EP0000083B1 - Verwendung von Pulvern aus Vinylchloridpolymeren zur Herstellung von Separatoren für Batterien - Google Patents

Verwendung von Pulvern aus Vinylchloridpolymeren zur Herstellung von Separatoren für Batterien Download PDF

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Publication number
EP0000083B1
EP0000083B1 EP78200027A EP78200027A EP0000083B1 EP 0000083 B1 EP0000083 B1 EP 0000083B1 EP 78200027 A EP78200027 A EP 78200027A EP 78200027 A EP78200027 A EP 78200027A EP 0000083 B1 EP0000083 B1 EP 0000083B1
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EP
European Patent Office
Prior art keywords
powders
soluble initiator
use according
water
vinyl chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78200027A
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English (en)
French (fr)
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EP0000083A1 (de
Inventor
André Petit
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Solvay SA
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Solvay SA
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Application filed by Solvay SA filed Critical Solvay SA
Publication of EP0000083A1 publication Critical patent/EP0000083A1/de
Application granted granted Critical
Publication of EP0000083B1 publication Critical patent/EP0000083B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/91—Suspending agents
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/911—Emulsifying agents

Definitions

  • the present invention relates to the use of powders of vinyl chloride polymers for the manufacture of separation plates for batteries and accumulators (battery separators).
  • the present invention aims to provide sinterable polyvinyl chloride powders suitable for the manufacture of good quality battery separators which do not have the abovementioned drawbacks.
  • the present invention relates to the use of powders of vinyl chloride polymers for the manufacture of separation plates for batteries and accumulators obtained by polymerization in aqueous suspension of vinyl chloride with the intervention of an oil-soluble initiator of the radical polymerization and in the presence of a dispersing system comprising a cellulose derivative and an anionic emulsifier, by a process according to which the polymerization is initially carried out using the oil-soluble initiator and a water-soluble initiator of the polymer is added during polymerization radical polymerization.
  • the Applicant has discovered in fact that when the polymerization in aqueous suspension of vinyl chloride is initiated by means of an oil-soluble initiator, in the presence of a cellulosic dispersing agent and of an anionic emulsifier, and that an initiator is added water-soluble during polymerization, it is possible to directly obtain sinterable vinyl chloride powder polymers, suitable for the manufacture of battery separators having good electrical and mechanical properties.
  • the time at which the addition of the water-soluble initiator is carried out is not particularly critical, provided, however, that this takes place during polymerization. It can therefore be performed at any time during polymerization, that is to say after the start but had the end of the polymerization.
  • end of polymerization is meant the moment when, the desired conversion rate having been reached, the polymerization reactor is degassed by lowering the pressure.
  • the degassing polymerization is interrupted when the conversion rate reaches approximately 85 to 95%.
  • the water-soluble initiator is therefore added before the conversion rate has reached 85%. It is particularly advantageous to add it before the conversion rate exceeds 80%.
  • the water-soluble initiator it is also not advisable to introduce the water-soluble initiator into the polymerization medium when the conversion rate is still relatively low, generally less than approximately 60%. In order to obtain a polyvinyl chloride powder whose properties are optimal, it is preferred to introduce the water-soluble initiator after the conversion rate has reached at least 70%.
  • a water-soluble initiator of the radical polymerization when the conversion rate is between approximately 70 and 80% and furthermore polymerization is continued until the conversion rate has reached a value of 85 to 95%.
  • the polymerization is continued at the same temperature.
  • water-soluble initiator is not critical and, in general, all initiators of radical polymerization in aqueous emulsion are suitable.
  • initiators mention may be made of persalts, peracids, and hydrogen peroxide (hydrogen peroxide).
  • persalts peracids
  • hydrogen peroxide hydrogen peroxide
  • inorganic persalts are used, more particularly still alkali metal and ammonium persulfates, or hydrogen peroxide.
  • an inorganic persalt such as for example potassium or ammonium persulfate
  • a basic substance for example, an alkali metal or ammonium hydroxide
  • the amount of basic substance to be used can be easily determined experimentally in each particular case. To fix the idea, an amount of about 0.1 to 1 part by weight per 1000 parts of vinyl chloride is generally suitable for improving the thermal stability of polyvinyl chloride.
  • water-soluble initiator One can just as easily implement a single water-soluble initiator as several. When several water-soluble initiators are used, they can be used at different times. They can also be added in fractions or continuously.
  • the amount of water-soluble initiator to be introduced into the aqueous suspension is not critical. It depends to a certain extent on the polymerization temperature, as well as on the chemical nature of the water-soluble initiator. To fix the ideas, the introduction of very small quantities of water-soluble initiator, of 0.1% 0 by weight relative to the vinyl chloride used generally brings already an improvement of the qualities of the polyvinyl chloride powders and in particular their sinterability. The introduction of higher amounts of water-soluble initiator reinforces this improvement. However, it is generally preferred not to exceed an amount of 3% o by weight. In the case where the water-soluble initiator is an inorganic persalt, the preferred concentration of water-soluble initiator is generally between 0.15 and 1% o approximately. In the case where it is hydrogen peroxide, the zone of the preferred concentrations is between 0.5 and 2.5% v approximately.
  • oil-soluble initiator used at the start of the polymerization in aqueous suspension is not critical. In general, all the oil-soluble initiators usually used for this type of polymerization are suitable. However, the best results are obtained with peroxydicarbonates of higher dialkyls and azo-bis-nitriles.
  • dialkyl peroxydicarbonate is intended to denote dialkyl peroxydicarbonates in which the alkyl chains, different or identical and optionally substituted, contain at least 7 carbon atoms and, preferably at least 12 carbon atoms.
  • peroxydicarbonates are used whose identical alkyl chains each contain from 12 to 20 carbon atoms.
  • a very particularly preferred peroxydicarbonate is diketyl peroxydicarbonate.
  • R represents an alkylene chain, straight or branched containing from 2 to 10 carbon atoms, and preferably of 4 to 8 carbon atoms.
  • azo-bis-nitriles there may be mentioned azo-bis-isobutyronitrile, azo-bis-valeronitrile, azo-bis-2,4-d imethylvalero nitrile.
  • a very particularly preferred azo-bis-nitrile is azo-bis-2,4-dimethylvaleronitrile.
  • the polymerization in aqueous suspension of vinyl chloride is therefore initiated by means of an oil-soluble initiator chosen from peroxydicarbonates of higher dialkyls and azo-bis-nitriles (or of a system including catalytic).
  • an oil-soluble initiator chosen from peroxydicarbonates of higher dialkyls and azo-bis-nitriles (or of a system including catalytic).
  • a higher dialkyl peroxydicarbonate is used.
  • the quantity of oil-soluble initiator used at the start of the polymerization is not critical. It depends in particular on the half-life of the initiator under the polymerization conditions, as well as on the heat exchange capacity of the installation. Usually, 0.01 to 0.5% by weight of oil-soluble initiator (or of a mixture of oil-soluble initiators) is used relative to vinyl chloride. Preferably, about 0.1% by weight of oil-soluble initiator is used.
  • the cellulosic dispersing agent used to manufacture the powders according to the invention can be chosen equally from all the water-soluble cellulosic derivatives usually used for the polymerization in aqueous suspension of vinyl chloride.
  • examples of such derivatives include alkylcelluloses such as methyl-, ethyl-, and propylcellulose, hydroxyalkylcelluloses such as hydroxyethyl-, hydroxypropyl- and hydroxybutylcellulose and mixed ethers.
  • cellulose such as (hydroxypropyl) (methyl) cellulose.
  • alkylcelluloses are used.
  • a very particularly preferred alkylcellulose is methylcellulose.
  • the amount of cellulosic dispersant is usually between 1 and 0 5% by weight relative to the vinyl chloride used initially, the best results are obtained when used from 2 to 2.5% o by weight.
  • the nature of the anionic emulsifier used to manufacture the powders according to the invention is not critical. However, the best results are obtained with sulfonated emulsifiers.
  • emulsifiers include the alkali metal salts, such as sodium, alkylsulfonic, arylsulfonic and alkylarenesulfonic acids.
  • Very particularly preferred emulsifiers are the alkali metal alkylarenesulfonates. Among these, preference is given to sodium dodecylbenzenesulfonate.
  • anionic emulsifier used is not particularly critical, it is recommended to use it in very small amounts, generally much less than the amount of cellulose derivative used.
  • it is used therefore in an amount of from 0.1 to 296 o by weight relative to the vinyl chloride used initially. The best results are obtained when using from 0.50 to 1.596% by weight of anionic emulsifier.
  • the polymerization in aqueous suspension of vinyl chloride is therefore started in the presence of diketyl peroxydicarbonate and of a dispersing system based on sodium methylcellulose and dodecylbenzenesulfonate and added hydrogen peroxide and / or an alkali metal or ammonium persulfate during polymerization when the conversion rate is between 70 and 80%.
  • the polymerization temperature is not critical and is generally between 50 and 75 ° C, advantageously between 55 and 65 ° C.
  • the polymers obtained generally have K values (measured at 25 ° C. in cyclohexanone) of between 53 and 74, preferably between 60 and 69.
  • the amount of water used is usually such that the total weight of the monomers represents from 20 to 50% of the total water plus monomers, advantageously from 40 to 50%.
  • the polyvinyl chloride powder of the invention is conventionally isolated from the polymerization medium, for example by filtration, and it is not necessary to subject it to special treatments or to add special additives to it. It can then be dried, with hot air for example, after which it is ready to be used.
  • vinyl chloride polymers is intended to denote both the polymers obtained by homopolymerization of vinyl chloride and those obtained by copolymerization of vinyl chloride with up to 20% by weight of an ethylenically unsaturated copolymerizable comonomer such as acetate. vinyl, ethylene, propylene and butylene. Particularly preferred are homopolymers of vinyl chloride.
  • Polyvinyl chloride powders used according to the invention are sinterable powders, reduced content, generally less than 2% c by weight, dispersing agent having a narrow particle size distribution and an average particle diameter of 30 to about 45 microns, as well as a low electrical resistance, generally less than 2 milliohm / dm 2 .
  • polyvinyl chloride powders are particularly suitable for the manufacture of separators for wettable batteries having excellent electrical and mechanical properties. To do this, conventional methods of manufacturing battery separators from polyvinyl chloride powders can be used.
  • Example 1 illustrates the preparation of the powders which can be used according to the invention.
  • Example 4R for reference, relates to obtaining a polyvinyl chloride powder by polymerization without the addition of a water-soluble initiator during polymerization.
  • This example is in accordance with Example 1, except that 0.3 g of sodium hydroxide is introduced into the aqueous charge after the introduction of demineralized water.
  • Example 2 This example is identical to Example 1 except that the ammonium persulfate is replaced by 0.6 g of hydrogen peroxide (100%).
  • This example is identical to Example 1, except that the introduction during the polymerization of ammonium persulfate is omitted.
  • the sintering ability of the polyvinyl chlorides obtained according to Examples 1 to 4R was also evaluated. To do this, 0.4 mm thick battery separator elements were made by roller coating the polyvinyl chloride powder with laboratory equipment.
  • Example 4R The comparison of the results of Examples 1, 2 and 3 with those of Example 4R indicates that the delayed introduction of a water-soluble initiator has a very marked effect on the sinterability of the polyvinyl chloride powders obtained.
  • the polyvinyl chloride powder produced according to Example 4R adheres strongly to the metal support during coating and leads to sintering of very poor quality, so much so that it has not been possible to '' assess the breaking stress of the sintered sample.
  • the polyvinyl chloride powders obtained according to Examples 1, 2 and 3 adhere little, if at all, to the roller and lead to the production of good-quality sintered samples having a tensile strength greater than 50 kg / cm 2 .

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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)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cell Separators (AREA)
  • Polymerization Catalysts (AREA)

Claims (9)

1. Verwendung von Vinylchloridpolymer-Pulvern zur Herstellung von Trennscheiben für Batteriezellen und Akkumulatoren, dadurch gekennzeichnet, daß diese Pulver erhalten sind durch Polymerisation von Vinylchlorid in wässriger Suspension unter Vermittlung eines öllöslichen Initiators der Radikalpolymerisation und in Anwesenheit eines Dispersionssystems bestehend aus einem Zellulosederivat und einem anionischen Emulgator durch ein Verfahren, wonach man die Polymerisation anfänglich mittels des öllöslichen Initiators bewirkt und im Laufe der Polymerisation einen wasserlöslichen Initiator der Radikalpolymerisation hinzufügt.
2. Verwendung gemäß Anspruch 1 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem man den wasserlöslichen Initiator zusetzt bevor der Umsetzungsgrad 80% überschreitet.
3. Verwendung gemäß Anspruch 1 oder 2 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem an den wasserlöslichen Initiator zusetzt nachdem der Umsetzungsgrad 70 % erreicht hat.
4. Verwendung gemäß einem der Ansprüche 1 bis 3 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, nach welchem man die Polymerisation unterbricht, wenn der Umsetzungsgrad 85 bis 95% erreicht hat.
5. Verwendung gemäß einem der Ansprüche 1 bis 4 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem der wasserlösliche Initiator ausgewählt ist unter den Persulfaten der Alkalimetalle und des Ammoniums und Wasserstoffperoxid und eingesetzt wird in einer Menge von 0,1 bis 3 Gew.-%o bezogen auf das eingesetzte Vinylchlorid.
6. Verwendung gemäß einem der Ansprüche 1 bis 5 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem das Zellulosederivat ausgewählt ist unter den Alkylzellulosen, den Hydroxyalkylzellulosen und den (Hydroxyalkyl)-(alkyl)zellulosen und angewandt wird in einer Menge von 1 bis 5 Gew: %o bezogen auf das eingesetzte Vinylchlorid.
7. Verwendung gemäß Anspruch 6 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem das Zellulosederivat eine Alkylzellulose ist.
8. Verwendung gemäß einem der Ansprüche 1 bis 7 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem der anionische Emulgator ausgewählt ist unter den Alkalimetallsalzen von Alkylsulfonsäuren, Alkylarensulfonsäuren und Arylsulfonsäuren und eingesetzt wird in einer Menge von 0,1 bis 2 Gew.-%o bezogen auf das eingesetzte Vinylchlorid.
9. Verwendung gemäß Anspruch 8 dadurch gekennzeichnet, daß die Pulver erhalten sind durch ein Verfahren, bei welchem der anionische Emulgator ein Alkalimetallsalz einer Alkylarensulfonsäure ist.
EP78200027A 1977-06-07 1978-06-01 Verwendung von Pulvern aus Vinylchloridpolymeren zur Herstellung von Separatoren für Batterien Expired EP0000083B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR777717798A FR2393815A1 (fr) 1977-06-07 1977-06-07 Procede pour la polymerisation en suspension aqueuse du chlorure de vinyle
FR7717798 1977-06-07

Publications (2)

Publication Number Publication Date
EP0000083A1 EP0000083A1 (de) 1978-12-20
EP0000083B1 true EP0000083B1 (de) 1981-12-02

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EP78200027A Expired EP0000083B1 (de) 1977-06-07 1978-06-01 Verwendung von Pulvern aus Vinylchloridpolymeren zur Herstellung von Separatoren für Batterien

Country Status (9)

Country Link
US (1) US4243562A (de)
EP (1) EP0000083B1 (de)
JP (1) JPS543895A (de)
AT (1) AT369754B (de)
DE (1) DE2861393D1 (de)
ES (1) ES470544A1 (de)
FI (1) FI63767C (de)
FR (1) FR2393815A1 (de)
IT (1) IT1098315B (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1165385A (en) * 1981-05-04 1984-04-10 Earl L. Vetor Sintered ethylene vinyl acetate vinyl chloride battery separator
US4532314A (en) * 1983-02-28 1985-07-30 Henkel Corporation Method of suspension polymerization of vinyl chloride utilizing hydroxypropyl guar
US4868238A (en) * 1987-12-23 1989-09-19 Aqualon Company Suspension polymerization of a vinyl monomer in the presence of (A) carboxymethyl hydrophobically modified hydroxyethylcellulose (CMHMHEC) or (B) CMHMHEC in combination with an electrolyte or polyelectrolyte
US5362581A (en) * 1993-04-01 1994-11-08 W. R. Grace & Co.-Conn. Battery separator
US5389433A (en) * 1993-04-01 1995-02-14 W. R. Grace & Co.-Conn. Battery separator
US5362582A (en) * 1993-04-01 1994-11-08 W.R. Grace & Co.-Conn. Battery separator
US5389463A (en) * 1993-04-01 1995-02-14 W. R. Grace & Co.-Conn. Battery separator
US5346788A (en) * 1993-04-01 1994-09-13 W. R. Grace & Co.-Conn. Microporous polyurethane based battery separator
WO1996014357A1 (en) * 1994-11-03 1996-05-17 Hercules Incorporated Cellulose ethers in emulsion polymerization dispersions
DE10335958A1 (de) * 2003-08-04 2005-02-24 Basf Ag Verfahren zur Herstellung wässriger Polymerisatdispersionen
JP5960099B2 (ja) * 2012-07-20 2016-08-02 富士フイルム株式会社 エッチング方法及びこれを用いた半導体基板製品及び半導体素子の製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB975381A (en) * 1962-08-30 1964-11-18 British Geon Ltd Process for the polymerisation of vinyl chloride
NL129050C (de) * 1963-06-18
JPS4911259B1 (de) * 1970-06-04 1974-03-15
JPS492189B1 (de) * 1970-10-28 1974-01-18
JPS5339477B2 (de) * 1971-12-07 1978-10-21
GB1397387A (en) * 1973-01-20 1975-06-11 Pfizer Ltd Preparation of 2-alkylaminoalkyl 6-methyl-7-nitro- 1,2,3,4-tetrahydroquinolines

Also Published As

Publication number Publication date
FI63767B (fi) 1983-04-29
DE2861393D1 (en) 1982-01-28
ATA410978A (de) 1982-06-15
JPS543895A (en) 1979-01-12
FI63767C (fi) 1983-08-10
AT369754B (de) 1983-01-25
US4243562A (en) 1981-01-06
ES470544A1 (es) 1979-01-01
FR2393815A1 (fr) 1979-01-05
EP0000083A1 (de) 1978-12-20
IT7824304A0 (it) 1978-06-07
FI781810A (fi) 1978-12-08
FR2393815B1 (de) 1980-01-18
IT1098315B (it) 1985-09-07

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