WO2006037755A1 - Sulfone polymer composition - Google Patents
Sulfone polymer composition Download PDFInfo
- Publication number
- WO2006037755A1 WO2006037755A1 PCT/EP2005/054936 EP2005054936W WO2006037755A1 WO 2006037755 A1 WO2006037755 A1 WO 2006037755A1 EP 2005054936 W EP2005054936 W EP 2005054936W WO 2006037755 A1 WO2006037755 A1 WO 2006037755A1
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- WIPO (PCT)
- Prior art keywords
- polymer
- recurring units
- sulfone
- composition according
- polymer composition
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 31
- 229920001519 homopolymer Polymers 0.000 claims abstract description 14
- 229920000491 Polyphenylsulfone Polymers 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 238000013329 compounding Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 4
- 229920003295 Radel® Polymers 0.000 description 3
- 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 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- OZUNPRDEUXITBO-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-4-[4-(4-chlorophenyl)sulfonylphenyl]benzene Chemical group C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(Cl)=CC=2)C=C1 OZUNPRDEUXITBO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010330 laser marking Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0333—Organic insulating material consisting of one material containing S
Definitions
- example 2 of said patent discloses a miscible blend composed of 50 parts by weight of polyphenylsulfone and 50 parts by weight of polybiphenyldisulfone.
- Example 12 of same patent discloses a miscible blend composed of 70 parts by weight of polyphenylsulfone and 30 parts by weight of a copolymer of polybiphenyldisulfone.
- the invention concerns a sulfone polymer composition having a good balance between high temperature performances and resilience, and an article comprising said composition.
- High glass transition temperature sulfone polymers are appreciated because of their outstanding heat resistance, dimensional stability, good chemical resistance and mechanical integrity up to operating temperature of about 250°C. Nevertheless, these high glass transition temperature sulfone polymers present several drawbacks, in particular a poor toughness, which make them unsuitable for application where impact resistance is required. Moreover, they are highly costly, due to the expensive monomers required for their synthesis. The above-mentioned drawbacks and others are remarkably overcome by a sulfone polymer composition comprising :
- sulfone polymer composition composed of 50 % wt of polybiphenyldisulfone, namely a homopolymer the recurring units thereof are
- sulfone polymer composition composed of 30 % wt of a polymer 75 % mol of the recurring units thereof are recurring units (Rl) and 25 % mol of the
- composition of the invention possesses advantageously thermal performances and toughness advantages in addition to minor cost with respect to high glass transition sulfone polymers.
- polymer is intended to denote any material consisting essentially of recurring units, and having a molecular weight above 2000.
- high glass transition temperature sulfone polymer is intended to denote any polymer, at least 50 % wt of recurring units thereof being recurring units (Rl) :
- - Q is a group chosen among the following structures
- n integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and mixtures thereof;
- - Ar is a group chosen among the following structures :
- n integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and mixtures thereof.
- Recurring units (R2) are preferably chosen from :
- Polymer (A) can be either a homopolymer or a random, alternating or block copolymer.
- polymer (A) Preferably 70 % wt, more preferably 75 % wt, even more preferably 80 % wt of the recurring units of polymer (A) are recurring units (Rl). Still more preferably, polymer (A) is a homopolymer of recurring units (Rl).
- Polymer (A) obtained from the polycondensation of 4,4'-bis-(4-chlorophenyl sulfonyl)biphenyl and 4,4'-dihydroxydiphenyl (polybiphenyldisulfone, hereinafter) is an example of homopolymer.
- Polymer (A) has a glass transition temperature of advantageously at least 230°C, preferably at least 240°C, more preferably at least 250°C.
- the sulfone polymer composition comprises less than 50 % wt, preferably less than or equal to
- the sulfone polymer composition advantageously comprises at least 10 % wt, preferably at least 15 % wt, more preferably at least 20 % wt, still more preferably at least 30 % wt, most preferably at least 40 % wt of polymer (A), with respect to the total weight of (A) and (B).
- the sulfone polymer composition comprises more than 50 % wt of polymer (A), preferably more that or equal to 51 % wt, more preferably more that or equal to 52 % wt, still more preferably more that or equal to 53 % wt with respect to the total weight of (A) and (B).
- the sulfone polymer composition comprises at most 90 % wt, preferably at most 85 % wt, more preferably at most 80 % wt, still more preferably at most 70 % wt, most preferably at most 60 % wt of polymer (A), with respect to the total weight of (A) and (B).
- highly tough sulfone polymer (B) is intended to denote any polymer, at least 50 % wt of recurring units thereof being recurring units (R3) :
- polymer (B) further comprises recurring units (R4) :
- Recurring units (R4) are preferably chosen from :
- Polymer (B) may notably be a homopolymer, a random, alternating or block copolymer. Preferably at least 70 % wt, more preferably at least 75 % wt of the recurring units of polymer (B) are recurring units (R3). Still more preferably, polymer (B) is a homopolymer of recurring units (R3).
- Polymer (B) has an impact resistance of advantageously at least 8 ft-lb/in, preferably of at least 9 ft-lb/in, more preferably of at least 10.0 ft-lb/in when measured by Notched Izod according to ASTM D256 (Test method A) at 25°C.
- the polymer composition of the invention exhibits a glass transition temperature of advantageously at least 220°C, preferably at least 225°C, more preferably at least 230°C.
- the polymer composition of the invention exhibits an impact resistance of advantageously at least 7 ft-lb/in, preferably of at least 8 ft-lb/in, more preferably of at least 9.0 ft-lb/in, still more preferably of at least 10.0 ft-lb/in when measured by Notched Izod according to ASTM D256 (Test method A) at 25°C.
- the polymer composition of the invention may notably further comprises at least one filler.
- the filler is preferably chosen from glass fiber, carbon or graphite fibers, fibers formed of silicon carbide, alumina, titania, boron, 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 polymer composition of the invention may also further comprise notably pigments, stabilizers, i.e., metal oxides such as zinc oxide, antioxidants and/or flame retardants.
- stabilizers i.e., metal oxides such as zinc oxide, antioxidants and/or flame retardants.
- Another object of the invention is an article comprising the polymer composition as above described.
- the article is an injection molded article, an extrusion molded article, a shaped article, a coated article or a casted article.
- the articles according to the invention can be fabricated by processing the polymer composition as above described following standard methods.
- Non limitative examples of articles are shaped articles, electronic components (such as printed circuit boards, electrical plug- in connectors, bobbins for relays and solenoids), pipes, fittings, housings, films, membranes, coatings.
- electronic components such as printed circuit boards, electrical plug- in connectors, bobbins for relays and solenoids
- pipes fittings, housings, films, membranes, coatings.
- Another aspect of the present invention concerns a process for manufacturing the polymer composition as above described, which comprises mixing the polymer (A) and the polymer (B).
- the process comprises mixing by dry blending and/or melt compounding the polymer (A) and the polymer (B).
- the polymer (A) and the polymer (B) are mixed by melt compounding.
- the polymer (A) and the polymer (B) are melt compounded in continuous or batch devices. Such devices are well-known to those skilled in the art.
- suitable continuous devices to melt compound the polymer composition of the invention are notably screw extruders.
- the polymer (A), the polymer (B), and optionally other ingredients are advantageously fed in powder or granular form in an extruder and the polymer composition, as above described is advantageously extruded into strands and the strands are advantageously chopped into pellets.
- fillers may be added to the composition during the compounding step.
- the polymer (A) and the polymer (B) are melt compounded in a twin-screw extruder.
- the polymer composition of the invention can be processed following standard methods for injection molding, extrusion, thermoforming, machining, and blow molding. Solution-based processing for coatings and membranes is also possible. Finished articles comprising the polymer 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.
- Polybiphenyldisulfone obtained from the polycondensation of 4,4'-bis-(4-chlorophenyl sulfonyl)biphenyl and 4,4'-dihydroxydiphenyl was used.
- the table 1 here below summarizes main properties of the material used in preparing the composition : Table 1 - Properties of the polybiphenyldisulfone
- RADEL® R-5800 NT polyphenylsulfone commercially available from Solvay Advanced Polymers, a sulfone polymer obtained from the polycondensation of a 4,4'-dihalodiphenylsulfone and 4,4'-dihydroxydiphenyl, has been used.
- Table 2 here below summarizes main properties of the material used in preparing the compositions : Table 2 - Properties of the polyphenylsulfone
- the resin pellets from the various resins and composition were dried for about 16 hrs in a 149°C (300 F) desiccated hot air oven with a due point of -37.2°C (-35 F).
- Parts were then injection molded into 1/8" thick ASTM tensile and flexural test specimens using a Wasp Mini- Jector benchtop injection molding machine equipped with a 3/4" general purpose screw and a 20 L/D.
- Injection molding machine temperature settings were 395°C, 400°C and 405°C for the rear, front and nozzle sections respectively.
- An injection pressure of 1100 psi was used along with a mold temperature of 85°C (185 F) and a screw speed of 60 RPM.
- a standard flexural bar 5" x 1 A” x 7 8 " was used for ASTM D648 HDT determinations and for ASTM D256 Notched Izod measurements (Test method A).
- a type I ASTM tensile bar, 4.5" in gage length x 1 A" wide x Vs " thick was used for ASTM D638 Tensile properties determinations.
- a blend of the polybiphenyldisulfone and of RADEL® R-5800 NT polyphenylsulfone was prepared by melt compounding as specified here above. Details of composition and characterization of the blend are summarized in Table 4 here below. Table 4 - Composition and characterization of the blend
- HDT Temperature
- ⁇ Tensile properties measured according to ASTM D 638.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a sulfone polymer composition comprising : - at least one high glass transition temperature sulfone polymer [polymer (A)] - at least one highly tough sulfone polymer [polymer (B)] with the exception of : - a sulfone polymer composition composed of 50 % wt of polybiphenyldisulfone, namely a homopolymer the recurring units thereof are recurring units (R1) : and 50 % wt of polyphenylsulfone, namely a homopolymer the recurring units thereof are recurring units (R3) : and - a sulfone polymer composition composed of 30 % wt of a polymer 75 % mol of the recurring units thereof are recurring units (R1) and 25 % mol of the recurring units thereof are recurring units (iii) and 70 % wt of polyphenylsulfone. The sulfone polymer composition of the invention possesses advantageously thermal performances and toughness advantages in addition to minor cost with respect to high glass transition temperature sulfo ne polymers.
Description
Sulfone polymer composition
REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. provisional application 60/614,973, filed October 4, 2004, to EP application 04106875.0, filed on December 22,
2004, to U.S. provisional application 60/615,023, filed October 4, 2004, to EP application 04106876.8, filed on December 22, 2004, to U.S. provisional application 60/614,974, filed October 4, 2004, to EP application 04106878.4, filed on December 22, 2004, to EP application 05102551.8, filed on March 31,
2005, to U.S. provisional application 60/619,695, filed October 19, 2004, to EP application 04106879.2, filed on December 22, 2004, to U.S. provisional application 60/619,694, filed October 19, 2004, to U.S. provisional application 60/670,266, filed April 12, 2005, whose disclosures are incorporated herein by reference.
Numerous blends of various poly(aryl ether sulfone) have been described in US 4,804,723 (to Amoco Corporation), to the specific purpose of providing miscible compositions. Thus, example 2 of said patent discloses a miscible blend composed of 50 parts by weight of polyphenylsulfone and 50 parts by weight of polybiphenyldisulfone. Example 12 of same patent discloses a miscible blend composed of 70 parts by weight of polyphenylsulfone and 30 parts by weight of a copolymer of polybiphenyldisulfone. The problem of providing a sulfone polymer composition having a good balance between high temperature performances and resilience, especially impact resistance, is not addressed.
In contrast, the invention concerns a sulfone polymer composition having a good balance between high temperature performances and resilience, and an article comprising said composition.
High glass transition temperature sulfone polymers are appreciated because of their outstanding heat resistance, dimensional stability, good chemical resistance and mechanical integrity up to operating temperature of about 250°C. Nevertheless, these high glass transition temperature sulfone polymers present several drawbacks, in particular a poor toughness, which make them unsuitable for application where impact resistance is required. Moreover, they are highly costly, due to the expensive monomers required for their synthesis.
The above-mentioned drawbacks and others are remarkably overcome by a sulfone polymer composition comprising :
- at least one high glass transition temperature sulfone polymer [polymer (A)]
- at least one highly tough sulfone polymer [polymer (B)] with the exception of :
- a sulfone polymer composition composed of 50 % wt of polybiphenyldisulfone, namely a homopolymer the recurring units thereof are
- a sulfone polymer composition composed of 30 % wt of a polymer 75 % mol of the recurring units thereof are recurring units (Rl) and 25 % mol of the
The composition of the invention possesses advantageously thermal performances and toughness advantages in addition to minor cost with respect to high glass transition sulfone polymers.
For the purpose of the invention, the term "polymer" is intended to denote any material consisting essentially of recurring units, and having a molecular weight above 2000. For the purpose of the invention, the term "high glass transition temperature sulfone polymer" is intended to denote any polymer, at least 50 % wt of recurring units thereof being recurring units (Rl) :
(Rl)
Op )
(R2) wherein :
- Q is a group chosen among the following structures
- Ar is a group chosen among the following structures :
Recurring units (R2) are preferably chosen from :
(0
(ϋ)
(Hi) and mixtures therefrom.
Polymer (A) can be either a homopolymer or a random, alternating or block copolymer.
Preferably 70 % wt, more preferably 75 % wt, even more preferably 80 % wt of the recurring units of polymer (A) are recurring units (Rl). Still more preferably, polymer (A) is a homopolymer of recurring units (Rl).
Polymer (A) obtained from the polycondensation of 4,4'-bis-(4-chlorophenyl sulfonyl)biphenyl and 4,4'-dihydroxydiphenyl (polybiphenyldisulfone, hereinafter) is an example of homopolymer.
Polymer (A) has a glass transition temperature of advantageously at least 230°C, preferably at least 240°C, more preferably at least 250°C.
In a first preferred embodiment of the invention, the sulfone polymer composition comprises less than 50 % wt, preferably less than or equal to
49 % wt, more preferably less than or equal to 48 % wt, still more preferably less than or equal to 47 % wt of polymer (A), with respect to the total weight of (A) and (B).
In this embodiment, excellent results were obtained with sulfone polymer compositions comprising less than or equal to 45 % wt of polymer (A), with respect to the total weight of (A) and (B).
In this embodiment, the sulfone polymer composition advantageously comprises at least 10 % wt, preferably at least 15 % wt, more preferably at least 20 % wt, still more preferably at least 30 % wt, most preferably at least 40 % wt of polymer (A), with respect to the total weight of (A) and (B).
In a second preferred embodiment of the invention, the sulfone polymer composition comprises more than 50 % wt of polymer (A), preferably more that or equal to 51 % wt, more preferably more that or equal to 52 % wt, still more preferably more that or equal to 53 % wt with respect to the total weight of (A) and (B).
In this embodiment, excellent results were obtained with sulfone polymer compositions comprising more than or equal to 55 % wt of polymer (A), with respect to the total weight of (A) and (B).
In this embodiment, the sulfone polymer composition comprises at most 90 % wt, preferably at most 85 % wt, more preferably at most 80 % wt, still more preferably at most 70 % wt, most preferably at most 60 % wt of polymer (A), with respect to the total weight of (A) and (B).
For the purpose of the invention, the term "highly tough sulfone polymer" (B) is intended to denote any polymer, at least 50 % wt of recurring units thereof being recurring units (R3) :
(R3)
Optionally, polymer (B) further comprises recurring units (R4) :
(R4) wherein Ar' is a group chosen among the following structures
Recurring units (R4) are preferably chosen from :
(j)
(Jj)
Polymer (B) may notably be a homopolymer, a random, alternating or block copolymer. Preferably at least 70 % wt, more preferably at least 75 % wt of the recurring units of polymer (B) are recurring units (R3). Still more preferably, polymer (B) is a homopolymer of recurring units (R3).
RADEL® R PPSF polyphenylsulfone from Solvay Advanced Polymers, L.L.C. is an example of homopolymer. Polymer (B) has an impact resistance of advantageously at least 8 ft-lb/in, preferably of at least 9 ft-lb/in, more preferably of at least 10.0 ft-lb/in when measured by Notched Izod according to ASTM D256 (Test method A) at 25°C.
The polymer composition of the invention exhibits a glass transition temperature of advantageously at least 220°C, preferably at least 225°C, more preferably at least 230°C.
The polymer composition of the invention exhibits an impact resistance of advantageously at least 7 ft-lb/in, preferably of at least 8 ft-lb/in, more preferably of at least 9.0 ft-lb/in, still more preferably of at least 10.0 ft-lb/in when measured by Notched Izod according to ASTM D256 (Test method A) at 25°C. The polymer composition of the invention may notably further comprises at least one filler. The filler is preferably chosen from glass fiber, carbon or graphite fibers, fibers formed of silicon carbide, alumina, titania, boron, 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 polymer composition of the invention may also further comprise notably pigments, stabilizers, i.e., metal oxides such as zinc oxide, antioxidants and/or flame retardants.
Another object of the invention is an article comprising the polymer composition as above described.
Advantageously the article is an injection molded article, an extrusion molded article, a shaped article, a coated article or a casted article. The articles according to the invention can be fabricated by processing the polymer composition as above described following standard methods.
Non limitative examples of articles are shaped articles, electronic components (such as printed circuit boards, electrical plug- in connectors, bobbins for relays and solenoids), pipes, fittings, housings, films, membranes, coatings.
Another aspect of the present invention concerns a process for manufacturing the polymer composition as above described, which comprises mixing the polymer (A) and the polymer (B).
Advantageously, the process comprises mixing by dry blending and/or melt compounding the polymer (A) and the polymer (B).
Preferably, the polymer (A) and the polymer (B) are mixed by melt compounding.
Advantageously, the polymer (A) and the polymer (B) 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, the polymer (A), the polymer (B), and optionally other ingredients, are advantageously fed in powder or granular form in an extruder and the polymer composition, as above described is advantageously extruded into strands and the strands are advantageously chopped into pellets.
Optionally, fillers, lubricating agents, heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO2, carbon black, acid scavengers, such as MgO, flame-retardants, smoke- suppressing agents may be added to the composition during the compounding step.
Preferably, the polymer (A) and the polymer (B) are melt compounded in a twin-screw extruder.
The polymer composition of the invention can be processed following standard methods for injection molding, extrusion, thermoforming, machining, and blow molding. Solution-based processing for coatings and membranes is also possible. Finished articles comprising the polymer 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.
The present invention is described in greater detail below by referring to the Examples; however, the present invention is not limited to these examples.
Raw materials :
Polybiphenyldisulfone obtained from the polycondensation of 4,4'-bis-(4-chlorophenyl sulfonyl)biphenyl and 4,4'-dihydroxydiphenyl was used. The table 1 here below summarizes main properties of the material used in preparing the composition : Table 1 - Properties of the polybiphenyldisulfone
(f) Melt flow index measured according to ASTM D 1238, at a temperature of 4000C, under a load of 5 kg.
(π) Tensile properties measured according to ASTM D 638.
(X) Notched Izod has been measured at 250C according to ASTM D256 (Test method A). (§) Test parts were annealed at 25O0C for 1 hour prior to HDT testing. Heat Deflection
Temperature (HDT) has been measured according to ASTM D648. (*) Izod break type : Complete.
RADEL® R-5800 NT polyphenylsulfone commercially available from Solvay Advanced Polymers, a sulfone polymer obtained from the polycondensation of a 4,4'-dihalodiphenylsulfone and 4,4'-dihydroxydiphenyl, has been used. Table 2 here below summarizes main properties of the material used in preparing the compositions :
Table 2 - Properties of the polyphenylsulfone
(f) Melt flow index measured according to ASTM D 1238, at a temperature of 4000C, under a load of 5 kg.
(π) Tensile properties measured according to ASTM D 638. (X) Notched Izod has been measured at 250C according to ASTM D256 (Test method A). (§) Test parts were annealed at 2000C for 1 hour prior to HDT testing. Heat Deflection
Temperature (HDT) has been measured according to ASTM D648. (f) Izod break type : Partial
Compounding procedure : The compositions were melt compounded using a 25 mm diameter twin screw double vented Berstorff extruder having an L/D ratio of 33/1 according to the temperature profile shown in Table 1. The first vent port was open to the atmosphere; the second was connected to a vacuum pump. The extruder was fitted with a double strand die. The polymer extrudate was pelletized after passing through a water trough for cooling. The blend was extruded and pelletized without incident at the throughput rates indicated in Table 3. Table 3 - Compounding conditions
Following compounding, the resin pellets from the various resins and composition were dried for about 16 hrs in a 149°C (300 F) desiccated hot air oven with a due point of -37.2°C (-35 F). Parts were then injection molded into 1/8" thick ASTM tensile and flexural test specimens using a Wasp Mini- Jector benchtop injection molding machine equipped with a 3/4" general purpose screw and a 20 L/D. Injection molding machine temperature settings were 395°C, 400°C and 405°C for the rear, front and nozzle sections respectively. An injection pressure of 1100 psi was used along with a mold temperature of 85°C (185 F) and a screw speed of 60 RPM. Mechanical Properties Determinations
A standard flexural bar 5" x 1A" x 78" was used for ASTM D648 HDT determinations and for ASTM D256 Notched Izod measurements (Test method A). A type I ASTM tensile bar, 4.5" in gage length x 1A" wide x Vs " thick was used for ASTM D638 Tensile properties determinations. Example 1
A blend of the polybiphenyldisulfone and of RADEL® R-5800 NT polyphenylsulfone was prepared by melt compounding as specified here above. Details of composition and characterization of the blend are summarized in Table 4 here below. Table 4 - Composition and characterization of the blend
(f) Melt flow index measured according to ASTM D 1238, at a temperature of 4000C, under a load of 5 kg.
(X) Notched Izod has been measured at 250C according to ASTM D256 (Test method A). (§) Test parts were annealed at 23O0C for 1 hour prior to HDT testing. Heat Deflection
Temperature (HDT) has been measured according to ASTM D648. (π) Tensile properties measured according to ASTM D 638.
Claims
C L A I M S
1 - Sulfone polymer composition comprising :
at least one high glass transition temperature sulfone polymer [polymer (A)], at least 50 % wt of the recurring units thereof are recurring units (Rl) :
(Ri);
- at least one highly tough sulfone polymer [polymer (B)], at least 50 % wt of the recurring units thereof are recurring units (R3) :
(R3)
with the exception of
a sulfone polymer composition composed of 50 % wt of polybiphenyldisulfone, namely a homopolymer the recurring units thereof are recurring units (Rl), and 50 % wt of polyphenylsulfone, namely a homopolymer the recurring units thereof are recurring units (R3), and
a sulfone polymer composition composed of 30 % wt of a polymer 75 % mol of the recurring units thereof are recurring units (Rl) and 25 % mol of the recurring units thereof are recurring units (iii)
(iii)
and 70 % wt of polyphenylsulfone.
2 - Composition according to Claim 1, characterized in that it comprises at least 40 % wt and less than 50 % wt of polymer (A), with respect to the total weight of (A) and (B) or it comprises more than 50 % wt of polymer (A).
3 - Composition according to Claim 1, characterized in that polymer (A) comprises recurring units (R2) :
(R2)
wherein :
- Q is a group chosen among the following structures :
- Ar is a group chosen among the following structures :
4 - Composition according to Claim 3, characterized in that recurring units (R2) are chosen from :
(0
(ϋ)
(iii)
5 - Composition according to anyone of the preceding Claims, characterized in that at least 75 % wt of the recurring units of polymer (A) are recurring units (Rl).
6 - Composition according to Claim 5, characterized in that polymer (A) is a homopolymer of recurring units (Rl).
7 - Composition according to anyone of Claims 1 to 6 characterized in that polymer (B) is a homopolymer of recurring units (R3) :
(R3)
8 - Composition according to anyone of the preceding Claims, characterized in that it comprises at least one filler.
9 - Article comprising the composition according to anyone of the preceding Claims.
10 - Process for manufacturing the composition according to anyone of Claims 1 to 8, which comprises mixing the polymer (A) and the polymer (B).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/576,313 US20080058480A1 (en) | 2004-10-04 | 2005-09-30 | Sulfone Polymer Composition |
| EP05794683.2A EP1802705B1 (en) | 2004-10-04 | 2005-09-30 | Sulfone polymer composition |
Applications Claiming Priority (22)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61502304P | 2004-10-04 | 2004-10-04 | |
| US61497404P | 2004-10-04 | 2004-10-04 | |
| US61497304P | 2004-10-04 | 2004-10-04 | |
| US60/615,023 | 2004-10-04 | ||
| US60/614,974 | 2004-10-04 | ||
| US60/614,973 | 2004-10-04 | ||
| US61969504P | 2004-10-19 | 2004-10-19 | |
| US61969404P | 2004-10-19 | 2004-10-19 | |
| US60/619,695 | 2004-10-19 | ||
| US60/619,694 | 2004-10-19 | ||
| EP04106879.2 | 2004-12-22 | ||
| EP04106876A EP1526158A1 (en) | 2004-12-22 | 2004-12-22 | Electronic components |
| EP04106875A EP1524297A1 (en) | 2004-12-22 | 2004-12-22 | Sulfone polymer composition |
| EP04106878A EP1524298A1 (en) | 2004-12-22 | 2004-12-22 | Sulfone polymer composition |
| EP20040106879 EP1518883A2 (en) | 2004-12-22 | 2004-12-22 | Polyethersulphone articles |
| EP04106876.8 | 2004-12-22 | ||
| EP04106875.0 | 2004-12-22 | ||
| EP04106878.4 | 2004-12-22 | ||
| EP05102551 | 2005-03-31 | ||
| EP05102551.8 | 2005-03-31 | ||
| US67026605P | 2005-04-12 | 2005-04-12 | |
| US60/670,266 | 2005-04-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006037755A1 true WO2006037755A1 (en) | 2006-04-13 |
Family
ID=35385564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2005/054936 WO2006037755A1 (en) | 2004-10-04 | 2005-09-30 | Sulfone polymer composition |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP1802705B1 (en) |
| WO (1) | WO2006037755A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8742062B2 (en) | 2007-12-18 | 2014-06-03 | Solvay Advanced Polymers, L.L.C. | Polyphenyl sulfone ketone copolymers |
| US10569227B2 (en) | 2013-10-15 | 2020-02-25 | Basf Se | Improving the chemical stability of filtration membranes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0176989A1 (en) * | 1984-09-28 | 1986-04-09 | Amoco Corporation | Molded articles manufactured from blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone) |
| EP0215580A2 (en) * | 1985-08-19 | 1987-03-25 | Union Carbide Corporation | Miscible blends of poly(aryl ether sulfones) |
| US4804723A (en) * | 1985-08-19 | 1989-02-14 | Amoco Corporation | Miscible blends of poly(aryl ether sulfones) |
| EP0332012A1 (en) * | 1988-03-05 | 1989-09-13 | BASF Aktiengesellschaft | High temperature resistant polyarylethersulfone-/polyaryleneetherketone moulding compounds with improved phase cohesion |
-
2005
- 2005-09-30 EP EP05794683.2A patent/EP1802705B1/en not_active Not-in-force
- 2005-09-30 WO PCT/EP2005/054936 patent/WO2006037755A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0176989A1 (en) * | 1984-09-28 | 1986-04-09 | Amoco Corporation | Molded articles manufactured from blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone) |
| EP0215580A2 (en) * | 1985-08-19 | 1987-03-25 | Union Carbide Corporation | Miscible blends of poly(aryl ether sulfones) |
| US4804723A (en) * | 1985-08-19 | 1989-02-14 | Amoco Corporation | Miscible blends of poly(aryl ether sulfones) |
| EP0332012A1 (en) * | 1988-03-05 | 1989-09-13 | BASF Aktiengesellschaft | High temperature resistant polyarylethersulfone-/polyaryleneetherketone moulding compounds with improved phase cohesion |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8742062B2 (en) | 2007-12-18 | 2014-06-03 | Solvay Advanced Polymers, L.L.C. | Polyphenyl sulfone ketone copolymers |
| US10569227B2 (en) | 2013-10-15 | 2020-02-25 | Basf Se | Improving the chemical stability of filtration membranes |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1802705A1 (en) | 2007-07-04 |
| EP1802705B1 (en) | 2014-05-21 |
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