CN109071799B - Compatibilized polymer composition - Google Patents
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- CN109071799B CN109071799B CN201780026575.2A CN201780026575A CN109071799B CN 109071799 B CN109071799 B CN 109071799B CN 201780026575 A CN201780026575 A CN 201780026575A CN 109071799 B CN109071799 B CN 109071799B
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- 239000000203 mixture Substances 0.000 title claims abstract description 196
- 229920000642 polymer Polymers 0.000 title claims abstract description 156
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 73
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 63
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 37
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 39
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 27
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 20
- 239000000155 melt Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 claims description 3
- 150000007522 mineralic acids Chemical group 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 18
- 229920013730 reactive polymer Polymers 0.000 description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 239000012763 reinforcing filler Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal bicarbonates Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002825 nitriles Chemical group 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 239000003086 colorant Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 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
- 238000010128 melt processing Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 description 1
- 239000002524 monosodium citrate Substances 0.000 description 1
- 235000018342 monosodium citrate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical group [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- UJRAXLUXHBUNDO-UHFFFAOYSA-M sodium;hydron;oxalate Chemical compound [Na+].OC(=O)C([O-])=O UJRAXLUXHBUNDO-UHFFFAOYSA-M 0.000 description 1
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
-
- 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
- C08G65/48—Polymers modified by chemical after-treatment
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
- C08G2261/3442—Polyetherketones
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
Abstract
A polymer composition comprising a component selected from the group consisting of: (i) at least one poly (aryl ether ketone) (PAEK), (ii) poly (ether sulfone) (PES), (iii) reactive poly (ether sulfone) (rPES), (iv) reactive poly (aryl ether ketone) (rPAEK), (v) an acid component, and (vi) at least one alkali metal carbonate. Preferably, the polymer composition is free or substantially free of solvent. One method includes melt mixing the components of the polymer composition.
Description
RELATED APPLICATIONS
This application claims priority from U.S. provisional application No. 62/329,499 filed on day 29, 2016 and european patent application No. 16187799.8 filed on day 8, 9, 2016, each of which is incorporated by reference in its entirety for all purposes.
Technical Field
The present invention relates to high performance compatibilized polymer compositions comprising poly (aryl ether ketone) (PAEK) and poly (ether sulfone) (PES).
Background
The polymers may be blended to obtain new compositions having desired properties; however, most polymers are miscible with each other. When the polymers are miscible with each other, attempts to blend these polymers often result in heterogeneous multiphase compositions. Such compositions may exhibit several thermal transition temperatures (Tg, Tm), often exhibit poor mechanical properties, and suffer from delamination and/or aesthetic defects.
In fact, the mechanical properties and ease of processing of a particular blend depend on the degree of compatibility of the polymer components. The major polymeric component is generally referred to as the continuous phase or matrix, while the minor polymeric component is typically defined as the dispersed phase. The degree of compatibility can be characterized by the size of the dispersed phase in the continuous phase and the level of adhesion between the matrix and the dispersed phase. Certain highly immiscible blends are not possible to extrude under normal operating conditions due to high die swell and are therefore not commercially available.
Blends of PAEK and PES are one example of such blends. PAEK is known to have excellent strength and chemical resistance, and PES is known to have excellent mechanical properties such as high modulus and low melt viscosity that are advantageous for manufacturing shaped articles with thin sections. Therefore, it is desirable to blend these polymers to achieve a combination of their beneficial properties; however, blends of PAEK and PES are known to be highly immiscible, exhibiting extreme die swell and low melt strength. As a result, there are currently no commercial blends of these polymers.
Thus, there is a need for new blends of PAEK and PES with increased compatibility.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the polymer composition of comparative example 1.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the polymer composition of comparative example 2.
Fig. 3 is a TEM image of the polymer composition of example 1.
Fig. 4 is a TEM image of the polymer composition of comparative example 5.
Fig. 5 is a TEM image of the polymer composition of comparative example 6.
Fig. 6 is a TEM image of the polymer composition of example 3.
Detailed Description
Applicants have now unexpectedly found that it is possible to prepare compatible blends of PAEK and PES.
Exemplary embodiments are directed to a polymer composition comprising a component selected from the group consisting of: (i) at least one poly (aryl ether ketone) (PAEK), (ii) poly (ether sulfone) (PES), (iii) reactive poly (ether sulfone) (rPES), (iv) reactive poly (aryl ether ketone) (rPAEK), (v) an acid component having a pKa ≦ 7.5, and (vi) about 0.05 wt.% to about 2 wt.% of at least one alkali metal carbonate, based on the total weight of polymers in the polymer composition, wherein the polymer composition comprises:
-components (i), (ii), (iii), (vi), and optionally (v),
-components (i), (ii), (iv), (vi), and optionally (v),
-components (i), (ii), (v), and (vi),
-components (iii), (iv), and (vi),
-components (iii), (iv), (v), and (vi),
-components (i), (iii), (vi), and optionally (v), or
-components (ii), (iv), (vi), and optionally (v).
In some embodiments, the polymer composition is substantially free of solvent, that is, the composition contains no solvent and comprises one or more solvents in an amount of no more than 2 wt.% (based on the total weight of the composition), for example, less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.%.
For clarity, throughout this application:
the term "alkali metal carbonate" includes alkali metal carbonates and any reagent that can derivatize the alkali metal carbonate in situ during processing at elevated temperatures, such as alkali metal bicarbonates.
The term "solvent" means a liquid in which at least one of the polymers in the polymer composition will be at least partially dissolved;
by "substantially free of solvent" is meant less than 2 wt.% solvent, e.g., less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.%;
"substantially free of rPES and/or rPAEK" means less than 2 wt.% of rPES and/or rPAEK, based on the total weight of the polymers in the polymer composition;
"substantially simultaneously" means within 30 seconds;
"substantially no die swell" means less than 5% die swell;
by "substantially free of nitro or nitrile end groups" is meant less than 1 micro equivalent per gram of nitro or nitrile end groups;
the term "halogen" includes fluorine, chlorine, bromine and iodine unless otherwise indicated. And
the adjective "aromatic" denotes any mononuclear or polynuclear cyclic group (or moiety) having a pi-electron number equal to 4n +2, where n is 1 or any positive integer; the aromatic groups (or moieties) may be aryl and arylene groups (or moieties).
In general, the PAEK or PES can have a weight average molecular weight (Mw) ranging from about 5,000g/mol to about 150,000g/mol, preferably from about 10,000g/mol to about 100,000g/mol, as determined by Gel Permeation Chromatography (GPC).
In the present application:
any description, even if described with respect to a specific embodiment, applies to and is interchangeable with other embodiments of the present disclosure;
-when an element or component is said to be included in and/or selected from a list of recited elements or components, it is to be understood that in the relevant embodiments explicitly contemplated herein, the element or component may also be any one of the individual recited elements or components and may also be selected from the group consisting of any two or more of the explicitly recited elements or components; any element or component listed in a list of elements or components may be omitted from this list; and
any recitation herein of numerical ranges by endpoints includes all numbers subsumed within that range and the endpoints of that range and equivalent amounts.
Poly (aryl ether ketone) (PAEK)
As used herein, "poly (aryl ether ketone) (PAEK)" means a polymer comprising more than 50 mole percent of repeating units (R)PAEK) The polymer of (1), the repeat unit comprising an Ar '-C (═ O) -Ar group, wherein Ar' and Ar, the same or different from each other, are aromatic groups. These repeating units (R)PAEK) Selected from the group consisting of units having the following formulae (J-A) to (J-D):
wherein:
-each R', equal to or different from each other, is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and is
-j' is zero or an integer ranging from 1 to 4.
In the repeating unit (R)PAEK) In (b), the corresponding phenylene moieties may independently have up to the repeating unit (R)PAEK) Other than R', is 1,2-, 1, 4-or 1, 3-linked. Preferably, the phenylene moieties have 1, 3-or 1, 4-linkages, more preferably they have 1, 4-linkages.
In the repeating unit (R)PAEK) Preferably, j' is zero at each occurrence, such that the phenylene moieties have no other substituents than those that are bonded to the backbone of the polymer.
In some embodiments, the PAEK is poly (ether ketone) (PEEK). As used herein, "poly (ether ketone) (PEEK)" means its repeating unit (R)PAEK) More than 50 mol% of is any polymer having repeating units of the formula J' -A:
preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units (R)PAEK) Is a repeating unit (J' -A).
In another preferred embodiment, the PAEK is poly (ether ketone) (PEKK). As used herein, "poly (etherketoneketone) (PEKK)" means a repeating unit (R) thereofPAEK) More than 50 mol% of any polymer having a combination of repeating units of formula J '-B and formula J' -B:
preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units (R)PAEK) Is a combination of repeating units (J '-B) and (J' -B).
In yet another preferred embodiment, the PAEK is a poly (ether ketone)) (PEK). As used herein, "poly (ether ketone) (PEK)" means a repeating unit (R) thereofPAEK) More than 50 mol% of is any polymer having a repeating unit of formula (J' -C):
preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units (R)PAEK) Is a repeating unit (J' -C).
In some embodiments, the PAEK is a PEEK-PEDEK copolymer. As used herein, "PEEK-PEDEK copolymer" refers to a repeating unit (R) thereofPAEK) More than 50 mol% of is any polymer having two repeating units of formula J '-A (PEEK) and formula J' -D (poly (diphenyloxide ketone) (PEDEK)):
the PEEK-PEDEK copolymer may comprise repeating units J '-a and J' -D (PEEK/PEDEK) in relative molar ratios ranging from 95/5 to 60/40. Preferably, the sum of the recurring units J '-a and J' -D constitutes at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% of the recurring units in the PAEK. In some aspects, the recurring units J '-a and J' -D represent all recurring units in the PAEK.
Most preferably, the PAEK is PEEK.
PEEK is commercially available from Solvay Specialty Polymers USA (LLC).
Polyether sulfone (PES)
As used herein, "Polyethersulfone (PES)" means any polymer of which at least 50 mol% of its repeating units are repeating units having formula (K):
preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units in the PES are recurring units having formula (K).
PES can be prepared by known methods and is notably available from Suweite polymers, Inc. of U.S.A
Available to PESU.
Reactive polymer
The at least one PAEK and PES may be present in a reactive form (i.e., a reactive polymer) or a non-reactive form.
In their reactive form, these polymers comprise at least 5, at least 10, at least 15, preferably at least 20, preferably at least 50, microequivalents per gram (. mu. eq/g) of hydroxyl (-OH) or thiol (-SH) end groups. One example of such a reactive polymer is reactive polyethersulfone (rPES) available from suwiter polymers llc of the united states as
Available to PESU.
In some embodiments, the polymer composition includes at least one reactive polymer (e.g., rPES or rPAEK) in addition to the at least one PAEK and PES. The rPAEK is preferably selected from the group consisting of reactive poly (ether ketone) (rPEK), reactive poly (ether ketone) (rPEKK), reactive poly (ether ketone) (rPEK) and reactive PEEK-PEDEK copolymer (r (PEEK-PEDEK)).
Preferably, the total amount of reactive polymer in the polymer composition is in the range of from 0 to 60 wt.%, 1 wt.% to 50 wt.%, 5 wt.% to 30 wt.%, 5 wt.% to 25 wt.%, 5 wt.% to 20 wt.%, 5 wt.% to 15 wt.%, most preferably about 10 wt.%, based on the total weight of the polymers in the polymer composition.
In their non-reactive form, the PAEK and PES polymers include one or more non-retro-polymersA reactive end group. The non-reactive end group is preferably-Cl, -F, or-O-CH3。
Preferably, the non-reactive polymer comprises at least 20, preferably more than 50 microequivalents per gram of non-reactive end groups.
In certain embodiments, PAEK and PES are free or substantially free of nitro or nitrile end groups, and the polymer composition is also optionally free of any agent capable of forming such end groups on the polymer. In some aspects, PAEK and PES comprise only-O-CH3Halogen, hydroxyl (-OH) or aryl end groups.
In some embodiments, the polymer composition may be free or substantially free of rPES and/or rPAEK.
Alkali metal carbonate
The polymer composition includes at least one alkali metal carbonate in an amount ranging from about 0.05 wt.% to about 2 wt.%, about 0.1 wt.% to about 1.8 wt.%, about 0.1 wt.% to about 1.6 wt.%, about 0.1 wt.% to about 1.5 wt.%, about 0.1 wt.% to about 1.3 wt.%, about 0.1 wt.% to about 1.0 wt.%, about 0.1 wt.% to about 0.8 wt.%, about 0.1 wt.% to about 0.5 wt.%, based on the total weight of the polymers in the polymer composition. In some embodiments, the amount of alkali metal carbonate ranges from about 0.1 wt.% to about 0.5 wt.%, about 0.2 wt.% to about 0.5 wt.%, about 0.4 wt.% to about 0.5 wt.%, based on the total weight of the polymers in the polymer composition. In some embodiments, the amount of alkali metal carbonate is less than or equal to 1.0 wt.%, 0.9 wt.%, 0.8 wt.%, 0.7 wt.%, 0.6 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.1 wt.% based on the total weight of the polymers in the polymer composition.
The alkali metal carbonate may be selected from sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate. Potassium carbonate is preferred. Mixtures of two or more alkali metal carbonates may be used.
In some aspects, the particle size D50 (median diameter or median value of the particle size distribution) is in the range from 2 microns to 1000 microns, preferably from 2 to 500 microns, most preferably from 3 to 200 microns.
Acid component
Has come to mindIt was found that they have pKa<7.5, preferably<The organic and inorganic acid components of 7 are capable of stabilizing the melt viscosity of the polymer compositions of the present invention. Having a pKa<7.5 non-limiting example of organic and inorganic Components is sodium hydrogen phosphate (NaH)2PO4) Monosodium citrate, sodium hydrogen oxalate, and sodium hydrogen phthalate. Preference is given to inorganic components, such as, for example, having a pKa<NaH of 72PO4. Excellent results were obtained with organic and inorganic components having pKa as follows: 2.5<pKa<7.5, preferably 3<pKa<7. Having a pKa<The organic or inorganic acid component of 7.5 may be present in an amount ranging from 0.05 wt.% to 5 wt.%, preferably from 0.1 wt.% to 2 wt.%, more preferably from 0.2 wt.% to 1 wt.%, based on the total weight of the polymers in the polymer composition.
Optional reinforcing fillers
A large amount of the selected reinforcing filler may be added to the polymer composition. They are preferably selected from fibrous fillers and particulate fillers. Fibrous reinforcing fillers are considered herein to be materials having a length, a width, and a thickness, wherein the average length is substantially greater than both the width and the thickness. Preferably, such materials have an aspect ratio (defined as the average ratio between length and the smallest of width and thickness) of at least 5. Preferably, the aspect ratio of the reinforcing fibers is at least 10, more preferably at least 20, still more preferably at least 50. The particulate filler has an aspect ratio of at most 5, preferably at most 2.
Preferably, the reinforcing filler is selected from mineral fillers such as talc, mica, titanium dioxide, kaolin, calcium carbonate, calcium silicate, magnesium carbonate; glass fibers; carbon fibers, boron carbide fibers; wollastonite; silicon carbide fibers; boron fibers, graphene, Carbon Nanotubes (CNTs), and the like.
The reinforcing filler may be present in the polymer composition in an amount of at least 5 wt.%, preferably at least 10 wt.%, more preferably at least 15 wt.%, based on the total weight of the polymer composition.
The reinforcing filler is also preferably present in an amount of up to 60 wt.%, more preferably up to 50 wt.%, still more preferably up to 40 wt.%, based on the total weight of the polymer composition.
Preferably, the amount of reinforcing filler is in the range of from 0.1 to 60 wt.%, more preferably from 5 to 50 wt.%, still more preferably from 10 to 40 wt.% of the polymer composition. According to some embodiments, the polymer composition is free of fibrous fillers. Alternatively, the polymer composition may be free of particulate filler. Preferably, the polymer composition is free of reinforcing fillers.
Additional ingredients
In some aspects, the polymer composition can include one or more optional additives, such as colorants (e.g., dyes and/or pigments, such as titanium dioxide, zinc sulfide, and zinc oxide), ultraviolet light stabilizers, heat stabilizers, antioxidants (such as organic phosphites and phosphonites), acid scavengers, processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, antiblock agents, and/or conductive additives (such as carbon black).
When one or more additional ingredients are present, their total weight is preferably less than 20 wt.%, less than 10 wt.%, less than 5 wt.% and most preferably less than 2 wt.%, based on the total weight of the polymer composition.
Preferred polymer compositions
Preferred polymer compositions are shown in table 1 below. Each polymer composition may include other ingredients in addition to those listed. Each polymer composition also includes at least one alkali metal carbonate (preferably potassium carbonate) in an amount ranging from 0.05 wt.% to about 2 wt.%, or in an additional amount as disclosed herein.
TABLE 1
In the polymer composition, the concentration of each of PAEK, PES, rPES and rPAEK is independently selected from 0 wt.%, preferably at least 1 wt.%, 2 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 98 wt.%, 99 wt.% of the total weight of polymers in the polymer composition.
In some embodiments, the polymer composition comprises 80 wt.%, preferably 65 wt.%, more preferably 50 wt.% PAEK (e.g., PEEK) or PES, and the other of 20 wt.%, preferably 35 wt.%, preferably 50 wt.% PAEK or PES, respectively, based on the total weight of polymers in the polymer composition.
In some aspects, the polymer composition comprises (i) from 20 to 80 wt.%, preferably 30 to 70 wt.%, 40 to 60 wt.%, 45 to 55 wt.%, most preferably about 45 wt.% of the at least one PAEK, (ii) from 80 to 20 wt.%, preferably 70 to 30 wt.%, 60 to 40 wt.%, 55 to 45 wt.%, most preferably about 45 wt.% of PES, and (iii) from 1 to 20 wt.%, preferably 5 to 15 wt.%, most preferably about 10 wt.% of rPES or rpaeks, based on the total weight of the polymers in the polymer composition.
Exemplary Properties of the Polymer composition
The polymer composition may comprise a dispersed phase dispersed in a continuous phase or matrix. Fig. 3 shows an example of a dispersed phase.
In some embodiments, the average surface area of each dispersed particle is preferably less than or equal to about 4 μm2About 3 μm2About 2 μm2About 1 μm2。
In some embodiments, the maximum particle size of the dispersed phase is 3 μm or less, preferably 2 μm or less, 1 μm or less, 0.8 μm or less, 0.6 μm or less, 0.4 μm or less, and most preferably 0.1 μm or less.
In an alternative embodiment, the polymer blend may include a co-continuous phase characterized by the presence of a continuous band of polymer components when viewed by Transmission Electron Microscopy (TEM). In such embodiments, the average width of the bands is preferably less than or equal to about 3 μm, more preferably less than or equal to about 2 μm, where the average width is calculated by taking 10 random measurements of the band width, discarding the longest and shortest measurements, and dividing the sum of the remaining measurements by 8.
The polymer composition may exhibit at least two different glass transition temperatures (Tg) corresponding to each polymer in the polymer composition; however, these tgs may be different (i.e., shifted) compared to the Tg of the same polymer when not in the polymer composition. In some embodiments, the difference between the corresponding tgs in the polymer composition (Δ Tg) is at least 0.5 ℃, preferably at least 1 ℃, more preferably from 5 ℃ to 50 ℃, even more preferably from 5 ℃ to 10 ℃.
In some preferred embodiments, the polymer composition has no or substantially no die swell when extruded as a melt from the melt mixing device, and the temperature of the melt is in the range of from 300 ℃ to 400 ℃.
Process for preparing polymer compositions
In some embodiments, the present invention includes a method of making a polymer composition described herein by melt mixing components selected from the group consisting of: (i) at least one poly (aryl ether ketone) (PAEK), (ii) poly (ether sulfone) (PES), (iii) reactive poly (ether sulfone) (rPES), (iv) reactive poly (aryl ether ketone) (rPAEK), (v) an acid component having a pKa ≦ 7.5, and (vi) about 0.05 wt.% to about 2 wt.% of at least one alkali metal carbonate, based on the total weight of polymers in the polymer composition, wherein the process comprises melt mixing:
-components (i), (ii), (iii), (vi), and optionally (v),
-components (i), (ii), (iv), (vi), and optionally (v),
-components (i), (ii), (v), and (vi),
-components (iii), (iv), and (vi),
-components (iii), (iv), (v), and (vi),
-components (i), (iii), (vi), and optionally (v), or
-components (ii), (iv), (vi), and optionally (v).
The components of the mixture may be added or mixed in any order, in any amount, or as a fraction of their total amount, and may be mixed separately or simultaneously.
The preparation of the polymer composition may be carried out by any known melt mixing process suitable for preparing thermoplastic molding compositions. Such a process may be carried out by heating the polymer above the melting temperature of the semi-crystalline polymer to form a melt of the polymer and/or above the Tg of the amorphous polymer. In some embodiments, the processing temperature is in the range of from about 250 ℃ to 450 ℃, preferably from about 280 ℃ to 420 ℃. Preferably, the processing temperature is at least 15 ℃, preferably at least 50 ℃, preferably at least 100 ℃ greater than the glass transition temperature (Tg) of the highest Tg polymer in the polymer composition and/or at least 15 ℃ greater than the melting temperature (Tm) of the highest Tm polymer in the polymer composition.
In some aspects of the method for preparing a polymer composition, the components that form the polymer composition are fed to and melt mixed in a melt mixing device. Suitable melt-mixing devices are, for example, kneaders, Banbury mixers, single-screw extruders and twin-screw extruders. Preferably, an extruder is used which is equipped with means for feeding the desired components into the extruder (either into the throat of the extruder or into the melt). Preferably, the extruder is equipped with one or more ports that allow feeding into the melt at different barrels during the extrusion process.
The components may be fed simultaneously or may be fed separately in the form of a powder mixture or a mixture of pellets (also referred to as a dry blend).
In some embodiments, all of the polymer and alkali metal carbonate are added to the throat of the extruder, preferably simultaneously or substantially simultaneously. In other aspects, one or more of the polymers may be added to the throat of an extruder along with an alkali metal carbonate, and then one or more other polymers are added to the melt at the barrel of the extruder. For example, PAEK and rPES may be added to the throat of an extruder along with an alkali metal carbonate, and PES may be subsequently added at a downstream barrel of the extruder. When added, the acid component may be added at the throat of the extruder, or to the melt at any barrel of the extruder. Preferably, the acid component is added to the melt at the downstream barrel such that it contacts the melt shortly before extruding the melt. Preferably, the acid component is added at some point after the alkali metal carbonate is added.
In an exemplary embodiment, multiple passes of extrusion may be performed. In multi-pass extrusion, the extrudate from the first pass is reintroduced into the extruder, preferably at the throat, for a second pass through the extruder. In multi-pass extrusion, two, three, four or more passes may be made, and the polymer, alkali metal carbonate, acid component, or other ingredient may be added at any point in the extruder line in any one pass. For example, the at least one PAEK may be added to the throat of an extruder along with an alkali metal carbonate, and then the extrudate from the first pass may be recycled to the extruder to which the PES is added, and the acid component may be added towards the end of the second pass. Alternatively, the extrudate resulting from the second pass may be recycled for a third pass during which, for example, the acid component and/or filler material may be added to the melt prior to extrusion into the final product.
In some aspects, at least two passes may be made, and components may be added to the extrudate and/or to the process (e.g., mixing) performed on the extrudate before it is recycled to the extruder for one or more additional passes.
The extruder may be operated at any suitable speed. The extruder speed and the temperature of the extruder barrel may be constant or variable. Preferably, the one or more extruder screws are rotated at about 100rpm to about 900rpm, preferably from about 200 to about 500 rpm; however, the speed and temperature may be adjusted based on the particular polymer composition being blended.
As used herein, "total residence time" means the total time the longest residence component spends in the extruder, including multiple passes, if any. The total residence time preferably ranges from about 15 seconds to about 4 minutes, preferably from about 30 seconds to about 2 minutes.
The polymer compositions described herein are advantageously provided in the form of pellets, which can be used in injection molding or extrusion processes known in the art.
An exemplary embodiment relates to a method, comprising:
(a1) contacting the at least one PAEK, PES, and an alkali metal carbonate to form a first initial mixture;
(a2) contacting the at least one PAEK with an alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with PES to form a second mixture;
(a3) contacting PES with an alkali metal carbonate to form a third initial mixture, and subsequently contacting the third initial mixture with the at least one PAEK to form a third mixture; or
(a4) Contacting the at least one PAEK and PES to form a fourth initial mixture, and subsequently contacting the fourth initial mixture with an alkali metal carbonate to form a fourth mixture; and
(b) contacting the first initial mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein.
In alternative embodiments, the at least one PAEK and/or PES described in step (a1), (a2), (a3), or (a4) above may be a reactive polymer (i.e., may be rPAEK or rPES, respectively).
In some embodiments, the method comprises:
(a1) contacting the at least one PAEK, PES, the at least one reactive polymer (e.g., rPES or rPAEK), and an alkali metal carbonate to form a first initial mixture;
(a2) contacting the at least one PAEK, the at least one reactive polymer, and an alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with PES to form a second mixture.
(a3) Contacting PES, the at least one reactive polymer, and an alkali metal carbonate to form a third initial mixture, and subsequently contacting the third initial mixture with the at least one PAEK to form a third mixture; or
(a4) Contacting the at least one PAEK, PES and the at least one reactive polymer to form a fourth initial mixture, and subsequently contacting the fourth initial mixture with an alkali metal carbonate to form a fourth mixture; and
(b) optionally contacting the first initial mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein.
In some embodiments, the method comprises:
(a1) contacting the at least one PAEK, PES and alkali metal carbonate to form a first initial mixture, and subsequently contacting the first initial mixture with the at least one reactive polymer to form a first mixture;
(a2) contacting the at least one PAEK and an alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with PES and the at least one reactive polymer to form a second mixture;
(a3) contacting PES and an alkali metal carbonate to form a third initial mixture, and subsequently contacting the third initial mixture with the at least one PAEK and the at least one reactive polymer to form a third mixture; or
(a4) Contacting the at least one PAEK and PES to form a fourth initial mixture, and subsequently contacting the fourth initial mixture with an alkali metal carbonate and the at least one reactive polymer to form a fourth mixture; and
(b) optionally contacting the first mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein.
Shaped article comprising a polymer composition
Exemplary embodiments also include articles comprising the polymer compositions described above.
The article may be made from the polymer composition using a suitable melt-processing method. In particular, they may be made by injection molding, extrusion molding, rotational molding, or blow molding.
The polymer composition may be well suited for making articles useful in a wide variety of end uses.
The invention will be explained in more detail below by way of non-limiting examples in the following sections.
If the disclosure of any patent, patent application, and publication incorporated by reference herein conflicts with the description of the present application to the extent that terminology may become unclear, the description shall take precedence.
Examples of the invention
Comparative examples 1,2 and 3 and examples 1 and 2
Comparative example 1: blend PEEK/PES 50/50 parts for a residence time of 5 min.
Comparative example 2: blend PEEK/PES/K2CO350/50/0.5 part, for a residence time of 5 min.
Comparative example 3: blend 7g of PEEK/PES/K2CO350/50/0.5 part, for 1min, and then PEEK/PES/Na was introduced2HPO445/45/10 wt.% of a 1g mixture with the blend, for 4min (total residence time of 5 min).
Example 1: blend 7g of PEEK/PES/K2CO350/50/0.5 part, for 1min, after which PEEK/PES/NaH is introduced2PO440/40/20 wt.% of a 1g mixture with the blend, for 4min (total residence time of 5 min).
Example 2: blend 7g of PEEK/PES/K2CO350/50/0.5 part, for 1min, after which PEEK/PES/NaH is introduced2PO445/45/10 wt.% of a 1g mixture with the blend, for 4min (total residence time of 5 min).
Materials:
poly (ether ketone) (PEEK)
KT-880 from Scotch polymers, Limited liability, USA
Poly (ether sulfone) (PES)
PESU 3600P from Suweiter Polymer, Inc. of USA
-Potassium carbonate K2CO3UNID EF-80
Sodium dihydrogen phosphate NaH2PO4(pKa＝6.8)
Disodium hydrogen phosphate Na2HPO4(pKa＝12.4)
Mixing:
DSM heated to 400 ℃ and equipped with a recirculation loop allowing control of residence time
The blend was compounded in a twin screw (100rpm) extruder. The material (7 g total) was introduced and mixed simultaneously for a certain time (residence time) before being extruded into a strand.
Measurement:
the torque required to rotate the extruder screw was measured during blending. Torque is related to the viscosity of the molten blend, with greater force indicating greater viscosity.
As a result:
the polymer compositions and measurements are shown in table 2 below. The morphology of the selected polymer compositions is shown in fig. 1-3.
TABLE 2
N.d. indicates the undetermined values.
Fig. 1 is a SEM scan of the polymer composition of comparative example 1, which is a PEEK/PES 50/50 wt.% blend that does not include any alkali metal carbonate. FIG. 2 is a TEM scan of a polymer composition of comparative example 2, which polymer composition comprises 0.5 wt.% K2CO3PEEK/PES 50/50 wt.% blend. A comparison of FIGS. 1 and 2 clearly shows that 0.5 wt.% K2CO3The incorporation of PEEK/PES 50/50 wt.% blend resulted in compatibilization of the blend, as indicated by the reduction in dispersed phase size. However, K2CO3Also resulted in a significant increase in the viscosity of the blend, as shown by the more than 10-fold increase in Δ final force (N) between comparative example 1 and comparative example 2 in table 2.
However, it was unexpectedly found that the NaH was introduced after 1min of mixing (examples 1 and 2)2PO4Immediately prevents viscosity increase-yielding a polymer composition suitable for further processing applications where lower viscosity is desired-while retaining the added K2CO3The compatibilization observed (TEM scan of example 1 is shown in figure 3). It was also unexpectedly found that, as shown by comparative example 3, Na was introduced2HPO4Instead of NaH2PO4The increase in viscosity observed in comparative example 2 was not prevented.
Comparative examples 4, 5 and 6 and example 3
Comparative example 4: blend PEEK/PES 50/50 parts for a residence time of 5 min.
Comparative example 5: blend PEEK/PES/rPES 45/45/10 parts for a residence time of 5 min.
Comparative example 6: blend PEEK/PES/rPES/ZnO 45/45/10/2 parts for a residence time of 3 min.
Example 3: blend PEEK/PES/rPES/K2CO345/45/10/0.5 part, for a residence time of 3 min.
Materials:
poly (ether ketone) (PEEK)
KT-880 from Scotch polymers, Limited liability, USA
Poly (ether sulfone) (PES)
PESU 3600P from Suweiter Polymer, Inc. of USA
-reactive poly (ether sulfone) (rPES): rPES synthesized according to known methods from 4, 4' -dichlorodiphenyl sulfone, bisphenol S (excess), potassium carbonate (excess) in sulfolane as solvent. End group titration of rPES polymer gives:
concentration of o hydroxy end group [ -OH ] -, 219 μ eq/g
Concentration of potassium phenoxide end group [ -OK ] & gt, 60 μ eq/g
Concentration of omicron chloride end group [ -Cl ] & gt, 7 μ eq/g
-number average molecular weight (Mn) — 2,000,000/([ -OH ] + [ -OK ] + [ -Cl ]) 7,000g/mol
-Potassium carbonate K2CO3UNID EF-80
-zinc oxide ZnO
Mixing:
the blend was compounded according to the method described in example 1 above.
Measurement:
the torque required to rotate the extruder screw was measured as in example 1 above.
The level of die swell at the exit of the extruder was observed and classified as follows: very large die swell, some die swell, + limited die swell, + no die swell.
The thermal properties, i.e. melting temperature and crystallization temperature, were determined by DSC.
The morphology of the blends was analyzed by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) to give the maximum diameter of the dispersed phase.
As a result:
the blend compositions and measurements are shown in table 3 below. The morphology of the blends is shown in figures 1 and 4-6.
TABLE 3
As shown in fig. 1, PEEK and PES are clearly immiscible. As shown in fig. 4, the introduction of rPES (hydroxyl terminated PES) did not significantly compatibilize the polymer, and very large die swell was observed. Furthermore, as shown in fig. 5, further addition of alkali ZnO also did not result in significant changes in the morphology of the PEEK and PES blend, and some die swell was still observed.
However, unexpectedly, when additional base K is added2CO3When added to PEEK, PES and rPES polymer compositions, excellent compatibilization of PEEK and PES was observed, as shown by the dispersed phase of example 3 (exhibiting a diameter of less than 1 μm) (fig. 6). Furthermore, the polymer composition of example 3 also unexpectedly exhibited no die swell, which is advantageous in extruded strands having, for example, standard dimensions.
If the disclosure of any patent, patent application, and publication incorporated by reference herein conflicts with the description of the present application to the extent that terminology may become unclear, the description shall take precedence.
Claims (17)
1. A polymer composition comprising a component selected from the group consisting of:
(i) at least one poly (aryl ether ketone) (PAEK),
(ii) poly (ether sulfone) (PES),
(iii) a reactive poly (ether sulfone) (rPES),
(iv) a reactive poly (aryl ether ketone) (rPAEK),
(v) an acid component having a pKa of less than or equal to 7.5, and
(vi) from 0.05 to 2 wt.%, based on the total weight of polymers in the polymer composition, of at least one alkali metal carbonate,
wherein the polymer composition comprises:
-components (i), (ii), (iii), (vi), and optionally (v),
-components (i), (ii), (iv), (vi), and optionally (v),
-components (i), (ii), (v), and (vi),
-components (iii), (iv), and (vi),
-components (iii), (iv), (v), and (vi),
-components (i), (iii), (vi), and optionally (v), or
-components (ii), (iv), (vi), and optionally (v).
2. The polymer composition of claim 1, wherein the polymer composition does not comprise one or more solvents or comprises one or more solvents in an amount of not more than 2 wt.%, based on the total weight of the composition.
3. The polymer composition of claim 1 or 2, wherein the polymer composition comprises components (i), (ii), (iii), (vi), and optionally (v).
4. The polymer composition of claim 1 or 2, wherein the polymer composition comprises components (i), (ii), (v), and (vi).
5. The polymer composition of claim 1 or 2, wherein the poly (aryl ether ketone) (PAEK) is selected from the group consisting of: poly (ether ketone) (PEEK), poly (ether ketone) (PEKK), poly (ether ketone) (PEK), PEEK-poly (diphenyl ether ketone) copolymer (PEEK-PEDEK copolymer), and combinations thereof.
6. The polymer composition of claim 5, wherein the poly (aryl ether ketone) (PAEK) is selected from PEEK.
7. The polymer composition of claim 1 or 2, wherein the at least one alkali metal carbonate comprises sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, or a combination thereof.
8. The polymer composition of claim 7, wherein the at least one alkali metal carbonate comprises potassium carbonate.
9. The polymer composition of claim 5, wherein the alkali metal carbonate is potassium carbonate in an amount ranging from 0.1 wt.% to 0.5 wt.%, based on the total weight of polymers in the polymer composition.
10. The polymer composition of claim 1 or 2, wherein the acid component is an inorganic acid component.
11. The polymer composition of claim 1 or 2, wherein the acid component is NaH2PO4。
12. The polymer composition of claim 1 or 2, wherein the polymer composition comprises a surface area of less than or equal to 4 μm per dispersed particle therein2The dispersed phase of (a).
13. The polymer composition of claim 1 or 2, wherein the polymer composition has no or substantially no die swell when extruded from an extruder as a melt having a temperature ranging from 300 ℃ to 400 ℃.
14. The polymer composition of claim 1 or 2, wherein the at least one poly (aryl ether ketone) (PAEK) and the poly (ether sulfone) (PES) comprise only-O-CH3Halogen, hydroxyl (-OH) or aryl end groups.
15. A method of making a polymer composition comprising melt mixing a component selected from the group consisting of:
(i) at least one poly (aryl ether ketone) (PAEK),
(ii) poly (ether sulfone) (PES),
(iii) a reactive poly (ether sulfone) (rPES),
(iv) a reactive poly (aryl ether ketone) (rPAEK),
(v) an acid component having a pKa of less than or equal to 7.5, and
(vi) 0.05 to 2 wt.%, based on the total weight of polymers in the composition, of at least one alkali metal carbonate,
wherein the method comprises melt mixing:
-components (i), (ii), (iii), (vi), and optionally (v),
-components (i), (ii), (iv), (vi), and optionally (v),
-components (i), (ii), (v), and (vi),
-components (iii), (iv), and (vi),
-components (iii), (iv), (v), and (vi),
-components (i), (iii), (vi), and optionally (v), or
-components (ii), (iv), (vi), and optionally (v).
16. A polymer composition made by the method of claim 15.
17. A shaped article comprising the polymer composition of any one of claims 1 to 14 and 16.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662329499P | 2016-04-29 | 2016-04-29 | |
| US62/329499 | 2016-04-29 | ||
| EP16187799.8 | 2016-09-08 | ||
| EP16187799 | 2016-09-08 | ||
| PCT/EP2017/060222 WO2017186925A1 (en) | 2016-04-29 | 2017-04-28 | Compatibilized polymer compositions |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0266791A2 (en) * | 1986-11-07 | 1988-05-11 | Phillips Petroleum Company | Poly (arylene sulfide) composition for molding articles |
| DE3843438A1 (en) * | 1988-12-23 | 1990-06-28 | Basf Ag | High-temperature-resistant thermoplastic moulding compositions having improved fire behaviour |
| EP0635548A1 (en) * | 1993-07-16 | 1995-01-25 | Mitsubishi Chemical Corporation | Thermoplastic resin composition |
| CN105348531A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Method for preparing polyaryl ether ketone sulfone random copolymer through quaternary copolycondensation technology |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125816B1 (en) * | 1983-05-12 | 1987-09-23 | Imperial Chemical Industries Plc | Method of increasing molecular weight of poly(aryl ethers) |
| US4624997A (en) * | 1984-09-28 | 1986-11-25 | Union Carbide Corporation | Article molded from a blend of a poly(aryl ether ketone) and a poly(aryl ether sulfone) |
| US4774296A (en) * | 1985-05-02 | 1988-09-27 | Amoco Corporation | Block polymers containing a poly(aryl ether ketone) and methods for their production |
| DE19525681A1 (en) * | 1995-07-14 | 1997-01-16 | Basf Ag | Molding compositions based on polyarylene ethers |
-
2017
- 2017-04-28 CN CN201780026575.2A patent/CN109071799B/en active Active
- 2017-04-28 WO PCT/EP2017/060222 patent/WO2017186925A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0266791A2 (en) * | 1986-11-07 | 1988-05-11 | Phillips Petroleum Company | Poly (arylene sulfide) composition for molding articles |
| DE3843438A1 (en) * | 1988-12-23 | 1990-06-28 | Basf Ag | High-temperature-resistant thermoplastic moulding compositions having improved fire behaviour |
| EP0635548A1 (en) * | 1993-07-16 | 1995-01-25 | Mitsubishi Chemical Corporation | Thermoplastic resin composition |
| CN105348531A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Method for preparing polyaryl ether ketone sulfone random copolymer through quaternary copolycondensation technology |
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