CA2010106A1 - Polyethers - Google Patents
PolyethersInfo
- Publication number
- CA2010106A1 CA2010106A1 CA 2010106 CA2010106A CA2010106A1 CA 2010106 A1 CA2010106 A1 CA 2010106A1 CA 2010106 CA2010106 CA 2010106 CA 2010106 A CA2010106 A CA 2010106A CA 2010106 A1 CA2010106 A1 CA 2010106A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- mol
- structural element
- polyarylene ether
- recurring structural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 8
- 229920000412 polyarylene Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 16
- 150000002170 ethers Chemical class 0.000 abstract description 14
- 239000012770 industrial material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 3
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 alkaline earth metal carbonates Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001643 poly(ether ketone) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 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 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- 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
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PISLKPDKKIDMQT-UHFFFAOYSA-N [3-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=CC(F)=CC=2)=C1 PISLKPDKKIDMQT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Novel polyethers Abstract The invention relates to polyarylene ethers which, relative to the total amount of the structural elements present in the polyether resin, contain 10-90 mol % of a recurring structural element of the formula I
(I) and 10-90 mol % of a recurring structural element of the formula II
(II) in which X and X' independendy of one another are -SO-, -SO2- or -CO-, R1, R2, R3 and R4 independently of one another are hydrogen or C1-C4alkyl and A is an aromatic radical.
These industrial materials are distinguished by very good mechanical and thermalproperties.
(I) and 10-90 mol % of a recurring structural element of the formula II
(II) in which X and X' independendy of one another are -SO-, -SO2- or -CO-, R1, R2, R3 and R4 independently of one another are hydrogen or C1-C4alkyl and A is an aromatic radical.
These industrial materials are distinguished by very good mechanical and thermalproperties.
Description
ZQ~nfi Novel polYethers The present invention relates to novel polyarylene ethers, to a process for their preparation and to their use as industrial materials.
Polyether-sulfones and polyether-ketones which are built up on a bisphenolspirobiindane basis are known from WO 88io6605. These do not, however, meet in all respects the high requirements which are nowadays set for a high-grade thermoplastic resin. Thus, in particular, the mechanical properties are not satisfactory, which manifests itself, inter alia, in a tensile strength which is inadequate in some cases.
The present invention relates to novel industrial materials having very good mechanical properties and an excellent dimensional stability under heat. Surprisingly, the polyarylene ethers having bisphenolspirobiindane structural units achieve, in spite of a relatively high aliphatic content, excellent mechanical and thermal properties.
.:
The high-grade thermoplastic resins according to the invention are polyarylene ethers which, rélative to the total amount of ~tructural elements present in the polyether resin, contain 10-90 mol % of a recurring structural element of the fonnula I
, .
, ~
Rl R2 to~3X-3-o~(l) and 10-90 mol % of a recurring structural element of the formula II
~3X~}o-A -o~ (n) in which X and X' independently of one another are SO-, -SO2- or -CO-, Rl, R2, R3 and R4 independently of one another are hydrogen or Cl-C4aL~cyl and A is a group of the formulae IIla-IIIe .
'~Y'{3 (Illd)or '~}Y'~3Y'~ (l~lo), in which Y is -CH2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO- and Y' is a direct bond, ' -CH2-, -C(CH3)2-, -C(CF3)2, -S-, -SO-, -SO2-, -O- or-CO-.
The polyarylene ethers according to the invention preferably contain 10-70 mol % of a recurring structural element of the formula I and 90-30 mol % of a recurring structural element of the formula II.
. ~ .
,, Polyarylene ethers which are particularly preferred contain 10-45 mol % of a recurring sl ~ structural element of the formula I and 90-55 mol % of a recurring structural element of ~, the formula II.
, The polyarylene ethers according to the invention have a reduced viscosity of about 0.1 to ~: 1.5 dVg. This corresponds to a molecular weight (weight average) of 2000 to about oo,ooo.
.
~, ~!
:
;, ,, , . . . " :' ' ': . ', . :, . ' "- '.., ' , ~,'. '.' ', ,',"",, ",,',',' ' '''"''' ',..' "'"' ' ". ', ", ,' ., fi The preferred meàning of X in the formula I and of X' in the formula II is -SO2- or -CO-.
If the radicals Rl, R2, R3 and R4 are Cl-C4aL~cyl, they can be methyl, ethyl, n-propyl, isopropyl or n-butyl. The profeIred meaning of Rl, R2, R3 and R4 is methyl.
The preferred meaning of Y in the formula IIIc is -S-, -SO2-, -O- or -CO- and of Y' in the forrnulae IIId and IIIe is a direct bond, -C(CH3)2-, -S-, -SO2-, -O- or -CO-.
The group A preferably has à formula IIIa or IIIc in which Y is -S-, -SO2-, -O- or -CO-.
A group A which has a forrnula IIIc in which Y is -SO2- is particularly preferred.
The polyarylene ethers according to the invention can be prepared, for example, by subjecting to polycondensation, in a manner known per se in the presence of aLkaline catalysts in a polar, aprotic solvent, a compound of the formula IV
i Hal ~X~ Hal (IV)-.~ .
in which Hal is halogen, in par~icular fluorine or chlorine, and X is as defined above, with a spirobiindane of the formula V
HO~OH (V), in which Rl, R2, R3 and R4 are as defined above, and with a mixture of a compound of the formula V and a phenol, present in the mixture to the extent of up to 90 mol %, of the fonnula VI
f~' HO-A-OH (VI) `~1 :~!
. ~ .
:'", ~ '- '.', ;' ': :'';' - ' ' ' , .' ~ ' ' ' '. ,. ' !:, . : : ' ~2(~ 6 in which A is as defined above.
Instead of the diphenols of the formulae V and VI, it is also possible to employ the corresponding alkali metal or alkaline earth metal phenates, for example the potassium or calcium phenates or mixtures thereof.
The polycondensation reaction is usually carried out with approximately equimolar ratios of the compounds IV:V and IV:(V+VI). Approximately equimolar amounts are to be understood in this connection as meaning a molar ratio of 0.8:1.2 to 1.2:0.8.
The alkaline catalysts used in this process are, as a rule, alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate;
however, it is also possible to use other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
Examples of polar, aprotic solvents which can be employed in the process for thepreparation of the polyether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and, preferably, diphenyl sulfone.
'.:
The reaction is preferably carried out at an elevated temperature, preferably up to the reflux temperature of the solvent, accordingly up to about 350C.
It is frequently advisable concomitantly to use an entraining agent, for example, chlorobenzene, xylene or toluene, in order to make it possible to remove azeotropically from the reaction mixture the water forrned in the reaction.
The compounds of the formula IV are known and in part are comrnercially available.
Examples of suitable compounds of the formula IV are 4,4'-difluorobenzophenone, 1,3-bis-(4-fluorobenzoyl)-benzene, 4,4'-dichlorobenzophenone, 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone.
The compounds of the formula V are also known and can be prepared, for example, in accordance with EP-0,264,026. In this regard the compound of the formula V~
- . .. . . . . . . .
.. . . . . . . . .
-.:, ,: ~: ,, ., . . ; . . .
,. ... . , . ~
. . . .. . ..... . . . . .
: . . . ., , , .. ~ . . . .
. . .
2Q~0106 ;~ OH (V'`), is particularly preferred.
The compounds of the formula VI are also known compounds and are for the most part commercially available. Examples of suitable dihydric phenols of the formula VI are hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl thioether or dihydroxynaphthalene.
The polyether resins according to the inven~ion can be employed in the manner customary for thermoplastics and can, for example, be processed to give mouldings or films or can be employed as matrix resins, adhesives or coating agents. Customary additives, for example fillers, pigments, stabilizers or reinforcing agents, such as carbon, boron or glass fibres, can be added before the processing of the polyarylene ethers, which are in the form of, for example, compression moulding powders, melts or solutions. The polyarylene ethers according to the invention can also be processed together with other then~oplastics In addition, they are suitable for use as modifying agents for heat-curable resins, such as epoxy resins or bismaleimides The polyarylene ethers according to the invention are preferentially suitable for use as matrix resins for the production of fibre composite systems, it being possible to employ the customary fibres used in the reinforcing of industrial materials as reinforcing fibres These can be organic or inorganic fibres, natural fibres or synthedc fibres, such as aramid fibres, and can be in the form of fibre bundles, oriented or non-oriented fibres or continuous fibres Reinforcing fibres used are, for example, glass, asbestos, boron, carbon and metal fibres As the range of applications described above shows, the polyarylene ethers according to the invention can be widely employed as lndustrial materials ~ .,.. , - .. ,. ., ~ .. . . . .. .. , . ~............ ... .. .
2Q~om~
Example 1: A mixture of 15.45 g (0.0501 mole) of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (prepared in accordance with Example 1 of EP-A Q,264,026), 5.54 g t0.0503 mole) of hydroquinone, 81.24 g of diphenyl sulfone, 7.64 g (0.0553 mole) of potassium carbonate, 5.88 g (0.0587 mole) of calcium carbonate and 52.24 g of xylene are heated under nitrogen in a round-bottomed flask equipped with a stirrer and an attachment for protective gas a~ a bath temperature of 200C, and a xylene/water mixture is distilled off. Towards the end of the distillation process a vacuum (200 Pa) is also applied for a short time. 21.89 g (0.1003 mole) of 4,4'-difluorobenzophenone are then added to the reaction mixture, and the temperature is raised to 250C and is kept there for 1 hour. This is followed by 1 hour at 300C and 2 hours at 320C, in the course of which the reaction mixture becomes increasingly viscous.
. ~
After cooling, the reaction mixture is taken out of the flask and powdered, and 2N
hydrochloric acid is added, the mixture is washed with water until neutral and extracted in a Soxhlet extractor, ~Irst with water and then with acetone. The polymer is then dried in a vacuum drying cabinet to a final temperature of 240C. A polyether ketone copolymer containing bisphenolspirobii;ldane units prepared in this manner has a glass transition temperature (Tg) of 189C, determined by DSC.
Examples 2-6: A mixture of 15.48 g (0.0502 mole) of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 10.78 g (0.0503 mole) of 4,4'-dihydroxybenzophenone, 81.24 g of diphenyl sulfone, 15.28 g (0.1106 mole) of potassium carbonate and 52.24 g of xylene is heated under nitrogen in a round-bottomed flask equipped with a stirrer and an attachment for protective gas at a bath temperature of 200C, and a xylene/water mixture is distilled off. Towards the end of the distillation process a vacuum is also applied for a short time. 21.89 g (0.1003 mole) of 4,4'-difluorobenzophenone are then added to the reaction mixture and the temperature is raised to 250C and is kept there for 1 hour. This is followed by 1 hour at 300C and 2 hours at 320C, in the course of which the reaction mixture becomes increasingly viscous.
After cooling the reaction mixture is taken out of the flask and powdered, and acedc acid is added and the mixture is washed with water until neutral and extracted in a Soxhlet extractor first with water and then with acetone. The polymer is then dissolved in a suitable solvent (in Example 4: N-methylpylrolidone; in Examples 5 and 6: methylene chloride) and in each case is precipitated in isopropanol. The polymer is then dried in a .t ' '' .. ,., ' . ' " ' ~ , ' ' . .
~ . ' 2~ fi vacuum drying cabinet to a final temperature of 240C. The glass transition temperatures (Tg), determined by DSC, of the polyarylene ethers containing bisphenolspirobiindane units prepared in this way are collated in the table below. The loss in weight is determined by TGA to demonstrate the good heat stability of the polyarylene e~thers described.
The results are also listed in the table below:
.
.
. . ~ . : - : .
. :
XQlO~Q6 ,_~
~o ~¢ 8 8 æ
~ ~ A A A ~
,_ ~2 o U~ .
~_~ ~ .0 ' ~ ~
O _- _, ~, ~ ~, ~
~ _ o C~
~, ~ ~0 ~ .. C Q;~
~ ~ C
~ ~ ~ ., '~ ~ C~l ~ o~o~
c ~ o~ 8 æ ~ ~ ~ O
~1 t ~ .
s~
~,. , , . ,.:.. ,:
,~' :. , . .~,, :"" , , . . ;.
2~
~' - -o ~
~ ~ o -~l o 1~
o ~ ~ v^~
.
~'3 ~ ~ ~c.c; .q .c .~.~i ~r .
: .
`...... : , -.. - ;.. . . . ...
Qfi For two examples the following table lists a few values which demonstrate the very good mechanical properties of the polyarylene ethers according to the invention containing bisphenol spirobiindane units.
Ex- Tensile strength Elongation at ample [N/mm2] break 2 Polyether-ketone copolymer 45 ¦ 7-9 6 Polyether sulfone copolymer 56 4.0 Measurement carr'ed out on hlms (thiclmess approx. 0.2 mm) as specifi~d in DIN 53,455.
.
,~.
~.
, ., .
~q `3 ., .~:
" . , . ~ ; . . :
Polyether-sulfones and polyether-ketones which are built up on a bisphenolspirobiindane basis are known from WO 88io6605. These do not, however, meet in all respects the high requirements which are nowadays set for a high-grade thermoplastic resin. Thus, in particular, the mechanical properties are not satisfactory, which manifests itself, inter alia, in a tensile strength which is inadequate in some cases.
The present invention relates to novel industrial materials having very good mechanical properties and an excellent dimensional stability under heat. Surprisingly, the polyarylene ethers having bisphenolspirobiindane structural units achieve, in spite of a relatively high aliphatic content, excellent mechanical and thermal properties.
.:
The high-grade thermoplastic resins according to the invention are polyarylene ethers which, rélative to the total amount of ~tructural elements present in the polyether resin, contain 10-90 mol % of a recurring structural element of the fonnula I
, .
, ~
Rl R2 to~3X-3-o~(l) and 10-90 mol % of a recurring structural element of the formula II
~3X~}o-A -o~ (n) in which X and X' independently of one another are SO-, -SO2- or -CO-, Rl, R2, R3 and R4 independently of one another are hydrogen or Cl-C4aL~cyl and A is a group of the formulae IIla-IIIe .
'~Y'{3 (Illd)or '~}Y'~3Y'~ (l~lo), in which Y is -CH2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO- and Y' is a direct bond, ' -CH2-, -C(CH3)2-, -C(CF3)2, -S-, -SO-, -SO2-, -O- or-CO-.
The polyarylene ethers according to the invention preferably contain 10-70 mol % of a recurring structural element of the formula I and 90-30 mol % of a recurring structural element of the formula II.
. ~ .
,, Polyarylene ethers which are particularly preferred contain 10-45 mol % of a recurring sl ~ structural element of the formula I and 90-55 mol % of a recurring structural element of ~, the formula II.
, The polyarylene ethers according to the invention have a reduced viscosity of about 0.1 to ~: 1.5 dVg. This corresponds to a molecular weight (weight average) of 2000 to about oo,ooo.
.
~, ~!
:
;, ,, , . . . " :' ' ': . ', . :, . ' "- '.., ' , ~,'. '.' ', ,',"",, ",,',',' ' '''"''' ',..' "'"' ' ". ', ", ,' ., fi The preferred meàning of X in the formula I and of X' in the formula II is -SO2- or -CO-.
If the radicals Rl, R2, R3 and R4 are Cl-C4aL~cyl, they can be methyl, ethyl, n-propyl, isopropyl or n-butyl. The profeIred meaning of Rl, R2, R3 and R4 is methyl.
The preferred meaning of Y in the formula IIIc is -S-, -SO2-, -O- or -CO- and of Y' in the forrnulae IIId and IIIe is a direct bond, -C(CH3)2-, -S-, -SO2-, -O- or -CO-.
The group A preferably has à formula IIIa or IIIc in which Y is -S-, -SO2-, -O- or -CO-.
A group A which has a forrnula IIIc in which Y is -SO2- is particularly preferred.
The polyarylene ethers according to the invention can be prepared, for example, by subjecting to polycondensation, in a manner known per se in the presence of aLkaline catalysts in a polar, aprotic solvent, a compound of the formula IV
i Hal ~X~ Hal (IV)-.~ .
in which Hal is halogen, in par~icular fluorine or chlorine, and X is as defined above, with a spirobiindane of the formula V
HO~OH (V), in which Rl, R2, R3 and R4 are as defined above, and with a mixture of a compound of the formula V and a phenol, present in the mixture to the extent of up to 90 mol %, of the fonnula VI
f~' HO-A-OH (VI) `~1 :~!
. ~ .
:'", ~ '- '.', ;' ': :'';' - ' ' ' , .' ~ ' ' ' '. ,. ' !:, . : : ' ~2(~ 6 in which A is as defined above.
Instead of the diphenols of the formulae V and VI, it is also possible to employ the corresponding alkali metal or alkaline earth metal phenates, for example the potassium or calcium phenates or mixtures thereof.
The polycondensation reaction is usually carried out with approximately equimolar ratios of the compounds IV:V and IV:(V+VI). Approximately equimolar amounts are to be understood in this connection as meaning a molar ratio of 0.8:1.2 to 1.2:0.8.
The alkaline catalysts used in this process are, as a rule, alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate;
however, it is also possible to use other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
Examples of polar, aprotic solvents which can be employed in the process for thepreparation of the polyether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and, preferably, diphenyl sulfone.
'.:
The reaction is preferably carried out at an elevated temperature, preferably up to the reflux temperature of the solvent, accordingly up to about 350C.
It is frequently advisable concomitantly to use an entraining agent, for example, chlorobenzene, xylene or toluene, in order to make it possible to remove azeotropically from the reaction mixture the water forrned in the reaction.
The compounds of the formula IV are known and in part are comrnercially available.
Examples of suitable compounds of the formula IV are 4,4'-difluorobenzophenone, 1,3-bis-(4-fluorobenzoyl)-benzene, 4,4'-dichlorobenzophenone, 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone.
The compounds of the formula V are also known and can be prepared, for example, in accordance with EP-0,264,026. In this regard the compound of the formula V~
- . .. . . . . . . .
.. . . . . . . . .
-.:, ,: ~: ,, ., . . ; . . .
,. ... . , . ~
. . . .. . ..... . . . . .
: . . . ., , , .. ~ . . . .
. . .
2Q~0106 ;~ OH (V'`), is particularly preferred.
The compounds of the formula VI are also known compounds and are for the most part commercially available. Examples of suitable dihydric phenols of the formula VI are hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl thioether or dihydroxynaphthalene.
The polyether resins according to the inven~ion can be employed in the manner customary for thermoplastics and can, for example, be processed to give mouldings or films or can be employed as matrix resins, adhesives or coating agents. Customary additives, for example fillers, pigments, stabilizers or reinforcing agents, such as carbon, boron or glass fibres, can be added before the processing of the polyarylene ethers, which are in the form of, for example, compression moulding powders, melts or solutions. The polyarylene ethers according to the invention can also be processed together with other then~oplastics In addition, they are suitable for use as modifying agents for heat-curable resins, such as epoxy resins or bismaleimides The polyarylene ethers according to the invention are preferentially suitable for use as matrix resins for the production of fibre composite systems, it being possible to employ the customary fibres used in the reinforcing of industrial materials as reinforcing fibres These can be organic or inorganic fibres, natural fibres or synthedc fibres, such as aramid fibres, and can be in the form of fibre bundles, oriented or non-oriented fibres or continuous fibres Reinforcing fibres used are, for example, glass, asbestos, boron, carbon and metal fibres As the range of applications described above shows, the polyarylene ethers according to the invention can be widely employed as lndustrial materials ~ .,.. , - .. ,. ., ~ .. . . . .. .. , . ~............ ... .. .
2Q~om~
Example 1: A mixture of 15.45 g (0.0501 mole) of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (prepared in accordance with Example 1 of EP-A Q,264,026), 5.54 g t0.0503 mole) of hydroquinone, 81.24 g of diphenyl sulfone, 7.64 g (0.0553 mole) of potassium carbonate, 5.88 g (0.0587 mole) of calcium carbonate and 52.24 g of xylene are heated under nitrogen in a round-bottomed flask equipped with a stirrer and an attachment for protective gas a~ a bath temperature of 200C, and a xylene/water mixture is distilled off. Towards the end of the distillation process a vacuum (200 Pa) is also applied for a short time. 21.89 g (0.1003 mole) of 4,4'-difluorobenzophenone are then added to the reaction mixture, and the temperature is raised to 250C and is kept there for 1 hour. This is followed by 1 hour at 300C and 2 hours at 320C, in the course of which the reaction mixture becomes increasingly viscous.
. ~
After cooling, the reaction mixture is taken out of the flask and powdered, and 2N
hydrochloric acid is added, the mixture is washed with water until neutral and extracted in a Soxhlet extractor, ~Irst with water and then with acetone. The polymer is then dried in a vacuum drying cabinet to a final temperature of 240C. A polyether ketone copolymer containing bisphenolspirobii;ldane units prepared in this manner has a glass transition temperature (Tg) of 189C, determined by DSC.
Examples 2-6: A mixture of 15.48 g (0.0502 mole) of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 10.78 g (0.0503 mole) of 4,4'-dihydroxybenzophenone, 81.24 g of diphenyl sulfone, 15.28 g (0.1106 mole) of potassium carbonate and 52.24 g of xylene is heated under nitrogen in a round-bottomed flask equipped with a stirrer and an attachment for protective gas at a bath temperature of 200C, and a xylene/water mixture is distilled off. Towards the end of the distillation process a vacuum is also applied for a short time. 21.89 g (0.1003 mole) of 4,4'-difluorobenzophenone are then added to the reaction mixture and the temperature is raised to 250C and is kept there for 1 hour. This is followed by 1 hour at 300C and 2 hours at 320C, in the course of which the reaction mixture becomes increasingly viscous.
After cooling the reaction mixture is taken out of the flask and powdered, and acedc acid is added and the mixture is washed with water until neutral and extracted in a Soxhlet extractor first with water and then with acetone. The polymer is then dissolved in a suitable solvent (in Example 4: N-methylpylrolidone; in Examples 5 and 6: methylene chloride) and in each case is precipitated in isopropanol. The polymer is then dried in a .t ' '' .. ,., ' . ' " ' ~ , ' ' . .
~ . ' 2~ fi vacuum drying cabinet to a final temperature of 240C. The glass transition temperatures (Tg), determined by DSC, of the polyarylene ethers containing bisphenolspirobiindane units prepared in this way are collated in the table below. The loss in weight is determined by TGA to demonstrate the good heat stability of the polyarylene e~thers described.
The results are also listed in the table below:
.
.
. . ~ . : - : .
. :
XQlO~Q6 ,_~
~o ~¢ 8 8 æ
~ ~ A A A ~
,_ ~2 o U~ .
~_~ ~ .0 ' ~ ~
O _- _, ~, ~ ~, ~
~ _ o C~
~, ~ ~0 ~ .. C Q;~
~ ~ C
~ ~ ~ ., '~ ~ C~l ~ o~o~
c ~ o~ 8 æ ~ ~ ~ O
~1 t ~ .
s~
~,. , , . ,.:.. ,:
,~' :. , . .~,, :"" , , . . ;.
2~
~' - -o ~
~ ~ o -~l o 1~
o ~ ~ v^~
.
~'3 ~ ~ ~c.c; .q .c .~.~i ~r .
: .
`...... : , -.. - ;.. . . . ...
Qfi For two examples the following table lists a few values which demonstrate the very good mechanical properties of the polyarylene ethers according to the invention containing bisphenol spirobiindane units.
Ex- Tensile strength Elongation at ample [N/mm2] break 2 Polyether-ketone copolymer 45 ¦ 7-9 6 Polyether sulfone copolymer 56 4.0 Measurement carr'ed out on hlms (thiclmess approx. 0.2 mm) as specifi~d in DIN 53,455.
.
,~.
~.
, ., .
~q `3 ., .~:
" . , . ~ ; . . :
Claims (8)
1. A polyarylene ether which, relative to the total amount of structural elements present in the polyether resin, contains 10-90 mol % of a recurring structural element of the formula (I) and 10-90 mol % of a recurring structural element of the formula II
(II) in which X and X' independently of one another are -SO-, -SO2- or -CO-, R1, R2, R3 and R4 independently of one another are hydrogen or C1-C4alkyl and A is a group of the formulae IIIa-IIIe (IIIa), (IIIb), (IIIc), (IIId) oder (IIIe), in which Y is -CH2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO- and Y' is a direct bond, -CH2-, -C(CH3)2, -C(CF3)2, -S-, -SO-, -SO2-, -O- or-CO-.
(II) in which X and X' independently of one another are -SO-, -SO2- or -CO-, R1, R2, R3 and R4 independently of one another are hydrogen or C1-C4alkyl and A is a group of the formulae IIIa-IIIe (IIIa), (IIIb), (IIIc), (IIId) oder (IIIe), in which Y is -CH2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO- and Y' is a direct bond, -CH2-, -C(CH3)2, -C(CF3)2, -S-, -SO-, -SO2-, -O- or-CO-.
2. A polyarylene ether according to claim 1, which contains 10-70 mol % of a recurring structural element of the forrnula I and 90-30 mol % of a recurring structural element of the formula II.
3. A polyarylene ether according to claim 1, which contains 10-55 mol % of a recurring structural elements of the formula I and 90-45 mol % of a recurring structural element of the formula II.
4. A polyarylene ether according to claim 1, in which X in formula I and X' in formula II
independently of one another are -SO2- or -CO-.
independently of one another are -SO2- or -CO-.
5. A polyarylene ether according to claim 1, in which the radicals R1, R2, R3 and R4 in formula I are methyl.
6. A polyarylene ether according to claim 1, in which Y in the formula IIIc is -S-, -SO2-, -O- or -CO- and Y' in the formulae IIId and IIIe is a direct bond, -C(CH3)2-, -S-, -SOr, -O- or-CO-.
7. A polyarylene ether according to claim 1, in which A is a group of the formulae IIIa or IIIc in which Y is -S-, -SO2-, -O- or-CO-.
8. A polyarylene ether according to claim 1, in which A is a group of the formula IIIc in which Y is -SO2-.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH558/89-9 | 1989-02-17 | ||
| CH55889 | 1989-02-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010106A1 true CA2010106A1 (en) | 1990-08-17 |
Family
ID=4189794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2010106 Abandoned CA2010106A1 (en) | 1989-02-17 | 1990-02-15 | Polyethers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0383725A3 (en) |
| JP (1) | JPH02247222A (en) |
| CA (1) | CA2010106A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5827907A (en) * | 1993-08-30 | 1998-10-27 | Ibm Corporation | Homo-, co- or multicomponent thermoplastic polymer dispersed in a thermoset resin |
| US8686075B2 (en) * | 2011-08-22 | 2014-04-01 | Sabic Innovative Plastics Ip B.V. | Polysulfone compositions and methods for the manufacture and use thereof |
| WO2014156910A1 (en) * | 2013-03-29 | 2014-10-02 | Jsr株式会社 | Composition, method for producing substrate having pattern formed thereon, film and method for producing same, and compound |
| US20150183929A1 (en) | 2013-12-30 | 2015-07-02 | Sabic Innovative Plastics Ip B.V | Bisphenol polyether oligomers, methods of manufacture, and polycarbonates made therefrom |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4672102A (en) * | 1985-12-23 | 1987-06-09 | The Dow Chemical Company | Polyhydroxy ethers containing spirobiindanols |
| US4808754A (en) * | 1987-02-27 | 1989-02-28 | General Electric Company | Spirobiindane bis-aminophenoxy ethers |
| US4789725A (en) * | 1987-03-17 | 1988-12-06 | General Electric Company | Phenylene ether-carbonate copolymer containing spiroindane group |
-
1990
- 1990-02-08 EP EP19900810089 patent/EP0383725A3/en not_active Withdrawn
- 1990-02-15 CA CA 2010106 patent/CA2010106A1/en not_active Abandoned
- 1990-02-16 JP JP3597890A patent/JPH02247222A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0383725A3 (en) | 1991-04-10 |
| JPH02247222A (en) | 1990-10-03 |
| EP0383725A2 (en) | 1990-08-22 |
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