WO2016170468A1

WO2016170468A1 - Polycarbonate blends with improved heat resistance

Info

Publication number: WO2016170468A1
Application number: PCT/IB2016/052208
Authority: WO
Inventors: Huanbing WANG; Hongtao Shi
Original assignee: Sabic Global Technologies B.V.
Priority date: 2015-04-21
Filing date: 2016-04-18
Publication date: 2016-10-27

Abstract

The disclosure concerns polycarbonate compositions comprising 55-90 wt% polycarbonate; 0-30 wt% filler; and 5-15 wt% flame retardant that comprises a homopolymer of (I) the composition having a heat deflection temperature (HDT) value of at least 100 °C at a load of 1.82 mPa on a 3.2 mm sample as measured according to ASTM D648.

Description

POLYCARBONATE BLENDS WITH IMPROVED HEAT RESISTANCE

RELATED APPLICATIONS

[0001] The application claims benefit of U.S. Patent Application No. 62/150,593 filed on April 21, 2015, the disclosure of which is incorporated herein in its entirety.

TECHNICAL FIELD

[0002] The disclosure concerns polycarbonate blends showing improved heat resistance.

BACKGROUND

[0003] Flame retardants like bisphenol A bis(diphenyl phosphate) (BPADP) or resorcinol bis(diphenyl phosphate) (RDP) are known to adversely affect the heat resistance of polymer compositions. In polycarbonate (PC) blends, a 2-4 °C reduction in heat deflection temperature (HDT) is typically observed with 1% phosphate flame retardant (FR) addition. The deterioration is particularly pronounced for PC and its blends versus many other polymer compositions. There is a need in the art for flame retardant PC compositions that maintain good heat deflection temperature.

SUMMARY

[0004] In some aspects the disclosure concerns polycarbonate compositions comprising: 55-90 wt% polycarbonate; 0-30 wt% filler; and 5-15 wt% flame retardant that comprises a homopolymer

the composition having a heat deflection temperature (HDT) value of at least 100 °C at a load of 1.82 mPa on a 3.2 mm sample as measured according to ASTM D648; wherein all weight percent values are based on the total weight of the composition and the combined weight percent value of all components does not exceed 100 wt%. Certain polycarbonate compositions comprise a blend of polycarbonates. Some polycarbonate compositions have 10-30 wt% filler. The polycarbonate composition may comprise a combination of (i) the homopolymer and (ii) a phosphate-containing flame retardant such as resorcinol diphosphate (RDP).

[0005] In other aspects, the disclosure concerns articles comprising polycarbonate compositions described herein.

[0006] In addition, the disclosure concerns methods of making such polycarbonate compositions and articles comprising such polycarbonate compositions.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

Polycarbonate Polymer

[0007] The terms "polycarbonate" or "polycarbonates" as used herein includes copolycarbonates, homopolycarbonates and (co)polyester carbonates. As used herein, the term "polycarbonate composition(s)" refers to polycarbonate-containing compositions of the instant invention.

[0008] The term polycarbonate can be further defined as having repeating structural units of the formula (1):

in which at least 60 percent of the total number of Rl groups are aromatic organic radicals and the balance thereof are aliphatic, alicyclic, or aromatic radicals. In a further aspect, each Rl is an aromatic organic radical and, more preferably, a radical of the formula (2):

-A1-Y1-A2- (2),

wherein each of Al and A2 is a monocyclic divalent aryl radical and Yl is a bridging radical having one or two atoms that separate Al from A2. In various aspects, one atom separates Al from A2. For example, radicals of this type include, but are not limited to, radicals such as— O— , — S— ,— S(O)— ,— S(Oi)— ,— C(O)— , methylene, cyclohexyl-methylene, 2-[2.2.1]- bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene,

cyclopentadecylidene, cyclododecylidene, and adamantylidene. The bridging radical Yl is preferably a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene. Polycarbonate materials include materials disclosed and described in U.S. Patent No. 7,786,246, which is hereby incorporated by reference in its entirety for the specific purpose of disclosing various polycarbonate compositions and methods for manufacture of the same. [0009] The polycarbonate may be substantially free of halogen atoms. By

"substantially free" it is intended that less than 1 wt % of the polycarbonate comprises halogen atoms.

[0010] A melt polycarbonate product may be utilized. The melt polycarbonate process is based on continuous reaction of a dihydroxy compound and a carbonate source in a molten stage. The reaction can occur in a series of reactors where the combined effect of catalyst, temperature, vacuum, and agitation allows for monomer reaction and removal of reaction byproducts to displace the reaction equilibrium and effect polymer chain growth. A common polycarbonate made in melt polymerization reactions is derived from bisphenol A (BPA) via reaction with diphenyl carbonate (DPC). This reaction can be catalyzed by, for example, tetra methyl ammonium hydroxide (TMAOH) or tetrabutyl phosphonium acetate (TBPA), which can be added in to a monomer mixture prior to being introduced to a first polymerization unit and sodium hydroxide (NaOH), which can be added to the first reactor or upstream of the first reactor and after a monomer mixer.

[0011] The polycarbonate produced by interfacial polymerization may be utilized. In some processes, bisphenol A and phosgene are reacted in an interfacial polymerization process. Typically, the disodium salt of bisphenol A is dissolved in water and reacted with phosgene which is typically dissolved in a solvent that not miscible with water (such as a chlorinated organic solvent like methylene chloride).

[0012] It is preferred that the polycarbonate is present in an amount of about 55 to about 90 wt% based on the weight of the composition. The polycarbonate may be present in an amount of about 55 to about 85 wt% of the composition. The polycarbonate bay be present in an amount of about 60 to about 90 wt%, or about 60 to about 85 wt%, or about 70 to about 85 wt%. Filler

[0013] Possible fillers or reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripoli, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonates (such as chalk, limestone, marble, and synthetic precipitated calcium carbonates) talc (including fibrous, modular, needle shaped, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicate or (armospheres), kaolin, whiskers of silicon carbide, alumina, boron carbide, iron, nickel, or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, heavy spar, T1O₂, aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch , lignin, ground nut shells, or rice grain husks, reinforcing organic fibrous fillers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, and poly(vinyl alcohol), as well combinations comprising at least one of the foregoing fillers or reinforcing agents. The fillers and reinforcing agents can be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polymer matrix.

[0014] It is preferred that the filler is present in an amount of about 0 to about 30 wt% based on the weight of the composition. The filler is present may be present in an amount of about 1 to about 30 wt% of the composition or an amount of about 10 to about 30 wt% or an about 0 to about 20 wt% or about 5 to about 20 wt%.

Flame Retardant (FR)

0015] Preferred flame retardants are of the formula:

, where n is about 22 to about 150.

This flame retardant can serve as the sole flame retardant or in combination with a secondary flame retardant. It is preferred that the flame retardant is present in an amount of about 5 to about 15 wt% based on the weight of the composition. The flame retardant may be present in an amount of about 7 to about 15 wt%, or about 8 to about 12 wt%. In one example, the above flame retardant is marketed under the trade name ME-P8 by Sanko and is a homopolymer of the compound pictured below.

[0016] The compound is sometimes referred to as butanedioic acid, (6H-dibenz[c,e] [l,2]oxaphosphorin-6-ylmethyl), bis(2-hydroxyethyl)ester, P-oxide homopolymer. The homopolymer is denoted as CAS No. 403614-60-8 and 7.8-8.2 wt % P. The homopolymer may have a molecular weight (Mw) of about 3,000 to about 12,000; or about 10,000.

[0017] In addition to the above described flame retardants, additional flame retardants such as organic compounds that include phosphorus, bromine, and/or chlorine may be used. Non-brominated and non-chlorinated phosphorus-containing flame retardants can be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0018] Additional flame retardants include phosphorus-containing flame retardants. Examples include phosphazene, aryl phosphate, bisphenol A disphosphate, resorcinol bis- diphenylphosphate, bisphenol A bis(diphenyl phosphate) (BABDP), or resorcinol diphosphate (RDP), or a combination thereof. Certain flame retardants are discussed in US 2014/0107266, which is incorporated herein in its entirety. A combination of flame retardants may show synergistic properties. Preferred second flame retardants include resorcinol- bis(diphenylphosphate) (RDP) and bisphenol-A diphenyl phosphate (DPADP).

[0019] Inorganic flame retardants can also be used, for example salts of Ci-i6 alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium

perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate. Salts such as Na₂CC>3, K₂CO₃, MgCC>3, CaCC>3, and BaCC>3, or fluoro-anion complexes such as Li₃AlF₆, BaSiF₆, KBF₄, K₃A1F₆, KAIF₄, K₂SiF₆, and/or Na₃AlF₆may also be used. When present, inorganic flame retardant salts are present in amounts of 0.01 to 10 parts by weight, more specifically 0.02 to 1 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

Additional Components

[0020] The additive composition can include an impact modifier, flow modifier, 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, anti-drip agent (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or a combination comprising one or more of the foregoing. For example, a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer can be used. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additive composition can be 0.001 to 10.0 wt%, or 0.01 to 5 wt%, each based on the total weight of all ingredients in the composition.

[0021] The polycarbonate composition can include 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 thermoplastic composition (good compatibility for example). Such additives can be mixed at a suitable time during the mixing of the components for forming the composition.

[0022] Examples of impact modifiers include natural rubber, fluoroelastomers, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene-propylene-diene monomer rubber (EPDM), acrylate rubbers, hydrogenated nitrile rubber (HNBR), silicone elastomers, styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-(ethylene-butene)- styrene (SEBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene- styrene (AES), styrene-isoprene-styrene (SIS), styrene-(ethylene-propylene)-styrene (SEPS), methyl methacrylate-butadiene-styrene (MBS), high rubber graft (HRG), and the like. Some suitable impact modifies include PC(polycarbonate)/ABS (such as Cycoloy PC/ABS) and MBS type formulations.

[0023] Heat stabilizer additives include organophosphites (e.g. triphenyl phosphite, tris- (2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like), phosphonates (e.g, dimethylbenzene phosphonate or the like), phosphates (e.g., trimethyl phosphate, or the like), or combinations comprising at least one of the foregoing heat stabilizers. The heat stabilizer can be tris(2,4-di-t-butylphenyl) phosphate available as IRGAPHOS™ 168. Heat stabilizers are generally used in amounts of 0.01 to 5 wt%, based on the total weight of polymer in the composition.

[0024] There is considerable overlap among plasticizers, lubricants, and mold release agents, which include, for example, glycerol tristearate (GTS), phthalic acid esters (e.g, octyl- 4,5-epoxy-hexahydrophthalate), tris-(octoxycarbonylethyl)isocyanurate, tristearin, 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); esters, for example, fatty acid esters (e.g, alkyl stearyl esters, such as, methyl stearate, stearyl stearate, and the like), waxes (e.g, beeswax, montan wax, paraffin wax, or the like), or combinations comprising at least one of the foregoing plasticizers, lubricants, and mold release agents. These are generally used in amounts of 0.01 to 5 wt%, based on the total weight of the polymer in the composition.

[0025] Light stabilizers, in particular ultraviolet light (UV) absorbing additives, also referred to as UV stabilizers, include hydroxybenzophenones (e.g., 2-hydroxy-4-n-octoxy benzophenone), hydroxybenzotriazines, cyanoacrylates, oxanilides, benzoxazinones (e.g., 2,2'- (1,4- phenylene)bis(4H-3,l-benzoxazin-4-one, commercially available under the trade name CYASORB UV-3638 from Cytec), aryl salicylates, hydroxybenzotriazoles (e.g., 2-(2-hydroxy-5- methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-(2H- benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)-phenol, commercially available under the trade name CYASORB 5411 from Cytec) or combinations comprising at least one of the foregoing light stabilizers. The UV stabilizers can be present in an amount of 0.01 to 1 wt%, specifically, 0.1 to 0.5 wt%, and more specifically, 0.15 to 0.4 wt%, based upon the total weight of polymer in the composition.

[0026] 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-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)- propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3 -(3 ,5 -di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis [3 -(3,5-di- tert-butyl-4-hydroxyphenyl)propionate ; amides of beta-(3 ,5 -di-tert-butyl-4-hydroxyphenyl)- propionic acid, or combinations comprising at least one of the foregoing antioxidants.

Antioxidants are used in amounts of 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0027] Anti-drip agents can also be used in the composition, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti- drip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. A TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. Antidrip agents can be used in amounts of 0.1 to 10 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

Polycarbonate Compositions

[0028] The polycarbonate compositions can be manufactured by various methods known in the art. For example, powdered polycarbonate, and other components are first blended, optionally with any fillers, in a high speed mixer or by hand mixing. The blend can then be fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding it directly into the extruder at the throat and/or downstream through a sidestuffer, or by being compounded into a masterbatch with a desired 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 can be immediately quenched in a water bath and pelletized.

[0029] It is preferred that the polycarbonate compositions have a heat deflection temperature (HDT) value of at least 100 °C at a load of 1.82 mPa on a 3.2 mm sample as measured according to ASTM D648.

Articles of Manufacture

[0030] In one aspect, the present disclosure pertains to shaped, formed, or molded articles comprising polycarbonate compositions described herein. The polycarbonate compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form articles. The polycarbonate compositions described herein can also be made into film and sheet as well as components of laminate systems. In a further aspect, a method of manufacturing an article comprises melt blending the polycarbonate component, the liquid polymer, catalyst and any optional ingredients; and molding the extruded composition into an article. In a still further aspect, the extruding is done with a twin-screw extruder.

[0031] In a further aspect, the article comprising the disclosed polycarbonate compositions is used in automotive applications. In a still further aspect, the article can be selected from computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cell phones, electrical connectors, medical devices, membrane devices, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool enclosures, and the like. Other representative articles that may be fabricated using the disclosed copolymer polycarbonate compositions provided herein include headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate enclosures, enclosures for electrical and telecommunication devices, building and construction applications such as glazing, roofs, windows, floors, decorative window furnishings or treatments; treated glass covers for pictures, paintings, posters, and like display items; optical lenses; ophthalmic lenses; corrective ophthalmic lenses; implantable ophthalmic lenses; wall panels, and doors; protected graphics; outdoor and indoor signs;

enclosures, housings, panels, and parts for automatic teller machines (ATM); enclosures, computer housings; desk-top computer housings; portable computer housings; lap-top computer housings; palm-held computer housings; monitor housings; printer housings; keyboards; FAX machine housings; copier housings; telephone housings; mobile phone housings; radio sender housings; radio receiver housings; light fixtures; lighting appliances; network interface device housings; and like applications. In a still further aspect, the article used in automotive applications is selected from instrument panels, overhead consoles, interior trim, center consoles, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate enclosures, steering wheels, radio speaker grilles, mirror housings, grille opening reinforcements, steps, hatch covers, knobs, buttons, and levers. Additional fabrication operations may be performed on articles, such as, but not limited to molding, in-mold decoration, baking in a paint oven, lamination, and/or thermoforming.

[0032] In various aspects, the article comprising the disclosed copolymer polycarbonate compositions are suitable for use in applications such as transparent keypads for mobile phones. Other typical such articles are automotive trim, automotive interior parts, portable

telecommunications and appliance fronts. In a further aspect, wherein the article is a film, it can further comprise visual effects pigments (such as coated Al and glass flakes). In a still further aspect, the article is a film comprising a disclosed copolymer composition can be used in direct film applications but also in processes like IMD (In Mould Decoration). In an even further aspect, the article comprising a disclosed copolymer composition is used in lighting applications including automotive headlamp lenses, covers and lenses for other optical devices, as well as transparent films and sheets. The article can also be used in a wide variety of molded products such as medical devices, radio and TV bezels, mobile phone keypads, notebook computer housings and keys, optical display films, automotive parts, and other electronic and consumer products. [0033] Polymers described herein are suited for use in electronic devices, for the production of thin-walled parts, like housings for cell phones and for automotive applications.

Examples

[0034] The invention is illustrated by the following non-limiting examples.

[0035] The molded samples disclosed herein were tested in accordance with the standards below.

[0036] Melt volume - flow rate ("MFR") was determined according to standard ASTM D1238 under the following test conditions: 300 °CI\ 2 kg load/1080 sec dwell time or 300 °C/1.2 kg load/360 sec dwell time or 260 °C/5 kg load or 260 °C/2.16 kg load. Data below are provided for MVR in g³/10 min.

[0037] The notched Izod impact ("Nil") test was carried out on 63.5 mm x 12.7 mm x 3.2 mm molded samples (bars) according to ASTM D256 at 0 °C and 23 °C. Data units are J/m.

[0038] Tensile properties were measured a Tensile Type 1 bar (50 mm x 13 mm) in accordance with ASTM D638 using sample bars prepared in accordance with a Tensile Type 1 bar (50 mm x 13 mm). Tensile strength for either at break or at yield is reported in units of MPa.

[0039] Heat deflection temperature (HDT) was determined per ASTM D648 with flatwise specimen orientation with specimen dimensions of 127 mm x 12.7 mm x 3.2 mm at 1.82 MPa. Data are provided below in units of °C.

[0040] Flex modulus and flex strength were measured according to Flex; ISO 178.

[0041] Unless otherwise stated to the contrary herein, all test standards are the most recent standard in effect at the time of filing this application.

[0042] Table 1 summarizes various components used in the examples. Test methods are summarized in the definitions presented herein.

Table 1 : Various components used in the illustrative examples.

12,800. CAS No. 111211-39-3

PC3 BPA polycarbonate-polysiloxane Sabic LP. LEXAN™- copolymer comprising about20 wt% EXL siloxane, 80 wt% BPA and end-capped

IM1 Bulk acrylonitrile-butadiene-styrene Sabic LP. C29449 comprising about 16-17 wt% butadiene

content (Grade C2449), CAS No.

9003-56-9

IM2 High rubber graft emulsion Kumho HR 181 polymerized ABS comprising about 50

wt% polybutadiene, CAS No. 9003-56- 9

SAN Bulk San. CAS No. 9003-54-7 Kumho SAN 320

FR1 Bisphenol A bis(dipenylphosophate). Dahaichi Chemical BPA-DP/CR- CAS No. 5945-33-5 Industry Co, Ltd. 741

FR2 Recorcinol diphosphate. CAS No. Fyroflex RDP

57583-54-7

FR3 9,10-Dihydro-9-oxa-10- Sanko DOPO

phosphenanthrene-10-oxide. CAS No.

35948-25-5

FR4 Butanedioic acid, (6H-dibenz[c,e] Sanko ME-P8

[1,2] oxaphosphorin-6-ylmethyl), bis(2- hydroxyethyl)ester, P-oxide

homopolymer. CAS No. 403614-60-8

Fl Non-bonding chopped glass fiber. Owens Corning 415A-14C

CAS No. 65997-17-3

ADD1 Polytetrafluoroethylene (PTFE) SABIC LP. TSAN

encapsulated by styrene-acrylonitrile

copolymer (SAN). Anti-drip. CAS No.

9002-84-0

ADD2 Pentaerythritol tetrastearate, a mold FACI Farsco PETS

release agent. CAS No. 115-83-3 Genova, Italy 14 ADD 3 Hindered phenol, Irganox 1076. CAS BASF Irganox^1M No. 2082-79-3 1076

15 ADD4 Tris(2,4-di-tert-butylphenyl)phosphite , BASF Irgafos™ 168 stabilizer, CAS NO. 31570.04-4

[0043] Table 2 shows the properties of unfilled PC blends. In comparison with CI including 10% phosphate flame retardant (FR) BPADP and C2 including 6.3% DOPO, Wl with 11.25% ME-P8 loading (conversion according to P% content) showed higher heat resistance. 4 than both BPADP and DOPO. The HDT was improved from 89.6 to 107 °C if BPADP was replaced by ME-P8 with the same phosphorous (P) content loading.

[0044] The key purpose of a flame retradant additive is to improve flame retardancy. Importantly, in UL 2.0 mm Vx test for FR performance, no significant difference was observed for the samples.

[0045] The inventive mixture also benefits flow. For example, DOPO degrades PC and flow was increased too high as a result. As such, most mechanical properties were decreased in C2 as the Mw of the PC resin dropped. Mw of PC showed a small drop in Wl . The flow was maintained. The modulus of Wl was comparable to CI.

[0046] Concurrent with the drop in the Mw of PC, C2 showed considerably poorer mechanical properties than Wl . In comparison with CI, notched Izod impact at 23 °C of Wl with ME-P8 was decreased but the ductile-brittle (D/B) transition of Wl was not as sensitive as CI . In the Nil test at 0 °C, Wl showed 20% ductility while CI showed 0 ductility.

Table 2. Formulation and Properties of unfilled PC blends

[0047] Table 3 shows the properties of glass fiber (GF) filled PC blends with DOPO (CI), RDP (C2), RDP/ME-P8 combination (W1-W4) and ME-P8 (W5). The combination of different types of FR (e.g., RDP/ME-P8) showed synergy in some cases. In the comparisons, the total P% is fixed but the ratio between phosphate type FR RDP and phosphinate type FR ME-P8 is adjusted.

[0048] In comparison with CI including 6.42% DOPO and C2 including 8.5% RDP, W5 with 11.5% ME-P8 showed higher HDT. The HDT was improved from 99.8 (C 1) and 94.3 (C2) to 123 °C (W5). Flow, modulus, and impact were comparable between the samples. FR of W5 with ME-P8 was worse than CI with RDP. The flame out time (FOT) was changed from 5.85 to 14.9 s at 1.5 mm bars test using UL-94 protocol. [0049] Samples having the combination of RDP and ME-P8 showed better balance of properties. W1-W5 are samples with RDP/ME-P8 (P%) ratios of 90/10, 75/25, 50/50, and 25/75, respectively. In comparison with CI, W1-W5 showed better mechanical properties. In comparison with C2, W1-W5 showed superior HDT properties while other properties were similar with C 1. With ME-P8 increasing, the heat resistance improved and other properties were maintained.

Table 3. Formulation and properties of filled PC blends

* The UL bars cannot be molded since too crisp. [0050] Table 4 shows results including C3 which contains HCA-HQ as flame retardant, C2 which has DOPO-HCA as a flame retardant, and W6 having ME-P8 as a flame

DOPO HCA HCA-HQ ME-P8

Table 4. Formulation and properties of filled PC blends

with

Unit CI C2 W6 HCA-HQ

FORMULATION

1 PC2 % 35.77 37.62 35.15 36.07

2 PCI % 35.77 37.62 35.15 36.07

3 PC3 % 14 14 14 14

4 IM1 % 3 3 3 3

5 ADD1 % 1 1 1 1

6 ADD2 % 0.08 0.08 0.08 0.08

7 ADD3 % 0.3 0.3 0.3 0.3

8 ADD4 % 0.08 0.08 0.08 0.08

9 FR1 BPADP % 10

10 FR3 DOPO(HCA) % 6.3

11 FR4 DOPO derivative (HCA-HQ) % 9.4

12 FR5 (ME-P8) % 11.25

Formulation

Total % 100 100 100 100

PROPERTIES

HDT, 1.82MPa/3.2mm °C 89.6 88.4 107 96.4

MFR 260°C/2.16KG g/lOmin 10.2 999 9 28.9 flex Modulus Mpa 2490 2700 2360 2660

Flex stress yld MPa 96 48 89 107

Tens Stress brk Mpa 66 46 58 53

NII,23°C J/m 816 22 139 91

Ductility % 100 0 20 0

Nil, 0°C J/M 130 22 133 85

Ductility % 0 0 20 0

FOT2 s 1.02 1.48 2.59 1.23

[email protected] mm DRIP 0 0 0 0

Mw D 51873 25261 48961 48099

GPC Mn D 19458 10968 17229 18246 2.67 2.3 2.84 2.64

Aspects

[0051] The present disclosure comprises at least the following aspects.

[0052] Aspect 1. A composition comprising:

55-90 wt% polycarbonate;

0-30 wt% filler; and

5-15 wt% er of

the composition having a heat deflection temperature (HDT) value of at least 100 °C at a load of 1.82 mPa on a 3.2 mm sample as measured according to ASTM D648;

wherein all weight percent values are based on the total weight of the composition and the combined weight percent value of all components does not exceed 100 wt%.

[0053] Aspect 2. The composition of Aspect 1 comprising a blend of at least two polycarbonates.

[0054] Aspect 3. The composition of Aspect 1 or Aspect 2, comprising 55-85 wt% of polycarbonate and 10-30 wt% filler.

[0055] Aspect 4. The composition of Aspect 1 or Aspect 2, comprising:

55-85 wt% polycarbonate;

1-30 wt% filler; and

5-15 wt% flame retardant, the flame retardant comprising

(i) the homopolymer having the formula

n is about 22 to about 150; (ii) 0-8 wt% of a second phosphate-containing flame retardant.

[0056] Aspect 5. The composition of Aspect 4, comprising about 1 to about 11 wt% of the homopolymer and about 2 to about 8 wt% of the second phosphate-containing flame retardant.

[0057] Aspect 6. The composition of any one of Aspects 1-5, comprising 70-85 wt% polycarbonate.

[0058] Aspect 7. The composition of claim 5 or claim 6, comprising about 2 to about 8 wt% of the second phosphate-containing flame retardant.

[0059] Aspect 8. The composition of claim 5 or claim 7, comprising about 3 to about 11 wt% of the homopolymer and about 3 to about 6 wt% of the second phosphate- containing flame retardant.

[0060] Aspect 9. The composition of any one of Aspects 1-8 having a notched Izod impact (Nil) value measured at 23 °C of at least 84 J/m when measured by ASTM D256.

[0061] Aspect 10. The composition of any one of Aspects 1-8 having a notched Izod impact (Nil) value measured at 0 °C of at least 57 J/m when measured by ASTM D256.

[0062] Aspect 11. The composition of any one of Aspects 4-10, wherein the second phosphate-containing flame retardant comprises resorcinol diphosphate.

[0063] Aspect 12. The composition of any one of Aspects 1-11, wherein the filler comprises glass.

[0064] Aspect 13. A method of forming a composition comprising blending 55-90 wt% polycarbonate; 0-30 wt% filler; and 5-15 wt% flame retardant comprising a homopolymer of the compound of the formula

to produce a composition having a heat deflection temperature (HDT) value of at least 100 °C at a load of 1.82 mPa on a 3.2 mm sample as measured according to ASTM D648; wherein all weight percent values are based on the total weight of the composition and the combined weight percent value of all components does not exceed 100 wt%.

[0065] Aspect 14. The method of Aspect 13, wherein the flame retardant comprises i) the homopolymer having the formula

(ii) 0-8 wt% of a second phosphate-containing flame retardant.

[0066] Aspect 15. The method of Aspect 14, comprising about 1 to about 11 wt% of the homopolymer and about 2 to about 8 wt% of the second phosphate-containing flame retardant.

[0067] Aspect 16. The method of Aspect 14 or Aspect 15, wherein the second phosphate-containing flame retardant comprises resorcinol diphosphate.

[0068] Aspect 17. The method of any one of Aspects 13-16, comprising 70-85 wt% polycarbonate.

[0069] Aspect 18. An article comprising the composition of any one of Aspects 1-12.

[0070] Aspect 19. The article of Aspect 18, wherein the article is wherein the article is a component in business equipment, a monitor, a portable electronic device or an automobile.

[0071] Aspect 20. A work piece comprising the composition of any one of Aspects 1-

12. Definitions

[0072] It is to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" can include the embodiments "consisting of and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0073] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural equivalents unless the context clearly dictates otherwise. Thus, for example, reference to "a polycarbonate polymer" includes mixtures of two or more

polycarbonate polymers.

[0074] As used herein, the term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0075] Ranges can be expressed herein as from one particular value to another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent 'about,' it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0076] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ±5% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such. It is understood that where "about" is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0077] Disclosed are the components to be used to prepare the polycarbonate compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the disclosure. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the disclosure.

[0078] References in the specification and concluding claims to parts by weight, of a particular element or component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0079] As used herein the terms "weight percent," "wt. %," and "wt.%" of a component, which can be used interchangeably, unless specifically stated to the contrary, are based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition or article is said to have 8% by weight, it is understood that this percentage is relative to a total compositional percentage of 100% by weight.

[0080] The abbreviation "mm" stands for millimeters.

[0081] The abbreviation "°C" means degrees Celsius.

[0082] The abbreviation "kg" stands for kilograms.

[0083] The abbreviation "sec" stands for the time unit second(s).

[0084] The abbreviation "MPa" means megapascal.

[0085] "J" is the abbreviation for Joule(s).

[0086] The abbreviation "M" or "m" stands for meter(s).

[0087] As used herein, the terms "weight average molecular weight" or "Mw" can be used interchangeably, and are defined by the formula: w Σ ΝΜ '

where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. Compared to Mn, Mw takes into account the molecular weight of a given chain in determining contributions to the molecular weight average. Thus, the greater the molecular weight of a given chain, the more the chain contributes to the Mw. Mw can be determined for polymers, e.g. polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

Claims

What is claimed:

1. A composition comprising:

55-90 wt% polycarbonate;

0-30 wt% filler; and

5-15 wt% er of

;

2. The composition of claim 1, comprising a blend of at least two polycarbonates.

3. The composition of claim 1 or claim 2. comprising:

55-85 wt% of polycarbonate and

10-30 wt% filler.

4. The composition of any one of claims 1-3, comprising:

55-85 wt% polycarbonate;

1-30 wt% filler; and

5-15 wt % flame retardant, the flame retardant comprising

(i) the homopolymer having the formula

, where n is about 22 to about 150; and (ii) 0-8 wt% of a second phosphate-containing flame retardant.

5. The composition of any one of claims 1-5, comprising about 70 wt% to about 85 wt% of polycarbonate.

6. The composition of claim 4, comprising about 2 to about 8 wt% of the second phosphate- containing flame retardant.

7. The composition of claim 4 or claim 5, comprising about 1 to about 11 wt% of the homopolymer and about 2 to about 8 wt% of the second phosphate-containing flame retardant.

8. The composition of claim 4 or claim 5, comprising about 3 to about 11 wt% of the homopolymer and about 3 to about 6 wt% of the second phosphate-containing flame retardant.

9. The composition of any one of claims 1-8 having a notched Izod impact (Nil) value measured at 23 °C of at least 84 J/m when measured by ASTM D256.

10. The composition of any one of claims 1-9 having a notched Izod impact (Nil) value measured at 0 °C of at least 57 J/m when measured by ASTM D256.

11. The composition of any one of claims 4-10, wherein the second phosphate-containing flame retardant comprises resorcinol diphosphate.

12. The composition of any one of claims 1-11, wherein the filler comprises glass.

13. A method of forming a composition comprising blending 55-90 wt% polycarbonate; 0-30 wt% filler; and 5-15 wt% flame retardant comprising a homopolymer of the compound of the formula

14. The method of claim 13, wherein the flame retardant comprises

i) the homopolymer having the formula

, where n is about 22 to about 150; and

(ii) a second phosphate-containing flame retardant.

15. The method of claim 14, comprising about 1 to about 11 wt% of the homopolymer and about 2 to about 8 wt% of the second phosphate-containing flame retardant.

16. The method of claim 14 or claim 15, wherein the second phosphate-containing flame retardant comprises resorcinol diphosphate.

17. The method of any one of claims 13-16, comprising about 70 wt% to about 85 wt% of polycarbonate.

18. An article comprising the composition of any one of claims 1-12.

19. The article of claim 18, wherein the article is a component in business equipment, a monitor, a portable electronic device, or an automobile.

20. The articles of claim 18 or claim 19, wherein the flame retardant comprises

(i) the homopolymer having the formula

, where n is about 22 to about 150; and

(ii) a second phosphate-containing flame retardant.