CN104725691A - Polyethylene powder - Google Patents

Polyethylene powder Download PDF

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Publication number
CN104725691A
CN104725691A CN201410803303.7A CN201410803303A CN104725691A CN 104725691 A CN104725691 A CN 104725691A CN 201410803303 A CN201410803303 A CN 201410803303A CN 104725691 A CN104725691 A CN 104725691A
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polyethylene powders
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alkyl
polyethylene
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CN104725691B (en
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樽谷淳祯
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention relates to polyethylene powder. The present invention provides high molecular weight polyethylene powder with excellent solubility even in high-speed production. The specific surface area obtained by the BET method of the polyethylene powder is more than 0.10 m2/g and less than 0.30 m2/g, the pore volume obtained by the mercury intrusion method is less than 0.85 mL/g, and the viscosity average molecular weigh (Mv) is more than 100 thousand and less than one million.

Description

Polyethylene powders
Technical field
The present invention relates to a kind of polyethylene powders.
Background technology
High molecular weight polyethylene powder is used to the various purposes such as film, thin slice, microporous membrane, fiber, foam and tubing.Particularly use High molecular weight polyethylene as with the raw material of lead storage battery, secondary battery membrane microporous membrane that lithium ion battery is representative and high strength fibre.
Be used to the reason of these purposes as High molecular weight polyethylene powder, can enumerate: stretch process is excellent, intensity is high, chemical stability is high and long-term reliability is excellent etc.The usual viscosity of High molecular weight polyethylene powder is high, by processing difficulties such as injection formings, therefore most by High molecular weight polyethylene powder dissolution in solvent postforming.Secondary battery membrane microporous membrane by by High molecular weight polyethylene powder in such as forcing machine under the state being dissolved in solvent, at high temperature mixing, except desolventizing and manufacturing after then stretching.
Like this secondary battery membrane microporous membrane that High molecular weight polyethylene powder dissolution obtains in solvent is required the quality improving shaping operation stability, productivity, film, therefore expect the excellent solvability that the High molecular weight polyethylene powder of non-melting in melting mixing operation for High molecular weight polyethylene powder can not remain as particle.
As raising polyethylene powders deliquescent technology in a solvent, such as, Patent Document 1 discloses, use that median size is 1 ~ 150 μm, Specific Surface Area Measurement is 0.7m 2the polyethylene of/more than g is as one of raw material.
In addition, Patent Document 2 discloses a kind of microporous membrane, loose density is 0.30g/cm by it 3above and 0.45g/cm 3following ethylene polymer composition powder is as raw material.
In addition, Patent Document 3 discloses a kind of polyethene microporous membrane, it uses molecular weight to be 1 × 10 4the poor high density polyethylene(HDPE) of following low molecular composition is as raw material.
Prior art document
Patent documentation:
Patent documentation 1: Japanese Patent No. 4799179 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-119751 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-208144 publication
Summary of the invention
Invent problem to be solved
But in recent years, particularly the growth of the needs of secondary battery membrane microporous membrane is remarkable, more strong expectation boosts productivity further and produces at low cost.Specifically, from the view point of boosting productivity, expecting can continous-stable and high-speed production and do not stop forcing machine etc., that is, expect the shaping of uniform microporous membrane.In addition, from the view point of enhancing productivity, being desirably in the compounding procedure of polyethylene powders and improving excellent solvability further, expect to improve above-mentioned known technology further.
Therefore, even if the object of the present invention is to provide a kind of polyethylene powders that solvability is also excellent when high-speed production.
For the means of dealing with problems
The present inventor conducts in-depth research to solve the problem, and found that: have the specific surface area of regulation, the High molecular weight polyethylene powder of pore volume can solve the problem, thus complete the present invention.
That is, the present invention is as follows.
[1]
A kind of polyethylene powders, the specific surface area of being tried to achieve by BET method of described polyethylene powders is 0.10m 2/ more than g and 0.30m 2/ below g, the pore volume of being tried to achieve by mercury penetration method are below 0.85mL/g and viscosity-average molecular weight (Mv) is more than 100,000 and less than 1,000,000.
[2]
Polyethylene powders as described in [1], wherein, in the pore distribution of being tried to achieve by mercury penetration method, in aperture, less than 30 μm do not exist maximum value.
[3]
Polyethylene powders as described in [1] or [2], the median size of described polyethylene powders is 1 ~ 200 μm, and total more than 60% of number of particles that measures has the form that the camber (UD) defined by formula (1) is more than 0.90 and less than 0.95;
UD＝A/(A+B) (1)
In formula (1), the shadow area of A indicated object particle, A+B represents the shadow area of being surrounded by the envelope curve of the protuberance of connecting object particle.
[4]
As the polyethylene powders according to any one of [1] ~ [3], it contains more than 1ppm and the titanium of below 200ppm.
[5]
As the polyethylene powders according to any one of [1] ~ [4], it is for secondary battery membrane.
[6]
As the polyethylene powders according to any one of [1] ~ [5], it is for lithium ion secondary battery membrane.
Invention effect
According to the present invention, even if the polyethylene powders that solvability is also excellent when high-speed production can be obtained
Accompanying drawing explanation
Fig. 1 is the figure illustrating that the camber of polyethylene powders measures.
Embodiment
Be described in detail for implementing mode of the present invention (hereinafter referred to as " present embodiment ") below.In addition, the present invention is not limited to present embodiment, suitably can be out of shape and implement in the scope of its main idea.
[polyethylene powders]
The polyethylene powders of present embodiment is the specific surface area of being tried to achieve by BET method is 0.10m 2/ more than g and 0.30m 2/ below g, the pore volume of being tried to achieve by mercury penetration method are below 0.85mL/g and viscosity-average molecular weight (Mv) is the polyethylene powders of more than 100,000 and less than 1,000,000.
As the polyethylene powders of present embodiment, can enumerate: the multipolymer of Alathon or ethene and other comonomer.
As other comonomer, be not particularly limited, can enumerate such as: alpha-olefin, vinyl compound etc.
As alpha-olefin, be not particularly limited, can enumerate such as: the alpha-olefin of carbonatoms 3 ~ 20, specifically can enumerate: propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene etc.Among those, from the view point of thermotolerance, the intensity of the molding being representative with film, fiber, preferred propylene and 1-butylene.
As vinyl compound, be not particularly limited, can enumerate such as: vinyl cyclohexane, Styrene and its derivatives etc.
In addition, as other comonomer, the unconjugated polyene such as 1,5-hexadiene, 1,7-octadiene can be used as required.Multipolymer can be ternary atactic copolymer.
Other comonomer can be used alone one, also can be used together two or more.
For polyethylene powders, from the view point of heat-resistant quality, be preferably Alathon.When polyethylene powders comprises the multipolymer of ethene and other comonomer, for multipolymer, preferably close with other comonomer in the scope that heat-resistant quality does not reduce.Specifically, as polyethylene powders, the mol ratio that in multipolymer, ethene occupies is preferably more than 50% and is less than 100%, is more preferably more than 80% and is less than 100%, and more preferably more than 90% and be less than 100%.
When polyethylene powders is multipolymer, the amount of other comonomer in multipolymer, can confirm by infrared analysis, NMR method etc.
The polyethylene powders of present embodiment can contain the additives such as neutralizing agent, antioxidant and photostabilizer.
Neutralizing agent can be used as halogen trapping agent or the formed machining auxiliary agents etc. such as the chlorine comprised in polyethylene powders.
As neutralizing agent, be not particularly limited, can enumerate such as: the stearate etc. of the alkaline-earth metal such as calcium, magnesium, barium.The content of neutralizing agent is not particularly limited, such as, be below 5000ppm, is preferably below 4000ppm, is more preferably below 3000ppm.
The ethene polymers using metalloscene catalyst to be obtained by slurry polymerization process, even if do not use neutralizing agent, also can remove halogen-containing composition from catalyzer constituent.
As antioxidant, be not particularly limited, can enumerate such as: butylated hydroxytoluene, tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], the phenol antioxidant such as 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl.The content of antioxidant is not particularly limited, such as, be below 5000ppm, is preferably below 4000ppm, is more preferably below 3000ppm.
As photostabilizer, be not particularly limited, can enumerate such as: the benzotriazole light stabilizers such as 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole; Two (2,2,6,6 ,-tetramethyl--4-piperidyls) sebate, poly-[{ 6-(1,1,3,3-tetramethyl butyl) amino-1,3,5-triazine-2,4-bis-base } { (2,2,6,6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidyl) imino-] etc. hindered amine light stabilizer.The content of photostabilizer is not particularly limited, such as, be below 5000ppm, is preferably below 4000ppm, is more preferably below 3000ppm.
The content of additive contained in polyethylene powders can carry out extracting for 6 hours to the additive in polyethylene powders by surname extraction by using tetrahydrofuran (THF) (THF), and is utilized by extracting solution liquid chromatography to carry out being separated, quantitatively obtaining.
In the polyethylene powders of present embodiment, can the different ethene polymers such as blended viscosity-average molecular weight, molecular weight distribution, also can other resin such as blended Low Density Polyethylene, linear low density polyethylene, polypropylene, polystyrene.
[specific surface area of being tried to achieve by BET method]
The specific surface area of being tried to achieve by BET method of the polyethylene powders of present embodiment is 0.10m 2/ more than g and 0.30m 2/ below g, is preferably 0.15m 2/ more than g and 0.30m 2/ below g, is more preferably 0.20m 2/ more than g and 0.30m 2/ below g.
Be 0.10m by the specific surface area of being tried to achieve by BET method 2/ more than g and 0.30m 2/ below g, can obtain the polyethylene powders that solvability is in a solvent excellent.
Usually, specific surface area is relevant to the Surface and internal structure of polyethylene powders, the polyethylene powders that specific surface area is little, its surface smoothing, and hole from surface to internal run-through and also few in the inner space isolating existence with outside.When melting mixing solvent and polyethylene powders, little with the area of the polyethylene powders of solvent contacts, solvability is in a solvent deteriorated.On the other hand, the polyethylene powders that specific surface area is large, except its surface, exist in inside to isolate the space of existence many with outside.Therefore, when with solvent melting mixing, solvent is difficult to be infiltrated up to polyethylene powders inside, and space part hinders thermal conduction, so solvability is deteriorated.
Therefore, in the present embodiment, by being set in above-mentioned scope by the specific surface area of being tried to achieve by BET method, the polyethylene powders that solvability is excellent can be obtained.
The specific surface area of being tried to achieve by BET method can use the determinator based on BET method to measure, be not particularly limited as determinator, can enumerate such as: the AUTOSOBE 3MP (オ ー ト ソ ー Block 3MP) etc. that the shallow Ionics of soup (Yuasa-ionics) company manufactures.Use the AUTOSOBE 3MP (オ ー ト ソ ー Block 3MP) that soup shallow Ionics (Yuasa-ionics) company manufactures, degassed process is carried out as pre-treatment to mensuration sample, use nitrogen to measure under the condition measuring temperature-196 DEG C as adsorbed gas, the specific surface area according to BET method can be measured thus.
In the present embodiment, control the method in above-mentioned scope as by the specific surface area of being tried to achieve by BET method, can enumerate such as: control the synthesis condition of catalyzer, control catalyzer to the addition means in poly-unit, the post-treating method etc. controlling pressure when being polymerized and the polyethylene slurry after control polymerization.
The synthesis condition of catalyzer can be controlled by the concentration of the raw material in catalyzer synthesis reactor and interpolation speed particularly.By dilution material concentration, reduce raw material interpolation speed, the solid catalyst evenly configured by the avtive spot of catalyzer can be synthesized.By using this solid catalyst to manufacture polyethylene powders, can obtain and not only at particle surface, there is the concavo-convex polyethylene powders with suitable specific surface area that simultaneously inhibit internal voids.
The polymer chain of solid catalyst is used to increase the avtive spot depending on solid catalyst surface.In high density and in the solid catalyst surface of synthesizing under adding the condition of speed fast, the dispersion that avtive spot occurs sometimes is bad, be present in partly on catalyst surface with the form that avtive spot is assembled.Therefore, in such solid catalyst surface, polymer chain also can locally increase.In this case, the growth of polymer chain is corresponding with the concentration class of avtive spot and become uneven, and concave-convex surface also forms the form of unstable distortion.In addition, when avtive spot does not disperse, the catalyst block of gathering can increase and become large before contacting with adjacent polymer chain, and therefore the isolated blank part of its inside also can increase.
By using the solid catalyst evenly configured by the avtive spot of catalyzer, the polyethylene powders with suitable specific surface area can be obtained.
[pore volume of being tried to achieve by mercury penetration method]
The pore volume of being tried to achieve by mercury penetration method of the polyethylene powders of present embodiment is below 0.85mL/g, is preferably below 0.80mL/g.
Be below 0.85mL/g by the pore volume of being tried to achieve by mercury penetration method, polyethylene polymer solvability in a solvent improves.
The internal structure of pore volume and polyethylene powders, the state of aggregation of polyethylene powders are relevant, the aggregate particles internal space volume refer to the volume in the hole internally through from surface, having when the particle of polyethylene powders is closely sealed gathering.
When typically hole volume increases, the internal holes through from surface increases, and solvent infiltration during melting mixing does not fully arrive inside particles, be therefore formed in the particle that internal package has gas, thus the solvability of polyethylene powders is deteriorated.
Therefore, in the present embodiment, by being set in above-mentioned scope by the pore volume of being tried to achieve by mercury penetration method, polyethylene polymer solvability in a solvent improves.
The pore volume of being tried to achieve by mercury penetration method can use mercury porosimeter to measure, and as determinator, is not particularly limited, and can enumerate such as: the AutoPore IV9500 type etc. that Shimadzu Seisakusho Ltd. manufactures.Use the AutoPore IV9500 type etc. that Shimadzu Seisakusho Ltd. manufactures, degassed process as pre-treatment is carried out to mensuration sample, mercury is filled in sample receiver, then slowly pressurize (high-voltage section) and mercury is pressed in the hole of sample, the pore volume according to mercury penetration method can be measured thus.
In the present embodiment, control the method in above-mentioned scope as by the pore volume of being tried to achieve by mercury penetration method, can enumerate such as: control the synthesis condition of catalyzer, control catalyzer to the pressure the etc. when addition means in poly-unit and control polymerization.
The synthesis condition of catalyzer can be controlled by the concentration of the raw material in catalyzer synthesis reactor and interpolation speed particularly.By dilution material concentration, reduce raw material and add speed, can the avtive spot of dispersed catalyst, and then suppress the gathering of the avtive spot in solid catalyst.When making the avtive spot dispersion in solid catalyst like this, the growth of polymer chain can not locally occur, and polymer chain is covered in whole solid catalyst surface, thus obtains the little polyethylene powders of pore volume.
By using the solid catalyst disperseed by the avtive spot of catalyzer, the polyethylene powders with suitable pore volume can be obtained.
The polyethylene powders of present embodiment, the specific surface area of being tried to achieve by BET method is 0.10m 2/ more than g and 0.30m 2/ below g, and the pore volume of being tried to achieve by mercury penetration method is below 0.85mL/g, exist concavo-convex at the particle surface of polyethylene powders thus, and at inside particles, there is the structure few with the empty position of external environment, solvability excellent when therefore having mixing with solvent, even if also do not remain undissolved polyethylene powders when high-speed production.By using the polyethylene powders of present embodiment, even if also uniform secondary battery membrane microporous membrane can be manufactured continuously and stably when high-speed production.
[viscosity-average molecular weight]
The viscosity-average molecular weight (Mv) of the polyethylene powders of present embodiment is more than 100,000 and less than 1,000,000, is preferably more than 150,000 and less than 800,000, is more preferably more than 200,000 and less than 700,000.
Be more than 100,000 by viscosity-average molecular weight (Mv) and less than 1,000,000, obtain productivity more excellent, when being shaped stretchiness and the more excellent polyethylene powders of film toughness.The polyethylene powders with such characteristic can be suitable for secondary battery membrane, can be more suitable for for lithium ion secondary battery membrane.
Viscosity-average molecular weight (Mv) can by being dissolved in decalin solutions by polyethylene polymer with different concns, the reduced viscosity obtained at 135 DEG C be extrapolated to concentration 0 and obtain limiting viscosity [η] (dL/g), utilizing following mathematical expression A to calculate by this limiting viscosity.
Mv=(5.34 × 10 4) × [η] 1.49mathematical expression A
In the present embodiment, as method viscosity-average molecular weight controlled in above-mentioned scope, can enumerate such as: the polymerization temperature, polymerization pressure etc. that change reactor when polyethylene polymer is polymerized.Generally speaking, there is the tendency that the higher then molecular weight of polymerization temperature is lower, there is the tendency that the lower then molecular weight of polymerization temperature is higher.In addition, as other method viscosity-average molecular weight (Mv) controlled in above-mentioned scope, can enumerate such as: add the chain-transfer agents etc. such as hydrogen when polymerising ethylene etc.By adding chain-transfer agent, the tendency that the molecular weight with the polyethylene polymer generated at same polymeric temperature reduces.
In present embodiment, preferably both Combination of Methods are controlled the viscosity-average molecular weight (Mv) of polyethylene polymer.
[pore distribution of being tried to achieve by mercury penetration method]
As the polyethylene powders of present embodiment, in the pore distribution of being tried to achieve by mercury penetration method, preferably in aperture less than 30 μm there is not maximum value.
Be greater than 30 μm, aperture by maximum value, the aperture that the particle surface of polyethylene powders exists is large, can obtain the polyethylene powders that solvent etc. is easily infiltrated up to inside particles, favorable solubility.
Pore distribution can be measured by mercury penetration method.The balance of the pressure of general work can be cut according to the surface tension of mercury and hole, measure the aperture corresponding with mercury pressure.
In the present embodiment, control the method in above-mentioned scope as by the pore distribution of being tried to achieve by mercury penetration method, can enumerate such as: the distortion fusing controlling the particle surface in the manufacturing process of polyethylene powders.That is, can be narrow by suppress the surface of polyethylene powders in polymerization, catalyst deactivation, drying process to be subject to hole plug that load, fusing, wearing and tearing, gathering etc. cause, stenosis, thus control.Specifically, in order to increase the maximum value in the aperture in the pore distribution of being tried to achieve by mercury penetration method, can enumerate: reduce polymerization temperature or reduce catalyst pulp concentration, temperature and stirring velocity etc. in the operation groove reducing catalyst deactivation, drying process.
[median size]
The median size of the polyethylene powders of present embodiment is preferably more than 1 μm and less than 200 μm, more preferably more than 50 μm and less than 180 μm, further preferably more than 120 μm and less than 160 μm.
Be more than 1 μm by median size, loose density and the mobility of polyethylene powders improve fully, therefore have the tendency that the operability such as feed intake, measure from hopper in hopper etc. are better.Being less than 200 μm by median size, when processing secondary battery membrane or fiber etc., there is the tendency that the flexibility of operation of productivity and/or stretchiness etc. is more excellent.Median size can be measured by the method recorded in embodiment.
In the present embodiment, as median size being controlled the method in above-mentioned scope, such as, can be controlled by the particle diameter of the catalyzer used; In addition, also can be controlled by the productivity of the polyethylene powders of per unit catalyzer.In addition, also can be subject to load, fusing, wearing and tearing and surface polishes by suppressing the surface of polyethylene powders in catalyst deactivation, drying process, thus control.In addition, also can be controlled by pressure during polymerization.Specifically, can enumerate: when catalyst deactivation, drying process, reduce the liquid holdup of solvent residual in polyethylene powders etc., and keep pressure during polymerization low.
[camber (UD)]
As the camber (UD) of the polyethylene powders of present embodiment, preferably there is UD and be more than 0.90 and the polyethylene powders of the form of less than 0.95 is more than 60% of total population, more preferably there is UD and be more than 0.91 and the polyethylene powders of the form of less than 0.94 is more than 60% of total population.
By camber (UD) in such scope, polyethylene powders solvability in a solvent can be improved.
Camber is 0 < UD≤1, and UD does not more more have concavo-convex close to 1 particle, means for smooth surface.
Camber (UD) can use the dynamic image method size-grade distribution particle shape evaluating apparatus QICPIC etc. that such as Japanese laser (Japan laser) company manufactures to measure.By using this device etc., air-flowing type dry dispersion device dispersion measurement sample can be utilized, take the image of dispersed particle continuously, use image analysis software to measure according to the graphic information obtained.
As shown in Figure 1, the shadow area of the object particle obtained is set to A, when the shadow area that the envelope curve of the protuberance by connecting object particle surrounds is set to A+B, camber (UD) is defined by following formula (1).
UD＝A/(A+B) (1)
In the present embodiment, as the method that camber (UD) is controlled in above-mentioned scope, can enumerate such as: control catalyzer to the addition means in poly-unit, the post-treating method etc. controlling pressure when being polymerized and the polyethylene slurry after control polymerization.
[titanium amount contained in polyethylene powders]
Titanium amount contained in the polyethylene powders of present embodiment is preferably more than 1ppm and below 200ppm, is more preferably more than 1ppm and below 12ppm, more preferably more than 1ppm and below 10ppm.
Titanium amount contained in polyethylene powders comes from the catalyst component used in polymerization process.
Be more than 1ppm by titanium amount, when using as lithium ion secondary battery membrane, the decomposition that easily absorption comes from electrolytic salt produces dysgenic hydrogen fluoride to cell reaction.Be below 200ppm by titanium amount, obtain the polyethylene powders that thermostability is more excellent, and when forming battery diaphragm, fiber, their permanent stability are also more excellent.Titanium amount contained in polyethylene powders can by measuring by the method recorded in embodiment.
Titanium amount contained in polyethylene powders can be controlled by the productivity of the polyethylene powders of per unit catalyzer.The productivity of polyethylene powders can be controlled by the polymerization temperature of reactor during manufacture, polymerization pressure, polyethylene slurry concentration.As the method for the productivity of raising polyethylene powders, can enumerate such as: improve polymerization temperature, improve polymerization pressure and/or improve polyethylene slurry concentration etc.As the catalyzer used, be not particularly limited, common ziegler natta catalyst can be used, preferably use catalyzer described later.
[manufacture method of polyethylene powders]
In the present embodiment, be not particularly limited, polyethylene powders can use common ziegler natta catalyst manufacture, preferably uses the ziegler natta catalyst recorded below.
As ziegler natta catalyst, preferably comprise the catalyzer of solid catalyst component [A] and organometallic compound composition [B], wherein, solid catalyst component [A] is the catalyst for olefines polymerizing that titanium compound (A-2) that the organo-magnesium compound (A-1) dissolving in unreactive hydrocarbons solvent by making formula 1 represent and formula 2 represent reacts and manufacture.
(A-1): (M 1) α(Mg) β(R 2) a(R 3) by 1 cformula 1
(in formula 1, M 1for belonging to by the atoms metal of the group of the periodic table of elements the 12nd race, the 13rd race and the 14th group composition, R 2and R 3for carbonatoms more than 2 and the alkyl of less than 20, Y 1for alkoxyl group, siloxy, allyloxy, amino, amide group ,-N=C-R 4r 5,-SR 6, beta-keto acid residue (wherein, R 4, R 5and R 6represent carbonatoms more than 1 and the alkyl of less than 20.When c is 2, Y 1separately can be different), α, β, a, b and c are the real number meeting following relation.0≤α, 0 < β, 0≤a, 0≤b, 0≤c, 0 < a+b, 0≤b/ (alpha+beta)≤2, (wherein, n represents M to n α+2 β=a+b+c 1valence))
(A-2): Ti (OR 7) dx 1 (4-d)formula 2
(in formula 2, d is the real number of more than 0 and less than 4, R 7for carbonatoms more than 1 and the alkyl of less than 20, X 1for halogen atom.)
The unreactive hydrocarbons solvent used in reaction as (A-1) and (A-2), is not particularly limited, can enumerates such as: the aliphatic hydrocarbons such as butane, pentane, hexane, heptane; The aromatic hydrocarbon such as benzene,toluene,xylene; And the alicyclic hydrocarbon etc. such as pentamethylene, hexanaphthene, methylcyclohexane, naphthane.
(A-1) although represent with the form of the organic-magnesium complex compound dissolving in unreactive hydrocarbons solvent, the complex compound of all dialkyl magnesium compounds and this compound and other metallic compound is comprised.Relational expression n α+2 β=a+b+c of symbol α, β, a, b and c represents the valence of atoms metal and substituent stoichiometry.
In formula 1, as by R 2and R 3represent carbonatoms more than 2 and the alkyl of less than 20, be not particularly limited, can enumerate such as: alkyl, cycloalkyl or aryl etc., specifically can enumerate: ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, phenyl etc.Wherein, preferred alkyl.
In formula 1, when α >0, as atoms metal M 1as long as, belong to by the atoms metal of the group of the periodic table of elements the 12nd race, the 13rd race and the 14th group composition, be just not particularly limited, can enumerate such as: zinc, boron, aluminium etc.Among those, preferred aluminium, zinc.
Magnesium and atoms metal M 1ratio beta/alpha be not particularly limited, be preferably more than 0.1 and less than 30, be more preferably more than 0.5 and less than 10.
In formula 1, during α=0, R 2and R 3be preferably any a group in group (1) shown below, group (2), group (3) three groups.
Group (1): R 2and R 3at least one be carbonatoms more than 4 and the secondary alkyl of less than 6 or tertiary alkyl, preferably R 2and R 3be carbonatoms more than 4 and the alkyl of less than 6 and at least one is for secondary alkyl or tertiary alkyl.
Group (2): R 2and R 3for alkyl, preferably R that carbonatoms is mutually different 2for alkyl, the R of carbonatoms 2 or 3 3for the alkyl of carbonatoms more than 4.
Group (3): R 2and R 3at least one be alkyl, the preferably R of carbonatoms more than 6 2and R 3in contained carbonatoms sum be the alkyl of more than 12.
As the carbonatoms more than 4 in group (1) and the secondary alkyl of less than 6 or tertiary alkyl, be not particularly limited, can enumerate such as: 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl, 2-methyl butyl, 2-ethyl propyl, 2,2-dimethyl propyl, 2-methyl amyl, 2-ethyl-butyl, 2,2-dimethylbutyls, 2-methyl-2-ethyl propyl etc.Among those, preferred 1-methyl-propyl.
In formula (1), during α=0, such as R 2when for 1-methyl-propyl etc., dissolve in unreactive hydrocarbons solvent, such compound also can bring preferred result to present embodiment.
As the alkyl of the carbonatoms 2 or 3 in group (2), be not particularly limited, can enumerate such as: ethyl, 1-methylethyl, propyl group etc.Among those, preferred ethyl.
As the alkyl of carbonatoms more than 4, be not particularly limited, can enumerate such as: butyl, amyl group, hexyl, heptyl, octyl group etc.Among those, preferred butyl, hexyl.
As the alkyl of the carbonatoms more than 6 in group (3), be not particularly limited, can enumerate such as: hexyl, heptyl, octyl group, nonyl, decyl, phenyl, 2-naphthyl etc.Among those, preferred alkyl, more preferably hexyl, octyl group in alkyl.
Generally speaking, when carbonatoms contained in alkyl increases, there is the tendency be easily dissolved in unreactive hydrocarbons solvent, but on the other hand, the tendency that the viscosity with solution increases.Therefore, operationally consider, preferably use the alkyl of the long-chain of appropriateness.(A-1) can use with after unreactive hydrocarbons solvent dilution, though in this solution containing or the lewis base property compound such as ether, ester, amine of residual minim also can allow to use.
In formula 1, Y 1for alkoxyl group, siloxy, allyloxy, amino, amide group ,-N=C-R 4r 5,-SR 6with any one in beta-keto acid residue.Wherein, R 4, R 5and R 6be the alkyl of carbonatoms more than 1 and less than 20 independently of one another.
Y 1be preferably alkoxyl group or siloxy.
As alkoxyl group, be not particularly limited, can enumerate such as: methoxyl group, oxyethyl group, propoxy-, 1-methyl ethoxy, butoxy, 1-methyl propoxy-, 1,1-dimethylethyloxy, pentyloxy, hexyloxy, 2-methyl pentyloxy, 2-ethyl-butoxy, 2-ethyl pentyloxy, 2-ethyl hexyl oxy, 2-ethyl-4-methyl pentyloxy, 2-propyl group oxygen in heptan base, 2-ethyl-5-methyl octyloxy, octyloxy, phenoxy group, naphthyloxy.Among those, preferred butoxy, 1-methyl propoxy-, 2-methyl pentyloxy and 2-ethyl hexyl oxy.
As siloxy, be not particularly limited, can enumerate such as: hydrogen dimethylamino base siloxy, ethyl hydrogen methyl siloxy, diethyl hydrogen siloxy, trimethylsiloxy group, ethyl dimethylsilyl bis, diethylmethyl siloxy, triethyl siloxy etc.Among those, preferred hydrogen dimethylamino base siloxy, ethyl hydrogen methyl siloxy, diethyl hydrogen siloxy, trimethylsiloxy group.
R 4, R 5and R 6be preferably carbonatoms more than 1 and the alkyl or aryl of less than 12, be more preferably the alkyl or aryl of carbonatoms more than 3 and less than 10.As carbonatoms more than 1 and the alkyl or aryl of less than 12, be not particularly limited, can enumerate such as: methyl, ethyl, propyl group, 1-methylethyl, butyl, 1-methyl-propyl, 1,1-dimethyl ethyl, amyl group, hexyl, 2-methyl amyl, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl, 2-ethyl-4-methyl amyl, 2-propylheptyl, 2-ethyl-5-Methyl Octyl, octyl group, nonyl, decyl, phenyl, naphthyl etc.Among those, preferred butyl, 1-methyl-propyl, 2-methyl amyl and 2-ethylhexyl.
In the present embodiment, the synthetic method of (A-1) is not particularly limited, such as can by making formula R 2mgX 1or formula R 2 2mg (R 2implication the same, X 1for halogen atom) organo-magnesium compound that represents and formula M 1r 3 nor M 1r 3 (n-1)h (M 1, R 3the same with the implication of n) organometallic compound that represents more than 25 DEG C and less than 150 DEG C reactions, then makes formula Y as required in unreactive hydrocarbons solvent 1-H (Y 1implication the same) compound that represents reaction or make that there is Y 1the organo-magnesium compound of the functional group represented and/or organo-aluminium compound reaction are synthesized.Among those, the organo-magnesium compound and the formula Y that dissolve in unreactive hydrocarbons solvent is made 1during the compound reaction that-H represents, the order for reaction is not particularly limited, and can be used in adding type Y in organo-metallic magnesium compound 1the method of the compound that-H represents, at formula Y 1any one method in the method for adding organo-magnesium compound in the compound that-H represents or the method that both are added simultaneously.
(A-1) Y in 1be 0≤c/ (alpha+beta)≤2 relative to the scope of the molar composition ratio c/ (alpha+beta) of whole atoms metal, be preferably 0≤c/ (alpha+beta) <1.Pass through Y 1be less than 2 relative to the molar composition ratio of whole atoms metal, there is the tendency that (A-1) improves with the reactivity of (A-2).
(A-2) titanium compound for being represented by formula 2.
(A-2): Ti (OR 7) dx 1 (4-d)formula 2
(in formula 2, d is the real number of more than 0 and less than 4, R 7for carbonatoms more than 1 and the alkyl of less than 20, X 1for halogen atom)
D is preferably more than 0 and the real number of less than 1, is more preferably 0.
As R 7represent carbonatoms more than 1 and the alkyl of less than 20, be not particularly limited, can enumerate such as: the aliphatic groups such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, 2-ethylhexyl, heptyl, octyl group, decyl, allyl group; The alicyclic hydrocarbon radicals such as cyclohexyl, 2-methylcyclohexyl, cyclopentyl; The aryl radical such as phenyl, naphthyl etc.Among those, preferred fat alkyl.
As X 1the halogen represented, can enumerate: chlorine, bromine, iodine etc.Among those, preferred chlorine.
In present embodiment, (A-2) is preferably titanium tetrachloride.In present embodiment, as (A-2), two or more may be used in combination.
(A-1) preferably carry out in unreactive hydrocarbons solvent with the reaction of (A-2), more preferably carry out in the aliphatic solvents such as hexane, heptane.About the mol ratio of (A-1) and (A-2) in above-mentioned reaction, be not particularly limited, (A-2) mol ratio (Ti/Mg) of Mg atom contained in Ti atom contained in and (A-1) is preferably more than 0.1 and less than 10, and more preferably more than 0.3 and less than 3.
About temperature of reaction, be not particularly limited, such as, be more than-80 DEG C and the scope of less than 150 DEG C, be preferably the scope of-40 DEG C ~ 100 DEG C.
And the order of addition of (A-2) (A-1), be not particularly limited, can be any one method of adding (A-2) after (A-1), adding (A-1) after (A-2), (A-1) and (A-2) is added simultaneously, preferably (A-1) and (A-2) be added simultaneously.
In addition, about the interval of adding (A-1) and (A-2), be not particularly limited, any one method of add continuously, adding off and on can, preferably with more than 3 minutes and the cycle of less than 20 minutes add off and on, more preferably with more than 5 minutes and the cycle of less than 15 minutes add off and on.About time of (A-1) and (A-2) of interpolation, be not particularly limited, preferably more than 1 hour and less than 10 hours, more preferably more than 2 hours and less than 5 hours.About the time by (A-1) and (A-2) slaking, be not particularly limited, preferably carried out in the scope of less than 10 hours more than 1 hour, more preferably more than 2 hours and less than 5 hours.By carrying out the reaction of (A-1) and (A-2) in above-mentioned mode, can the avtive spot of dispersed catalyst more equably, and then the gathering of the avtive spot in solid catalyst can be suppressed.Therefore, the growth of polymer chain can not locally occur, polymer chain is covered in whole solid catalyst surface, thus obtains the little polyethylene powders of pore volume, obtains having concave-convex surface and inhibits the polyethylene powders with suitable specific surface area of internal voids.
In present embodiment, preferably after (A-1) with the reaction of (A-2), remove unreacted (A-1) and (A-2).By removing unreacted (A-1) and (A-2), the generation of the polymkeric substance of the indefinite shapes such as block can be suppressed or adhere on reactor wall or block to extract pipeline etc., there is the tendency that continuous seepage is excellent.In order to remove unreacted (A-1) and (A-2), can by repeating to extract supernatant liquor out under the state of catalyst pulp sedimentation and the operation adding new unreactive hydrocarbons solvent reduces.In addition, also can be removed by the filtration of strainer etc.Preferably, the concentration of residual chlorine deriving from (A-2) is adjusted to 1 mmole/below L.
In present embodiment, can be used to use the form of the pulp solution of unreactive hydrocarbons solvent by the above-mentioned solid catalyst component [A] be obtained by reacting.
As another example of the Ziegler-Natta catalyst composition used in present embodiment, the catalyst for olefines polymerizing etc. comprising solid catalyst component [C] and organometallic compound composition [B] can be enumerated, the carrier (C-3) that solid catalyst component [C] is reacted by the chlorizating agent (C-2) represented in the organo-magnesium compound (C-1) dissolving in unreactive hydrocarbons solvent making formula 3 represent and formula 4 and prepares is gone up the organo-magnesium compound (C-4) dissolving in unreactive hydrocarbons solvent that load type 1 represents and the titanium compound (C-5) that formula 2 represents and manufactures.
(C-1): (M 2) γ(Mg) δ(R 8) e(R 9) f(OR 10) gformula 3
(in formula 3, M 2for belonging to by the atoms metal of the group of the periodic table of elements the 12nd race, the 13rd race and the 14th group composition, R 8, R 9and R 10be the alkyl of carbonatoms more than 1 and less than 20 separately, γ, δ, e, f and g are the real number meeting following relation.0≤γ, 0< δ, 0≤e, 0≤f, 0≤g, 0<e+f, 0≤g/ (γ+δ)≤2, (wherein, k represents M to k γ+2 δ=e+f+g 2valence))
(C-2): H hsiCl ir 11 (4-(h+i))formula 4
(in formula 4, R 11for carbonatoms more than 1 and the alkyl of less than 12, h and i is the real number meeting following relation.0<h、0<i、0<h+i≤4)
(C-4): (M 1) α(Mg) β(R 2) a(R 3) by 1 cformula 1
(in formula 1, M 1for belonging to by the atoms metal of the group of the periodic table of elements the 12nd race, the 13rd race and the 14th group composition, R 2and R 3for carbonatoms more than 2 and the alkyl of less than 20, Y 1for alkoxyl group, siloxy, allyloxy, amino, amide group ,-N=C-R 4r 5,-SR 6, beta-keto acid residue (wherein, R 4, R 5and R 6represent carbonatoms more than 1 and the alkyl of less than 20.When c is 2, Y 1separately can be different.), α, β, a, b and c are the real number meeting following relation.0≤α, 0 < β, 0≤a, 0≤b, 0≤c, 0 < a+b, 0≤b/ (alpha+beta)≤2, (wherein, n represents M to n α+2 β=a+b+c 1valence))
(C-5): Ti (OR 7) dx 1 (4-d)formula 2
(in formula 2, d is the real number of more than 0 and less than 4, R 7for carbonatoms more than 1 and the alkyl of less than 20, X 1for halogen atom)
In the present embodiment, as (C-4), the organo-magnesium compound same with (A-1) can be used, as (C-5), the titanium compound same with (A-2) can be used.About the formula 1 in (C-4) and (C-5) and formula 2, as above about as described in (A-1) and (A-2).
(C-1) although represent with the form of the organic-magnesium complex compound dissolving in unreactive hydrocarbons solvent, the complex compound of all dialkyl magnesium compounds and this compound and other metallic compound is comprised.Relational expression k γ+2 δ=e+f+g of symbol γ, δ, e, f and g of formula 3 represents the valence of atoms metal and substituent stoichiometry.
In formula 3, as R 8and R 9represent carbonatoms more than 1 and the alkyl of less than 20, be not particularly limited, can enumerate such as: alkyl, cycloalkyl or aryl, specifically can enumerate: methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, phenyl etc.Among those, alkyl is preferably.
In formula 3, when α >0, as atoms metal M 2as long as, belong to by the atoms metal of the group of the periodic table of elements the 12nd race, the 13rd race and the 14th group composition, be just not particularly limited, can enumerate such as: zinc, boron, aluminium etc.Among those, preferred aluminium, zinc.Magnesium and atoms metal M 2ratio δ/γ, be not particularly limited, be preferably more than 0.1 and less than 30, be more preferably more than 0.5 and less than 10.
In formula 3, when γ=0, R 8and R 9be preferably any a group in group (4) shown below, group (5), group (6) three groups.
Group (4): R 8and R 9at least one be carbonatoms more than 4 and the secondary alkyl of less than 6 or tertiary alkyl, preferred R 8and R 9be carbonatoms more than 4 and the alkyl of less than 6 and at least one is for secondary alkyl or tertiary alkyl.
Group (5): R 8and R 9for the alkyl that carbonatoms is mutually different, more preferably R 8for alkyl, the R of carbonatoms 2 or 3 9for the alkyl of carbonatoms more than 4.
Group (6): R 8and R 9at least one be the alkyl of carbonatoms more than 6, more preferably R 8and R 9in contained carbonatoms sum be the alkyl of more than 12.
As the carbonatoms more than 4 in group (1) and the secondary alkyl of less than 6 or tertiary alkyl, be not particularly limited, can enumerate such as: 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl, 2-methyl butyl, 2-ethyl propyl, 2,2-dimethyl propyl, 2-methyl amyl, 2-ethyl-butyl, 2,2-dimethylbutyls, 2-methyl-2-ethyl propyl etc.Among those, preferred 1-methyl-propyl.
In formula 3, when γ=0, such as R 8when for 1-methyl-propyl etc., dissolve in unreactive hydrocarbons solvent, such compound also can bring preferred result to present embodiment.
As the alkyl of the carbonatoms 2 or 3 in group (2), be not particularly limited, can enumerate such as: ethyl, 1-methylethyl, propyl group etc.Among those, preferred ethyl.
As the alkyl of carbonatoms more than 4, be not particularly limited, can enumerate such as: butyl, amyl group, hexyl, heptyl, octyl group etc.Among those, preferred butyl, hexyl.
As the alkyl of the carbonatoms more than 6 in group (3), be not particularly limited, can enumerate such as: hexyl, heptyl, octyl group, nonyl, decyl, phenyl, 2-naphthyl etc.Among those, preferred alkyl, in alkyl, more preferably hexyl, octyl group.
Generally speaking, when carbonatoms contained in alkyl increases, there is the tendency be easily dissolved in unreactive hydrocarbons solvent, and the tendency that the viscosity with solution increases.Therefore, operationally consider, preferably use the alkyl of the long-chain of appropriateness.(C-1) can use with after unreactive hydrocarbons solvent dilution, but even if in this solution containing or the lewis base property compound such as ether, ester, amine of residual minim also can allow to use.
In formula 3, as R 10the carbonatoms more than 1 represented and the alkyl of less than 20, preferred carbonatoms more than 1 and the alkyl or aryl of less than 12, more preferably carbonatoms more than 3 and the alkyl or aryl of less than 10.
As carbonatoms more than 1 and the alkyl of less than 20, be not particularly limited, can enumerate such as: methyl, ethyl, propyl group, 1-methylethyl, butyl, 1-methyl-propyl, 1,1-dimethyl ethyl, amyl group, hexyl, 2-methyl amyl, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl, 2-ethyl-4-methyl amyl, 2-propylheptyl, 2-ethyl-5-Methyl Octyl, octyl group, nonyl, decyl, phenyl, naphthyl etc.Among those, preferred butyl, 1-methyl-propyl, 2-methyl amyl and 2-ethylhexyl.
In present embodiment, the synthetic method of (C-1) is not particularly limited, such as, preferably make formula R 8mgX 1or formula R 8 2mg (R 8implication the same, X 1for halogen atom) organo-magnesium compound that represents and formula M 2r 9 kor formula M 2r 9 (k-1)h (M 2, R 9the same with the implication of k) organometallic compound that represents reacts at the temperature of less than 150 DEG C in unreactive hydrocarbons solvent more than 25 DEG C, as required then with there is R 9(R 9implication the same) alcohol of alkyl that represents or dissolve in unreactive hydrocarbons solvent there is R 9the method of the alkoxyl magnesium compound of the alkyl represented and/or alkoxy aluminum compound reaction.Among those, make to dissolve in the organo-magnesium compound of unreactive hydrocarbons solvent and alcohol when reacting, order for reaction is not particularly limited, and can be used in organo-magnesium compound any one method in the method for adding alcohol, the method for adding organo-magnesium compound in alcohol or the method for both simultaneously being added.
About the reactive ratio of organo-magnesium compound and alcohol, be not particularly limited, the result of reaction is obtained is 0≤g/ (γ+δ)≤2 containing alkoxyl group in alkoxyl group organo-magnesium compound relative to the molar composition ratio g/ (γ+δ) of whole atoms metal, is preferably 0≤g/ (γ+δ) <1.
(C-2) represented, have the silicon chloride compound of at least one Si-H key by formula 4.
(C-2): H hsiCl ir 11 (4-(h+i))formula 4
(in formula 4, R 11for carbonatoms more than 1 and the alkyl of less than 12, h and i is the real number meeting following relation.0<h、0<i、0<h+i≤4)
In formula 4, R 11represent carbon atom more than 1 and the alkyl of less than 12 be not particularly limited, can enumerate such as: aliphatic group, alicyclic hydrocarbon radical, aryl radical, specifically can enumerate: methyl, ethyl, propyl group, 1-methylethyl, butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, phenyl etc.Among those, preferred carbonatoms more than 1 and the alkyl of less than 10, the more preferably alkyl of the carbonatoms 1 ~ 3 such as methyl, ethyl, propyl group, 1-methylethyl.In addition, h and i be the relation meeting h+i≤4 be greater than 0 real number, preferred i is the real number of more than 2 and less than 3.
As (C-2), be not particularly limited, specifically can enumerate: HSiCl 3, HSiCl 2cH 3, HSiCl 2c 2h 5, HSiCl 2(C 3h 7), HSiCl 2(2-C 3h 7), HSiCl 2(C 4h 9), HSiCl 2(C 6h 5), HSiCl 2(4-Cl-C 6h 4), HSiCl 2(CH=CH 2), HSiCl 2(CH 2c 6h 5), HSiCl 2(1-C 10h 7), HSiCl 2(CH 2cH=CH 2), H 2siCl (CH 3), H 2siCl (C 2h 5), HSiCl (CH 3) 2, HSiCl (C 2h 5) 2, HSiCl (CH 3) (2-C 3h 7), HSiCl (CH 3) (C 6h 5), HSiCl (C 6h 5) 2deng.Among those, preferred HSiCl 3, HSiCl 2cH 3, HSiCl (CH 3) 2, HSiCl 2(C 3h 7), more preferably HSiCl 3, HSiCl 2cH 3.In the present embodiment, as (C-2), two or more may be used in combination.
When the reaction of (C-1) and (C-2), preferably use unreactive hydrocarbons solvent in advance; The hydrochloric ethers such as 1,2-ethylene dichloride, orthodichlorobenzene, methylene dichloride; The ether solvent such as ether, tetrahydrofuran (THF); Or their mixed solvent uses after (C-2) dilution.Among those, consider from the aspect of performance of catalyzer, more preferably unreactive hydrocarbons solvent.
For (C-1) reactive ratio with (C-2), be not particularly limited, (C-2) Siliciumatom contained in is preferably more than 0.01 mole and less than 100 moles relative to magnesium atom 1 mole contained in (C-1), is more preferably more than 0.1 mole and less than 10 moles.
For (C-1) reaction method with (C-2), be not particularly limited, can use (C-1) and (C-2) is imported reactor simultaneously and the method for adding while carrying out reacting, (C-2) is dropped into reactor in advance after (C-1) is imported reactor method or any one method of after (C-1) is dropped into reactor in advance, (C-2) being imported in the method for reactor.Among those, after preferably (C-2) being dropped into reactor in advance, (C-1) is imported the method for reactor.The carrier (C-3) be obtained by reacting by this, preferably after being separated by filtration or decantation, uses unreactive hydrocarbons solvent fully to clean to remove unreacted reactant or by product etc.
For the temperature of reaction of (C-1) and (C-2), be not particularly limited, such as, be more than 25 DEG C and less than 150 DEG C, preferably more than 30 DEG C and less than 120 DEG C, more preferably more than 40 DEG C and less than 100 DEG C.(C-1) and (C-2) is being imported reactor simultaneously and in the method for adding while carrying out reacting, preferably by advance the temperature of reactor being adjusted to specified temperature, while adding, the temperature in reactor is adjusted to specified temperature simultaneously, thus temperature of reaction is adjusted to specified temperature.After (C-2) is dropped into reactor in advance, (C-1) is imported in the method for reactor, specified temperature is adjusted to preferably by input there being the temperature of the reactor of (C-2), while (C-1) is imported reactor, the temperature in reactor is adjusted to specified temperature, thus temperature of reaction is adjusted to specified temperature.After (C-1) is dropped into reactor in advance, (C-2) is imported in the method for reactor, specified temperature is adjusted to preferably by input there being the temperature of the reactor of (C-1), while (C-2) is imported reactor, the temperature in reactor is adjusted to specified temperature, thus temperature of reaction is adjusted to specified temperature.
About the usage quantity of (C-4), magnesium atom contained in (C-4) is preferably more than 0.1 relative to the mol ratio of titanium atom contained in (C-5) and less than 10, is more preferably more than 0.5 and less than 5.
About (C-4) temperature of reaction with (C-5), be not particularly limited, such as, be more than-80 DEG C and less than 150 DEG C, be preferably more than-40 DEG C and less than 100 DEG C.
Concentration when using about (C-4), is not particularly limited, such as with titanium atom contained in (C-4) for benchmark, for more than 0.1mol/L and below 2mol/L, be preferably more than 0.5mol/L and below 1.5mol/L.(C-4) preferably unreactive hydrocarbons solvent is used in dilution.
The order of adding (C-4) and (C-5) in (C-3) is not particularly limited, can for any one method of adding (C-5) afterwards at (C-4), adding (C-4) afterwards, (C-4) and (C-5) added at (C-5) simultaneously.Among those, preferably by method that (C-4) and (C-5) adds simultaneously.(C-4) carry out in unreactive hydrocarbons solvent with the reaction of (C-5), preferably use the aliphatic solvents such as hexane, heptane as unreactive hydrocarbons solvent.
About the interval of adding (C-4) and (C-5), be not particularly limited, any one the method for add continuously, adding off and on can, preferably with more than 3 minutes and the cycle of less than 20 minutes add off and on, more preferably with more than 5 minutes and the cycle of less than 15 minutes add off and on.About time of (C-4) and (C-5) of interpolation, be not particularly limited, preferably more than 1 hour and less than 10 hours, more preferably more than 2 hours and less than 5 hours.About the time by (C-4) and (C-5) slaking, be not particularly limited, preferably more than 1 hour and less than 10 hours, more preferably more than 2 hours and less than 5 hours.Can be used to use the form of the pulp solution of unreactive hydrocarbons solvent by the above-mentioned catalyzer be obtained by reacting.
About the usage quantity of (C-5), be not particularly limited, with the molar ratio computing relative to magnesium atom contained in carrier (C-3), be preferably more than 0.01 and less than 20, be more preferably more than 0.05 and less than 10.
About the temperature of reaction of (C-5), be not particularly limited, such as, be more than-80 DEG C and less than 150 DEG C, be preferably more than-40 DEG C and less than 100 DEG C.In present embodiment, be not particularly limited in the method for (C-3) upper load (C-5), the method that (C-5) excessive relative to (C-3) can be used to react, by use the 3rd composition the method for load effectively (C-5), carry out the method for load preferably by the reaction of (C-5) and organo-magnesium compound (C-4).
The ziegler natta catalyst used in present embodiment, by solid catalyst component (A) or solid catalyst component (C) being combined with organometallic compound composition [B], and becomes highly active catalyst for polymerization.Organometallic compound composition [B] is sometimes referred to as " promotor ".
As organometallic compound composition [B], be not particularly limited, can enumerate such as: containing the compound etc. belonged to by the metal of the group of the periodic table of elements the 1st race, the 2nd race, the 12nd race and the 13rd group composition.Among those, machine aluminium compound and/or organo-magnesium compound is preferably had.
As organo-aluminium compound, be preferably used alone or as a mixture the compound that formula 5 represents.
AlR 12 kz 1 (3-j)formula 5
(in formula 5, R 12for carbonatoms more than 1 and the alkyl of less than 20, Z 1for hydrogen, halogen, alkoxyl group, allyloxy, siloxy, j is the real number of more than 2 and less than 3.)
In formula 5, as R 12represent carbonatoms more than 1 and the alkyl of less than 20 be not particularly limited, can enumerate such as: aliphatic group, aryl radical, alicyclic hydrocarbon radical etc.
As the compound that formula 5 represents, be not particularly limited, can enumerate such as: the trialkyl aluminium compound such as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three (2-methyl-propyl) aluminium (also referred to as triisobutyl aluminium), three amyl group aluminium, three (3-methyl butyl) aluminium, three hexyl aluminium, trioctylaluminum, three decyl aluminium; The aluminum halide compounds such as diethyl aluminum chloride, ethylaluminum dichloride, two (2-methyl-propyl) aluminum chloride, ethyl aluminium sesquichloride, diethyl aluminum bromide; The alkoxy aluminum compounds such as diethylaluminum ethoxide, two (2-methyl-propyl) butoxy aluminium; The siloxy aluminum compounds etc. such as dimethyl hydrogen siloxy dimethyl aluminium, ethyl-methyl hydrogen siloxy diethyl aluminum, ethyl dimethylsilyl bis diethyl aluminum.Among those, preferred trialkyl aluminium compound.
As organo-magnesium compound, be preferably used alone or as a mixture as the organo-magnesium compound dissolving in unreactive hydrocarbons solvent represented by formula 3 shown in (C-1).
(M 2) γ(Mg) δ(R 8) e(R 9) f(OR 10) gformula 3
(in formula 3, M 2for belonging to by the atoms metal of the group of the periodic table of elements the 12nd race, the 13rd race and the 14th group composition, R 8, R 9and R 10be the alkyl of carbonatoms more than 2 and less than 20 separately, γ, δ, e, f and g are the real number meeting following relation.0≤γ, 0< δ, 0≤e, 0≤f, 0≤g, 0<e+f, 0≤g/ (γ+δ)≤2, (wherein, k represents M to k γ+2 δ=e+f+g 2valence))
As the organo-magnesium compound of organometallic compound composition [B], with as identical in the organo-magnesium compound represented by formula 3 as described in as (C-1), but the solvability of this organo-magnesium compound in unreactive hydrocarbons solvent is more high better, therefore preferred beta/alpha is in the scope of 0.5 ~ 10, in addition, more preferably M 2for the compound of aluminium.
About the method in polymerization system solid catalyst component [A] or solid catalyst component [C] and organometallic compound composition [B] added under polymerizing condition, be not particularly limited, both can be added in polymerization system respectively, add in polymerization system after also can making both reactions in advance.In addition, both ratios for combination are not particularly limited, and relative to solid catalyst component 1g, organometallic compound composition is preferably more than 1 mmole and below 3000 mmoles.
In present embodiment, the polymerization process in the manufacture method of polyethylene powders can be enumerated: the method etc. ethene or the monomer (being total to) containing ethene being polymerized by suspension polymerization or gaseous polymerization.Wherein, the suspension polymerization of heat of polymerization can preferably effectively be removed.In suspension polymerization, unreactive hydrocarbons medium can be used as medium, in addition, alpha-olefin itself also can use as solvent.
As unreactive hydrocarbons medium, be not particularly limited, can enumerate such as: the aliphatic hydrocarbons such as propane, butane, Trimethylmethane, pentane, iso-pentane, hexane, heptane, octane, decane, dodecane, kerosene; The alicyclic hydrocarbon such as pentamethylene, hexanaphthene, methylcyclopentane; The aromatic hydrocarbon such as benzene,toluene,xylene; The halohydrocarbon such as ethylene dichloride, chlorobenzene, methylene dichloride; Or their mixture etc.
Polymerization temperature in the manufacture method of polyethylene powders is not particularly limited, such as, be more than 30 DEG C and less than 100 DEG C, is preferably more than 35 DEG C and less than 90 DEG C, is more preferably more than 40 DEG C and less than 80 DEG C.If polymerization temperature is more than 30 DEG C, then can industrially effectively manufacture.If polymerization temperature is less than 100 DEG C, then can steady running continuously.
Polymerization pressure in the manufacture method of polyethylene powders is not particularly limited, from the view point of the specific surface area of polyethylene powders, pore volume, median size, viscosity-average molecular weight and camber, such as be more than 0.1MPa and below 1.0MPa, be preferably more than 0.1MPa and below 0.8MPa, more preferably more than 0.1MPa and below 0.5MPa.
Polyreaction in the manufacture method of polyethylene powders can be undertaken by any one method in intermittent type, semi continuous, continous way, is polymerized preferably by continous way.By ethylene gas, solvent, catalyzer etc. to be supplied to continuously in polymerization system and to discharge continuously together with ethene (being total to) polymkeric substance generated, can suppress the local high-temperature state that the reaction of violent ethene causes, polymerization system is more stable.In addition, be preferred by being supplied to that the ethylene gas before polymerization reactor, solvent, catalyzer etc. supply with the temperature identical with in reactor, this is because make in system stable equally.In addition, when ethene reacts under uniform state in system, can suppress in polymer chain, to generate side chain, double bond etc., can also suppress by the decomposition of ethene (being total to) polymkeric substance, the crosslinked and surface deformation etc. of polyethylene powders that causes.Therefore, become in preferred polymeric system evenly continous way.More than two stages that can reaction conditions is divided into different polymerization carry out.
By adding hydrogen as chain-transfer agent in polymerization system, can by molecular weight control in suitable scope, the method is recorded in Deutsches Reichs-Patent application and discloses in No. 3127133 specification sheets.By adding hydrogen in polymerization system, except controlling except molecular weight, can also promoting catalyst chain tra nsfer and suppress aggregation growth, thus the growth of polymer chain sharply can be suppressed, prevent the generation of the particle be out of shape.When adding hydrogen in polymerization system, the molar fraction of hydrogen is preferably more than 0 % by mole and less than 30 % by mole, is more preferably more than 3 % by mole and less than 25 % by mole, more preferably more than 5 % by mole and less than 20 % by mole.
In addition, from the view point of the specific surface area of polyethylene powders, pore volume and camber, after preferably making hydrogen and catalyst exposure in advance, import pipeline from catalyzer and add in polymerization system.Just catalyzer being imported to after in polymerization system, the catalyst concn imported near pipeline outlet is high, ethene reacts tempestuously, the possibility becoming local high-temperature state thus improves, but contacted before importing in polymerization system with catalyzer by making hydrogen, the initial activity of catalyzer can be suppressed, also can suppress due to being polymerized as the change in shape of the polymerization initial stage particle shape of the polyethylene powders of the condition of high temperature sharply.
Method for deactivating for the synthesis of the ziegler natta catalyst of polyethylene powders is not particularly limited, and is preferably undertaken after polyethylene powders and separated from solvent.By with separated from solvent after import medicament for making catalyst deactivation, residual low molecular weight compositions can be reduced in solvent, and suppresses the low molecular composition fusing in the particle that caused by the reaction heat of inactivation and block the distortion of the particle surfaces such as the hole of particle surface.
During separated from solvent operation, liquid holdup residual in polyethylene slurry, from the view point of specific surface area and the camber of polyethylene powders, be preferably more than 10 % by weight and less than 60 % by weight, be more preferably more than 15 % by weight and less than 55 % by weight, more preferably more than 20 % by weight and less than 50 % by weight.When liquid holdup is less than 10 % by weight, the particle surface tension force of polyethylene powders becomes large, and in catalyst deactivation operation, inactivating agent becomes difficulty to the infiltration of particle, and the possibility that inactivation inequality occurs increases.When liquid holdup is greater than 60 % by weight, polyethylene powders residual low molecular weight composition increases, and therefore melting position increases, and result produces the shape distortion of powder.
As the reagent making catalyst system inactivation, be not particularly limited, can enumerate such as: oxygen, water, alcohols, glycols, phenols, carbon monoxide, carbonic acid gas, ethers, carbonyl compound, alkynes class etc.
Drying temperature in the manufacture method of polyethylene powders is not particularly limited, from the view point of the specific surface area of polyethylene powders, pore distribution and camber, such as be more than 50 DEG C and less than 150 DEG C, be preferably more than 50 DEG C and less than 140 DEG C, be more preferably more than 50 DEG C and less than 130 DEG C.
If drying temperature is more than 50 DEG C, then can be effectively dry.If drying temperature is less than 150 DEG C, then can carry out drying under ethene suppressing polymer unwinds, crosslinked state.In addition, when drying temperature is more than 150 DEG C, polyethylene powders surface melting, thus surface hole avalanche or diminish.In addition, while surface melting, the particle of polyethylene powders collides each other and is transferred, and thus the concavo-convex of particle surface also can homogenizing, thus close to proper sphere shape, therefore generate surface blocking, solvent is difficult to penetrate into inner polyethylene powders.
[purposes]
The polyethylene powders of present embodiment can be processed by various working method.The molding using polyethylene powders to obtain may be used for various uses.Such as, the molding that obtains of polyethylene powders is used to be suitable as secondary battery membrane microporous membrane, wherein especially lithium ion secondary battery membrane microporous membrane, high strength fibre, gel spinning etc.
As the manufacture method of microporous membrane, specifically can enumerate: in the damp process using solvent, utilize there is T-shaped die head forcing machine through extruding, stretching, extract, dry working method.The polyethylene powders solvability in a solvent of present embodiment is excellent, therefore can be suitable as battery diaphragm microporous membrane and use.Secondary battery membrane, particularly lithium ion secondary battery membrane that it is representative that such microporous membrane can be suitable for lithium-ion secondary cell, lead storage battery.Using molding, lithium ion secondary battery membrane etc. that polyethylene powders obtains in the present embodiment, can be the molding containing polyethylene powders, lithium ion secondary battery membrane etc.
Embodiment
Below, by using embodiment and comparative example, the present invention will be described in more detail, and the present invention is not by the following any restriction of embodiment.In addition, the evaluation method used in the present embodiment and measuring method as follows.
(1) specific surface area of being tried to achieve by BET method
Use the AUTOSOBE 3MP measurement the specific area that Yuasa-ionics company manufactures.As pre-treatment, polyethylene powders 1g is put into sample tube, with sample pretreating device 80 DEG C, under the condition of below 0.01mmHg, carry out heat de-airing 12 hours.Subsequently, nitrogen is used to measure according to BET method under the condition measuring temperature-196 DEG C as adsorbed gas.
(2) pore volume of being tried to achieve by mercury penetration method and pore distribution
As mercury porosimeter, use Autopore IV 9500 type that company of Shimadzu Seisakusho Ltd. manufactures, measure pore volume and pore distribution.As pre-treatment, polyethylene powders 0.5g is put into sample tube, after the degassed drying of low pressure determination part normal temperature, mercury is filled in sample receiver.Pressurize (high-voltage section) lentamente, by the hole of mercury pressing in sample.
Pressure condition is set as follows.
Low voltage section: with 69Pa (0.01psia) with N 2air pressure measures, high-voltage section: 21 ~ 228MPa (3000 ~ 33000pisa)
(3) viscosity-average molecular weight (Mv)
About the viscosity-average molecular weight (Mv) of polyethylene powders, according to ISO1628-3 (2010), obtained by method shown below.First, in melting tube, weigh polyethylene powders 20mg, melting tube is carried out nitrogen replacement, then add 20mL naphthane (being added with 2,6 di tert butyl 4 methyl phenol 1g/L), stir 2 hours at 150 DEG C, polyethylene powders is dissolved.This solution is used in the thermostatic bath of 135 DEG C Cannon-Fenske viscometer (Chai Tian instruments for scientific research industrial manufactures, goods model-100), measure the lowering time (t between graticule s).Similarly, for by polyethylene powders quantitative change being the lowering time (t that sample that 10mg, 5mg, 2mg obtain similarly measures between graticule s).As blank, do not add polyethylene powders, measure the lowering time (t of independent naphthane b).By the reduced viscosity (η of polyethylene powders obtained according to following formula sp/ C) map respectively, derive the reduced viscosity (η of concentration (C) (unit: g/dL) and polyethylene powders sp/ C) linear equation, and obtain the limiting viscosity ([η]) being extrapolated to concentration 0.
η sp/ C=(t s/ t b-1)/0.1 (unit: dL/g)
Then, use following mathematical expression A, use the value of above-mentioned limiting viscosity [η], calculate viscosity-average molecular weight (Mv).
Mv=(5.34 × 10 4) × [η] 1.49mathematical expression A
(4) median size
The median size of polyethylene powders, use 10 kinds of sieves (aperture: 710 μm, 500 μm, 425 μm, 355 μm, 300 μm, 212 μm, 150 μm, 106 μm, 75 μm, 53 μm) of JIS Z8801 regulation, in the integrated curve obtained by integration side large from aperture for the weight of polyethylene powders residual on each sieve obtained when classification 100g polyethylene powders, will the particle diameter of weight of 50% be reached as median size.
(5) camber (UD)
For camber (UD), the dynamic image method size-grade distribution particle shape evaluating apparatus QICPIC using Japanese laser (Japan laser) company to manufacture.Utilize air-flowing type dry dispersion device to disperse sample, continuously the image of shooting record dispersed particle, use image analysis software to measure according to the graphic information of record.
Specimen Determination condition is set as follows.
Air dispersion device: RODOS tM
Compressed air dispersive pressure: 1.0bar
Analytical model: EQPC (being equivalent to the diameter of the area of a circle)
Analyst coverage: M6 (minimum pixel is 5 μm)
The shadow area of the object particle obtained is set to A, when the shadow area that the envelope curve of the protuberance by connecting object particle surrounds is set to A+B, using the UD that represented by following formula (1) camber as particle.
UD＝A/(A+B) (1)
(6) titaniferous amount
Use microwave decomposition device (model ETHOS TC, マ イ Le ス ト ー Application ゼ ネ ラ Le (Milestone General) company manufactures) polyethylene powders pressurization is decomposed, utilize marker method, utilize ICP-MS (inductivity coupled plasma mass spectrometry device, model X series of X 7, Sai Mo flies your science and technology (Thermo Fisher Scientific) company of generation and manufactures) measure titanium elements concentration in polyethylene powders, as titaniferous amount.
(7) solvability evaluation
Using polyethylene powders 14g, tetramethylolmethane four [3-(3 as antioxidant, 5-di-tert-butyl-hydroxy phenyl) propionic ester] mixture of 0.4g and whiteruss (P-350 that Song Cun oil company manufactures) 36g puts in small-sized mixing roll (LABPLASTOMILL30C150 that TOYOSEIKI company manufactures), 200 DEG C, carry out under the condition of screw speed 50rpm mixing.Be implement under two kinds of conditions for 2 minutes and 10 minutes at mixing time.These mixing things are clipped between metal sheet and carry out hot pressing to thickness 1mm with compressing forming machine (refreshing rattan metal company manufactures SFA-37) at 190 DEG C, after forming sheet, form gel sheet 25 DEG C of quenchings.
After biaxial stretcher is stretched to 7 × 7 times while of use at 120 DEG C by this gel sheet, use dichloromethane extraction removing whiteruss, then dry.Then under the condition of 125 DEG C, 3 minutes, carry out heat setting type and obtain microporous membrane.About the solvability of polyethylene powders, utilize the foreign matter of more than 50 μm of estimating and counting and existing in the microporous membrane 250mm × 250mm obtained (when with viewed in transmitted light microporous membrane, the stain observed), based on the number that this obtains, utilize following judgement criteria to evaluate.
(solvability judgement criteria)
Zero: foreign matter is less than 1.
△: foreign matter is less than 5.
×: foreign matter is more than 5.
[Production Example]
[preparation of solid catalyst component [A-1]]
1600mL hexane is added in the stainless steel autoclave of 8L after fully carrying out nitrogen replacement.Repeat to add, stop adding and use the composition formula AlMg of titanium tetrachloride hexane solution 800mL and 1mol/L simultaneously adding 1mol/L for 4 hours with the cycle of 5 minutes while 10 DEG C are stirred 5(C 4h 9) 11(OSiH) 2the hexane solution 800mL of the organo-magnesium compound represented.After interpolation, heat up lentamente, continue reaction 1 hour at 10 DEG C.After reaction terminates, removing 1600mL supernatant liquor, with 1600mL hexanes wash five times, prepares solid catalyst component [A-1] thus.Titanium amount contained in this solid catalyst component [A-1] 1g is 3.05 mmoles.
[preparation of solid catalyst component [A-2]]
1600mL hexane is added in the stainless steel autoclave of 8L after fully carrying out nitrogen replacement.Continuously with the composition formula AlMg of titanium tetrachloride hexane solution 800mL and 1mol/L adding 1mol/L for 4 hours simultaneously while 10 DEG C are stirred 5(C 4h 9) 11(OSiH) 2the hexane solution 800mL of the organo-magnesium compound represented.After interpolation, heat up lentamente, continue reaction 1 hour at 10 DEG C.After reaction terminates, removing 1600mL supernatant liquor, with 1600mL hexanes wash five times, prepares solid catalyst component [A-2] thus.Titanium amount contained in this solid catalyst component [A-2] 1g is 3.12 mmoles.
[preparation of solid catalyst component [A-3]]
1600mL hexane is added in the stainless steel autoclave of 8L after fully carrying out nitrogen replacement.Continuously with the composition formula AlMg of titanium tetrachloride hexane solution 800mL and 1mol/L adding 1mol/L for 0.5 hour simultaneously while 10 DEG C are stirred 5(C 4h 9) 11(OSiH) 2the hexane solution 800mL of the organo-magnesium compound represented.After interpolation, heat up lentamente, continue reaction 1 hour at 10 DEG C.After reaction terminates, removing 1600mL supernatant liquor, with 1600mL hexanes wash five times, prepares solid catalyst component [A-3] thus.Titanium amount contained in this solid catalyst component [A-3] 1g is 3.10 mmoles.
[embodiment 1]
(polyvinyl polymerization process)
Hexane, ethene, hydrogen, catalyzer are supplied to continuously and have in the container type 300L polymerization reactor of whipping appts.Polymerization pressure is 0.5MPa.Polymerization temperature remains on 83 DEG C by chuck cooling.Hexane supplies with the bottom of the speed of 40L/ hour from polymerizer.Use solid catalyst component [A-1] and the triisobutyl aluminium as promotor.Solid catalyst component [A-1] is added into polymerizer with the speed of 0.2g/ hour, triisobutyl aluminium with 10 mmoles/hour speed be added into polymerizer.Polyvinyl manufacturing speed is 10kg/ hour.Supplying hydrogen continuously with pump, to make relative to the density of hydrogen of the ethene of gas phase be 14 % by mole.In addition, in order to make hydrogen in advance with catalyst exposure, hydrogen from catalyzer import pipeline supply, ethene supplies from the bottom of polymerizer.Catalyst activity is 80000g-PE/g-solid catalyst component [A-1].Polyethylene slurry is retracted to continuously in the flash distillation post of pressure 0.05MPa, temperature 70 C, makes the liquid level of polymerization reactor keep constant, and by unreacted ethene and Hydrogen Separation.
Then, polyethylene slurry is delivered to continuously separating centrifuge and make the liquid level of polymerization reactor keep constant, polymkeric substance is separated with the solvent etc. beyond it.Be now 45% relative to the liquid holdup of the solvent etc. of polymkeric substance.
Drying is carried out while isolated polyethylene powders carries out nitrogen purging at 85 DEG C.In this drying step, to the powder spray steam after polymerization, implement the inactivation of catalyzer and promotor.In obtained polyethylene powders, add 1500ppm calcium stearate (large day, chemical Inc. made, C60), use Henschel mixer Homogeneous phase mixing.The polyethylene powders obtained uses the sieved sieve in 425 μm, aperture, by the powder removing not by sieve, obtains the polyethylene powders of embodiment 1 thus.
The polyethylene powders obtained in embodiment 1 is measured according to aforesaid method, measures peak maximum value (4) median size in the pore distribution of the pore volume of specific surface area, (2) of (1) being tried to achieve by BET method being tried to achieve by mercury penetration method and pore distribution, (3) viscosity-average molecular weight (Mv), (4) being tried to achieve by mercury penetration method, (5) camber (UD) more than 0.90 and less than 0.95 account for ratio, (7) titaniferous amount of all measuring particle.Show the result in table 1.
In addition about solvability, according to above-mentioned method, evaluate the foreign matter in the microporous membrane that foreign matter in the microporous membrane that (8) obtained by 2 minutes mixing and (9) are obtained by 10 minutes mixing, the results are shown in table 1.
[embodiment 2]
In polymerization process, do not use solid catalyst component [A-1], and use solid catalyst component [A-2], in addition, by operation similarly to Example 1, obtain the polyethylene powders of embodiment 2.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[embodiment 3]
In polymerization process, density of hydrogen is set as 3 % by mole, in addition, by operation similarly to Example 1, obtains the polyethylene powders of embodiment 3.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[embodiment 4]
In drying process, drying temperature is set as 140 DEG C, in addition, by operation similarly to Example 1, obtains the polyethylene powders of embodiment 4.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[comparative example 1]
In polymerization process, do not use solid catalyst component [A-1], and use solid catalyst component [A-3], in addition, by operation similarly to Example 1, obtain the polyethylene powders of comparative example 1.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[comparative example 2]
In drying process, drying temperature is set as 160 DEG C, in addition, by operation similarly to Example 1, obtains the polyethylene powders of comparative example 2.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[comparative example 3]
Before drying process, in the solvent centrifugation be separated polymkeric substance with the solvent etc. beyond it, the liquid holdup of the solvent relative to polymkeric substance etc. is set as 70%, in addition, by operation similarly to Example 1, obtain the ethene polymers powder of comparative example 3.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[comparative example 4]
Polymerization pressure is set as 1.2MPa, in addition, carries out operation similarly to Example 1.Catalyst activity is 120000g-PE/g-solid catalyst component [A-1].Obtain the polyethylene powders of comparative example 4 like this.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
[comparative example 5]
In polymerization process, in order to make hydrogen not in advance with catalyst exposure and be supplied to polymerizer, from the bottom supply hydrogen of polymerizer, in addition, by operation similarly to Example 1, obtain the ethene polymers powder of comparative example 5.The evaluation result of polyethylene powders and microporous membrane is shown in table 1.
Table 1
Industrial applicability
Polyethylene powders of the present invention may be used for lithium ion battery separator, lead storage battery barrier film, high strength fibre, shaping purposes etc.

Claims (6)

1. a polyethylene powders, described polyethylene powders
The specific surface area of being tried to achieve by BET method is 0.10m 2/ more than g and 0.30m 2/ below g,
The pore volume of being tried to achieve by mercury penetration method be below 0.85mL/g and
Viscosity-average molecular weight (Mv) is more than 100,000 and less than 1,000,000.
2. polyethylene powders as claimed in claim 1, wherein, in the pore distribution of being tried to achieve by mercury penetration method, in aperture, less than 30 μm do not exist maximum value.
3. polyethylene powders as claimed in claim 1 or 2, the median size of described polyethylene powders is 1 ~ 200 μm, and total more than 60% of population that measures has the form that the camber (UD) defined by formula (1) is more than 0.90 and less than 0.95;
UD＝A/(A+B) (1)
In formula (1), the shadow area of A indicated object particle, A+B represents the shadow area of being surrounded by the envelope curve of the protuberance of connecting object particle.
4. the polyethylene powders according to any one of claims 1 to 3, it contains more than 1ppm and the titanium of below 200ppm.
5. the polyethylene powders according to any one of Claims 1 to 4, it is for secondary battery membrane.
6. the polyethylene powders according to any one of Claims 1 to 5, it is for lithium ion secondary battery membrane.
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