WO2020033547A1 - Compositions de polyoléfine et de polycarbonate avec fibre de verre - Google Patents

Compositions de polyoléfine et de polycarbonate avec fibre de verre Download PDF

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WO2020033547A1
WO2020033547A1 PCT/US2019/045509 US2019045509W WO2020033547A1 WO 2020033547 A1 WO2020033547 A1 WO 2020033547A1 US 2019045509 W US2019045509 W US 2019045509W WO 2020033547 A1 WO2020033547 A1 WO 2020033547A1
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measured
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weight percent
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Robert Russell Gallucci
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Sabic Global Technologies B.V.
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • thermoplastic compositions and in particular to compositions including a polyolefin, a polycarbonate, and glass fibers.
  • Polymer compositions can include blends of miscible polymers, immiscible polymers, or a combination of miscible and immiscible polymers. Blends comprising immiscible polymers have two or more phases and such blends may be compatible or incompatible.
  • Incompatible blends of immiscible polymers can suffer from phase separation as demonstrated by delamination or the formation of skin-core layered structures, often resulting in poor mechanical properties and undesirable surface appearance.
  • Compatible blends of immiscible polymers typically do not delaminate and can result in acceptable end-use properties.
  • Polyolefins and polycarbonate are immiscible and form incompatible blends. These polymers are distinctively different in molecular structure, molecular weight, and molecular weight distribution, and have different physical and mechanical properties. Blends of polyolefins and polycarbonates are desirable because the polyolefin component can provide a higher melt flow and good chemical resistance, whereas the polycarbonate component can provide a higher modulus and reduce warp.
  • thermoplastic compositions having compatibilized blends of polyolefins and polycarbonates. It would be a further advantage if the compositions had a high heat resistance and increased high temperature modulus.
  • thermoplastic composition comprising 10 to 80 weight percent (wt%), preferably 25 to 75 wt%, more preferably 30 to 70 wt% of a polyolefin; 5 to 60 wt%, preferably 10 to 50 wt%, more preferably 15 to 30 wt% of an aromatic polycarbonate; and 5 to 60 wt%, preferably 10 to 50 wt%, more preferably 15 to 40 wt% of a glass fiber coated with a sizing composition, wherein all weight percent values are based on the total weight of the composition, wherein a weight ratio of the polyolefin to the aromatic polycarbonate is 90:10 to 25:75, preferably 85:15 to 30:70, more preferably 70:30 to 50:50, wherein the polyolefin comprises a homopolymer or copolymer comprising at least 80 weight percent of units derived from polymerization of ethylene, propylene, or a combination thereof, preferably wherein the polyolef
  • thermoplastic composition prepared from the thermoplastic composition, wherein the article has a light transmission of less than 40%, when measured according to ASTM D1003 at a thickness of 3.2 millimeters.
  • FIG. 1 is a transmission electron microscope (TEM) image of a composition in accordance with an aspect of the present disclosure.
  • FIG. 2 is a graph of modulus (megapascals, MPa) versus temperature (°C) for compositions in accordance with an aspect of the present disclosure.
  • coated glass fibers can be used to compatibilize blends of polycarbonates and polyolefins.
  • the polyolefin component comprises the majority portion of the polymer blend and the composition includes a glass fiber coated with a material having a low affinity for the polyolefin
  • the compositions can overcome the problem of delamination typically found in immiscible, incompatible polymer blends.
  • the coated glass fibers include a coating agent having compatibility with, for example good adhesion to, the polycarbonate component, which results in the formation of polycarbonate fibrils that are wrapped around the coated glass fibers.
  • This entangled morphology, where the coated glass fibers are larger than the polycarbonate fibrils, is sufficiently stable to accommodate the dispersion of the polycarbonate component in the polyolefin component of the polymer blend during melt processing conditions, for example extrusion and injection molding.
  • the compatibilization is further enhanced by use of a lower molecular weight polycarbonate that can aid in fibrillation of the polycarbonate phase leading to further entanglement with the glass fibers.
  • the compositions further include improved dimensional stability allowing for the production of articles such as light weight parts with good fit and flatness in end use assembly.
  • polystyrene resin including both polycarbonate and polyolefin components.
  • the polyolefin which is found in the major phase of the polymer blend, provides high melt flow, good chemical resistance, and lower density.
  • the polycarbonate which is the minor phase dispersed in the polyolefin, provides enhanced modulus, including superior modulus at higher temperatures, and reduces the warpage of the polymer blend giving enhanced dimensional stability.
  • the combination of the two polymers also results is a surprising degree of opacity (e.g., a lower transmission of light) and a greater degree of whiteness, even in the absence of an added pigment.
  • thermoplastic composition including 10 to 80 wt% or 15 to 75 wt%, preferably 20 to 70 wt% or 25 to 75 wt%, more preferably 30 to 70 wt% or 35 to 65 wt% of a polyolefin; 5 to 60 wt%, preferably 10 to 50 wt%, more preferably 15 to 30 wt% of an aromatic polycarbonate; and 5 to 60 wt%, preferably 10 to 50 wt%, more preferably 15 to 40 wt% of a glass fiber coated with a sizing composition, wherein all weight percent values are based on the total weight of the composition.
  • the molar ratio of the polyolefin to the aromatic polycarbonate is 90:10 to 25:75, preferably 85:15 to 30:70, more preferably 70:30 to 50:50.
  • the thermoplastic composition can include 30 to 65 wt% of a polyolefin, 15 to 30 wt% of an aromatic polycarbonate, and 10 to 45 wt% of a glass fiber coated with a sizing
  • composition wherein the molar ratio of the polyolefin to the aromatic polycarbonate is 85:15 to 60:40.
  • the polyolefin of the thermoplastic composition includes a homopolymer or copolymer comprising at least 80 wt% of units derived from polymerization of ethylene, propylene, or a combination thereof.
  • polyolefins include polyethylenes, polypropylenes, polybutene- 1, copolymers of ethylene and/or propylene with other olefins, and combinations thereof.
  • Polyethylenes are lightweight, semicrystalline thermoplastics that are prepared by the catalytic polymerization of ethylene.
  • HDPE high- density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • HDPE high- density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • Most properties of polyethylenes are a function of their density and molecular weight. As density decreases, the strength, modulus, and hardness decrease, and flexibility, impact, and clarity increase. Hence HDPE exhibits a greater degree of crystallinity, greater flexural modulus, rigidity, improved heat deformation resistance, and increased resistance to permeability than LDPE and LLDPE.
  • the composition can include one or more polyolefins.
  • LDPE is prepared at high temperatures and pressures, which results in complex branched molecular structures.
  • the amount of branching and the density can be controlled by the polymerization conditions.
  • LLDPE is prepared by using an a-olefin co-monomer during polymerization. Hence branching is introduced in a controlled manner, and the branch chain length is uniform.
  • the co-monomers comprise 1 -butene, 1 -hexene, l-octene, and 4- methyl- l-pentene (4M1P).
  • Specialty grades of polyethylene include very low density (VLDPE), medium density (MDPE), and ultra-high molecular weight polyethylene (UHMWPE).
  • Polypropylenes are semicrystalline thermoplastics, and have improved properties over HDPE. Polypropylenes are prepared by the catalytic polymerization of propylene.
  • Crystallinity is a key property of polypropylene.
  • the degree of crystallinity is a function of the geometric orientation of the methyl groups on the polymer chain (backbone).
  • backbone There are three possible geometric (stereoisomeric) forms of polypropylene— isotactic, syndiotactic, and atactic.
  • the geometric form of the polypropylene is referred to as“tacticity”.
  • isotactic polypropylene the methyl groups are predominantly aligned on the same side of the polymer backbone.
  • syndiotactic polypropylene the methyl groups have alternating configurations relative to the polymer backbone.
  • atactic polypropylene the methyl groups are randomly positioned along the polymer backbone.
  • Isotactic polypropylene is highly crystalline, and exhibits low density, rigidity, good chemical resistance to hydrocarbons, alcohols and oxidizing agents, negligible water absorption, excellent electrical properties, and high flexural modulus.
  • polypropylene has the highest flexural modulus of the commercially available polyolefins.
  • polypropylene has poor impact resistance
  • polypropylene-elastomer blends have improved impact strength. Both isotactic and syndiotactic polypropylene will crystallize when cooled from molten states. Physical properties of isotactic polypropylene can be controlled to some extent by varying the relative amounts of three different crystalline phases. Syndiotactic polypropylene has a different crystalline morphology, and a different balance of flexural modulus and toughness. In general, syndiotactic polypropylene is less crystalline and exhibits greater clarity, elasticity, and impact resistance than other forms. Nucleating agents, such as talc, can control the crystal morphology.
  • Some control of the tacticity of polypropylene can be achieved by the choice of polymerization catalyst.
  • the classic catalysts are Ziegler-Natta catalysts. More recent metallocene catalysts offer greater control over tacticity than Ziegler-Natta catalysts.
  • the proper choice of catalyst can produce isotactic, syndiotactic, atactic polypropylene, or a combination of these.
  • Polypropylene thermoplastic elastomers can be obtained when isotactic blocks alternate with atactic blocks.
  • Polypropylene can be copolymerized with ethylene and/or higher a-olefins.
  • the melt temperature (T m ) of polypropylene can be from 140 to l80°C, for example from 150 to 175° C, for example from 155 to l70°C.
  • the crystallization temperature (T c ) of polypropylene can be from 140 to l70°C, for example from 145 to l65°C, for example from 150 to l60°C.
  • the melt and crystallization temperatures can be measured using DSC according to ASTM D3418-08 with a scan rate of 20°C per minute using the second heating cycle.
  • Polybutene- 1 is a high molecular weight, linear, isotactic, and semi-crystalline polymer. Isotactic polybutene- 1 exhibits a T m of 110 to l40°C and a T g of -l7°C. Polybutene- 1 is a flexible, linear polyolefin that can be a homopolymer of 1 -butene or a copolymer with ethylene. Polybutene- 1 combines physical properties of other polyolefins with excellent creep resistance, heat deformation resistance, and resistance to environmental stress cracking.
  • the polyolefin can comprise a polyolefin block copolymer comprising an end group consisting essentially of a polyolefin homopolymer of C2-3 olefins and a middle block comprising a copolymer of C2-12 olefins.
  • the polyolefin can also comprise a combination of homopolymer and copolymer, a combination of homopolymers having different melt temperatures, and/or a combination of homopolymers having different melt flow rates.
  • the polyolefin can also comprise a random copolymer of ethylene with a polar monomer, for example vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, maleic anhydride, glycidyl methacrylate, or a combination thereof.
  • a polar monomer for example vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, maleic anhydride, glycidyl methacrylate, or a combination thereof.
  • the polyolefin can include a polyethylene homopolymer, an ethylene-containing copolymer, a polypropylene homopolymer, a polypropylene-containing copolymer, or a combination thereof, and in particular a polypropylene homopolymer.
  • the polyolefin can include a homopolymer or copolymer having at least 80 wt% of units derived from polymerization of ethylene, propylene, or a combination thereof.
  • the polyolefin comprises at least 95 wt%, based on the weight of the polyolefin, of repeating units derived from propylene.
  • the polypropylene is a copolymer of propylene and another copolymerizable monomer, for example, ethylene, a C4-C12 alkene, a Ci-C 6 -alkyl acrylate, a Ci-C 6 -alkyl methacrylate, or a combination thereof.
  • the polyolefin can have a heat of fusion that is from 20 to 150 Joules per gram (J/g), as measured by DSC.
  • the polyolefin can be polypropylene having a heat of fusion that is from 20 to 150 J/g.
  • the heat of fusion can be from 50 to 100 J/g with a heat of crystallization from -50 to -100 J/g.
  • the polyolefin can have a crystalline melting temperature from 100 to l70°C and a melt flow rate of 2 to 30 cubic centimeters per ten minutes (cc/lO min) at 230°C and at a load of 2.16 kg.
  • the polyolefin has a heat of fusion of 20 to 120 J/g.
  • the polyolefin optionally can further include at least 10 parts per million (ppm) of nickel, titanium, zirconium, hafnium, vanadium, calcium, magnesium, aluminum,
  • the polyolefin can have less than 50 ppm of an alkyl phthalate.
  • “Aromatic polycarbonate” as used herein means a homopolymer or copolymer having repeating structural carbonate units of formula (1)
  • R 1 can be derived from an aromatic dihydroxy compound of the formula HO-R ⁇ OH, in particular of formula (2)
  • 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 .
  • Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 .
  • one atom can separate A 1 from A 2 .
  • each R 1 can be derived from a bisphenol of formula (3)
  • R a and R b are each independently a halogen, C 1-12 alkoxy, or C 1-12 alkyl, and p and q are each independently integers of 0 to 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 bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group.
  • the bridging group X a can be single bond, -O-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a Ci-is organic group.
  • the Ci-is organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the Ci-is organic group can be disposed such that the C 6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-is 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.
  • Groups of these types include methylene, cyclohexylmethylidene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2. l]-bicycloheptylidene, cyclohexylidene, 3,3-dimethyl-5-methylcyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.
  • X a can be a Ci-is alkylene, a C3-18 cycloalkylene, a fused C 6 -i 8 cycloalkylene, or a group of the formula -J'-G-J 2 - wherein J 1 and J 2 are the same or different Ci -6 alkylene and G is a C3-12 cycloalkylidene or a C 6 - l6 arylene.
  • each R h is independently a halogen atom, Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C 6 -io aryl, or a halogen-substituted C 6 -io aryl, and n is 0 to 4.
  • the halogen is usually bromine.
  • dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, l,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1- naphthylmethane, l,2-bis(4-hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2- bis(4-hydroxy-3-bromophenyl)propane, l,l-bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis
  • 1.6-bis(4-hydroxyphenyl)-l,6-hexanedione ethylene glycol bis(4-hydroxyphenyl)ether, bis(4- hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4- hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6'- dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7- dihydroxyphenoxathin, 2,7-dihydroxy-9, lO-dimethylphenazine, 3,6-dihydroxydibenzofuran,
  • resorcinol substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone
  • bisphenol compounds of formula (3) include l,l-bis(4- hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (hereinafter“bisphenol A” or“BPA”), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4- hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, 3,3- bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane (
  • the aromatic polycarbonates can have a weight average molecular weight of 10,000 to 200,000 grams per mole (g/mol), specifically 20,000 to 100,000 g/mol, as measured by gel permeation chromatography (GPC) using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopolycarbonate references.
  • the aromatic polycarbonate can have a weight average molecular weight of 15,000 to 26,000 g/mol.
  • polycarbonate includes 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 or siloxane units.
  • aromatic polycarbonate is a linear homopolymer containing bisphenol A carbonate units (BPA-PC), commercially available under the trade name LEX AN from SABIC.
  • a specific type of copolymer is a poly(ester-carbonate), also known as a polyester-polycarbonate.
  • Poly(ester-carbonate)s further contain, in addition to recurring carbonate chain units of formula (1), repeating ester units of formula (5)
  • J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a Ci-io alkylene, a C 6 -2o cycloalkylene, a C5-20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), such as a C1-20 alkylene, a C5-20 cycloalkylene, or a C6-20 arylene.
  • the polyester units can be branched or linear.
  • Exemplary dihydroxy compound precursors to the ester moieties include aromatic dihydroxy compounds of formula (4) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol A), a Ci -8 aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1, 4-butane diol, 1, 4-cyclohexane diol, l,4-hydroxymethylcyclohexane, or a combination thereof.
  • aromatic dihydroxy compounds of formula (4) e.g., resorcinol
  • bisphenols of formula (3) e.g., bisphenol A
  • a Ci -8 aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1, 4-butane diol, 1, 4-cyclohexane diol, l,4-hydroxymethylcyclohexane, or
  • Aliphatic dicarboxylic acids that can be used include C5-20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), specifically linear C 8 -i2 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-Ci2 dicarboxylic acids such as dodecanedioic acid (DDDA).
  • Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, or a combination thereof.
  • ester units include ethylene terephthalate units, n-propylene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A.
  • the molar ratio of ester units to carbonate units can be from 1:99 to 99:1, or from 25:75 to 75:25.
  • a specific copolycarbonate includes bisphenol A and bulky bisphenol carbonate units, i.e., derived from bisphenols containing at least 12 carbon atoms, for example 12 to 60 carbon atoms or 20 to 40 carbon atoms.
  • Examples of such copolycarbonates include
  • copolycarbonates comprising bisphenol A carbonate units and 2-phenyl-3,3’-bis(4- hydroxyphenyl) phthalimidine carbonate units (a BPA-PPPBP copolymer, commercially available under the trade name LEXAN XHT from SABIC).
  • poly(aromatic ester- carbonate ⁇ comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly(carbonate-ester)s (PCE) or poly(phthalate- carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units.
  • PCE poly(carbonate-ester)s
  • PPC poly(phthalate- carbonate)s
  • Another specific poly(ester-carbonate) comprises resorcinol isophthalate and terephthalate units and bisphenol A carbonate units, such as those commercially available under the trade name LEXAN SLX from SABIC.
  • Polycarbonates can be manufactured by processes such as interfacial
  • An end-capping agent can be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p- cyanophenol, and C1-22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as p- methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl
  • chloroformates p-cumyl phenyl chloroformate, and toluene chloroformate.
  • Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization.
  • branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
  • trimellitic acid trimellitic anhydride
  • trimellitic trichloride tris-p-hydroxyphenylethane
  • isatin-bis-phenol tris-phenol TC (l,3,5-tris((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
  • benzophenone tetracarboxylic acid The branching agents can be added at a level of 0.05 to 2.0 wt%.
  • the aromatic polycarbonate can have less than 100 ppm by weight of phenolic (- OH) end groups.
  • the amount of phenolic end groups is less than 50 ppm by weight.
  • the lower amounts of phenolic end groups may contribute to lower color formation in processing and end use and after other exposures to heat and oxygen.
  • the thermoplastic composition includes 5 to 60 wt% of the coated glass fiber based on the total weight of the thermoplastic composition.
  • the thermoplastic composition can include 10 to 50 wt% or preferably 15 to 40 wt% of the coated glass fiber.
  • a plurality of coated glass fibers can be used, wherein the glass fibers and/or the sizing
  • compositions are the same or different.
  • the term“coated glass fiber” is the same as“a glass fiber coated with a sizing composition”.
  • the amount of coated glass fiber is inclusive of the sizing composition, meaning the stated amount of coated glass fiber includes the total weight of the glass fiber and the sizing composition that is disposed thereon.
  • the term“glass” refers to a material, natural or synthetic, which contains silicon dioxide (Si0 2 ) or silica as its main material.
  • the glass fibers can be textile glass fibers such as E, A, C, ECR, R, S, D, and/or NE glass fibers, and are desirably E type glass fibers.
  • the glass fibers can be provided in the form of monofilament or multifilament fibers and can be used either alone or in combination with other types of fibers, for example, co-weaving or
  • the glass fibers can be supplied in the form of rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements such as braids.
  • the preferred filaments for plastic reinforcement are made by mechanical pulling.
  • the glass fibers can be continuous or chopped, preferably chopped.
  • Glass fibers in the form of chopped strands may have a length of 0.3 millimeters (mm) to 10 centimeters (cm), preferably 0.5 mm to 5 cm or 3 mm to 13 mm.
  • the glass fibers can have a length from 0.2-20 mm, preferably 0.2-10 mm, more preferably 0.7-7 mm.
  • the glass fibers can have any cross-section, such as a round (or circular), flat, bilobe, or irregular cross-section.
  • the average diameter of the glass fibers can be from 1-25 micrometers (pm), preferably 3-20 pm, more preferably 4-18 pm, even more preferably 5-17 pm.
  • the glass fiber can be a short glass fiber having a diameter of 10 pm or 14 pm. Without being bound by theory, chopped glass fibers can facilitate the entanglement of the polycarbonate component and the concomitant
  • the glass fibers are coated with a sizing composition (i.e., a coating) to improve adhesion to the polymer matrix.
  • a sizing composition i.e., a coating
  • the sizing composition can be disposed on substantially all of the glass fibers or on a portion of the glass fibers in the thermoplastic composition.
  • the sizing provides a coated glass fiber that can be either bonding or non-bonding towards the polymers of the matrix in which it is disposed.
  • a matrix including a polycarbonate
  • polycarbonate bonding glass fibers have a sizing on the surface of the glass fibers that promotes adhesion with polycarbonate, whereas polycarbonate non-bonding glass fibers have a sizing on their surface that does not promote strong adhesion to polycarbonate.
  • the glass fibers herein are coated with a sizing composition to provide glass fibers that are bonding towards aromatic polycarbonates. The coated glass fibers are therefore non-bonding towards the polyolefin component.
  • the sizing composition can include a polyepoxide, a poly(meth)acrylate, a poly(arylene ether), a polyurethane, or a combination thereof.
  • the polyepoxide can be a phenolic epoxy resin, an epoxylated carboxylic acid derivative (e.g., a reaction product of an ester of a polycarboxylic acid having one or more unesterified carboxyl groups with a compound including more than one epoxy group), an epoxidized diene polymer, an epoxidized polyene polymer, or a combination thereof.
  • the sizing composition can further include a silane coupling agent to facilitate bonding with the glass fiber.
  • the silane coupling agent can be tri(Ci- 6 alkoxy)monoamino silane, tri(Ci- 6 alkoxy)diamino silane, tri(Ci- 6 alkoxy)(Ci- 6 alkyl ureido) silane, tri(Ci- 6 alkoxy)(epoxy Ci -6 alkyl) silane, tri(Ci- 6 alkoxy)(glycidoxy Ci -6 alkyl) silane, tri(Ci- 6 alkoxy)(mercapto Ci -6 alkyl) silane, or a combination thereof.
  • the silane coupling agent is (3 -aminopropyl)triethoxy silane, (3-glycidoxypropyl)trimethoxysilane, (2-(3,4- epoxycyclohexyl)ethyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-(2- aminoethylamino)propyl)triethoxysilane, (3 -ureidopropyl)triethoxy silane, or a combination thereof.
  • the silane coupling agent is aminopropyltriethoxysilane,
  • glycidylpropyltrimethoxysilane or a combination thereof.
  • Other materials that can be included in the sizing composition include, but are not limited to, anti-static agents, coupling agents, lubricants, wetting agents, or the like.
  • the sizing composition can be used in an amount from 0.1 to 5 wt% based on the weight of the glass fibers.
  • the sizing composition may be applied to the glass fibers by any means, such as immersing the glass fibers in the sizing composition or contacting the glass fibers with an aqueous emulsion, or suspension of the sizing composition.
  • Other coating methods include using an aqueous dispersion of the sizing composition applied to the uncoated glass fibers by a roller in a continuous fashion, which can be followed by a heat treatment or curing step.
  • Each glass fiber can be substantially coated (e.g., entirely coated) with the sizing composition, or at least a portion of the glass fiber can be coated with the sizing composition.
  • the thermoplastic composition can further include a reactive impact modifier, such as a maleic anhydride functionalized polypropylene (for example, EXXELOR PO1020 obtainable from ExxonMobil Chemical).
  • a reactive impact modifier such as a maleic anhydride functionalized polypropylene (for example, EXXELOR PO1020 obtainable from ExxonMobil Chemical).
  • Other exemplary reactive impact modifiers include polypropylene grafted with a carboxylic acid or a salt thereof, an anhydride, an ester, or a combination thereof.
  • the reactive impact modifier can be present in the thermoplastic composition in an amount of 0.3 to 10 wt%, preferably 0.5 to 9 wt%, more preferably 1 to 8 wt%, based on the total weight of the thermoplastic composition.
  • thermoplastic composition can further include a compatibilizer, such as a block copolymer, with at least one block of the copolymer having an affinity to the
  • the compatibilizer can be a copolymer (i) styrene and (ii) at least one of ethylene, propylene, and butylene blocks.
  • a preferred compatibilizer is styrene-ethylene-butylene-styrene (SEBS).
  • SEBS styrene-ethylene-butylene-styrene
  • Other compatibilizers are hydrogenated styrene isoprene copolymer, functionalized metallocene polypropylene waxes, styrene-maleic anhydride copolymers, and hydrogenated styrenic block copolymers.
  • the thermoplastic composition can further include an impact modifier.
  • 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-butylene-styrene (SEBS), acrylonitrile- butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), acrylonitrile-ethylene-propylene- diene-styrene (AES), styrene-isoprene- styrene (SIS), styrene-(ethylene-propylene)-styren
  • the thermoplastic composition can include an additive composition, with the proviso that the additive(s) do not significantly adversely affect a desired property of the thermoplastic composition.
  • the additive composition or individual additives can be mixed at any time during the mixing of the components for forming the composition.
  • the additive can be soluble or non-soluble in polycarbonate.
  • Exemplary additives include a flow modifier, 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, flame retardant, anti-drip agent, or a combination thereof.
  • the total amount of the additive composition can be 0.001 to 10 wt%, or 0.01 to 5 wt%, each based on the total weight of the thermoplastic composition.
  • Reinforcing fillers can include, but are not limited to, glass spheres such as hollow and solid glass spheres, silicate spheres, or the like; kaolin clay, including hard kaolin, soft kaolin, calcined kaolin, kaolin comprising various coatings known in the art to facilitate compatibility with the polymer matrix, or the like; flaked fillers such as glass flakes, glass spheres, flaked silicon carbide, aluminum oxides, or the like; organic fillers such as
  • the reinforcing filler can include milled glass, glass flakes, glass or ceramic bubbles, and glass spheres may also be used as less isotropic fillers.
  • the polyester composition can include a combination of glass fiber and a platy filler such as glass flake, mica, or a combination thereof. Without being bound by theory, combinations of glass fiber with platy fillers may be beneficial in producing molded articles with greater strength and less warp, and with better flatness and improved dimensional stability over the use of cylindrical glass fibers.
  • the thermoplastic composition can further include talc in an amount of 0.1 to 10 wt% based on the total weight of the thermoplastic composition.
  • the thermoplastic composition can include 0.1 to 10 wt% of a microtalc having an average particle size of less than 5 micrometers.
  • talc as a lipophilic mineral, has an affinity for the polyolefin component and can be an effective nucleating agent that enhances polyolefin crystallization.
  • Fillers and reinforcing agents having a high Mohs hardness such as titanium dioxide (Mohs hardness of 6.5), can degrade the mechanical properties of the compositions, for example by breaking the glass fibers.
  • the composition is substantially free (e.g., including less than 500 ppm) of fillers and reinforcing agent having a high Mohs hardness, which also includes compounds such as inorganic pigments and metal oxides.
  • the composition can be substantially free of titanium dioxide.
  • Exemplary flame retardants include organic compounds that include phosphorus, bromine, and/or chlorine. While brominated flame retardants are effective in terms of safety, 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.
  • Inorganic flame retardants can also be used, for example salts of Ci-i 6 alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium
  • perfluoroctane sulfonate tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate
  • salts such as Na 2 C0 3 , K2CO3, MgC0 3 , CaC0 3 , and BaC0 3
  • fluoro-anion complexes such as Li 3 AlF 6 , BaSiF 6 , KBF 4 , K 3 A1F 6 , KA1F 4 , K2S1F6, and/or
  • 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.
  • thermoplastic compositions can be manufactured by various methods known in the art. For example, powdered polycarbonate, and other optional components are first blended, optionally with any fillers, in a high speed mixer or by hand mixing. The blend is then 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 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. Such pellets can be used for subsequent molding, shaping, or forming.
  • the thermoplastic composition has excellent physical properties, including a heat deflection temperature of at least 125°C, preferably 125 to 160°C, more preferably 130 to 155°C, measured in accordance with ASTM D648 at 0.46 megapascals (MPa).
  • the thermoplastic composition has a flexural modulus of greater than or equal to 1,900 MPa, preferably greater than or equal to 3,000 MPa, more preferably greater than or equal to 4,000 MPa, when measured according to ASTM D790 at 1.27 mm/min and at 23°C.
  • the thermoplastic composition can have a flexural strength of greater than or equal to 40 MPa, preferably greater than or equal to 45 MPa, more preferably greater than or equal to 50 MPa, when measured according to ASTM D790 at 1.27 mm/min and at 23°C.
  • thermoplastic compositions can have a tensile modulus of greater than or equal to 2,300 MPa, preferably greater than or equal to 3,500 MPa, more preferably greater than or equal to 4,000 MPa, as measured according to ASTM D638 at 5 mm/min and at 23°C.
  • thermoplastic compositions can have a tensile strength of greater than or equal to 25 MPa, preferably greater than or equal to 30 MPa, when measured according to ASTM D638 at 5 mm/min and at 23°C.
  • the thermoplastic composition can have a transmission measured on a 3.2 mm thick plaque of less than 40%, preferably less than 30%, more preferably less than 20%.
  • the thermoplastic composition can include less than 0.01 wt% of titanium dioxide and have a transmission measured on a 3.2 mm thick plaque of less than 40%, preferably less than 20%.
  • the thermoplastic composition can include less than 0.01 wt% of zinc oxide and zinc sulfide, and have a transmission measured on a 3.2 mm thick plaque of less than 40%, preferably less than 20%.
  • thermoplastic composition can include less than 0.01 wt% of titanium dioxide, less than 0.01 wt% of zinc oxide, and less than 0.01 wt% of zinc sulfide and have a transmission measured on a 3.2 mm thick plaque of less than 40%, preferably less than 20%.
  • the thermoplastic composition also has excellent flexural modulus at elevated temperatures.
  • the thermoplastic composition can have a flexural modulus of greater than 410 MPa, preferably greater than 600 MPa, more preferably greater than 1,000 MPa, as measured at l30°C.
  • the thermoplastic composition can have a flexural modulus of greater than 200 MPa, preferably greater than 400 MPa, more preferably greater than 600 MPa, as measured at l45°C.
  • the thermoplastic composition can have a flexural modulus of greater than 400 MPa, as measured at l50°C.
  • thermoplastic compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming.
  • Exemplary articles include computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cell phones, electrical connectors, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool enclosures, and the like.
  • the fiber length is typically shorter presumably due to fiber fragmentation during compounding of the composition. The length of such short fibers present in articles can be less than 4 mm.
  • An article prepared from the thermoplastic composition can have improved opacity.
  • the chopped glass fibers GF-l, GF-2, and GF-3 have coatings (i.e. sizing) and diameters (10 or 14 micrometers) as specified in Table 1. All fibers start with a 4 millimeter (mm) bundle (chop) length. Fiber length is reduced during extrusion and molding due to mechanical attrition.
  • Samples were prepared as follows. The components were pre-mixed in a paint shaker, and the glass fibers were added after initial mixing to prevent excessive fuzzing. The blends were extruded under a minimal vacuum (e.g., 0.15 to 0.6 atmospheres (atm)) on a 30 millimeter (mm) co-rotating twin screw extruder. The extrusion conditions are shown in Table 2. Resultant pellets were dried for 3 to 4 hours at l20°C in a forced air-circulating oven. The compositions were not pre-dried prior to extrusion. Injection molding using the resultant pellets was performed on an 80 ton van Dorn injection molding machine at 240 to 265°C. Parts were injection molded and tested under ASTM conditions.
  • a minimal vacuum e.g. 0.15 to 0.6 atmospheres (atm)
  • mm millimeter
  • Molecular weight was determined by gel permeation chromatography (GPC) and molecular weights were reported relative to polycarbonate by using a calibration curve based on monodisperse polystyrene standards.
  • Melt volume flow rate MVR was measured according to ASTM D1238 at 260°C with a 2.16 kg load for 6 minutes.
  • Notched Izod impact (NI) and unnotched Izod impact (UNI) were measured at 23°C per ASTM D256 on 3.2 mm thick bars using a 5-pound hammer.
  • Tensile properties were measured on 3.2 millimeter type I bars per ASTM method D638 at 23°C with a crosshead speed of 5 millimeters per minute (mm/min).
  • Tensile strength is measured at yield (Y), and tensile modulus is measured as tangent. Tensile modulus and tensile strength at yield are reported in MPa (mega Pascal). Percent elongation was measured at break (B). Flexural modulus and strength were measured using the ASTM D790 method using 3.2 mm injection molded bars and a cross head speed of 1.27 mm/min. Heat deflection temperature (HDT) was measured per ASTM D648 at 0.46 MPa (66 psi) or 1.82 MPa (264 psi) stress at a heating rate of 120°C per hour using a 3.2 mm thick injection molded bar. Specific gravity was measured per ASTM D792 on injection molded parts.
  • HDT Heat deflection temperature
  • Vicat softening temperature was measured per ASTM D1525 with a 10 Newton (N) load at a heating rate of 120°C per hour.
  • Dynamic mechanical analysis (DMA) in ambient atmosphere with a heating rate of 3°C/minute and at a frequency of 10 Hz was used to determine flexural modulus in a temperature range of 40 to 160°C on a 3.2 mm bar.
  • Crystallinity, melting, and solidification were measured by differential scanning calorimetry (DSC) with a heating rate of 20°C per minute per ASTM D3418-15.
  • the sample was heated to melting and the temperature was recorded in degrees centigrade (Tml) and the approximate heat of fusion (dH-Ml) measured in Joules per gram (J/g).
  • the molten sample was then cooled at l20°C per minute and the heat of crystallization (solidification) was recorded as a peak temperature (Tc) and a heat of crystallization (dH-Tc) noted. Samples were reheated and the melting point (Tm2) and heat of fusion (dH-M2) were measured a second time.
  • T g Glass transition temperature was determined by solid state rheology (dynamic mechanical analysis, DMA) with the modulus as function of temperature at a constant frequency of 1 Hertz (Hz) and a flex mode with a 3°C per minute heating rate on a 3.2 mm bar.
  • DMA dynamic mechanical analysis
  • Warp is measured by the deviation from flatness of 101.6 mm x 15.9 mm side gated discs as molded and after annealing at l35°C for 1 hour or at l50°C for 2 hours. Warp is measured by holding one side of the disc to a flat surface and measuring the maximum space between the flat surface and bottom of the disc, and reported in millimeters (mm). The warp value is an average measurement from 5 samples. Light transmission was measured on 3.2 mm injection molded discs in accordance with ASTM D1003, and is reported as percent
  • Opacity is inversely proportionate to percent transmission, such that a lower percent transmission shows higher opacity.
  • the polypropylene was analyzed for the elements of interest, including nickel, calcium, sodium, and phosphorous, using inductively coupled plasma- optical emission spectrometry (ICP-OES).
  • Table 3 shows the crystallinity, melting, and solidification properties for the PP used in the examples.
  • Examples 1-9 are compositions having PP and from 10 to 50 wt% of HF-PC, with 30 wt% of chopped glass fiber and 0.1 wt% of a hindered phenol antioxidant.
  • PC and PP have no mutual affinity and form blends that delaminate, are difficult to extrude and pelletize, and further have poor mechanical properties.
  • the glass fiber, especially glass fiber coated with a coating agent having an affinity for PC i.e., GF-l in
  • Examples 1-4 enhances the compatibility of the PC and PP components in the compositions.
  • FIG. 1 is an SEM image of the composition of Example 2, and shows a continuous PP phase that the PC (present in a lower volume percent than the PP) forms thin fibrils that entangle (wrap around) the larger glass fibers.
  • the affinity of the PC for the coating agent in GF-l helps to secure the position of the PC within the PP, further retarding phase separation (phase coarsening) and delamination to give a compatibilized blend of PP-PC that can be molded into articles without excessive delamination or coinciding poor mechanical properties.
  • the compatibilized PC-PP gives rise to improved properties such as higher HDT, increased modulus, and notably increased modulus at high temperature (Table 5 and FIG. 2).
  • the crystallization properties of the PP component were retained in the compositions, as reflected by the observed Tc and Tm of the composition.
  • the compositions also demonstrated a reduced amount of warpage when compared to the warpage observed with GF-PP compositions of Comparative Examples 1 and 2. In some instances warpage was reduced by greater than 20% (Examples 3, 4, and 6-8) relative to the warpage observed for Comparative Examples 1 and 2.
  • compositions including GF-l (Examples 1-4), which has a polar coating with greater affinity for PC compared to the olefinic coated GF-2, had superior strength and modulus properties.
  • Examples 1-9 had a greater degree of whiteness and higher opacity as compared to Comparative Examples 1 and 2. This enhanced whiteness and opacity was achieved without the addition of hard pigments, such as Ti0 2 , which causes glass fiber breakage resulting in deteriorated mechanical properties and added part weight.
  • Examples 1-9 had greater flexural modulus at high temperatures compared to Comparative Examples 1 and 2. Moreover, it was discovered that during cooling, the molten polymer mixtures of Examples 1-9 developed a higher modulus more rapidly than Comparative Examples 1 and 2 which allowed, in some instances, for ejection of the molded part at a higher temperature leading to shorter molding cycle time and enhanced productivity.
  • Table 6 shows the results for the 10 wt% GF-PP-PC compositions of Examples
  • Examples 10 and 11 reduce the warpage by greater than 20% compared to Comparative Example 3 and 4, respectively.
  • Examples 10 and 11 also had increased HDT at both 0.46 MPa and 1.82 MPa loads, and had increased high temperature flexural modulus as compared to Comparative Examples 3 and 4. While both GF-l and GF-2 are effective compatibilizers at 10 wt%, the polar-coated GF-l was more effective in improving tensile and flexural strength.
  • Table 7 shows the high temperature flexural modulus (MPa) for Examples 10 and
  • Table 8 shows the compositions and properties of Examples 12 to 17 (E12 to E17), which were prepared and evaluated as described above.
  • compositions including 15 to 30 wt% of GF-l or a combination of GF-l and GF-2 are effective compatibilizers as evidenced by HDT (0.46 MPa) of greater than l25°C for Examples 12 to 17.
  • HDT high-density polyethylene
  • the affinity of the coating in GF-l for polycarbonate (PC) provides a greater amount of surface area for interactions with the PC component, thus improving compatibilization and stabilizing morphology, as compared to the combination of GF-l and GF-2.
  • Table 9 shows the flexural modulus (MPa) for Examples 12 to 17.
  • the PC component provides high temperature modulus of greater than 200 MPa for temperatures below the T g of the polycarbonate component (ca. l50°C).
  • Table 10 shows the compositions and properties of Examples 18 to 21 (E18 to E21), which were prepared and evaluated as described above.
  • melt flow (MVR) is sharply reduced with the
  • polycarbonate with greater molecular weight incorporation of polycarbonate with greater molecular weight. Without being bound by theory, this may be due to poor viscosity matching with the polycarbonate continuous phase because polycarbonate components having the greater molecular weights are not sufficiently elongated into fibrils to wrap around the glass fiber component. This reduced fibrillation of the higher molecular weight, higher viscosity polycarbonates resulted in reduced compatibilization, lower glass fiber entanglement, and reduced modulus and strength. From these results, polycarbonates having weight average molecular weights of less than 25,000 g/mol are preferred.
  • Table 11 shows the flexural modulus (MPa) for Examples 18 to 21.
  • polycarbonate components in Examples 18 and 19 resulted in greater high temperature modulus.
  • incorporation of the polycarbonate components in Examples 18 to resulted in improved high temperature modulus resulted in improved high temperature modulus.
  • Table 12 shows the compositions and properties of Examples 22 to 25 (E22 to E25), which were prepared and evaluated as described above.
  • glass fiber-polypropylene blends were prepared with a tetrabromo-copolycarbonate (Br-PC) alone or in combination with HF-PC.
  • the crystalline properties of the polypropylene component were retained based on the observed T c .
  • the Br-PC blends had high opacity and whiteness.
  • Table 13 shows the flexural modulus (MPa) for Examples 22 to 25.
  • compositions including the Br-PC component show improved high temperature modulus compared to Comparative Example 1.
  • the compositions including the Br-PC component also had improved high temperature modulus above l45°C compared to Example 22 and other polycarbonate blends.
  • Table 14 shows the compositions and properties of Examples 26 to 29 (E26 to E29), which were prepared and evaluated as described above. Annealing (warp testing) was performed by heating 1.6 mm molded discs at l35°C for 1 hour.
  • compositions prepared with 3 or 5 wt% of an SEBS elastomer have an HDT of greater than l25°C and reduced warpage compared to Comparative Examples 1 and 2.
  • Table 15 shows the compositions and properties of Examples 30 to 36 (E30 to E36), which were prepared and evaluated as described above. Table 15.
  • compositions including PPgMA demonstrated improved notched (NI) and unnotched (UNI) Izod impact strengths.
  • NI notched
  • UNI unnotched
  • the glass fibers GF-3 which have a 10 micron fiber diameter and a coating that has high PC affinity, also provided superior mechanical properties and PC-PP compatibilization beyond that observed with the thicker 14 micron diameter glass fibers of the previous examples. Without being bound by theory, the greater surface area of the narrower diameter fibers can provide the advantageous effects.
  • Table 16 shows the compositions and properties of Examples 37 to 39 (E37 to E39) and Comparative Examples 5 to 7 (C5 to C7), which were prepared and evaluated as described above.
  • GF-3 PC bonding glass fiber
  • Examples 37 to 39 all demonstrated light transmission at 3.2 mm of less than 20%, whereas Comparative Examples 5 to 7 had greater than double the amount of light transmission.
  • Examples 37 to 39 showed a high degree of whiteness and good light blocking capacity without added pigments.
  • the inclusion of the polycarbonate component in Examples 37 to 39 also resulted in a reduction in warp in 1.6 mm thin parts as molded and as annealed for 2 hours at l50°C.
  • Table 17 shows the flexural modulus (MPa) for Examples 37 to 39.
  • compositions of Examples 37 to 39 each had a flexural modulus of greater than 400 MPa at l30°C.
  • a thermoplastic composition comprising: 10-80 wt%, preferably 20-70 wt% or 25-75 wt%, more preferably 30-70 wt% of a polyolefin; 5-60 wt%, preferably 10-50 wt%, more preferably 15-30 wt% of an aromatic polycarbonate; and 5-60 wt%, preferably 10-50 wt%, more preferably 15-40 wt% of a glass fiber coated with a sizing composition, wherein all weight percent values are based on the total weight of the composition, wherein a weight ratio of the polyolefin to the aromatic polycarbonate is 90: 10 to 25:75, preferably 85: 15 to 30:70, more preferably 70:30 to 50:50, wherein the polyolefin comprises a homopolymer or copolymer comprising at least 80 wt% of units derived from polymerization of ethylene, propylene, or a combination thereof, preferably wherein the polyolefin
  • Aspect 2 The thermoplastic composition of Aspect 1, wherein the aromatic polycarbonate comprises a polycarbonate homopolymer or copolymer comprising repeating
  • p and q are each independently integers of 0 to 4, and X a is a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, a Ci-
  • R e is a divalent C1-10 hydrocarbon group; preferably wherein the polycarbonate comprises BPA carbonate units; more preferably wherein the polycarbonate has a weight average molecular weight of 15,000 to 26,000 g/mol as determined by GPC using BPA polycarbonate standards.
  • Aspect 3 The thermoplastic composition of any one or more of Aspects 1 to 2, wherein the sizing composition comprises a polyepoxide; a poly(meth)acrylate; a poly(arylene ether); a polyurethane; a polyolefin; or a combination thereof.
  • Aspect 4 The thermoplastic composition of Aspect 3, wherein the sizing composition further comprises a silane coupling agent, wherein the silane coupling agent comprises tri(Ci- 6 alkoxy)monoamino silane, tri(Ci- 6 alkoxy)diamino silane, tri(Ci- 6 alkoxy)(Ci- 6 alkyl ureido) silane, tri(Ci- 6 alkoxy)(epoxy C1-6 alkyl) silane, tri(Ci- 6 alkoxy) (glycidoxy C1-6 alkyl) silane, tri(Ci- 6 alkoxy)(mercapto C1-6 alkyl) silane, or a combination thereof; more preferably wherein the silane coupling agent comprises (3 -aminopropyl)triethoxy silane, (3- glycidoxypropyl)trimethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)triethoxys
  • Aspect 5 The thermoplastic composition of any one or more of Aspects 1 to 4, further comprising a reactive impact modifier, wherein the reactive impact modifier is a polypropylene grafted with a carboxylic acid or a salt thereof, an anhydride, an ester, or a combination thereof, preferably wherein the reactive impact modifier is a homopolypropylene grafted with maleic anhydride.
  • the reactive impact modifier is a polypropylene grafted with a carboxylic acid or a salt thereof, an anhydride, an ester, or a combination thereof, preferably wherein the reactive impact modifier is a homopolypropylene grafted with maleic anhydride.
  • Aspect 6 The thermoplastic composition of any one or more of Aspects 1 to 5, further comprising 1 to 15 weight percent of an impact modifier, preferably wherein the impact modifier comprises methyl methacrylate-butadiene- styrene, acrylonitrile -butadiene-styrene, acrylonitrile-styrene-butyl acrylate, methyl methacrylate-acrylonitrile-butadiene-styrene, acrylonitrile-ethylene-propylene-diene- styrene, styrene-ethylene-butylene- styrene, a poly(ether ester), or a combination thereof.
  • the impact modifier comprises methyl methacrylate-butadiene- styrene, acrylonitrile -butadiene-styrene, acrylonitrile-styrene-butyl acrylate, methyl methacrylate-acrylonitrile-butadiene-
  • Aspect 7 The thermoplastic composition of any one or more of Aspects 1 to 6, wherein the glass fiber is present in an amount of 10-20 wt%, based on the total weight of the composition; and wherein the composition has: a heat deflection temperature of greater than l25°C, measured in accordance with ASTM D648 at 0.46 MPa, a flexural modulus of greater than 410 MPa, measured in accordance with ASTM D790 at l30°C, a tensile modulus of greater than or equal to 2,300 MPa, measured according to ASTM D638 at 5 mm/min and at 23°C, a tensile strength of greater than or equal to 25 MPa, when measured according to ASTM D638 at 5 mm/min and at 23°C, a flexural modulus of greater than or equal to 1,900 MPa, when measured according to ASTM D790 at 1.27 mm/min and at 23°C, and a flexural strength of greater than or equal to 50 MP
  • Aspect 8 The thermoplastic composition of any one or more of Aspects 1 to 6, wherein the glass fiber is present in an amount of 20-30 wt%, based on the total weight of the composition; and wherein the composition has: a heat deflection temperature of greater than l30°C, measured in accordance with ASTM D648 at 0.46 MPa, a flexural modulus of greater than 600 MPa, measured in accordance with ASTM D790 at l30°C, a tensile modulus of greater than or equal to 2,600 MPa, measured according to ASTM D638 at 5 mm/min and at 23°C, a tensile strength of greater than or equal to 25 MPa, when measured according to ASTM D638 at 5 mm/min and at 23°C, a flexural modulus of greater than or equal to 1,900 MPa, when measured according to ASTM D790 at 1.27 mm/min and at 23°C, and a flexural strength of greater than or equal to 40 MPa
  • Aspect 9 The thermoplastic composition of any one or more of Aspects 1 to 6, wherein the glass fiber is present in an amount of 30-40 wt%, based on the total weight of the composition; and wherein the composition has: a heat deflection temperature of greater than l35°C, measured in accordance with ASTM D648 at 0.46 MPa, a flexural modulus of greater than 200 MPa, measured in accordance with ASTM D790 at l45°C, a tensile modulus of greater than or equal to 3,500 MPa, measured according to ASTM D638 at 5 mm/min and at 23°C, a tensile strength of greater than or equal to 25 MPa, when measured according to ASTM D638 at 5 mm/min and at 23°C, a flexural modulus of greater than or equal to 3,000 MPa, when measured according to ASTM D790 at 1.27 mm/min and at 23°C, and a flexural strength of greater than or equal to 45 MPa
  • Aspect 10 The thermoplastic composition of any one or more of Aspects 1 to 6, wherein the polycarbonate has a weight average molecular weight of 18,000-25,000 g/mol as determined by gel permeation chromatography using bisphenol A homopolycarbonate standards; and wherein the composition has: a heat deflection temperature of greater than l30°C, measured in accordance with ASTM D648 at 0.46 MPa, a flexural modulus of greater than 1,000 MPa, measured in accordance with ASTM D790 at l30°C, a flexural modulus of greater than 400 MPa, measured in accordance with ASTM D790 at l45°C, a tensile modulus of greater than or equal to 4,000 MPa, measured according to ASTM D638 at 5 mm/min and at 23°C, a tensile strength of greater than or equal to 30 MPa, when measured according to ASTM D638 at 5 mm/min and at 23°C, a flexural modulus of
  • Aspect 11 The thermoplastic composition of any one or more of Aspects 1 to 6, wherein the composition further comprises 10-30 wt% of a halogen-substituted polycarbonate; and wherein the composition has: a heat deflection temperature of greater than l40°C, measured in accordance with ASTM D648 at 0.46 MPa, a flexural modulus of greater than 1,000 MPa, measured in accordance with ASTM D790 at l30°C, a flexural modulus of greater than 600 MPa, measured in accordance with ASTM D790 at l45°C, a flexural modulus of greater than 400 MPa, measured in accordance with ASTM D790 at l50°C, a tensile modulus of greater than or equal to 4,600 MPa, measured according to ASTM D638 at 5 mm/min and at 23°C, a tensile strength of greater than or equal to 30 MPa, when measured according to ASTM D638 at 5 mm/min
  • Aspect 12 The thermoplastic composition of any one or more of Aspects 1 to 11, wherein the composition is substantially free of inorganic pigments and metal oxides, preferably wherein the composition is substantially free of titanium dioxide.
  • Aspect 13 The thermoplastic composition of any one or more of Aspects 1 to
  • Aspect 14 The thermoplastic composition of any one or more of Aspects 1 to
  • the polyolefin is present in an amount of 30 to 65 wt%
  • the aromatic polycarbonate is present in an amount of 15 to 30 wt%
  • the coated glass fiber is present in an amount of 10 to 45 wt%
  • the molar ratio of the polyolefin to the aromatic polycarbonate is 85:15 to 60:40.
  • Aspect 15 The thermoplastic composition of any one or more of Aspects 1 to 13, wherein the polyolefin is present in an amount of 30-65 wt%, preferably 40-65 wt%; the aromatic polycarbonate is present in an amount of 15-30 wt%, preferably 15-25 wt%; the coated glass fiber is present in an amount of 15-40 wt%, preferably 15-30 wt%; further comprising 0.1- 0.5 wt%, preferably 0.1 -0.3 wt% of talc; and wherein the molar ratio of the polyolefin to the aromatic polycarbonate is 85:15 to 60:40.
  • Aspect 16 The thermoplastic composition of any one or more of Aspects 1 to 13, wherein the polyolefin is present in an amount of 40-65 wt%, preferably 45-62.5 wt%; the aromatic polycarbonate is present in an amount of 17.5-30 wt%, preferably 19-27.5 wt%; the coated glass fiber is present in an amount of 10-35 wt%, preferably 10-30 wt%; further comprising 0.1-0.5 wt%, preferably 0.1-0.3 wt% of talc; further comprising 1-8 wt%, preferably 2-6 wt% of a homopolypropylene grafted with maleic anhydride; and wherein the molar ratio of the polyolefin to the aromatic polycarbonate is 85:15 to 60:40.
  • Aspect 17 The thermoplastic composition of any one or more of Aspects 1 to 13, wherein the polyolefin is present in an amount of 40-65 wt%, preferably 40-55 wt%; the aromatic polycarbonate is present in an amount of 15-30 wt%, preferably 15-25 wt%; the coated glass fiber is present in an amount of 10-40 wt%, preferably 15-35 wt%; further comprising 1-8 wt%, preferably 2-6 wt% of a copolymer comprising styrene and at least one of ethylene, propylene, and butylene, preferably styrene-ethylene-butylene-styrene; and wherein the molar ratio of the polyolefin to the aromatic polycarbonate is 85:15 to 60:40.
  • Aspect 18 An article having improved opacity prepared from the thermoplastic composition of any one or more of Aspects 1 to 17, wherein the article has a light transmission of less than 40%, preferably less than 30%, more preferably less than 20% when measured according to ASTM D1003 at a thickness of 3.2 millimeters.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles can 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.
  • hydrocarbyl and“hydrocarbon” refer to any chemical group comprising at least hydrogen and carbon.
  • Alkyl means a branched or straight chain, unsaturated hydrocarbon group.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O).
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group.
  • Cycloalkylene means a divalent cyclic alkylene group, -C n H 2n-x , wherein x is the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent mono- or multicyclic group having one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
  • Aryl means a monovalent aromatic hydrocarbon group that can be a single ring or multiple rings (e.g., from 1 to 3 rings), which are fused together or linked covalently.
  • “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.
  • 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 can be present.
  • hetero means that the compound or group herein is a stable group that includes at least one 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.
  • a heteroatom e.g., 1, 2, or 3 heteroatom(s)
  • each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound.“Substituted” means that the compound, group, or atom is substituted with at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, where each substituent is independently nitro (-N0 2 ), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 haloalkyl, C 1-9 alkoxy, C 1-6 haloalkoxy, C 3-12 cycloalkyl, C 5-18 cycloalkenyl, C 6 -i 2 aryl, C 7-i3 arylalkylene (e.g., benzyl), C 7-i
  • the indicated number of carbon atoms is the number of carbon atoms in the compound or group, excluding those of any substituents.
  • a group of the formula - CH 2 CH 2 CN is a substituted C 2 alkyl group, in other words a C 2 alkyl group that is substituted with a cyano group.

Abstract

L'invention concerne une composition thermoplastique comprenant : 10 à 80 % en poids d'une polyoléfine ; 5 à 60 % en poids d'un polycarbonate aromatique ; et 5 à 60 % en poids d'une fibre de verre revêtue d'une composition d'encollage, le rapport en poids de la polyoléfine au polycarbonate aromatique étant de 90:10 à 25:75, la polyoléfine comprenant un homopolymère ou un copolymère comprenant au moins 80 % en poids d'unités dérivées de la polymérisation de l'éthylène, du propylène, ou d'une combinaison de ces derniers, de préférence la polyoléfine ayant une température de fusion de 20 à 120 J/g, mesurée par calorimétrie différentielle à balayage, et de préférence la composition thermoplastique ayant une température de fléchissement sous charge d'au moins 125 °C conformément à la norme ASTM D648 ; et un module de flexion supérieur à 400 MPa, conformément à la norme ASTM D790.
PCT/US2019/045509 2018-08-07 2019-08-07 Compositions de polyoléfine et de polycarbonate avec fibre de verre WO2020033547A1 (fr)

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CN111875944A (zh) * 2020-08-10 2020-11-03 青岛科技大学 一种复合材料及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
US4454287A (en) * 1982-12-22 1984-06-12 General Electric Company Glass reinforced polyolefin composites modified with aromatic polycarbonates
EP0673949A1 (fr) * 1994-03-16 1995-09-27 Kawasaki Steel Corporation Compositions rendues compatibles de résines polycarbonates/polyoléfines
CN101875770B (zh) * 2010-07-14 2012-06-13 深圳市科聚新材料有限公司 一种玻纤增强pc/pe合金材料及其制备方法
WO2013175448A1 (fr) 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Compositions thermoplastiques ignifugeantes, leurs procédés de fabrication et articles les contenant
JP2014058610A (ja) * 2012-09-14 2014-04-03 Tsubakuro Kagaku Kogyo Kk 樹脂成形体
WO2014072923A1 (fr) 2012-11-07 2014-05-15 Sabic Innovative Plastics Ip B.V. Procédé pour la production de compositions de polycarbonate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4454287A (en) * 1982-12-22 1984-06-12 General Electric Company Glass reinforced polyolefin composites modified with aromatic polycarbonates
EP0673949A1 (fr) * 1994-03-16 1995-09-27 Kawasaki Steel Corporation Compositions rendues compatibles de résines polycarbonates/polyoléfines
CN101875770B (zh) * 2010-07-14 2012-06-13 深圳市科聚新材料有限公司 一种玻纤增强pc/pe合金材料及其制备方法
WO2013175448A1 (fr) 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Compositions thermoplastiques ignifugeantes, leurs procédés de fabrication et articles les contenant
JP2014058610A (ja) * 2012-09-14 2014-04-03 Tsubakuro Kagaku Kogyo Kk 樹脂成形体
WO2014072923A1 (fr) 2012-11-07 2014-05-15 Sabic Innovative Plastics Ip B.V. Procédé pour la production de compositions de polycarbonate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875944A (zh) * 2020-08-10 2020-11-03 青岛科技大学 一种复合材料及其制备方法和应用

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