WO2016123526A1 - Engineered minerals for use as polycarbonate fillers, and methods of using the same to reinforce polycarbonates - Google Patents
Engineered minerals for use as polycarbonate fillers, and methods of using the same to reinforce polycarbonates Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
Definitions
- the present disclosure generally relates to a reinforced resin composition having improved thermal degradation properties comprising a polycarbonate and at least one functionalized inorganic filler. Methods of reinforcing resin compositions consistent with the foregoing are also disclosed.
- PC resins have been used as an engineering plastic in numerous applications that take advantage of the resin's various beneficial properties including impact resistance, heat resistance, and dimensional stability.
- the use of reinforcing additives for polycarbonate has been limited primarily to glass fiber, due to the tendency of minerals to contribute to degradation of polycarbonate at elevated temperatures (greater than or equal to 30Q°C), which may deteriorate the performance of resulting mineral-PC compounds.
- reinforced resin compositions thai may have improved thermal degradation properties, as measured by an acceptable melt flow index, comprising a polycarbonate and at least one inorganic filler that has been functionalized with a functionalizing agent.
- an acceptable melt flow index comprising a polycarbonate and at least one inorganic filler that has been functionalized with a functionalizing agent.
- applicants have discovered that a number of variables can lead to improved thermal degradation properties, including the use of lower BET surface area minerals, such as a material having a surface area less than 12 m 2 /g, an acceptable functionalizing agent attached to the minerals, and a reduced moisture content of the filled polycarbonate material. The moisture content may be reduced by drying the filled polycarbonate material.
- a reinforced resin composition may include a polycarbonate in an amount ranging from 75 to 99 percent by weight of the resin composition, a functionalizing agent, and an inorganic filler functionalized with the functionalizing agent, the functionalized inorganic filler being present in an amount ranging from 1 to 25 percent by weight of the resin composition, wherein the reinforced resin may exhibit a melt flow index of 25 or less, when measured at a load of 1.2 kg, after allowing the resin to remain at a temperature of 300°C for 10 minutes.
- a method for reinforcing a resin composition may provide improved thermal degradation properties, as measured by an acceptable melt flow index.
- the method may include adding to a polycarbonate resin at least one inorganic filler that has been functionalized with a functionalizing agent.
- a method of reducing thermal degradation of a reinforced polycarbonate material may include introducing into said polycarbonate material at least one inorganic filler functionalized with a functionalizing agent to modify the surface activity of said inorganic filler, such that the reinforced resin exhibits a melt flow index of 25 or less, when measured at a load of 1.2 kg, after allowing the resin to remain at a temperature of 300°C for 10 minutes.
- polycarbonate or “PC” refers to any long-chain linear polyesters of carbonic acid and dihydric phenols, such as bisphenol A.
- polycarbonate that may be used is LexanTM from Sabic.
- unfilled PC resin refers to polycarbonate resin in which inorganic fillers have not been added.
- melt Flow Index refers to the measure of the ease of flow of the melt of a thermoplastic polymer. It is defined as the mass of polymer, in grams, flowing in ten minutes through a capillary of 2.095 mm diameter and 8 mm in length under a 1.2 kg weight for 10 minutes. In the present description, melt flow index was measured at 1.2 kg load at 300°C after allowing the resin or compound to remain at 300°C inside the tester for 10 minutes.
- a resin composition as described herein and which includes the functionalized inorganic filler typically exhibits a melt flow index of 30 or less, such as 25 or less, 20 or less, and even 15 or less, which is an indication that the resin has desired thermal degradation properties.
- talc means a hydrafed magnesium silicate mineral, optionally associated with other minerals, for example, chlorite, dolomite and/or magnesite.
- the term “functionalization” refers to the addition of functionalizing agent onto the surface of a mineral (inorganic filler) by chemical synthesis methods.
- a “functionalizing agent” refers to the material that is attached to, or associated with, the surface by functionalization.
- the functionalizing agent is not necessarily adsorbed onto the surface, but may be connected by a permanent chemical bond, such as by covalent bonding.
- the term "coated" means particles of the talc are surface treated or contacted with a compound, which adheres (e.g., physisorbed or bonded) or is otherwise associated with the surface of the talc.
- BET specific surface area
- talc e.g., microcrystalline or macrocrystalline
- M morphology index
- Ml morphology index
- talcs having a relatively high Ml may be considered “platy” or “lamellar” talcs and generally may have a macrocrystalline structure, whereas talcs having a relatively lower Ml are less platy and may have a microcrystalline structure.
- plaque refers to a talc composition having an Ml greater than or equal to about 0.8.
- the morphology index of the talc may be greater than or equal to 0.7, greater than or equal to 0.75, greater than or equal to 0.8, greater than or equal to 0.85, or greater than or equal to 0.9.
- Particle size properties referred to herein for the talc particulate materials are as measured in a well-known manner by sedimentation of the particulate material in a fully dispersed condition in an aqueous medium using a Sedigraph 5100 machine as supplied by Micromeritics Instruments Corporation, 30 Norcross, Georgia, USA
- Such a machine provides measurements and a plot of the cumulative percentage by weight of particles having a size, referred to in the art as the 'equivalent spherical diameter' (e.s.d.), less than given e.s.d. values.
- the mean particle size d 5 o is the value determined in this way of the particle e.s.d. at which there are 50% by weight of the particles which have an equivalent spherical diameter less than that dso value.
- a mineral reinforcement or filler that is compatible with polycarbonate and does not significantly degrade PC resin at elevated processing temperatures (greater than or equal to about 300°C).
- a reinforced resin composition comprising, in its simplest form, a
- Polycarbonates suitable for use in the present invention are any of those known in the art, such as the aromatic polycarbonates.
- aromatic polycarbonates useful herein are homopolymers, copolymers, and mixtures thereof, which have an intrinsic viscosity of from about 0.3 to about 1 .0 dl/g as measured in methylene chloride at 25° C.
- polycarbonates are derived from dihydric phenols such as, for example, 2,2-bis(4-hydroxyphenyl)propane; bis(4-hydroxyphenyl)methane; 2 1 2 ⁇ bis(4-hydroxy-3-methy!pheny!propane; 4,4-bis(4-bydroxyphenyl)heptane; 2,2- (S.S ⁇ ' ⁇ '-tetrachloro ⁇ -dihydroxypheny propane; and (3,3' ⁇ dichloro ⁇ 4,4 ! ⁇
- dihydroxyphenyl)mefhane dihydroxyphenylmefhane.
- dihydric phenols that are also suitable for use in the preparation of the above polycarbonates are disclosed in U.S. Pat. Nos. 3,334,154 and 4,131 ,575, which are incorporated by reference herein.
- polycarbonates can be manufactured by known processes, such as, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene, a haioformate or a carbonate ester, in accordance with methods set forth in the above-cited literature and U.S. Pat. Nos. 4,018,750 and 4,123,438, or by
- polycarbonates also include the polymeric derivatives of a dihydric phenol, a dicarboxylic acid, and a carbonic acid such as disclosed in U.S. Pat. No. 3,169,121 , incorporated herein by reference.
- the polycarbonate may be a general purpose, medium viscosity PC resin, e.g., Lexan 141TM sold by Sabic.
- the polycarbonate materials described herein can be found in the resin composition in an amount ranging from 70 to 99 percent by weight of the resin composition, from 75 to 99 percent, from 80 to 99 percent, from 85 to 99 percent, from 70 to 95 percent, from 70 to 90 percent, from 70 to 85 percent, from 70 to 80 percent, and from 70 to 75 percent.
- Inorganic fillers that might be particularly useful in the present invention include talc, mica, kaolin, perlite, and combinations thereof.
- Talc is an oleophilic mineral composed of hydrated magnesium silicate generally having the chemical formula H2 g 3 (Si0 3 ⁇ 4 or Mg 3 Si40io(OH)2. According to some embodiments, talc may also be chemically described by one or more of the following formulas; ⁇ Si 2 0 5 )2 g 3 (OH)2 ! Sis geOaoCOH ⁇ , or Mg 12 Si 16 0 4 o(OH)8.
- impurities which can include inorganics, such as carbonates, other magnesium silicates, ferrous iron compounds, and various organic materials that may be present, Such impurities generally occur in minor amounts, but can occur in larger amounts as well,
- the impurities found in talcs may vary as to type and amount depending on the geographic source of the talc. There may also be minor elemental substitution of Mg with Fe, or other elements in the crystalline structure of talc,
- Talc may be characterized as being either microcrystalline or
- talc may generally be in the form of individual platelets.
- the individual platelet size of the talc e.g., the median particle diameter as measured by the Sedigraph method
- a few thousand elementary sheets may vary from approximately 1 micron to over 100 microns, depending on the conditions of formation of the talc deposit.
- microcrystalline talc has small crystals, which provide a compact, dense ore.
- Macrocrystalline talc has large crystals in papery layers.
- talc elementary particles are composed of small plates as compared to macrocrystalline structures, which are composed of larger plates.
- the talc has a Hegman rating of 4 or greater, a Hegman rating of 5 or greater, a Hegman rating of 6 or greater, a Hegman rating of 7 or greater, or a Hegman rating of 7.5 or greater.
- the talc has a BET surface area greater than 2 m 2 /g, a BET surface area greater than 4 m 2 /g, a BET surface area greater than 8 m 2 /g, a BET surface area less than 12 m /g, or a BET surface area less than 10 m 2 /g. According to some
- the talc has a BET surface area ranging from 2 m 2 /g to 12 m 2 /g, a BET surface area ranging from 4 m 2 /g to 10 m 2 /g,
- the inorganic filler comprises a ta!c from
- the talc has a desired size and
- the talc used according to some embodiments may have a d 5 o ranging from 0.5 to 5 ⁇ , such as 2 pm, an aspect ratio of greater than 2.8, and Hegman value about 7.
- the inorganic talc may have a morphology index greater than or equal to 0.8.
- the talc may have a morphology index greater than or equal to 0.7, greater than or equal to 0.75, greater than or equal to 0.8, greater than or equal to 0.85, greater than or equa! to 0.9, or greater than or equal to 0.95.
- the inorganic filler includes a mica chosen from phiogopite mica, muscovite mica, and combinations thereof.
- Mica refers to any of a group of hydrous potassium, aluminum silicate minerals, it is a type of phyllosilicafe, exhibiting a two-dimensional sheet or layer structure.
- the inorganic filler includes kaolin, also referred to as "kaolin clay,” “china clay,” or “hydrous kaolin.”
- Kaolin contains predominantly the mineral kaolinite, together with small concentrations of various other minerals.
- Kaolinite may also be generally described as an aluminosiiicate, aluminosilicate clay, or hydrous
- the inorganic filler added to the PC material includes a kaolin chosen from calcined kaolin, hydrous kaolin, and combinations thereof,
- composition in an amount ranging from 1 to 30 percent by weight of the resin
- composition from 1 to 25 percent, from 1 to 20 percent, from 1 to 15 percent, from 1 to 10 percent, from 1 to 5 percent, from 5 to 30 percent, from 10 to 30 percent, from 15 to 30 percent, from 20 to 30 percent, and from 25 to 30 percent.
- the inorganic filler may have a d 50 ranging from 0.5 to 15 pm, from 0,5 to 10 pm, from 0,5 to 5 pm, from 1.0 to 15 pm, from 2.0 to 15 pm, from 5.0 to 15 pm, from 10 to 15 pm, and from 5.0 to 10 pm.
- particularly useful functionalizing agents may include organic groups that could be used to functionalize the inorganic fillers are chosen from organo-modified silanes.
- the surface of the inorganic fillers can be functionalized with at least one of methacrylate-silane (MEMO-silane), vinyl silane, phenyl silane. epoxy silane, and combinations thereof.
- MEMO-silane methacrylate-silane
- vinyl silane vinyl silane
- phenyl silane phenyl silane
- epoxy silane and combinations thereof.
- the functionalizing agents for example, organic groups, may be functionalized on the surface of the inorganic filler materials in an amount ranging from 0.1 to 3.0 wt% loading based on the dried mineral, such as 0.2 to 3.0 wt%, 0.3 to 3.0 wt%, 0.1 to 2,5 wt%, 0.1 to 2.0 wt%, 0, 1 to 1.0 wt%.
- the methacrylate-silane may include 3-methacryl oxypropyl trimethoxysilane (MEMO-silane).
- the vinyl silane may be chosen from vinyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof.
- the phenyl silane may include phenytrimeihoxysi!ane.
- the epoxy silane may include 3-g!acidoxypropy! trimeihoxysilane.
- the functionalizing agent may include at least one of modified styrene acrylic polymer, monomeric carbodimide, and polymeric carbodimide.
- the functionalizing agent may include one or more of the above-referenced organic groups in addition to at least one of modified styrene acrylic polymer, monomeric carbodimide, and polymeric carbodimide, Modified styrene acrylic polymer may also serve as a til-functional chain extender for polymer matrix chains. Carbodimides may also serve as anti-hydrolysis agents.
- the modified styrene acrylic polymer, monomeric carbodimide, and/or polymeric carbodimide may be added to the reinforced resin composition before, at the same time, or after the inorganic filler is added to the reinforced resin composition.
- the modified styrene acrylic polymer, monomeric carbodimide, and/or polymeric carbodimide may be added to the reinforced resin composition before, at the same time, or after organic groups are added to the inorganic filler.
- the resin composition described herein may include at least one additional component, for example, plasticizers, impact modifiers, pigments, dyes, colorants, stabilizers, and/or other additives or processing aids.
- additional component for example, plasticizers, impact modifiers, pigments, dyes, colorants, stabilizers, and/or other additives or processing aids.
- the inorganic filler functionalized with the functionalizing agent may have a reduced moisture adsorption by at least 45%, when tested at 97% relative humidity and 23°C for 120 hours, relative to the inorganic filler when it has not been functionalized.
- a splay formation may be reduced as compared to the splay formation relative to a reinforce resin composition including the inorganic filler when it has not been functionalized.
- the inorganic filler may have a purity greater than 85%.
- the inorganic filler may have a purity greater than 88%, greater than 90%, greater than 92%, greater than 95%, or greater than 97%.
- the inorganic filler may be talc that has a purity greater than 85%.
- the talc may have a purity greater than 88%, greater than 90%, greater than 92%, greater than 95%, or greater than 97%.
- the method may include introducing into a polycarbonate material at least one inorganic filler, that has been functionalized to a level sufficient to modify the surface activity of the inorganic filler such that the reinforced resin exhibits a melt flow index of 25 or less, such as 20 or less, when measured under the conditions described herein, e.g., at a load of 1.2 kg, after allowing the resin to remain at a temperature of 300°C for a time of 10 minutes.
- the introducing step may include a shear mixing step.
- the shear mixing step may include extrusion.
- the inorganic filler functionalized with the functionalizing agent may have a reduced moisture adsorption by at least 45%, when tested at 97% relative humidity and 23°C for 120 hours, relative to the inorganic filler when it has not been functionalized.
- a splay formation may be reduced as compared to the splay formation relative to a reinforce resin composition including the inorganic filler when if has not been functiona!ized.
- the inorganic filler may have a purity greater than 85%.
- the inorganic filler may have a purity greater than 88%, greater than 90%, greater than 92%, greater than 95%, or greater than 97%.
- the inorganic filler may be talc that has a purity greater than 85%.
- the talc may have a purity greater than 88%, greater than 90%, greater than 92%, greater than 95%, or greater than 97%.
- modifying the surface activity of the inorganic filler typically includes isolating a majority of active sites on the surface of the inorganic filler. This can be accentuated by treating the surface of the inorganic filler prior to it being functionalized, such as by treating the surface of the inorganic filler with a step that is sufficient to increase the hydrophobicity of the inorganic filler.
- the inorganic fillers that can be used in the disclosed methods include those minerals that were previously described, and are chosen from talc, such as macrocrystalline talc having a d 50 ranging from 0.5 to 5 pm; mica, such as phlogopite mica, or muscovite mica; kaolin, such as hydrous kaolin; perlite, and combinations thereof.
- talc such as macrocrystalline talc having a d 50 ranging from 0.5 to 5 pm
- mica such as phlogopite mica, or muscovite mica
- kaolin such as hydrous kaolin
- perlite and combinations thereof.
- the method includes adding at least one additional component chosen from plasticizers, impact modifiers, pigments, dyes, colorants, stabilizers, and processing aids.
- the funcfionalizing agents that can be attached to the inorganic fillers in the disclosed methods are those organo-modified silane that were previously described, and are chosen from a meihacrylate-silane (3 ⁇ methacry! oxypropy! trimethoxysilane), a vinyl silane (vinyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof), a phenyl silane (phenytrimethoxysilane), an epoxy silane (3-glacidoxypropyl
- the functionalizing agent may include at least one of modified styrene acrylic polymer, monomeric carbodimide, and polymeric carbodimsde.
- inorganic fillers functionalized with functionalizing agents as described herein may result in reduced moisture adsorption of the functionalized inorganic fillers as compared to the same inorganic fillers that have not been functionalized with the functionalizing agents.
- Moisture adsorption of inorganic fillers is believed to be associated with the stability of polycarbonates including the inorganic fillers.
- higher moisture adsorption of inorganic fillers may reduce the stability of polycarbonates including the inorganic fillers.
- the inorganic filler may include a micronized microcrystalline talc treated with MEIvlO-silane. Treatment with the
- MEMO-silane may reduce moisture adsorption by at least 40% when tested at 97% relative humidity and 23°C for 120 hours, relative to the talc in its untreated form.
- the inorganic filler of micronized microcrystalline talc treated with MEIvlO-silane may reduce moisture adsorption by at least 45%, at least 50%, at least 55%, or at least 80%, when tested at 97% relative humidity and 23°C for 120 hours, relative to the talc in its untreated form.
- the inorganic filler prior to being functionalized, may include a mean particle size ranging from 1 micron to 3 microns (e.g., 2 microns), a Hegman fineness of grind ranging from 5 to 7 (e.g., 6), a 325 mesh (% passing) ranging from 90 to 100% (e.g., 100%), an oi! absorption ranging from 35 to 45 grams oil/100 grams talc (e.g., 41 grams oil/100 grams talc), a specific gravity ranging from 2.0 to 3.5 (e.g., 2.8), and a bulking value ranging from 20 to 27 lbs/gallon (e.g., 23.3 lbs/gallon).
- a mean particle size ranging from 1 micron to 3 microns (e.g., 2 microns), a Hegman fineness of grind ranging from 5 to 7 (e.g., 6), a 325 mesh (% passing) ranging from 90 to 100% (e.g., 100%), an
- the minerals tested in this Example were a macrocrystalline talc made using Chinese Guangxi ore (7 Hegman with d 50 of about 2 ⁇ ); and a fine phlogopite mica (sedigraph d 50 of about 8-10 pm).
- Table 1 shows the effect of moisture and the behavior of unfilled PC and filled compounds.
- talc and mica both clearly increased the melt flow, which was attributed to PC degradation. Drying had no clear effect on the melt flow of unfilled PC, but drying the filled PC compounds significantly reduced the melt flow compared to und ied compounds (both for talc and mica). This suggested that water/moisture played a role in intensifying the effect of minerals on PC degradation at elevated temperatures.
- This microcrystalline talc was modified with 0.5% by weight organo-modified alkyl siloxane from Evonik (45% emulsion in wafer).
- Example 1 surface treated or untreated minerals compounded at 20 wt% loading in a general purpose PC resin (LexanTM 141) were tested for PC degradation properties.
- This example evaluated additional minerals and surface treatments not tested in Example 1.
- this Example evaluated Muscovite mica, kaolin, chlorite, perlite, and additional macro-crystalline talcs.
- MEMO silane was used for the surface treatment of all minerals tested in this Example (except talc).
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/547,362 US10316186B2 (en) | 2015-01-29 | 2016-01-29 | Engineering minerals for use as polycarbonate fillers, and methods of using the same to reinforce polycarbonates |
EP16744208.6A EP3250639B1 (en) | 2015-01-29 | 2016-01-29 | Engineered minerals for use as polycarbonate fillers, and methods of using the same to reinforce polycarbonates |
KR1020177023931A KR20170140159A (en) | 2015-01-29 | 2016-01-29 | Engineered minerals for use as polycarbonate fillers and methods for their use in reinforcing polycarbonates |
CN201680018808.XA CN107531976A (en) | 2015-01-29 | 2016-01-29 | Engineering mineral as makrolon filler and the method using its polycarbafil |
JP2017559271A JP6710223B2 (en) | 2015-01-29 | 2016-01-29 | Minerals designed to be used as polycarbonate fillers and methods of using said minerals to strengthen polycarbonate |
BR112017016276A BR112017016276B8 (en) | 2015-01-29 | 2016-01-29 | REINFORCED RESIN COMPOSITION AND METHOD OF REDUCING THERMAL DEGRADATION OF A REINFORCED POLYCARBONATE MATERIAL |
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WO2022043149A1 (en) * | 2020-08-31 | 2022-03-03 | Imerys Usa, Inc. | Scratch resistant mineral-filled polymer compositions, production methods and uses |
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EP3775043B1 (en) * | 2018-04-09 | 2022-12-07 | Covestro Intellectual Property GmbH & Co. KG | Polycarbonate composition, molded article prepared from same, and use thereof |
KR102194062B1 (en) * | 2018-04-27 | 2020-12-22 | 롯데첨단소재(주) | Thermoplastic resin composition and article including same |
EP4230702A1 (en) * | 2022-02-16 | 2023-08-23 | IMI Fabi S.p.A. | Talc particulate with a particularly low migration factor for the use as fillers in food contact materials (fcms) |
WO2023156371A1 (en) * | 2022-02-16 | 2023-08-24 | Imi Fabi S.P.A. | Talc particulate with a particularly low migration factor for the use as fillers in food contact materials (fcms) |
Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3153008A (en) | 1955-07-05 | 1964-10-13 | Gen Electric | Aromatic carbonate resins and preparation thereof |
US3169121A (en) | 1957-08-22 | 1965-02-09 | Gen Electric | Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids |
US3334154A (en) | 1963-02-21 | 1967-08-01 | Gen Electric | Flame retardant mixed polycarbonate resins prepared from tetrabromo bisphenol-a |
US4018750A (en) | 1975-02-03 | 1977-04-19 | Sanyo Trading Co., Ltd. | Curable compositions containing chloroprene rubber |
US4123436A (en) | 1976-12-16 | 1978-10-31 | General Electric Company | Polycarbonate composition plasticized with esters |
US4131575A (en) | 1975-02-22 | 1978-12-26 | Bayer Aktiengesellschaft | Thermoplastic polycarbonate molding materials with improved mold release |
US4172735A (en) * | 1976-07-13 | 1979-10-30 | Akzona Incorporated | Filled foams of regenerated cellulose and process for the manufacturing of said foams |
US4943324A (en) * | 1988-05-23 | 1990-07-24 | Georgia Kaolin Company, Inc. | High performance paper filler and method of producing same |
EP0440442A1 (en) * | 1990-02-02 | 1991-08-07 | The Dow Chemical Company | Polymer blend compositions containing a styrenic copolymer, an acetal polymer and a thermoplastic polyester or polycarbonate resin ingredient |
US20010014705A1 (en) * | 1996-03-22 | 2001-08-16 | Isola Laminate Systems Corp. | Fillers for improved epoxy laminates |
US20010050217A1 (en) * | 1998-06-19 | 2001-12-13 | Katsuhiro Uehara | Distillation of (meth) acryloxy-bearing alkoxysilane |
US6569527B1 (en) * | 1998-05-22 | 2003-05-27 | Imerys Minerals, Limited | Particulate carbonates and their preparation and use in thermoplastic film compositions |
US20050267277A1 (en) * | 2004-05-26 | 2005-12-01 | Masaru Takahama | Composition for forming anti-reflective coating film, anti-reflective coating film composed of the composition, and method of forming resist pattern using the composition |
US20070045893A1 (en) * | 2005-08-26 | 2007-03-01 | Himanshu Asthana | Multilayer thermoplastic films and methods of making |
US20070072960A1 (en) * | 2005-09-28 | 2007-03-29 | General Electric Company | Thermoplastic polycarbonate compositions, method of manufacture, and method of use thereof |
US20070138702A9 (en) * | 1999-11-12 | 2007-06-21 | General Electric Company | Molded, filled polymer compositions with reduced splay and a method of making |
US20100004381A1 (en) * | 2006-12-13 | 2010-01-07 | Avakian Roger W | Functionalized translucent compounds |
US20130164653A1 (en) * | 2010-09-03 | 2013-06-27 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of a functionalized mineral filler for chemically stabilizing a polymer, membrane thus stabilized, process for preparing same and uses thereof |
US20130164154A1 (en) * | 2011-12-22 | 2013-06-27 | Huilin Tu | Elastomer compositions with silane functionalized silica as reinforcing fillers |
WO2014001158A1 (en) * | 2012-06-29 | 2014-01-03 | Imerys Talc Europe | Nucleation efficiency of talc in the foaming behaviour and cellular structure of polymer-based foams |
US20140051782A1 (en) * | 2012-08-16 | 2014-02-20 | Joshua James Cheetham | Process for producing a dental filler |
US20140200303A1 (en) | 2013-01-11 | 2014-07-17 | Sabic Innovative Plastics Ip B.V. | Polycarbonate compositions for reduced splay in combination with sustained or improved impact resistance |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4357271A (en) | 1980-12-31 | 1982-11-02 | General Electric Company | Thermoplastic polycarbonate resins reinforced with silane treated fillers |
US6364203B2 (en) * | 1998-03-19 | 2002-04-02 | The Procter & Gamble Company | Articulable food container |
CN1329421C (en) * | 2002-01-18 | 2007-08-01 | Sika技术股份公司 | Two-constituent polyurethane composition having high early strength |
CN100479920C (en) * | 2004-03-11 | 2009-04-22 | 卡塔勒公司 | Exhausting purifying catalyst |
US7905178B2 (en) * | 2005-01-10 | 2011-03-15 | Raytheon Company | Methods and apparatus for selectable velocity projectile system |
US7498401B2 (en) * | 2005-03-03 | 2009-03-03 | Sabic Innovative Plastics Ip B.V. | Thermoplastic polycarbonate compositions, articles made therefrom and method of manufacture |
JP5146650B2 (en) | 2005-06-21 | 2013-02-20 | 日清紡ホールディングス株式会社 | Substrate filler and inorganic-organic composite substrate molding composition |
US20070007296A1 (en) * | 2005-06-30 | 2007-01-11 | Guyot Joshua N | Flexible bottle mouth insert |
CN100374513C (en) * | 2005-09-15 | 2008-03-12 | 成都理工大学 | Epoxy silane surface modified microcrystal muscovite active filler and its preparation method |
-
2016
- 2016-01-29 US US15/547,362 patent/US10316186B2/en active Active
- 2016-01-29 KR KR1020177023931A patent/KR20170140159A/en active Search and Examination
- 2016-01-29 EP EP16744208.6A patent/EP3250639B1/en active Active
- 2016-01-29 BR BR112017016276A patent/BR112017016276B8/en active IP Right Grant
- 2016-01-29 WO PCT/US2016/015728 patent/WO2016123526A1/en active Application Filing
- 2016-01-29 JP JP2017559271A patent/JP6710223B2/en active Active
- 2016-01-29 CN CN201680018808.XA patent/CN107531976A/en active Pending
Patent Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3153008A (en) | 1955-07-05 | 1964-10-13 | Gen Electric | Aromatic carbonate resins and preparation thereof |
US3169121A (en) | 1957-08-22 | 1965-02-09 | Gen Electric | Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids |
US3334154A (en) | 1963-02-21 | 1967-08-01 | Gen Electric | Flame retardant mixed polycarbonate resins prepared from tetrabromo bisphenol-a |
US4018750A (en) | 1975-02-03 | 1977-04-19 | Sanyo Trading Co., Ltd. | Curable compositions containing chloroprene rubber |
US4131575A (en) | 1975-02-22 | 1978-12-26 | Bayer Aktiengesellschaft | Thermoplastic polycarbonate molding materials with improved mold release |
US4172735A (en) * | 1976-07-13 | 1979-10-30 | Akzona Incorporated | Filled foams of regenerated cellulose and process for the manufacturing of said foams |
US4123436A (en) | 1976-12-16 | 1978-10-31 | General Electric Company | Polycarbonate composition plasticized with esters |
US4943324A (en) * | 1988-05-23 | 1990-07-24 | Georgia Kaolin Company, Inc. | High performance paper filler and method of producing same |
EP0440442A1 (en) * | 1990-02-02 | 1991-08-07 | The Dow Chemical Company | Polymer blend compositions containing a styrenic copolymer, an acetal polymer and a thermoplastic polyester or polycarbonate resin ingredient |
US20010014705A1 (en) * | 1996-03-22 | 2001-08-16 | Isola Laminate Systems Corp. | Fillers for improved epoxy laminates |
US6569527B1 (en) * | 1998-05-22 | 2003-05-27 | Imerys Minerals, Limited | Particulate carbonates and their preparation and use in thermoplastic film compositions |
US20010050217A1 (en) * | 1998-06-19 | 2001-12-13 | Katsuhiro Uehara | Distillation of (meth) acryloxy-bearing alkoxysilane |
US20070138702A9 (en) * | 1999-11-12 | 2007-06-21 | General Electric Company | Molded, filled polymer compositions with reduced splay and a method of making |
US20050267277A1 (en) * | 2004-05-26 | 2005-12-01 | Masaru Takahama | Composition for forming anti-reflective coating film, anti-reflective coating film composed of the composition, and method of forming resist pattern using the composition |
US20070045893A1 (en) * | 2005-08-26 | 2007-03-01 | Himanshu Asthana | Multilayer thermoplastic films and methods of making |
US20070072960A1 (en) * | 2005-09-28 | 2007-03-29 | General Electric Company | Thermoplastic polycarbonate compositions, method of manufacture, and method of use thereof |
US20100004381A1 (en) * | 2006-12-13 | 2010-01-07 | Avakian Roger W | Functionalized translucent compounds |
US20130164653A1 (en) * | 2010-09-03 | 2013-06-27 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of a functionalized mineral filler for chemically stabilizing a polymer, membrane thus stabilized, process for preparing same and uses thereof |
US20130164154A1 (en) * | 2011-12-22 | 2013-06-27 | Huilin Tu | Elastomer compositions with silane functionalized silica as reinforcing fillers |
WO2014001158A1 (en) * | 2012-06-29 | 2014-01-03 | Imerys Talc Europe | Nucleation efficiency of talc in the foaming behaviour and cellular structure of polymer-based foams |
US20140051782A1 (en) * | 2012-08-16 | 2014-02-20 | Joshua James Cheetham | Process for producing a dental filler |
US20140200303A1 (en) | 2013-01-11 | 2014-07-17 | Sabic Innovative Plastics Ip B.V. | Polycarbonate compositions for reduced splay in combination with sustained or improved impact resistance |
Non-Patent Citations (2)
Title |
---|
H.J. HOLLANDM.J. MURTAGH: "An XRD Morphology Index for Tales: The Effect of Particle Size and Morphology on the Specific Surface Area", ADVANCES IN X-RAY ANALYSIS, vol. 42, 2000, pages 421 - 428 |
See also references of EP3250639A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022043149A1 (en) * | 2020-08-31 | 2022-03-03 | Imerys Usa, Inc. | Scratch resistant mineral-filled polymer compositions, production methods and uses |
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EP3250639A4 (en) | 2018-08-15 |
KR20170140159A (en) | 2017-12-20 |
CN107531976A (en) | 2018-01-02 |
US20180037735A1 (en) | 2018-02-08 |
BR112017016276A2 (en) | 2018-03-27 |
BR112017016276B1 (en) | 2021-10-26 |
JP6710223B2 (en) | 2020-06-17 |
EP3250639A1 (en) | 2017-12-06 |
JP2018505292A (en) | 2018-02-22 |
BR112017016276B8 (en) | 2023-03-21 |
EP3250639B1 (en) | 2021-08-25 |
US10316186B2 (en) | 2019-06-11 |
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