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POLY(ARYLENE SULFIDE) COMPOSITION

20240317999 ยท 2024-09-26

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention relates to a poly(arylene sulfide) composition including a combination of a limited amount of an antioxidant compound and of an epoxy-functional polyorganosiloxane polymer, possessing improved mechanical performances and outstanding thermal ageing resistance, to a process for its manufacturing, as well as to an article, part or composite material comprising said composition, and to the use of this composition for the manufacture of 3D objects

    Claims

    1. A polymer composition [composition (C)] comprising: at least one poly(arylene sulfide) polymer [polymer (PAS)], and at least one polyorganosiloxane polymer having at least one functional group selected from epoxy groups and amine groups [polymer (POS)]; and at least one antioxidant compound [compound (O)], in an amount of 0.03 to 0.4% wt, with respect to the weight of polymer (PAS).

    2. The composition (C) according to claim 1, wherein the polymer (PAS) comprises recurring units (R.sub.PAS1) represented by the following formula:
    [-Ar.sub.1-S](R.sub.PAS1) wherein -Ar.sub.1- is selected from the group of formulae consisting of: ##STR00059## wherein: R, at each instance, is independently selected from the group consisting of a C.sub.1-C.sub.12 alkyl group, a C.sub.7-C.sub.24 alkylaryl group, a C.sub.7-C.sub.24 aralkyl group, a C.sub.6-C.sub.24 arylene group, and a C.sub.6-C.sub.18 aryloxy group; T is selected from the group consisting of a bond, CO, SO.sub.2, O, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, phenyl and CH.sub.2; i, at each instance, is an independently selected integer from 0 to 4; j, at each instance, is an independently selected integer from 0 to 3.

    3. The composition (C) according to claim 2, wherein in formula (R.sub.PAS1), -Ar.sub.1- is represented by any of the following formulae: ##STR00060## wherein: R, at each instance, is independently selected from the group consisting of a C.sub.1-C.sub.12 alkyl group, a C.sub.7-C.sub.24 alkylaryl group, a C.sub.7-C.sub.24 aralkyl group, a C.sub.6-C.sub.24 arylene group, and a C.sub.6-C.sub.18 aryloxy group; i, at each instance, is an independently selected integer from 0 to 4; preferably i is zero.

    4. The composition (C) according to claim 2, wherein polymer (PAS) essentially consists of recurring units (R.sub.PAS1).

    5. The composition (C) according to claim 4, wherein polymer (PAS) is a poly(phenylene sulfide) (PPS) polymer having units (R.sub.PAS1) of formula (a1) where i is zero, i.e. having units (R.sub.PAS1) of formula: ##STR00061## and optionally additionally comprising units of any of formulae: ##STR00062## being understood that when polymer (PPS) further comprises units (RPPS-m) and/or (R.sub.PPS-o), the total concentration of recurring units (R.sub.PPS-m) and/or (R.sub.PPS-o) in the polymer (PPS) is at most 10 mol %, at most 5 mol %, at most 3 mol %, at most 1 mol %, based on total amount of units (R.sub.PPS), (R.sub.PPS-m) and (R.sub.PPS-o).

    6. The composition (C) according to claim 5, wherein polymer (PAS) has a melt flow rate (at 315.6? C. under a weight of 1.27 kg according to ASTM D1238, procedure B) of at most 700 g/10 min, more preferably of at most 500 g/10 min, even more preferably of at most 200 g/10 min, still more preferably of at most 50 g/10 min, yet more preferably of at most 35 g/10 min; and/or has a melt flow rate (at 315.6? C. under a weight of 1.27 kg according to ASTM D1238, procedure B) of at least 1 g/10 min, more preferably of at least 5 g/10 min, even more preferably of at least 10 g/10 min, still more preferably of at least 15 g/10 min.

    7. The composition (C) according to claim 1, wherein compound (O) is selected from the group consisting of hindered amine compounds, hindered phenol compounds, and phosphorous compounds selected from the group consisting of phosphite esters, phosphonites and mixtures thereof; and wherein the compound (O) is preferably selected from the group consisting of hindered phenol compounds, and phosphite esters represented by the formula P(OR).sub.3, wherein each of R, can be the same or different and is independently selected from the group consisting of a C.sub.1-20 alkyl, C.sub.3-22 alkenyl, C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene, aryl, alkaryl or arylalkyl moiety.

    8. The composition (C) according to claim 7, wherein the compound (O) is selected from the group consisting of: hindered phenol compounds selected from the group consisting of (d1) tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (aka e.g. Irganox? 1010), (d2) Thiodiethylene bis[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)propionate] (aka e.g. Irganox? 1035), (d3) Octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate (aka e.g. Irganox? 1076), and (d4) N,N-hexane-1,6-diylbis(3-(3,5-di-tert.-butyl-4-hydroxyphenylpropionamide)) (aka e.g. Irganox? 1098); and phosphite esters selected from the group consisting of (e3) Tris(2,4-di-tert.-butylphenyl)phosphite (aka e.g. IRGAFOS? 168); (e5) Bis(2,4-di-tert-butylphenol)pentaerythritol diphosphate (aka e.g. IRGAFOS? 126); (e6) Bis(2,6-di-terbutyl-4-methylphenyl)pentaerythritol-diphosphite (aka e.g. ADK STAB PEP-36); (e8) bis(2,4-di-tert-butyl-6-methyl phenyl) ethyl phosphite (aka e.g. IRGAFOS? 38); and wherein the compound (O) is preferably selected from the group consisting of: (d4) N,N-hexane-1,6-diylbis(3-(3,5-di-tert.-butyl-4-hydroxyphenylpropionamide)) (aka e.g. Irganox? 1098); and (e3) Tris(2,4-di-tert.-butylphenyl)phosphite (aka e.g. IRGAFOS? 168).

    9. The composition (C) according to claim 1, wherein the polymer (POS) may comprise only one of said epoxy or amine functional groups, or it may comprise a plurality thereof; and wherein said at least one epoxy or amine functional group may be comprised in polymer (POS) as a pendant group in a recurring unit, or may be comprised as chain ends.

    10. The composition (C) according to claim 9, wherein the polymer (POS) complies with formula (II): ##STR00063## wherein: each of Q, equal to or different from each other, is one group selected from the group consisting of epoxy groups and amine groups, preferably an epoxy group, or a group selected from C.sub.1-C.sub.10 alkyl groups and C.sub.6-C.sub.10 aromatic groups, with the provisio that at least one Q is one group selected from the group consisting of epoxy groups and amine groups, preferably is an epoxy group; R.sub.1, R.sub.2, R.sub.3 and R.sub.4, equal to or different from each other, are selected from C.sub.1-C.sub.10 alkyl groups and C.sub.6-C.sub.10 aromatic groups, n varies between 2 and 70, preferably between 2 and 60, and p is zero or 1.

    11. The composition (C) according to claim 10, wherein the polymer (POS) complies with formula (III): ##STR00064## wherein: each of Q, equal to or different from each other, is a group selected from the group consisting of epoxy groups and amine groups, preferably an epoxy group, or a group selected from C.sub.1-C.sub.10 alkyl groups and C.sub.6-C.sub.10 aromatic groups, with the provisio that at least one Q is group selected from the group consisting of epoxy groups and amine groups, preferably an epoxy group, preferably is an epoxy group; and n varies between 2 and 70, preferably between 2 and 60.

    12. A process comprising blending in the molten state: at least one poly(arylene sulfide) polymer [polymer (PAS)], and at least one polyorganosiloxane polymer having at least one epoxy functional group [polymer (POS)]; and at least one antioxidant compound [compound (O)], in an amount of 0.03 to 0.4% wt, with respect to the weight of polymer (PAS).

    13. The process of claim 12, wherein said blending in the molten state is performed by melt compounding, in continuous or batch devices.

    14. The process of claim 12, wherein during the said blending in the molten state, polymer (POS) at least partially reacts with polymer (PAS), creating block copolymer structures, including blocks derived from polymer (POS) and blocks derived from polymer (PAS).

    15. An article, part or composite material comprising a composition (C), the composition (C) comprising: at least one poly(arylene sulfide) polymer [polymer (PAS)], and at least one polyorganosiloxane polymer having at least one functional group selected from epoxy groups and amine groups [polymer (POS)]; and at least one antioxidant compound [compound (O)], in an amount of 0.03 to 0.4% wt, with respect to the weight of polymer (PAS), said article, part or composite material being selected from the group consisting of a cable coating, a cable tie, a metal pipe coating, a molded article, an extruded article or a three-dimensional (3D) object.

    16. The process of claim 12, further comprising manufacturing a three-dimensional (3D) object comprising the blend of the polymer (PAS), the polymer (POS), and the compound (O) using additive manufacturing.

    17. The process of claim 12, wherein said blending is performed in a twin-screw extruder.

    18. The process of claim 16, wherein the additive manufacturing is a method selected from the group consisting of fused deposition modelling (FDM), selective laser sintering (SLS), and multi-jet fusion (MJF).

    19. The process of claim 12, further comprising manufacturing an article, part or composite material comprising the blend of the polymer (PAS), the polymer (POS), and the compound (O), the article, part or composite material being selected from the group consisting of a cable coating, a cable tie, a metal pipe coating, a molded article, an extruded article, or a three-dimensional (3D) object.

    20. The process of claim 12, wherein the polymer (PAS) comprises recurring units (R.sub.PAS1) represented by the following formula:
    [-Ar.sub.1-S](R.sub.PAS1) wherein -Ar.sub.1- is selected from the group of formulae consisting of: ##STR00065## wherein: R, at each instance, is independently selected from the group consisting of a C.sub.1-C.sub.12 alkyl group, a C.sub.7-C.sub.24 alkylaryl group, a C.sub.7-C.sub.24 aralkyl group, a C.sub.6-C.sub.24 arylene group, and a C.sub.6-C.sub.18 aryloxy group; T is selected from the group consisting of a bond, CO, SO.sub.2, O, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, phenyl and CH.sub.2; i, at each instance, is an independently selected integer from 0 to 4; j, at each instance, is an independently selected integer from 0 to 3.

    Description

    EXPERIMENTAL SECTION

    Materials

    [0153] Ryton? QA200N PPS is a poly(phenylene sulfide) (PPS) commercially available from Solvay Specialty Polymers USA, LLC (PPS, hereinafter).

    [0154] KF105 is a dual-end type/epoxy modified reactive silicone fluid of formula:

    ##STR00057##

    whereas organic group is

    ##STR00058##

    with R=H or CH.sub.3, whereas n is such that the viscosity at 25? C. is 15 and the equivalent weight is 490 g/mol, commercially available from Shin-Etsu (KF105, hereinafter).

    [0155] IRGANOX? 1010 is tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl-propionate)] methane, commercially available from BASF (1010, herein after)

    [0156] IRGAFOS? 168 is Tris(2,4-di-tert.-butylphenyl)phosphite, commercially available from BASF (168, hereinafter)

    Methods

    DSC/Heat of Fusion

    [0157] DSC analyses were carried out on a TA Q2000 Differential Scanning calorimeter according to ISO 11357 and data was collected through a two heat-one cool method. The protocol used is the following: 1.sup.st heat cycle from ?10.00? C. to 320.00? C. at 10.00? C./min; isothermal for 5 minutes; 1.sup.st cool cycle from 320.00? C. to ?10.00? C. at 10.00? C./min; 2.sup.nd heat cycle from ?10.00? C. to 320.00? C. at 10.00? C./min. The melting temperature (T.sub.m) is recorded during the 2.sup.nd heat cycle and the melt crystallization temperature (T.sub.mc) is recorded during the cool cycle.

    Mechanical Properties

    [0158] Tensile properties were determined at room temperature (23? C.) according to ISO 527-2 at a speed of 1 mm/min for Tensile Modulus and 5 mm/min for the rest of the experiment (ISO527-1A specimens) and ISO 179/1eA for impact properties.

    Ageing Tests

    [0159] The samples were heat aged in a re-circulating air oven (Thermo Scientific Heratherm OMH60) set at set-point temperature (150, 175 or 200? C.). At various heat ageing times (48 hours, 96 hours, 240 hours, 504 hours and 1008 hours), the samples were removed from the oven, allowed to cool to room temperature and placed into sealed aluminium lined bags until ready for testing. Mechanical properties were measured according to the same procedure as before ageing.

    General Procedure for Making Compositions

    [0160] To make these experiments, a dry blend is first realized and for each formulation, the targeted mass ratios of the components were mixed in a vibratory shaker for 2-3 minutes to assure homogeneity. The contents of the bucket was then placed in gravimetric feeder and fed into the extruder (Coperion ZSK 26 in Alpharetta and a Clextral D32 in Lyon), melted, and mixed with screws designed to achieve a homogeneous melt composition. Temperature during extrusion is controlled under 320? C.

    [0161] The melt stream was cooled and fed into a pelletizer. The pellets were collected and kept in sealed plastic buckets until used for injection molding. Specimens obtained from injection molding were tested for their mechanical properties as such (DAM: dry-as-molded), and after aging, in the conditions listed in the tables below.

    [0162] The ingredients and their reciprocal amounts in the compositions and the mechanical properties of the samples before and after air oven ageing are reported in Tables below.

    TABLE-US-00006 TABLE 1 Formulations based on IRGAFOS? 168 Ingredient weight Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. parts 1C 2C 3 4 5 6 7C 8C PPS 100 100 100 100 100 100 100 100 KF105 1.5 1.5 1.5 1.5 1.5 1.5 1.5 168 1 0.05 0.1 0.2 0.3 0.5 1.0

    TABLE-US-00007 TABLE 2 Mechanical properties on DAM specimens Ex. 1C Ex. 2C Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7C Ex. 8C Tensile n.d. 3819 ? 3655 ? 3618 ? 3618 ? 3665 ? 3849 ? 3972 ? Modulus 44 12 26 22 60 46 62 (MPa).sup.(*.sup.) Strain at n.d. 16.46 ? 27.67 ? 28.24 ? 24.24 ? 28.03 ? 15.11 ? 12.06 ? break 2.03 2.73 2.46 3.23 4.78 4.46 2.10 (%).sup.(*.sup.) Notched n.d. 3.5 ? 3.3 ? 3.41 ? 3.53 ? 3.5 ? n.d. n.d. Charpy 0.4.sup.(**.sup.) 0.3 0.31 0.29 0.4 Impact .sup.(**.sup.)determined at 1 mm/m; ?standard deviation; .sup.(**.sup.)determined on a specimen comprising 1.6 phr of KF105.

    [0163] Mechanical properties on DAM specimens, as summarized above, are also sketched in graphical mode in FIG. 1; such graph well demonstrate that the addition of low amounts of compound (O), when combined with polymer (POS), is surprisingly effective in increasing significantly the flexibility, as represented by the strain at break values, while not significantly detrimentally affecting the mechanical strength (expressed by tensile modulus) nor the toughness (expressed by the Charpy impact).

    [0164] Mechanical properties of specimens before and after aging at temperatures of 150? C., 175? C. and 200? C. are summarized in Tables below.

    TABLE-US-00008 TABLE 3 Tensile strain at break on DAM and aged specimens Ex. 1C Ex. 2C Ex. 4 Tensile strain value value value at break (%) retention (%) retention (%) retention 150? C. DAM 7.12 100% 27.9 100% 27.93 100% 48 h 6.76 95% n.d. n.d. 21.6 77% 96 h 5.13 72% 9.95 36% 22.78 82% 240 h 4.77 67% 9.6 34% 25.2 90% 504 h 5.1 72% 8.69 31% 20.27 73% 1008 h 4.85 68% n.d. n.d. 19.14 69% 175? C. DAM 7.12 100% n.d. n.d. 27.93 100% 48 h 5.98 84% n.d. n.d. 23.06 83% 96 h 4.21 59% n.d. n.d. 17.46 63% 240 h 4.31 61% n.d. n.d. 15.16 54% 504 h 5.31 75% n.d. n.d. 14.36 51% 1008 h 3.04 43% n.d. n.d. 11.92 43% 200? C. DAM 7.12 100% n.d. 100% 27.93 100% 48 h 5.78 81% n.d. n.d. 10.95 39% 96 h 3.69 52% n.d. n.d. 11.77 42% 240 h 2.51 35% n.d. n.d. 8.35 30% 504 h 2.8 39% n.d. n.d. 2.14 8% 1008 h 1.38 19% n.d. n.d. 1.4 5% Ex. 7C Ex. 8C Tensile strain value value at break (%) retention (%) retention 150? C. DAM 15.11 100% 12.06 100% 48 h 16.95 112% 12.69 105% 96 h 13.94 92% 10.29 85% 240 h 9.21 61% 9.06 75% 504 h 9.17 61% 7.06 59% 1008 h 9.26 61% 6.6 55% 175? C. DAM 15.11 100% 12.06 100% 48 h 12.81 85% 9.36 78% 96 h 7 46% 8.41 70% 240 h 5.62 37% 6.6 55% 504 h 6.79 45% 4.45 37% 1008 h 4.3 28% 3.13 26% 200? C. DAM 15.11 100% 12.06 100% 48 h 8.27 55% 4.36 36% 96 h 4.08 27% 6.53 54% 240 h 4.4 29% 3.26 27% 504 h 2.12 14% 1.57 13% 1008 h 1.08 7% 0.85 7%

    [0165] Retention of Tensile Strength at break upon aging at temperatures of 150?, 175?, and 200? C. is also sketched, in graphical mode, in FIGS. 2, 3 and 4. From those pictures, it is clearly shown that the use of compound (O), even at high concentrations (1% wt) is not effective in achieving retention of mechanical properties of PPS in the absence of polymer (POS). When polymer (POS) is present, a synergistic effect is achieved when low amounts of compound (O) are used (see Ex. 4), with optimized performances, which is totally unexpected.

    TABLE-US-00009 TABLE 4 Formulations based on IRGANOX? 1010 Ingredient weight parts Ex. 2C Ex. 9C Ex. 10 Ex. 11C Ex. 12C PPS 100 100 100 100 100 KF105 1.5 1.5 1.5 1.5 1010 0.10 0.10 0.50 1.00

    TABLE-US-00010 TABLE 2 Mechanical properties on DAM specimens Ex. 2C Ex. 10 Ex. 11C Ex. 12C Tensile 3819 ? 44 3712 ? 23 3910 ? 36 3994 ? 36 Modulus (MPa).sup.(*.sup.) Strain 16.46 ? 2.03 25.41 ? 6.55 14.16 ? 1.81 130.58 ? 1.88 at break (%).sup.(*.sup.) (**) determined at 1 mm/m; ?standard deviation; (**) determined on a specimen comprising 1.6 phr of KF105.

    [0166] Mechanical properties on DAM specimens, as summarized above, confirm that, as already shown from FIG. 1, the addition of low amounts of compound (O), when combined with polymer (POS), is surprisingly effective in increasing significantly the flexibility, as represented by the strain at break values, while not significantly detrimentally affecting the mechanical strength (expressed by tensile modulus), while higher amounts of same compound (O) are such to detrimentally affect flexibility/toughening effect which is provided by the addition of polymer (POS)

    TABLE-US-00011 TABLE 3 Tensile strain at break on DAM and aged specimens Ex. 9C Ex. 10 Ex. 11C Tensile strain value value value at break (%) retention (%) retention (%) retention 150? C. DAM 4.93 100% 25.41 100% 14.16 100% 48 h 4.37 89% 12.62 89% 96 h 3.47 70% 11.45 81% 240 h 3.04 62% 10.57 75% 504 h 3.46 70% 9.76 69% 1008 h 3.82 77% 10.79 76% 175? C. DAM 4.93 100% 25.41 100% 14.16 100% 48 h 3.75 76% 11.44 81% 96 h 3.73 76% 7.18 51% 240 h 2.82 57% 6.72 47% 504 h 3.86 78% 4.03 28% 1008 h 3.31 67% 4.52 32% 200? C. DAM 4.93 100% 25.41 100% 14.16 100% 48 h 3.39 69% 5.42 38% 96 h 3.19 65% 5.41 38% 240 h 1.86 38% 4.23 30% 504 h 1.86 38% 1.26 9% 1008 h 1.25 25% 1.09 8%

    [0167] The data above show that the addition of large amounts of compound (O) in combination with polymer (POS) is not effective in achieving thermal stability, while low amounts of compound (O) have proven to be effective.