thickness is 40um, porosity
For 50%, average pore size is between 0.05-0.1um, and punctured resistance is more than 500g/20um, and tensile strength is more than 1400kg/
cm2.Closed pore temperature is at 136 DEG C, and broken film temperature is at 152 DEG C.Meet requirement of the dynamic lithium battery to barrier film.
Embodiment 27
The powder for being obtained the embodiment 19 of 20 parts by weight using multifunctional mini-mixer and the atoleine mixing of 80 parts of weight
Thing mixes 60min at 120 DEG C, is transferred in tablet press machine, is rapidly heated to 200 DEG C, is pressed into 1.0mm thin slice, at 150 DEG C
Biaxial tension is to original 6-8 times.Then extracted using dichloromethane, carrying out heat on tentering stretching device at 117 DEG C determines
Type processing, cooling obtains microporous barrier.After tested, the micropore film thickness is 35um, and porosity is 55%, and average pore size is in 0.05-
Between 0.1um, punctured resistance is more than 500g/20um, and tensile strength is more than 1400kg/cm2.Closed pore temperature is in 138 DEG C, rupture of membranes
Temperature is at 155 DEG C.Meet requirement of the dynamic lithium battery to barrier film.
Embodiment 28
The powder that the embodiment 20 of 80 parts by weight is obtained is mixed with the atoleine of 20 parts of weight using multifunctional mini-mixer
Thing mixes 30min at 100 DEG C, is transferred in Small-size Twin-Screw Extruders extruder, keep outlet of extruder temperature at 130 DEG C, along squeeze
Outgoing direction stretches 6-8 times, and vertical direction stretches 2-3 times.Then extracted using dichloromethane, obtain microporous barrier.After tested,
The micropore film thickness is 5um, and porosity is 80%, and average pore size is between 0.05-0.1um, and air permeability was in 300 seconds/100ml.
Suitable for fields such as sewage disposal, resource regenerations.
Embodiment 29
The powder that the embodiment 20 of 80 parts by weight is obtained is mixed with the atoleine of 20 parts of weight using multifunctional mini-mixer
Thing is mixed at normal temperatures, is transferred in Small-size Twin-Screw Extruders extruder, keeps outlet of extruder temperature at 150 DEG C, along extrusion direction
6-8 times of stretching, vertical direction stretches 2-3 times.Then extracted using dichloromethane, obtain microporous barrier.After tested, the micropore
Film thickness is 2um, and porosity is 80%, and average pore size is between 0.01-0.05um, and air permeability was in 200 seconds/100ml.It is applied to
The fields such as gas separation membrane.
Embodiment 30
The powder and the decahydronaphthalene of 70 parts of weight for being obtained the embodiment 21 of 30 parts by weight using multifunctional mini-mixer are at 120 DEG C
Lower mixing 30min, is transferred in Small-size Twin-Screw Extruders extruder, keeps outlet of extruder temperature at 140 DEG C, along the stretching of extrusion direction
6-8 times, vertical direction stretches 2-3 times.Then extracted using dichloromethane, carry out heat at 120 DEG C on tentering stretching device
Heat treatment, cooling obtains microporous barrier.After tested, the micropore film thickness is 10um, and porosity is 60%, and average pore size exists
Between 0.05-0.1um, punctured resistance is more than 600g/20um, and tensile strength is more than 1400kg/cm2.Closed pore temperature is 135
DEG C, broken film temperature is at 152 DEG C.Meet requirement of the lithium battery to barrier film.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of powder for being used to prepare polyethene microporous membrane, it is characterised in that included in every 100 parts by weight of the powder with the following group
Point：1-99 parts of polyethylene material A, remaining is polyethylene material B；
Described polyethylene material A viscosity average molecular weigh is 800,000-500 ten thousand, and molecular weight distribution ＞ 3, branching content is 0-20%；
Described polyethylene material B viscosity average molecular weigh is 500,000-200 ten thousand, and molecular weight distribution is 1-3, and branching content is 0-10%.
2. a kind of powder for being used to prepare polyethene microporous membrane according to claim 1, it is characterised in that described poly- second
Alkene material A is prepared from by Mg-Ti systems ziegler natta catalyst controllable polymerization, and viscosity average molecular weigh is 1,000,000-500 ten thousand, and
Side chain in described polyethylene material A is introduced by ethene and alpha-olefin copolymer, and branching content is 0-10%.
3. a kind of powder for being used to prepare polyethene microporous membrane according to claim 2, it is characterised in that described poly- second
Alkene material B is prepared from by single active center's polyethylene catalysts controllable polymerization, and the long-chain branch in described polyethylene material B
Insertion is eliminated by β-hydrogen to introduce, short-chain branch is introduced by ethene and alpha-olefin copolymer, and branching content is 0-5%.
4. a kind of powder for being used to prepare polyethene microporous membrane according to claim 3, it is characterised in that described poly- second
Tangle the alkene that few, described alpha-olefin is C3-C20 between strand in alkene material A, polyethylene material B.
5. a kind of powder for being used to prepare polyethene microporous membrane according to claim 4, it is characterised in that described α-alkene
Hydrocarbon is one kind in 1- propylene, 1- butylene, 1- hexenes, 1- octenes, cyclohexene or ENB.
6. a kind of preparation method for being used to prepare the powder of polyethene microporous membrane as claimed in claim 1, it is characterised in that should
Method specifically includes following steps：
Step (1)：Polyethylene material A is mixed by weight with polyethylene material B, diluent is added, is well mixed, mixing is made
Material；
Step (2)：Mixed material is passed sequentially through into extruder or plasticator, mixed material higher than melting point polymer and is being less than
In the range of polymer decomposition temperature, rapidly and uniformly plasticizing mixing completes extrusion/compressing tablet；
Step (3)：The melt of extrusion/compressing tablet is cooled fast to below melting point polymer, diluent and polyethylene is produced phase
Separation, obtains micropore, then carries out extracting and then carrying out again biaxial tension at least one times or proceeds directly to few once two-way
Stretching and then extraction；
Step (4)：By washing and drying, make to remain in the diluent in micropore and wash and evaporate, then drawn in tentering
Stretch progress thermal finalization processing on machine, you can.
7. a kind of preparation method for being used to prepare the powder of polyethene microporous membrane according to claim 6, it is characterised in that
Diluent described in step (1) accounts for the 30-90% of mixed material gross mass, and described diluent is C6's and more than C6
One or more in liquid alkane, arene or esters；
The outlet temperature of extruder or plasticator described in step (2) is 130-240 DEG C；
The temperature of cooling is 30-150 DEG C in step (3), and the solvent that described extraction is used is volatile alkane, C1-C6
One or more in halogenated alkane, alcohols or ketone；
Alkane, C1-C6 halogenated alkane, ketone or C1-C5 that the used solvent of washing is more than C4 alcohols in step (4)
In one or more, the temperature of described thermal finalization processing is 90-130 DEG C.
8. a kind of preparation method for being used to prepare the powder of polyethene microporous membrane according to claim 7, it is characterised in that
Described diluent is selected from octane, nonane, dodecane, toluene, atoleine, white oil, naphthane and decahydronaphthalene, phthalic acid
One or more in dioctyl ester or dibutyl phthalate, the solvent that described extraction is used be selected from dichloromethane, heptane,
One or more in hexane, ethanol or acetone.
9. a kind of application for being used to prepare the powder of polyethene microporous membrane as claimed in claim 1, it is characterised in that described
Powder is used to prepare ultra-high molecular mass polyethylene micropore film, and the ultra-high molecular mass polyethylene micropore film is used as battery diaphragm, gas
Seperation film or gas liquid separating filtering film.
10. a kind of application for being used to prepare the powder of polyethene microporous membrane according to claim 9, it is characterised in that institute
The thickness for the ultra-high molecular mass polyethylene micropore film stated is 1-500 μm, and aperture is 0.01-1 μm, and porosity is 20-80%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484964A (en) * | 2018-04-28 | 2018-09-04 | 青岛蓝科途膜材料有限公司 | High-strength polyethylene microporous barrier, preparation method and its application |
| CN108525529A (en) * | 2018-04-28 | 2018-09-14 | 青岛蓝科途膜材料有限公司 | High-strength polyethylene microporous barrier, preparation method and its application |
| CN110054855A (en) * | 2019-02-18 | 2019-07-26 | 浙江格尔泰斯环保特材科技股份有限公司 | A kind of polytetrafluoroethylene (PTFE) bubble point film and preparation method thereof |
| CN111100364A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyethylene composition, preparation method thereof and blow-molded packaging product |
| CN111100365A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyethylene composition, preparation method thereof and extrusion molding packaging product |
| CN112978081A (en) * | 2021-02-26 | 2021-06-18 | 莱阳诚丰食品有限公司 | Fruit and vegetable preservative film and preparation method and application thereof |
| CN113209835A (en) * | 2021-05-11 | 2021-08-06 | 杭州科百特科技有限公司 | Ultra-high molecular weight polyethylene flat membrane and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484964A (en) * | 2018-04-28 | 2018-09-04 | 青岛蓝科途膜材料有限公司 | High-strength polyethylene microporous barrier, preparation method and its application |
| CN108525529A (en) * | 2018-04-28 | 2018-09-14 | 青岛蓝科途膜材料有限公司 | High-strength polyethylene microporous barrier, preparation method and its application |
| CN111100364A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyethylene composition, preparation method thereof and blow-molded packaging product |
| CN111100365A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyethylene composition, preparation method thereof and extrusion molding packaging product |
| CN111100365B (en) * | 2018-10-26 | 2022-07-12 | 中国石油化工股份有限公司 | Polyethylene composition, preparation method thereof and extrusion molding packaging product |
| CN110054855A (en) * | 2019-02-18 | 2019-07-26 | 浙江格尔泰斯环保特材科技股份有限公司 | A kind of polytetrafluoroethylene (PTFE) bubble point film and preparation method thereof |
| CN110054855B (en) * | 2019-02-18 | 2021-10-15 | 浙江格尔泰斯环保特材科技股份有限公司 | Polytetrafluoroethylene bubble point membrane and preparation method thereof |
| CN112978081A (en) * | 2021-02-26 | 2021-06-18 | 莱阳诚丰食品有限公司 | Fruit and vegetable preservative film and preparation method and application thereof |
| CN113209835A (en) * | 2021-05-11 | 2021-08-06 | 杭州科百特科技有限公司 | Ultra-high molecular weight polyethylene flat membrane and preparation method and application thereof |
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