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EP4021978A1 - Transparente, hochhitzebeständige, flammhemmende zusammensetzungen für dünnwandanwendungen - Google Patents

Transparente, hochhitzebeständige, flammhemmende zusammensetzungen für dünnwandanwendungen

Info

Publication number
EP4021978A1
EP4021978A1 EP20775407.8A EP20775407A EP4021978A1 EP 4021978 A1 EP4021978 A1 EP 4021978A1 EP 20775407 A EP20775407 A EP 20775407A EP 4021978 A1 EP4021978 A1 EP 4021978A1
Authority
EP
European Patent Office
Prior art keywords
bisphenol
weight percent
carbonate
weight
transparent composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20775407.8A
Other languages
English (en)
French (fr)
Inventor
Fabrizio Micciche
Tony Farrell
Mark Adrianus Johannes van der Mee
Roland Sebastian Assink
Robert Dirk Van De Grampel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHPP Global Technologies BV
Original Assignee
SHPP Global Technologies BV
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Filing date
Publication date
Application filed by SHPP Global Technologies BV filed Critical SHPP Global Technologies BV
Publication of EP4021978A1 publication Critical patent/EP4021978A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates

Definitions

  • This disclosure relates to polycarbonate compositions, and in particular to transparent polycarbonate compositions, methods of manufacture, and uses thereof.
  • Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances.
  • a transparent composition comprising: greater than 40 to 97.5 weight percent of a poly(carbonate-bisphenol phthalate ester) comprising 1-50 weight percent of aromatic carbonate units and 50-99 weight percent of bisphenol phthalate ester units, each based on the sum of the weight of the carbonate units and the bisphenol phthalate ester units; 2.5-60 weight percent of a high heat copolycarbonate derived from high heat carbonate units derived from l,l-bis(4- hydroxyphenyl)-3, 3, 5-trimethyl-cyclohexane, N-phenyl phenolphthalein bisphenol, 4,4'-(l- phenylethylidene)bisphenol, 4,4'-(3,3-dimethyl-2,2-dihydro-lH-indene-I,l-diyl)diphenol, 1,1- bis(4-hydroxyphenyl)cyclododecane, 3,8-dihydroxy-5a,10b-diphenyl-coumarano-2’,
  • a method of manufacture comprises combining the above- described components to form a transparent composition.
  • an article comprises the above-described transparent composition.
  • a method of manufacture of an article comprises molding, extruding, or shaping the above-described transparent composition into an article.
  • compositions for thin- walled compositions are needed having a UL-94 flammability rating of V0 at 1.0 millimeter (mm) and/or 0.8 mm.
  • Some commercially available chlorine-free and bromine-free transparent compositions include anti -drip agents that result in decreased transparency or increased haziness.
  • compositions having high heat resistance and flammability ratings of VO at thicknesses of 1.5 mm, 1.2 mm, 1.0 mm, and/or 0.8 mm.
  • These compositions comprise a poly(carbonate-bisphenol phthalate ester), a high-heat copolycarbonate derived from high heat carbonate units and optionally, low heat carbonate units, and a Ci-i 6 alkyl sulfonate salt flame retardant.
  • the transparent compositions have a bromine or chlorine content, or a combined bromine and chlorine content of less than or equal to 100 parts per million by weight, less than or equal to 75 parts per million by weight, or less than or equal to 50 parts per million by weight, each based on the total parts by weight of the composition.
  • a molded sample of the transparent compositions have a UL 94 rating of V0 at a thickness of 1.5 mm, a UL 94 rating of V0 at a thickness of 1.2 mm, a UL 94 rating of V0 at a thickness of 1.0 mm, a UL 94 rating of V0 at a thickness of 0.8 mm, a percent transmission of greater than 80% determined according to ASTM D1003 at a thickness of 1.0 mm and/or 2.5 mm, and a haze of less than 5%, or less than 2%, or less than 1% determined according to ASTM D1003 at a thickness of 2.5 millimeter.
  • Polycarbonate as used herein means a polymer having repeating structural carbonate units of formula (1)
  • each R 1 is a C6-30 aromatic group, that is, contains at least one aromatic moiety.
  • R 1 may be derived from an aromatic dihydroxy compound of the formula HO-R'-OH, in particular of the formula
  • each of A 1 and A 2 is a monocyclic divalent aromatic group and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 .
  • one atom separates A 1 from A 2 .
  • each R 1 may be derived from a bisphenol of formula (2) wherein R a and R b are each independently a halogen, Ci-12 alkoxy, or Ci-12 alkyl, and p and q are each independently integers of 0-4. It will be understood that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen.
  • X a is a C1-60 bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each G, arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group.
  • the bridging group X a is single bond, -0-, -S-, -S(O)-, -S(0)2-, -C(O)-, or a C1- 60 organic group.
  • the C1- 60 organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the C 1-60 organic group may be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C 1-60 organic bridging group.
  • p and q is each 1
  • R a and R b are each a C 1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.
  • Polycarbonates include homopolycarbonates (wherein each R 1 in the polymer is the same), copolymers comprising different R 1 moieties in the carbonate (“copolycarbonates”), and copolymers comprising carbonate units and other types of polymer units, such as ester units.
  • a specific type of copolymer is a poly(ester-carbonate), also known as a polyester-polycarbonate.
  • Such polycarbonates further contain, in addition to recurring carbonate units of formula (1), repeating ester units of formula (3) wherein J is a divalent group derived from an aromatic dihydroxy compound (including a reactive derivative thereof), such as a bisphenol of formula (2), e.g., bisphenol A; and T is a divalent group derived from an aromatic dicarboxylic acid (including a reactive derivative thereof), preferably isophthalic or terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.
  • Copolyesters containing a combination of different T or J groups may be used.
  • the polyester units may be branched or linear.
  • J is derived from a bisphenol of formula (2), e.g., bisphenol A.
  • a portion of the groups J for example up to 20 mole percent (mol%) may be an aromatic dihydroxy compound, e.g., resorcinol, or C2-30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure, for example ethylene, n-propylene, i-proplyene, 1,4-butylene, 1,4-cyclohexylene, or 1, 4-methyl enecyclohexane.
  • all J groups are bisphenol groups of formula (2).
  • Aromatic dicarboxylic acids that may be used to prepare the polyester units include isophthalic or terephthalic acid, l,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, or a combination thereof. Acids containing fused rings may also be present, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or a combination thereof.
  • a specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91 :9 to 2:98.
  • a portion of the groups T for example up to 20 mol%, may be aliphatic, for example derived from 1,4-cyclohexane dicarboxylic acid. Preferably all T groups are aromatic.
  • the molar ratio of ester units to carbonate units in the polycarbonates may vary broadly, for example 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 25:75 to 75:25, or 2:98 to 15:85, depending on the desired properties of the final composition.
  • Specific poly(ester-carbonate)s are those including bisphenol A carbonate units and isophthalate/terephthalate-bisphenol A ester units, i.e., a poly (bisphenol A carbonate)-co- (bisphenol A-phthalate-ester) of formula (4a) wherein x and y represent the weight percent of bisphenol A carbonate units and isophthalate/terephthalate -bisphenol A ester units, respectively. Generally, the units are present as blocks. In an aspect, the weight ratio of carbonate units x to ester units y in the polycarbonates is 1:99 to 50:50, or 5:95 to 25:75, or 10:90 to 45:55.
  • Copolymers of formula (5) comprising 35- 45 wt% of carbonate units and 55-65 wt% of ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of 45:55 to 55:45 are often referred to as poly(carbonate- ester)s (PCE).
  • Copolymers comprising 15-25 wt% of carbonate units and 75-85 wt% of ester units wherein the ester units have a molar ratio of isophthalate to terephthalate from 98:2 to 88:12 are often referred to as poly(phthalate-carbonate)s (PPC).
  • the poly(ester-carbonate)s may for example may have, for example, an Mw of 2,000-100,000 g/mol, preferably 3,000-75,000 g/mol, more preferably 4,000-50,000 g/mol, more preferably 5,000-35,000 g/mol, and still more preferably 17,000-30,000 g/mol.
  • Mw 2,000-100,000 g/mol, preferably 3,000-75,000 g/mol, more preferably 4,000-50,000 g/mol, more preferably 5,000-35,000 g/mol, and still more preferably 17,000-30,000 g/mol.
  • Molecular weight determinations are performed using GPC using a cross linked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with bisphenol A homopolycarbonate standards. Samples are eluted at a flow rate of 1.0 ml/min with methylene chloride as the eluent.
  • the poly(ester-carbonate)s may be, for example, present from greater than 40-97.5 wt%, 45-97.5 wt%, 49-97.5 wt%, 41-90 wt%, 50-90 wt%, or 40-60 wt%, each based on the total weight of the composition.
  • the transparent composition includes a high heat copolycarbonate that includes a high heat carbonate group, optionally together with a low heat carbonate group.
  • a combination of different high heat groups or low heat groups may be used.
  • the low heat carbonate group may be derived from bisphenols of formula (2) as described above wherein X a is a Ci-is bridging group.
  • the low heat carbonate group is derived from bisphenol A, which provides the low heat group of the following formula. (Bisphenol A group)
  • the high heat carbonate group is derived from a high heat bisphenol monomer.
  • a high heat bisphenol monomer is a monomer where the corresponding homopolycarbonate of the monomer has a glass transition temperature (Tg) of 170°C or higher, determined per ASTM D3418 with a 20 °C/min heating rate.
  • Examples of such high heat bisphenol groups include groups of formulas (6) to (12) wherein R c and R d are each independently a Ci-12 alkyl, C2-12 alkenyl, C3-8 cycloalkyl, or Ci-12 alkoxy, each R f is hydrogen or both R f together are a carbonyl group, each R 3 is independently Ci- 6 alkyl, R 4 is hydrogen, Ci- 6 alkyl, or phenyl optionally substituted with 1-5 Ci- 6 alkyl groups, each R 6 is independently C1-3 alkyl, or phenyl, preferably methyl, X a is a C6-12 polycyclic aryl, C3-18 mono- or polycycloalkylene, C3-18 mono- or polycycloalkylidene, -C(R h )(R g )- wherein R h is hydrogen, Ci-12 alkyl, or C6-12 aryl and R g is C6-10 alkyl, C 6-8 cycloalkyl, or
  • R c and R d are each independently a C1-3 alkyl, or Ci- 3 alkoxy, each R 6 is methyl, each R 3 is independently C1-3 alkyl, R 4 is methyl, or phenyl, each R 6 is independently C1-3 alkyl or phenyl, preferably methyl,
  • X a is a C6-12 polycyclic aryl, C3- 18 mono- or polycycloalkylene, C3-18 mono- or polycycloalkylidene, -C(R f )(R g )- wherein R f is hydrogen, Ci-12 alkyl, or C6-12 aryl and R g is C6-10 alkyl, C 6 -8 cycloalkyl, or C6-12 aryl, or -(Q ⁇ x- G-(Q 2 ) y - group, wherein Q 1 and Q 2 are each independently a C1-3 alkylene and G is a C3-10 cycl
  • R c and R d are the same as defined for formulas (6) to (12), each R 2 is independently C1-4 alkyl, m and n are each independently 0-4, each R 3 is independently C1-4 alkyl or hydrogen, R 4 is Ci- 6 alkyl or phenyl optionally substituted with 1-5 Ci- 6 alkyl groups, and g is 0-10.
  • each bond of the bisphenol group is located para to the linking group that is X a .
  • R c and R d are each independently a C1-3 alkyl, or C1-3 alkoxy
  • each R 2 is methyl
  • x is 0 or 1
  • y is 1
  • m and n are each independently 0 or 1.
  • the high heat bisphenol group is preferably of formula (1 la-2) or (12a-2) wherein R 4 is methyl or phenyl, each R 2 is methyl, and g is 1-4.
  • the high heat bisphenol group is derived from N-phenyl phenolphthalein bisphenol (PPPBP, also known as 2- phenyl-3,3’-bis(4-hydroxyphenyl)) or from l,l-bis(4-hydroxyphenyl)-3, 3, 5-trimethyl- cyclohexane (BP-TMC). group)
  • This high heat copolycarbonate may include 0-90 mol%, or 10-80 mol% of low heat aromatic carbonate units, preferably bisphenol A carbonate units; and 10-100 mol%, preferably 20-90 mol% of high heat aromatic carbonate units, even more preferably wherein the high heat carbonate units are derived from l,l-bis(4-hydroxyphenyl)-3, 3, 5-trimethyl- cyclohexane, , 4,4'-(l-phenylethylidene)bisphenol, 4, 4 '-(3, 3-dimethyl-2, 2-dihydro- lH-indene- 1 , 1 -diy Ijdiphenol, 1 , 1 -bis(4-hydroxyphenyl)cyclododecane, 3 , 8-dihydroxy-5a, 1 Ob-diphenyl- coumarano-2 , ,3’,2,3-coumarane, or a combination thereof, wherein each amount is based on the total mo
  • the high heat copolycarbonate includes 60-80 mol% of bisphenol A carbonate units and 20-40 mol% of high heat aromatic carbonate units derived from l,l-bis(4-hydroxyphenyl)-3, 3, 5-trimethyl-cyclohexane, N-phenyl phenolphthalein bisphenol, or a combination thereof, wherein each amount is based on the total moles of the carbonate units, which sums to 100 mol%.
  • the high heat copolycarbonates comprising high heat carbonate units may have, for example, an Mw of 10,000-50,000 g/mol, or 16,000-300,000 g/mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopolycarbonate references. GPC samples are prepared at a concentration of 1 mg per ml and are eluted at a flow rate of 1.5 ml per minute.
  • GPC gel permeation chromatography
  • the high heat copolycarbonates may be present, for example, from 2.5-60 wt%, 2.5-55 wt%, 2.5-51 wt%, 10-69 wt%, 10-59 wt%, 10-50 wt%, or 40-60 wt%, each based on the total weight of the composition.
  • the transparent compositions may include a homopolycarbonate (wherein each R 1 in the polymer is the same).
  • the homopolycarbonate in the transparent composition is derived from a bisphenol of formula (2), preferably bisphenol A, in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene in formula (2).
  • the homopolycarbonate may have, for example, an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3-1.5 deciliters per gram (dl/gm), preferably 0.45-1.0 dl/gm.
  • the homopolycarbonate may have, for example, a weight average molecular weight (Mw) of 10,000-200,000 grams per mol (g/mol), preferably 20,000-100,000 g/mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopolycarbonate references.
  • Mw weight average molecular weight
  • the homopolycarbonate is a bisphenol A homopolycarbonate having an Mw of 18,000-35,000 grams/mole, preferably 20,000-25,000 g/mol; or a bisphenol A homopolycarbonate having a weight average molecular weight of 25,000-35,000 g/mol, preferably 27,000-32,000 g/mol; or a combination thereof, each as measured as described above.
  • the polycarbonates may be manufactured by processes such as interfacial polymerization and melt polymerization, which are known, and are described, for example, in WO 2013/175448 A1 and WO 2014/072923 Al.
  • An end-capping agent also referred to as a chain stopper agent or chain terminating agent
  • Branched polycarbonate blocks may be prepared by adding a branching agent during polymerization, for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p- hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (1,3,5 -tri s((p- hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • a branching agent for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p- hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (1,3,5 -tri s((p- hydroxypheny
  • the branching agents may be added at a level of 0.05-2.0 wt%. Combinations comprising linear polycarbonates and branched polycarbonates may be used.
  • the transparent compositions include Ci-i 6 alkyl sulfonate salt flame retardants. Examples include potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, and tetraethylammonium perfluorohexane sulfonate.
  • the Ci-i 6 alkyl sulfonate salt flame retardant may be present, for example, from 0.1-0.5 wt%, 0.1-0.3 wt%, 0.2-0.5 wt%, or 0.2-0.4 wt% of the transparent composition.
  • potassium diphenyl sulfone sulfonate or salts such as NaiCC , K2CO3, MgCCE, CaCCE, and BaCCE, or fluoro-anion complexes such as L13AIF6, BaSiF 6 , KBF4, K3AIF6, KAIF4, K2S1F6, or Na3AlF 6 may also be used in addition to the C1-16 alkyl sulfonate salt flame retardants.
  • An additional flame retardant different from the C1-16 alkyl sulfonate salt flame retardants may be present.
  • the flame retardant different from the C1-16 alkyl sulfonate salt flame retardant is an organophosphorus flame retardant.
  • the aromatic group may be a substituted or unsubstituted C3-30 group containing one or more of a monocyclic or polycyclic aromatic moiety (which may optionally contain with up to three heteroatoms (N, O, P, S, or Si)) and optionally further containing one or more nonaromatic moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl.
  • the aromatic moiety of the aromatic group may be directly bonded to the organophosphorus flame retardant, or bonded via another moiety, for example an alkylene group.
  • the aromatic moiety of the aromatic group may be directly bonded to the organophosphorus flame retardant, or bonded via another moiety, for example an alkylene group.
  • the aromatic group is the same as an aromatic group of the polycarbonate backbone, such as a bisphenol group (e.g., bisphenol A), a monoarylene group (e.g., a 1,3- phenylene or a 1,4-phenylene), or a combination comprising at least one of the foregoing.
  • a combination of different organophosphorus flame retardants may be used.
  • the aromatic group may be directly or indirectly bonded to the phosphorus, or to an oxygen of the organophosphorus flame retardant (i.e., an ester).
  • the organophosphorus flame retardant is a monomeric phosphate.
  • G corresponds to a monomer used to form the polycarbonate, e.g., resorcinol.
  • Exemplary phosphates include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like.
  • Di- or polyfunctional organophosphorus flame retardants are also useful, for example, compounds of the formulas o wherein each G 1 is independently a Ci-30 hydrocarbyl; each G 2 is independently a Ci-30 hydrocarbyl or hydrocarbyloxy; X a is as defined in formula (3) or formula (4); each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30.
  • X a is a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene.
  • Specific organophosphorus flame retardants are inclusive of acid esters of formula (9) wherein each R 16 is independently Ci-s alkyl, C 5-6 cycloalkyl, C 6-20 aryl, or C 7-12 arylalkylene, each optionally substituted by Ci- 12 alkyl, specifically by C 1-4 alkyl and X is a mono- or poly nuclear aromatic C 6-30 moiety or a linear or branched C 2-30 aliphatic radical, which may be OH- substituted and may contain up to 8 ether bonds, provided that at least one R 16 or X is an aromatic group; each n is independently 0 or 1; and q is from 0.5 to 30.
  • each R 16 is independently C 1-4 alkyl, naphthyl, phenyl(Ci- 4 )alkylene, aryl groups optionally substituted by Ci- 4 alkyl; each X is a mono- or poly-nuclear aromatic C 6-30 moiety, each n is 1; and q is from 0.5 to 30.
  • each R 16 is aromatic, e.g., phenyl; each X is a mono- or poly-nuclear aromatic C 6-30 moiety, including a moiety derived from formula (2); n is one; and q is from 0.8 to 15.
  • each R 16 is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl, one of the following divalent groups or a combination comprising one or more of the foregoing; n is 1; and q is from 1 to 5, or from 1 to 2.
  • at least one R 16 or X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A, resorcinol, or the like.
  • Organophosphorus flame retardants of this type include the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts.
  • the organophosphorus flame retardants containing a phosphorus-nitrogen bond may be a phosphazene, phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. These flame- retardant additives are commercially available.
  • the organophosphorus flame retardant containing a phosphorus-nitrogen bond is a phosphazene or cyclic phosphazene of the formulas wherein wl is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w is independently a Ci-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group.
  • at least one hydrogen atom of these groups may be substituted with a group having an N, S, O, or F atom, or an amino group.
  • each R w may be a substituted or unsubstituted phenoxy, an amino, or a polyoxyalkylene group.
  • R w may further be a crosslink to another phosphazene group.
  • exemplary crosslinks include bisphenol groups, for example bisphenol A groups. Examples include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like.
  • the phosphazene has a structure represented by the formula
  • phenoxyphosphazenes having the aforementioned structures are LY202 manufactured and distributed by Lanyin Chemical Co., Ltd, FP-110 manufactured and distributed by Fushimi Pharmaceutical Co., Ltd, and SPB-100 manufactured and distributed by Otsuka Chemical Co., Ltd.
  • the organosulfonic stabilizer may be an aryl or aliphatic sulfonic acid, including a polymer thereof, an aryl or an aliphatic sulfonic acid anhydride, or an aryl or aliphatic ester of an aryl or aliphatic sulfonic acid, or a polymer thereof.
  • the organosulfonic stabilizer is a Ci-30 alkyl sulfonic acid, a C6-30 aryl sulfonic acid, a C7-30 alkylarylene sulfonic acid, a C7-30 arylalkylene sulfonic acid, or an aromatic sulfonic acid polymer; an anhydride of a Ci-30 alkyl sulfonic acid, a C6-30 aryl sulfonic acid, a C7-30 alkylarylene sulfonic acid, or a C7-30 arylalkylene sulfonic acid; or a C6-30 aryl ester of a Ci-30 alkyl sulfonic acid, a C6-30 aryl sulfonic acid, a C7-30 alkylarylene sulfonic acid, a C7-30 arylalkylene sulfonic acid, or an aromatic sulfonic acid polymer; or a Ci-30 alipha
  • organosulfonic stabilizers are preferably represented by formula (14)
  • R 7 is each independently a Ci- 30 alkyl, C 6-30 aryl, C 7-30 alkylarylene, C 7-30 arylalkylene, or a polymer unit derived from a C 2-32 ethylenically unsaturated aromatic sulfonic acid or its corresponding Ci- 32 alkyl ester.
  • the C 2-32 ethylenically unsaturated aromatic sulfonic acid may be of the formula wherein R 9 is hydrogen or methyl, and R 8 is as defined in formula (14).
  • R 9 is hydrogen or methyl
  • R 8 is as defined in formula (14).
  • the ethylenically unsaturated group and the sulfonic acid or ester group are located para on the phenyl ring.
  • each R 7 in the compound of formula (8) may be the same or different, but preferably each R 7 is the same.
  • R 7 is a C7-10 alkylarylene or a polymer unit derived from a C2-14 ethylenically unsaturated aromatic sulfonic acid
  • R 7 is a C7-10 alkylarylene and R 8 is a hydrogen or Ci- 6 alkyl.
  • R 7 is a C7-10 alkylarylene and R 8 is a hydrogen or C12-25 alkyl, or R 8 is a C14-20 alkyl.
  • R 7 is a polymer unit derived from a C2-14 ethylenically unsaturated aromatic sulfonic acid, preferably p-styrene sulfonic acid or para-methyl styrene sulfonic acid, such that in formula (14) R 8 is hydrogen.
  • the organosulfonic stabilizer is a Ci-10 alkyl ester of a C7-12 alkylarylene sulfonic acid, preferably of p-toluene sulfonic acid. More preferably the stabilizer is a Ci- 6 alkyl ester of p-toluene sulfonic acid, and even more preferably is butyl tosylate.
  • the organosulfonic stabilizer is an anhydride of a C7-12 alkylarylene sulfonic acid, preferably para-toluene sulfonic anhydride as shown in Table 13.
  • R 7 is a Cn-24 alkylarylene sulfonic acid, and R 8 is hydrogen.
  • R 7 is a C16-22 alkylarylene sulfonic acid, and R 8 is hydrogen.
  • the organosulfonic stabilizer may be used in an amount of 2 to 40 ppm, more preferably 2 to 20 ppm, still more preferably 4 to 15 ppm, or 4 to 10 ppm, or 4 to 8 ppm by weight based on the total weight composition.
  • the transparent compositions may further comprise an additive composition that includes various additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the transparent composition, in particular heat resistance, transparency, and flame retardance. Combinations of additives may be used.
  • the additive composition may include an impact modifier, flow modifier, particulate filler (e.g., a particulate polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive, plasticizer, lubricant, release agent (such as a mold release agent), antistatic agent, anti-fog agent, antimicrobial agent, colorant (e.g., a dye or pigment), surface effect additive, radiation stabilizer, a flame retardant different from the C1-16 alkyl sulfonate salt flame retardant, or a combination thereof.
  • particulate filler e.g., a particulate polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal
  • antioxidant heat stabilizer
  • light stabilizer light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive
  • plasticizer such as a mold release agent
  • release agent such as a mold release agent
  • antistatic agent such as
  • plasticizers which include, for example, phthalic acid esters (e.g., octyl-4, 5-epoxy- hexahydrophthalate), tris-(octoxycarbonylethyl)isocyanurate, di- or polyfunctional aromatic phosphates (e.g., resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A); poly-alpha-olefins; epoxidized soybean oil; silicones, including silicone oils (e.g., poly(dimethyl diphenyl siloxanes); fatty acid esters (e.g., Ci-32alkyl stearyl esters, such as methyl stearate and stearyl stearate and esters of stearic acid such as pentaeryth
  • phthalic acid esters e.g., octy
  • Antioxidant additives include organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert- butyl-4-hydroxyhydrocinnamate)] methane; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene- bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-
  • the transparent composition is essentially free of chlorine and bromine.
  • Essentially free of chlorine and bromine refers to materials produced without the intentional addition of chlorine or bromine or chlorine or bromine containing materials. It is understood however that in facilities that process multiple products a certain amount of cross contamination may occur resulting in bromine or chlorine levels typically on the parts per million by weight scale. With this understanding it may be readily appreciated that “essentially free of bromine and chlorine” may be defined as having a bromine or chlorine content of less than or equal to 100 parts per million by weight (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm.
  • “essentially free of bromine and chlorine” means a total bromine and chlorine content of less than or equal to 100 parts per million by weight, or less than or equal to 75 ppm, or less than or equal to 50 ppm.
  • this definition is applied to the flame retardant it is based on the total weight of the flame retardant.
  • this definition is applied to the transparent composition it is based on the total parts by weight of the transparent composition.
  • the transparent compositions may be manufactured by various methods. For example, powdered polycarbonates, flame retardant, or other optional components are first blended, optionally with fillers in a HENSCHEL-Mixer high speed mixer. Other low shear processes, including but not limited to hand mixing, may also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components, for example the reinforcing filler, may be incorporated into the composition by feeding directly into the extruder at the throat or downstream through a sidestuffer. Additives may also be compounded into a masterbatch with a desired polymeric polymer and fed into the extruder.
  • the extruder is generally operated at a temperature higher than that necessary to cause the composition to flow.
  • the extrudate is immediately quenched in a water bath and pelletized.
  • the pellets so prepared may be one-fourth inch long or less as desired. Such pellets may be used for subsequent molding, shaping, or forming.
  • Transparent compositions may be produced by manipulation of the process used to manufacture the polycarbonate composition.
  • One example of such a process to produce transparent polycarbonate compositions is described in U.S. Patent Application No. 2003/0032725.
  • a molded sample of the transparent composition may have a UL 94 rating of V0 at a thickness of 1.5 millimeter.
  • a molded sample of the transparent composition may have a UL 94 rating of V0 at a thickness of 1.2 millimeter.
  • a molded sample of the transparent composition may have a UL 94 rating of V0 at a thickness of 1.0 millimeter.
  • a molded sample of the transparent composition may have a UL 94 rating of V0 at a thickness of 0.8 millimeter.
  • a molded sample of the transparent composition may have a Vicat B120 softening temperature of at least 160°C as measured according to ISO 306.
  • a molded sample of the transparent composition may have a heat deflection temperature a heat deformation temperature of at least 145°C measured according to the ISO-75 standard with a 5.5 Joule hammer on 4 millimeter-thick bars and a load of 1.8 megapascals.
  • a molded sample of the transparent composition may have a flame test rating of V0, as measured according to UL-94 at a thickness of 0.8 millimeter or at a thickness of 0.6 millimeter.
  • a molded sample of the transparent composition may have a percent transmission of greater than 80%, or greater than 85%, as determined according to ASTM D1003, and a haze of less than 5%, or less than 2%, or less than 1% determined according to ASTM D1003 at a thickness of 2.5 millimeter.
  • the transparent compositions may be used in articles including a molded article, a thermoformed article, an extruded film, an extruded sheet, one or more layers of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article.
  • the article has no significant part distortion or discoloration when the article is subjected to a secondary operation such as over-molding, lead-free soldering, wave soldering, low temperature soldering, or coating, or a combination thereof.
  • the articles may be partially or completely coated with, e.g., a hard coat, a UV protective coat, an anti-refractive coat, an anti -reflective coat, a scratch resistant coat, or a combination thereof, or metallized.
  • Exemplary articles include a lens, a light guide, a waveguide, a collimator, an optical fiber, a window, a door, a visor, a display screen, an electronic device, a scientific or medical device, a safety shield, a fire shield, wire or cable sheathing, a mold, a dish, a tray, a screen, an enclosure, glazing, packaging, a gas barrier, an anti-fog layer, or an anti-reflective layer.
  • Vicat softening temperatures were measured on 4 mm-thick ISO bars in accordance with the ISO-306 standard at a load of 50 N and a speed of 120°C per hour (B120).
  • ASTM Izod notched impact (“ASTM INI”) values were determined according to ASTM D256-2010 on a 3.2 mm-thick bar at room temperature.
  • ISO Izod notched impact (“ISO INI”) values were determined according to ISO 180/1 A at room temperature using a 5.5 J hammer on a multi-purpose ISO 3167 type A sample having a thickness of 4 mm.
  • Comparative Examples 1-3 and 6 in Table 3 show that the inclusion of Rimar salt in poly(phthalate-carbonate) (PPC) compositions resulted in molded samples that were opaque (haze greater than 1%) at 2.5 mm.
  • Comparative Examples 3-4 in Table 3 show that the addition of KSS instead of Rimar salt to PPC resulted in an adverse affect on the flammability, (i.e.,V2 at thicknesses of 1.5 mm and 1.2 mm).
  • compositions that contain 0 to 5 wt% of PPPBP-BPA are opaque.
  • Examples 28-36 show that haze lower than 1% was maintained for all PPPBP- BPA/PPC compositions within the range 10/90 to 90/10. However, a loading of PPPBP-BPA that was equal to or higher than about 69 wt% (see Comparative Examples 34 and 36) adversely affected the flammability properties (e.g., UL 94 flame test rating of V2 at 1.0 mm thickness and significant number of flaming drips).
  • a transparent composition comprising: 40-97.5 weight percent of a poly(carbonate-bisphenol phthalate ester) comprising 1-50 weight percent of aromatic carbonate units and 50-99 weight percent of bisphenol phthalate ester units, each based on the sum of the weight of the carbonate units and the bisphenol phthalate ester units; 2.5-60 weight percent of a high heat copolycarbonate derived from high heat carbonate units derived from l,l-bis(4- hydroxyphenyl)-3, 3, 5-trimethyl-cyclohexane, N-phenyl phenolphthalein bisphenol, 4,4'-(l- phenylethylidene)bisphenol, 4,4'-(3,3-dimetliyl-2,2-dihydro-lH-indene-l,l-diyl)diphenol, 1,1- bis(4-hydroxyphenyl)cyclododecane, 3,8-dihydroxy-5a,10b-diphenyl-coumar
  • Aspect 2 The transparent composition of aspect 1, comprising greater than 40 to 60 weight percent, preferably 45-55 weight percent, of the poly(carbonate-bisphenol phthalate ester); 40-60 weight percent, preferably 45-55 weight percent, of the high heat copolycarbonate, optionally, 1-20 weight percent of bisphenol A homopolycarbonate as the homopolycarbonate;
  • Aspect 3 The transparent composition of any one of the preceding aspects, wherein the poly(carbonate-bisphenol phthalate ester) has the formula wherein the weight ratio of carbonate units x to ester units y is 10:90-45:55, and the ester units have a molar ratio of isophthalate to terephthalate from 98:2-88:12.
  • Aspect 4 The transparent composition of any one of the preceding aspects, wherein the weight ratio of carbonate units to ester units is 75:25-85: 15.
  • Aspect 5 The transparent composition of any one of the preceding aspects, wherein the high heat aromatic carbonate units of the high heat copolycarbonate are derived from l,l-bis(4-hydroxyphenyl)-3, 3, 5-trimethyl-cyclohexane, N-phenyl phenolphthalein bisphenol, or a combination thereof.
  • Aspect 6 The transparent composition of any one of the preceding aspects, wherein low heat aromatic carbonate units are present and comprise bisphenol A carbonate units.
  • Aspect 7 The transparent composition of any one of the preceding aspects, wherein the C M6 alkyl sulfonate salt flame retardant comprises potassium perfluorobutane sulfonate, potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, or a combination thereof, preferably potassium perfluorobutane sulfonate.
  • Aspect 8 The transparent composition of any one of the preceding aspects comprising 0.1-0.3 weight percent of the Ci-i 6 alkyl sulfonate salt flame retardant.
  • Aspect 9 The transparent composition of any one of the preceding aspects, wherein a molded sample has a heat deformation temperature of at least 145°C measured according to the ISO-75 standard with a 5.5 Joule hammer on 4 millimeter-thick bars and a load of 1.8 megapascals; a Vicat softening temperature of at least 160°C as measured according to the ISO-306 standard at a load of 50 newtons and a speed of 120°C per hour on 4 millimeter bars; or a combination thereof.
  • Aspect 10 The transparent composition of any one of the preceding aspects, wherein the additive composition is present and comprises an impact modifier, a flow modifier, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, an ultraviolet absorbing additive, a plasticizer, a lubricant, a release agent, an antistatic agent, an anti-fog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, optionally, a flame retardant different from the Ci-i 6 alkyl sulfonate salt flame retardant, or a combination thereof.
  • Aspect 11 The transparent composition of aspect 10, wherein flame retardant different from the C M6 alkyl sulfonate salt flame retardant is an organophosphorus flame retardant comprising a phosphazene, phosphate, phosphite, phosphonate, phosphinate, phosphine oxide, phosphine, or a combination thereof, preferably comprising an aromatic group.
  • Aspect 12 The transparent composition of any one of the preceding aspects comprising greater than 40 to 60 weight percent of a poly(bisphenol A carbonate-bisphenol A phthalate ester) as the poly(carbonate-bisphenol phthalate ester), wherein the weight ratio of carbonate units to ester units is 10:90-45:55, and the ester units have a molar ratio of isophthalate to terephthalate from 98:2-88:12; 40-60 weight percent of the high heat copolycarbonate, wherein the high heat carbonate units of the copolycarbonate comprise units derived from l,l-bis(4-hydroxyphenyl)-3, 3, 5 -trimethyl-cyclohexane, N-phenyl phenolphthalein bisphenol, or a combination thereof; optionally, 1-20 weight percent of bisphenol A homopolycarbonate as the homopolycarbonate;
  • Aspect 13 The transparent composition of any one of the preceding aspects, wherein the organosulfonic stabilizer is present and comprises a Ci-io alkyl ester of a C7-12 alkylarylene sulfonic acid, preferably of p-toluene sulfonic acid, more preferably a Ci- 6 alkyl ester of p-toluene sulfonic acid, even more preferably butyl tosylate; or a bisphenol A homopolycarbonate as the homopolycarbonate is present and has a weight average molecular weight from 18,000-35,000 grams/mole, preferably 20,000-25,000 grams/mole; or a weight average molecular weight from 25,000-35,000 grams/mole, preferably 27,000-32,000 grams/mole; or a combination thereof, each as measured via gel permeation chromatography using bisphenol A homopolycarbonate standards; or a combination thereof.
  • the organosulfonic stabilizer is present and comprises a Ci-io
  • Aspect 14 An article comprising the transparent composition of any one of the preceding aspects, preferably wherein the article is a lens, a light guide, a waveguide, a collimator, an optical fiber, a window, a door, a visor, a display screen, an electronic device, a scientific or medical device, a safety shield, a fire shield, wire or cable sheathing, a mold, a dish, a tray, a screen, an enclosure, glazing, packaging, a gas barrier, an anti-fog layer, or an anti- reflective layer.
  • Aspect 15 A method for forming the article according to aspect 14, comprising molding, casting, or extruding the transparent composition to provide the article.
  • compositions, methods, and articles may alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
  • alkyl means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or, propylene (-(CH 2 ) 3 - )).
  • Cycloalkylene means a divalent cyclic alkylene group, -CiTHn-x, wherein x is the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
  • Aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.
  • Arylene means a divalent aryl group.
  • Alkylarylene means an arylene group substituted with an alkyl group.
  • Arylalkylene means an alkylene group substituted with an aryl group (e.g., benzyl).
  • halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups may be present.
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
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EP20775407.8A 2019-08-30 2020-08-28 Transparente, hochhitzebeständige, flammhemmende zusammensetzungen für dünnwandanwendungen Withdrawn EP4021978A1 (de)

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US20030032725A1 (en) 2001-06-26 2003-02-13 General Electric Company Transparent polycarbonate polyester composition and process
US9115283B2 (en) * 2011-03-31 2015-08-25 Sabic Global Technologies B.V. Heat resistant clear polycarbonate-polysiloxane compounds
EP2764075A1 (de) 2011-10-08 2014-08-13 SABIC Innovative Plastics IP B.V. Flammengehäuse aus kunststofff und verfahren zu seiner herstellung
US20130317142A1 (en) 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Flame retardant thermoplastic compositions, methods of manufacture thereof and articles comprising the same
EP2730618B1 (de) 2012-11-07 2016-10-12 SABIC Global Technologies B.V. Verfahren zur Herstellung von Polycarbonatzusammensetzungen
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