WO2023185162A1 - Insulator for batteries - Google Patents
Insulator for batteries Download PDFInfo
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- WO2023185162A1 WO2023185162A1 PCT/CN2022/143137 CN2022143137W WO2023185162A1 WO 2023185162 A1 WO2023185162 A1 WO 2023185162A1 CN 2022143137 W CN2022143137 W CN 2022143137W WO 2023185162 A1 WO2023185162 A1 WO 2023185162A1
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- 239000012212 insulator Substances 0.000 title description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 124
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 124
- 229920000642 polymer Polymers 0.000 claims description 122
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 31
- 239000003365 glass fiber Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- -1 aromatic diol Chemical class 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000012763 reinforcing filler Substances 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000012764 mineral filler Substances 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 54
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 36
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 28
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 24
- 239000000178 monomer Substances 0.000 description 22
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 17
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 14
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- 239000002253 acid Substances 0.000 description 11
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- 101150110438 Lcp4 gene Proteins 0.000 description 8
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
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- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
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- GSYIVQLTSZFJRV-UHFFFAOYSA-N 3-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1 GSYIVQLTSZFJRV-UHFFFAOYSA-N 0.000 description 5
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- 230000006835 compression Effects 0.000 description 5
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- NFTLBCXRDNIJMI-UHFFFAOYSA-N 6-acetyloxynaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OC(=O)C)=CC=C21 NFTLBCXRDNIJMI-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
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- 125000001072 heteroaryl group Chemical group 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
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- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 2
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 2
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 description 2
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 2
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 2
- NYYMNZLORMNCKK-UHFFFAOYSA-N 5-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1O NYYMNZLORMNCKK-UHFFFAOYSA-N 0.000 description 2
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 2
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 2
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- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
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- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005495 pyridazyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
- H01M50/293—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by the material
-
- 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
Definitions
- the present invention relates to an insulating sheet suitable for use in battery stack, notably for automotive application.
- Plastic materials have been disclosed for use in the manufacturing of fuel cells components, e.g. endplates and casings.
- endplates and casings For example, reference is made to JP 2001-236982 (in the name of Toray Ind. ) , US 2002/182470 (in the name of Ticona LLC. ) and US 2003/0152819 (in the name of Panasonic Intellectual Property Management CO., Ltd. ) .
- the Applicant faced the problem of providing an insulating material that is suitable for use in batteries, easy to manufacture at industrial scale and with a very reduced thickness.
- the present invention relates to a sheet [sheet (P) ] having a thickness equal to or lower than 3 mm and made from at least one liquid crystal polymer [polymer LCP] .
- said sheet (P) is made from a composition comprising:
- the present invention relates to a battery system (1) comprising:
- a battery block comprising at least two adjacently stacked battery cells (2) ;
- sheet (P) according to the present invention provides for an insulating layer capable of withstanding very high temperatures, notably from 200 to 600°C or even higher, for 30-60 minutes, thus allowing delaying or even preventing the thermal runaway from the failed cell to its neighbouring cell or other modules.
- the present invention relates to the use of said sheet (P)as above defined, for the manufacture of a battery system comprising a pair of endplates, wherein said sheet (P) is applied to each of the endplates of said battery system.
- Fig. 1 is a side view of an exemplary battery system.
- alkyl as well as derivative terms such as “alkoxy” , “acyl” and “alkylthio” include straight chain, branched chain and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1, 1 dimethylethyl, and cyclo-propyl.
- each alkyl and aryl group may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, sulfo, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 acyl, formyl, cyano, C 6 -C 15 aryloxy or C 6 -C 15 aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied;
- halogen or “halo” includes fluorine, chlorine, bromine and iodine, with fluorine being preferred;
- aryl refers to a phenyl, indanyl or naphthyl group.
- the aryl group may comprise one or more alkyl groups, and are called sometimes in this case “alkylaryl” ; for example may be composed of an aromatic group and two C 1 -C 6 groups (e.g. methyl or ethyl) .
- the aryl group may also comprise one or more heteroatoms, e.g. N, O or S, and are sometimes called ′′heteroaryl” group; these heteroaromatic rings may be fused to other aromatic systems.
- heteroaromatic rings include, but are not limited to furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl and triazinyl ring structures.
- the aryl or heteroaryl substituents may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, C 1 -C 6 alkoxy, sulfo, C 1 -C 6 alkylthio, C 1 -C 6 acyl, formyl, cyano, C 6 -C 15 aryloxy or C 6 -C 15 aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied;
- the expression “derived from” refers to the recurring unit formed from polycondensation of the recited monomer.
- said composition comprises from 50 to 90 wt. %, more preferably from 55 to 88.9 wt. %and even more preferably from 60 to 70 wt. %of said polymer LCP, based on the total weight of the composition.
- said polymer LCP is obtained from the polycondensation reaction of: (I) terephthalic acid, (II) at least one aromatic diol, (III) at least one aromatic dicarboxylic and/or hydroxycarboxylic acid.
- said (II) at least one aromatic diol is represented by a formula selected from the following group of formulae:
- said (II) at least one aromatic diol is selected from the group consisting of 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, 2, 5-diphenyl diol, 4, 4’-biphenol, 4, 4'- (propane-2, 2-diyl) diphenol, 4, 4'- (ethane-1, 2-diyl) diphenol, 4, 4'-methylenediphenol, bis (4-hydroxyphenyl) methanone, 4, 4'-oxydiphenol, 4, 4'-sulfonyldiphenol, 4, 4'-thiodiphenol, naphthalene-2, 6-diol, and naphthalene-1, 5-diol.
- the aromatic diol is 4, 4’-biphenol.
- said (III) at least one aromatic dicarboxylic acid is represented by a formula selected from the following group of formulae:
- Ar 1 to Ar 3 are independently selected and have the meanings as defined above;
- T 2 is selected from the group consisting of a sigma bond, O and S.
- said aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, 4, 4′-biphenyldicarboxylic acid, 4, 4′-oxydibenzoic acid, 4, 4'- (ethylenedioxy) dibenzoic acid, 4, 4'-sulfanediyldibenzoic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, and naphthalene-2, 3-dicarboxylic acid.
- said aromatic dicarboxylic acids is selected from the group consisting of isophthalic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, and naphthalene-2, 3-dicarboxylic acid.
- said aromatic dicarboxylic acid is isophthalic acid.
- said at least one aromatic hydroxycarboxylic acid is represented by a formula selected from the group consisting of
- Ar 1 to Ar 3 are independently selected and have the meanings as defined above.
- said aromatic hydroxycarboxylic acid is selected from the group consisting of 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 5-hydroxy-1-naphthoic acid, and 4'-hydroxy- [1, 1'-biphenyl] -4-carboxylic acid.
- the aromatic hydroxycarboxylic acid is selected from the group consisting of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 5-hydroxy-1-naphthoic acid.
- the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid.
- said at least one aromatic dicarboxylic acid and said aromatic hydroxycarboxylic acid are free of a naphthyl group.
- said polymer LCP comprises recurring units R LCP1 to R LCP4 , wherein:
- said recurring unit R LCP2 is represented by either one of the following formulae:
- said recurring unit R LCP3 is represented by either one of the following formulae:
- said recurring unit R LCP4 is represented by either one of the following formulae:
- Ar 1 to Ar 3 , T 1 and T 2 are independently selected and have the meanings defined above.
- R LCP1 is formed from terephthalic acid
- said R LCP2 according to formulae (2a) and (2b) are respectively formed from monomers according to formulae (1) and(2)
- said R LCP3 according to formulae (3a) and (3b) are respectively formed from monomers according to formulae (3) and (4)
- said R LCP4 according to formulae (4a) and (4b) are formed from monomers according to formulae (5) and (6) .
- the selection of Ar 1 to Ar 3 , T 1 and T 2 for the monomers in formulae (1) to (6) also selects Ar 1 to Ar 3 , T 1 and T 2 for recurring units R LCP2 to R LCP4 .
- recurring units R LCP1 to R LCP4 are respectively formed from the polycondensation of terephthalic acid, 4, 4’-biphenol, isophthalic acid, and 4-hydroxybenzoic acid.
- the total concentration of recurring units R LCP1 to R LCP4 is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or at least 99.9 mol%.
- the concentration of recurring units R LCP1 is from 5 mol%to 35 mol%, preferably from 10 mol%to 30 mol%.
- the concentration of recurring units R LCP2 is from 5 mol%to 35 mol%, preferably from 10 mol%to 30 mol%.
- the concentration of recurring units R LCP3 is 0 mol%or from 1 mol%to 20 mol%. According to a preferred embodiment, the concentration of recurring units R LCP3 is 0 mol%.
- the concentration of recurring units R LCP4 is from 35 mol%to 80 mol%, preferably from 40 mol%to 70 mol%, most preferably from 45 mol%to 65 mol%.
- the R LCP1 , R LCP2 and R LCP4 are, respectively, derived from terephthalic acid, 4, 4’-biphenol and 4-hydroxybenzoic acid, where the concentration ranges for each recurring unit are within the ranges given above.
- said polymer LCP has a melting temperature ( “Tm” ) of at least 300°C, at least 320°C, or at least 340°C.
- Tm melting temperature
- the polymer composition has a Tm of no more than 460°C, no more than 450°C, or no more than 440°C.
- the polymer composition has a Tm of from 360°C to 460°C, from 380°C to 450°C, or from 400°C to 430°C. Tm can be measured according to ASTM D3418.
- the sheet (P) of the present invention is advantageous manufactured starting from a LCP complying with this first embodiment.
- said polymer LCP comprises:
- polymer LCP when the polymer LCP comprises additional repeat units, they are chosen in the group consisting of:
- Each of these repeating units (IV) , (V) and/or (VI) may be present in the polymer LCP in a molar amount ranging from 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
- the polymer LCP comprises additional repeating units that are chosen in the group consisting of:
- Each of these repeating units (VII) , (VIII) , (IX) , (X) , (XI) and/or (XI) may be present in the polymer LCP in a molar amount ranging from 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
- the polymer LCP when the polymer LCP comprises additional repeat units, they are chosen from the group consisting of (IV) , (V) , (VI) , (VII) , (VIII) , (IX) , (X) , (XI) and (XI) .
- the polymer LPC may comprise one, two, three, four, five, six, seven, eight or nine of these repeat units. Each of them may be present in the polymer LCP in a molar amount ranging 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
- polymer LCP comprises from 40 to 98 mol. %of repeat units of formula (I) , preferably from 40 to 90 mol. %, more preferably from 50 to 85 mol. %or from 60 to 81 mol. %of repeat units of formula (I) , based on the total number of moles in the polymer LCP.
- the polymer LCP further comprises from 1 to 22 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) , preferably from 5 to 21 mol. %or from 10 to 20 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) , based on the total number of moles in the polymer LCP.
- the polymer LCP also comprises from 1 to 12 mol. %of repeat units of formula (IIIa) and/or (IIIb) , preferably from 2 to 12 mol. %, or from 2 to 11 mol. %, or from 3 to 11 mol. %, or from 3 to 10 mol. %or from 4 to 9.5 mol. %or from 4.5 to 8.5 mol. %repeat units of formula (IIIa) and/or (IIIb) , based on the total number of moles in the polymer LCP.
- the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , hydroquinone (HQ) (or derivative, for example diacetoxybenzene (AcHQ) ) , and cyclohexanedicarboxylic acid (CHDA) .
- HNA 6-hydroxy-2-naphthoic acid
- AcHNA 6-acetoxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- CHDA cyclohexanedicarboxylic acid
- the CHDA monomer is generally a cis/trans isomer blend wherein the cis/trans ratio may vary between 1: 99 to 99: 1, for example varying between 10: 90 and 90: 10.
- the polymer LCP may be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , and cyclohexanedicarboxylic acid (CHDA) .
- HNA hydroxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- CHDA cyclohexanedicarboxylic acid
- the polymer LCP may be made exclusively of these three or four monomers.
- Various isomers of biphenol (BP) can be used to prepare the polymer LCP.
- Biphenol (BP) may be for example be in the form of 4, 4’-biphenol (4, 4’-BP) , 3, 4’-biphenol (3, 4’-BP) or 3, 3’-biphenol (3, 3’-BP) .
- 4, 4’-biphenol is used to prepare the polymer LCP.
- HQ hydroquinone
- the polymer LCP according to this second embodiment may additionally comprise repeat units (IV) , (V) and/or (VI) .
- the polymer LCP may be made of the following monomers: 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) and bibenzoic acid (BB) (or derivative) .
- Bibenzoic acid (BB) may be in the form of 4, 4’-bibenzoic acid (4, 4’-BB) and/or 3, 4’-bibenzoic acid (3, 4’-BB) .
- the polymer LCP comprises:
- the polymer LCP comprises or consists essentially of:
- the polymer LCP according to this second embodiment may additionally comprise repeat units (VII) , (VIII) , (IX) , (X) , (XI) and/or (XII) .
- the polymer LCP may be made of the following monomers: hydroxybenzoic acid (HBA) (or derivative, for example acetoxybenzoic acid (AcHBA) ) , terephthalic acid (TPA) (or derivative) , isophthalic acid (IPA) (or derivative) , resorcinol (RS) (or derivative) and/or catechol (CT) (or derivative) .
- HBA hydroxybenzoic acid
- AcHBA acetoxybenzoic acid
- TPA terephthalic acid
- IPA isophthalic acid
- RS resorcinol
- CT catechol
- the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , hydroquinone (HQ) (or derivative, for example diacetoxybenzene (AcHQ) ) , cyclohexanedicarboxylic acid (CHDA) , terephthalic acid (TPA) (or derivative) and/or isophthalic acid (IPA) (or derivative) .
- HNA 6-hydroxy-2-naphthoic acid
- AcHNA 6-acetoxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- HQ or derivative, for example diacetoxybenzene (AcHQ)
- CHDA cyclohexanedicarboxy
- the polymer LCP may be made exclusively of HNA (or derivative) , BP or (derivative) , HQ (or derivative) , CHDA (or derivative) , and TPA (or derivative) .
- the polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , HQ (or derivative) , CHDA (or derivative) , and IPA (or derivative) .
- the polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , HQ (or derivative) , CHDA (or derivative) , TPA (or derivative) and IPA (or derivative) .
- HBA hydroxybenzoic acid
- 4-HBA 4-hydroxybenzoic acid
- 3-HBA 3-hydroxybenzoic acid
- the polymer LCP is such that the number of moles of repeat units is as follows:
- the polymer LCP may be made exclusively of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) , hydroquinone (HQ) (or derivative) , cyclohexanedicarboxylic acid (CHDA) (or derivative) , 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) , bibenzoic acid (BB) (or derivative) .
- HNA 6-hydroxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- CHDA cyclohexanedicarboxylic acid
- NDA 2, 6-naphthalene dicarboxylic acid
- BB bibenzoic acid
- the polymer LCP of the present invention may be such that the number of moles of repeat units is as follows:
- the polymer LCP may be made exclusively of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) , cyclohexanedicarboxylic acid (CHDA) , preferably 1, 4-CHDA, and 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) .
- HNA 6-hydroxy-2-naphthoic acid
- BP biphenol
- CHDA cyclohexanedicarboxylic acid
- NDA 6-naphthalene dicarboxylic acid
- the polymer LCP described herein has a melting temperature (Tm) above 260°C, for example ranging between 260 and 320°C, for example between 270 and 310°C, or between 280 and 300°C, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (cool-down, heating/cooling rate of 20°C/min) .
- Tm melting temperature
- ASTM D3418 differential scanning calorimetry
- the polymer LCP described herein has a crystallisation temperature (Tc) less than 260°C, for example ranging between 150 and 260°C, for example ranging between 155 and 250°C, or between 160 and 246°C, or between 160 and 240°C, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (cool-down, heating/cooling rate of 20°C/min) .
- Tc crystallisation temperature
- the polymer LCP has a dielectric constant Dk at 5 GHz of less than 3.5, preferably less than 3.4, or less than or equal to 3.3, as measured in the in-plane direction on 4 cm x 4 cm x 150 ⁇ m (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (5 GHz) .
- SCR method Split Cylinder Resonator
- the polymer LCP has a dissipation factor Df at 5 GHz of less than 0.0060, preferably less than 0.0058, or less than or equal to 0.0055, as measured in the in-plane direction on 4 cm x 4 cm x 150 ⁇ m (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (5 GHz) .
- SCR method Split Cylinder Resonator
- the polymer LCP has a dielectric constant Dk at 20 GHz of less than 3.6, preferably less than 3.5, or less than or equal to 3.4, as measured in the in-plane direction on 4 cm x 4 cm x 150 ⁇ m (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (20 GHz) .
- SCR method Split Cylinder Resonator
- the polymer LCP has a dissipation factor Df at 20 GHz of less than 0.0030, preferably less than 0.0025, or less than or equal to 0.0020, as measured in the in-plane direction on 4 cm x 4 cm x 150 ⁇ m (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (20 GHz) .
- the polymer LCP more preferably has a dissipation factor Df at 20 GHz of from 0.0010 to 0.0020 or from 0.0011 to 0.0019.
- said polymer LCP comprises:
- the additional repeat units may be chosen in the group consisting of
- each of such repeating units (VII) and (VIII) may be present in the polymer LCP in a molar amount ranging from 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
- Each of such repeating units (IX) and (X) may be present in the polymer LCP in a molar amount ranging from 0.1 and 25 mol. %, for example from 0.5 to 22 mol. %, from 1 to 21 mol. %, from 2 to 20 mol. %or from 3 to 18 mol. %, based on the total number of moles in the polymer LCP; or
- Each of these repeat units (I) , (XI) , (IIIa) , (IIIb) and/or (XII) may be present in the polymer LCP in a molar amount ranging from 0.1 and 20 mol. %, for example from 0.5 to 18 mol. %, from 1 to 15 mol. %, from 2 to 13 mol. %or from 3 to 10 mol. %, based on the total number of moles in the polymer LCP.
- the polymer LCP comprises from 40 to 98 mol. %, preferably from 40 to 90 mol. %, more preferably from 50 to 85 mol. %or from 60 to 81 mol. %of repeat units of formula (i) , based on the total number of moles in the polymer LCP.
- the polymer LCP further comprises from 1 to 30 mol. %, preferably from 5 to 25 mol. %or from 10 to 22 mol. %of repeating units of formula (ii) , that-is-to say repeating units of formula (iia) , (iib) , (iic) and/or (iid) , based on the total number of moles in the polymer LCP.
- the polymer LCP further comprises repeat units of formula (iii) , which is to say repeating units of formula (iiia) and/or of formula (iiib) .
- repeat units of formula (iiia) which is to say repeating units of formula (iiia) and/or of formula (iiib) .
- their molar ratio varies from 1 to 23 mol. %, preferably from 2 to 22 mol. %or from 3 to 21 mol. %or from 4 to 20 mol. %, based on the total number of moles in the polymer LCP.
- the polymer LCP described herein comprise repeating units of formula (iiib)
- their molar ratio varies from 1 to 13 mol. %, preferably from 2 to 12 mol.
- polymer LCP from 3 to 11 mol. %or from 4 to 10 mol. %, based on the total number of moles in the polymer LCP.
- their total molar ratio may vary from 1 to 25 mol. %, preferably from 2 to 23 mol. %or from 3 to 21 mol. %or from 4 to 20 mol. %, based on the total number of moles in the polymer LCP.
- the molar ratio of 4, 4’-bibenzoic acid (4, 4’- BB) /3, 4’-bibenzoic acid (3, 4’BB) can vary between 1: 99 to 99: 1, preferably 10:90 to 90: 10, even more preferably 20: 80 to 80: 20.
- the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , hydroquinone (HQ) (or derivative, for example diacetoxybenzene (AcHQ) ) , and bibenzoic acid (BB) (or derivative) .
- HNA 6-hydroxy-2-naphthoic acid
- AcHNA 6-acetoxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- BB bibenzoic acid
- BB bibenzoic acid
- BB bibenzoic acid
- Bibenzoic acid (BB) may be in the form of 4, 4’-bibenzoic acid (4, 4’-BB) and/or 3, 4’-bibenzoic acid (3, 4’-BB) .
- the polymer LCP may be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , and 4, 4’-bibenzoic acid (4, 4’-BB) .
- HNA hydroxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- the polymer LCP may also be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , and 3, 4’-bibenzoic acid (3, 4’-BB) .
- HNA hydroxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- 3, 4’-BB 3, 4’-bibenzoic acid
- the polymer LCP may also comprise a combination of 3, 4’-BB and 4, 4’-BB, for example the polymer LCP may be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , 3, 4’-bibenzoic acid (3, 4’-BB) and 4, 4’-bibenzoic acid (4, 4’-BB) .
- HNA hydroxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- the polymer LCP may be made exclusively of these three, four or five monomers.
- BP biphenol
- Biphenol (BP) may be for example be in the form of 4, 4’-biphenol (4, 4’-BP) , 3, 4’-biphenol (3, 4’-BP) or 3, 3’-biphenol (3, 3’-BP) .
- 4 4’-biphenol
- 3, 4’-BP 3, 4’-biphenol
- 3, 3’-BP 3, 3’-biphenol
- HQ hydroquinone
- the polymer LCP according to this third embodiment may additionally comprise repeat units (VII) , (VIII) , (IX) and/or (X) as defined above.
- the polymer LCP may be made of the following monomers: hydroxybenzoic acid (HBA) (or derivative, for example acetoxybenzoic acid (AcHBA) ) , terephthalic acid (TPA) (or derivative) , isophthalic acid (IPA) (or derivative) .
- HBA hydroxybenzoic acid
- TPA terephthalic acid
- IPA isophthalic acid
- HBA Various isomers of hydroxybenzoic acid
- HBA can be used to prepare the polymer LCP.
- HBA can be in the form of 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA) .
- the polymer LCP is manufactured from TPA (or derivative) , in addition to HNA, BP, and BB (or their derivatives) .
- the polymer LCP according to this third embodiment comprises or consists essentially of:
- the polymer LCP comprises or consists essentially of:
- polymer LCP of this third embodiment comprises or consists essentially of:
- the polymer LCP may additionally comprise repeat units (I) , (XI) , (IIIa) , (IIIb) and/or (XII) .
- the polymer LCP may be made of the following monomers: cyclohexanedicarboxylic acid (CHDA) , preferably 1, 4-CHDA, 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) , resorcinol (RS) (or derivative) and/or catechol (CT) (or derivative) .
- CHDA cyclohexanedicarboxylic acid
- NDA 2, 6-naphthalene dicarboxylic acid
- RS resorcinol
- CT catechol
- the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , terephthalic acid (TPA) (or derivative) , as well as bibenzoic acids (BB) .
- HNA 6-hydroxy-2-naphthoic acid
- AcHNA 6-acetoxy-2-naphthoic acid
- BP biphenol
- TPA terephthalic acid
- BB bibenzoic acids
- the polymer LCP may be made exclusively of HNA (or derivative) , BP or (derivative) , TPA(or derivative) and BB (or derivative) .
- the polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , CHDA (or derivative) , HNA (or derivative) , TPA (or derivative) and BB (or derivative) .
- the polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , HQ (or derivative) , and BB (or derivative) , for example 4, 4’-BB, 3, 4’-BB or a combination of both, preferably 3, 4’-BB.
- the polymer LCP is such that the number of moles of repeat units is as follows:
- the polymer LCP may be made exclusively of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) , hydroquinone (HQ) (or derivative) , bibenzoic acid (BB) (or derivative) , hydroxybenzoic acid (HBA) (or derivative, for example acetoxybenzoic acid (AcHBA) ) , for example 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA) , and bibenzoic acid (BB) (or derivative) .
- HNA 6-hydroxy-2-naphthoic acid
- BP biphenol
- HQ hydroquinone
- BB bibenzoic acid
- HBA hydroxybenzoic acid
- AcHBA acetoxybenzoic acid
- BB bibenzoic acid
- the polymer LCP of this third embodiment may be such that the number of moles of repeat units is as follows:
- the polymer LCP according to the third embodiment has a melting temperature (Tm) above 255°C, for example ranging between 256 and 340°C, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (2nd heat, heating/cooling rate of 20°C/min) , for example between 260 and 335°C, or between 261 and 330°C.
- Tm melting temperature
- ASTM D3418 (2nd heat, heating/cooling rate of 20°C/min
- the polymer LCP according to the third embodiment has a crystallisation temperature (Tc) less than 275°C, for example ranging between 150 and 275°C, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (cool-down, heating/cooling rate of 20°C/min) , for example ranging between 155 and 260°C, or between 160 and 255°C.
- Tc crystallisation temperature
- the polymer LCP can be prepared by any conventional method adapted to the synthesis of liquid crystal polymers.
- the polymer LCP can be prepared by thermal polycondensation of monomers and comonomers.
- the polymer LCP may contain a chain limiter, which is a monofunctional molecule capable of reacting with the hydroxyl or carboxylic acid moiety, and is used to control the molecular weight of the polymer LCP.
- the chain limiter can be acetic acid, propionic acid and/or benzoic acid.
- Acatalyst can also be used. Examples of catalysts are phosphorus acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid.
- Astabiliser, such as a phosphite may also be used.
- the polymer LCP can be prepared by a solvent-free process, that-is-to-say a process conducted in the melt, in the absence of a solvent.
- the condensation can be carried out in equipment made from materials inert toward the monomers.
- the equipment is chosen in order to provide enough contact of the monomers, and in which the removal of volatile reaction products is feasible. Suitable equipment includes agitated reactors, extruders and kneaders.
- composition suitable for manufacturing sheet (P) according to the present invention is advantageously free from boron nitride and/or zinc oxide.
- said reinforcing filler is preferably selected from glass fibres, carbon fibres, and/or from mineral fillers, such as wollastonite, talc, calcium carbonate, silica, clay, mica, glass beads, and mixtures of the same.
- said composition comprises from 1 to 75 wt. %, more preferably from 5 to 60 wt. %, even more preferably from 10 to 45 wt. %, and still more preferably from 20 to 40 wt. %of a reinforcing filler based on the total weight of the composition.
- said reinforcing filler is glass fibres, carbon fibres or mixtures thereof. Glass fibres are even more preferred.
- Glass fibres are silica-based glass compounds that contain several metal oxides which can be tailored to create different types of glass.
- the main oxide is silica in the form of silica sand; the other oxides such as calcium, sodium and aluminium are incorporated to reduce the melting temperature and impede crystallisation.
- the glass fibres are chopped glass fibres.
- All glass fibre types such as A, C, D, E, M, S, R, T glass fibres (as described in chapter 5.2.3, pages 43-48 of Additives for Plastics Handbook, 2nd ed, John Murphy) , or any mixtures thereof or mixtures thereof may be used.
- R, Sand T glass fibres are high modulus glass fibres that have typically an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343.
- Glass fibres may have a circular cross-section or a non-circular cross-section, such as oval, elliptical, rectangular, cocoon-shaped. Circular glass fibres are herein preferred.
- the diameter of the circular glass fibres can be 10 ⁇ m (microns) , or from 2 ⁇ m to 15 ⁇ m, or from 5 ⁇ m to 12 ⁇ m.
- the glass fibres may include milled or chopped glass fibres. They may be in the form of whiskers or flakes. In further examples, they may be short glass fibre or long glass fibre.
- the glass fibres may have a length of about 4 millimetres or longer are referred to as long fibres, and fibres shorter than this are referred to as short fibres. Short glass fibres are more preferred.
- said LCP polymer or said composition comprises from 0.5 to 5 wt. %, preferably from 0.7 to 3 wt. %of PTFE based on the total weight of the composition.
- Said composition can comprise additional ingredients, such as additional reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilisers, light stabilisers, flame retardants, nucleating agents and antioxidants.
- Each of said additional ingredients can be present in an amount from 0.1 to about 5 wt. %based on the total weight of the composition.
- Said additional reinforcing agents can be selected for example from: synthetic polymeric fibres, aramid fibres, aluminium fibres, titanium fibres, magnesium fibres, boron carbide fibres, rock wool fibres, steel fibres; talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, wollastonite, barium sulphate.
- Said toughners can be selected for example from: elastomeric backbones comprising polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene-rubbers (EPR) ; ethylene-propylene-diene monomer rubbers (EPDM) ; ethylene-acrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA) , ethylene-vinylacetate (EVA) ; acrylonitrile-butadiene-styrene rubbers (ABS) , block copolymers styrene ethylene butadiene styrene (SEBS) ; block copolymers styrene butadiene styrene (SBS) ; core-shell elastomers of methacrylate-butadiene
- the composition can be prepared by melt-blending said polymer LCP, the reinforcing filler and optionally the PTFE and any other additive.
- any suitable melt-blending method known in the art may be used for mixing the ingredients of said composition.
- the ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches.
- a melt mixer such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer
- the addition step may be addition of all ingredients at once or gradual addition in batches.
- the polymer LCP and the reinforcing filler are gradually added in batches, apart of the polymer LCP and/or of the reinforcing filler is first added, and then is melt-mixed with the remaining polymer LCP and with the other optional ingredients that are subsequently added, until an adequately mixed composition is obtained.
- composition is then moulded into sheet (P) .
- Any moulding technique can be used for the manufacturer of sheet (P) , such as injection moulding, compression moulding or extrusion.
- said sheet (P) has a thickness of from about 0.1 to 1 mm, preferably from 0.2 to 0.9 mm and more preferably from 0.3 to 0.7 mm.
- Sheet (P) according to the present invention is not restricted in use within a specific battery system. However, it is advantageously used in a battery system to be used in automotive, such as hybrid cars or electric cars.
- the present invention relates to a battery system comprising:
- a battery block comprising at least two adjacently stacked battery cells
- - fastening components that hold said at least two adjacent battery cells, comprising (i) apair of endplates, each disposed at one end of said at least two battery cells, and (ii) metal bands disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates;
- each of said endplates is applied to at least one sheet (P) as defined above.
- Fig. 1 shows an exemplary battery system comprising sheet (P) according to this embodiment of the present invention, wherein the shape, dimension and thickness of the different parts are not scaled to each other.
- the battery system comprises a battery block 1 having a plurality of adjacently stacked battery cells 2 and fastening components 3 that hold the battery cells 2 of the battery block 1.
- the battery cells 2 are lithium ion batteries.
- other types of batteries can be used depending on the circumstances.
- said battery cells 2 are represented as rectangular batteries. However, batteries having other shapes and disposed in different configurations can be provided.
- the battery cells 2 are held in a fixed position by the fastening components 3, which comprise a pair of endplates 4 disposed at the end of the adjacently stacked battery cells 2 and metal bands 5 connected to said endplates 4 to hold the battery stack in a compressed state.
- the fastening components 3 comprise a pair of endplates 4 disposed at the end of the adjacently stacked battery cells 2 and metal bands 5 connected to said endplates 4 to hold the battery stack in a compressed state.
- apair of side plates (not represented in Fig. 1) can be disposed at the side-walls of the battery block 1, extending in the stacking direction of the battery cells 2 and connected with said endplates 4 or said metal bands 5.
- the endplates 4 have a rectangular shape that is the same shape of the battery cells 2. It is preferred that the endplates 4 are of the same shape and dimension of the battery cells 2 (or slightly larger) so that the endplates 4 connected by the metal bands 5 do not distort and can hence prevent the expansion at the centre region of the battery cells 2.
- the endplates 4 can be provided of any shape and dimension, depending on the shape and dimension of the battery cells 2 and on the final use for which the battery system 1 is intended.
- the endplates 4 are made of metal, such as aluminium or an alloy of aluminium, or from a plastic resin, more preferably a thermoplastic resin.
- the sheet (P) 6 according to the present invention has the same shape and dimension of the endplates 4.
- said sheet (P) 6 can be provided of any shape and dimension, depending on the final shape and dimensions of each of the endplates 4, the battery cells 2 and the battery system 1.
- sheet 6 is applied to said endplates 4 via an adhesive layer, such as a pressure-sensitive adhesive, or alternatively sheet 6 can be laminated onto said endplates 4.
- an adhesive layer such as a pressure-sensitive adhesive, or alternatively sheet 6 can be laminated onto said endplates 4.
- At least one sheet (P) 6 can be interposed between at least one pair, more preferably between each pair, of the adjacently stacked battery cells 2 (not shown in Figure 1) .
- said sheet 6 is interposed between at least one pair of the adjacently stacked battery cells 2 and hold in position via the mechanical action of the metal bands 5.
- said sheet 6 is hold in position via an adhesive layer, such as a pressure-sensitive adhesive.
- the present invention relates to a battery system comprising:
- a battery block comprising at least two adjacently stacked battery cells
- - fastening components that hold said at least two battery cells, comprising (i) a pair of endplates, each disposed at one end of said at least two adjacently stacked battery cells, and (ii) metal bands disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates;
- At least one sheet (P) as defined above is interposed between at least two, more preferably between all, adjacently stacked battery cells (2) .
- sheet (P) as replacement of the traditional spacer used to date, which is called aerogel, allows to obtain advantages in terms of enhanced resistance to high temperature (even above 400°C) , aprolonged lifetime and a consistent performance under severe environmental conditions, for example under extreme low or high temperatures and with severe compression.
- the present invention relates to a battery system (1) comprising:
- a battery block comprising at least two adjacently stacked battery cells
- - fastening components that hold said at least two battery cells, comprising (i) a pair of endplates, each disposed at one end of said at least two adjacently stacked battery cells, and (ii) metal bands disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates;
- sheet (P) coupled with the end plates and interposed between each pair of the adjacently stacked battery cells allow to achieve an outstanding electrical insulation of the whole battery system.
- LCP SRT 300 (terephthalic acid/biphenol/4-hydroxybenzoic acid 25/25/50 mol. ratio) was obtained by Solvay Specialty Polymers U.S.A., LLC..
- 100 sheets having a dimension of 150mm*100mm and thickness of 0.5 mm were prepared by blending the LCP polymer and 30 wt. %of glass fibres and injection moulding said bland at a temperature from 350 to 430°C, at a pressure of 80 to 120 Mpa, using a high speed injection moulding machine.
- compositions comprising
- PC polycarbonate
- the sheets according to the present invention after 30 minutes maintained a good shape and passed all tests (A1) , (B1) and (C1) .
- the aim of this test was to confirm whether the sheets cracked or met the insulation withstand voltage requirements.
- the test was performed as follows.
- An environmental box was allowed to reach a temperature of-30°C by decreasing its temperature of 5°C/min. Once-30°C were reached, the temperature was kept stable and 5 sheets according to the present invention (each put onto an aluminium plate) were put into the environmental box. The sheets were stored for 1 hour.
- the sheets were extracted from the environmental box and a pressure of 20 KN was applied onto the sheets for 30 minutes. The sheets were then bended at 10° at a rate of 1°/s, then released, and back and forth for 50 times.
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Abstract
The present invention relates to an insulating sheet suitable for use in battery stack, notably for automotive application.
Description
Cross-reference to related patent applications
_______________________________________________________________________
This application claims priority filed on 30 March 2022 with Nr. PCT/CN2022/084165, the whole content of this application being incorporated herein by reference for all purposes.
_______________________________________________________________________
The present invention relates to an insulating sheet suitable for use in battery stack, notably for automotive application.
Background Art
_______________________________________________________________________
Nowadays, electric vehicles are spreading and lithium batteries having increased and faster charging capacity are required by car manufacturers.
At the same time, the safety of lithium batteries is more than ever a need.
Indeed, when a battery is charged with a known amount of energy, the exact same energy is not being delivered during discharge in the form of electrical energy. There are always losses, in which the energy is released into the environment in the form of heat.
To prevent the enormous heat transfer between a failed cell to its neighbouring cell or other modules, insulator materials need to be installed, which might be difficult in view of the little space available in the battery stack.
Plastic materials have been disclosed for use in the manufacturing of fuel cells components, e.g. endplates and casings. For example, reference is made to JP 2001-236982 (in the name of Toray Ind. ) , US 2002/182470 (in the name of Ticona LLC. ) and US 2003/0152819 (in the name of Panasonic Intellectual Property Management CO., Ltd. ) .
Summary of invention
_______________________________________________________________________
In this frame, the Applicant perceived that as lithium batteries are becoming more efficient, the requirements for insulators and insulating materials are increasing.
Hence, the Applicant faced the problem of providing an insulating material that is suitable for use in batteries, easy to manufacture at industrial scale and with a very reduced thickness.
Thus, in a first aspect the present invention relates to a sheet [sheet (P) ] having a thickness equal to or lower than 3 mm and made from at least one liquid crystal polymer [polymer LCP] .
Preferably, said sheet (P) is made from a composition comprising:
- at least one liquid crystal polymer [polymer LCP] and
-from about 5 wt. %to about 50 wt. %of a reinforcing filler.
In a further aspect, the present invention relates to a battery system (1) comprising:
- a battery block comprising at least two adjacently stacked battery cells (2) ;
- fastening components (3) that hold said at least two battery cells, comprising (i) apair of endplates (4) , each disposed at one end of said at least two adjacently stacked battery cells, and (ii) metal bands (5) disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates (4) ; wherein at least one sheet (P) (6) as defined above is
- applied to each of said endplates (4) ; and/or
- interposed between two adjacently stacked battery cells (2) .
Advantageously, sheet (P) according to the present invention provides for an insulating layer capable of withstanding very high temperatures, notably from 200 to 600℃ or even higher, for 30-60 minutes, thus allowing delaying or even preventing the thermal runaway from the failed cell to its neighbouring cell or other modules.
In a further aspect, the present invention relates to the use of said sheet (P)as above defined, for the manufacture of a battery system comprising a pair of endplates, wherein said sheet (P) is applied to each of the endplates of said battery system.
Brief description of drawings
_______________________________________________________________________
Fig. 1 is a side view of an exemplary battery system.
Description of embodiments
_______________________________________________________________________
In the present application and in the following claims:
- any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present invention;
- any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents;
- the term “alkyl” , as well as derivative terms such as “alkoxy” , “acyl” and “alkylthio” include straight chain, branched chain and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1, 1 dimethylethyl, and cyclo-propyl. Unless specifically stated otherwise, each alkyl and aryl group may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, sulfo, C
1-C
6 alkoxy, C
1-C
6 alkylthio, C
1-C
6 acyl, formyl, cyano, C
6-C
15 aryloxy or C
6-C
15 aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied;
- the term “halogen” or “halo” includes fluorine, chlorine, bromine and iodine, with fluorine being preferred;
- the term “aryl” refers to a phenyl, indanyl or naphthyl group. The aryl group may comprise one or more alkyl groups, and are called sometimes in this case “alkylaryl” ; for example may be composed of an aromatic group and two C
1-C
6 groups (e.g. methyl or ethyl) . The aryl group may also comprise one or more heteroatoms, e.g. N, O or S, and are sometimes called ″heteroaryl” group; these heteroaromatic rings may be fused to other aromatic systems. Such heteroaromatic rings include, but are not limited to furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl and triazinyl ring structures. The aryl or heteroaryl substituents may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, C
1-C
6 alkoxy, sulfo, C
1-C
6 alkylthio, C
1-C
6 acyl, formyl, cyano, C
6-C
15 aryloxy or C
6-C
15 aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied;
- “mol%” of each recurring unit is relative to the total number of moles of recurring units in the polymer, unless explicitly indicated otherwise; and
- the expression “derived from” refers to the recurring unit formed from polycondensation of the recited monomer.
Preferably, said composition comprises from 50 to 90 wt. %, more preferably from 55 to 88.9 wt. %and even more preferably from 60 to 70 wt. %of said polymer LCP, based on the total weight of the composition.
According to a first embodiment, said polymer LCP is obtained from the polycondensation reaction of: (I) terephthalic acid, (II) at least one aromatic diol, (III) at least one aromatic dicarboxylic and/or hydroxycarboxylic acid.
Preferably, said (II) at least one aromatic diol is represented by a formula selected from the following group of formulae:
HO-Ar
1-OH (1)
HO-Ar
2-T
1-Ar
3-OH (2)
wherein
Ar
1 to Ar
3 are each independently selected C
6-C
30 aryl groups, optionally substituted with one or more substituents selected from the group consisting of halogen, aC
1-C
15 alkyl, and a C
6-C
15 aryl; and T
1 is selected from the group consisting of a bond, O, S, -SO
2-, -C (=O) -, and a C
1-C
15 alkyl.
More preferably, said (II) at least one aromatic diol is selected from the group consisting of 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, 2, 5-diphenyl diol, 4, 4’-biphenol, 4, 4'- (propane-2, 2-diyl) diphenol, 4, 4'- (ethane-1, 2-diyl) diphenol, 4, 4'-methylenediphenol, bis (4-hydroxyphenyl) methanone, 4, 4'-oxydiphenol, 4, 4'-sulfonyldiphenol, 4, 4'-thiodiphenol, naphthalene-2, 6-diol, and naphthalene-1, 5-diol.
Even more preferably, the aromatic diol is 4, 4’-biphenol.
Preferably, said (III) at least one aromatic dicarboxylic acid is represented by a formula selected from the following group of formulae:
HOOC-Ar
1-COOH (3)
HOOC-Ar
2-T
2-Ar
3-COOH (4)
wherein
Ar
1 to Ar
3 are independently selected and have the meanings as defined above; and
T
2 is selected from the group consisting of a sigma bond, O and S.
Preferably, said aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, 4, 4′-biphenyldicarboxylic acid, 4, 4′-oxydibenzoic acid, 4, 4'- (ethylenedioxy) dibenzoic acid, 4, 4'-sulfanediyldibenzoic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, and naphthalene-2, 3-dicarboxylic acid.
More preferably, said aromatic dicarboxylic acids is selected from the group consisting of isophthalic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, and naphthalene-2, 3-dicarboxylic acid.
Even more preferably, said aromatic dicarboxylic acid is isophthalic acid.
Preferably, said at least one aromatic hydroxycarboxylic acid is represented by a formula selected from the group consisting of
HO-Ar
1-COOH (5)
HO-Ar
2-Ar
3-COOH (6)
wherein
Ar
1 to Ar
3 are independently selected and have the meanings as defined above.
Preferably, said aromatic hydroxycarboxylic acid is selected from the group consisting of 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 5-hydroxy-1-naphthoic acid, and 4'-hydroxy- [1, 1'-biphenyl] -4-carboxylic acid.
More preferably, the aromatic hydroxycarboxylic acid is selected from the group consisting of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 5-hydroxy-1-naphthoic acid.
Even more preferably, the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid.
Preferably, said at least one aromatic dicarboxylic acid and said aromatic hydroxycarboxylic acid are free of a naphthyl group.
Preferably, said polymer LCP comprises recurring units R
LCP1 to R
LCP4, wherein:
said recurring unit R
LCP1 is represented by the following formula:
said recurring unit R
LCP2 is represented by either one of the following formulae:
- [-O-Ar
1-O-] - (2a)
- [-O-Ar
2-T
1-Ar
3-O-] - (2b) ;
said recurring unit R
LCP3 is represented by either one of the following formulae:
- [-OC-Ar
1-CO-] - (3a)
- [-OC-Ar
2-T
2-Ar
3-CO-] - (3b) ;
said recurring unit R
LCP4 is represented by either one of the following formulae:
- [-O-Ar
1-CO-] - (4a)
- [-O-Ar
2-Ar
3-CO-] - (4b) ;
wherein
Ar
1 to Ar
3, T
1 and T
2 are independently selected and have the meanings defined above.
The person of ordinary skill in the art will recognize that said R
LCP1 is formed from terephthalic acid; said R
LCP2 according to formulae (2a) and (2b) are respectively formed from monomers according to formulae (1) and(2) ; said R
LCP3 according to formulae (3a) and (3b) are respectively formed from monomers according to formulae (3) and (4) ; and said R
LCP4 according to formulae (4a) and (4b) are formed from monomers according to formulae (5) and (6) .
As such, the selection of Ar
1 to Ar
3, T
1 and T
2 for the monomers in formulae (1) to (6) also selects Ar
1 to Ar
3, T
1 and T
2 for recurring units R
LCP2 to R
LCP4.
Preferably, recurring units R
LCP1 to R
LCP4 are respectively formed from the polycondensation of terephthalic acid, 4, 4’-biphenol, isophthalic acid, and 4-hydroxybenzoic acid.
Preferably, the total concentration of recurring units R
LCP1 to R
LCP4 is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or at least 99.9 mol%.
In some embodiments, the concentration of recurring units R
LCP1 is from 5 mol%to 35 mol%, preferably from 10 mol%to 30 mol%.
In some embodiments, the concentration of recurring units R
LCP2 is from 5 mol%to 35 mol%, preferably from 10 mol%to 30 mol%.
In some embodiments, the concentration of recurring units R
LCP3 is 0 mol%or from 1 mol%to 20 mol%. According to a preferred embodiment, the concentration of recurring units R
LCP3 is 0 mol%.
In some embodiments, the concentration of recurring units R
LCP4 is from 35 mol%to 80 mol%, preferably from 40 mol%to 70 mol%, most preferably from 45 mol%to 65 mol%.
In one embodiment, the R
LCP1, R
LCP2 and R
LCP4 are, respectively, derived from terephthalic acid, 4, 4’-biphenol and 4-hydroxybenzoic acid, where the concentration ranges for each recurring unit are within the ranges given above.
Preferably, said polymer LCP has a melting temperature ( “Tm” ) of at least 300℃, at least 320℃, or at least 340℃. In some embodiments, the polymer composition has a Tm of no more than 460℃, no more than 450℃, or no more than 440℃. In some embodiments, the polymer composition has a Tm of from 360℃ to 460℃, from 380℃ to 450℃, or from 400℃ to 430℃. Tm can be measured according to ASTM D3418.
The sheet (P) of the present invention is advantageous manufactured starting from a LCP complying with this first embodiment.
According to a second embodiment, said polymer LCP comprises:
- from 40 to 98 mol. %of repeat units of formula (I) :
- from 1 to 20 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) :
and
- from 1 to 12 mol. %of repeat units of formula (IIIa) and/or (IIIb) :
based on the total number of moles in the polymer LCP.
In some embodiments, when the polymer LCP comprises additional repeat units, they are chosen in the group consisting of:
Each of these repeating units (IV) , (V) and/or (VI) may be present in the polymer LCP in a molar amount ranging from 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
In some other embodiments, the polymer LCP comprises additional repeating units that are chosen in the group consisting of:
Each of these repeating units (VII) , (VIII) , (IX) , (X) , (XI) and/or (XI) may be present in the polymer LCP in a molar amount ranging from 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
According to this embodiment, when the polymer LCP comprises additional repeat units, they are chosen from the group consisting of (IV) , (V) , (VI) , (VII) , (VIII) , (IX) , (X) , (XI) and (XI) . The polymer LPC may comprise one, two, three, four, five, six, seven, eight or nine of these repeat units. Each of them may be present in the polymer LCP in a molar amount ranging 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP.
Preferably, according to this second embodiment, polymer LCP comprises from 40 to 98 mol. %of repeat units of formula (I) , preferably from 40 to 90 mol. %, more preferably from 50 to 85 mol. %or from 60 to 81 mol. %of repeat units of formula (I) , based on the total number of moles in the polymer LCP.
The polymer LCP further comprises from 1 to 22 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) , preferably from 5 to 21 mol. %or from 10 to 20 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) , based on the total number of moles in the polymer LCP.
The polymer LCP also comprises from 1 to 12 mol. %of repeat units of formula (IIIa) and/or (IIIb) , preferably from 2 to 12 mol. %, or from 2 to 11 mol. %, or from 3 to 11 mol. %, or from 3 to 10 mol. %or from 4 to 9.5 mol. %or from 4.5 to 8.5 mol. %repeat units of formula (IIIa) and/or (IIIb) , based on the total number of moles in the polymer LCP.
In these embodiment, the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , hydroquinone (HQ) (or derivative, for example diacetoxybenzene (AcHQ) ) , and cyclohexanedicarboxylic acid (CHDA) .
The CHDA monomer is generally a cis/trans isomer blend wherein the cis/trans ratio may vary between 1: 99 to 99: 1, for example varying between 10: 90 and 90: 10.
For example, the polymer LCP may be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , and cyclohexanedicarboxylic acid (CHDA) .
For example, the polymer LCP may be made exclusively of these three or four monomers. Various isomers of biphenol (BP) can be used to prepare the polymer LCP. Biphenol (BP) may be for example be in the form of 4, 4’-biphenol (4, 4’-BP) , 3, 4’-biphenol (3, 4’-BP) or 3, 3’-biphenol (3, 3’-BP) . One or several of these isomers can be used. Preferably, at least 4, 4’-biphenol is used to prepare the polymer LCP. Various isomers of hydroquinone (HQ) can also be used.
The polymer LCP according to this second embodiment may additionally comprise repeat units (IV) , (V) and/or (VI) . In these embodiments, the polymer LCP may be made of the following monomers: 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) and bibenzoic acid (BB) (or derivative) .
Various isomers of bibenzoic acid (BB) can be used to prepare the polymer LCP according to this embodiment. Bibenzoic acid (BB) may be in the form of 4, 4’-bibenzoic acid (4, 4’-BB) and/or 3, 4’-bibenzoic acid (3, 4’-BB) .
In some embodiments, the polymer LCP comprises:
- from 65 to 75 mol. %of repeat units of formula (I) ,
- from 13 to 18 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) , and
- from 3 to 9 mol. %of repeat units of formula (IIIa) and/or (IIIb) , optionally at least one of the following repeat units:
- from 3 to 11 mol. %of repeat units of formula (IV) ,
- from 3 to 11 mol. %of repeat units of formula (V) , and/or
- from 3 to 11 mol. %of repeat units of formula (VI) .
In some preferred embodiments, the polymer LCP comprises or consists essentially of:
- from 65 to 75 mol. %of repeat units of formula (I) ,
- from 13 to 18 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) ,
- from 3 to 9 mol. %of repeat units of formula (IIIa) and/or (IIIb) , and
- optionally from 3 to 11 mol. %of repeat units of formula (IV) .
The polymer LCP according to this second embodiment may additionally comprise repeat units (VII) , (VIII) , (IX) , (X) , (XI) and/or (XII) .
In these embodiments, the polymer LCP may be made of the following monomers: hydroxybenzoic acid (HBA) (or derivative, for example acetoxybenzoic acid (AcHBA) ) , terephthalic acid (TPA) (or derivative) , isophthalic acid (IPA) (or derivative) , resorcinol (RS) (or derivative) and/or catechol (CT) (or derivative) .
In these embodiments, the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , hydroquinone (HQ) (or derivative, for example diacetoxybenzene (AcHQ) ) , cyclohexanedicarboxylic acid (CHDA) , terephthalic acid (TPA) (or derivative) and/or isophthalic acid (IPA) (or derivative) .
For example, the polymer LCP may be made exclusively of HNA (or derivative) , BP or (derivative) , HQ (or derivative) , CHDA (or derivative) , and TPA (or derivative) . The polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , HQ (or derivative) , CHDA (or derivative) , and IPA (or derivative) . The polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , HQ (or derivative) , CHDA (or derivative) , TPA (or derivative) and IPA (or derivative) .
Various isomers of hydroxybenzoic acid (HBA) can be used to prepare the polymer LCP according to this embodiment. Notably, HBA can be in the form of 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA) .
In some embodiments, the polymer LCP is such that the number of moles of repeat units is as follows:
- formulas (I) + (II) + (III) + (IV) + (V) + (VI) + (VII) + (VIII) + (IX) + (X) + (XI) + (XII) =100 mol. %, wherein the number of moles of repeat units of formula (IV) , (V) , (VI) , (VII) , (VIII) , (IX) , (X) , (XI) and/or (XII) ≥0 mol. %,
- formulas (I) + (II) + (III) + (IV) + (V) + (VI) =100 mol. %, wherein the number of moles of repeat units of formula (IV) , (V) and/or (VI) ≥0 mol. %, and
- formulas (I) + (II) + (III) + (VII) + (VIII) + (IX) + (X) + (XI) + (XII) =100 mol. %, wherein the number of moles of repeat units of formula (VII) , (VIII) , (IX) , (X) , (XI) and/or (XII) ≥0 mol. %.
In these embodiments, the polymer LCP may be made exclusively of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) , hydroquinone (HQ) (or derivative) , cyclohexanedicarboxylic acid (CHDA) (or derivative) , 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) , bibenzoic acid (BB) (or derivative) .
For example, the polymer LCP of the present invention may be such that the number of moles of repeat units is as follows:
- formulas (I) + (II) + (III) =100 mol. %, for example formulas (I) + (IIa) + (IIIa) =100 mol. %,
- formulas (I) + (II) + (III) + (IV) =100 mol. %, for example formulas (I) + (IIa) + (IIIa) + (IV) =100 mol. %,
- formulas (I) + (II) + (III) + (V) =100 mol. %,
- formulas (I) + (II) + (III) + (VI) =100 mol. %,
- formulas (I) + (II) + (III) + (IX) =100 mol. %, or
- formulas (I) + (II) + (III) + (X) =100 mol. %.
In some embodiments, the polymer LCP may be made exclusively of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) , cyclohexanedicarboxylic acid (CHDA) , preferably 1, 4-CHDA, and 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) .
According to this second embodiment, the polymer LCP described herein has a melting temperature (Tm) above 260℃, for example ranging between 260 and 320℃, for example between 270 and 310℃, or between 280 and 300℃, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (cool-down, heating/cooling rate of 20℃/min) .
According to this second embodiment, the polymer LCP described herein has a crystallisation temperature (Tc) less than 260℃, for example ranging between 150 and 260℃, for example ranging between 155 and 250℃, or between 160 and 246℃, or between 160 and 240℃, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (cool-down, heating/cooling rate of 20℃/min) .
According to this second embodiment, the polymer LCP has a dielectric constant Dk at 5 GHz of less than 3.5, preferably less than 3.4, or less than or equal to 3.3, as measured in the in-plane direction on 4 cm x 4 cm x 150 μm (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (5 GHz) .
According to this second embodiment, the polymer LCP has a dissipation factor Df at 5 GHz of less than 0.0060, preferably less than 0.0058, or less than or equal to 0.0055, as measured in the in-plane direction on 4 cm x 4 cm x 150 μm (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (5 GHz) .
According to this second embodiment, the polymer LCP has a dielectric constant Dk at 20 GHz of less than 3.6, preferably less than 3.5, or less than or equal to 3.4, as measured in the in-plane direction on 4 cm x 4 cm x 150 μm (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (20 GHz) .
According to this second embodiment, the polymer LCP has a dissipation factor Df at 20 GHz of less than 0.0030, preferably less than 0.0025, or less than or equal to 0.0020, as measured in the in-plane direction on 4 cm x 4 cm x 150 μm (thickness) films obtained from the “dry-as-molded’ compression molded films, using a Split Cylinder Resonator (SCR method) according to ASTM D2520 (20 GHz) . The polymer LCP more preferably has a dissipation factor Df at 20 GHz of from 0.0010 to 0.0020 or from 0.0011 to 0.0019.
According to a third embodiment, said polymer LCP comprises:
a) from 40 to 98 mol. %of repeat units of formula (i) :
b) from 1 to 30 mol. %of repeat units of formula (ii) :
and
c) repeat units with two carboxyl groups of formula (iii) :
- from 1 to 23 mol. %of repeat units of formula (iiia) :
- from 1 to 13 mol. %of repeat units of formula (iiib) :
If the polymer LCP according to this third embodiment comprises additional repeat units, the additional repeat units may be chosen in the group consisting of
- recurring units of formula (VII) , (VIII) , (IX) and (X) as defined above. Each of such repeating units (VII) and (VIII) , may be present in the polymer LCP in a molar amount ranging from 0.1 and 15 mol. %, for example from 0.5 to 13 mol. %, from 1 to 11 mol. %, from 2 to 9 mol. %or from 3 to 8 mol. %, based on the total number of moles in the polymer LCP. Each of such repeating units (IX) and (X) may be present in the polymer LCP in a molar amount ranging from 0.1 and 25 mol. %, for example from 0.5 to 22 mol. %, from 1 to 21 mol. %, from 2 to 20 mol. %or from 3 to 18 mol. %, based on the total number of moles in the polymer LCP; or
- recurring units of formula (I) , (XI) , (IIIa) , (IIIb) and/or (XII) as defined above.
Each of these repeat units (I) , (XI) , (IIIa) , (IIIb) and/or (XII) may be present in the polymer LCP in a molar amount ranging from 0.1 and 20 mol. %, for example from 0.5 to 18 mol. %, from 1 to 15 mol. %, from 2 to 13 mol. %or from 3 to 10 mol. %, based on the total number of moles in the polymer LCP.
According to this third embodiment, the polymer LCP comprises from 40 to 98 mol. %, preferably from 40 to 90 mol. %, more preferably from 50 to 85 mol. %or from 60 to 81 mol. %of repeat units of formula (i) , based on the total number of moles in the polymer LCP.
The polymer LCP further comprises from 1 to 30 mol. %, preferably from 5 to 25 mol. %or from 10 to 22 mol. %of repeating units of formula (ii) , that-is-to say repeating units of formula (iia) , (iib) , (iic) and/or (iid) , based on the total number of moles in the polymer LCP.
The polymer LCP further comprises repeat units of formula (iii) , which is to say repeating units of formula (iiia) and/or of formula (iiib) . When the polymer LCP described herein comprise repeating units of formula (iiia) , their molar ratio varies from 1 to 23 mol. %, preferably from 2 to 22 mol. %or from 3 to 21 mol. %or from 4 to 20 mol. %, based on the total number of moles in the polymer LCP. When the polymer LCP described herein comprise repeating units of formula (iiib) , their molar ratio varies from 1 to 13 mol. %, preferably from 2 to 12 mol. %or from 3 to 11 mol. %or from 4 to 10 mol. %, based on the total number of moles in the polymer LCP. When the polymer LCP described herein comprise both repeat units of formula (iiia) and of formula (iiib) , their total molar ratio may vary from 1 to 25 mol. %, preferably from 2 to 23 mol. %or from 3 to 21 mol. %or from 4 to 20 mol. %, based on the total number of moles in the polymer LCP.
In this third embodiment, the molar ratio of 4, 4’-bibenzoic acid (4, 4’- BB) /3, 4’-bibenzoic acid (3, 4’BB) can vary between 1: 99 to 99: 1, preferably 10:90 to 90: 10, even more preferably 20: 80 to 80: 20.
In this third embodiment, the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , hydroquinone (HQ) (or derivative, for example diacetoxybenzene (AcHQ) ) , and bibenzoic acid (BB) (or derivative) . Various isomers of bibenzoic acid (BB) can be used to prepare the polymer LCP according to such embodiment. Bibenzoic acid (BB) may be in the form of 4, 4’-bibenzoic acid (4, 4’-BB) and/or 3, 4’-bibenzoic acid (3, 4’-BB) . For example, the polymer LCP may be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , and 4, 4’-bibenzoic acid (4, 4’-BB) . The polymer LCP may also be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , and 3, 4’-bibenzoic acid (3, 4’-BB) . The polymer LCP may also comprise a combination of 3, 4’-BB and 4, 4’-BB, for example the polymer LCP may be made of hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) and/or hydroquinone (HQ) (or derivative) , 3, 4’-bibenzoic acid (3, 4’-BB) and 4, 4’-bibenzoic acid (4, 4’-BB) . For example, the polymer LCP may be made exclusively of these three, four or five monomers. Various isomers of biphenol (BP) can be used to prepare the polymer LCP according to this embodiment. Biphenol (BP) may be for example be in the form of 4, 4’-biphenol (4, 4’-BP) , 3, 4’-biphenol (3, 4’-BP) or 3, 3’-biphenol (3, 3’-BP) . One or several of these isomers can be used. Preferably, at least 4, 4’-biphenol is used to prepare the polymer LCP according to this embodiment. Various isomers of hydroquinone (HQ) can also be used.
The polymer LCP according to this third embodiment may additionally comprise repeat units (VII) , (VIII) , (IX) and/or (X) as defined above. In these embodiments, the polymer LCP may be made of the following monomers: hydroxybenzoic acid (HBA) (or derivative, for example acetoxybenzoic acid (AcHBA) ) , terephthalic acid (TPA) (or derivative) , isophthalic acid (IPA) (or derivative) . Various isomers of hydroxybenzoic acid (HBA) can be used to prepare the polymer LCP. Notably, HBA can be in the form of 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA) .
According to this embodiment, the polymer LCP is manufactured from TPA (or derivative) , in addition to HNA, BP, and BB (or their derivatives) .
Preferably, the polymer LCP according to this third embodiment comprises or consists essentially of:
- from 50 to 80 mol. %of repeat units of formula (i) ,
- from 9 to 25 mol. %of repeat units of formula (ii) and
- from 2 to 12 mol. %of repeat units of formula (iiib) .
Alternatively, under this third embodiment, the polymer LCP comprises or consists essentially of:
- from 50 to 80 mol. %of repeat units of formula (i) ,
- from 9 to 25 mol. %of repeat units of formula (ii) and
- from 2 to 21 mol. %of repeat units of formula (iiia) .
Also alternatively, the polymer LCP of this third embodiment comprises or consists essentially of:
- from 50 to 80 mol. %of repeat units of formula (i) ,
- from 9 to 25 mol. %of repeat units of formula (ii) ,
- from 2 to 15 mol. %of repeat units of formula (iiia) , and
- from 2 to 11 mol. %of repeat units of formula (iiib) .
The polymer LCP may additionally comprise repeat units (I) , (XI) , (IIIa) , (IIIb) and/or (XII) . According to one alternative, the polymer LCP may be made of the following monomers: cyclohexanedicarboxylic acid (CHDA) , preferably 1, 4-CHDA, 2, 6-naphthalene dicarboxylic acid (NDA) (or derivative) , resorcinol (RS) (or derivative) and/or catechol (CT) (or derivative) . Alternatively, the polymer LCP may be made of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative, for example 6-acetoxy-2-naphthoic acid (AcHNA) ) , biphenol (BP) (or derivative, for example diacetoxybiphenyl (AcBP) ) , terephthalic acid (TPA) (or derivative) , as well as bibenzoic acids (BB) . For example, the polymer LCP may be made exclusively of HNA (or derivative) , BP or (derivative) , TPA(or derivative) and BB (or derivative) . The polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , CHDA (or derivative) , HNA (or derivative) , TPA (or derivative) and BB (or derivative) . The polymer LCP may also be made exclusively of HNA (or derivative) , BP (or derivative) , HQ (or derivative) , and BB (or derivative) , for example 4, 4’-BB, 3, 4’-BB or a combination of both, preferably 3, 4’-BB.
In some embodiments, the polymer LCP is such that the number of moles of repeat units is as follows:
- formulas (i) + (ii) + (iii) + (VII) + (VIII) + (IX) + (X) + (I) + (XI) + (IIIa) + (IIIb) + (XII) = 100 mol. %, wherein the number of moles of repeat units of formula (VII) , (VIII) , (IX) , (X) , (I) , (XI) , (IIIa) , (IIIb) and/or (XII) ≥0 mol. %,
- formulas (i) + (ii) + (iii) + (VII) + (VIII) + (IX) =100 mol. %, wherein the number of moles of repeat units of formula (VII) , (VIII) and/or (IX) ≥0 mol. %, and
- formulas (i) + (ii) + (iii) + (X) + (I) + (XI) + (IIIa) + (IIIb) + (XII) =100 mol. %, wherein the number of moles of repeat units of formula (X) , (I) , (XI) , (IIIa) , (IIIb) and/or (XII) ≥0 mol. %.
In these embodiments, the polymer LCP may be made exclusively of the following monomers: 6-hydroxy-2-naphthoic acid (HNA) (or derivative) , biphenol (BP) (or derivative) , hydroquinone (HQ) (or derivative) , bibenzoic acid (BB) (or derivative) , hydroxybenzoic acid (HBA) (or derivative, for example acetoxybenzoic acid (AcHBA) ) , for example 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA) , and bibenzoic acid (BB) (or derivative) .
For example, the polymer LCP of this third embodiment may be such that the number of moles of repeat units is as follows:
- formulas (i) + (ii) + (iii) =100 mol. %, for example formulas (i) + (iia) + (iiia) =100 mol. %, or formulas (i) + (iia) + (iiib) =100 mol. %
- formulas (i) + (ii) + (iii) + (X) =100 mol. %, for example formulas (i) + (iia) + (iiia) + (X) =100 mol. %, or formulas (i) + (iia) + (iiib) + (X) =100 mol. %,
- formulas (i) + (ii) + (iii) + (VII) =100 mol. %,
- formulas (i) + (ii) + (iii) + (VIII) =100 mol. %,
- formulas (i) + (ii) + (iii) + (IIIa) =100 mol. %, or
- formulas (i) + (ii) + (iii) + (IIIb) =100 mol. %.
The polymer LCP according to the third embodiment has a melting temperature (Tm) above 255℃, for example ranging between 256 and 340℃, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (2nd heat, heating/cooling rate of 20℃/min) , for example between 260 and 335℃, or between 261 and 330℃.
The polymer LCP according to the third embodiment has a crystallisation temperature (Tc) less than 275℃, for example ranging between 150 and 275℃, as determined using differential scanning calorimetry (DSC) according to ASTM D3418 (cool-down, heating/cooling rate of 20℃/min) , for example ranging between 155 and 260℃, or between 160 and 255℃.
The polymer LCP can be prepared by any conventional method adapted to the synthesis of liquid crystal polymers.
The polymer LCP can be prepared by thermal polycondensation of monomers and comonomers. The polymer LCP may contain a chain limiter, which is a monofunctional molecule capable of reacting with the hydroxyl or carboxylic acid moiety, and is used to control the molecular weight of the polymer LCP. For example, the chain limiter can be acetic acid, propionic acid and/or benzoic acid. Acatalyst can also be used. Examples of catalysts are phosphorus acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid. Astabiliser, such as a phosphite, may also be used.
The polymer LCP can be prepared by a solvent-free process, that-is-to-say a process conducted in the melt, in the absence of a solvent. When the condensation is solvent-free, the reaction can be carried out in equipment made from materials inert toward the monomers. In this case, the equipment is chosen in order to provide enough contact of the monomers, and in which the removal of volatile reaction products is feasible. Suitable equipment includes agitated reactors, extruders and kneaders.
The composition suitable for manufacturing sheet (P) according to the present invention is advantageously free from boron nitride and/or zinc oxide.
When present, said reinforcing filler is preferably selected from glass fibres, carbon fibres, and/or from mineral fillers, such as wollastonite, talc, calcium carbonate, silica, clay, mica, glass beads, and mixtures of the same.
Preferably, said composition comprises from 1 to 75 wt. %, more preferably from 5 to 60 wt. %, even more preferably from 10 to 45 wt. %, and still more preferably from 20 to 40 wt. %of a reinforcing filler based on the total weight of the composition.
According to a preferred embodiment, said reinforcing filler is glass fibres, carbon fibres or mixtures thereof. Glass fibres are even more preferred.
Glass fibres are silica-based glass compounds that contain several metal oxides which can be tailored to create different types of glass. The main oxide is silica in the form of silica sand; the other oxides such as calcium, sodium and aluminium are incorporated to reduce the melting temperature and impede crystallisation.
Preferably, the glass fibres are chopped glass fibres.
All glass fibre types, such as A, C, D, E, M, S, R, T glass fibres (as described in chapter 5.2.3, pages 43-48 of Additives for Plastics Handbook, 2nd ed, John Murphy) , or any mixtures thereof or mixtures thereof may be used. For example, R, Sand T glass fibres are high modulus glass fibres that have typically an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343.
Glass fibres may have a circular cross-section or a non-circular cross-section, such as oval, elliptical, rectangular, cocoon-shaped. Circular glass fibres are herein preferred. In one aspect, the diameter of the circular glass fibres can be 10μm (microns) , or from 2μm to 15μm, or from 5μm to 12μm.
The glass fibres may include milled or chopped glass fibres. They may be in the form of whiskers or flakes. In further examples, they may be short glass fibre or long glass fibre. The glass fibres may have a length of about 4 millimetres or longer are referred to as long fibres, and fibres shorter than this are referred to as short fibres. Short glass fibres are more preferred.
Advantageously, said LCP polymer or said composition comprises from 0.5 to 5 wt. %, preferably from 0.7 to 3 wt. %of PTFE based on the total weight of the composition.
Said composition can comprise additional ingredients, such as additional reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilisers, light stabilisers, flame retardants, nucleating agents and antioxidants.
Each of said additional ingredients can be present in an amount from 0.1 to about 5 wt. %based on the total weight of the composition.
Said additional reinforcing agents can be selected for example from: synthetic polymeric fibres, aramid fibres, aluminium fibres, titanium fibres, magnesium fibres, boron carbide fibres, rock wool fibres, steel fibres; talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, wollastonite, barium sulphate.
Said toughners can be selected for example from: elastomeric backbones comprising polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene-rubbers (EPR) ; ethylene-propylene-diene monomer rubbers (EPDM) ; ethylene-acrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA) , ethylene-vinylacetate (EVA) ; acrylonitrile-butadiene-styrene rubbers (ABS) , block copolymers styrene ethylene butadiene styrene (SEBS) ; block copolymers styrene butadiene styrene (SBS) ; core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or mixture of one or more of the above.
The composition can be prepared by melt-blending said polymer LCP, the reinforcing filler and optionally the PTFE and any other additive.
Any suitable melt-blending method known in the art may be used for mixing the ingredients of said composition. For example, the ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches. When the polymer LCP and the reinforcing filler are gradually added in batches, apart of the polymer LCP and/or of the reinforcing filler is first added, and then is melt-mixed with the remaining polymer LCP and with the other optional ingredients that are subsequently added, until an adequately mixed composition is obtained.
The composition is then moulded into sheet (P) .
Any moulding technique can be used for the manufacturer of sheet (P) , such as injection moulding, compression moulding or extrusion.
Advantageously, said sheet (P) has a thickness of from about 0.1 to 1 mm, preferably from 0.2 to 0.9 mm and more preferably from 0.3 to 0.7 mm.
Sheet (P) according to the present invention is not restricted in use within a specific battery system. However, it is advantageously used in a battery system to be used in automotive, such as hybrid cars or electric cars.
According to an embodiment, the present invention relates to a battery system comprising:
- a battery block comprising at least two adjacently stacked battery cells;
- fastening components that hold said at least two adjacent battery cells, comprising (i) apair of endplates, each disposed at one end of said at least two battery cells, and (ii) metal bands disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates;
wherein each of said endplates is applied to at least one sheet (P) as defined above.
Fig. 1 shows an exemplary battery system comprising sheet (P) according to this embodiment of the present invention, wherein the shape, dimension and thickness of the different parts are not scaled to each other.
Referring to Fig. 1, the battery system comprises a battery block 1 having a plurality of adjacently stacked battery cells 2 and fastening components 3 that hold the battery cells 2 of the battery block 1.
Preferably, the battery cells 2 are lithium ion batteries. However, other types of batteries can be used depending on the circumstances.
In Fig. 1, said battery cells 2 are represented as rectangular batteries. However, batteries having other shapes and disposed in different configurations can be provided.
The battery cells 2 are held in a fixed position by the fastening components 3, which comprise a pair of endplates 4 disposed at the end of the adjacently stacked battery cells 2 and metal bands 5 connected to said endplates 4 to hold the battery stack in a compressed state.
Optionally, apair of side plates (not represented in Fig. 1) can be disposed at the side-walls of the battery block 1, extending in the stacking direction of the battery cells 2 and connected with said endplates 4 or said metal bands 5.
As represented in Fig. 1, the endplates 4 have a rectangular shape that is the same shape of the battery cells 2. It is preferred that the endplates 4 are of the same shape and dimension of the battery cells 2 (or slightly larger) so that the endplates 4 connected by the metal bands 5 do not distort and can hence prevent the expansion at the centre region of the battery cells 2.
However, the endplates 4 can be provided of any shape and dimension, depending on the shape and dimension of the battery cells 2 and on the final use for which the battery system 1 is intended.
Preferably, the endplates 4 are made of metal, such as aluminium or an alloy of aluminium, or from a plastic resin, more preferably a thermoplastic resin.
As represented in Fig. 1, the sheet (P) 6 according to the present invention has the same shape and dimension of the endplates 4.
However, said sheet (P) 6 can be provided of any shape and dimension, depending on the final shape and dimensions of each of the endplates 4, the battery cells 2 and the battery system 1.
Preferably, sheet 6 is applied to said endplates 4 via an adhesive layer, such as a pressure-sensitive adhesive, or alternatively sheet 6 can be laminated onto said endplates 4.
According to another embodiment, at least one sheet (P) 6 can be interposed between at least one pair, more preferably between each pair, of the adjacently stacked battery cells 2 (not shown in Figure 1) .
Preferably, said sheet 6 is interposed between at least one pair of the adjacently stacked battery cells 2 and hold in position via the mechanical action of the metal bands 5. Alternatively, said sheet 6 is hold in position via an adhesive layer, such as a pressure-sensitive adhesive.
According to this embodiment, the present invention relates to a battery system comprising:
- a battery block comprising at least two adjacently stacked battery cells;
- fastening components that hold said at least two battery cells, comprising (i) a pair of endplates, each disposed at one end of said at least two adjacently stacked battery cells, and (ii) metal bands disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates;
wherein at least one sheet (P) as defined above is interposed between at least two, more preferably between all, adjacently stacked battery cells (2) .
According to this embodiment, the use of sheet (P) as replacement of the traditional spacer used to date, which is called aerogel, allows to obtain advantages in terms of enhanced resistance to high temperature (even above 400℃) , aprolonged lifetime and a consistent performance under severe environmental conditions, for example under extreme low or high temperatures and with severe compression.
According to another and preferred embodiment, the present invention relates to a battery system (1) comprising:
- a battery block comprising at least two adjacently stacked battery cells;
- fastening components that hold said at least two battery cells, comprising (i) a pair of endplates, each disposed at one end of said at least two adjacently stacked battery cells, and (ii) metal bands disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates;
wherein at least one sheet (P) as defined above is
- applied to each of said endplates; and
- interposed between at least two adjacently stacked battery cells.
According to this embodiment, the use of sheet (P) coupled with the end plates and interposed between each pair of the adjacently stacked battery cells allow to achieve an outstanding electrical insulation of the whole battery system.
Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
The present invention will be further described with reference to the following examples.
Experimental section
_________________________________________________________________
Materials
LCP SRT 300 (terephthalic acid/biphenol/4-hydroxybenzoic acid 25/25/50 mol. ratio) was obtained by Solvay Specialty Polymers U.S.A., LLC..
Round chopped E-glass fibres, polycarbonate (PC) and the epoxy resin were commercially available.
Manufacture of the sheets
100 sheets having a dimension of 150mm*100mm and thickness of 0.5 mm were prepared by blending the LCP polymer and 30 wt. %of glass fibres and injection moulding said bland at a temperature from 350 to 430℃, at a pressure of 80 to 120 Mpa, using a high speed injection moulding machine.
The sheets were tested as described below.
For comparison, sheets having the same dimensions and thickness were obtained from compositions comprising
- polycarbonate (PC) without glass fibres
- a commercial epoxy resin comprising 30 wt. %of glass fibres.
Test 1-Evaluation of ageing and electric properties
32 sheets were put in an oven at 400℃ and kept at the same temperature for 30 minutes.
After this time, the sheets were tested for the following properties:
(A1) 1000V DC (direct current) for 15 seconds: the insulation resistance had to be>1 GΩ (giga-ohms)
(B1) 3000V DC for 15 seconds: withstand voltage leakage current had to be<0.1 mA
(C1) thermal conductivity had to be<0.05 W/ (m·K)
The sheets according to the present invention after 30 minutes maintained a good shape and passed all tests (A1) , (B1) and (C1) .
The sheets made from polycarbonate after 30 minutes had decarbonized.
The sheets made from the epoxy resin after 30 minutes decomposed and turned into separate glass fibre cloths.
Test 2-Fatigue test under low temperature
The aim of this test was to confirm whether the sheets cracked or met the insulation withstand voltage requirements.
The test was performed as follows.
1. An environmental box was allowed to reach a temperature of-30℃ by decreasing its temperature of 5℃/min. Once-30℃ were reached, the temperature was kept stable and 5 sheets according to the present invention (each put onto an aluminium plate) were put into the environmental box. The sheets were stored for 1 hour.
2. The sheets were extracted from the environmental box and a pressure of 20 KN was applied onto the sheets for 30 minutes. The sheets were then bended at 10° at a rate of 1°/s, then released, and back and forth for 50 times.
After this treatment, the sheets were evaluated as follows:
(A2) Insulation resistance under load pressure test≥1000MΩ@1000V DC, lasting 60 seconds;
(B2) withstand voltage leakage current≤1 mA@3000V DC, lasting 60 seconds.
The tests (A2) and (B2) were repeated every 50 times, until 2000 bending was achieved.
After completing the fatigue test (2000 bendings) , the appearance of the sample did not changed significantly and the sheets according to the present invention passed both tests (A2) and (B2) .
Claims (17)
- A sheet [sheet (P) ] having a thickness equal to or lower than 3 mm and made from at least one liquid crystal polymer [polymer LCP] .
- The sheet (P) according to Claim 1, which is made from a composition comprising:- at least one liquid crystal polymer [polymer LCP] ;- from about 5 wt. %to about 50 wt. %of at least one reinforcing filler.
- The sheet (P) according to Claim 2, said composition comprising from 50 to 90 wt. %of said polymer LCP, based on the total weight of the composition.
- The sheet (P) accordion to Claim 2, said composition comprising from 1 to 75 wt. %of at least one reinforcing filler based on the total weight of the composition.
- The sheet (P) according to anyone of the preceding Claims, wherein said polymer LCP is obtained from the polycondensation reaction of: (I) terephthalic acid, (II) at least one aromatic diol, (III) at least one aromatic dicarboxylic and/or hydroxycarboxylic acid.
- The sheet (P) according to Claim 5, wherein said- at least one aromatic diol is represented by a formula selected from the following group of formulae:HO-Ar 1-OH (1)HO-Ar 2-T 1-Ar 3-OH (2)whereinAr 1 to Ar 3 are each independently selected C 6-C 30 aryl groups, optionally substituted with one or more substituents selected from the group consisting of halogen, aC 1-C 15 alkyl, and a C 6-C 15 aryl; andT 1 is selected from the group consisting of a bond, O, S, -SO 2-, -C (=O) -, and a C 1-C 15 alkyl;and/or- at least one aromatic dicarboxylic acid is represented by a formula selected from the following group of formulae:HOOC-Ar 1-COOH (3)HOOC-Ar 2-T 2-Ar 3-COOH (4)whereinAr 1 to Ar 3 are independently selected and have the meanings as defined above; andT 2 is selected from the group consisting of a sigma bond, O and S;and/or- said at least one aromatic hydroxycarboxylic acid is represented by a formula selected from the group consisting ofHO-Ar 1-COOH (5)HO-Ar 2-Ar 3-COOH (6)whereinAr 1 to Ar 3 are independently selected and have the meanings as defined above.
- The sheet (P) according to anyone of Claims 1 to 4, wherein said polymer LCP comprises:- from 40 to 98 mol. %of repeat units of formula (I) :
- from 1 to 20 mol. %of repeat units of formula (IIa) , (IIb) , (IIc) and/or (IId) :
and- from 1 to 12 mol. %of repeat units of formula (IIIa) and/or (IIIb) :
based on the total number of moles in the polymer LCP. - The sheet (P) according to anyone of Claims 1 to 4, wherein said polymer LCP comprises:a) from 40 to 98 mol. %of repeat units of formula (i) :
b) from 1 to 30 mol. %of repeat units of formula (ii) :
andc) repeat units with two carboxyl groups of formula (iii) :- from 1 to 23 mol. %of repeat units of formula (iiia) :and/or
- from 1 to 13 mol. %of repeat units of formula (iiib) :
- The sheet (P) according to anyone of Claims 2 to 8, wherein said at least one reinforcing filler is selected from glass fibres, carbon fibres, glass beads, and/or from mineral fillers, and mixtures of the same.
- The sheet (P) according to anyone of the preceding Claims, wherein said polymer LCP or said composition further comprises 0.5 to 5 wt. %of poly (tetrafluoroethylene) (PTFE) based on the total weight of said polymer LCP or of said composition.
- A battery system (1) comprising:- a battery block comprising at least two adjacently stacked battery cells (2) ;- fastening components (3) that hold said at least two battery cells, comprising (i) apair of endplates (4) , each disposed at one end of said at least two battery cells, and (ii) metal bands (5) disposed at the battery block side-walls extending in the stacking direction of the battery cells and connected at both ends to the endplates (4) ;wherein at least one sheet (P) (6) as defined in any one of Claims 1 to 10 is:- applied to each of said endplates (4) ; and/or- interposed between at least two adjacently stacked battery cells (2) .
- The battery system 1 according to Claim 11, wherein at least one sheep (P) as defined in any one of Claims 1 to 10 is applied to each of said endplates (4) .
- The battery system 1 according to Claim 12, wherein said sheet (P) (6) is applied to said endplates (4) via an adhesive layer, such as a pressure-sensitive adhesive.
- The battery system 1 according to Claim 13, wherein said sheet (P) (6) is laminated onto said endplates (4) .
- The battery system 1 according to Claim 11, wherein at least one sheet (P) (6) as defined in any one of Claims 1 to 10 is interposed between at least two adjacently stacked battery cells (2) .
- The battery system 1 according to Claim 11 or 15, wherein at least one sheet (P) (6) as defined in any one of Claims 1 to 10 is interposed between each pair of adjacently stacked battery cells (2) .
- The battery system 1 according to Claim 11, wherein at least one sheet (P) (6) as defined in any one of Claims 1 to 10 is- applied to each of said endplates (4) and- interposed between at least two, preferably between all pairs of, adjacently stacked battery cells (2) .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNPCT/CN2022/084165 | 2022-03-30 | ||
| CN2022084165 | 2022-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023185162A1 true WO2023185162A1 (en) | 2023-10-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2022/143137 WO2023185162A1 (en) | 2022-03-30 | 2022-12-29 | Insulator for batteries |
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| Country | Link |
|---|---|
| WO (1) | WO2023185162A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360647A (en) * | 1990-09-28 | 1994-11-01 | Daicel Chemical Industries, Ltd. | Composite metal sheets |
| US20100167115A1 (en) * | 2008-12-27 | 2010-07-01 | Wataru Okada | Battery system with battery cells held in a stack by metal bands |
| US20190097189A1 (en) * | 2017-09-28 | 2019-03-28 | GM Global Technology Operations LLC | Polymeric battery frames and battery packs incorporating the same |
| WO2021180759A1 (en) * | 2020-03-13 | 2021-09-16 | Solvay Specialty Polymers Usa, Llc | Liquid crystal polymer compositions and corresponding articles |
-
2022
- 2022-12-29 WO PCT/CN2022/143137 patent/WO2023185162A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360647A (en) * | 1990-09-28 | 1994-11-01 | Daicel Chemical Industries, Ltd. | Composite metal sheets |
| US20100167115A1 (en) * | 2008-12-27 | 2010-07-01 | Wataru Okada | Battery system with battery cells held in a stack by metal bands |
| US20190097189A1 (en) * | 2017-09-28 | 2019-03-28 | GM Global Technology Operations LLC | Polymeric battery frames and battery packs incorporating the same |
| WO2021180759A1 (en) * | 2020-03-13 | 2021-09-16 | Solvay Specialty Polymers Usa, Llc | Liquid crystal polymer compositions and corresponding articles |
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