WO2013079383A1 - Polymer composition - Google Patents
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- WO2013079383A1 WO2013079383A1 PCT/EP2012/073286 EP2012073286W WO2013079383A1 WO 2013079383 A1 WO2013079383 A1 WO 2013079383A1 EP 2012073286 W EP2012073286 W EP 2012073286W WO 2013079383 A1 WO2013079383 A1 WO 2013079383A1
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- recurring units
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- SSCDIEGELDTHCQ-UHFFFAOYSA-N CC(c(cc1C(N2c3ccc(Cc(cc4)ccc4NC)cc3)=O)ccc1C2=O)=O Chemical compound CC(c(cc1C(N2c3ccc(Cc(cc4)ccc4NC)cc3)=O)ccc1C2=O)=O SSCDIEGELDTHCQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Definitions
- the invention pertains to a polymer composition having improved flammability properties, to a process for its manufacture and to its use for the manufacture of shaped articles.
- High performance plastics in particular polyetherketone polymers, thanks to their attractive properties, are currently used for the manufacture of several parts and articles intended to deliver outstanding mechanical properties, as replacement for materials like metals, alloys and the like.
- Polyether ether ketone (PEEK) polymer for instance, is well known as an ultra-performance polymer. It is a semi-crystalline, highly chemically resistant, fatigue resistant and dimensionally stable material at high temperatures; these unique properties place it in the ultra-performance class of polymers. While generally considered as an inherently flame retardant materials, flammability performances of high performance plastics might still not be adequate in certain high end fields of use, wherein they are called to compete with non-carbonaceous materials and wherein flammability rating should be extremely highly, including compliance with UL (Underwrite Laboratories) 94 V-0 flame ratings.
- UL Underwrite Laboratories
- Flame retardants including brominated compounds, chlorinated compounds, organophosphorus compounds, and minerals such as aluminium hydroxide ATH, magnesium hydroxide MDH, hydromagnesite, various hydrates, red phosphorus, and boron compounds have thus already been proposed for filling this gap in flammability performance which might make it difficult for ultra-performance polymers, and especially for PEEK, to compete and be specified as the material of choice for certain field of use.
- a polymer composition comprising: - at least one polycondensation polymer having a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymer (P)]; - at least one fluorinated sulfonate salt [salt (F)] of either of formulae: (X n+ ) 1/n - O 3 S-R* d F -SO 3 - (X n+ ) 1/n and R* m F -SO 3 - (X n+ ) 1/n wherein R* d F is a divalent C 1 -C 14 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; R* m F is a monovalent C 1 -C 14 perfluorocarbon group, possibly comprising
- the salt (F) is selected from the group consisting of perfluoroalkoxysulphonic derivatives [salt (OF)] of either of formulae: (X n+ ) 1/n - O 3 S-(CF 2 ) s -CF 2 CF 2 O-R d f -OCF 2 CF 2 -(CF 2 ) s -SO 3 - (X n+ ) 1/n and R m f -OCF 2 CF 2 -(CF 2 ) s’ -SO 3 - (X n+ ) 1/n wherein R d f is a divalent C 1 -C 12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; s and s’ are independently zero or integers from 1 to 5; R m f is a monovalent C
- salts (OF) as above mentioned can be synthesized and isolated as pure materials with well defined chemical structure: possibility of finely controlling chemical structure of these compounds would enable predict and control with much more accuracy toxicological and environmental behaviour, which both are extremely sensitive to structural parameters.
- the salts (OF) useful in the compositions according to this first embodiment of the invention preferably comply with formula: R alk f -OCF 2 CF 2 -(CF 2 ) s” -SO 3 - (Y m+ ) 1/m wherein R alk f is a C 1 -C 12 per(halo)fluoroalkyl group possibly comprising one or more ethereal oxygen atom, optionally comprising one or more halogen atoms different from fluorine, typically Cl, Y being NH 4 or an alkaline or alkali-earth metal cation, s” is zero or an integer of 1 to 3; and m being the valence of the cation Y.
- R alk f can be a linear or branched per(halo)fluoroalkyl group.
- Non limitative examples of compounds which have been found useful to the purpose of this first embodiment of the invention include notably CF 3 -CF 2 -OCF 2 CF 2 -SO 3 K, CF 3 -CF 2 -OCF 2 CF 2 -SO 3 Na, CF 3 -CF 2 -OCF 2 CF 2 -SO 3 NH 4 , (CF 3 -CF 2 -OCF 2 CF 2 -SO 3 ) 2 Ba, (CF 3 -CF 2 -OCF 2 CF 2 -SO 3 ) 2 Ca, CF 3 -CF 2 -OCF 2 CF 2 CF 2 -SO 3 K, CF 3 -CF 2 -OCF 2 CF 2 CF 2 -SO 3 Na, CF 3 -CF 2 -OCF 2 CF 2 CF 2 -SO 3 NH 4 , (CF 3 -CF 2 -OCF 2 CF 2 CF 2 -SO 3 ) 2 Ba, (CF 3 -CF 2 -OCF 2 CF
- the perfluoroalkoxysulphonic derivatives can be advantageously obtained from corresponding sulphonyl fluoride precursors by appropriate hydrolysis and/or neutralization procedures, as taught notably in BURDON, J., et al, Fluorinated sulphonic acids.
- Part I Perfluoro-methane-, -octane- and -decane-sulphonic acids and their simple derivatives, J. Chem Soc., 1957, 2574 BURDON J. et al Fluorinated sulphonic acids.
- Part I Perfluoro-methane-, -octane- and -decane-sulphonic acids and their simple derivatives J. Chem Soc. 1957 2574
- the salts (AF) useful in the compositions according to this second embodiment of the invention preferably comply with formula: CF 3 (CF 2 ) z -SO 3 - (Y m+ ) 1/m wherein z is an integer of 1 to 5, preferably 2 or 3, even preferably 3, Y being NH 4 or an alkaline or alkali-earth metal cation and m being the valence of the cation Y.
- Non limitative examples of compounds which have been found useful to the purpose of this second embodiment of the invention include notably CF 3 -CF 2 CF 2 CF 2 -SO 3 K, CF 3 -CF 2 CF 2 CF 2 -SO 3 Na, CF 3 -CF 2 CF 2 CF 2 -SO 3 NH 4 , (CF 3 -CF 2 CF 2 CF 2 -SO 3 ) 2 Ba, (CF 3 -CF 2 CF 2 CF 2 -SO 3 ) 2 Ca, CF 3 -CF 2 CF 2 CF 2 CF 2 -SO 3 K, CF 3 -CF 2 CF 2 CF 2 -SO 3 Na, CF 3 -CF 2 CF 2 CF 2 CF 2 -SO 3 NH 4 , (CF 3 -CF 2 CF 2 CF 2 -SO 3 ) 2 Ba, (CF 3 -CF 2 CF 2 CF 2 -SO 3 ) 2 Ca.
- the salt (F) is generally used in the inventive composition in amounts of from 1 to about 3 000 ppm, preferably about 100 ppm to about 2 000 ppm, most preferably about 150 ppm to about 1500 ppm, by weight based on the total weight of the composition.
- High performance plastics suitable for the compositions of the invention are as mentioned above polycondensation polymers that have a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymers (P)]. Typical heat deflection temperatures of certain high performance plastics are listed in Table 1.
- Heat deflection temperatures of polymer (P) can be determined according to ASTM D648, Method A, using a span of 4 inches.
- the polymer is injection moulded into plaques that are 5 inches long, 1/2 inch wide, and 1/8 inch thick.
- the plaques are immersed in a suitable liquid heat-transfer medium, such as oil, during the HDT test.
- a suitable liquid heat-transfer medium such as oil, during the HDT test.
- Dow Corning 710 silicone oil for example, can be used.
- High performance plastics useful herein include, but are not limited to, aromatic polyimides (PI), in particular polyester-imides (PEI) and polyamide-imides (PAI), polyaryletherketones (PAEK), such as polyetheretherketone (PEEK) and polyetherketoneketone (PEKK), liquid crystal polymers (LCP), and aromatic sulfone polymers (SP).
- PI aromatic polyimides
- PEI polyester-imides
- PAI polyamide-imides
- PAEK polyaryletherketones
- PEEK polyetheretherketone
- PEKK polyetherketoneketone
- LCP liquid crystal polymers
- SP aromatic sulfone polymers
- the high performance polymer [polymer (P)] is a polyaryletherketones (PAEK).
- aromatic polyimide (PI) is intended to denote any polymer comprising recurring units, more than 50 % moles of said recurring units comprising at least one aromatic ring and at least one imide group, as such (formula 1A) or in its amic acid form (formula 1B) [recurring units (R PI )] :
- the imide group as such or in its corresponding amic acid form, is advantageously linked to an aromatic ring, as illustrated below : whereas Ar’ denotes a moiety containing at least one aromatic ring.
- the imide group is advantageously present as condensed aromatic system, yielding a five- or six-membered heteroaromatic ring, such as, for instance, with benzene (phthalimide-type structure, formula 3) and naphthalene (naphthalimide-type structure, formula 4).
- VESPEL ® polyimides Commercialized by DuPont as VESPEL ® polyimides or by Mitsui as AURUM ® polyimides are suitable for the purpose of the invention.
- the recurring units (R PI ) of the aromatic polyimide can comprise one or more functional groups other than the imide group, as such and/or in its amic acid form.
- Non limitative examples of polymers complying with this criterion are aromatic polyetherimides (PEI), aromatic polyesterimides and aromatic polyamide-imides (PAI).
- aromatic polyesterimide is intended to denote any polymer more than 50 wt. % of the recurring units comprise at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one ester group [recurring units (R PEI )].
- aromatic polyesterimides are made by reacting at least one acid monomer chosen from trimellitic anhydride and trimellitic anhydride monoacid halides with at least one diol, followed by reaction with at lest one diamine.
- aromatic polyamide-imide PAI
- PAI aromatic polyamide-imide
- R PAI The recurring units
- the aromatic polyamide-imide comprises more than 50 % of recurring units (R PAI ) comprising an imide group in which the imide group is present as such, like in recurring units (R PAI -a), and/or in its amic acid form, like in recurring units (R PAI -b).
- R PAI recurring units
- R PAI -a recurring units
- R PAI -b amic acid form
- Recurring units are preferably chosen from recurring units (l), (m) and ( n), in their amide-imide (a) or amide-amic acid (b) forms: (l) wherein the attachment of the two amide groups to the aromatic ring as shown in (l-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations; (m) wherein the attachment of the two amide groups to the aromatic ring as shown in (m-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations; and (n) wherein the attachment of the two amide groups to the aromatic ring as shown in (n-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations.
- the aromatic polyamide-imide comprises more than 90 wt. % of recurring units (R PAI ). Still more preferably, it contains no recurring unit other than recurring units (R PAI ).
- Polymers commercialized by Solvay Advanced Polymers, L.L.C., as TORLON ® polyamide-imides comply with this criterion.
- the aromatic polyamide-imide can be notably manufactured by a process including the polycondensation reaction between at least one acid monomer chosen from trimellitic anhydride and trimellitic anhydride monoacid halides and at least one comonomer chosen from diamines and diisocyanates.
- trimellitic anhydride monoacid chloride is preferred.
- the comonomer comprises preferably at least one aromatic ring. Besides, it comprises preferably at most two aromatic rings. More preferably, the comonomer is a diamine. Still more preferably, the diamine is chosen from the group consisting of 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, m ⁇ phenylenediamine and mixtures thereof.
- Fully aromatic liquid crystalline polyester generally comprise recurring units derived from polycondensation of - an aromatic acid component [monomer (AA)] comprising one or more than one aromatic dicarboxylic acid or derivative thereof, preferably selected from phthalic acids, naphthalene dicarboxylic acids and pyridine dicarboxylic acids, and corresponding substituted counterparts; and - a dihydroxyl component [monomer (BB)] comprising one or more than one di-hydroxyl aromatic derivative or derivative thereof, preferably selected from biphenol, 4,4’-dihydroxy-1,1-biphenyl, and corresponding substituted counterparts; and/or from polycondensation of one or more than one aromatic hydroxyl-substituted carboxylic acid or derivatives thereof [monomer (AB)], preferably selected from 4-hydroxybenzoic acid, 6-hydroxy-é-naphthoic acids, and corresponding substituted counterparts, being understood that monomers (AB) can be polymerized alone or in combinations with monomers (AA
- Fully aromatic liquid crystalline polyesters can be produced in the melt by three main processes :
- Non limitative examples of commercially available fully aromatic liquid crystalline polyesters are notably VECTRA ® LCP from Hoechst-Celanese, known for possessing T g of 145°C or above and XYDAR ® LCP from Solvay Specialty Polymers USA, L.L.C, generally characterized by HDT values exceeding 200°C, when determined under a 1.8 MPa load according to ASTM D648.
- VECTRA ® LCP is typically synthesized from 4-hydrobenzoic acid and 6-hydroxy-2-naphtoic acid; VECTRA ® LCP is a polymer the recurring units of which are recurring units (lcp-A) and (lcp-B), typically in a ratio (lcp-A)/(lcp-B) of about 25/75 :
- XYDAR ® LCP is typically synthesized from 4-hydroxybenzoic acid, 4,4’ ⁇ dihydroxy-1,1’-biphenyl, and terephthalic acid; the basic structure can be modified by using other monomers such as isophthalic acid or 4-aminobenzoic acid;
- XYDAR ® LCP is generally a polymer the recurring units of which are recurring units (lcp-C), (lcp-D) and (lcp-B), typically in a ratio [(lcp ⁇ C)+(lcp ⁇ D)]/(lcp-B) of about 1/2 :
- the polymer (P) is preferably an aromatic sulfone polymer (SP).
- SP aromatic sulfone polymer
- the expression “aromatic sulfone polymer (SP)” is intended to denote any polymer, at least 50 % moles of the recurring units thereof comprise at least one group of formula (SP) [recurring units (R SP )]: -Ar-SO 2 -Ar’- formula (SP) with Ar and Ar’, equal to or different from each other, being aromatic groups.
- the Applicant has found that by the use of the salt (F) as above detailed in the sulfone polymer (SP), it is not only possible to improve flammability properties, but also simultaneously maintain transparency, which is a particularly valuable property for sulfone polymers (SP).
- fluoropolymers like PTFE, PFA or MFA have been used in the past for improvement of flammability properties in said sulfone polymers (SP): nevertheless, incorporation of said flammability additives makes the polymer composition opaque and the fluoropolymer tends to delaminate during extrusion and cause issues owing to it immiscibility.
- the salt (F) does not cause such issues, while suitably improving flammability.
- polymer (SP) as above preferably more than 60 %, more preferably more than 80 %, still more preferably more than 90 % moles of the recurring units are recurring units (R SP ), as above detailed.
- substantially all recurring units of polymer (SP) are recurring units (R SP ), as above detailed; chain defects, or very minor amounts of other units might be present, being understood that these latter do not substantially modify the properties of polymer (SP).
- Recurring units can be notably selected from the group consisting of those of formulae (S-A) to (S-D) herein below: wherein: - each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - j’ is zero or is an integer from 0 to 4; - T and T’, equal to or different from each other are a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T’ is selected from the group consisting of a bond, -CH 2 -, -C(O)-, -
- the aromatic sulfone polymer (P) has a glass transition temperature of advantageously at least 150°C, preferably at least 160°C, more preferably at least 175°C.
- At least 50 % wt of the recurring units of aromatic sulfone polymer (SP) are recurring units (R SP-1 ), in their imide form (R SP-1 -A) and/or amic acid forms [(R SP-1 -B) and (R SP-1 -C)] : wherein :
- At least 50 % wt of the recurring units of aromatic sulfone polymer (SP) are recurring units (R SP-2 ) and/or recurring units (R SP-3 ) : wherein :
- Recurring units ( R SP-2 ) are preferably chosen from :
- Recurring units ( R SP-3 ) are preferably chosen from : and mixtures thereof.
- Aromatic sulfone polymer (SP) according to the second preferred embodiment of the invention comprises at least 50 % wt, preferably 70 % wt, more preferably 75 % wt of recurring units (R SP-2 ) and/or (R SP-3 ), still more preferably, it contains no recurring unit other than recurring units (R SP-2 ) and/or (R SP-3 ).
- Polyphenylsulfone is notably available as RADEL ® R PPSU from Solvay Specialty Polymers USA, L.L.C.
- Polysulfone is notably available as UDEL ® PSF from Solvay Specialty Polymers USA, L.L.C.
- Polyethersulfone is notably available as RADEL ® A PES from Solvay Specialty Polymers USA, L.L.C.
- aromatic sulfone polymer is chosen among the group consisting of polybiphenyldisulfone, polysulfone, polyphenylsulfone, polyethersulfone, copolymers and mixtures thereof.
- the polymer (P) is preferably a polyaryletherketone (PAEK) polymer.
- PAEK polyaryletherketone
- the term “polyaryletherketone (PAEK)” is intended to denote any polymer, comprising recurring units, more than 50 % moles of said recurring units are recurring units (R PAEK ) comprising a Ar-C(O)-Ar’ group, with Ar and Ar’, equal to or different from each other, being aromatic groups.
- PAEK polymer
- R PAEK recurring units
- substantially all recurring units of polymer are recurring units (R PAEK ), as above detailed; chain defects, or very minor amounts of other units might be present, being understood that these latter do not substantially modify the properties of polymer (PAEK).
- Said recurring units (R PAEK ) are generally selected from the group consisting of formulae (J-A) to (J-O), herein below: wherein: - each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - j’ is zero or is an integer from 0 to 4.
- the respective phenylene moieties may independently have 1,2-, 1,4- or 1,3 -linkages to the other moieties different from R’ in the recurring unit.
- said phenylene moieties have 1,3- or 1,4- linkages, more preferably they have 1,4-linkage.
- PAEK polymer
- j’ is at each occurrence zero, that is to say that the phenylene moieties have no other substituents than those enabling linkage in the main chain of the polymer.
- R PAEK Preferred recurring units
- Polyaryletherketones are generally crystalline aromatic polymers, readily available from a variety of commercial sources.
- the polyaryletherketones (PAEK) have preferably reduced viscosities in the range of from about 0.8 to about 1.8 dl/g as measured in concentrated sulfuric acid at 25° C and at atmospheric pressure.
- Non limitative examples of commercially available polyaryletherketone (PAEK) resins suitable for the invention include the KETASPIRE ® polyetheretherketone commercially available from Solvay Advanced Polymers and VICTREX ® PEEK polyetheretherketone, from Imperial Chemicals, Inc., which are polymers, the recurring units of which are recurring units (J’-A), as above detailed.
- the salt (F) as above detailed is particularly effective in improving flammability properties of polyaryletherketone (PAEK) polymers, as above detailed, and more particularly of polymers (PAEK) comprising recurring units (R PAEK ) of formula (J’-A), as above detailed.
- PAEK polyaryletherketone
- a preferred composition of the invention thus includes a polymer (PAEK), as above detailed, and more preferably a polymer (PAEK) comprising recurring units (R PAEK ) of formula (J’-A), as above detailed and a salt (F), preferably selected from salts (OF) and salts (AF), as above detailed.
- PAEK polymer
- R PAEK recurring units
- F salt
- OF salts
- AF salts
- the polymer composition of the invention can further comprise fillers, lubricating agents, flow modifiers, heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO 2 , carbon black, antioxidants, and the like.
- the composition of the invention can advantageously comprise at least one filler chosen from reinforcing fillers, structural fibers and mixtures thereof.
- Structural fibers may include glass fiber, carbon or graphite fibers, and fibers formed of silicon carbide, alumina, titania, boron and the like, and may include mixtures comprising two or more such fibers.
- Reinforcing fillers which can also be used in the composition of the invention include notably pigments, flake, spherical and fibrous particulate filler reinforcements and nucleating agents such as talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, and the like.
- the reinforcing fillers and structural fibers can be used alone or in any combination.
- Another aspect of the present invention concerns a process for manufacturing the polymer composition as above described, which comprises mixing :
- the process of the invention comprises mixing by dry blending and/or melt compounding polymer (P) and salt (F).
- polymer (P) and salt (F) are mixed by melt compounding.
- polymer (P) and salt (F) are melt compounded in continuous or batch devices. Such devices are well-known to those skilled in the art.
- polymer (P) and salt (F) and, optionally, other ingredients are advantageously fed in powder or granular form in an extruder and the composition is extruded into strands and the strands are chopped into pellets.
- fillers may be added to the composition during the compounding step.
- lubricating agents may be added to the composition during the compounding step.
- flow modifiers heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO 2 , carbon black, antioxidants, flame retardants, smoke-suppressing agents.
- polymer (P) and salt (F) are melt compounded in a twin-screw extruder.
- composition can be further processed following standard methods for injection moulding, extrusion, thermoforming, machining, and blow moulding. Solution-based processing for coatings and membranes is also possible. Finished articles comprising the composition as above described can undergo standard post-fabrication operations such as ultrasonic welding, adhesive bonding, and laser marking as well as heat staking, threading, and machining.
- Another object of the invention is a shaped article comprising the polymer composition as above described.
- the article is an injection moulded article, an extrusion moulded article, a shaped article, a coated article or a casted article.
- the articles according to the invention can be fabricated by processing the composition as above described following standard methods.
- KetaSpire ® PEEK KT-820 NT and KetaSpire ® PEEK KT-880 NT are polyetheretherketone polymers commercially available from Solvay Specialty Polymers USA, LLC.
- UDEL® PSU P-1700 NT is a polysulfone polymer commercially available from Solvay Specialty Polymers USA, LLC.
- the viscosity of a melt was measured as a function of shear rate at several temperatures using an LCR-7000 Capillary Rheometer.
- the viscosity of a melt was measured as a function of shear rate at several temperatures using an LCR-7000 Capillary Rheometer.
Abstract
The invention pertains to a polymer composition having improved flammability properties comprising: - at least one polycondensation polymer having a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymer (P)]; - at least one fluorinated sulfonate salt [salt (F)] of either of formulae: (Xn+)1/n O3S-R*dF-SO3-(Xn+)1/n and R*m
F-SO3-(Xn+)1/n wherein R*d
F is a divalent C1-C14 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular CI; R*mp is a monovalent C1-C 14 perfluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular CI; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
Description
The invention pertains to a polymer composition having improved flammability properties, to a process for its manufacture and to its use for the manufacture of shaped articles.
High performance plastics, in particular polyetherketone polymers, thanks to their attractive properties, are currently used for the manufacture of several parts and articles intended to deliver outstanding mechanical properties, as replacement for materials like metals, alloys and the like.
Polyether ether ketone (PEEK) polymer, for instance, is well known as an ultra-performance polymer. It is a semi-crystalline, highly chemically resistant, fatigue resistant and dimensionally stable material at high temperatures; these unique properties place it in the ultra-performance class of polymers. While generally considered as an inherently flame retardant materials, flammability performances of high performance plastics might still not be adequate in certain high end fields of use, wherein they are called to compete with non-carbonaceous materials and wherein flammability rating should be extremely highly, including compliance with UL (Underwrite Laboratories) 94 V-0 flame ratings. Complying with such rating is particularly challenging when submitting to the test shaped articles of reduced thickness, which are nevertheless representative of actual spare parts which might be used in aerospace applications or other highly demanding fields of use, wherein a variety of parts (especially electrical parts) with thin wall geometries are required.
Flame retardants including brominated compounds, chlorinated compounds, organophosphorus compounds, and minerals such as aluminium hydroxide ATH, magnesium hydroxide MDH, hydromagnesite, various hydrates, red phosphorus, and boron compounds have thus already been proposed for filling this gap in flammability performance which might make it difficult for ultra-performance polymers, and especially for PEEK, to compete and be specified as the material of choice for certain field of use.
Nevertheless, high processing temperatures of the plastics require additives to possess outstanding stability; moreover, their addition should not impair all other relevant properties of the high performance plastics hosting the same.
There is thus a continuous shortfall in the art for additives which could improve flammability behaviour of ultra-performance polymers, and in particular PEEK, which are able to withstand processing temperatures without undergoing degradation phenomena, and which can effectively improve said flammability behaviour, without negatively affecting their mechanical performances.
It is thus an object of the present invention a polymer composition comprising:
- at least one polycondensation polymer having a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymer (P)];
- at least one fluorinated sulfonate salt [salt (F)] of either of formulae:
(Xn+)1/n -O3S-R*d F-SO3 -(Xn+)1/n and
R*m F-SO3 -(Xn+)1/n
wherein R*d F is a divalent C1-C14 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; R*m F is a monovalent C1-C14 perfluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
- at least one polycondensation polymer having a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymer (P)];
- at least one fluorinated sulfonate salt [salt (F)] of either of formulae:
(Xn+)1/n -O3S-R*d F-SO3 -(Xn+)1/n and
R*m F-SO3 -(Xn+)1/n
wherein R*d F is a divalent C1-C14 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; R*m F is a monovalent C1-C14 perfluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
The Applicant has found that the incorporation of the salt (F) as above detailed in said high performance plastics successfully enables achievement of improved flammability behaviour, significantly enhancing rating under UL 94 standard and enabling achieving V-0 rating also for thinner articles, without affecting mechanical properties of polymer (P) hosts nor undergoing decomposition/degradation phenomena at processing conditions of said polymer (P).
According to a first embodiment of the invention, the salt (F) is selected from the group consisting of perfluoroalkoxysulphonic derivatives [salt (OF)] of either of formulae:
(Xn+)1/n -O3S-(CF2)s-CF2CF2O-Rd f-OCF2CF2-(CF2)s-SO3 -(Xn+)1/n and
Rm f-OCF2CF2-(CF2)s’-SO3 -(Xn+)1/n
wherein Rd f is a divalent C1-C12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; s and s’ are independently zero or integers from 1 to 5; Rm f is a monovalent C1-C12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
(Xn+)1/n -O3S-(CF2)s-CF2CF2O-Rd f-OCF2CF2-(CF2)s-SO3 -(Xn+)1/n and
Rm f-OCF2CF2-(CF2)s’-SO3 -(Xn+)1/n
wherein Rd f is a divalent C1-C12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; s and s’ are independently zero or integers from 1 to 5; Rm f is a monovalent C1-C12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
Methods for manufacturing salts (OF) as above detailed are known, and include the reaction of beta-sultone of tetrafluoroethylene with fluorine in the presence of a catalyst to yield corresponding hypofluorite and reaction thereof with haloolefins, notably as described in US 4962282 AUSIMONT SRL 19901009 , possibly followed by dehalogenation and fluorination, if required for providing perfluoroderivatives, and subsequent hydrolysis/salification ; the reaction of a fluoroacyl sulfonyl derivative with fluorine and olefin in liquid phase, notably as described in US 7157600 SOLVAY SOLEXIS SPA 20041007 , possibly followed by dehalogenation and fluorination, if required for providing perfluoroderivatives, and subsequent hydrolysis/salification; the reaction of perfluorovinylsulphonyl fluoride with hypofluorites or bis-hypofluorites, notably as described in US 5374770 AUSIMONT SPA 19941220 , and subsequent hydrolysis/salification; by fluorination of perfluorinated vinylethers having fluorosulphonyl group, notably such as those described in WO WO 2004/060857 3M INNOVATIVE PROPERTIES CO 20040722 and US 2006111584 ASAHI GLASS CO LTD 20060525 , and subsequent hydrolysis/salification.
The Applicant has found that salts (OF) as above mentioned, which are endowed with more favourable environmental profile thanks to the presence of their oxygen atoms in the molecule chain are effective in providing polymer compositions possessing improved flammability behaviour, with no impact on mechanical properties nor general appearance of articles made therefrom.
Further, in addition, the salts (OF) as above mentioned can be synthesized and isolated as pure materials with well defined chemical structure: possibility of finely controlling chemical structure of these compounds would enable predict and control with much more accuracy toxicological and environmental behaviour, which both are extremely sensitive to structural parameters.
The salts (OF) useful in the compositions according to this first embodiment of the invention preferably comply with formula:
Ralk f-OCF2CF2-(CF2)s”-SO3 -(Ym+)1/m
wherein Ralk f is a C1-C12 per(halo)fluoroalkyl group possibly comprising one or more ethereal oxygen atom, optionally comprising one or more halogen atoms different from fluorine, typically Cl, Y being NH4 or an alkaline or alkali-earth metal cation, s” is zero or an integer of 1 to 3; and m being the valence of the cation Y.
Ralk f-OCF2CF2-(CF2)s”-SO3 -(Ym+)1/m
wherein Ralk f is a C1-C12 per(halo)fluoroalkyl group possibly comprising one or more ethereal oxygen atom, optionally comprising one or more halogen atoms different from fluorine, typically Cl, Y being NH4 or an alkaline or alkali-earth metal cation, s” is zero or an integer of 1 to 3; and m being the valence of the cation Y.
It is further understood that Ralk
f can be a linear or branched per(halo)fluoroalkyl group.
Among classes of compounds which have been found particularly useful as salts (OF) in the composition of this first embodiment of the invention mention can be notably made of following compounds:
(i) CF3-(CF2)w-OCF2CF2-SO3 -(Zp+)1/p
wherein w is an integer from 1 to 3, preferably w = 1, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(ii) CF2Cl-CFCl-(CF2)z-OCF2CF2-SO3 -(Zp+)1/p
wherein z is an integer from 0 to 3, preferably z = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(iii) CF2Cl-CF2-(CF2)z”-OCF2CF2-SO3 -(Zp+)1/p
wherein z” is an integer from 0 to 3, preferably z” = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(iv) CF3-CFCl-(CF2)z”-OCF2CF2-SO3 -(Zp+)1/p
wherein z”’ is an integer from 0 to 3, preferably z’” = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(v) CF3-(CF2)w’OCF2CF2-OCF2CF2-SO3 -(Zp+)1/p
wherein w’ is an integer from 0 to 2, preferably w’ = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(vi) CF2Cl-CFCl-(CF2)z’OCF2CF2-OCF2CF2-SO3 -(Zp+)1/p
wherein z’ is an integer from 0 to 2, preferably z’ = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(vii) CF3-(CF2)q-(OCF2CFXF)r-OCF2CF2-SO3 -(Zp+)1/p
wherein q and r being integers from 1 to 3, preferably q = 1 and r = 1, XF is F or CF3 and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z; and
(viii) CF3-CF2-OCF2CF2-(CF2)t’-SO3 -(Zp+)1/p
wherein t’ is an integer from 1 to 3, preferably t’ is 1 or 2, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z.
(i) CF3-(CF2)w-OCF2CF2-SO3 -(Zp+)1/p
wherein w is an integer from 1 to 3, preferably w = 1, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(ii) CF2Cl-CFCl-(CF2)z-OCF2CF2-SO3 -(Zp+)1/p
wherein z is an integer from 0 to 3, preferably z = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(iii) CF2Cl-CF2-(CF2)z”-OCF2CF2-SO3 -(Zp+)1/p
wherein z” is an integer from 0 to 3, preferably z” = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(iv) CF3-CFCl-(CF2)z”-OCF2CF2-SO3 -(Zp+)1/p
wherein z”’ is an integer from 0 to 3, preferably z’” = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(v) CF3-(CF2)w’OCF2CF2-OCF2CF2-SO3 -(Zp+)1/p
wherein w’ is an integer from 0 to 2, preferably w’ = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(vi) CF2Cl-CFCl-(CF2)z’OCF2CF2-OCF2CF2-SO3 -(Zp+)1/p
wherein z’ is an integer from 0 to 2, preferably z’ = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;
(vii) CF3-(CF2)q-(OCF2CFXF)r-OCF2CF2-SO3 -(Zp+)1/p
wherein q and r being integers from 1 to 3, preferably q = 1 and r = 1, XF is F or CF3 and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z; and
(viii) CF3-CF2-OCF2CF2-(CF2)t’-SO3 -(Zp+)1/p
wherein t’ is an integer from 1 to 3, preferably t’ is 1 or 2, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z.
Non limitative examples of compounds which have been found useful to the purpose of this first embodiment of the invention include notably CF3-CF2-OCF2CF2-SO3K, CF3-CF2-OCF2CF2-SO3Na, CF3-CF2-OCF2CF2-SO3NH4, (CF3-CF2-OCF2CF2-SO3)2Ba, (CF3-CF2-OCF2CF2-SO3)2Ca, CF3-CF2-OCF2CF2CF2-SO3K, CF3-CF2-OCF2CF2CF2-SO3Na, CF3-CF2-OCF2CF2CF2-SO3NH4, (CF3-CF2-OCF2CF2CF2-SO3)2Ba, (CF3-CF2-OCF2CF2CF2-SO3)2Ca, CF3-CF2-OCF2CF2CF2CF2-SO3K, CF3-CF2-OCF2CF2CF2CF2-SO3Na, CF3-CF2-OCF2CF2CF2CF2-SO3NH4, (CF3-CF2-OCF2CF2CF2CF2-SO3)2Ba, (CF3-CF2-OCF2CF2CF2CF2-SO3)2Ca, CClF2-CFCl-OCF2CF2-SO3K, CClF2-CFCl-OCF2CF2-SO3Na, CClF2-CFCl-OCF2CF2-SO3NH4, (CClF2-CFCl-OCF2CF2-SO3)2Ba, (CClF2-CFCl-OCF2CF2-SO3)2Ca, CF3-CFCl-OCF2CF2-SO3K, CF3-CFCl-OCF2CF2-SO3Na, CF3-CFCl-OCF2CF2-SO3NH4, (CF3-CFCl-OCF2CF2-SO3)2Ba, (CF3-CFCl-OCF2CF2-SO3)2Ca, CF2Cl-CF2-OCF2CF2-SO3K, CF2Cl-CF2-OCF2CF2-SO3Na, CF2Cl-CF2-OCF2CF2-SO3NH4, (CF2Cl-CF2-OCF2CF2-SO3)2Ba, (CF2Cl-CF2-OCF2CF2-SO3)2Ca, CF3-OCF2CF2-OCF2CF2-SO3K, CF3-OCF2CF2-OCF2CF2-SO3Na, CF3-OCF2CF2-OCF2CF2-SO3NH4, (CF3-OCF2CF2-OCF2CF2-SO3)2Ba, (CF3-OCF2CF2-OCF2CF2-SO3)2Ca, CF3CF2-OCF2CF(CF3)-OCF2CF2-SO3K, CF3CF2-OCF2CF(CF3)-OCF2CF2-SO3Na, CF3CF2-OCF2CF(CF3)-OCF2CF2-SO3NH4, (CF3CF2-OCF2CF(CF3)-OCF2CF2-SO3)2Ba and (CF3CF2-OCF2CF(CF3)-OCF2CF2-SO3)2Ca.
The perfluoroalkoxysulphonic derivatives can be advantageously obtained from corresponding sulphonyl fluoride precursors by appropriate hydrolysis and/or neutralization procedures, as taught notably in BURDON, J., et al, Fluorinated sulphonic acids. Part I. Perfluoro-methane-, -octane- and -decane-sulphonic acids and their simple derivatives, J. Chem Soc., 1957, 2574
According to a second embodiment of the invention, the salt (F) is selected from the group consisting of perfluoroalkylsulphonic derivatives [salt (AF)] of either of formulae:
(Xn+)1/n -O3S-Rd af-SO3 -(Xn+)1/n and
Rm af-SO3 -(Xn+)1/n
wherein Rd af is a divalent C1-C6 perfluoroalkyl group; Rm af is a monovalent C1-C6 perfluoroalkyl group; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
(Xn+)1/n -O3S-Rd af-SO3 -(Xn+)1/n and
Rm af-SO3 -(Xn+)1/n
wherein Rd af is a divalent C1-C6 perfluoroalkyl group; Rm af is a monovalent C1-C6 perfluoroalkyl group; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
The Applicant has found that such short chain perfluoroalkylsulphonic derivatives [salt (AF)] are endowed with good performances in improving the flammability performances of polymer (P), and possess appropriate stability in polymer (P) processing conditions, and widely recognized acceptable toxicological behaviour.
The salts (AF) useful in the compositions according to this second embodiment of the invention preferably comply with formula:
CF3(CF2)z-SO3 -(Ym+)1/m
wherein z is an integer of 1 to 5, preferably 2 or 3, even preferably 3, Y being NH4 or an alkaline or alkali-earth metal cation and m being the valence of the cation Y.
CF3(CF2)z-SO3 -(Ym+)1/m
wherein z is an integer of 1 to 5, preferably 2 or 3, even preferably 3, Y being NH4 or an alkaline or alkali-earth metal cation and m being the valence of the cation Y.
Non limitative examples of compounds which have been found useful to the purpose of this second embodiment of the invention include notably CF3-CF2CF2CF2-SO3K, CF3-CF2CF2CF2-SO3Na, CF3-CF2CF2CF2-SO3NH4, (CF3-CF2CF2CF2-SO3)2Ba, (CF3-CF2CF2CF2-SO3)2Ca, CF3-CF2CF2CF2CF2-SO3K, CF3-CF2CF2CF2CF2-SO3Na, CF3-CF2CF2CF2CF2-SO3NH4, (CF3-CF2CF2CF2CF2-SO3)2Ba, (CF3-CF2CF2CF2CF2-SO3)2Ca.
The salt (F) is generally used in the inventive composition in amounts of from 1 to about 3 000 ppm, preferably about 100 ppm to about 2 000 ppm, most preferably about 150 ppm to about 1500 ppm, by weight based on the total weight of the composition.
High performance plastics suitable for the compositions of the invention are as mentioned above polycondensation polymers that have a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymers (P)]. Typical heat deflection temperatures of certain high performance plastics are listed in Table 1. Table 1
| Polycondensation Polymer | Heat Deflection Temperature (°C) |
| Polysulfone (PSU) | 174 |
| Polyethersulfone (PES) | 203 |
| Polyphenylsulfone | 204 |
| Polyphthalamide | 120 |
| Polyamideimide | 278 |
| Liquid crystalline polymers (LCP) | 180 – 310 |
| Polyimide | 360 |
| Polyetherimide | 200 |
| Polyetheretherketone (low flow) | 160 |
| Polyetheretherketone (high flow) | 171 |
| Polyphenylene sulfide | 135 |
| Polycarbonate | 132 |
Heat deflection temperatures of polymer (P) can be determined according to ASTM D648, Method A, using a span of 4 inches. The polymer is injection moulded into plaques that are 5 inches long, 1/2 inch wide, and 1/8 inch thick. The plaques are immersed in a suitable liquid heat-transfer medium, such as oil, during the HDT test. Dow Corning 710 silicone oil, for example, can be used.
High performance plastics useful herein include, but are not limited to, aromatic polyimides (PI), in particular polyester-imides (PEI) and polyamide-imides (PAI), polyaryletherketones (PAEK), such as polyetheretherketone (PEEK) and polyetherketoneketone (PEKK), liquid crystal polymers (LCP), and aromatic sulfone polymers (SP). Preferably, the high performance polymer [polymer (P)] is a polyaryletherketones (PAEK).
To the purpose of the present invention, “aromatic polyimide (PI)” is intended to denote any polymer comprising recurring units, more than 50 % moles of said recurring units comprising at least one aromatic ring and at least one imide group, as such (formula 1A) or in its amic acid form (formula 1B) [recurring units (RPI)] : 
The imide group, as such or in its corresponding amic acid form, is advantageously linked to an aromatic ring, as illustrated below : 
whereas Ar’ denotes a moiety containing at least one aromatic ring.
The imide group is advantageously present as condensed aromatic system, yielding a five- or six-membered heteroaromatic ring, such as, for instance, with benzene (phthalimide-type structure, formula 3) and naphthalene (naphthalimide-type structure, formula 4). 
The formulae here below depict examples of recurring units (RPI) (formulae 5A to 5C) :
wherein :
- Ar represents an aromatic tetravalent group; typically Ar is selected from the group consisting of following structures: and corresponding optionally substituted structures, with X being –O-, -C(O)-, -CH2-, -C(CF3)2-, -(CF2)n-, with n being an integer from 1 to 5;
- R represents an aromatic divalent group; typically R is selected from the group consisting of following structures: and corresponding optionally substituted structures, with Y being –O-, -S-, -SO2-, -CH2-, -C(O)-, -C(CF3)2-, -(CF2)n, n being an integer from 0 to 5.
Polyimides commercialized by DuPont as VESPEL® polyimides or by Mitsui as AURUM® polyimides are suitable for the purpose of the invention.
The recurring units (RPI) of the aromatic polyimide can comprise one or more functional groups other than the imide group, as such and/or in its amic acid form. Non limitative examples of polymers complying with this criterion are aromatic polyetherimides (PEI), aromatic polyesterimides and aromatic polyamide-imides (PAI).
To the purpose of the present invention, “aromatic polyesterimide” is intended to denote any polymer more than 50 wt. % of the recurring units comprise at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one ester group [recurring units (RPEI)]. Typically, aromatic polyesterimides are made by reacting at least one acid monomer chosen from trimellitic anhydride and trimellitic anhydride monoacid halides with at least one diol, followed by reaction with at lest one diamine.
To the purpose of the present invention, “aromatic polyamide-imide (PAI)” is intended to denote any polymer comprising recurring units, more than 50 % moles of said recurring units comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one amide group which is not included in the amic acid form of an imide group [recurring units (RPAI)].
The recurring units (RPAI) are advantageously chosen among : 
wherein :
- Ar is a trivalent aromatic group; typically Ar is selected from the group consisting of following structures: and corresponding optionally substituted structures, with X being –O-, -C(O)-, -CH2-, -C(CF3)2-, -(CF2)n-, with n being an integer from 1 to 5;
- R is a divalent aromatic group; typically R is selected from the group consisting of following structures: and corresponding optionally substituted structures, with Y being –O-, -S-, -SO2-, -CH2-, -C(O)-, -C(CF3)2-, -(CF2)n, n being an integer from 0 to 5.
Preferably, the aromatic polyamide-imide comprises more than 50 % of recurring units (RPAI) comprising an imide group in which the imide group is present as such, like in recurring units (RPAI-a), and/or in its amic acid form, like in recurring units (RPAI-b).
Recurring units (RPAI) are preferably chosen from recurring units (l), (m) and (n), in their amide-imide (a) or amide-amic acid (b) forms:
(l)
wherein the attachment of the two amide groups to the aromatic ring as shown in (l-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations;
(m)
wherein the attachment of the two amide groups to the aromatic ring as shown in (m-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations; and
(n)
wherein the attachment of the two amide groups to the aromatic ring as shown in (n-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations.
(l)
(m)
(n)
Very preferably, the aromatic polyamide-imide comprises more than 90 wt. % of recurring units (RPAI). Still more preferably, it contains no recurring unit other than recurring units (RPAI). Polymers commercialized by Solvay Advanced Polymers, L.L.C., as TORLON® polyamide-imides comply with this criterion.
The aromatic polyamide-imide can be notably manufactured by a process including the polycondensation reaction between at least one acid monomer chosen from trimellitic anhydride and trimellitic anhydride monoacid halides and at least one comonomer chosen from diamines and diisocyanates.
Among the trimellitic anhydride monoacid halides, trimellitic anhydride monoacid chloride is preferred.
The comonomer comprises preferably at least one aromatic ring. Besides, it comprises preferably at most two aromatic rings. More preferably, the comonomer is a diamine. Still more preferably, the diamine is chosen from the group consisting of 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, m‑phenylenediamine and mixtures thereof.
Fully aromatic liquid crystalline polyester generally comprise recurring units derived from polycondensation of
- an aromatic acid component [monomer (AA)] comprising one or more than one aromatic dicarboxylic acid or derivative thereof, preferably selected from phthalic acids, naphthalene dicarboxylic acids and pyridine dicarboxylic acids, and corresponding substituted counterparts; and
- a dihydroxyl component [monomer (BB)] comprising one or more than one di-hydroxyl aromatic derivative or derivative thereof, preferably selected from biphenol, 4,4’-dihydroxy-1,1-biphenyl, and corresponding substituted counterparts;
and/or from polycondensation of one or more than one aromatic hydroxyl-substituted carboxylic acid or derivatives thereof [monomer (AB)], preferably selected from 4-hydroxybenzoic acid, 6-hydroxy-é-naphthoic acids, and corresponding substituted counterparts,
being understood that monomers (AB) can be polymerized alone or in combinations with monomers (AA) and (BB), as above detailed.
- an aromatic acid component [monomer (AA)] comprising one or more than one aromatic dicarboxylic acid or derivative thereof, preferably selected from phthalic acids, naphthalene dicarboxylic acids and pyridine dicarboxylic acids, and corresponding substituted counterparts; and
- a dihydroxyl component [monomer (BB)] comprising one or more than one di-hydroxyl aromatic derivative or derivative thereof, preferably selected from biphenol, 4,4’-dihydroxy-1,1-biphenyl, and corresponding substituted counterparts;
and/or from polycondensation of one or more than one aromatic hydroxyl-substituted carboxylic acid or derivatives thereof [monomer (AB)], preferably selected from 4-hydroxybenzoic acid, 6-hydroxy-é-naphthoic acids, and corresponding substituted counterparts,
being understood that monomers (AB) can be polymerized alone or in combinations with monomers (AA) and (BB), as above detailed.
Fully aromatic liquid crystalline polyesters can be produced in the melt by three main processes :
- direct esterification of optionally substituted diphenols with aromatic carboxylic acids in the presence of catalysts such as titanium tetrabutyrate or dibutyl tin diacetate at high temperature;
- reaction between phenyl esters of aromatic carboxylic acids with relevant optionally substituted diphenols;
- acidolysis of diphenolic acetates with aromatic carboxylic acids.
Non limitative examples of commercially available fully aromatic liquid crystalline polyesters are notably VECTRA® LCP from Hoechst-Celanese, known for possessing Tg of 145°C or above and XYDAR® LCP from Solvay Specialty Polymers USA, L.L.C, generally characterized by HDT values exceeding 200°C, when determined under a 1.8 MPa load according to ASTM D648.
VECTRA® LCP is typically synthesized from 4-hydrobenzoic acid and 6-hydroxy-2-naphtoic acid; VECTRA® LCP is a polymer the recurring units of which are recurring units (lcp-A) and (lcp-B), typically in a ratio (lcp-A)/(lcp-B) of about 25/75 :
XYDAR® LCP is typically synthesized from 4-hydroxybenzoic acid, 4,4’‑dihydroxy-1,1’-biphenyl, and terephthalic acid; the basic structure can be modified by using other monomers such as isophthalic acid or 4-aminobenzoic acid; XYDAR® LCP is generally a polymer the recurring units of which are recurring units (lcp-C), (lcp-D) and (lcp-B), typically in a ratio [(lcp‑C)+(lcp‑D)]/(lcp-B) of about 1/2 :
According to a first preferred embodiment of the invention, the polymer (P) is preferably an aromatic sulfone polymer (SP). For the purpose of the invention, the expression “aromatic sulfone polymer (SP)” is intended to denote any polymer, at least 50 % moles of the recurring units thereof comprise at least one group of formula (SP) [recurring units (RSP)]:
-Ar-SO2-Ar’- formula (SP)
with Ar and Ar’, equal to or different from each other, being aromatic groups.
-Ar-SO2-Ar’- formula (SP)
with Ar and Ar’, equal to or different from each other, being aromatic groups.
The Applicant has found that by the use of the salt (F) as above detailed in the sulfone polymer (SP), it is not only possible to improve flammability properties, but also simultaneously maintain transparency, which is a particularly valuable property for sulfone polymers (SP). Actually, fluoropolymers like PTFE, PFA or MFA have been used in the past for improvement of flammability properties in said sulfone polymers (SP): nevertheless, incorporation of said flammability additives makes the polymer composition opaque and the fluoropolymer tends to delaminate during extrusion and cause issues owing to it immiscibility. The salt (F) does not cause such issues, while suitably improving flammability.
In the polymer (SP) as above detailed preferably more than 60 %, more preferably more than 80 %, still more preferably more than 90 % moles of the recurring units are recurring units (RSP), as above detailed.
Still, it is generally preferred that substantially all recurring units of polymer (SP) are recurring units (RSP), as above detailed; chain defects, or very minor amounts of other units might be present, being understood that these latter do not substantially modify the properties of polymer (SP).
Said recurring units (RSP) generally comply with formula:
-Ar1-(T’-Ar2)n-O-Ar3-SO2-[Ar4-(T-Ar2)n-SO2]m-Ar5-O-
wherein:
- Ar1, Ar2, Ar3, Ar4, and Ar5, equal to or different from each other and at each occurrence, are independently a aromatic mono- or polynuclear group;
- T and T’, equal to or different from each other and at each occurrence, is independently a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T’ is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -SO2-,
-C(CH3)(CH2CH2COOH)-, and a group of formula:
preferably T is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, and a group of formula:
- n and m, equal to or different from each other, are independently zero or an integer of 1 to 5.
Recurring units (RSP) can be notably selected from the group consisting of those of formulae (S-A) to (S-D) herein below:
wherein:
- each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- j’ is zero or is an integer from 0 to 4;
- T and T’, equal to or different from each other are a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T’ is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, -SO2-, and a group of formula:
preferably T is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, and a group of formula:
.
-Ar1-(T’-Ar2)n-O-Ar3-SO2-[Ar4-(T-Ar2)n-SO2]m-Ar5-O-
wherein:
- Ar1, Ar2, Ar3, Ar4, and Ar5, equal to or different from each other and at each occurrence, are independently a aromatic mono- or polynuclear group;
- T and T’, equal to or different from each other and at each occurrence, is independently a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T’ is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -SO2-,
-C(CH3)(CH2CH2COOH)-, and a group of formula:
- n and m, equal to or different from each other, are independently zero or an integer of 1 to 5.
Recurring units (RSP) can be notably selected from the group consisting of those of formulae (S-A) to (S-D) herein below:
wherein:
- each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- j’ is zero or is an integer from 0 to 4;
- T and T’, equal to or different from each other are a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T’ is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, -SO2-, and a group of formula:
The aromatic sulfone polymer (P) has a glass transition temperature of advantageously at least 150°C, preferably at least 160°C, more preferably at least 175°C.
In a variant of this first preferred embodiment, at least 50 % wt of the recurring units of aromatic sulfone polymer (SP) are recurring units (RSP-1), in their imide form (RSP-1-A) and/or amic acid forms [(RSP-1-B) and (RSP-1-C)] :
wherein :
- the → denotes isomerism so that in any recurring unit the groups to which the arrows point may exist as shown or in an interchanged position;
- Ar” is selected from the group consisting of : and corresponding optionally substituted structures, with Y being –O-, -C(O)-, -(CH2)n-, -C(CF3)2-, -(CF2)n-, with n being an integer from 1 to 5, and mixtures thereof.
In another variant of this first preferred embodiment of the invention, at least 50 % wt of the recurring units of aromatic sulfone polymer (SP) are recurring units (RSP-2) and/or recurring units (RSP-3) :
wherein :
- Q and Ar*, equal or different from each other and at each occurrence, are independently a divalent aromatic group; preferably Ar* and Q equal or different from each other and at each occurrence, are independently selected from the group consisting of the following structures :
and corresponding optionally substituted structures, with Y being –O-, -CH=CH-, -C≡C-, -S-, -C(O)-, -(CH2)n-, -C(CF3)2-, -C(CH3)2-, -SO2-, -(CF2)n-, with n being an integer from 1 to 5 and mixtures thereof; and mixtures thereof.
Recurring units (RSP-2
) are preferably chosen from :
Recurring units (RSP-3
) are preferably chosen from :
and mixtures thereof.
and mixtures thereof.
Aromatic sulfone polymer (SP) according to the second preferred embodiment of the invention comprises at least 50 % wt, preferably 70 % wt, more preferably 75 % wt of recurring units (RSP-2) and/or (RSP-3), still more preferably, it contains no recurring unit other than recurring units (RSP-2) and/or (RSP-3).
Good results were obtained with aromatic sulfone polymer (P) the recurring units of which are recurring units (ii) (polybiphenyldisulfone, herein after), with aromatic sulfone polymer (P) the recurring units of which are recurring units (j) (polyphenylsulfone, hereinafter), with aromatic sulfone polymer (P) the recurring units of which are recurring units (jj) (polyetherethersulfone, hereinafter), with aromatic sulfone polymer (P) the recurring units of which are recurring units (jjj) and, optionally in addition, recurring units (jj) (polyethersulfone, hereinafter), and with aromatic sulfone polymer (P) the recurring units of which are recurring units (jv) (polysulfone, hereinafter).
Polyphenylsulfone is notably available as RADEL® R PPSU from Solvay Specialty Polymers USA, L.L.C. Polysulfone is notably available as UDEL® PSF from Solvay Specialty Polymers USA, L.L.C. Polyethersulfone is notably available as RADEL® A PES from Solvay Specialty Polymers USA, L.L.C.
Preferably, aromatic sulfone polymer (SP) is chosen among the group consisting of polybiphenyldisulfone, polysulfone, polyphenylsulfone, polyethersulfone, copolymers and mixtures thereof.
According to another preferred embodiment of the invention, the polymer (P) is preferably a polyaryletherketone (PAEK) polymer. For the purpose of the invention, the term “polyaryletherketone (PAEK)” is intended to denote any polymer, comprising recurring units, more than 50 % moles of said recurring units are recurring units (RPAEK) comprising a Ar-C(O)-Ar’ group, with Ar and Ar’, equal to or different from each other, being aromatic groups.
In the polymer (PAEK) as above detailed preferably more than 60 %, more preferably more than 80 %, still more preferably more than 90 % moles of the recurring units are recurring units (RPAEK), as above detailed.
Still, it is generally preferred that substantially all recurring units of polymer (PAEK) are recurring units (RPAEK), as above detailed; chain defects, or very minor amounts of other units might be present, being understood that these latter do not substantially modify the properties of polymer (PAEK).
Said recurring units (RPAEK) are generally selected from the group consisting of formulae (J-A) to (J-O), herein below:
wherein:
- each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- j’ is zero or is an integer from 0 to 4.
- each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- j’ is zero or is an integer from 0 to 4.
In recurring unit (RPAEK), the respective phenylene moieties may independently have 1,2-, 1,4- or 1,3 -linkages to the other moieties different from R’ in the recurring unit. Preferably, said phenylene moieties have 1,3- or 1,4- linkages, more preferably they have 1,4-linkage.
Preferably, all recurring units of polymer (PAEK) are
Still, in recurring units (RPAEK), j’ is at each occurrence zero, that is to say that the phenylene moieties have no other substituents than those enabling linkage in the main chain of the polymer.
Preferred recurring units (RPAEK) are thus selected from those of formulae (J'-A) to (J'-O) herein below:
Polyaryletherketones (PAEK) are generally crystalline aromatic polymers, readily available from a variety of commercial sources. The polyaryletherketones (PAEK) have preferably reduced viscosities in the range of from about 0.8 to about 1.8 dl/g as measured in concentrated sulfuric acid at 25° C and at atmospheric pressure.
Non limitative examples of commercially available polyaryletherketone (PAEK) resins suitable for the invention include the KETASPIRE® polyetheretherketone commercially available from Solvay Advanced Polymers and VICTREX® PEEK polyetheretherketone, from Imperial Chemicals, Inc., which are polymers, the recurring units of which are recurring units (J’-A), as above detailed.
The Applicant has found that the salt (F) as above detailed is particularly effective in improving flammability properties of polyaryletherketone (PAEK) polymers, as above detailed, and more particularly of polymers (PAEK) comprising recurring units (RPAEK) of formula (J’-A), as above detailed.
A preferred composition of the invention thus includes a polymer (PAEK), as above detailed, and more preferably a polymer (PAEK) comprising recurring units (RPAEK) of formula (J’-A), as above detailed and a salt (F), preferably selected from salts (OF) and salts (AF), as above detailed.
Optionally, the polymer composition of the invention can further comprise fillers, lubricating agents, flow modifiers, heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO2, carbon black, antioxidants, and the like.
The composition of the invention can advantageously comprise at least one filler chosen from reinforcing fillers, structural fibers and mixtures thereof. Structural fibers may include glass fiber, carbon or graphite fibers, and fibers formed of silicon carbide, alumina, titania, boron and the like, and may include mixtures comprising two or more such fibers. Reinforcing fillers which can also be used in the composition of the invention include notably pigments, flake, spherical and fibrous particulate filler reinforcements and nucleating agents such as talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, and the like. The reinforcing fillers and structural fibers can be used alone or in any combination.
Another aspect of the present invention concerns a process for manufacturing the polymer composition as above described, which comprises mixing :
- at least one polymer (P), as above detailed;
- at least one salt (F), as above detailed.
Advantageously, the process of the invention comprises mixing by dry blending and/or melt compounding polymer (P) and salt (F).
Preferably, polymer (P) and salt (F) are mixed by melt compounding.
Advantageously, polymer (P) and salt (F) are melt compounded in continuous or batch devices. Such devices are well-known to those skilled in the art.
Examples of suitable continuous devices to melt compound the polymer composition of the invention are notably screw extruders. Thus, polymer (P) and salt (F) and, optionally, other ingredients, are advantageously fed in powder or granular form in an extruder and the composition is extruded into strands and the strands are chopped into pellets.
Optionally, fillers, lubricating agents, flow modifiers, heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO2, carbon black, antioxidants, flame retardants, smoke-suppressing agents may be added to the composition during the compounding step.
Preferably, polymer (P) and salt (F) are melt compounded in a twin-screw extruder.
The composition can be further processed following standard methods for injection moulding, extrusion, thermoforming, machining, and blow moulding. Solution-based processing for coatings and membranes is also possible. Finished articles comprising the composition as above described can undergo standard post-fabrication operations such as ultrasonic welding, adhesive bonding, and laser marking as well as heat staking, threading, and machining.
Another object of the invention is a shaped article comprising the polymer composition as above described.
Advantageously, the article is an injection moulded article, an extrusion moulded article, a shaped article, a coated article or a casted article.
The articles according to the invention can be fabricated by processing the composition as above described following standard methods.
The invention will be now described in more details with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.
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.
Raw materials
KetaSpire® PEEK KT-820 NT and KetaSpire® PEEK KT-880 NT are polyetheretherketone polymers commercially available from Solvay Specialty Polymers USA, LLC.
UDEL® PSU P-1700 NT is a polysulfone polymer commercially available from Solvay Specialty Polymers USA, LLC.
KetaSpire® PEEK KT-820 NT and KetaSpire® PEEK KT-880 NT are polyetheretherketone polymers commercially available from Solvay Specialty Polymers USA, LLC.
UDEL® PSU P-1700 NT is a polysulfone polymer commercially available from Solvay Specialty Polymers USA, LLC.
Preparative Example 1 : Synthesis of CF 3 -CF 2 -OCF 2 CF 2 -SO 3 K (additive #1, hereinafter)
In a 250ml round-bottom glass flask equipped with thermometer, reflux condenser, dropping funnel and magnetic stirrer in the following order were introduced 12.4 g of KOH 86% and 126 g of de-mineralized water; then 27.6 g of neat 2-perfluoroethoxyethylsulfonylfluoride (C4F10SO3) were added at 20°C while stirring. The flask was then heated at 55°C for 30 minutes. Upon completion of the reaction, the crude mixture turned into a single aqueous phase. Heating and stirring were set off and the reactor was left cooling slowly to room temperature. The product crystallized spontaneously in white needles and was recovered by filtration, rinsed with cold water and dried. 28.8 g of substantially pure CF 3 -CF 2 -OCF 2 CF 2 -SO 3 K were recovered.
In a 250ml round-bottom glass flask equipped with thermometer, reflux condenser, dropping funnel and magnetic stirrer in the following order were introduced 12.4 g of KOH 86% and 126 g of de-mineralized water; then 27.6 g of neat 2-perfluoroethoxyethylsulfonylfluoride (C4F10SO3) were added at 20°C while stirring. The flask was then heated at 55°C for 30 minutes. Upon completion of the reaction, the crude mixture turned into a single aqueous phase. Heating and stirring were set off and the reactor was left cooling slowly to room temperature. The product crystallized spontaneously in white needles and was recovered by filtration, rinsed with cold water and dried. 28.8 g of substantially pure CF 3 -CF 2 -OCF 2 CF 2 -SO 3 K were recovered.
Preparative Example 2 : Synthesis of CF 2 Cl-CFCl-OCF 2 CF 2 -SO 3 K (additive #2, hereinafter)
In a 500ml round-bottom glass flask equipped with thermometer, reflux condenser, dropping funnel and magnetic stirrer were introduced 21,5 g of KOH 86% and 236 g of de-mineralized water; then 50,0 g of neat 2-(1,2 dichlorodifluoroethoxy)tetrafluoroethylsulfonylfluoride were added (C4Cl2F8SO3) at 20°C while stirring. The flask was then heated at 65°C for 3 hours. Heating and stirring were set off and the reactor was left cooling slowly to room temperature. The product crystallized spontaneously in white needles and was recovered by filtration, rinsed with cold water and dried. 53.1 g of substantially pure ClCF 2 -CFCl-OCF 2 CF 2 -SO 3 K were recovered.
In a 500ml round-bottom glass flask equipped with thermometer, reflux condenser, dropping funnel and magnetic stirrer were introduced 21,5 g of KOH 86% and 236 g of de-mineralized water; then 50,0 g of neat 2-(1,2 dichlorodifluoroethoxy)tetrafluoroethylsulfonylfluoride were added (C4Cl2F8SO3) at 20°C while stirring. The flask was then heated at 65°C for 3 hours. Heating and stirring were set off and the reactor was left cooling slowly to room temperature. The product crystallized spontaneously in white needles and was recovered by filtration, rinsed with cold water and dried. 53.1 g of substantially pure ClCF 2 -CFCl-OCF 2 CF 2 -SO 3 K were recovered.
General description of the compounding process of PEEK resins
A dry blend of PEEK resins with the desired amount of salt (F) additive was first prepared by tumble blending. The preblended mixture was then fed into a Berstorff 25 mm twin screw extruder. The barrel temperatures of the extruder were maintained at 350°C to give an adequate melt temperature. The screw speed was set at 250 rpm. The extrusion conditions are summarized in table 5. The melt was extruded through a single hole die and the polymer strands were cooled using a water bath prior to pelletization. Composition, flammability, physical and mechanical properties of the blends are summarized in table 2, 3, and 4 (control experiments) respectively.
A dry blend of PEEK resins with the desired amount of salt (F) additive was first prepared by tumble blending. The preblended mixture was then fed into a Berstorff 25 mm twin screw extruder. The barrel temperatures of the extruder were maintained at 350°C to give an adequate melt temperature. The screw speed was set at 250 rpm. The extrusion conditions are summarized in table 5. The melt was extruded through a single hole die and the polymer strands were cooled using a water bath prior to pelletization. Composition, flammability, physical and mechanical properties of the blends are summarized in table 2, 3, and 4 (control experiments) respectively.
Capillary Rheology Test Method (viscosity):
The viscosity of a melt was measured as a function of shear rate at several temperatures using an LCR-7000 Capillary Rheometer.
| Run | 1 | 2 | 3 | 4 | 5 | 6 | |
| PEEK | type | KetaSpire® PEEK KT-820 NT | |||||
| additive | type | #1 | #1 | #1 | #2 | #2 | #2 |
| (%wt) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| Flammability properties | |||||||
| Nominal thickness | mm | 3 | 1.5 | 0.8 | 3 | 1.5 | 0.8 |
| flame rating | UL(1) | V-0 | V-0 | NR | V-0 | V-0 | V-1 |
| Rheological Properties | |||||||
| VR40 (2) | 1.02 | - | - | 0.99 | - | - | |
| MFR(3) | g/10 min | 7.24 | - | - | 6.54 | - | - |
| Run | 7 | 8 | 9 | 10 | 11 | 12 | |
| PEEK | type | KetaSpire® PEEK KT-880 NT | |||||
| additive | type | #1 | #1 | #1 | #2 | #2 | #2 |
| (%wt) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| Flammability properties | |||||||
| Nominal thickness | mm | 3 | 1.5 | 0.8 | 3 | 1.5 | 0.8 |
| Flame rating | UL(1) | V-0 | V-0 | NR | V-0 | V-0 | V-0 |
| Rheological Properties | |||||||
| VR40 (2) | 0.9 | - | - | 0.86 | - | - | |
| MFR(3) | g/10 min | 46.78 | - | - | 46.84 | - | - |
| Run | Comparative | Control 2 | |||||
| Polymer | Type | KetaSpire® PEEK KT-820 NT | KetaSpire® PEEK KT-880 NT | ||||
| Flammability Properties | |||||||
| Nominal thickness | mm | 3 | 1.5 | 0.8 | 3 | 1.5 | 0.8 |
| Flame Rating | UL(1) | V-0 | V-1 | NR | V-0 | NR | NR |
| Rheological Properties | |||||||
| VR40 (2) | 1.18 | - | - | 0.99 | - | - | |
| MFR(3) | g/10min | 7.13 | - | - | 46.63 | - | - |
Notes for tables 2 to 4:
(1) Flame rating based on UL 94 vertical burn test; this flame rating, with V-0 being best, followed by V-1, V-2 and NR (not rated), depends on both the average of burn times and the variability in burn times. Each bar is subjected to a vertical flame burn twice and typically five bars are tested leading to a population of 10 burn times to assign the flame rating; (2) ratio of melt viscosity after 40 min heating at 410°C at a shear rate of 46 s-1 over melt viscosity after 10 minutes at 410°C at same shear rate; (3) Melt flow rate at 365°C, under a piston load of 5.0 kg.
(1) Flame rating based on UL 94 vertical burn test; this flame rating, with V-0 being best, followed by V-1, V-2 and NR (not rated), depends on both the average of burn times and the variability in burn times. Each bar is subjected to a vertical flame burn twice and typically five bars are tested leading to a population of 10 burn times to assign the flame rating; (2) ratio of melt viscosity after 40 min heating at 410°C at a shear rate of 46 s-1 over melt viscosity after 10 minutes at 410°C at same shear rate; (3) Melt flow rate at 365°C, under a piston load of 5.0 kg.
| Extrusion parameters | Set Point | Run Value |
| Zone 1 (°C) | 300 | 300 |
| Zone 2 (°C) | 340 | 340 |
| Zone 3 (°C) | 350 | 350 |
| Zone 4 (°C) | 350 | 350 |
| Zone 5 (°C) | 350 | 350 |
| Die (°C) | 350 | 350 |
| Screw Speed (rpm) | 250 | 250 |
| Drive torque (%) | 65 | |
| Pelletizer rate (Hz) | 182 | |
| Feed rate (lb/h) | 4 | |
| Vacuum (mm Hg) | ~ 800 |
General description of the compounding process of sulfone polymers
A dry blend of sulfone polymers (UDEL® polysulfone P-1700 NT) with the desired amount of salt (F) additive was first prepared by tumble blending. The preblended mixture was then fed into a Berstorff 25 mm twin screw extruder. The barrel temperatures of the extruder were maintained at 340°C to give an adequate melt temperature. The screw speed was set at 200 rpm. The extrusion conditions are summarized in table 6. The melt was extruded through a single hole die and the polymer strands were cooled using a water bath prior to pelletization. Composition, flammability, physical and mechanical properties of the blends are summarized in table 7.
A dry blend of sulfone polymers (UDEL® polysulfone P-1700 NT) with the desired amount of salt (F) additive was first prepared by tumble blending. The preblended mixture was then fed into a Berstorff 25 mm twin screw extruder. The barrel temperatures of the extruder were maintained at 340°C to give an adequate melt temperature. The screw speed was set at 200 rpm. The extrusion conditions are summarized in table 6. The melt was extruded through a single hole die and the polymer strands were cooled using a water bath prior to pelletization. Composition, flammability, physical and mechanical properties of the blends are summarized in table 7.
Capillary Rheology Test Method (viscosity):
The viscosity of a melt was measured as a function of shear rate at several temperatures using an LCR-7000 Capillary Rheometer.
| Extrusion parameters | Set Point | Run Value |
| Zone 1 (°C) | 300 | 300 |
| Zone 2 (°C) | 325 | 325 |
| Zone 3 (°C) | 330 | 330 |
| Zone 4 (°C) | 335 | 335 |
| Zone 5 (°C) | 340 | 340 |
| Melt temp (°C) | 365 | 364 |
| Die (°C) | 345 | 345 |
| Screw Speed (rpm) | 200 | 209 |
| Drive torque (%) | 60 | 59 |
| Pelletizer rate (Hz) | 163 | |
| Feed rate (lb/h) | 2.8 | |
| Vacuum (mmHg) | ~ 500 |
| Run | 13 | 14 | 15 | 16 | 17 | ||
| SP polym | type | UDEL® PSU P-1700 NT | |||||
| additive | type | none | #1 | #1 | #2 | #2 | |
| (%wt) | - | 0.2 | 0.4 | 0.2 | 0.4 | ||
| Flammability properties | |||||||
| Nominal thickness = 3 mm | |||||||
| Flame rating | UL | NR | V-0 | V-0 | V-0 | V-0 | |
| Nominal thickness = 1.5 mmV-2 | |||||||
| Flame rating | UL | NR | NR | NR | V-2 | V-2 | |
| Nominal thickness = 0.8 mm | |||||||
| Flame rating | UL | NR | NR | NR | V-2 | V-2 | |
Claims (15)
- A polymer composition comprising:- at least one polycondensation polymer having a heat deflection temperature (HDT) of above 80°C under a load of 1.82 MPa when measured according to ASTM D648 [polymer (P)];- at least one fluorinated sulfonate salt [salt (F)] of either of formulae:(Xn+)1/n -O3S-R*d F-SO3 -(Xn+)1/n andR*m F-SO3 -(Xn+)1/nwherein R*d F is a divalent C1-C14 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; R*m F is a monovalent C1-C14 perfluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, in particular Cl; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
- The polymer composition of claim 1, wherein the salt (F) is selected from the group consisting of perfluoroalkylsulphonic derivatives [salt (AF)] of either of formulae:(Xn+)1/n -O3S-Rd af-SO3 -(Xn+)1/n andRm af-SO3 -(Xn+)1/nwherein Rd af is a divalent C1-C6 perfluoroalkyl group; Rm af is a monovalent C1-C6 perfluoroalkyl group; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
- The polymer composition of claim 1, wherein the salt (F) is selected from the group consisting of perfluoroalkoxysulphonic derivatives [salt (OF)] of either of formulae:(Xn+)1/n -O3S-(CF2)p-CF2CF2O-Rd f-OCF2CF2-(CF2)p-SO3 -(Xn+)1/n andRm f-OCF2CF2-(CF2)p-SO3 -(Xn+)1/nwherein Rd f is a divalent C1-C12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; p is zero or an integer from 1 to 5; Rm f is a monovalent C1-C12 per(halo)fluorocarbon group, possibly comprising one or more ethereal oxygen atom, comprising optionally one or more halogen atom(s) different from fluorine, preferably Cl; X = H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.
- The polymer composition of claim 3, wherein the salt (OF) is selected from the group consisting of:(i) CF3-(CF2)w-OCF2CF2-SO3 -(Zp+)1/pwherein w is an integer from 1 to 3, preferably w = 1, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;(ii) CF2Cl-CFCl-(CF2)z-OCF2CF2-SO3 -(Zp+)1/pwherein z is an integer from 0 to 3, preferably z = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;(iii) CF2Cl-CF2-(CF2)z”-OCF2CF2-SO3 -(Zp+)1/pwherein z” is an integer from 0 to 3, preferably z” = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;(iv) CF3-CFCl-(CF2)z”-OCF2CF2-SO3 -(Zp+)1/pwherein z”’ is an integer from 0 to 3, preferably z’” = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;(v) CF3-(CF2)w’OCF2CF2-OCF2CF2-SO3 -(Zp+)1/pwherein w’ is an integer from 0 to 2, preferably w’ = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;(vi) CF2Cl-CFCl-(CF2)z’OCF2CF2-OCF2CF2-SO3 -(Zp+)1/pwherein z’ is an integer from 0 to 2, preferably z’ = 0, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z;(vii) CF3-(CF2)q-(OCF2CFXF)r-OCF2CF2-SO3 -(Zp+)1/pwherein q and r being integers from 1 to 3, preferably q = 1 and r = 1, XF is F or CF3 and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z; and(viii) CF3-CF2-OCF2CF2-(CF2)t’-SO3 -(Zp+)1/pwherein t’ is an integer from 1 to 3, preferably t’ is 1 or 2, and Z is NH4 or a alkaline or alkali-earth metal cation, and p being the valence of the cation Z.
- The polymer composition of anyone of claims 1 to 4, wherein polymer (P) is selected among aromatic polyimides (PI), polyaryletherketones (PAEK), liquid crystal polymers (LCP), and aromatic sulfone polymers (SP).
- The polymer composition of claim 5, wherein polymer (P) is an aromatic polyimide (PI) comprising recurring units, wherein more than 50 % moles of said recurring units comprising at least one aromatic ring and at least one imide group, as such (formula 1A) or in its amic acid form (formula 1B) [recurring units (RPI)] :and wherein said recurring units (RPI) are selected from formulae 5A to 5C :
wherein :
Ar represents an aromatic tetravalent group; typically Ar is selected from the group consisting of following structures:and corresponding optionally substituted structures, with X being –O-, -C(O)-, -CH2-, -C(CF3)2-, -(CF2)n-, with n being an integer from 1 to 5;
R represents an aromatic divalent group; typically R is selected from the group consisting of following structures:and corresponding optionally substituted structures, with Y being –O-, -S-, -SO2-, -CH2-, -C(O)-, -C(CF3)2-, -(CF2)n, n being an integer from 0 to 5.
- The polymer composition of claim 5, wherein polymer (P) is a polyaryletherketone (PAEK) polymer, comprising recurring units, more than 50 % moles of said recurring units being recurring units (RPAEK) selected from the group consisting of formulae (J-A) to (J-O), herein below:
wherein:
- each of R’, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;- j’ is zero or is an integer from 0 to 4. - The polymer composition of claim 4, wherein polymer (P) is an aromatic sulfone polymer (SP), wherein at least 50 % wt of the recurring units thereof comprise at least one group of formula (SP) [recurring units (RSP)]:.
- The polymer composition of claim 7, wherein at least 50 % wt of the recurring units of aromatic sulfone polymer (SP) are recurring units (RSP-1), in their imide form (RSP-1-A) and/or amic acid forms [(RSP-1-B) and (RSP-1-C)] :wherein :
the → denotes isomerism so that in any recurring unit the groups to which the arrows point may exist as shown or in an interchanged position;Ar” is chosen among the following structures :and corresponding optionally substituted structures, with Y being –O-, -C(O)-, -(CH2)n-, -C(CF3)2-, -(CF2)n-, with n being an integer from 1 to 5and mixtures thereof.
- The polymer composition of claim 7, wherein at least 50 % wt of the recurring units of aromatic sulfone polymer (SP) are recurring units (RSP-2) and/or recurring units (RSP-3) :wherein :
- Q and Ar*, equal or different from each other and at each occurrence, are independently a divalent aromatic group; preferably Ar* and Q equal or different from each other and at each occurrence, are independently selected from the group consisting of the following structures :and corresponding optionally substituted structures, with Y being –O-, -CH=CH-, -C≡C-, -S-, -C(O)-, -(CH2)n-, -C(CF3)2-, -C(CH3)2-, -SO2-, -(CF2)n-, with n being an integer from 1 to 5 and mixtures thereof; and mixtures thereof.
- The polymer composition of claim 10, wherein recurring units (RSP-2 ) are chosen from :and mixtures thereof, and wherein recurring units (RSP-3 ) are chosen from :
and mixtures thereof.
- A process for manufacturing the polymer composition according to anyone of claim 1 to 11, which comprises mixing :- at least one polymer (P);- at least one salt (F).
- The process of claim 12, wherein polymer (P) and salt (F) are mixed by melt compounding.
- A shaped article comprising the polymer composition according to anyone of claim 1 to 11.
- The article of claim 14, selected among an injection moulded article, an extrusion moulded article, a shaped article, a coated article or a casted article.
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| Application Number | Priority Date | Filing Date | Title |
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| EP12788549.9A EP2785781A1 (en) | 2011-11-28 | 2012-11-22 | Polymer composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161564136P | 2011-11-28 | 2011-11-28 | |
| US61/564,136 | 2011-11-28 |
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| WO2013079383A1 true WO2013079383A1 (en) | 2013-06-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/EP2012/073286 WO2013079383A1 (en) | 2011-11-28 | 2012-11-22 | Polymer composition |
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| EP (1) | EP2785781A1 (en) |
| WO (1) | WO2013079383A1 (en) |
Cited By (5)
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| WO2017087438A1 (en) * | 2015-11-20 | 2017-05-26 | Ticona Llc | High flow polyaryletherketone composition |
| US20170267838A1 (en) * | 2016-03-18 | 2017-09-21 | Ticona Llc | Polyaryletherketone Composition |
| US20170275454A1 (en) * | 2014-08-21 | 2017-09-28 | Ticona Llc | Composition Containing a Polyaryletherketone and Low Naphthenic Liquid Crystalline Polymer |
| CN108976152A (en) * | 2018-09-10 | 2018-12-11 | 江汉大学 | A kind of alkyl ether sulfonyl fluoride compound and its synthetic method |
| US20210370614A1 (en) * | 2018-10-22 | 2021-12-02 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymer compositions and corresponding laser welding applications |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170275454A1 (en) * | 2014-08-21 | 2017-09-28 | Ticona Llc | Composition Containing a Polyaryletherketone and Low Naphthenic Liquid Crystalline Polymer |
| US10774215B2 (en) * | 2014-08-21 | 2020-09-15 | Ticona Llc | Composition containing a polyaryletherketone and low naphthenic liquid crystalline polymer |
| US9988529B2 (en) | 2015-11-20 | 2018-06-05 | Ticona Llc | High flow polyaryletherketone composition |
| CN108473674B (en) * | 2015-11-20 | 2021-03-02 | 提克纳有限责任公司 | High flow polyaryletherketone compositions |
| WO2017087438A1 (en) * | 2015-11-20 | 2017-05-26 | Ticona Llc | High flow polyaryletherketone composition |
| CN108473674A (en) * | 2015-11-20 | 2018-08-31 | 提克纳有限责任公司 | Height flowing poly(aryl ether ketone) composition |
| TWI742014B (en) * | 2015-11-20 | 2021-10-11 | 美商堤康那責任有限公司 | High flow polyaryletherketone composition |
| CN108779244A (en) * | 2016-03-18 | 2018-11-09 | 提克纳有限责任公司 | Poly(aryl ether ketone) composition |
| US20170267838A1 (en) * | 2016-03-18 | 2017-09-21 | Ticona Llc | Polyaryletherketone Composition |
| CN108779244B (en) * | 2016-03-18 | 2021-02-02 | 提克纳有限责任公司 | Polyaryletherketone compositions |
| WO2017160439A1 (en) * | 2016-03-18 | 2017-09-21 | Ticona Llc | Polyaryletherketone composition |
| US11352480B2 (en) | 2016-03-18 | 2022-06-07 | Ticona Llc | Polyaryletherketone composition |
| CN108976152B (en) * | 2018-09-10 | 2020-10-23 | 江汉大学 | Alkyl ether sulfonyl fluoride compound and synthesis method thereof |
| CN108976152A (en) * | 2018-09-10 | 2018-12-11 | 江汉大学 | A kind of alkyl ether sulfonyl fluoride compound and its synthetic method |
| US20210370614A1 (en) * | 2018-10-22 | 2021-12-02 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymer compositions and corresponding laser welding applications |
| US11794417B2 (en) * | 2018-10-22 | 2023-10-24 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymer compositions and corresponding laser welding applications |
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| Publication number | Publication date |
|---|---|
| EP2785781A1 (en) | 2014-10-08 |
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