WO2023111086A1 - Dispositifs électroniques personnels comprenant une composition de polyamide - Google Patents

Dispositifs électroniques personnels comprenant une composition de polyamide Download PDF

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WO2023111086A1
WO2023111086A1 PCT/EP2022/085970 EP2022085970W WO2023111086A1 WO 2023111086 A1 WO2023111086 A1 WO 2023111086A1 EP 2022085970 W EP2022085970 W EP 2022085970W WO 2023111086 A1 WO2023111086 A1 WO 2023111086A1
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Prior art keywords
personal electronic
electronic device
mol
polyamide
polymer composition
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PCT/EP2022/085970
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English (en)
Inventor
Stéphane JEOL
Arthur René Henri BERTRAND
Véronique Bossennec
Lindsey ANDERSON
Xianhai FU
Xiaoling Xu
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Solvay Specialty Polymers Usa, Llc
Solvay Sa
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Publication of WO2023111086A1 publication Critical patent/WO2023111086A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • PC polymer composition
  • PA polyamide
  • Personal electronic devices exposed to challenging environments e.g., those having high moisture (e.g., >50% humidity), high temperature (e.g., >35 °C), or comprising biological or environmental contaminants, must exhibit a diverse array of properties in order to garner commercial acceptance.
  • high moisture e.g., >50% humidity
  • high temperature e.g., >35 °C
  • biological or environmental contaminants must exhibit a diverse array of properties in order to garner commercial acceptance.
  • Moisture absorption can provide access for contaminants and cause surface irregularities that are visually unappealing, as well as a reduction in strength, rigidity and dimensional stability.
  • Portions of the devices in contact with heating elements or otherwise exposed to elevated temperatures are desirably heat resistant and/or flame retardant. Such devices must also be physically strong enough to tolerate routine handling, as well as accidentally applied forces, without breaking.
  • UV resistance of external surfaces of devices used outdoors or in areas with high UV exposure is also desirable, so that the devices retain their color and/or visual appeal for their useful life.
  • polysulfones Due to their inherent heat resistance, polysulfones have conventionally been used in the manufacture of personal electronic devices that incorporate heating elements. Polysulfones also typically have glass transition temperatures sufficiently high so that, even if some moisture absorption occurs, mechanical properties are not appreciably detrimentally impacted. However, many polysulfones may not naturally exhibit appreciable UV resistance. And so, while personal electronic devices comprising polysulfones enjoy commercial acceptance, some such devices may not possess the UV resistance needed to retain color integrity over their useful life. In these instances, additional ingredients, such as paints, stains or dyes, may be used in order to maintain visual appeal of the device for its lifetime. Though effective, this solution can add to the cost and complexity of the manufacturing process for the device.
  • Some semi-crystalline polyamides have also been used in the manufacture of personal electronic devices, and many perform very well in this capacity.
  • semi-crystalline polyamides have glass transition temperatures sufficient to provide devices comprising the polyamide with mechanical integrity at high temperatures.
  • some semi-crystalline polyamides may be prone to moisture absorption, which can lead not only to additive migration, but also, to a decrease in the glass transition temperature Tg.
  • Additive migration can provide the personal electronic device with a “mottled” or irregular surface appearance, which can result in a reduction in, or loss of, commercial acceptance.
  • a decrease in Tg can translate into changes in mechanical properties that may render the polyamides less suitable for certain applications.
  • the invention relates to a personal electronic device as defined in any one of claims 1-30.
  • the invention also relates to a flavor delivery system as defined in claim 31 .
  • the invention also relates to the use as defined in claim 30 or 31 . [0014] These subject-matters are defined more precisely below.
  • a personal electronic device comprises a polymer composition (PC).
  • the polymer composition (PC) comprises at least 30.0 wt.% of a polyamide (PA) comprising at least 70.0 mol% recurring units R(PAI) according to formula (VII): wherein R2 is a C4 to C30, Ce to C24, or Cs to C alkylene group, mol% is relative to the total moles of recurring units in the polyamide and wt.% is relative to the total weight of the polymer composition (PC).
  • PA polyamide
  • VII formula
  • the polymer composition (PC) optionally comprises at least one halogen free flame retardant, at least on reinforcing agent and at least one additive other than the halogen free flame retardant. More particularly, the polymer composition (PC) may comprise from 0 wt.% to 20 wt.% of the at least one halogen free flame retardant, from 0 wt.% to 50 wt.% of the at least one reinforcing agent, and from 0 wt.% to 30 wt.% of at least one additive other than the halogen free flame retardant.
  • Personal electronic devices that find particular benefit from this combination of properties include mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices, flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/ medical equipment and portable game consoles.
  • the invention relates to a personal electronic device comprising a polymer composition (PC) comprising a polyamide (PA).
  • the polyamide (PA) is derived from the polycondensation of a diamine component (A) comprising 4,4- diaminodicyclohexylmethane (“PACM”) and a dicarboxylic acid component (B) comprising an aliphatic dicarboxylic acid (“X”).
  • the polyamide (PA) comprises at least 70.0 mol% of “PACMX” recurring units.
  • the diamine component (A) may optionally comprise an additional diamine and/or the dicarboxylic acid component (B) may comprise an additional dicarboxylic acid.
  • the polyamide thus comprises at least one other recurring unit comprising a diamine different from PACM and/or a dicarboxylic acid different from the aliphatic dicarboxylic acid.
  • the polymer composition (PC) comprising the polyamide (PA) exhibits a combination of properties such as impact, break and moisture resistance.
  • the polymer composition (PC) provides heat/flame resistance on par with that provided by the polysulfones conventionally used in applications where the same is desired.
  • the polymer composition (PC) also exhibits UV resistance better than that exhibited by polymer compositions not including polyamides comprising the PACMX recurring units. UV resistance can provide the polymer composition (PC) with color integrity (notably of the surface) that otherwise must be provided by paints, stains or dyes.
  • the personal electronic device comprising the polymer composition (PC)Zpolyamide (PA) also avoids the development of surface imperfections via the migration of additives upon exposure of the device to moisture. Such surface imperfections are significant factors leading to market rejection of personal electronic devices comprising polymer compositions/polyamides other than those provided here.
  • thermoplastic polymer The amount of energy in the form of heat required to bring about a change of state of a thermoplastic polymer from the solid to the liquid form is the heat of fusion (“AHf”) of the polymer, and the temperature at which this change of state occurs is called the melting temperature (“Tm”).
  • AHf heat of fusion
  • Tm melting temperature
  • Amorphous materials lack a measurable Tm and have a AHf less than 5.0 J/g.
  • halogen or “halo” include fluorine, chlorine, bromine and iodine.
  • aliphatic denotes an open chain chemical structure. Aliphatic compounds may be saturated or unsaturated, and linear or branched.
  • cycloaliphatic refers to an aliphatic compound that includes a nonaromatic ring structure.
  • alkyl as well as derivative terms such as “alkoxy”, “acyl” and “alkylthio”, include within their scope straight chain and branched chain. Examples of alkyl groups are methyl, ethyl, 1 -methylethyl, propyl and
  • aryl is inclusive of both mono- and polynuclear aryl groups.
  • aryl thus refers for instance to a phenyl, indanyl or naphthyl group.
  • the polyamide (PA) is formed and comprises recurring units formed from a reaction mixture (RM) comprising a diamine component (A) and a dicarboxylic acid component (B).
  • RM reaction mixture
  • A diamine component
  • B dicarboxylic acid component
  • the diamine component (A) contains each diamine in the reaction mixture and the dicarboxylic acid component (B) contains each dicarboxylic acid in the reaction mixture.
  • the diamine component (A) comprises 4,4-diaminodicyclohexylmethane (PACM) and optionally at least one diamine different from 4,4- diaminodicyclohexylmethane.
  • PAM 4,4-diaminodicyclohexylmethane
  • At least 30.0 mol%, at least 40.0 mol%, or at least 50.0 mol% of the 4,4-diaminodicyclohexylmethane are in the trans/trans configuration.
  • a trans/trans content of at least 30.0 mol% of the total isomer mol% of the 4,4-diaminodicyclohexylmethane i.e., trans- trans, cis-trans and cis-cis
  • a polyamide produced from a reaction mixture comprising the same is semi-crystalline.
  • the proportion of the 4,4-diaminodicyclohexylmethane in the diamine component (A) is at least 70.0 mol%, at least 75.0 mol%, at least 80.0 mol%, or at least 85.0 mol%.
  • the diamine component (A) consists essentially of 4,4-diaminodicyclohexylmethane.
  • the expression “consist essentially” means in the context of the invention in relation to the diamine component that the diamine component (A) comprises 4,4-diaminodicyclohexylmethane and may also comprise up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least another diamine, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
  • the diamine component (A) consists of 4,4- diaminodicyclohexylmethane, i.e., the proportion of 4,4- diaminodicyclohexylmethane in the diamine component (A) is 100 mol%.
  • the proportion of 4,4-diaminodicyclohexylmethane in the diamine component is from 70.0 mol% to 100 mol%, from 75.0 mol% to 99.0 mol%, from 80.0 mol% to 98.0 mol%, or from 85.0 mol% to 97.0 mol%.
  • mol% of the referenced diamine is relative to the total number of moles of diamines in the diamine component.
  • the Dicarboxylic Acid Component (B) comprises an aliphatic dicarboxylic acid (“X”) of formula (III):
  • R2 is more particularly -(CH2)n- where n is an integer between 4 and 30 or between 6 and 24 or between 8 and 18.
  • n 12, 14, 15 or 16.
  • the dicarboxylic acid component (B) comprises at least one dicarboxylic acid(s), different from the aliphatic dicarboxylic acid of formula (III).
  • the dicarboxylic acid component (B) consists essentially of the aliphatic dicarboxylic acid (“X”) of formula (III).
  • the expression “consist essentially” means in the context of the invention in relation to the dicarboxylic acid component that the dicarboxylic acid component (B) comprises the aliphatic dicarboxylic acid (“X”) of formula (III) and may also comprise up to 2.0 mol%, preferably up to 1 .0 mol%, even more preferably up to 0.5 mol%, of at least another diacid, this proportion in mol% being based on the total amount of diacids in the dicarboxylic acid component (B).
  • the polyamide (PA) is formed by the polycondensation reaction of the components of the reaction mixture (RM), i.e., the diamine component (A), the dicarboxylic acid component (B). More specifically, the condensation leads to the formation of amide bonds.
  • the polyamide comprises recurring units R(PAI) represented by formula (VII): wherein R2 is as defined above.
  • RAI recurring units
  • the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is at least 70.0 mol%. This proportion may be at least 75.0 mol%, at least 80.0 mol% or at least 85.0 mol%.
  • the polyamide (PA) consists of the recurring units R(PAI) according to formula (VII), i.e. , the proportion of recurring units R( AI) in the polyamide (PA) is 100 mol%.
  • the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is no more than 99.0 mol%, no more than 98.0 mol%, or no more than 97.0 mol%. In some embodiments, the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is from 70.0 mol% to 100.0 mol%, from 75.0 mol% to 99.0 mol%, from 80.0 mol% to 98.0 mol%, or from 85.0 mol% to 97.0 mol%. [0055] As used herein, mol% in reference to a recurring unit of the polyamide (PA) is relative to the total moles of all recurring units in the polyamide.
  • the end-groups in the polyamide (PA) are selected in the group of -NH2, - COOH and amide end-groups. Indeed, the end-groups in the polyamide (PA) may be -NH2 or -COOH. Yet, when the polycondensation involves the addition of an end-capping agent, these end-groups may be converted, partially or totally, into amide end-groups.
  • R is more particularly a linear or branched C2-C18 alkyl group or a C5-C10 cycloalkyl group.
  • R' is more particularly a linear or branched C2-C18 alkyl group.
  • the monocarboxylic acid may advantageously be selected in the group consisting of benzoic acid; cyclohexanoic acid; R-COOH where R is a linear or branched C2-C18 alkyl group and combination of two or more of these acids.
  • R is the radical derived from the acid of formula R-COOH.
  • the monocarboxylic acid may more particularly be selected in the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combination of two or more of these acids.
  • the monocarboxylic acid (end-capping agent) is more particularly of formula CH3-(CH2)n-COOH where n is an integer between 0 and 16.
  • the primary amine (end-capping agent) may advantageously be selected in the group consisting of the amines of formula R'-NH2 where R' is a linear or branched C2-C18 alkyl group. R' is the radical derived from the amine of formula R'-NH2.
  • the primary amine (end-capping agent) is more particularly of formula CH3- (CH2)n'-NH2 where n' is an integer between 2 and 18.
  • the primary amine may more particularly be selected in the group consisting of propyl amine, butylamine, pentylamine, hexylamine, 2- ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n- hexadecylamine, stearylamine, cyclohexylamine and combination of two or more of these amines.
  • the proportion of the end groups can be quantified by 1 H NMR or by potentiomtric techniques.
  • the polyamide (PA) generally has a glass transition temperature Tg of at least 90 °C.
  • the Tg may be at least 100 °C or at least 110 °C.
  • Tg is advantageously at least 120°C.
  • the Tg is generally no more than 200 °C.
  • the Tg may be no more than 190
  • the Tg may be from 90 °C to 200 °C, from 100 °C to 190 °C or from 110 °C to 180 °C.
  • the Tg may also be from 90 °C to 190 °C, from 90 °C to 180 °C, or from 90 °C to 170 °C.
  • Tg may more particularly be between 120°C and 140°C.
  • the polyamide (PA) has a Tm of at least 180 °C, at least 190 °C, or at least
  • Tm may also be at least 220°C.
  • the polyamide has a Tm of no more than 290 °C, no more than 285 °C, or no more than 280 °C. Tm may also be no more than 240°C.
  • Tm may be from 180 °C to 290 °C, from 190 °C to 285 °C or from 200 °C to 280 °C. Tm may also from 220°C to 240°C.
  • the polyamide (PA) is semi-crystalline or microcrystalline.
  • the polyamide has a AHf of at least 5.0 J/g, preferably at least 7.0 J/g, or at least 10.0 J/g. In some embodiments, the polyamide has a AHf of no more than 80.0 J/g, no more than 70.0 J/g or no more than 60.0 J/g. In some embodiments, the polyamide has a AHf of from 5.0 J/g to 80.0 J/g, from 7.0 J/g to 70.0 J/g, or from 10.0 J/g to 60.0 J/g. AHf may befrom 5.0 J/g to 50.0 J/g, from 5.0 J/g to 40.0 J/g, or from 5.0 J/g to 30.0 J/g.
  • Tg, Tm and AHf of the polyamide are measured according to ASTM D3418.
  • the polyamide (PA) has a number average molecular weight (“Mn”) from 1 ,000 g/mol to 40,000 g/mol.
  • Mn may be from 2,000 g/mol to 35,000 g/mol, from 4,000 to 30,000 g/mol, or from 5,000 g/mol to 20,000 g/mol.
  • Mn may also advantageously be between 10,000 and 20,000 g/mol.
  • the number average molecular weight Mn can be determined by gel permeation chromatography (GPC) using ASTM D5296.
  • the polyamide (PA) has preferably a water absorption, by immersion in water at 23°C of less than 8 wt.%, preferably less than 7.0 wt.%, preferably less than
  • the water absorption is most preferably lower than 3.0 wt%.
  • the water absorption at 23°C is determined by
  • Wbefore is the weight of the shaped specimen in its original dry state and Wafter is the weight of the shaped specimen after immersion for the specified time.
  • the polyamide (PA) described herein is prepared by polycondensation through reacting the components of the reaction mixture (RM).
  • the total number of moles of diamines in the reaction mixture is substantially equimolar to the total number of moles of dicarboxylic acids in the reaction mixture.
  • substantial equimolar denotes a value that is ⁇ 3.0% of the indicated number of moles.
  • total number of moles of diamines in the reaction mixture is ⁇ 3.0% of the total number of moles of dicarboxylic acids in the reaction mixture.
  • the polyamide (PA) is generally prepared by reacting the monomers (e.g. the diamines, dicarboxylic acids) of the reaction mixture (RM) in the presence of less than 40 wt.%, less than 30 wt.%, less than 20 wt.%, less than 10 wt.% or even with no added water.
  • the monomers e.g. the diamines, dicarboxylic acids
  • RM reaction mixture
  • Catalysts are usually added to the reaction mixture (RM).
  • catalysts are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid. Phosphites are suitable stabilizers.
  • reaction mixture (RM) may also comprise at least one end capping agent as disclosed above.
  • the monomers may be caused to react by heating the reaction mixture (RM) to a temperature of at least Tm + 10°C, Tm being the melting temperature of the polyamide.
  • the temperature at which the reaction mixture is heated is generally at least 200°C or even at least 250°C.
  • the polyamide (PA) and/or the polymer composition (PC) of the invention exhibit(s) at least one, at least two, at least three, at least four, at least five, at least six or all of the following properties:
  • a glass transition temperature of greater than 90°C preferably greater than 100°C, preferably greater than 110°C, preferably greater than 120°C.
  • the polyamide (PA) and/or the polymer composition (PC) advantageously exhibit(s) a AE no more than 5.0, preferably no more than 4.0, preferably no more than 3.0, preferably no more than 2.0, after 240 hours as measured according to ISO4892-2:2013/AMD1 :2021.
  • Formula of AE is given in the experimental section.
  • the polyamide (PA) and/or the polymer composition (PC) advantageously exhibit(s) a break resistance, as evidenced by an IZOD impact strength of at least 50.0 KJ/m 2 , preferably at least 60.0 KJ/m 2 , preferably at least 70.0 KJ/m 2 , preferably at least 80.0 KJ/m 2 , as measured according to ISO180.
  • the polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) a flame resistance, as evidenced by a flammability rating of V1 or V2 measured according to the LIL94 standard.
  • UL 94 is the Standard for Safety of Flammability of Plastic Materials for Parts in Devices and Appliances testing, is a plastics flammability standard released by Underwriters Laboratories of the United States. The standard determines the material’s tendency to either extinguish or spread the flame once the specimen has been ignited.
  • the polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) an Elongation at Break of greater than 2.0%, or greater than 2.5%, or greater than 3.0%, as measured according to ISO527-2.
  • the polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) a strength at yield (Break) of greater than 45 MPa, preferably greater than 50 MPa, preferably greater than 55 MPa, as measured according to
  • the polymer composition (PC) consists of the polyamide (PA), i.e., the proportion of the polyamide (PA) in the polymer composition (PC) is 100 wt.%. As used herein and unless explicitly stated otherwise, the proportion of a component in the polymer composition (PC) is relative to the total weight of the polymer composition (PC).
  • the polymer composition (PC) may comprise the polyamide (PA) in a proportion of at least 30.0 wt.%, at least 35.0 wt.%, at least 40.0 wt.%, or at least 45.0 wt.%.
  • the proportion of polyamide (PA) in the polymer composition (PC) may be no more than 99.0 wt.%, no more than 95.0 wt.%, no more than 90.0 wt.%, or no more than 85.0 wt.%.
  • the proportion of the polyamide (PA) in the polymer composition (PC) is from 30.0 wt.% to 100.0 wt.%, from 35.0 wt.% to 99.0 wt.%, from 40.0 wt.% to 95.0 wt.%, or from 45.0 wt.% to 90.0 wt.%.
  • the polymer composition includes one or more polymeric materials in addition to the at least one polyamide described herein. Suitable additional polymeric material(s) include other polyamides, poly(arylene sulphides) poly(phenylene sulphides), poly(aryl ether sulfones), poly(biphenyl ether sulfones), polysulfones, poly(aryl ether ketones) and poly(ether ether ketones). [00101] In some embodiments, the polymer composition comprises a halogen free flame retardant, one or more reinforcing agents and/or one or more additives different from the halogen free flame retardant.
  • the polymer composition (PC) may optionally comprise at least one halogen free flame retardant.
  • halogen free flame retardants include, but are not limited to, metal dialkyl phosphinates (e.g. aluminum diethyl phosphinate), organophosphates (e.g. triphenylphosphates) and phosphonates (e.g. dimethyl methylphosphonates).
  • halogen free flame retardant may be selected in the group consisting of the compounds according to the formulae below:
  • R a and Rb are identical or different and are selected in the group consisting of linear or branched Ci-Cs-alkyl groups and aryl groups
  • R c is selected in the group consisting of linear or branched Ci-C -alkylene groups
  • M is a metal ion selected in the group of Al, Ca and
  • n is 1 or 3
  • x is 1 or 2.
  • the halogen free flame retardant may for instance be of formula [00106] If the polymer composition (PC) comprises at least one halogen free flame retardant, the total proportion of halogen free flame retardant(s) in the polymer composition (PC) is at least 1.0 wt.%, at least 2.0 wt.%, or at least 5.0 wt.%. The total proportion of halogen free flame retardant(s) may be no more than 20.0 wt. %, no more than 18.0 wt. %, nor more than 17.0 wt.%, or no more than 15.0 wt.
  • the total proportion of halogen free flame retardant(s) is from 0 wt.% to 20.0 wt.%, from 1.0 wt.% to 18.0 wt.%, from 2.0 wt.% to 17.0 wt. % or from 5.0 wt.% to 15.0 wt.%.
  • suitable reinforcing agents include, but are not limited to, mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite and any combination of these.
  • mineral fillers such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate
  • Suitable reinforcing agents can be selected from fibrous and particulate reinforcing agents.
  • a fibrous reinforcing agent is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least 5, at least 10, at least 20 or at least 50.
  • Suitable fibrous reinforcing agents e.g. glass fibers or carbon fibers
  • the fibers have an average length of from 3 mm to 10 mm, from 3 mm to 8 mm, from 3 mm to 6 mm, or from 3 mm to 5 mm. In other embodiments, the fibers have an average length of from 10 mm to 50 mm, from 10 mm to 45 mm, from 10 mm to 35 mm, from 10 mm to 30 mm, from 10 mm to 25 mm, or from 10 mm to 20 mm.
  • the average length of the fibers can be taken as the average length of the fibers prior to incorporation into the polymer composition or can be taken as the average length of the fibers within the polymer composition.
  • the reinforcing agent is desirably a fibrous filler and preferably a fibrous filler that is able to withstand the high temperature applications. Glass fibers are particularly preferred.
  • All glass fiber types such as A, C, D, E, M, S, R, T glass fibers (as described in chapter 5.2.3, pages 43-48 of Additives for Plastics Handbook, 2nd ed., John Murphy), or any mixtures thereof may be used. Additional descriptions of E, R, S and T glass fibers can be found in, e.g., Fiberglass and Glass Technology, Wallenberger, Frederick T.; Bingham, Paul A. (Eds.), 2010, XIV, chapter s, pages 197-225.
  • the glass fiber is a high modulus glass fiber.
  • High modulus glass fibers have an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343.
  • Examples of high modulus glass fibers include, but are not limited to, R, S and T glass fibers.
  • R, S and T glass fibers are composed essentially of oxides of silicon, aluminum and magnesium, and typically from 62-75 wt. % of SiO , from 16-28 wt. % of AI2O3 and from 5-14 wt. % of MgO.
  • R, S and T glass fibers comprise less than 10 wt. % of CaO.
  • High modulus glass fibers include S-1 and S-2 glass fibers, commercially available from Taishan and AGY, respectively.
  • the morphology of the glass fiber is not particularly limited and the glass fiber can be round, i.e. , have a circular cross-section, or flat, i.e. , have a non-circular (e.g., oval, elliptical or rectangular) cross-section.
  • the use of a reinforcing agent in the polymer composition is optional.
  • the total concentration of reinforcing agents in the polymer composition is at least 5 wt. %, at least 10 wt. %, or at least 15 wt. %.
  • the total concentration of reinforcing agents is no more than 50 wt. %, no more than 45 wt. %, or no more than 40 wt. %,
  • the total concentration of reinforcing agents is from 0 wt. % to 50 wt.%, from 5 wt.% to 50 wt.%, from 10 wt.% to 45 wt. % or from 15 wt.% to 40 wt.%, based upon the total weight of the polymer composition.
  • the polymer composition (PC) may optionally comprise one or more additives selected from the group consisting of tougheners, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, nucleating agents, antioxidants and any combination thereof.
  • additives selected from the group consisting of tougheners, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, nucleating agents, antioxidants and any combination thereof.
  • the polymer composition (PC) includes a toughener.
  • a toughener is generally a low Tg polymer, with a Tg for example below room temperature, below 0°C or even below -25°C. As a result of its low Tg, the toughener is typically elastomeric at room temperature. Tougheners can be functionalized polymers and are therefore typically reactive with other components of the polymer composition.
  • Suitable tougheners can be selected from polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene-rubbers (EPR); ethylene-propylene-diene monomer rubbers (EPDM); ethyleneacrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA), ethylene-vinylacetate (EVA); acrylonitrile-butadiene-styrene rubbers (ABS), block copolymers styrene ethylene butadiene styrene (SEBS); block copolymers styrene butadiene styrene (SBS); core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or mixture of one or more of the above.
  • EPR ethylene
  • a toughener can be functionalized by copolymerization of monomers containing reactive functionalities or from the grafting of reactive groups onto the toughener.
  • functionalized tougheners are notably terpolymers of ethylene, acrylic ester and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate; copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styreneacrylonitrile copolymers grafted with maleic anhydride; ABS copolymers grafted with maleic anhydride.
  • the total additive proportion in the polymer composition is at least 0.1 wt.%, at least 0.2 wt.%, at least 0.3 wt.%, at least 0.4 wt.%, or at least 0.5 wt.%.
  • the total additive concentration in the polymer composition is no more than 30 wt.%, no more than 25 wt.%., no more than 20 wt.%, no more than 15 wt.% or no more than 10 wt.%.
  • the total additive concentration in the polymer composition is from 0 wt.
  • % to 30 wt.% 0.1 wt.% to 30 wt.%, from 0.2 wt.% to 25 wt.%, from 0.3 wt.% to 20 wt.%, from 0.4 wt.% to 15 wt.% or from 0.5 wt.% to 10 wt.%.
  • the polymer composition (PC) can be prepared according to methods well known in the art.
  • the polymer composition (PC) can be made by melt-blending the polyamide (PA) and the other ingredients of the polymer composition (PC) (e.g. any desired halogen free flame retardants, reinforcing agents, and/or other additives).
  • Any melt-blending method may be used to combine the polyamide and any other desired components.
  • polymeric ingredients and non- polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer.
  • the ingredients may be fed all at once, via gradual addition, or in batches. If a reinforcing agent presents a long physical shape (for example, a long glass fiber), drawing extrusion molding may be used to prepare a reinforced composition.
  • the personal electronic device can be prepared in a two-step process wherein the polymer composition (PC) is formed into pellets, and then the pellets are injection molded to produce the personal electronic device.
  • the personal electronic device may be prepared directly from the polymer composition in an integrated, one-step process.
  • the personal electronic device can be made from the polymer composition (PC) by methods including, but not limited to, melt-mixing processes. Meltmixing processes are typically carried out by heating the polymer components above the highest melting temperature and glass transition temperature of the thermoplastic polymers thereby forming a melt of the thermoplastic polymers. In some embodiments, the processing temperature ranges from about 240- 400°C, preferably from about 250-380°C, from about 260-360°C.
  • the polymer composition (PC) is melt-mixed in an extruder, and the high temperature personal electronic device injection molded therefrom.
  • an extruder fitted with means for dosing all the desired components of the polymer composition to the extruder, whether to the extruder's throat or to the melt.
  • the components may be fed simultaneously as a powder or granule mixture, also known as dry-blend, or may be fed separately.
  • the order of combining the components during melt-mixing is not critical.
  • the components can be mixed in a single batch, such that the desired amounts of each component are added together and subsequently mixed. However, the total desired amount of each component does not have to be mixed as a single quantity.
  • a partial quantity of one or more components can be initially added and mixed and, subsequently, some or all of the remainder can be added and mixed.
  • the method may comprise if needed several successive steps of melt-mixing or extrusion under different conditions.
  • the method may also comprise one or more cooling steps.
  • Exemplary personal electronic devices that find particular benefit from the combination of properties exhibited by the present polyamide (PA) and polymer composition (PC) include personal electronic devices, and particularly those that incorporate a heating element or are exposed to high temperatures (e.g., greater than 40°C) during use.
  • Examples of such personal electronic devices include, but are not limited to, mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices (e.g., a smart watch, smart glasses and the like), flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/medical equipment and portable game consoles.
  • the polymer composition (PC) can be used to form all, or a part of, any component of the personal electronic device. Significant benefit from the combination of properties provided by the polymer composition may be realized when the polymer composition (PC) is used in a component that is expected to be exposed to UV radiation, moisture, temperature and/or mechanical challenge in the course of its useful life. Housings or casings and parts thereof are but one example of a component wherein the advantages provided by the polymer composition (PC) may find particular applicability.
  • housing is meant to indicate any portion of a personal electronic device that provides cover and/or protection to the/other operative components of the device.
  • housings or parts thereof can function to protect internal and electronic components from impact or damage from environmental influences, such as moisture or UV radiation and can also function to give the personal electronic device strength.
  • Housings or housing parts include covers, cover plates, backbones (structural components to which other components attach), mouthpieces, hoods or lids, frames and parts or components that support these.
  • One example of a personal electronic device that finds particular advantage in the combination of properties provided by the present polyamide (PA) and polymer composition (PC) is a flavor delivery device. And so, in some embodiments, the personal electronic device is a flavor delivery device.
  • Flavor delivery devices can be used for delivery of an aerosol containing one or more active ingredients and/or flavors to the user of the flavor delivery system via inhalation.
  • Flavor delivery systems typically include a reservoir or compartment for holding a liquid, gel or solid flavor vehicle, a heating element operatively disposed relative to the reservoir or compartment, and a power source, among other components.
  • a plastic housing typically surrounds and supports the reservoir, heating element and power source.
  • An air inlet may be provided at an end of the plastic housing, with a mouthpiece provided at an opposing end.
  • the flavor delivery system may be activated by the press of a button, detection of an inhalation at the mouthpiece, or wireless communication with an external controller. Once activated, heat provided by the heating element releases the flavor from the flavor vehicle.
  • Flavor delivery devices are well known in the art and are described in, e.g., International Publication No. WO 2020/150400, US Publication No. 2015/025669 and US Publication No. 2018/0274110. The entire contents of each of these is hereby incorporated by reference herein, for any and all purposes.
  • the polymer composition (PC) or the polyamide (PA) can thus be used to form at least a portion of the housing of the flavor delivery device.
  • the polymer composition forms at least a portion of an exterior surface of the housing.
  • the housing of flavor delivery devices may be exposed to sweat, humidity, high temperature and/or UV exposure during use, the advantages of the polymer composition provided herein will be particularly appreciated by a user of such devices.
  • the polyamide composition (PC) is not used to form interior components.
  • the invention thus also relates to a flavor delivery system for delivery of an aerosol containing one or more active ingredients and/or flavors including a reservoir for holding the ingredient(s) and/or flavor(s), a heating element and a power source wherein the system also includes a housing made of or comprising the polymer composition (PC) of the invention.
  • PC polymer composition
  • PA10T (Vicnyl® 6100 Kingfa).
  • Test specimens according to Comparative Examples C1 and C2 and Inventive Example E1 were injection molded into standard dumbbell-shaped ISO type 1A tensile specimens on a Toshiba ISG 150 Injection Molder.
  • the test specimens has the following nominal dimensions: full length of 170 mm, gauge length of 75 mm, parallel section length of 80 mm, parallel section width of 10 mm, grip section width of 20 mm, and thickness of 4 mm.
  • IZOD impact strength of inventive and comparative unnotched samples was measured according to ISO180.
  • UV resistance was measured according to ISO4892-2:2013/AMD1 :2021 , Method B, cycle n.1 . Samples were visually inspected every 24 hours. Color parameters L*, a* and b* were measured after 96 hours, 168 hours, 216 hours and 240 hours. Delta E was calculated as follows:
  • the pH of the solution was adjusted to a value of 6.5 ⁇ 0.1 using ammonium hydroxide solution (1 % by weight).
  • a piece of cotton gauze was moistened with the sweat solution and placed over one end of the surface of the samples, covering no more than 20% of the length of the sample. The other end of each sample was placed into a bath of the solution. The samples and bath were placed into a sealed container and the sealed container placed into a temperature controlled chamber at 60C. After 48 hours, the samples were wiped dry with a clean cloth and allowed to cool to room temperature.
  • PC polymer compositions
  • the components were initially mixed in a plastic bucket and sealed.
  • the bucket was placed on a vibratory shaker for 2-3 minutes to assure homogeneity.
  • the so obtained mixture was then placed in a K-TronT-35 gravimetric feeder and fed into the Coperion ZSK-26 twin screw extruder, melted, and mixed with screws designed to achieve a homogeneous melt composition.
  • the melt stream was cooled and fed into a Maag Primo 60E pelletizer.
  • the pellets were collected and kept in sealed plastic buckets until used for injection molding.
  • Tg was measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans were used for each DSC test: a first heat up to 340°C, followed by a first cool down to 30°C, followed by a second heat up to 350°C.
  • DSC Differential Scanning Calorimetry
  • the Tg was determined from the second heat up.
  • inventive sample E1 exhibits outstanding resistance to UV, especially as compared to comparative samples C1 and C2. Only sample E1 exhibited an elongation at yield, thereby exhibiting ductile behavior. Samples C1 and C2 broke before yielding, thereby exhibiting fragile behavior. Further, E1 could not be broken in the impact resistance test, indicating that this sample would provide a personal electronic device into which it is incorporated with robust protection against damage from impact.

Abstract

L'invention concerne un dispositif électronique personnel. Le dispositif électronique personnel comprend une composition polymère. La composition polymère comprend au moins 30 % en poids d'un polyamide qui à son tour comprend au moins 70 % en moles de motifs récurrents de PACMX. La composition de polyamide et/ou polymère présente une combinaison unique de propriétés qui la rendent appropriée pour une utilisation dans des dispositifs électroniques personnels exposés à des environnements difficiles. En particulier, les compositions de polyamide/polymère présentent une résistance, une rigidité, une stabilité dimensionnelle, une résistance à l'humidité, une résistance à la flamme/chaleur ainsi qu'une stabilité aux UV suffisantes pour être utilisées dans des dispositifs électroniques personnels sélectionnés dans le groupe constitué par des téléphones mobiles, des assistants numériques personnels, des ordinateurs portables ou des tablettes, des dispositifs informatiques pouvant être portés, des systèmes de libération d'arômes, des caméras, des lecteurs audio ou des radios portables, des récepteurs de système de géolocalisation, des dispositifs médicaux/équipements médicaux et des consoles de jeux portables.
PCT/EP2022/085970 2021-12-15 2022-12-14 Dispositifs électroniques personnels comprenant une composition de polyamide WO2023111086A1 (fr)

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US20180274110A1 (en) 2017-03-23 2018-09-27 Kabushiki Kaisha Toshiba Laminated electrolyte membrane, membrane electrode assembly, water electrolysis cell, stack, and water electrolysis apparatus
WO2020150400A1 (fr) 2019-01-15 2020-07-23 Juul Labs, Inc. Dispositifs de vaporisateur
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US20100062272A1 (en) * 2006-12-13 2010-03-11 Evonik Degussa Gmbh Transparent part
US20140179850A1 (en) * 2012-12-21 2014-06-26 Ems-Patent Ag Stain-resistant article and use thereof
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