WO2022128307A1 - Sulphur-containing aromatic polymer composition having improved processability - Google Patents
Sulphur-containing aromatic polymer composition having improved processability Download PDFInfo
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- WO2022128307A1 WO2022128307A1 PCT/EP2021/082107 EP2021082107W WO2022128307A1 WO 2022128307 A1 WO2022128307 A1 WO 2022128307A1 EP 2021082107 W EP2021082107 W EP 2021082107W WO 2022128307 A1 WO2022128307 A1 WO 2022128307A1
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- composition
- aromatic polymer
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- fluoropolymer
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- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 229920000642 polymer Polymers 0.000 title claims abstract description 84
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000005864 Sulphur Substances 0.000 title claims abstract description 15
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 42
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims description 59
- 230000000996 additive effect Effects 0.000 claims description 48
- 229920001973 fluoroelastomer Polymers 0.000 claims description 41
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 35
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 28
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 25
- -1 poly(arylene sulfide Chemical compound 0.000 claims description 25
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 25
- 230000002708 enhancing effect Effects 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 23
- 229920002959 polymer blend Polymers 0.000 claims description 20
- 239000008188 pellet Substances 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 14
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 13
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 5
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000010561 standard procedure Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical class FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims description 2
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical class FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 claims description 2
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920002449 FKM Polymers 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 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 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- IGZBSJAMZHNHKE-UHFFFAOYSA-N 2-[[4-[bis[4-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 IGZBSJAMZHNHKE-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910014585 C2-Ce Inorganic materials 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920003295 Radel® Polymers 0.000 description 1
- 239000004736 Ryton® Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 125000006267 biphenyl group Chemical group 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides 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
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- ATPFMBHTMKBVLS-UHFFFAOYSA-N n-[6-(cinnamylideneamino)hexyl]-3-phenylprop-2-en-1-imine Chemical compound C=1C=CC=CC=1C=CC=NCCCCCCN=CC=CC1=CC=CC=C1 ATPFMBHTMKBVLS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- 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
- C08L81/02—Polythioethers; Polythioether-ethers
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
Definitions
- the present invention relates to a polymer composition
- a polymer composition comprising a sulphur-containing aromatic polymer and at least one fluoropolymer, which has high melt viscosity.
- the invention also relates to a process for the preparation of said polymer composition and to an article comprising the same.
- Sulphur-containing aromatic polymer such as polyarylene sulfides and polyarylsulfones are thermally stable engineering plastics consisting mainly of phenyl or biphenyl groups linked by sulfide, ether and/or sulfone groups. Those materials have excellent heat resistance and chemical resistance. However, they have poor mechanical properties, in particular impact resistance.
- Blending sulphur-containing aromatic polymers with fluorine-containing polymers can produce novel materials combining the performances and properties of both classes.
- Blends of sulphur-containing aromatic polymers with fluorine-containing polymers tend however to have morphology with large regions or domains of the individual polymers rather than fine, well-dispersed domains.
- the large domains tend to produce a material with poor mechanical properties, e.g. injection molded parts having poor tensile properties.
- a compatibilizer can be added.
- WO 2018/193020 discloses polymer alloys comprising sulphur-containing aromatic polymers and uncrosslinked fluoroelastomers wherein the compatibilization is improved by mixing said fluoroelastomer with certain amounts of at least one divalent metal oxide.
- Said polymer alloys show improved mechanical properties, in particular tensile properties, but they are characterized by a melt viscosity at low shear that is not high enough to allow the use of the same in extrusion and blow molding processes.
- compositions comprising sulphur-containing aromatic polymer and a fluoropolymer having a melt viscosity sufficiently high to manufacture articles by extrusion or blow molding, or similar processes, which have improved flexibility and toughness, while retaining the thermal and chemical resistance of both neat polymers.
- melt compounding polyphenylene sulfide with fluoropolymers with certain additives allows to obtain improved compounds having a melt viscosity sufficiently high to manufacture articles for extrusion-type applications.
- composition (C) having improved melt flow index can be obtained by a process including a series of steps to be carried out in a specific order.
- Another object of the present invention is thus a process for preparing composition (C) as above defined, said process comprising the following steps:
- step A melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A);
- step B melt compounding the compound obtained in step A with at least one fluoropolymer (F).
- the present invention is directed to articles made of said polymer composition (C).
- Aromatic polymer (A) to be used in the present invention may be a poly(arylene sulfide) (PAS) or an aromatic sulfone polymer (SP).
- PAS poly(arylene sulfide)
- SP aromatic sulfone polymer
- PASs are polymers comprising the repeating unit of the formula -(Ar-S)- as the main structural unit, preferably containing the repeating unit in an amount of 80 mol% or more.
- Ar represents an aromatic group, and examples include units (RU1) represented by the formulas (I) to (XI) given below, among which the formula (I) is particularly preferred:
- R1 and R2 each represent a substituent selected from hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, arylene of 6 to 24 carbon atoms, and halogen, and R1 and R2 may be the same or different.
- poly(arylene sulfide) is preferably polyphenylene sulfide (PPS).
- aromatic sulfone polymer SP
- RU2 recurring units
- Ar being a group chosen among the following structures: with RD being:
- the recurring units are preferably chosen from:
- aromatic sulfone polymer is preferably chosen among the group consisting of polysulfone (PSU), polyphenylsulfone (PPSLI), polyethersulfone (PESLI), copolymers and mixtures thereof and is most preferably a polysulfone (PSU) or polyphenylsulfone (PPSU).
- Polysulfone is notably available as UDEL® PSU from Solvay Specialty Polymers USA, L.L.C.
- Polysulfone is made by condensing bisphenol A and 4,4'-dichlorodiphenyl sulfone.
- Polyphenylsulfone is notably available as RADEL® R from Solvay Specialty Polymers USA, L.L.C and is made by reacting units of 4,4'-dichlorodiphenyl sulfone and 4,4'-biphenol.
- the viscosity enhancing additive (A) may be multivalent cation hydroxyde, a multifunctional organo silane or a multifunctional epoxy compound of both monomeric or polymeric nature.
- multivalent cation hydroxyde it is hereby intended to denote an hydroxide of a multivalent cation preferably selected from alkali metal metals cations such as Ca ++ , Ba ++ or Mg ++ .
- Example of suitable multifunctional organosilane compounds are (3- glycidyloxy propyl) trimethoxysilane, (3-Aminopropyl) trimethoxysilane, (3- Aminopropyl) triethoxysilane, N-[3-(Trimethoxy silyl)propyl]ethylenediamine.
- Examples of suitable multifunctional epoxy compounds are diglycidyl bisphenol ether, tris(4-hydroxyphenyl)methane triglycidyl ether, epoxy resins of different kinds, glycidyl-functionalized polyolephins.
- the additive may be used in amounts of, for example, 0.2 to 5% by weight, preferably 0.5 to 1.5% by weight based on total weight of the composition (C).
- Fluoropolymer (F) is fluorinated, that is to say it comprises recurring units derived from at least one (per)fluorinated monomer [monomer (F)].
- the fluoropolymer (F) is preferably a partially fluorinated fluoropolymer.
- partially fluorinated fluoropolymer is intended to denote a polymer comprising recurring units derived from at least one fluorinated monomer, wherein at least one of said fluorinated monomer comprises at least one hydrogen atom.
- fluorinated monomer it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one fluorine atom.
- fluorinated monomer is understood to mean that the fluoropolymer (F) may comprise recurring units derived from one or more than one fluorinated monomers.
- fluorinated monomers is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that they denote both one or more than one fluorinated monomers as defined above.
- the monomer (F) is generally selected from the group consisting of: (a) C2-C8 perfluoroolefins, such as tetrafluoroethylene, and hexafluoropropene; (b) C2-C8 hydrogenated fluoroolefins, such as vinyl fluoride, 1 ,2- difluoroethylene, vinylidene fluoride and trifluoroethylene;
- CF2 CFOXO (per)fluoro-oxyalkylvinylethers, in which Xo is a C1-C12 alkyl, or a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups, like perfluoro-2-propoxy-propyl;
- (g) (per)fluoroalkylvinylethers complying with formula CF2 CFOCF2ORf2 in which Rf2 is a Ci-Ce fluoro- or perfluoroalkyl, e.g. CF3, C2F5, C3F7 or a Ci- Ce (per)fluorooxyalkyl having one or more ether groups, like -C2F5-O-CF3;
- (h) functional (per)fluoro-oxyalkylvinylethers complying with formula CF2 CFOYO, in which Yo is a C1-C12 alkyl or (per)fluoroalkyl, or a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups and Yo comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
- fluorodioxoles of formula (I): wherein each of Rf3, Rf ⁇ Rf5, Rf6, equal or different each other, is independently a fluorine atom, a Ci-Ce fluoro- or per(halo)fluoroalkyl, optionally comprising one or more oxygen atom, e.g. -CF3, -C2F5, -C3F7, - OCF3, -OCF2CF2OCF3.
- the fluoropolymer (F) is a partially fluorinated fluoropolymer comprising recurring units derived from vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE) or tetrafluoroethylene (TFE), and, optionally, recurring units derived from at least one fluorinated monomer different from VDF, CTFE or TFE or recurring units derived from a hydrogenated monomer.
- VDF vinylidene fluoride
- CTFE chlorotrifluoroethylene
- TFE tetrafluoroethylene
- hydrogenated monomer it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
- the fluoropolymer (F) is a (per)fluoroelastomer [elastomer (E)].
- the term “(per)fluoroelastomer” is intended to designate a fluoropolymer resin serving as a base constituent for obtaining a true elastomer, said fluoropolymer resin comprising more than 10 % wt, preferably more than 30 % wt, of recurring units derived from at least one (perfluorinated monomer (F) as above defined and, optionally, recurring units derived from at least one ethylenically unsaturated monomer free from fluorine atom (hereafter, hydrogenated monomer).
- True elastomers are defined by the ASTM, Special Technical Bulletin, No. 184 standard as materials capable of being stretched, at room temperature, to twice their intrinsic length and which, once they have been released after holding them under tension for 5 minutes, return to within 10 % of their initial length in the same time.
- Examples of hydrogenated monomers are notably hydrogenated alphaolefins, including ethylene, propylene, 1 -butene, diene monomers, styrene monomers, alpha-olefins being typically used.
- (Per)fluoroelastomers (E) are in general amorphous products or products having a low degree of crystallinity (crystalline phase less than 20 % by volume) and a glass transition temperature (T g ) below room temperature. In most cases, the (per)fluoroelastomer has advantageously a T g below 10 °C, preferably below 5°C, more preferably 0°C.
- the (per)fluoroelastomer (E) is preferably selected among:
- VDF-based copolymers in which VDF is copolymerized with at least one comonomer selected from the group consisting of the followings classes, with the provision that such comonomer is different from VDF: (a1) C2-C8 perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene;
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- hexafluoroisobutylene hexafluoroisobutylene
- C2-C8 chloro and/or bromo and/or iodo-fluoroolefins such as chlorotrifluoroethylene (CTFE);
- (d1) (per)fluoroalkylvinylethers of formula CF2 CFORf, wherein Rf is a Ci-Ce (per)fluoroalkyl group; preferably perfluoroalkylvinylethers (PAVE) of above formula wherein Rf is Ci-Ce perfluoroalkyl group, e.g. CF3, C2F5, C3F7;
- (e1) (per)fluoro-oxy-alkylvinylethers of formula CF2 CFOX, wherein X is a C1-C12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms, e.g. the perfluoro-2-propoxypropyl group;
- (f1) (per)fluorodioxoles having formula : wherein Rf3, Rf4, Rf5, Rf6, equal or different from each other, are independently selected among fluorine atoms and Ci-Ce (per)fluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; preferably, perfluorodioxoles;
- CFX 2 CX 2 OCF 2 OR" f
- R"f is selected among Ci-Ce (per)fluoroalkyls, linear or branched; C5-C6 cyclic (per)fluoroalkyls; and C2-C6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary oxygen atoms
- X 2 F, H; preferably X 2 is F and R" f is -CF2CF3 (MOVE1); -CF2CF2OCF3 (MOVE2); or -CF 3 (MOVE3);
- TFE-based copolymers in which TFE is copolymerized with at least one comonomer selected from the group consisting of the classes (a1), (c1), (d1), (e1), (g1), (hi), and class (i2) below, with the provision that such comonomer is different from TFE:
- Most preferred (per)fluoroelastomers (E) are those having following compositions (in mol %):
- VDF vinylidene fluoride
- HFP hexafluoropropene
- TFE tetrafluoroethylene
- PAVE perfluoroalkyl vinyl ethers
- VDF vinylidene fluoride
- PAVE perfluoroalkyl vinyl ethers
- TFE tetrafluoroethylene
- VDF vinylidene fluoride
- Ol C2-C8 non-fluorinated olefins
- HFP hexafluoropropene
- PAVE perfluoroalkyl vinyl ethers
- TFE tetrafluoroethylene
- PAVE perfluoroalkyl vinyl ethers
- TFE tetrafluoroethylene
- Ol C2-C8 non-fluorinated olefins
- TFE tetrafluoroethylene
- Ol C2-C8 non-fluorinated olefins
- PAVE perfluoroalkyl vinyl ethers
- MOVE fluorovinyl ethers
- TFE tetrafluoroethylene
- PAVE perfluoroalkyl vinyl ethers
- VDF vinylidene fluoride
- VDF vinylidene fluoride
- MOVE fluorovinyl ethers
- PAVE perfluoroalkyl vinyl ethers
- TFE tetrafluoroethylene
- HFP hexafluoropropene
- TFE tetrafluoroethylene
- MOVE fluorovinyl ethers
- (per)fluoroelastomer (E) also comprises recurring units derived from a bis-olefin [bis-olefin (OF)] having general formula : wherein Ri, R2, R3, R4, Rs and Re, equal to or different from each other, are H, halogen, a group RAIK or ORAIK, wherein RAIK is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; Z is a linear or branched C1-C18 alkylene or cycloalkylene radical, optionally containing oxygen atoms, preferably at least partially fluorinated, or a (per)fluoropolyoxyalkylene radical, e.g. as described in EP 661304 A (AUSIMONT SPA) 7/5/1995 .
- a bis-olefin [bis-olefin (OF)] having general formula : wherein Ri, R2, R3, R4, Rs and Re, equal to or
- the bis-olefin (OF) is preferably selected from the group consisting of those complying with formulae (OF-1), (OF-2) and (OF-3) : (OF-1) wherein j is an integer between 2 and 10, preferably between 4 and 8, and R1 , R2, R3, R4, equal or different from each other, are H, F or C1-5 alkyl or (per)fluoroalkyl group;
- the (per)fluoroelastomer (E) is preferably uncrosslinked.
- composition (C) may include additional additives, some of them being able, at least at certain temperature ranges, to act as crosslinker.
- (per)fluoroelastomer (E) may be crosslinked or at least partially crosslinked.
- composition (C) of the present invention may include at least one further additive (AD).
- AD additives
- HF fluoropolymer
- aromatic polymer (A) aromatic polymer
- melt viscosity of the composition The reason to use an acid scavenger in the composition of the present invention is that HF is a strong reactant which may hinder other reactions.
- the additives (AD) may be used in amounts of, for example, 0.05 to 5% by weight, preferably 0.3 to 3% by weight based on total weight of the composition (C).
- a further object of the present invention is thus a polymer composition (C) comprising: - (a) from 1 to 98% by weight of at least one aromatic polymer (A),
- the fluoropolymer (F) is a (per)fluoroelastomer (E)
- the present invention provides a polymer composition (C) comprising:
- the polymer composition (C) according to the present invention may preferably comprise:
- the average particle size of the discrete domains in the polymer composition (C) of the present invention is conveniently less than 2 microns, preferably less than 1 micron, more preferably less than 0.5 microns.
- the average particle size of the components of the polymer composition (C) according to the present invention can be measured by Scanning Electron Microscopy on the freeze fractured blend obtained after melt mixing the blend above the temperature where all the components are in the molten form, as the average over 100 particles obtained by analyzing pictures at about 1000x magnification.
- composition (C) as above defined, said process comprising the following steps:
- step A melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM);
- step B melt compounding the mixture (AM) obtained in step A with at least one fluoropolymer (F).
- step A at least one aromatic polymer (A) is premixed with at least one a viscosity enhancing additive (A), preferably in a mixer, such as a roller mixer, for obtaining a premixture comprising at least one aromatic polymer (A) with at least one a viscosity enhancing additive (A).
- the premixture can be obtained by simultaneously feeding at least one aromatic polymer (A) and at least one viscosity enhancing additive (A) into the melt mixer. Said premixture is then melted to provide an aromatic polymer mixture (AM) before being compounded with at least one fluoropolymer (F) in step B.
- step Aa melt mixing the premixture comprising at least one aromatic polymer (A) with at least one viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM) is obtained in the same equipment for melt compounding that is then used in the following step B.
- step Ab the premixture obtained after mixing at least one aromatic polymer (A) with at least one a viscosity enhancing additive (A) is melted, extruded, solidified and then pelletized or granulated to obtain the aromatic polymer mixture (AM) in pellet or granular form.
- the Applicant has surprisingly found that it is precisely the fact of having subjected the premixture comprising at least one aromatic polymer (A) with at least one a viscosity enhancing additive (A) in step (A) to a melt mixing phase to obtain an aromatic polymer mixture (AM) before adding the fluoropolymer (F) in step B that allows to obtain a composition (C) having the characteristics of melt viscosity and melt flow index sufficiently high to manufacture articles for extrusion-type applications.
- step B Melt compounding in step B is carried out at a temperature where all the components are already in the molten form, thus at a temperature above the glass transition temperature or above the melting temperature of all the components.
- the aromatic polymer mixture (AM) and the at least one fluoropolymer (F) can be melted together, brought separately to their respective melting temperature and then mixed with each other, or subsequently added to a first melted polymer according to different variants.
- step Ba the melt compounding is carried out by adding the fluoropolymer (F) to the aromatic polymer mixture (AM) which is already in the molten form.
- step Bb both the aromatic polymer mixture (AM) and the fluoropolymer (F) are fed into the equipment for melt compounding through the same gate, melted together and compounded.
- step Bb a process for preparing composition (C) as above defined is provided, said process comprising Step Aa and step Ba.
- composition (C) as above defined comprising Step Ab and step Ba.
- composition (C) as above defined is provided, said process comprising Step Ab and step Bb.
- the present invention provides a process for preparing composition (C) as above defined, said process comprising the following steps:
- step A melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM);
- step B1 melt compounding the mixture (AM) obtained in step A with at least one (per)fluoroelastomer (E) and at least one additive (AD).
- the at least one additive (AD) is mixed with (per)fluoroelastomer (E) to give a (per)fluoroelastomer mixture (EM) which can be added in step B to the aromatic polymer mixture (AM) to obtain composition (C).
- the (per)fluoroelastomer mixture (EM) to be used in the present invention is preferably a physical mixture, which comprises at least one (per)fluoroelastomer (E) and at least one additive (AD).
- the term "physical mixture” refers to a composition in which the constituent components are combined or mixed with no chemical bonding, in particular with substantially no covalent chemical bonding between the constituents.
- the (per)fluoroelastomer mixture (EM) to be used in the present invention preferably comprise at least one additive (AD) in an amount comprised in the range from 0.2 to 20 parts per 100 parts of the (per)fluoroelastomer mixture (EM).
- (per)fluoroelastomer mixture (EM) comprises 100 parts of at least one (per)fluoroelastomer (E), from 0.2 to 20 parts of MgO and from 0.2 to 5 parts of a diamino-derivatives.
- the (per)fluoroelastomer mixture (EM) is typically provided in the form of powder.
- the (per)fluoroelastomer mixture (EM) may be pressed, compacted and then granulated to obtain the (per)fluoroelastomer mixture (EM) is in the form of pellets or dices.
- the (per)fluoroelastomer mixture (EM) may be pressed, compacted and then extruded or calendered to obtain the (per)fluoroelastomer mixture (EM) in the form of a strip, which can be fed to the extruder by suitable equipment.
- step B1 the aromatic polymer mixture (AM), either already in the molten form or in the form of pellets or granules, according to any of variants Aa or Ab, is melt compounded with at least one (per)fluoroelastomer (E) or with the (per)fluoroelastomer mixture (EM) according to either the two variants Ba or Bb.
- AM aromatic polymer mixture
- composition (C) is typically provided in the form of pellets.
- Preferred equipment to achieve melt compounding in step B, and possibly the overall process is a twin screw extruder.
- the process can also be realized using other common equipment to compound molten thermoplastic and elastomers, such as single screw extruders and internal mixers.
- the polymer composition (C) of the present invention has increased melt viscosities and improved toughness and flexibility compared to neat aromatic polymers (A), while maintaining the excellent properties of the parent aromatic polymers.
- the polymer composition (C) of the present invention is suitably used in various applications wherein extrusion processes are required, such as to extrude tubes with standard equipment for use in automotive and Oil and Gas applications.
- the present invention provides an article comprising the polymer composition (C) as defined above.
- the article according to the present invention can be a pipe or a piece of equipment formed by extrusion or blow molding technologies.
- extrusion and blow molding is used to obtain the wanted piece of equipment.
- PPS Polyphenylene sulfide, commercially available as Ryton® QA200 from Solvay.
- Glymo (3-Glycidyloxypropyl)trimethoxysilane, commercially available from Sigma Aldrich.
- AMS (3-Aminopropyl)trimethoxysilane, commercially available from Sigma Aldrich.
- IC-1 Hexamethylenediamine carbamate, commercially available as lntercure-1 from INTERBUSINESS S.r.L, Via Spartaco 25, 20135, Milano (Italy).
- IC-3 N,N’-dicinnamylidene-1 ,6 hexanediamine, commercially available as lntercure-3 from INTERBUSINESS S.r.L, Via Spartaco 25, 20135, Milano (Italy).
- a powdery premixture containing the wanted amounts of PPS and Ca(OH)2 or Glymo was mixed in a roller mixer for 24 hours. Then, the powder mixture was extruded in a Coperion ZSK 26 extruder at 12 kg/h with first zone set a 150 °C and all the others zones set at 300 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
- FKM1 or FKM2 was mixed in an open mill at room temperature with the other additives, then formed into a 3 mm thick sheet by calendaring and finally granulated to prepare roughly 3 x 3 x 3 mm 3 dices.
- These dices and the PPS pellets of P1 or P2 were fed at the main gate of the Coperion ZSK 26 extruder using two separate K-Tron feeders equipped with pellets screws.
- the two feeding streams were compounded into the extruder at 8 kg/h with first zone set a 150 °C and all the others zones set at 300 °C.
- FKM3, IC-3 and MgO in the amounts shown in Table 1 were mixed in a roller mill at room temperature for 24 hours. Then, this mixture and the precursor pellets of P2 were fed at the main gate of the Coperion ZSK 26 extruder via two separate feeders. The overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, the remaining zones are set at 300 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
- FKM4 powder and the other additives are mixed in roller mill at room temperature for 24 hours to obtain the fluoroelastomer mixture.
- a powdery premixture containing PPS and Ca(OH)2 or AMS was obtained by mixing the components together in a roller mixer for 24 hours. Then, the PPS powdery premixture was fed into the Coperion ZSK 26 extruder at the main gate while the fluoroelastomer mixture was fed via the side feeder in zone 5.
- the overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, zones 2 to 4 at 320 °C, zones 5 and 6 at 290 °C, the remaining zones are at 280 °C.
- the extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
- FKM4 or FKM5 were mixed in an open mill at room temperature with the other additives, then formed into a 3 mm thick sheet by calendaring and finally granulated to prepare roughly 3 x 3 x 3 mm 3 dices.
- a powdery premixture containing PPS and aminosilane was obtained by mixing the components together in a roller mixer for 24 hours. Then, the PPS powdery premixture was fed into the Coperion ZSK 26 extruder at the main gate while the fluoroelastomer mixture was fed via the side feeder in zone 5.
- the overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, zones 2 to 4 at 300 °C, zones 5 and 6 at 290 °C, the remaining zones are at 280 °C.
- the extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
- FKM1 , FKM2 or FKM4 and the other additives are mixed in roller mill at room temperature for 24 hours to obtain the fluoroelastomer mixture.
- a powdery mixture containing PPS and Ca(OH)2 or Glymo was obtained by mixing the components together in a roller mixer for 24 hours.
- both the PPS based powdery premixture and the fluoroelastomer mixtures were fed into the Coperion ZSK 26 extruder at the main gate using two separate feeders.
- the overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, and the remaining zones were set at 300 °C.
- the extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
- compositions of comparative examples C3-C8 and C10-C13 were obtained, as detailed in Table 1 below.
- the polymer composition according to the present invention shows a markedly improved melt viscosity at low shear rate in comparison with compositions comprising no or little amounts of viscosity enhancing additive (see C9).
- the viscosity at low shear rate above a certain value is required to allow the molten material to keep the shape of the tube before reaching the solidification point; in addition, high viscosity at low shear rates allows the molten material to be stretched or biaxially deformed without losing continuity (breaking, piercing).
- This result demonstrates that, thanks to the presence of at least one certain viscosity enhancing additive, the composition according to the present invention has sufficient melt strength to undergo a strong uniaxial or biaxial deformation process.
- tubes were extruded in a PD45 extruder using a die and a tip having a diameter of 20 mm and 14.6 mm, respectively.
- the screw speed and the line speed were set at 20 rpm and 1.5 m/min, respectively.
- the barrel and the die head temperature was set at 290 °C.
- the external diameter of the tube was set using a calibrator of 15.1 mm positioned at 95 mm from the die. Then, after a water gap of 30 mm, the tube was cooled in a water bath.
- Example 16 was then aged in air at 150 °C for 3 hours to give the tube of Example 16bis.
- tubes were extruded in a 19 mm Brabender single screw extruder using a die and a tip having a diameter of 10 mm and 8 mm, respectively.
- the die is provided with an inlet for air flow in the bore of the tube.
- the screw speed and the line speed were set at 150 rpm and 1.8 m/min, respectively.
- the barrel and the die head temperature was set at 300 °C.
- “Blow molding” experiments were performed by inflating air in the bore of the tube which is getting out the die while closing the tube diameter at about 30 cm from the die before the tube itself is cooled by the water.
- the polymer composition according to the present invention allows obtaining tubes by extrusion process with improved tensile properties in comparison with compositions having a higher melt viscosity at low share rate and higher melt flow index.
Abstract
The present invention relates to a polymer composition comprising a sulphur-containing aromatic polymer and at least one fluoropolymer, which has high melt viscosity.The invention also relates to a process for the preparation of said polymer composition and to an article comprising the same.
Description
SULPHUR-CONTAINING AROMATIC POLYMER COMPOSITION HAVING IMPROVED PROCESSABILITY
Cross-reference to related applications
[0001] This application claims priority to US provisional application number 63/124975 filed on 14 December 2020 and to European application No. 21159309.0 filed on 25 February 2021 , the whole content of this application being incorporated herein by reference for all purposes.
Technical Field
[0002] The present invention relates to a polymer composition comprising a sulphur-containing aromatic polymer and at least one fluoropolymer, which has high melt viscosity.
[0003] The invention also relates to a process for the preparation of said polymer composition and to an article comprising the same.
Background Art
[0004] Sulphur-containing aromatic polymer such as polyarylene sulfides and polyarylsulfones are thermally stable engineering plastics consisting mainly of phenyl or biphenyl groups linked by sulfide, ether and/or sulfone groups. Those materials have excellent heat resistance and chemical resistance. However, they have poor mechanical properties, in particular impact resistance.
[0005] There has long been interest in improving the mechanical properties of sulphur-containing aromatic polymers.
[0006] Blending sulphur-containing aromatic polymers with fluorine-containing polymers can produce novel materials combining the performances and properties of both classes.
[0007] Blends of sulphur-containing aromatic polymers with fluorine-containing polymers tend however to have morphology with large regions or domains of the individual polymers rather than fine, well-dispersed domains. The large domains tend to produce a material with poor mechanical properties, e.g. injection molded parts having poor tensile properties.
[0008] To improve the dispersibility of the blend, a compatibilizer can be added.
[0009] WO 2018/193020 discloses polymer alloys comprising sulphur-containing aromatic polymers and uncrosslinked fluoroelastomers wherein the compatibilization is improved by mixing said fluoroelastomer with certain amounts of at least one divalent metal oxide.
[0010] Said polymer alloys show improved mechanical properties, in particular tensile properties, but they are characterized by a melt viscosity at low shear that is not high enough to allow the use of the same in extrusion and blow molding processes.
[0011] There is still hence a shortfall in the art for improved compositions comprising sulphur-containing aromatic polymer and a fluoropolymer having a melt viscosity sufficiently high to manufacture articles by extrusion or blow molding, or similar processes, which have improved flexibility and toughness, while retaining the thermal and chemical resistance of both neat polymers.
Summary of invention
[0012] The Applicant has surprisingly found that melt compounding polyphenylene sulfide with fluoropolymers with certain additives allows to obtain improved compounds having a melt viscosity sufficiently high to manufacture articles for extrusion-type applications.
[0013] It is thus a first object of the present invention to provide a polymer composition (C) comprising:
- (a) from 1 to 98% by weight of at least one aromatic polymer (A),
- (b) from 1 to 50% by weight of at least one fluoropolymer (F),
- (c) from 0.4 to 10% by weight of at least one viscosity enhancing additive (A), all the aforementioned percentages by weight being referred to the total weight of polymer composition (C), wherein said polymer composition (C) has a melt flow index (MFI) lower than 30 g/10 min, the melt flow index (MFI) being measured according to ASTM D 1238 standard method by applying a weight of 5 Kg at 316°C.
[0014] The Applicant has also surprisingly found that the composition (C) having improved melt flow index can be obtained by a process including a series of steps to be carried out in a specific order.
[0015] Another object of the present invention is thus a process for preparing composition (C) as above defined, said process comprising the following steps:
- step A: melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A);
- step B: melt compounding the compound obtained in step A with at least one fluoropolymer (F).
[0016] In a further object, the present invention is directed to articles made of said polymer composition (C).
Description of embodiments
[0017] Aromatic polymer (A)
[0018] Aromatic polymer (A) to be used in the present invention may be a poly(arylene sulfide) (PAS) or an aromatic sulfone polymer (SP).
[0019] PASs are polymers comprising the repeating unit of the formula -(Ar-S)- as the main structural unit, preferably containing the repeating unit in an amount of 80 mol% or more. Ar represents an aromatic group, and examples include units (RU1) represented by the formulas (I) to (XI) given below, among which the formula (I) is particularly preferred:
SUBSTITUTE SHEET (RULE 26)
SUBSTITUTE SHEET (RULE 26)
wherein R1 and R2 each represent a substituent selected from hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, arylene of 6 to 24 carbon atoms, and halogen, and R1 and R2 may be the same or different.
[0020] Accordingly, poly(arylene sulfide) (PAS) is preferably polyphenylene sulfide (PPS).
[0021] For the purposes of the present invention, the definition “aromatic sulfone polymer (SP)" is intended to denote any polymer of which more than 50 wt %, preferably more than 70 wt%, more preferably more than 90 wt%, of recurring units (RU2) comprise at least one group of formula (XII):
Ar’ being a group chosen among the following structures:
with RD being:
SUBSTITUTE SHEET (RULE 26)
with n = integer from 1 to 6.
[0022] The recurring units (RU2) are preferably chosen from:
[0023] Accordingly, aromatic sulfone polymer (SP) is preferably chosen among the group consisting of polysulfone (PSU), polyphenylsulfone (PPSLI), polyethersulfone (PESLI), copolymers and mixtures thereof and is most preferably a polysulfone (PSU) or polyphenylsulfone (PPSU).
[0024] Polysulfone is notably available as UDEL® PSU from Solvay Specialty Polymers USA, L.L.C.
[0025] Polysulfone is made by condensing bisphenol A and 4,4'-dichlorodiphenyl sulfone.
[0026] Polyphenylsulfone is notably available as RADEL® R from Solvay Specialty Polymers USA, L.L.C and is made by reacting units of 4,4'-dichlorodiphenyl sulfone and 4,4'-biphenol.
[0027] Methods well known in the art for the preparation of polyphenylsulfone are for instance those described in documents US3634355; US4008203;
US4108837 and US4175175, the whole content of which is incorporated herein by reference.
[0028] Viscosity enhancing additive (A)
[0029] The viscosity enhancing additive (A) may be multivalent cation hydroxyde, a multifunctional organo silane or a multifunctional epoxy compound of both monomeric or polymeric nature.
[0030] By the term “multivalent cation hydroxyde” it is hereby intended to denote an hydroxide of a multivalent cation preferably selected from alkali metal metals cations such as Ca++, Ba++ or Mg++.
[0031] Example of suitable multifunctional organosilane compounds are (3- glycidyloxy propyl) trimethoxysilane, (3-Aminopropyl) trimethoxysilane, (3- Aminopropyl) triethoxysilane, N-[3-(Trimethoxy silyl)propyl]ethylenediamine.
[0032] Examples of suitable multifunctional epoxy compounds are diglycidyl bisphenol ether, tris(4-hydroxyphenyl)methane triglycidyl ether, epoxy resins of different kinds, glycidyl-functionalized polyolephins.
[0033] The additive may be used in amounts of, for example, 0.2 to 5% by weight, preferably 0.5 to 1.5% by weight based on total weight of the composition (C).
[0034] Fluoropolymer (F)
[0035] Fluoropolymer (F) is fluorinated, that is to say it comprises recurring units derived from at least one (per)fluorinated monomer [monomer (F)].
[0036] The fluoropolymer (F) is preferably a partially fluorinated fluoropolymer.
[0037] For the purpose of the present invention, the term “partially fluorinated fluoropolymer” is intended to denote a polymer comprising recurring units derived from at least one fluorinated monomer, wherein at least one of said fluorinated monomer comprises at least one hydrogen atom.
[0038] By the term “fluorinated monomer” it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one fluorine atom.
[0039] The term “at least one fluorinated monomer” is understood to mean that the fluoropolymer (F) may comprise recurring units derived from one or more than one fluorinated monomers. In the rest of the text, the expression “fluorinated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that they denote both one or more than one fluorinated monomers as defined above.
[0040] The monomer (F) is generally selected from the group consisting of: (a) C2-C8 perfluoroolefins, such as tetrafluoroethylene, and hexafluoropropene;
(b) C2-C8 hydrogenated fluoroolefins, such as vinyl fluoride, 1 ,2- difluoroethylene, vinylidene fluoride and trifluoroethylene;
(c) perfluoroalkylethylenes complying with formula CH2=CH-Rro, in which Rro is a Ci-Ce perfluoroalkyl;
(d) chloro- and/or bromo- and/or iodo-C2-Ce fluoroolefins, like chlorotrifluoroethylene;
(e) (per)fluoroalkylvinylethers complying with formula CF2=CFORfi in which Rn is a Ci-Ce fluoro- or perfluoroalkyl, e.g. CF3, C2F5, C3F7 ;
(f) CF2=CFOXO (per)fluoro-oxyalkylvinylethers, in which Xo is a C1-C12 alkyl, or a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups, like perfluoro-2-propoxy-propyl;
(g) (per)fluoroalkylvinylethers complying with formula CF2=CFOCF2ORf2 in which Rf2 is a Ci-Ce fluoro- or perfluoroalkyl, e.g. CF3, C2F5, C3F7 or a Ci- Ce (per)fluorooxyalkyl having one or more ether groups, like -C2F5-O-CF3;
(h) functional (per)fluoro-oxyalkylvinylethers complying with formula CF2=CFOYO, in which Yo is a C1-C12 alkyl or (per)fluoroalkyl, or a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups and Yo comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
(i) fluorodioxoles, of formula (I):
wherein each of Rf3, Rf< Rf5, Rf6, equal or different each other, is independently a fluorine atom, a Ci-Ce fluoro- or per(halo)fluoroalkyl, optionally comprising one or more oxygen atom, e.g. -CF3, -C2F5, -C3F7, - OCF3, -OCF2CF2OCF3.
[0041] According to a first embodiment of the invention, the fluoropolymer (F) is a partially fluorinated fluoropolymer comprising recurring units derived from vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE) or tetrafluoroethylene (TFE), and, optionally, recurring units derived from at least one fluorinated monomer different from VDF, CTFE or TFE or recurring units derived from a hydrogenated monomer.
[0042] By the term “hydrogenated monomer” it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
[0043] According to a preferred embodiment, the fluoropolymer (F) is a (per)fluoroelastomer [elastomer (E)].
[0044] For the purposes of this invention, the term “(per)fluoroelastomer” is intended to designate a fluoropolymer resin serving as a base constituent for obtaining a true elastomer, said fluoropolymer resin comprising more than 10 % wt, preferably more than 30 % wt, of recurring units derived from at least one (perfluorinated monomer (F) as above defined and, optionally, recurring units derived from at least one ethylenically unsaturated monomer free from fluorine atom (hereafter, hydrogenated monomer).
[0045] True elastomers are defined by the ASTM, Special Technical Bulletin, No. 184 standard as materials capable of being stretched, at room temperature, to twice their intrinsic length and which, once they have been released after holding them under tension for 5 minutes, return to within 10 % of their initial length in the same time.
[0046] Examples of hydrogenated monomers are notably hydrogenated alphaolefins, including ethylene, propylene, 1 -butene, diene monomers, styrene monomers, alpha-olefins being typically used.
[0047] (Per)fluoroelastomers (E) are in general amorphous products or products having a low degree of crystallinity (crystalline phase less than 20 % by volume) and a glass transition temperature (Tg) below room temperature. In most cases, the (per)fluoroelastomer has advantageously a Tg below 10 °C, preferably below 5°C, more preferably 0°C.
[0048] The (per)fluoroelastomer (E) is preferably selected among:
(1) VDF-based copolymers, in which VDF is copolymerized with at least one comonomer selected from the group consisting of the followings classes, with the provision that such comonomer is different from VDF: (a1) C2-C8 perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene;
(b1) hydrogen-containing C2-C8 olefins, such as C2-C8 non-fluorinated
olefins (01); C2-C8 partially fluorinated olefins, vinyl fluoride (VF), trifluoroethylene (TrFE), perfluoroalkyl ethylenes of formula CH2 = CH-Rf, wherein Rf is a Ci-Ce perfluoroalkyl group;
(c1) C2-C8 chloro and/or bromo and/or iodo-fluoroolefins such as chlorotrifluoroethylene (CTFE);
(d1) (per)fluoroalkylvinylethers of formula CF2 = CFORf, wherein Rf is a Ci-Ce (per)fluoroalkyl group; preferably perfluoroalkylvinylethers (PAVE) of above formula wherein Rf is Ci-Ce perfluoroalkyl group, e.g. CF3, C2F5, C3F7;
(e1) (per)fluoro-oxy-alkylvinylethers of formula CF2 = CFOX, wherein X is a C1-C12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms, e.g. the perfluoro-2-propoxypropyl group;
(f1) (per)fluorodioxoles having formula :
wherein Rf3, Rf4, Rf5, Rf6, equal or different from each other, are independently selected among fluorine atoms and Ci-Ce (per)fluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; preferably, perfluorodioxoles;
(g1) (per)fluoro-methoxy-vinylethers (MOVE, hereinafter) having formula: CFX2 = CX2OCF2OR"f wherein R"f is selected among Ci-Ce (per)fluoroalkyls, linear or branched; C5-C6 cyclic (per)fluoroalkyls; and C2-C6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary oxygen atoms, and X2 = F, H; preferably X2 is F and R"f is -CF2CF3 (MOVE1); -CF2CF2OCF3 (MOVE2); or -CF3 (MOVE3);
(hi) C2-C8 non-fluorinated olefins (Ol), for example ethylene and propylene; and
(2) TFE-based copolymers, in which TFE is copolymerized with at least one comonomer selected from the group consisting of the classes (a1), (c1), (d1), (e1), (g1), (hi), and class (i2) below, with the provision that such
comonomer is different from TFE:
(i2) perfluorovinyl ethers containing cyanide groups, such as notably those described in patents US 4281 092, US 5447 993 and US 5 789489.
[0049] Most preferred (per)fluoroelastomers (E) are those having following compositions (in mol %):
(i) vinylidene fluoride (VDF) 35-85 %, hexafluoropropene (HFP) IQ-
45 %, tetrafluoroethylene (TFE) 0-30 %, perfluoroalkyl vinyl ethers (PAVE) 0-15 %;
(ii) vinylidene fluoride (VDF) 50-80 %, perfluoroalkyl vinyl ethers (PAVE) 5-50 %, tetrafluoroethylene (TFE) 0-20 %;
(iii) vinylidene fluoride (VDF) 20-30 %, C2-C8 non-fluorinated olefins (Ol) 10-30 %, hexafluoropropene (HFP) and/or perfluoroalkyl vinyl ethers (PAVE) 18-27 %, tetrafluoroethylene (TFE) 10-30 %;
(iv) tetrafluoroethylene (TFE) 50-80 %, perfluoroalkyl vinyl ethers (PAVE) 20-50 %;
(v) tetrafluoroethylene (TFE) 45-65 %, C2-C8 non-fluorinated olefins (Ol) 20-55 %, vinylidene fluoride 0-30 %;
(vi) tetrafluoroethylene (TFE) 32-60 % mol %, C2-C8 non-fluorinated olefins (Ol) 10-40 %, perfluoroalkyl vinyl ethers (PAVE) 20-40 %, fluorovinyl ethers (MOVE) 0-30 %;
(vii) tetrafluoroethylene (TFE) 33-75 %, perfluoroalkyl vinyl ethers (PAVE) 15-45 %, vinylidene fluoride (VDF) 5-30 %, hexafluoropropene HFP 0-
30 %;
(viii) vinylidene fluoride (VDF) 35-85 %, fluorovinyl ethers (MOVE) 5-40 %, perfluoroalkyl vinyl ethers (PAVE) 0-30 %, tetrafluoroethylene (TFE) 0- 40 %, hexafluoropropene (HFP) 0-30 %;
(ix) tetrafluoroethylene (TFE) 20-70 %, fluorovinyl ethers (MOVE) 30-
80 %, perfluoroalkyl vinyl ethers (PAVE) 0-50 %.
[0050] Optionally, (per)fluoroelastomer (E) also comprises recurring units derived from a bis-olefin [bis-olefin (OF)] having general formula :
wherein Ri, R2, R3, R4, Rs and Re, equal to or different from each other, are H, halogen, a group RAIK or ORAIK, wherein RAIK is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; Z is a linear or branched C1-C18 alkylene or cycloalkylene radical, optionally containing oxygen atoms, preferably at least partially fluorinated, or a (per)fluoropolyoxyalkylene radical, e.g. as described in EP 661304 A (AUSIMONT SPA) 7/5/1995 .
[0051] The bis-olefin (OF) is preferably selected from the group consisting of those complying with formulae (OF-1), (OF-2) and (OF-3) : (OF-1)
wherein j is an integer between 2 and 10, preferably between 4 and 8, and R1 , R2, R3, R4, equal or different from each other, are H, F or C1-5 alkyl or (per)fluoroalkyl group;
(OF-2)
wherein each of A, equal or different from each other and at each occurrence, is independently selected from F, Cl, and H; each of B, equal or different from each other and at each occurrence, is independently selected from F, Cl, H and ORB, wherein RB is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; E is a divalent group having 2 to 10 carbon atom, optionally fluorinated, which may be inserted with ether linkages; preferably E is a - (CF2)m- group, with m being an integer from 3 to 5; a preferred bis-olefin of (OF-2) type is F2C=CF-O-(CF2)5-O-CF=CF2.
(OF-3)
wherein E, A and B have the same meaning as above defined; R5, R6, R7, equal or different from each other, are H, F or C1-5 alkyl or (per)fluoroalkyl group.
[0052] In one embodiment of the present invention, the (per)fluoroelastomer (E) is preferably uncrosslinked.
[0053] Nevertheless, composition (C) may include additional additives, some of them being able, at least at certain temperature ranges, to act as crosslinker. Thus, in some embodiments, (per)fluoroelastomer (E) may be crosslinked or at least partially crosslinked.
[0054] To further improve the melt viscosity of composition (C) and the dispersibility of the fluoropolymer (F) in the aromatic polymer (A), in particular when the fluoropolymer (F) is a (per)fluoroelastomer (E), composition (C) of the present invention may include at least one further additive (AD).
[0055] Examples of suitable additives (AD) are:
- MgO, which is used as HF scavenger, though it may have also some positive effect on compatibility of fluoropolymer (F) in the aromatic polymer (A) and also a moderate effect on melt viscosity of the composition. The reason to use an acid scavenger in the composition of the present invention is that HF is a strong reactant which may hinder other reactions.
- diamino-derivatives. Their use is advantageous to promote the compatibility of fluoropolymer (F) in the aromatic polymer (A) and provide beneficial effects during extrusion processes.
- bisphenol AF and onium salts;
[0056] The additives (AD) may be used in amounts of, for example, 0.05 to 5% by weight, preferably 0.3 to 3% by weight based on total weight of the composition (C).
[0057] A further object of the present invention is thus a polymer composition (C) comprising:
- (a) from 1 to 98% by weight of at least one aromatic polymer (A),
- (b) from 1 to 50% by weight of at least one fluoropolymer (F),
- (c) from 0.4 to 10% by weight of at least one viscosity enhancing additive (A), all the aforementioned percentages by weight being referred to the total weight of polymer composition (C), and
- (d) at least one additional additive (AD) selected from the group consisting of MgO, diamino-derivatives, bisphenol AF and onium salts, wherein said polymer composition (C) has a melt flow index (MFI) lower than 30 g/10 min, the melt flow index (MFI) being measured according to ASTM D 1238 standard method by applying a weight of 5 Kg at 316°C.
[0058] In a preferred embodiment, when the fluoropolymer (F) is a (per)fluoroelastomer (E), the present invention provides a polymer composition (C) comprising:
- (a) at least one a sulphur-containing aromatic polymer [aromatic polymer (A)],
- (b) at least one (per)fluoroelastomer (E),
- (c) at least one viscosity enhancing additive (A), and
- (d) at least one additional additive (AD) selected from the group consisting of MgO, diamino-derivatives, bisphenol AF and onium salts, wherein said polymer composition (C) has a melt flow index (MFI) lower than 30 g/10 min, the melt flow index (MFI) being measured according to ASTM D 1238 standard method by applying a weight of 5 Kg at 316°C.
[0059] The polymer composition (C) according to the present invention may preferably comprise:
- (a) from 1 to 98% by weight of at least one aromatic polymer (A);
- (b) from 1 to 50% by weight of at least one fluoropolymer (F);
- (c) from 0.4 to 10% by weight of at least one viscosity enhancing additive (A); and
- (d) optionally, from 0.05 to 5% by weight of at least one additional additive (AD) all the aforementioned percentages by weight being referred to the total weight of polymer composition (C).
[0060] The average particle size of the discrete domains in the polymer composition (C) of the present invention is conveniently less than 2 microns, preferably less than 1 micron, more preferably less than 0.5 microns. The average particle size of the components of the polymer composition (C) according to the present invention can be measured by Scanning Electron Microscopy on the freeze fractured blend obtained after melt mixing the blend above the temperature where all the components are in the molten form, as the average over 100 particles obtained by analyzing pictures at about 1000x magnification.
[0061] Another object of the present invention is a process for preparing composition (C) as above defined, said process comprising the following steps:
- step A: melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM);
- step B: melt compounding the mixture (AM) obtained in step A with at least one fluoropolymer (F).
[0062] In step A, at least one aromatic polymer (A) is premixed with at least one a viscosity enhancing additive (A), preferably in a mixer, such as a roller mixer, for obtaining a premixture comprising at least one aromatic polymer (A) with at least one a viscosity enhancing additive (A). Alternatively, the premixture can be obtained by simultaneously feeding at least one aromatic polymer (A) and at least one viscosity enhancing additive (A) into the melt mixer. Said premixture is then melted to provide an aromatic polymer mixture (AM) before being compounded with at least one fluoropolymer (F) in step B.
[0063] In a first variant of step A, hereinafter called step Aa, melt mixing the premixture comprising at least one aromatic polymer (A) with at least one viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM) is obtained in the same equipment for melt compounding that is then used in the following step B.
[0064] According to this first variant Aa, no intermediate solidification of the aromatic polymer mixture (AM) is carried out before the addition of the
fluoropolymer (F) in step B. That is, aromatic polymer mixture (AM) already in melted form is provided and melt compounded with fluoropolymer (F) in step B
[0065] In a second variant of step A, hereinafter called step Ab, the premixture obtained after mixing at least one aromatic polymer (A) with at least one a viscosity enhancing additive (A) is melted, extruded, solidified and then pelletized or granulated to obtain the aromatic polymer mixture (AM) in pellet or granular form.
[0066] The Applicant has surprisingly found that it is precisely the fact of having subjected the premixture comprising at least one aromatic polymer (A) with at least one a viscosity enhancing additive (A) in step (A) to a melt mixing phase to obtain an aromatic polymer mixture (AM) before adding the fluoropolymer (F) in step B that allows to obtain a composition (C) having the characteristics of melt viscosity and melt flow index sufficiently high to manufacture articles for extrusion-type applications.
[0067] Melt compounding in step B is carried out at a temperature where all the components are already in the molten form, thus at a temperature above the glass transition temperature or above the melting temperature of all the components.
[0068] In the melt compounding procedure in step B, the aromatic polymer mixture (AM) and the at least one fluoropolymer (F) can be melted together, brought separately to their respective melting temperature and then mixed with each other, or subsequently added to a first melted polymer according to different variants.
[0069] In a first variant of step B, hereinafter called step Ba, the melt compounding is carried out by adding the fluoropolymer (F) to the aromatic polymer mixture (AM) which is already in the molten form.
[0070] In the second variant of step B, hereinafter called step Bb, both the aromatic polymer mixture (AM) and the fluoropolymer (F) are fed into the equipment for melt compounding through the same gate, melted together and compounded.
[0071] In one embodiment of the present invention, a process for preparing composition (C) as above defined is provided, said process comprising Step Aa and step Ba.
[0072] In still another embodiment of the present invention, a process for preparing composition (C) as above defined is provided, said process comprising Step Ab and step Ba.
[0073] In a further embodiment of the present invention, a process for preparing composition (C) as above defined is provided, said process comprising Step Ab and step Bb.
[0074] According to a preferred embodiment of the process of the invention, when the fluoropolymer (F) is a (per)fluoroelastomer (E), the present invention provides a process for preparing composition (C) as above defined, said process comprising the following steps:
- step A: melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM);
- step B1 : melt compounding the mixture (AM) obtained in step A with at least one (per)fluoroelastomer (E) and at least one additive (AD).
[0075] In one embodiment of the present invention, the at least one additive (AD) is mixed with (per)fluoroelastomer (E) to give a (per)fluoroelastomer mixture (EM) which can be added in step B to the aromatic polymer mixture (AM) to obtain composition (C).
[0076] (Per)fluoroelastomer mixture (EM)
[0077] The (per)fluoroelastomer mixture (EM) to be used in the present invention is preferably a physical mixture, which comprises at least one (per)fluoroelastomer (E) and at least one additive (AD).
[0078] As used herein, the term "physical mixture" refers to a composition in which the constituent components are combined or mixed with no chemical bonding, in particular with substantially no covalent chemical bonding between the constituents.
[0079] The (per)fluoroelastomer mixture (EM) to be used in the present invention preferably comprise at least one additive (AD) in an amount comprised in
the range from 0.2 to 20 parts per 100 parts of the (per)fluoroelastomer mixture (EM).
[0080] In a further preferred embodiment, (per)fluoroelastomer mixture (EM) comprises 100 parts of at least one (per)fluoroelastomer (E), from 0.2 to 20 parts of MgO and from 0.2 to 5 parts of a diamino-derivatives.
[0081] The (per)fluoroelastomer mixture (EM) is typically provided in the form of powder.
[0082] In an alternative embodiment, the (per)fluoroelastomer mixture (EM), may be pressed, compacted and then granulated to obtain the (per)fluoroelastomer mixture (EM) is in the form of pellets or dices.
[0083] In an alternative embodiment, the (per)fluoroelastomer mixture (EM) may be pressed, compacted and then extruded or calendered to obtain the (per)fluoroelastomer mixture (EM) in the form of a strip, which can be fed to the extruder by suitable equipment.
[0084] In step B1 , the aromatic polymer mixture (AM), either already in the molten form or in the form of pellets or granules, according to any of variants Aa or Ab, is melt compounded with at least one (per)fluoroelastomer (E) or with the (per)fluoroelastomer mixture (EM) according to either the two variants Ba or Bb.
[0085] At the end of the process of the invention, composition (C) is typically provided in the form of pellets.
[0086] The applicant has surprisingly found that to the sake of achieving higher melt viscosity, as necessary for extruding notably large diameter pipes, the process including melt compounding the fluoropolymer (F) with the aromatic polymer mixture (AM) as provided in step Ab, thus already solidified in the form of pellets or granules, is very effective.
[0087] Preferred equipment to achieve melt compounding in step B, and possibly the overall process, is a twin screw extruder. The process can also be realized using other common equipment to compound molten thermoplastic and elastomers, such as single screw extruders and internal mixers.
[0088] The polymer composition (C) of the present invention has increased melt viscosities and improved toughness and flexibility compared to neat
aromatic polymers (A), while maintaining the excellent properties of the parent aromatic polymers.
[0089] Therefore, the polymer composition (C) of the present invention is suitably used in various applications wherein extrusion processes are required, such as to extrude tubes with standard equipment for use in automotive and Oil and Gas applications.
[0090] In a further object, therefore, the present invention provides an article comprising the polymer composition (C) as defined above. Preferably, the article according to the present invention can be a pipe or a piece of equipment formed by extrusion or blow molding technologies. Preferably, extrusion and blow molding is used to obtain the wanted piece of equipment.
[0091] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
[0092] The invention will be now described with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.
[0093] EXPERIMENTAL PART
[0094] RAW MATERIALS
PPS: Polyphenylene sulfide, commercially available as Ryton® QA200 from Solvay.
FKM1 = vinylidene fluoride/Zhexafluoropropylene copolymer having 66.0 % fluorine content and Mooney viscosity (ML 1+10’) measured at 121 °C according to ASTM D1646 = 27 MU.
FKM2= vinylidene fluoride/Zhexafluoropropylene copolymer having 66.0 % fluorine content and Mooney viscosity (ML 1+10’) measured at 121 °C according to ASTM D1646 = 20 MU.
FKM3 = vinylidene fluoride/Zhexafluoropropylene copolymer having 66.0 % fluorine content which contains 5% of MgO as antipacking agent; Mooney viscosity (ML 1+10’) measured at 121 °C according to ASTM D1646 = 62 MU.
FKM4: vinylidene fluoride/Zhexafluoropropylene copolymer having 66.0 % fluorine content which is cryoground and contains calcium stearate as antipacking agent; Mooney viscosity (ML 1+10’) measured at 121 °C according to ASTM D1646 = 47 MU.
FKM5, Tecnoflon® FOR 539, commercially available from Solvay.
Glymo = (3-Glycidyloxypropyl)trimethoxysilane, commercially available from Sigma Aldrich.
AMS = (3-Aminopropyl)trimethoxysilane, commercially available from Sigma Aldrich.
IC-1 = Hexamethylenediamine carbamate, commercially available as lntercure-1 from INTERBUSINESS S.r.L, Via Spartaco 25, 20135, Milano (Italy).
IC-3 = N,N’-dicinnamylidene-1 ,6 hexanediamine, commercially available as lntercure-3 from INTERBUSINESS S.r.L, Via Spartaco 25, 20135, Milano (Italy).
Ca(OH)2, commercially available as Rhenofit®-CF from Rhein Chemie. MgO, commercially available as Maglite-DE®from Hallstar.
[0095] General procedure or the preparation of aromatic polymer mixture (AM) in pellet form
[0096] A powdery premixture containing the wanted amounts of PPS and Ca(OH)2 or Glymo was mixed in a roller mixer for 24 hours. Then, the powder mixture was extruded in a Coperion ZSK 26 extruder at 12 kg/h with first zone set a 150 °C and all the others zones set at 300 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[0097] The amounts of Ca(OH)2 or Glymo in the PPS/ viscosity enhancing additive mix of Preparation Examples P1 and P2 are reported in Table 1 below.
[0098] Preparation of PPS/FKM composition Examples 1 , 4, 5, 6 and 7
[0099] FKM1 or FKM2was mixed in an open mill at room temperature with the other additives, then formed into a 3 mm thick sheet by calendaring and finally granulated to prepare roughly 3 x 3 x 3 mm3 dices. These dices and the PPS pellets of P1 or P2 were fed at the main gate of the Coperion ZSK
26 extruder using two separate K-Tron feeders equipped with pellets screws. The two feeding streams were compounded into the extruder at 8 kg/h with first zone set a 150 °C and all the others zones set at 300 °C.
[00100] Composition of Examples 3, 4, 5, 6 and 7 were obtained, as detailed in Table 1 below.
[00101] Preparation of PPS/FKM composition Example 11
[00102] FKM3, IC-3 and MgO in the amounts shown in Table 1 were mixed in a roller mill at room temperature for 24 hours. Then, this mixture and the precursor pellets of P2 were fed at the main gate of the Coperion ZSK 26 extruder via two separate feeders. The overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, the remaining zones are set at 300 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[00103] Composition of example 11 was obtained, as detailed in Table 1 below.
[00104] Preparation of PPS in pellet form Comparative Example C1
[00105] An amounts of powdery PPS was put in a roller mixer for 24 hours. Then, it was extruded in a Coperion ZSK 26 extruder at 12 kg/h with first zone set a 150 °C and all the others zones set at 300 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[00106] The composition of Comparative Example C1 is reported in Table 1 below.
[00107] Preparation of PPS/FKM composition Examples 8, 9, and 10
[00108] FKM4 powder and the other additives were mixed in roller mill at room temperature for 24 hours. Then, the obtained powder mixture was fed into a Coperion ZSK 26 via side feeder in zone 5, while the precursor pellets from P2 were fed at the main gate. The overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, zones 2 to 4 at 320 °C, zones 5 and 6 at 290 °C, the remaining zones were at 280 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[00109] Compositions of examples 8, 9 and 10 were obtained, as detailed in Table 1 below.
[00110] Preparation of PPS/FKM composition Examples 12, 13, 14 and C9
[00111] FKM4 powder and the other additives are mixed in roller mill at room temperature for 24 hours to obtain the fluoroelastomer mixture. A powdery premixture containing PPS and Ca(OH)2 or AMS was obtained by mixing the components together in a roller mixer for 24 hours. Then, the PPS powdery premixture was fed into the Coperion ZSK 26 extruder at the main gate while the fluoroelastomer mixture was fed via the side feeder in zone 5. The overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, zones 2 to 4 at 320 °C, zones 5 and 6 at 290 °C, the remaining zones are at 280 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[00112] Compositions of Examples 12, 13, 14 and C9 were obtained, as detailed in Table 1 below.
[00113] Preparation of PPS/FKM composition Example 15
[00114] FKM4 or FKM5 were mixed in an open mill at room temperature with the other additives, then formed into a 3 mm thick sheet by calendaring and finally granulated to prepare roughly 3 x 3 x 3 mm3 dices. A powdery premixture containing PPS and aminosilane was obtained by mixing the components together in a roller mixer for 24 hours. Then, the PPS powdery premixture was fed into the Coperion ZSK 26 extruder at the main gate while the fluoroelastomer mixture was fed via the side feeder in zone 5. The overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, zones 2 to 4 at 300 °C, zones 5 and 6 at 290 °C, the remaining zones are at 280 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[00115] Compositions of example 15 was obtained, as detailed in Table 1 below.
[00116] Preparation of PPS/FKM composition Comparative Examples C3-C8 and C10-C13 (Step Aa + Step Bb)
[00117] FKM1 , FKM2 or FKM4 and the other additives are mixed in roller mill at room temperature for 24 hours to obtain the fluoroelastomer mixture. A powdery mixture containing PPS and Ca(OH)2 or Glymo was obtained by mixing the components together in a roller mixer for 24 hours. Then, both the PPS based powdery premixture and the fluoroelastomer mixtures were fed into the Coperion ZSK 26 extruder at the main gate using two separate feeders. The overall throughput was kept at 8 kg/h and the composition was determined by the partial throughput of the two feeders; the temperature profile was formed by a first zone set a 150 °C, and the remaining zones were set at 300 °C. The extruded strand was cooled in a water bath and pelletized, then the pellets were dried in an oven at 135 °C overnight.
[00118] Compositions of comparative examples C3-C8 and C10-C13 were obtained, as detailed in Table 1 below.
Table 1
[00119] Measurement of melt viscosity
[00120] Melt viscosities of the compositions prepared in the above examples, obtained using a Gottfert capillary rheometer at 316 °C following ASTM D3835 (the capillary bore has a diameter of 1 mm and a length of 20 mm), are shown in Table 2.
[00121] Measurement of melt flow index (MFI)
[00122] Melt flow index of the compositions prepared in the above examples, measured according to the procedure ASTM D1230 5 kg at 316 °C, are shown in Table 2.
Table 2
[00123] The polymer composition according to the present invention shows a markedly improved melt viscosity at low shear rate in comparison with compositions comprising no or little amounts of viscosity enhancing additive (see C9). The viscosity at low shear rate above a certain value is required to allow the molten material to keep the shape of the tube before reaching the solidification point; in addition, high viscosity at low shear rates allows the molten material to be stretched or biaxially deformed without losing continuity (breaking, piercing).
[00124] This result demonstrates that, thanks to the presence of at least one certain viscosity enhancing additive, the composition according to the present invention has sufficient melt strength to undergo a strong uniaxial or biaxial deformation process.
[00125] Moreover, the results demonstrate that with the same amount and nature of additives present, the process that includes the addition of the fluoropolymer to the PPS mixture with viscosity enhancing additives which has already been melted, further improves the viscosity values at low shear rate.
[00126] General procedure for Tube extrusion
[00127] Starting from compositions of examples 3 and C8, tubes were extruded in a PD45 extruder using a die and a tip having a diameter of 20 mm and 14.6 mm, respectively. The screw speed and the line speed were set at 20 rpm and 1.5 m/min, respectively. The barrel and the die head temperature was set at 290 °C. The external diameter of the tube was set using a calibrator of 15.1 mm positioned at 95 mm from the die. Then, after a water gap of 30 mm, the tube was cooled in a water bath.
[00128] Tubes of Example 16 and Comparative Example 14 were obtained.
[00129] The tube of Example 16 was then aged in air at 150 °C for 3 hours to give the tube of Example 16bis.
[00130] The results are shown in table 3 below.
[00131] General procedure for Tube extrusion and “blow molding”
[00132] Starting from compositions of examples 3, 9 and C8, tubes were extruded in a 19 mm Brabender single screw extruder using a die and a tip having a diameter of 10 mm and 8 mm, respectively. The die is provided with an inlet for air flow in the bore of the tube. The screw speed and the line speed were set at 150 rpm and 1.8 m/min, respectively. The barrel and the die head temperature was set at 300 °C. Then, after a water gap of 80 mm, the tube was cooled in a water bath. “Blow molding” experiments were performed by inflating air in the bore of the tube which is getting out the die while closing the tube diameter at about 30 cm from the die before the tube itself is cooled by the water.
[00133] Tubes of Examples 17, 18 and Comparative Example 15 were obtained.
[00134] The results are shown in table 3 below.
Table 3
[00135] Tensile measurement of compression molded specimen made of composition (C)
[00136] Tensile measurements were carried out according to ASTM D638 specimen type V on specimens obtained from a 0.6 mm thick film prepared by compression molding compositions of examples 5, 6, 7 or C6. Molding cycle was composed of a heating step of 5 minutes at 310 °C without pressure, followed by a compression step of 2 minutes at 310 °C and 16 tons, followed by a solidification step at 135 °C x 2 minutes.
[00137] The results are shown in Table 4.
Table 4
[00138] Tensile measurement of tubes of examples 16 and 16bis
[00139] Tensile measurements were carried out according to ASTM D638 specimen type V on tubes obtained in examples 16 and 16bis. The tensile specimens were die-cut directly from the tube.
[00140] The results are shown in Table 5.
Table 5
[00141] The polymer composition according to the present invention allows obtaining tubes by extrusion process with improved tensile properties in comparison with compositions having a higher melt viscosity at low share rate and higher melt flow index.
Claims
Claim 1. A polymer composition (C) comprising:
- (a) from 1 to 98% by weight of at least one aromatic polymer (A),
- (b) from 1 to 50% by weight of at least one fluoropolymer (F),
- (c) from 0.4 to 10% by weight of at least one viscosity enhancing additive (A), all the aforementioned percentages by weight being referred to the total weight of polymer composition (C), wherein said polymer composition (C) has a melt flow index (MFI) lower than 30 g/10 min, the melt flow index (MFI) being measured according to ASTM D 1238 standard method by applying a weight of 5 Kg at 316°C.
Claim 2. The composition (C) according to claim 1 wherein the aromatic polymer (A) is a poly(arylene sulfide (PAS), preferably polyphenylene sulfide (PPS), or an aromatic sulfone polymer (SP), preferably polysulfone (PSU) or polyphenylsulfone (PPSLI).
Claim 3. The composition (C) according to any of claims 1 or 2 wherein the fluoropolymer (F) is partially fluorinated fluoropolymer comprising recurring units derived from vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE) or tetrafluoroethylene (TFE), and, optionally, recurring units derived from at least one fluorinated monomer different from VDF, CTFE or TFE or recurring units derived from a hydrogenated monomer.
Claim 4. The composition (C) according to anyone of the preceding claims wherein the viscosity enhancing additive (A) is selected from the group consisting of multivalent cation hydroxyde, a multifactional organo silane or a multifunctional epoxy compound of both monomeric or polymeric nature
Claim 5. The composition (C) according to anyone of the preceding claims that further comprises:
- (d) at least one additional additive (AD) selected from the group consisting of MgO, diamino-derivatives, bisphenol AF and onium salts.
30
Claim 6. The composition (C) according to anyone of the preceding claims that comprises:
- (a) from 1 to 98% by weight of at least one aromatic polymer (A);
- (b) from 1 to 50% by weight of at least one fluoropolymer (F);
- (c) from 0.4 to 10% by weight of at least one viscosity enhancing additive (A); and
- (d) optionally, from 0.05 to 5% by weight of at least one additional additive (AD) all the aforementioned percentages by weight being referred to the total weight of polymer composition (C).
Claim 7. The composition (C) according to claims 3 wherein the fluoropolymer (F) is a (per)fluoroelastomer [elastomer (E)].
Claim 8. The composition (C) according to claim 7 wherein the (per)fluoroelastomer [elastomer (E)] is selected among:
(1) VDF-based copolymers, in which VDF is copolymerized with at least one comonomer selected from the group consisting of the followings classes, with the provision that such comonomer is different from VDF:
(a1) C2-C8 perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene;
(b1) hydrogen-containing C2-C8 olefins, such as C2-C8 non-fluorinated olefins (Ol); C2-C8 partially fluorinated olefins, vinyl fluoride (VF), trifluoroethylene (TrFE), perfluoroalkyl ethylenes of formula CH2 = CH-Rf, wherein Rf is a Ci-Ce perfluoroalkyl group;
(c1) C2-C8 chloro and/or bromo and/or iodo-fluoroolefins such as chlorotrifluoroethylene (CTFE);
(d1) (per)fluoroalkylvinylethers of formula CF2 = CFORf, wherein Rf is a Ci-Ce (per)fluoroalkyl group; preferably perfluoroalkylvinylethers (PAVE) of above formula wherein Rf is Ci-Ce perfluoroalkyl group, e.g. CF3, C2F5, C3F7;
(e1) (per)fluoro-oxy-alkylvinylethers of formula CF2 = CFOX, wherein X is a C1- C12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms, e.g. the perfluoro-2-propoxypropyl group;
(f1) (per)fluorodioxoles having formula :
wherein Rf3, Rf4, Rf5, Rf6, equal or different from each other, are independently selected among fluorine atoms and Ci-C6 (per)fluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, - C3F7, -OCF3, -OCF2CF2OCF3; preferably, perfluorodioxoles;
(g1) (per)fluoro-methoxy-vinylethers (MOVE, hereinafter) having formula:
CFX2 = CX2OCF2OR"f wherein R"f is selected among Ci-Ce (per)fluoroalkyls, linear or branched; C5- Ce cyclic (per)fluoroalkyls; and C2-C6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary oxygen atoms, and X2 = F, H; preferably X2 is F and R"f is -CF2CF3 (MOVE1); -CF2CF2OCF3 (MOVE2); or -CF3 (MOVE3);
(hi) C2-C8 non-fluorinated olefins (Ol), for example ethylene and propylene; and
(2) TFE-based copolymers, in which TFE is copolymerized with at least one comonomer selected from the group consisting of the classes (a1), (c1), (d1), (e1), (g1), (hi), and class (i2) below, with the provision that such comonomer is different from TFE:
(i2) perfluorovinyl ethers containing cyanide groups, such as notably those described in patents US 4 281 092, US 5 447 993 and US 5 789 489.
Claim 9. A process for preparing composition (C) according to anyone of claims 1 to 8, said process comprising the following steps:
- step A: melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM);
- step B: melt compounding the mixture (AM) obtained in step A with at least one fluoropolymer (F).
Claim 10. The process according to claim 9, wherein in step A the aromatic polymer mixture (AM) is provided in melted form.
Claim 11. The process according to claim 9, wherein in step A the aromatic polymer mixture (AM) is provided in pellet or granular form.
Claim 12. The process according to claim 9, wherein step B is carried out at a temperature where all the components are in the molten form.
Claim 13. The process according to claim 9, wherein in step B the melt compounding is carried out by adding the fluoropolymer (F) to the aromatic polymer mixture (AM) which is already in the molten form.
Claim 14. The process according to claim 9, comprising the following steps:
- step A: melt mixing at least one sulphur-containing aromatic polymer [aromatic polymer (A)] with at least one a viscosity enhancing additive (A) to provide an aromatic polymer mixture (AM);
- step B1 : melt compounding the mixture (AM) obtained in step A with a (per)fluoroelastomer mixture (EM) comprising at least one (per)fluoroelastomer (E) and at least one additive (AD).
Claim 15. An article comprising the polymer composition (C) according to any of claims 1 to 8.
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| US202063124975P | 2020-12-14 | 2020-12-14 | |
| US63/124,975 | 2020-12-14 | ||
| EP21159309.0 | 2021-02-25 | ||
| EP21159309 | 2021-02-25 |
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| WO2022128307A1 true WO2022128307A1 (en) | 2022-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
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