CN103540020B - A kind of Production method of lithium ion battery barrier membrane homo-polypropylene special material - Google Patents

A kind of Production method of lithium ion battery barrier membrane homo-polypropylene special material Download PDF

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CN103540020B
CN103540020B CN201310519301.0A CN201310519301A CN103540020B CN 103540020 B CN103540020 B CN 103540020B CN 201310519301 A CN201310519301 A CN 201310519301A CN 103540020 B CN103540020 B CN 103540020B
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lithium ion
ion battery
donor
special material
polypropylene
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CN103540020A (en
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曹豫新
况成承
梁万军
张锋
周宝森
王胜利
薛正伟
侯卫峰
徐剑虹
张双萍
汪东华
毛健康
李中新
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China Petroleum and Chemical Corp
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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of lithium ion battery homopolypropylene to obstruct film special material production method.The present invention uses the moderate catalyst for polymerization of propylene of high activity, hydrogen response.Propylene polymerization activator is triethyl aluminum, and addition is controlled at 7.0L/ hours or less.External electron donor presses 1 using Bicvclopentyl dimethoxysilane and tetraethoxysilane：1‑1：8 molar ratios.The stabiliser system being made of primary antioxidant, auxiliary anti-oxidant and plumper etc. is added in the prilling section of the present invention；The present invention is finally made a kind of isotacticity and is more than 98%, melt flow rate（MFR）Control is in 2.8 ± 0.2g/10min, and in 50 100ppm, fugitive constituent is less than 100ppm for ash content control, and oxidation induction period is more than 15min, BOPP film PP Pipe Compound for lithium ion Obstruct membrane production of the molecular weight distribution control 7.0 10.0.

Description

A kind of Production method of lithium ion battery barrier membrane homo-polypropylene special material
Technical field
The present invention relates to a kind of production methods of lithium ion battery barrier membrane homo-polypropylene special material, and it is poly- to belong to polyolefin Conjunction field.
Background technology
Due to operating voltage is high, self-discharge rate is low, energy density is big (light weight), memory-less effect, cycle life The advantages that long and pollution-free, oneself gradually substitutes traditional lead acid batteries and cadmium-nickel accumulator to lithium ion battery, becomes each electron-like Main force's power supply of product, in addition to being widely used in portable electronic product（Such as mobile phone, laptop, video camera）Required fills Outside battery, also applied in the fields such as aerospace, navigation, artificial satellite, small medical, military communications equipment, Be becoming tight in particular with the day of the non-renewable resources such as oil and the raising of environmental protection requirement, new-energy automobile it is gradual It promotes, lithium ion battery enters high-speed development period in power battery with field.The demand of global lithium ion battery is average annual It is incremented by 30% or more, market is very huge.According to Japan IIT in 2009（Japanese industries research institute）The prediction of report, by watt-hour Demand to calculate lithium ion battery in 2018 will increase by 4 times or more than 2008, and wherein power battery development will be more fast Suddenly.Account for about the 40% of lithium ion battery total amount to lithium ion batteries for automobiles yield in 2018.China's lithium ion battery is given birth at present Yield accounts for the one third of world's total amount or more, and 100 Duo Jia lithium ion batteries manufacturing enterprises are prosperous to lithium ion battery material demand It contains.
Lithium ion battery is made of major parts such as positive and negative electrode, electrolyte and polymer barrier films, the property of Obstruct membrane Can, directly affect the characteristics such as the capacity, cycle performance and security performance of battery.China's lithium ion battery Obstruct membrane industry hair Quickly, the properties of product of individual enterprises have reached external water product, but price only has the 1/3-1/2 of external product for exhibition.Total water There are larger gaps compared with Japan and Korea S for product.First, polypropylene Obstruct membrane raw material are mainly by import；Second is that polypropylene Obstruct membrane Production technology is mainly by introduction；Third, polypropylene barrier film production line causes polypropylene entirely by introducing additionally, due to various factors Obstruct membrane unstable product quality.
" a kind of PP Pipe Compound being used to prepare lithium ion battery separator and its preparation side that document number is CN101914259A Method " patent describes the polyethylene special-purpose material for lithium-ion membrane；Document number is " a kind of wide point of CN101724111A The preparation method and its polymer of son amount distribution polypropylene " patent, molecule can preferably be changed by dispatch from foreign news agency daughter by describing Amount distribution, does not refer exclusively to which kind of purposes the polymer is suitble to；Document number be CN1884313 " polyacrylic molecular weight distribution exists Adjustable continuous polymerization method and its equipment in wider range " describes to control in the different stages of reaction different Add hydrogen amount, realizes a kind of produced on-site technique of the wide distributed controll of molecular weight；Document number is a kind of " low ash of CN102040690A The preparation method of component polypropylene " describes to reduce acrylic polymers using the HA catalyst for polymerization of propylene that Bei Hua institutes develop Ash content.Above-mentioned related patents are not directed to the correlation of preparation and its application of lithium ion electronics Obstruct membrane homopolypropylene PP Pipe Compound Content.
Invention content
The present invention relates to the production methods that a kind of lithium ion battery Obstruct membrane homopolypropylene obstructs film special material.Realize this The technical solution of invention is：Propylene polymerization is using liquid-phase bulk polymerization and two kettle of gas phase bulk polymerization series connection continuous reaction process. Liquid-phase bulk polymerization first is carried out in A units, propylene, catalyst system is added, is carried out at 70 ± 1 DEG C；Afterwards gas phase is carried out in unit B Propylene, catalyst system is added in bulk polymerization, is carried out at 80 ± 1 DEG C.A units and unit B control different density of hydrogen, Middle A units density of hydrogen control is in 300-2000ppm and the control of the density of hydrogen of unit B in 100-800ppm, wherein catalyst Major catalyst in system requires high activity and the performance moderate to hydrogen response, and external electron donor uses Bicvclopentyl Dimethoxysilane（D-donor）And tetraethoxysilane（T-donor）Bi-component compounds, and the addition of activator strictly controls Within 7.0L/ hours, it is then respectively adding A, unit B；A units and the polymer of unit B, which enter C cell, to be flashed, is done Dry, control flash temperature is not less than 82 DEG C, and drying temperature is at 105 DEG C or so.Under polymer obtained is sent by the above process One procedure carries out granulation packaging.Additive formulations in granulation process are designed as：1010,3114,168, calcium stearate according to Certain ratio mixing is added.It is finally made a kind of high isotactic, low ash content, low-volatile, high oxidation induction period, wide molecular weight point The BOPP film PP Pipe Compound for the production of lithium ion Obstruct membrane of cloth.
The propylene of liquid phase polymerizer is added using the moderate catalyst for polymerization of propylene of high activity, hydrogen response in the present invention A concentration of 40L/ hours -60L/ hours of polymerization catalyst, the catalyst for polymerization of propylene that gas fluidised bed polymerisation kettle is added are a concentration of - 60L/ hours 40L/ hours.
The propylene polymerization activator that the present invention uses is triethyl aluminum, and addition is controlled at 7.0L/ hours or less.
In the technique that the present invention uses, external electron donor is pressed using Bicvclopentyl dimethoxysilane and tetraethoxysilane 1：1-1：8 molar ratios, and be separately added into liquid phase polymerizer and gas fluidised bed polymerisation kettle and carry out propylene polymerization.Liquid phase is poly- Close the external electron donor addition of kettle -0.8L/ hours 0.3L/ hours, the external electron donor addition of gas fluidised bed polymerisation kettle It is -0.8L/ hours 0.3L/ hours.
The stabilizer body being made of primary antioxidant, auxiliary anti-oxidant and plumper etc. is added in the prilling section of the present invention System.Primary antioxidant used in it can be：1010（Four [β（3,5 di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythrite Ester）、3114（Three [3,5 di-tert-butyl-4-hydroxyl benzyl] chlorinated isocyanurates）With 1076（β（3,5 di-t-butyl-4-hydroxy benzenes Base) propionic acid octadecyl）；Auxiliary anti-oxidant used in it can be：168（Three (2,4- di-tert-butyl-phenyl) phosphite esters）、 626（The double diphosphorous acids of pentaerythrite（2,4- tert-butyl-phenyls）Ester）With DLTDP thiodipropionic acid dilauryl cinnamic acid esters；It is wherein used Plumper can be：Calcium stearate, zinc stearate and hydrotalcite.
The present invention is finally made a kind of isotacticity and is more than 98%, melt flow rate（MFR）Control is in 2.8 ± 0.2g/ 10min, ash content controls in 50-100ppm, is preferably controlled in 30ppm hereinafter, fugitive constituent is less than 100ppm, and oxidation induction period is more than 30min, molecular weight distribution control the BOPP film PP Pipe Compound for the production of lithium ion Obstruct membrane in 7.0-10.0.
Homopolypropylene barrier film special material produced by the present invention is for producing polypropylene lithium ion Obstruct membrane, Obstruct membrane production The film surfaces of product, defect rate, film comprehensive performance, lithium ion battery breakdown voltage test, film forming, thickness evenness, porosity, Film grammes per square metre, puncture strength etc. can meet user demand.
Specific implementation mode
Technical solution according to the invention carries out propylene polymerization under the following conditions.Major catalyst：It selects commercially available ND-II propylene polymerization major catalysts；External electron donor：D donor +T-donor（Mixing ratio is 1：4）, compound concentration is 0.5mol/L, addition 0.6L/ hours；Triethyl aluminum addition is 6.0L/ hours；Liquid phase reactor kettle adds hydrogen amount 4.8NM3/ small When, 70 DEG C of reaction temperature, pressure 30MPa；80 DEG C, pressure 17.0MPa of gas phase reaction kettle polymerization temperature polymerize average load 9.5 Ton hour.Required polypropylene powder is made.
The compound additive configuration proportion used when polypropylene powder is granulated for：1010：3114：168：Calcium stearate= 1.0：0.5：1.0：0.2.Compound additive is prepared according to 10 tons of polypropylene granules of production, specific amount of preparation is：1010：3114： 168：Calcium stearate=10kg：5kg：10 kg：2 kg.Temperature of the comminutor from feed end to discharge port, which controls, when granulation is：One 230 DEG C of area, 250 DEG C of 2nd area, 250 DEG C of 3rd area, 250 DEG C of 4th area, 250 DEG C of 5th area.The lithium ion produced according to above-mentioned technology controlling and process The main performance index that Obstruct membrane homopolypropylene obstructs film special material is as follows：MFR=2.82g/10min, isotacticity 98.1% are bent Take stress 35.8MPa, tensile modulus of elasticity 1403MPa, Film Haze 4.1%, powder ash content 77ppm, pellet ash content 90ppm, powder Expect fugitive constituent 110ppm, molecular weight distribution（Mw/Mn）8.3, oxidation induction period 35min.The product is produced in lithium-ion membrane Line is tried out, the results showed that the thickness of film, air penetrability, wettability, chemical stability, aperture, puncture strength, thermostabilization The indices such as property, porosity can meet user demand.

Claims (1)

1. a kind of Production method of lithium ion battery barrier membrane homo-polypropylene special material, it is characterized in that：Propylene polymerization uses liquid phase Bulk polymerization and two kettle of gas phase bulk polymerization series connection continuous reaction process, major catalyst are moderate using high activity, hydrogen response Major catalyst, external electron donor use Bicvclopentyl dimethoxysilane (D-donor) and tetraethoxysilane (T-donor) Bi-component compounds, and the addition of activator was strict controlled within 7.0L/ hours, passed through polymer made from above-mentioned technical process Various functions auxiliary agent is added in granulation process, additive formulations are designed as:1010,3114,168, calcium stearate, is finally made A kind of high isotactic, low ash content, low-volatile, high oxidation induction period, wide molecular weight distribution it is equal for lithium ion battery Obstruct membrane Poly- polypropylene dedicated material；
Further, external electron donor presses (T- using Bicvclopentyl dimethoxysilane (D-donor) and tetraethoxysilane Donor 1) is pressed:1-1:8 molar ratios are uniformly mixed；
Further, be finally made a kind of isotacticity and be more than 98%, melt flow rate (MFR) control in 2.8 ± 0.2g/10min, Ash content control is less than 100ppm in 50-100ppm, fugitive constituent, and oxidation induction period is more than 30min, and molecular weight distribution is controlled in 7.0- 10.0 be used for lithium ion battery barrier membrane homo-polypropylene special material；
Further, the system that stabilizer is made of primary antioxidant, auxiliary anti-oxidant and plumper is added in prilling section of the invention； Primary antioxidant used in it is：1010 (four [β (3,5 di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol esters) and 3114 (three [3,5 di-t-butyl-4-Qiang Ji Benzyl yls] chlorinated isocyanurates)；Auxiliary anti-oxidant used in it is：168 (three (2, 4- di-tert-butyl-phenyls) phosphite ester)；Plumper used in it is：Calcium stearate.
CN201310519301.0A 2013-10-29 2013-10-29 A kind of Production method of lithium ion battery barrier membrane homo-polypropylene special material Active CN103540020B (en)

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CN106700224B (en) * 2015-07-23 2020-08-28 中国石化扬子石油化工有限公司 Polypropylene composition and preparation method thereof
JP6729695B2 (en) * 2016-06-24 2020-07-22 王子ホールディングス株式会社 Biaxially oriented polypropylene film, metallized film, and capacitor
CN106543319A (en) * 2016-11-25 2017-03-29 联泓新材料有限公司 A kind of production method of HOPP
CN109306030A (en) * 2017-07-28 2019-02-05 中国石油天然气股份有限公司 Special material for lithium battery diaphragm and preparation method thereof
EP3674331A1 (en) * 2018-12-27 2020-07-01 Sumitomo Chemical Company, Limited Olefin polymer and method for producing olefin polymer
CN114426596A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer
CN112876591A (en) * 2021-02-26 2021-06-01 陕西延长中煤榆林能源化工有限公司 Industrial production method of polypropylene resin for battery diaphragm

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1156999A (en) * 1994-02-04 1997-08-13 埃克森化学专利公司 Dual donor catalyst system for polymerization of olefins
CN102911300A (en) * 2012-10-15 2013-02-06 中国科学院化学研究所 Method for preparing BOPP (Biaxially-oriented Polypropylene)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1156999A (en) * 1994-02-04 1997-08-13 埃克森化学专利公司 Dual donor catalyst system for polymerization of olefins
CN102911300A (en) * 2012-10-15 2013-02-06 中国科学院化学研究所 Method for preparing BOPP (Biaxially-oriented Polypropylene)

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