Classifications

• • 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
  • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
  • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
• • 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
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

• the present invention relates to the development and use of sustainable blends of polylactic acid (PLA) and isosorbide-based copolymers for formation of articles with desirable impact strengths.
• PLA polylactic acid
• isosorbide-based copolymers for formation of articles with desirable impact strengths.
• Aliphatic polyester polymers such as polylactic acid (PLA) based polymers are desired for their excellent porosity and decomposition characteristics. These bio-based polymers however lack formability, mechanical strength, and heat resistance. Since polylactic acid polymers have a low resistance against high temperature, a molded product can be distorted at 60°C or higher.
• PLA polylactic acid
• Polylactic acid polymer resins have been blended with petroleum-based thermoplastics such as polycarbonate resins, but the addition of the PLA makes the blends brittle.
• the polycarbonate/polylactic acid blends have low compatibility as these blends have low flow marks and continued impact strength issues.
• Resin compositions composed of PLA and polycarbonate have demonstrated varying degrees of improved flow properties and heat resistance.
• many of these polycarbonates are petroleum-based and, despite the use of PLA, the goal of achieving a reduced environmental load has yet to be attained.
• the present invention is directed to a blended composition that comprises (a) one or more polycarbonates, wherein at least one of the polycarbonates is formed from a reaction between isosorbide, bisphenol A, a carbonate source, and a C36 diol; (b) one or more polylactide polymers having the following structural unit wherein n is 1000 to 3000 and (c) an impact modifier.
• the composition may have an overall biocontent of at least 50% according to ASTM D6866 and a notched impact value of at least 48 kilojoules per meter squared (kJ/m ) at 23°C.
• the C36 diol may have the following structure:
• reaction between isosorbide, bisphenol A, and a C36 diol may be a melt
• the carbonate source may be one or more of phosgene, a triphosgene, diacyl halide, dihaloformate, dicyanate, diester, diepoxy, diarylcarbonate, dianhydride, dicarboxylic acid, and/or diacid chloride.
• the impact modifier may be a styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), styrene-acrylonitrile (SAN), or Paraloid BPM 520.
• the impact modifier may be Paraloid BPM 520.
• the isosorbide unit may be derived from an isosorbide such as l,4:3,6-dianhydro-D-sorbitol; 2,6-dioxabicyclo[3.3.0]octan-4,8-diol; 1,4:3,6- dianhydro-D-glucitol; 2,3,3a,5,6a-hexahydrofuro[3,2-b]furan-3,6-diol, or an isomer thereof.
• the impact modifier may be Paraloid BPM 520, and the blended composition may have a notched izod impact value of at least 20 kJ/m at -20°C.
• the biocontent of the isosorbide-containing polycarbonate may be from 50 weight % to 80 weight %.
• the biocontent of the isosorbide-containing polycarbonate may be 59%.
• the isosorbide-containing polycarbonate may have a notched izod impact value of from 2 kJ/m to 10 kJ/m at 23°C.
• the isosorbide-containing polycarbonate may have a notched izod impact value of 4 kJ/m 2 at 23°C.
• the polylactide content of the blend composition may be from 10 to 30 weight %.
• the polylactide may have an onset melting point from 120°C to 165°C.
• the polylactide may have an onset melting point of 138.5°C [+/-10°C].
• the polylactide may have a glass transition temperature of from 50°C to 70°C.
• the polylactide may have a glass transition temperature of 59.3°C [+/-10°C].
• the polylactide may have an onset melting point of 138.5°C [+/-10°C] and a glass transition temperature of 59.3°C [+/-10°C].
• the polylactide may have an onset degradation temperature in air from 320°C to 345°C.
• the polylactide may have an onset degradation temperature in air of 332.8°C [+/-10°C].
• the composition may have a notched izod impact value of at least 35 kJ/m at -20°C.
• the composition may have a vicat softening temperature of less than 87°C.
• the blend composition may further have an additive such as a heat stabilizer, mold release agent, glass, colorant, or a mixture thereof.
• the one or more polycarbonates of the blend may contain isosorbide.
• the present invention is directed to an article formed from the blended composition.
• the article has an overall biocontent of greater than 35% according to ASTM D6866.
• the article may be a computer or business machine housing, a housing for a hand-held electronic device, a component of a lighting fixture or home appliance, a component of a medical application or device, or a component of an interior or exterior component of an automobile.
• the present invention is directed to a blended composition
• a blended composition comprising (a) one or more polycarbonates wherein at least one of the polycarbonates contains at least one structural unit having the formula:
• Ri is an isosorbide unit and R2-R9 are independently selected from the group consisting of a hydrogen, a halogen, a Ci-C 6 alkyl, a methoxy, an ethoxy, and an alkyl ester; (b) one or more polylactide polymers having the following structural unit wherein n is from 1000 to 3000; and (c) an impact modifier.
• the blended composition may have an overall biocontent of at least 50% according to ASTM D6866 and a notched izod impact value of at least 48 kJ/m at 23 °C.
• Described herein is a high impact isosorbide-based polylactide blend composition
• a high impact isosorbide-based polylactide blend composition comprising a combination of one or more isosorbide polycarbonates, a polylactide or polylactic acid (PLA) polymer, and an impact modifier.
• the inventors have discovered that the combination of an isosorbide-based polycarbonate copolymer, a polylactide polymer, and an impact modifier imparts desirable impact strength for the formation of articles molded from the composition. While increasing the overall biocontent of the composition over at least 30% according to ASTM D-6866, the composition favorably provides impact strengths of over 35 kJ/m .
• compositions may further comprise other additives such as heat stabilizers, mold release agents, impact modifiers, UV stabilizers, flame retardants, antistatic agents, anti-drip agents, blowing agents, radiation stabilizers and/or colorants.
• additives such as heat stabilizers, mold release agents, impact modifiers, UV stabilizers, flame retardants, antistatic agents, anti-drip agents, blowing agents, radiation stabilizers and/or colorants.
• These high biocontent, high impact strength compositions may be formed into a number of different articles such as computer or business machine housings, housings for hand-held devices, components for light fixtures or home appliances, components for medical applications or devices, or components for interior or exterior components of an automobile.
• Alkyl as used herein may mean a linear, branched, or cyclic group, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, cyclopentyl group, cyclohexyl group, and the like.
• alkenyl as used herein may be a straight or branched hydrocarbyl chain containing one or more double bonds. Each carbon-carbon double bond may have either cis or trans geometry within the alkenyl moiety, relative to groups substituted on the double bond carbons.
• alkenyl groups include ethenyl (vinyl), 2-propenyl, 3-propenyl,
• 1,4-pentadienyl 1,4-pentadienyl, 1 ,4-butadienyl, 1-butenyl, 2-butenyl, and 3-butenyl.
• alkenylene as used herein may be a divalent unsaturated hydrocarbyl chain which may be linear or branched and which has at least one carbon-carbon double bond.
• Antistatic agent as used herein may be monomeric, oligomeric, or polymeric materials that can be processed into polymer resins and/or sprayed onto materials or articles to improve conductive properties and overall physical performance. These monomeric, oligomeric, or polymeric materials may also be used as additives.
• Biocontent may mean a polymer or composition containing a polymer derived, at least in part, from biologically-based molecular units.
• the biologically-based unit may be a biologically-derived monomer.
• the biologically based monomer may be derived from a plant, for example.
• the plant may be any plant, such as a starch-based plant, castor bean, palm oil, vegetable oil, sugar cane, corn, rice, switch-grass, etc.
• the biologically-based unit may be isosorbide, sebacic acid, azelaic acid, etc.
• Copolymer as used herein may mean a polymer derived from two or more structural units or monomeric species, as opposed to a homopolymer, which is derived from only one structural unit or monomer.
• C 3 -C 6 cycloalkyl as used herein may mean cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• Glass Transition Temperature may mean the maximum temperature that a polymer, such as a polycarbonate, will have one or more useful properties. These properties include impact resistance, stiffness, strength, and shape retention.
• the Tg of a polycarbonate therefore may be an indicator of its useful upper temperature limit, particularly in plastics applications.
• the Tg may be measured using a differential scanning calorimetry method and expressed in degrees Celsius.
• the glass transition temperature of a polymer may depend primarily on the composition of the polymer.
• Polycarbonates that are formed from monomers having more rigid and less flexible chemical structures than Bisphenol-A generally have higher glass transition temperatures than Bisphenol-A polycarbonate, while polycarbonates that are formed from monomers having less rigid and more flexible chemical structures than Bisphenol- A generally have lower glass transition temperatures than Bisphenol-A polycarbonate.
• a polycarbonate described herein formed from 33 mole % of a rigid monomer, 3,3- bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one (“PPPBP”), and 67 mole % Bisphenol-A has a glass transition temperature of 198 °C
• a polycarbonate described herein formed from Bisphenol-A, but also having 6 wt % of siloxane units, a flexible monomer has a glass transition temperature of 145 °C.
• Mixing of two or more polycarbonates having different glass transition temperatures may result in a glass transition temperature value for the mixture that is intermediate between the glass transition temperatures of the polycarbonates that are mixed.
• the glass transition temperature of a polycarbonate may also be an indicator of the molding or extrusion temperatures required to form polycarbonate parts. The higher the glass transition temperature of the polycarbonate the higher the molding or extrusion temperatures that are needed to form polycarbonate parts.
• the glass transition temperatures (Tg) described herein are measures of heat resistance of the corresponding polycarbonate and polycarbonate blends.
• the Tg can be determined by differential scanning calorimetry.
• the calorimetric method may use a TA Instruments Q1000 instrument, for example, with a setting of 20°C/min ramp rate and 40°C start temperature and 200°C end temperature.
• Halo as used herein may be a substituent to which the prefix is attached is substituted with one or more independently selected halogen radicals.
• Ci-C 6 haloalkyl means a Ci-C 6 alkyl substituent wherein one or more hydrogen atoms are replaced with independently selected halogen radicals.
• Non-limiting examples of Ci-C 6 haloalkyl include chloromethyl, 1-bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and 1,1,1- trifluoroethyl. It should be recognized that if a substituent is substituted by more than one halogen radical, those halogen radicals may be identical or different (unless otherwise stated).
• Halogen or "halogen atom” as used herein may mean a fluorine, chlorine, bromine, or iodine atom.
• Heat deflection temperature or “Heat distortion temperature” or “HDT” as used herein may mean the temperature at which a polymer or plastic sample deforms under a specified load. This property of a given plastic material is applied in many aspects of product design, engineering, and manufacture of products using thermoplastic components.
• Heat Distortion Temperature is determined by the following test procedure outlined in ASTM D648. The test specimen is loaded in three-point bending in the edgewise direction. The outer fiber stress used for testing is either 0.455 MPa or 1.82 MPa, and the temperature is increased at 2 °C/min until the specimen deflects 0.25 mm. This is similar to the test procedure defined in the ISO
• the HDT of a particular material can also be very sensitive to stress experienced by the component which is dependent on the component's dimensions.
• the selected deflection of 0.25 mm (which is 0.2% additional strain) is selected arbitrarily and has no physical meaning.
• Heat of fusion may be the change in enthalpy resulting from the addition or removal of heat from 1 mole of a substance to change its state from a solid to a liquid
• the heat of fusion can be observed by measuring the temperature of water as it freezes. If a closed container of room temperature water is plunged into a very cold environment (e.g., -20°C), the temperature will fall steadily until it drops just below the freezing point (0°C). The temperature then will rebound and hold steady while the water crystallizes. Once the water is completely frozen, its temperature will fall steadily again.
• the units of heat of fusion may be expressed as kilojoules per mole (SI units).
• Heteroaryl as used herein may mean any aromatic heterocyclic ring which may comprise an optionally benzocondensed 5- or 6-membered heterocycle with from 1 to 3 heteroatoms selected among N, O or S.
• Non limiting examples of heteroaryl groups may include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, imidazolyl, thiazolyl, isothiazolyl, pyrrolyl, phenyl-pyrrolyl, furyl, phenyl-furyl, oxazolyl, isoxazolyl, pyrazolyl, thienyl, benzothienyl, isoindolinyl, benzoimidazolyl, quinolinyl, isoquinolinyl, 1,2,3-triazolyl, 1 -phenyl- 1, 2, 3-triazolyl, and the like.
• Hindered phenol stabilizer as used herein may mean 3,5-di-tert-butyl-4- hydroxyhydrocinnamic acid, octadecyl ester.
• (Meth)acrylic acid includes both acrylic and methacrylic acid monomers.
• (Meth)acrylate includes both acrylate and methacrylate monomers.
• MVR Melt Volume Rate
• the MVR measurement is flow rate of a polymer in a melt phase as determined using the method of ASTM-D1238-10 or ISO 1133.
• the MVR of a molten polymer is measured by determining the amount of polymer that flows through a capillary of a specific temperature over a specified time using standard weights at a fixed temperature. MVR is expressed in cubic centimeters per 10 minutes at a particular temperature per weight value.
• MVR may be measured according to the method of ASTM-D1238-10 at 1.2 kilogram at 300°C.
• MVR may be measured according to the method of ISO 1133 at either 5kg/5minutes at 240°C or 265°C. The higher the MVR value of a polymer at a specific temperature, the greater the flow of that polymer at that specific temperature.
• Onset degradation temperature may mean thermal degradation of polymers as a result of high temperatures or overheating. At high temperatures, the components of the long chain backbone of the polymer can begin to separate (molecular scission) and react with one another to change the properties of the polymer. Thermal degradation can present an upper limit to the service temperature of plastics as much as the possibility of mechanical property loss. Indeed unless correctly prevented, significant thermal degradation can occur at temperatures much lower than those at which mechanical failure is likely to occur. The chemical reactions involved in thermal degradation lead to physical and optical property changes relative to the initially specified properties.
• Thermal degradation generally involves changes to the molecular weight (and molecular weight distribution) of the polymer and typical property changes include reduced ductility and embrittlement, chalking, color changes, cracking, and general reduction in most other desirable physical properties. Thermal degradation may occur through random chain scission, side-group elimination, or oxidation of the polymer.
• PETS release agent as used herein may mean pentaerythritol tetrastearate, mold release.
• Phosphite stabilizer as used herein may mean tris-(2,4-di-tert-butylphenyl) phosphite.
• Polycarbonate as used herein may mean an oligomer or polymer comprising residues of one or more polymer structural units, or monomers, joined by carbonate linkages.
• “Straight or branched C 1 -C 3 alkyl” or “straight or branched C 1 -C 3 alkoxy” as used herein may mean methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy and isopropoxy.
• each of the foregoing groups may be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound.
• PCI-PLA-IM High Impact Polycarbonate/Isosorbide-Polylactide-Impact Modifier
• the present invention is directed to a high impact strength polylactide blend composition
• a high impact strength polylactide blend composition comprising a combination of one or more isosorbide-based polycarbonates, polylactide or polylactic acid (PLA) polymer, and an impact modifier.
• the isosorbide component of the polycarbonates may provide an interface that interacts with PLA favorably to provide stability, and, in combination with the impact modifier, imparts increased ductility and impact strength over standard polycarbonate/polylactide polymer blends.
• the melt flow rate of the composition is similar to standard polycarbonate.
• the PCI-PLA-IM blend composition may possess 60% or greater, 65% or greater, 70% or greater, 75% or greater, 80% or greater, 85% or greater, 90% or greater, or 95% or greater ductility in a notched izod test at -20°C, -15°C, -10°C, 0°C, 5°C, 10°C, 15°C, 20°C, 23 °C, 25°C, 30°C, or 35°C at a thickness of 0.125 inches according to an ISO 180 standard.
• the PCI-PLA-IM composition may possess 100% ductility in a notched izod test at -20°C, -15°C, -10°C, 0°C, 5°C, 10°C, 15°C, 20°C, 23 °C, 25°C, 30°C, or 35°C at a thickness of 0.125 inches according to an ISO 180 standard. Notched izod measurements, in accordance with ASTM D 256-10, may be conducted on test bars that measure 0.125 inches thickness by 0.5 inches wide and 2.5 inches long at room temperature (23°C).
• the polycarbonate blend composition may possess an 80% or greater ductility in a notched izod test at 0°C at a thickness of 0.125 inches according to ASTM D 256-10.
• a sample may mean a PCI-PLA-IM composition test bar.
• the test bar may have a defined thickness.
• the PCI-PLA-IM test bar has undergone ductile failure in a notched izod test if, after impact, the bar remains as a single piece, with the two ends of the bar attached and rigid (i.e. self supporting).
• a test bar has undergone brittle failure if after impact either the two ends of the bar have broken into two separate pieces or if they are attached by only a thin, flexible connection of plastic.
• the PCI-PLA-IM blend composition may comprise 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60% (by weight of total composition) of PLA in combination with at least the one isosorbide-based polycarbonate, and still maintain ductility (100%) at -20°C, 10°C and 23°C according to ISO 180.
• ductility 100% at -20°C, 10°C and 23°C according to ISO 180.
• the addition of more than 5% of PLA to other PC- copolymers creates blend compositions that are brittle.
• the PCI-PLA-IM blend composition may have an impact strength average of greater than
• the PCI-PLA-IM blend composition may have an impact strength average of greater the 30 kJ/m 2 or greater than 40 kJ/m 2 according to ISO 180.
• the PCI-PLA-IM composition may have an impact strength average of greater than
• the PCI-PLA-IM blend composition may have an impact strength average of greater than 20 kJ/m 2 , greater than 25 kJ/m 2 , greater than 30 kJ/m 2 , greater than 35 kJ/m 2 , greater than 40 kJ/m 2 , greater than 45 kJ/m 2 , greater than 50 kJ/m 2 , greater than 55 kJ/m 2 , or greater than 60 kJ/m 2 at 0°C according to ISO 180.
• the PCI-PLA-IM blend composition may have an impact strength of greater than 40 kJ/m according to ISO 180.
• the error rate of measuring the impact strength may be + ⁇ 5kJ/m 2 .
• the PCI-PLA-IM blend composition may have a melt volume rate (MVR) of 10 to 60 grams per cubic centimeter (gm/cc) measured at 260°C per Kg load with a dwell time of 4 minutes.
• MVR melt volume rate
• the PCI-PLA-IM blend composition may have a melt volume rate (MVR) of 15 to 55 gm/cc measured at 260°C per Kg load with a dwell time of 4 minutes, of 20 to 50 gm/cc measured at 260°C per Kg load with a dwell time of 4 minutes, of 25 to 45 gm/cc measured at 260°C per Kg load with a dwell time of 4 minutes, of 30 to 40 gm/cc measured at 260°C per Kg load with a dwell time of 4 minutes, or from 33 to 37 gm/cc measured at 260°C per Kg load with a dwell time of 4 minutes according to ISO 1133.
• the PCI-PLA-IM blend composition may have a melt volume rate (MVR) of 2 to 8 kg/5 minutes at 240°C, 2.25 to 7.50 kg/5minutes at 240°C, 2.50 to 6.50 kg/5 minutes at 240°C, 3.0 to 6.0 kg/5 minutes at 240°C, 3.5 to 5.5 kg/5 minutes at 240°C, or 4.0 to 5.0 kg/5 minutes at 240°C according to ISO 1133.
• MVR melt volume rate
• the PCI-PLA-IM blend composition may have a glass transition temperature (Tg) from 130°C to 147°C, from 132°C to 145°C, from 133°C to 142°C, from 134°C to 139°C, or from 135°C to 137°C as measured using differential scanning calorimetry.
• Tg glass transition temperature
• the PCI-PLA-IM blend composition may have a glass transition temperature of 135°C.
• the PCI-PLA-IM blend composition may have a biocontent according to ASTM-D6866 of at least 25 weight %, at least 30 weight %, at least 35 weight %, at least 40 weight %, at least 45 weight %, at least 50 weight %, at least 55 weight %, at least 60 weight %, or at least 65 weight %.
• the PCI-PLA-IM blend composition may have a biocontent according to ASTM- D6866 from 45 weight % to 95 weight ; from 50 weight % to 85 weight ; from 50 weight % to 75 weight ; from 50 weight % to 70 weight ; from 50 weight % to 65 weight ; from 50 weight % to 60 weight ; or from 50 weight % to 55 weight %.
• the PCI-PLA-IM blend composition may have at least 3.0 weight %, at least 4.0%, at least 5.0 weight %, at least 6.0 weight %, at least 7.0 weight %, at least 8.0 weight %, at least 9.0 weight %, at least 10.0 weight %, at least 15.0 weight %, at least 20.0 weight %, at least 25.0 weight %, at least 30.0 weight %, at least 35.0 weight %, at least 40.0 weight %, at least 45.0 weight %, at least 50.0 weight %, at least 55.0 weight %, or at least 60.0 weight % of isosorbide content according to ASTM-D6866.
• the PCI-PLA-IM blend composition may have from 20.0 weight % to 90 weight %; from 25.0 weight % to 80 weight %; from 30.0 weight % to 70 weight %; from 40.0 weight % to 60 weight %; from 50.0 weight % to 90 weight %; from 50.0 weight % to 80 weight %; from 50.0 weight % to 70 weight %; from 50.0 weight % to 60 weight %; or from 50.0 weight % to 55 weight % of isosorbide content according to ASTM-D6866.
• the polylactide blend composition comprises one or more polycarbonates, wherein at least one of the polycarbonates contains isosorbide ("PCI").
• the one or more polycarbonates may each contain at least one isosorbide unit.
• PCI isosorbide
• Polycarbonates and “polycarbonate resins” may include homopolycarbonates, copolymers comprising different moieties in the carbonate (referred as “copolycarbonates”), copolymers comprising carbonate units and other types of polymer units such as polyester units, and combinations comprising at least one
• the polycarbonates may contain from 5 weight % to 10 weight % isosorbide, from 10 weight % to 20 weight % isosorbide, from 20 weight % to 30 weight % isosorbide, from 30 weight % to 40 weight % isosorbide, from 40 weight % to 50 weight % isosorbide, from 50 weight % to 60 weight % isosorbide, from 60 weight % to 70 weight % isosorbide, from 70 weight % to 80 weight % isosorbide, from 80 weight % to 90 weight % isosorbide, from 55 weight % to 70 weight % isosorbide, or from 50 weight % to 80 weight % isosorbide.
• the one or more polycarbonates may be a copolymer containing 65 weight % isosorbide.
• the one or more polycarbonates that contain 65 weight % isosorbide may further contain 28 weight % bisphenol A and 7 weight % C36 diol polymer.
• the C36 diol polymer may have the following structure:
• the isosorbide, bisphenol A, and the C36 diol polymer may be reacted via melt polymerization or interfacial phase transfer polymerization, for example.
• the isosorbide content may be measured according to ASTM-D6866.
• the biocontent of the PCI may from 5 weight % to 90 weight %, from 5 weight % to 25 weight %; from 10 weight % to 30 weight %; from 15 weight % to 35 weight %; from 20 weight % to 40 weight %; from 25 weight % to 45 weight %; from 30 weight % to 50 weight %; from 35 weight % to 55 weight %; from 40 weight % to 60 weight %; from 45 weight % to 65 weight %; from 55 weight % to 70% weight %; from 60 weight % to 75 weight %; from 50 weight % to 80 weight %; or from 50 weight % to 90 weight %.
• the biocontent may be measured according to ASTM D6866.
• the PCI may exhibit a notched izod impact value from 2 to 10 kJ/m at 23 °C; from 2 to 8 kJ/m 2 at 23°C; from 2 to 6 kJ/m 2 at 23°C; from 2 to 4 kJ/m 2 at 23°C; from 3 to 5 kJ/m 2 at 23°C; or from 3 to 8 kJ/m 2 at 23°C.
• the PCI may exhibit a notched izod impact value of 4 kJ/m 2 at
• the polycarbonate may be a homopolycarbonate or a copolycarbonate.
• polycarbonate and polycarbonate resin mean compositions having repeating structural carbonate units of the formula (1):
• R 1 groups may contain aromatic organic groups and the balance thereof are aliphatic or alicyclic, or aromatic groups.
• R 1 in the carbonate units of formula (1) may be a C 6 -C36 aromatic group wherein at least one moiety is aromatic.
• Each R 1 may be an aromatic organic group, for example, a group of the formula (2): A 1 Y 1 A 2 (2)
• each of the A 1 and A2 is a monocyclic divalent aryl group and Y 1 is a bridging group having one or two atoms that separate A 1 and A2.
• one atom may separate A 1 from A , with illustrative examples of these groups including -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecyclidene, cyclododecylidene, and
• the bridging group of Y 1 may be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.
• the polycarbonates may be produced from dihydroxy compounds having the formula HO-R ⁇ -OH, wherein R 1 is defined as above for formula (1).
• the formula HO-R ⁇ OH includes bisphenol compounds of the formula (3):
• the dihydroxy monomer unit of formula (3) may include bisphenol compounds of the general formula (4):
• X a may be 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 may be single bond, -0-, -S-, -C(O)-, or a C 1-18 organic group.
• the C 1-18 organic bridging group may 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 C 1-18 organic bridging group.
• R a and R b may each represent a halogen, C 1-12 alkyl group or combination thereof.
• R a and R b may each be a C 1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.
• the designation (e) is 0 or 1.
• the numbers p and q are each independently integers of 0 to 4. It will be understood that R a is hydrogen when p is 0, and likewise R b is hydrogen when q is 0.
• This may include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]- bicycloheptylidene, cyclohexyhdene, cyclopentyhdene, cyclododecyhdene, and adamantyhdene.
• X a is a substituted cycloalkylidene is the cyclohexylidene-bridged, alkyl-substituted bisphenol of formula (5):
• R a and R b are each independently C 1-12 alkyl, R g is C 1-12 alkyl or halogen, r and s are each independently 1 to 4, and t is 0 to 10. R a and R b may be disposed meta to the
• R a , R b and R g may, when comprising an appropriate number of carbon atoms, be straight chain, cyclic, bicyclic, branched, saturated, or unsaturated.
• R a , R b and R g may be each independently Q_ 4 alkyl, r and s are each 1, and t is 0 to 5.
• R a , R b and R g may each be methyl, r and s are each 1, and t is 0 or 3.
• the cyclohexylidene-bridged bisphenol can be the reaction product of two moles of o- cresol with one mole of cyclohexanone.
• the cyclohexylidene-bridged bisphenol may be the reaction product of two moles of a cresol with one mole of a hydrogenated isophorone (e.g., l,l,3-trimethyl-3-cyclohexane-5-one).
• a hydrogenated isophorone e.g., l,l,3-trimethyl-3-cyclohexane-5-one.
• Such cyclohexane-containing bisphenols for example the reaction product of two moles of a phenol with one mole of a hydrogenated isophorone, are useful for making polycarbonate polymers with high glass transition temperatures and high heat distortion temperatures.
• Cyclohexyl bisphenol-containing polycarbonates, or a combination comprising at least one of the foregoing with other bisphenol polycarbonates, are supplied by Bayer Co. under the APEC trade name.
• X a may be a C 1-18 alkylene group, a C 3 _is cycloalkylene group, a fused C 6-18 cycloalkylene group, or a group of the formula -Bi-W-B 2 - wherein Bi and B 2 are the same or different C 1-6 alkylene group and W is a C 3-12 cycloalkylidene group or a C 6-16 arylene group.
• X a may be a substituted C 3-18 cycloalkylidene of the formula (6):
• R r , R p , R q and R l are independently hydrogen, halogen, oxygen, or C 1-12 organic groups;
• I is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)- where Z is hydrogen, halogen, hydroxy, C 1-12 alkyl, C 1-12 alkoxy, C 6-12 aryl, or C 1-12 acyl;
• h is 0 to 2
• j is 1 or 2
• i is an integer of 0 or 1
• k is an integer of 0 to 3, with the proviso that at least two of R r , R p , R q and R l taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring.
• the ring as shown in formula (6) will have an unsaturated carbon-carbon linkage where the ring is fused.
• the ring as shown in formula (6) contains 4 carbon atoms; when i is 0, h is 0, and k is 2, the ring as shown contains 5 carbon atoms, and when i is 0, h is 0, and k is 3, the ring contains 6 carbon atoms.
• two adjacent groups e.g., R q and R l taken together
• R q and R l taken together form one aromatic group
• R r and R p taken together form a second aromatic group.
• R p can be a double-bonded oxygen atom, i.e., a ketone.
• each R h is independently a halogen atom, a C 1-10 hydrocarbyl such as a C 1-10 alkyl group, a halogen substituted C 1-10 hydrocarbyl such as a halogen- substituted C 1-10 alkyl group, and n is 0 to 4.
• the halogen is usually bromine.
• Bisphenol-type dihydroxy aromatic compounds may include the following: 4,4'- dihydroxybiphenyl, 1 ,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, 1 , 1 -bis(hydroxyphenyl)cyclopentane, 1 , 1 -bis(4- hydroxyphenyl)cyclohexane, l,l-bis(
• Examples of the types of bisphenol compounds represented by formula (3) may include 1 , 1 -bis(4-hydroxyphenyl)methane, 1 , 1 -bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)propane (hereinafter "bisphenol A” or "BPA”), 2,2-bis(4-hydroxyphenyl)butane,
• the dihydroxy compounds of formula (3) may be the following formula (8):
• R 3 and R5 are each independently a halogen or a Ci_ 6 alkyl group
• R4 is a Ci_ 6 alkyl, phenyl, or phenyl substituted with up to five halogens or Ci_ 6 alkyl groups
• c is 0 to 4.
• R4 is a C 1-6 alkyl or phenyl group.
• R4 is a methyl or phenyl group.
• each c is 0.
• the dihydroxy compounds of formula (3) may be the following formula (9):
• PPPBP 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one
• dihydroxy compounds of formula (3) may be the following formula
• dihydroxy compounds of formula (3) may be the following formula (1
• dihydroxy compounds having adamantane units are dihydroxy compounds having adamantane units, as described in U.S. Patent No. 7,112,644 and U.S. Patent No. 3,516,968, which are fully incorporated herein by reference.
• a compound having adamantane units may have repetitive units of the following formula (12) for high heat applications:
• Ri represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms
• R 2 represents a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms, or a fluoroalkyl group having 1 to 12 carbon atoms
• m represents an integer of 0 to 4
• n represents an integer of 0 to 14.
• dihydroxy compounds that might impart high Tgs to the polycarbonate as a homopolycarbonate or copolycarbonate are dihydroxy compounds having fluorene-units, as described in U.S. Patent No. 7,244,804.
• fluorene-unit containing dihydroxy compound is represented by the following formula (13) for high heat applications:
• Ri to R 4 are each independently a hydrogen atom, a hydrocarbon group with 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.
• Exemplary copolymers containing carbonate units may be derived from bisphenol A.
• a polyester-polycarbonate as described below way can also be used that contains units derived from a mixture of bisphenol A and PBPP, in a molar ratio of BPA:PBPP of 10:90 to 90:10, specifically 15:85 to 85: 15.
• the isosorbide of the PCI-PLA-IM blend may be derived from isosorbide-bisphenol represented by formula (14).
• Formula (14) may be used for making the polycarbonate-isosorbide polymers of the PCI-PLA-IM blend.
• Ri is an isosorbide unit and R2-R9 may be independently selected from the group consisting of a hydrogen, a halogen, a Ci-C 6 alkyl, a methoxy, an ethoxy, and an alkyl ester.
• the isosorbide unit may be represented by formula (15):
• the isosorbide unit may be derived from an isosorbide, a mixture of isosorbide, a mixture of isomers of isosorbide, and/or from individual isomers of isosorbide.
• the stereochemistry for the isosorbide-based carbonate units of formula (16) is not particularly limited. Specifically, isosorbide has the general formula (16):
• Aliphatic diols of formula (16) include l,4:3,6-dianhydro-D glucitol, of formula 17; l,4:3,6-dianhydro-D mannitol, of formula (18); and l,4:3,6-dianhydro-L iditol, of formula (19), and any combination thereof.
• Isosorbides are available commercially from various chemical suppliers including Cargill, Roquette, and Shanxi.
• the diol of formula (17) may be desirable because it is a rigid, chemically and thermally stable aliphatic diol that may be used to produce higher Tg copolymers than the other diols of formulas (18) and (19).
• the isosorbide-bisphenol may have a pKa of between 8 and 11.
• An isosorbide-bisphenol reacting compound may react with the isosorbide-bisphenol represented by formula (14).
• the isosorbide-bisphenol reacting compound may be one or more of phosgene, a triphosgene, diacyl halide, dihaloformate, dicyanate, diester, diepoxy, diarylcarbonate, dianhydride, dicarboxylic acid, and/or diacid chloride.
• the isosorbide- bisphenol reacting compound and the isosorbide-bisphenol may react under polymerization conditions to form a polymer structural unit, which can be polymerized.
• the one or more isosorbide-bisphenol structural unit(s), which may be identical or different, may be polymerized with one or more other non-isosorbide-containing monomer compounds ("other monomers") (e.g. a second, third, fourth, fifth, sixth, etc., monomer compound).
• other monomers e.g. a second, third, fourth, fifth, sixth, etc., monomer compound.
• the other monomer(s) or compounds may be optionally selected for incorporation into the product polymer. Therefore, the polymers or polycarbonates may be isosorbide- containing copolymers.
• the isosorbide-bisphenol monomers and other monomers may be randomly incorporated into the polymer.
• the copolymer may be arranged in an alternating sequence following a statistical distribution, which is independent of the mole ratio of the structural units present in the polymer chain.
• a random copolymer may have a structure, which can be indicated by the presence of several block sequences of isosorbide-containing monomers (I-I) and other monomers (O-O) and alternate sequences (TO) or (O-I), that follow a statistical distribution.
• the copolymer may have alternating copolymers with regular alternating I and O units (- I-O-I-O-I-O-I-O-), I and O units arranged in a repeating sequence (e.g. a periodic copolymer having the formula: (I-O-I-O-O-I-I-I-I-O-O)n).
• the copolymer may be a statistical copolymer in which the sequence of monomer residues follows a statistical rule. For example, if the probability of finding a given type monomer residue at a particular point in the chain is equal to the mole fraction of that monomer residue in the chain, then the polymer may be referred to as a truly random copolymer.
• the copolymer may be a block copolymer that comprises two or more homopolymer subunits linked by covalent bonds (- ⁇ - ⁇ - ⁇ - ⁇ - ⁇ -0-0-0-0-0-). The union of the homopolymer subunits may require an intermediate non-repeating subunit, known as a junction block.
• Block copolymers with two or three distinct blocks are called diblock copolymers and triblock copolymers, respectively.
• the other monomer may be a dihydroxy compound.
• the dihydroxy compound may be represented by formula (20):
• Z may be an aromatic compound or an aliphatic compound.
• the dihydroxy compound may be any bisphenol compound.
• the dihydroxy compound may be a 4,4'-(3,3,5-trimethylcyclohexylidene)diphenol; a 4,4'-bis(3,5-dimethyl)diphenol, a 1,1- bis(4-hydroxy-3-methylphenyl)cyclohexane, a 1 , 1 -bis(4'hydroxy-3 'methylphenyl)cyclohexane (DMBPC), a 4,4'-l-methyl-4-(l-methyl-ethyl)-l,3-cyclohexandiyl]bisphenol (1,3 BHPM), a 4- [l-[3-(4-hydroxyphenyl)-4-methylcyclohexyl]-l-methyl-ethyl]-phenol (2,8 BHPM), a 3,8- dihydroxy-5a,10b-diphenyl-coumarano-2', 3', 2, 3-coumarane (DCBP), a 2-phenyl
• the dihydroxy compound may be 1,3-propylene glycol, 1 ,2-propylene glycol, 2,2-diethyl-l,3-propanediol, 2,2-dimethyl-l,3-propanediol, 2-ethyl- 2-butyl-l,3-polypropanediol, 2-ethyl-2-isobutyl-l,3-propanediol, 1,3-tertbutanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-l,6-hexanediol, 1,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, or a 2,2,4,4-tetramethyl-l,3- cyclobutanediol .
• the isosorbide-bisphenol polycarbonate may be polymerized to form a homopolymer, the isosorbide-bisphenol may be polymerized with one or more other isosorbide-bisphenol structural units and/or it may be polymerized with one or more other non-isosorbide-containing monomers to form a copolymer.
• the homopolymers may be manufactured by selecting and reacting a single polymerizable isosorbide-containing monomer.
• Copolymers can be manufactured by selecting and reacting two or more different polymerizable monomers, wherein at least one monomer is an isosorbide-containing monomer, such as isosorbide bisphenol-containing structural unit.
• the isosorbide-containing polymer may be a polyurethane, a polyurea, a polyarylate, a polyester, a polyether, a polyetheramide, a polyformal, or a polyphenylene ether.
• the polymer may have a weight average molecular weight (Mw) from about 3,000 to about 150,000, from about 10,000 to about 125,000, from about 50,000 to about 100,000, or from about 75,000 to about 90,000, and a glass transition temperature (Tg) from about 80°C to about 300°C, from about 100°C to about 275°C, from about 125°C to about 250°C, from about 150°C to about 225°C, or from about 175°C to about 200°C.
• Mw weight average molecular weight
• Tg glass transition temperature
• the polymer may have a high mechanical strength.
• the elastic modulus may be about 2.0 GPa to about 6 GPa or about 3.0 GPa to about 5 GPa, as determined by, for example, an instrumented indentation technique.
• the polymer may have a hardness from about 150 MPa to about 350 MPa, from about 200 MPa to about 325 MPa, from about 225 MPa to about 300 MPa, or from about 250 MPa to about 275 MPa.
• the polymer may have a Fries product concentration of less than about 500 ppm, less than about 400 ppm, less than about 300 ppm, less than about 200 ppm, or less than about 100 ppm.
• the Fries product concentration may be determined by high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• the polymer may exhibit lower refractive index (RI), higher scratch resistance and/or lower oxygen permeability compared to conventional homo- or copolymers.
• the polymer may be optically active.
• the herein described polymers may be blended with other polymers, such as
• thermoplastics and thermosets may be blended with polycarbonates including, but not limited to, conventional BPA polycarbonate and polycarbonates made using monomers such as resorcinol, l,l-bis(4'-hydroxy-3' -methyl phenyl)cyclohexane and 4,4'[l-methyl-4-(l-methylethyl)-l,3-cyclohexandiyl]bisphenol.
• the herein described polymers may be blended with an aliphatic polyester.
• the aliphatic polyester may be polycyclohexylidene cyclohexanedicarboxylate (PCCD).
• the PCI may be manufactured using an interfacial phase transfer process or melt polymerization.
• an exemplary process generally involves dissolving or dispersing a dihydric phenol reactant in aqueous caustic soda or potash, adding the resulting mixture to a water-immiscible solvent medium such as for example methylene chloride, and contacting the reactants with a carbonate precursor (such as phosgene) in the presence of a catalyst such as, for example, triethylamine or a phase transfer catalyst salt, under controlled pH conditions, e.g., about 8 to about 10.
• a catalyst such as, for example, triethylamine or a phase transfer catalyst salt
• the PCI may alternatively be prepared by a melt polymerization process.
• polycarbonates are prepared by co-reacting, in a molten state, the dihydroxy reactant(s) (i.e., isosorbide, aliphatic diol and/or aliphatic diacid, and any additional dihydroxy compound) and a diaryl carbonate ester, such as diphenyl carbonate, or more specifically in an aspect, an activated carbonate such as bis(methyl salicyl)carbonate, in the presence of a transesterification catalyst.
• the dihydroxy reactant(s) i.e., isosorbide, aliphatic diol and/or aliphatic diacid, and any additional dihydroxy compound
• a diaryl carbonate ester such as diphenyl carbonate
• an activated carbonate such as bis(methyl salicyl)carbonate
• polymerization equipment such as one or more continuously stirred reactors (CSTR's), plug flow reactors, wire wetting fall polymerizers, free fall polymerizers, wiped film polymerizers, BANBURY® mixers, single or twin screw extruders, or combinations of the foregoing.
• volatile monohydric phenol can be removed from the molten reactants by distillation and the polymer is isolated as a molten residue.
• a useful melt process for making polycarbonates utilizes a diaryl carbonate ester having electron-withdrawing substituents on the aryls.
• diaryl carbonate esters with electron withdrawing substituents include bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4- chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl)carbonate, bis(2-acetylphenyl)carboxylate, bis(4-acetylphenyl)carboxylate, or a combination comprising at least one of the foregoing.
• the melt polymerization can include a transesterification catalyst comprising a first catalyst, also referred to herein as an alpha catalyst, comprising a metal cation and an anion.
• the cation is an alkali or alkaline earth metal comprising Li, Na, K, Cs, Rb, Mg, Ca, Ba, Sr, or a combination comprising at least one of the foregoing.
• the anion is hydroxide (OH ), superoxide ( ( 3 ⁇ 4 " ), thiolate (HS ⁇ ), sulfide (S 2 " ), a C1-C20 alkoxide, a C6-C20 aryloxide, a C1-C20 carboxylate, a phosphate including biphosphate, a C1-C20 phosphonate, a sulfate including bisulfate, sulfites including bisulfites and metabisulfites, a C1-C20 sulfonate, a carbonate including bicarbonate, or a combination comprising at least one of the foregoing.
• salts of an organic acid comprising both alkaline earth metal ions and alkali metal ions can also be used.
• Salts of organic acids useful as catalysts are illustrated by alkali metal and alkaline earth metal salts of formic acid, acetic acid, stearic acid and ethyelenediamine tetraacetic acid.
• the catalyst can also comprise the salt of a non-volatile inorganic acid.
• nonvolatile it is meant that the referenced compounds have no appreciable vapor pressure at ambient temperature and pressure. In particular, these compounds are not volatile at temperatures at which melt polymerizations of polycarbonate are typically conducted.
• the salts of nonvolatile acids are alkali metal salts of phosphites; alkaline earth metal salts of phosphites; alkali metal salts of phosphates; and alkaline earth metal salts of phosphates.
• Exemplary transesterification catalysts include, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium formate, sodium formate, potassium formate, cesium formate, lithium acetate, sodium acetate, potassium acetate, lithium carbonate, sodium carbonate, potassium carbonate, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium
• the transesterification catalyst is an alpha catalyst consisting essentially of an alkali or alkaline earth salt.
• the transesterification catalyst consists essentially of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, NaH 2 P0 4 , or a combination comprising at least one of the foregoing.
• the amount of alpha catalyst can vary widely according to the conditions of the melt polymerization, and can be about 0.001 to about 500 ⁇ . In an aspect, the amount of alpha catalyst can be about 0.01 to about 20 ⁇ , specifically about 0.1 to about 10 ⁇ , more specifically about 0.5 to about 9 ⁇ , and still more specifically about 1 to about 7 ⁇ , per mole of aliphatic diol and any other dihydroxy compound present in the melt polymerization.
• a second transesterification catalyst also referred to herein as a beta catalyst, can optionally be included in the melt polymerization process, provided that the inclusion of such a second transesterification catalyst does not significantly adversely affect the desirable properties of the isosorbide-based polycarbonate.
• exemplary transesterification catalysts can further include a combination of a phase transfer catalyst of formula (R 3 ) 4 Q + X, wherein each R 3 is the same or different, and is a C 1-10 alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a Ci_8 alkoxy group or C 6-18 aryloxy group.
• phase transfer catalyst salts include, for example, [CH 3 (CH 2 ) 3 ] 4 NX, [CH 3 (CH 2 ) 3 ] 4 PX, [CH 3 (CH 2 ) 5 ] 4 NX, [CH 3 (CH 2 ) 6 ] 4 NX,
• melt transesterification catalysts include alkaline earth metal salts or alkali metal salts.
• the beta catalyst can be present in a molar ratio, relative to the alpha catalyst, of less than or equal to 10, specifically less than or equal to 5, more specifically less than or equal to 1, and still more specifically less than or equal to 0.5.
• the melt polymerization reaction disclosed herein uses only an alpha catalyst as described hereinabove, and is substantially free of any beta catalyst.
• the beta catalyst is present in an amount of less than about 10 ppm, specifically less than 1 ppm, more specifically less than about 0.1 ppm, more specifically less than or equal to about 0.01 ppm, and more specifically less than or equal to about 0.001 ppm, based on the total weight of all components used in the melt polymerization reaction.
• activated carbonate is defined as a diarylcarbonate that is more reactive than diphenylcarbonate in transesterification reactions.
• activated carbonates include bis(o-methoxycarbonylphenyl)carbonate, bis(o-chlorophenyl)carbonate, bis(o-nitrophenyl)carbonate, bis(o-acetylphenyl)carbonate, bis(o-phenylketonephenyl)carbonate, bis(o-formylphenyl)carbonate.
• ester- substituted diarylcarbonates include, but are not limited to, bis(methylsalicyl)carbonate (CAS Registry No. 82091-12-1) (also known as BMSC or bis(o- methoxycarbonylphenyl)carbonate), bis(ethylsalicyl)carbonate, bis(propylsalicyl)carbonate, bis(butylsalicyl)carbonate, bis(benzylsalicyl)carbonate, bis(methyl-4-chlorosalicyl)carbonate and the like.
• bis(methylsalicyl)carbonate is used as the activated carbonate in melt polycarbonate synthesis due to its lower molecular weight and higher vapor pressure.
• non-limiting examples of non-activating groups which, when present in an ortho position, would not be expected to result in activated carbonates are alkyl, cycloalkyl or cyano groups.
• Some specific and non-limiting examples of non-activated carbonates are bis(o- methylphenyl)carbonate, bis(p-cumylphenyl)carbonate, bis(p-(l , 1,3,3- tetramethyl)butylphenyl)carbonate and bis(o-cyanophenyl)carbonate. Unsymmetrical combinations of these structures can also be used as non-activated carbonates.
• An end-capping agent (also referred to as a chain- stopper) may optionally be used to limit molecular weight growth rate, and so control molecular weight in the polycarbonate.
• exemplary chain-stoppers include certain monophenolic compounds (i.e., phenyl compounds having a single free hydroxy group), monocarboxylic acid chlorides, and/or monochloroformates.
• Phenolic chain-stoppers are exemplified by phenol and C1-C22 alkyl- substituted phenols such as p-cumyl -phenol, resorcinol monobenzoate, and p- and tertiary-butyl phenol, cresol, and monoethers of diphenols, such as p-methoxyphenol.
• Alkyl-substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms can be specifically mentioned.
• Certain monophenolic UV absorbers can also be used as a capping agent, for example 4-substituted-2- hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2- hydroxyaryl)-l,3,5-triazines and their derivatives, and the like.
• endgroups can derive from the carbonyl source (i.e., the diaryl carbonate), from selection of monomer ratios, incomplete polymerization, chain scission, and the like, as well as any added end-capping groups, and can include derivatizable functional groups such as hydroxy groups, carboxylic acid groups, or the like.
• the endgroup of a polycarbonate, including an isosorbide-based polycarbonate polymer as defined herein can comprise a structural unit derived from a diaryl carbonate, where the structural unit can be an endgroup.
• the endgroup is derived from an activated carbonate.
• Such endgroups can derive from the transesterification reaction of the alkyl ester of an appropriately substituted activated carbonate, with a hydroxy group at the end of a polycarbonate polymer chain, under conditions in which the hydroxy group reacts with the ester carbonyl from the activated carbonate, instead of with the carbonate carbonyl of the activated carbonate.
• structural units derived from ester containing compounds or substructures derived from the activated carbonate and present in the melt polymerization reaction can form ester endgroups.
• ester endgroup derived from a salicylic ester can be a residue of BMSC or other substituted or unsubstituted bis(alkyl salicyl)carbonate such as bis(ethyl salicyl)carbonate, bis(propyl salicyl)carbonate, bis(phenyl salicyl)carbonate, bis(benzyl salicyl)carbonate, or the like.
• an isosorbide-based polycarbonate polymer prepared from an activated carbonate may comprise endgroups in an amount of less than 2,000 ppm, less than 1,500 ppm, or less than 1,000 ppm, based on the weight of the polycarbonate.
• an isosorbide-based polycarbonate polymer prepared from an activated carbonate can comprise endgroups in an amount of less than or equal to 500 ppm, less than or equal to 400 ppm, less than or equal to 300 ppm, or less than or equal to 200 ppm, based on the weight of the polycarbonate.
• the reactants for the polymerization reaction using an activated aromatic carbonate can be charged into a reactor either in the solid form or in the molten form.
• Initial charging of reactants into a reactor and subsequent mixing of these materials under reactive conditions for polymerization can be conducted in an inert gas atmosphere such as a nitrogen atmosphere.
• the charging of one or more reactant can also be done at a later stage of the polymerization reaction.
• Mixing of the reaction mixture is accomplished by any methods known in the art, such as by stirring.
• Reactive conditions include time, temperature, pressure and other factors that affect polymerization of the reactants.
• the activated aromatic carbonate is added at a mole ratio of 0.8 to 1.3, and more preferably 0.9 to 1.3, and all subranges there between, relative to the total moles of monomer unit compounds (i.e., isosorbide, aromatic dihydroxy compound, and aliphatic diacid or diol).
• the molar ratio of activated aromatic carbonate to monomer unit compounds is 1.013 to 1.29, specifically 1.015 to 1.028.
• the activated aromatic carbonate is BMSC.
• the melt polymerization reaction may be conducted by subjecting the reaction mixture to a series of temperature-pressure-time protocols. In some aspects, this involves gradually raising the reaction temperature in stages while gradually lowering the pressure in stages. In one aspect, the pressure is reduced from about atmospheric pressure at the start of the reaction to about 1 millibar (100 Pa) or lower, or in another aspect to 0.1 millibar (10 Pa) or lower in several steps as the reaction approaches completion.
• the temperature can be varied in a stepwise fashion beginning at a temperature of about the melting temperature of the reaction mixture and subsequently increased to final temperature. In one aspect, the reaction mixture is heated from room temperature to about 150°C. In such an aspect, the polymerization reaction starts at a temperature of about 150°C to about 220°C.
• the polymerization temperature can be up to about 220°C.
• the polymerization reaction can then be increased to about 250°C and then further increased to a temperature of about 320°C, and all subranges there between.
• the total reaction time can be from about 30 minutes to about 200 minutes and all subranges there between. This procedure will generally ensure that the reactants react to give polycarbonates with the desired molecular weight, glass transition temperature and physical properties.
• the reaction proceeds to build the polycarbonate chain with production of ester-substituted alcohol by-product such as methyl salicylate.
• efficient removal of the by-product can be achieved by different techniques such as reducing the pressure. Generally the pressure starts relatively high in the beginning of the reaction and is lowered progressively throughout the reaction and temperature is raised throughout the reaction.
• the progress of the reaction can be monitored by measuring the melt viscosity or the weight average molecular weight of the reaction mixture using techniques known in the art such as gel permeation chromatography. These properties can be measured by taking discreet samples or can be measured on-line. After the desired melt viscosity and/or molecular weight is reached, the final polycarbonate product can be isolated from the reactor in a solid or molten form. It will be appreciated by a person skilled in the art, that the method of making aliphatic
• homopolycarbonate and aliphatic-aromatic copolycarbonates as described in the preceding sections can be made in a batch or a continuous process and the process disclosed herein is essentially preferably carried out in a solvent free mode. Reactors chosen should ideally be self- cleaning and should minimize any "hot spots.” However, vented extruders similar to those that are commercially available can be used.
• the aliphatic homopolycarbonate and aliphatic-aromatic copolycarbonate can be prepared in an extruder in presence of one or more catalysts, wherein the carbonating agent is an activated aromatic carbonate.
• the reactants for the polymerization reaction can be fed to the extruder in powder or molten form.
• the reactants are dry blended prior to addition to the extruder.
• the extruder can be equipped with pressure reducing devices (e.g., vents), which serve to remove the activated phenol by-product and thus drive the polymerization reaction toward completion.
• the molecular weight of the polycarbonate product can, in various aspects, be manipulated by controlling, among other factors, the feed rate of the reactants, the type of extruder, the extruder screw design and configuration, the residence time in the extruder, the reaction temperature and the pressure reducing techniques present on the extruder.
• the molecular weight of the polycarbonate product can also depend upon the structures of the reactants, such as, activated aromatic carbonate, aliphatic diol, dihydroxy aromatic compound, and the catalyst employed.
• Many different screw designs and extruder configurations are commercially available that use single screws, double screws, vents, back flight and forward flight zones, seals, sidestreams and sizes.
• One skilled in the art can find the best designs using generally known principals of commercial extruder design.
• the most important variable controlling the Mw when using an activated carbonate is the ratio diarylcarbonate/diol, specifically BMSC/diol. A lower ratio will give a higher molecular weight.
• decomposition by-products of the reaction that are of low molecular weight can be removed by, for example, devolatilization during reaction and/or extrusion to reduce the amount of such volatile compounds.
• the volatiles typically removed can include unreacted starting diol materials, carbonate precursor materials, but are more specifically the decomposition products of the melt-polymerization reaction,
• All types of polycarbonate end groups are contemplated as being useful in the high and low Tg polycarbonates, provided that such end groups do not significantly adversely affect desired properties of the compositions.
• An end-capping agent also referred to as a chain- stopper
• exemplary chain-stoppers include certain monophenolic compounds (i.e., phenyl compounds having a single free hydroxy group), monocarboxylic acid chlorides, and/or monochloroformates.
• Phenolic chain-stoppers are exemplified by phenol and C1-C22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p- and tertiary-butyl phenol, cresol, and monoethers of diphenols, such as p-methoxyphenol.
• Alkyl- substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms can be specifically mentioned.
• Endgroups can be derived from the carbonyl source (i.e., the diaryl carbonate), from selection of monomer ratios, incomplete polymerization, chain scission, and the like, as well as any added end-capping groups, and can include derivatizable functional groups such as hydroxy groups, carboxylic acid groups, or the like.
• the endgroup of a polycarbonate can comprise a structural unit derived from a diaryl carbonate, where the structural unit can be an endgroup.
• the endgroup is derived from an activated carbonate.
• Such endgroups can derive from the transesterification reaction of the alkyl ester of an appropriately substituted activated carbonate, with a hydroxy group at the end of a polycarbonate polymer chain, under conditions in which the hydroxy group reacts with the ester carbonyl from the activated carbonate, instead of with the carbonate carbonyl of the activated carbonate.
• structural units derived from ester containing compounds or substructures derived from the activated carbonate and present in the melt polymerization reaction can form ester endgroups.
• the ester endgroup derived from a salicylic ester can be a residue of bis(methyl salicyl) carbonate (BMSC) or other substituted or unsubstituted bis(alkyl salicyl) carbonate such as bis(ethyl salicyl) carbonate, bis(propyl salicyl) carbonate, bis(phenyl salicyl) carbonate, bis(benzyl salicyl) carbonate, or the like.
• BMSC bis(methyl salicyl) carbonate
• the endgroup is derived from and is a residue of BMSC, and is an ester endgroup derived from a salicylic acid ester, having the structure of formula (21):
• the reactants for the polymerization reaction using an activated aromatic carbonate can be charged into a reactor either in the solid form or in the molten form.
• Initial charging of reactants into a reactor and subsequent mixing of these materials under reactive conditions for polymerization may be conducted in an inert gas atmosphere such as a nitrogen atmosphere.
• the charging of one or more reactant may also be done at a later stage of the polymerization reaction.
• Mixing of the reaction mixture is accomplished by any methods known in the art, such as by stirring.
• Reactive conditions include time, temperature, pressure and other factors that affect polymerization of the reactants.
• the activated aromatic carbonate is added at a mole ratio of 0.8 to 1.3, and more preferably 0.9 to 1.3, and all sub-ranges there between, relative to the total moles of monomer unit compounds.
• the molar ratio of activated aromatic carbonate to monomer unit compounds is 1.013 to 1.29, specifically 1.015 to 1.028.
• the activated aromatic carbonate is BMSC.
• 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-hydroxy phenyl ethane
• 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 about 0.05 to about 2.0 wt %. Mixtures comprising linear polycarbonates and branched polycarbonates can be used.
• the polylactide blend composition comprises a polylactide or polylactic acid (either referred to as "PLA") polymer.
• PLA is a biodegradable, thermoplastic, aliphatic polyester derived from renewable resources such as corn, tapioca products, or sugarcane. It is
• PLA is a biopolymer that generates low amounts of greenhouse gases during production. PLA production is due to bacterial fermentation producing lactic acid, which is oligomerized and catalytically dimerized to make the monomer for ring-opening polymerization. PLA may be easily produced in high molecular weight form through ring-opening
• PLA production and consumption provide a lower total energy consumption than other non-biocontent polymers.
• the PLA polymer may be a melt processed polymer based on D and/or L isomeric lactic acid.
• the isomers may be used singularly or in combination to form a PLA polymer.
• the PLA polymer may include an L-isomeric lactic acid, a D-isomeric lactic acid, or an L,D-isomeric lactic acid.
• the PLA may be a mixture of standard PLA and those with D-lactide monomers that form a stereocomplex PLA as discussed below.
• PLA may be a blend of poly-L-lactide (PLLA) and poly-D-lactide (PDLA) at particular rations. Standard PLA has a higher content of PLLA (around 70-80%).
• PLA may be stereocomplex PLA, which is a 50/50 blend of PLLA and PDLA.
• the PLA may have the following structural unit
• n is from 400 to 4000, 500 to 4500, 600 to 4400, 700 to 4300, 800 to 4200, 900 to 4100, 1000 to 4000, 1000 to 3900, 1000 to 3800, 1000 to 3700, 1000 to 3600, 1000 to 3500, 1000 to 3400, 1000 to 3300, 1000 to 3200, 1000 to 3100, 1000 to 3000, 1000 to 2900, 1000 to 2800, 1000 to 2700, 1000 to 2600, 1000 to 2500, 1100 to 2400, 1200 to 2300, 1300 to 2200, 1400 to 2100, 1500 to 2000, 1600 to 1900, or 1700 to 1800.
• the PLA may not have any particular limitation on the molecular weight or molecular weight distribution in the composition as long as the composition can be molded.
• the PLA may have an overall average molecular weight of from 100,000 to 300,000, 110,000 to 290,000, 120,000 to 280,000, 130,000 to 270,000, 140,000 to 260,000, 150,000 to 250,000, 160,000 to 240,000, 170,000 to 230,000, 180,000 to 220,000, 190,000 to 210,000, 190,000 to 205,000, or 195,000 to 205,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• the PLA may have an overall average molecular weight of 100,000 to 300,000, 150,000 to 250,000, 175,000 to 225,000, or 160,000 to 200,000 as measured by gel permeation chromatography using polystyrene standards.
• the PLA may have an overall average molecular weight of 160,000 to 200,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• the PLA may have an overall average molecular weight of less or equal to: 300,000 g/mole, 275,000 g/mole, 250,000 g/mole, 245,000 g/mole, 240,000 g/mole, 235,000 g/mole, 230,000 g/mole, 225,000 g/mole, 220,000 g/mole, 215,000 g/mole, 210,000 g/mole, 205,000 g/mole, 200,000 g/mole, 195,000 g/mole, 190,000 g/mole, 185,000 g/mole, 180,000 g/mole, 175,000 g/mole, 170,000 g/mole, 160,000 g/mole, 145,000 g/mole, 130,000 g/mole, 125,000 g/mole 120,000 g/mole, 115,000 g/mole, 110,000 g/mole, 105,000 g/mole, or 100,000 g/mole as measured by gel permeation chromatography using poly
• the PLA may have a weight average molecular weight of greater than or equal to: 150,000 grams per mole (g/mole), 160,000 g/mole, 170,000 g/mole, 180,000 g/mole, 190,000 g/mole, 200,000 g/mole, 205,000 g/mole, 210,000 g/mole, 215,000 g/mole, 220,000 g/mole, 225,000 g/mole, 230,000 g/mole, 235,000 g/mole, 240,000 g/mole, 245,000 g/mole, 250,000 g/mole, 260,000 g/mole, 265,000 g/mole, 270,000 g/mole, or 275,000 g/mole in order to provide a molded product with balanced mechanical strength and heat resistance.
• the error rate of the molecular weight of PLA may be +1,000 g/mole.
• the PLA weight % content of the composition may be from 2 to 30 weight percent (%), from 3 to 28 weight %, from 4 to 27 weight %, from 5 to 25 weight %, from 6 to 23 weight %, from 7 to 20 weight %, from 8 to 18 weight %, from 9 to 16 weight %, from 10 to 15 weight %, or from 11 to 13 weight %.
• the PLA weight % content of the composition may be 2.0 weight %, 2.5 weight %, 3.0 weight %, 3.5 weight , 4.0 weight %, 4.5 weight %, 5 weight %, 6 weight %, 1 weight %, 8 weight %, 9 weight %, 10 weight %, 11 weight %, 12 weight %, 13 weight %, 14 weight %, 15 weight %, 16 weight %, 17 weight %, 18 weight %, 19 weight %, 20 weight %, 21 weight %, 22 weight %, 23 weight %, 24 weight %, or 25 weight %.
• the PLA may be from 2.5% to 15%, or from 5% to 25% of the total composition.
• the PLA may be from 5 to 25% weight of the total composition.
• the onset degradation temperature of PLA may be from 325°C to 340°C or from 330°C to 335°C.
• the onset degradation temperature of PLA may be 325°C, 326°C, 327°C, 328°C, 329°C, 330 °C, 331°C, 332°C, 332.1°C, 332.2°C, 332.3°C, 332.4°C, 332.5 °C, 332.6°C, 332.7°C, 332.8°C, 332.9°C, 333.0°C, 334°C, 335°C, 336°C, 337°C, 338 C, 339°C, or 340°C as measured in air.
• the onset degradation temperature of PLA may be 332.8°C as measured in air.
• the onset degradation temperature of PLA may be 325 °C, 326°C, 327°C, 328°C, 329°C, 330°C, 331°C, 332°C, 333°C, 333.1°C, 333.2°C, 333.3°C, 333.4°C, 333.5°C, 333.6°C, 333.7°C, 333.8°C, 333.9°C, 334°C, 335°C, 336°C, 337°C, 338°C, 339°C, or 340°C as measured in nitrogen.
• the onset degradation temperature of PLA may be 333.4°C as measured in nitrogen.
• the heat of fusion temperature for PLA may be -16.0°C, -16.5°C, -17.0°C, -18.0°C, - 18.1°C, -18.2°C, -18.3°C, -18.4°C, -18.5°C, -18.6°C, -18.7°C, -18.8°C, -18.9°C, -19.0°C, - 19.5°C, or -20.0°C.
• the heat of fusion temperature for PLA may be -18.3°C.
• the overall melt flow rate of the PLA may be from 1 to 200, 2 to 50, or 3 to about 20 g/10 minutes as determined according to ASTM D1238-E (210 °C/2.16kg).
• the PLA may have a melting point (Tm) of 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C, 160°C, 161°C, 162°C, 163°C, 164°C, 165°C, 166°C, 167°C, 168°C, 169°C, 170°C, 171°C, 172°C, 173°C, 174°C, 175°C, 176°C, 177°C, or 178°C.
• Tm melting point
• the PLA may have a melting point of 165°C.
• the PLA may have a glass transition temperature of from 50°C to 70°C, from 55°C to 65°C, or from 58°C to 63°C.
• the PLA may have a glass transition temperature of 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, or 70°C.
• the PLA may have a glass transition temperature of 59.3 °C [ + " 10°C] or 60°C [ + " 10°C].
• the PLA may have a melting point of 178°C.
• the PLA may have an onset melting point of from 120°C to 165 °C ; from 125 °C to 160°C; from 130°C to 155°C; from 135°C to 150°C; from 140°C to 150°C; from 130°C to 140°C; or from 135°C to 140°C.
• the PLA may have an onset melting point of 138.5°C.
• An L-isomeric lactic acid may lead to synthesis of a poly-L-lactide (PLLA).
• the poly- L-lactide (PLLA) is a product from the polymerization of L,L-lactide and is a homopolymer.
• the PLLA may have a molecular weight of 1,000,000.
• PLLA has a crystalline percentage around 37%, a glass transition temperature between 50-80 °C and a melting temperature between 173-178 °C.
• the PLLA may be combined with poly-D-lactide (PDLA) to make poly-DL-lactide (PDLLA).
• PLLA may have an average molecular weight of 100,000 to 180,000 g/mole, 110,000 to 170,000 g/mole, 120,000 to 160,000 g/mole, 130,000 to 150,000 g/mole, or 135,000 to 145,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• PLLA may have an average molecular weight of 140,000 to 220,000 g/mole, 150,000 to 200,000 g/mole, 160,000 to 180,000 g/mole, or 170,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• the D-isomeric lactic acid or lactide may lead to the synthesis of poly-D-lactide (PDLA).
• Poly-D-lactide (PDLA) is a nucleating agent that increases the crystallization rate of overall PLA copolymer blends.
• the poly-D-lactide may be a monomer developed and is commercially available by Purac, Frankfurt, Germany.
• the D-lactide monomer can be polymerized into a PDLA homopolymer, with L-lactide to make PDLLA (discussed below), or the PLA (which is a mixture of PLLA and PDLA) to make a stereocomplex PLA.
• PDLA may have an average molecular weight of 140,000 to 240,000 g/mole, 150,000 to 230,000 g/mole, 160,000 to 220,000 g/mole, 170,000 to 210,000 g/mole, 180,000 to 200,000 g/mole, or 185,000 to 195,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• PDLA may have an average molecular weight of 140,000 to 220,000 g/mole, 150,000 to 210,000 g/mole, 160,000 to 200,000 g/mole, or 170,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• PDLLA poly-DL-lactide
• the PDLLA may have an overall average molecular weight of 100,000 to 300,000 g/mole, 110,000 to 290,000 g/mole, 120,000 to 280,000 g/mole, 130,000 to 270,000 g/mole, 140,000 to 260,000 g/mole, 150,000 to 250,000 g/mole, 160,000 to 240,000 g/mole, 170,000 to 230,000 g/mole, 180,000 to 220,000 g/mole, 190,000 to 210,000 g/mole, 190,000 to 205,000 g/mole, or 195,000 to 205,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• the PDLLA may have an overall average molecular weight of 100,000 to 300,000 g/mole, 150,000 to 250,000 g/mole, or 175,000 to 225,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• the PDLLA may have an overall average molecular weight of 160,000 to 200,000 g/mole as measured by gel permeation chromatography using polystyrene standards.
• PLA may be a blend of PLLA and PDLA at particular ratios. Standard PLA has a higher content of PLLA (around 70-80%).
• PLA may be stereocomplex PLA, which is a 50/50 blend of PLLA and PDLA.
• PLA may be processed like most thermoplastics into fiber and file using methods such as the melt spinning process.
• PDLA poly-D-lactide
• PLLA poly-L- lactide
• D-lactide as discussed above may be combined with standard commercial PLA, with mostly PLLA with small amounts of PDLA impurities to make the stereocomplex PLA (50-50 blend).
• This PLA 50/50 blend has a melt temperature range of 428 to 446 °F over 300 to 320 °F of standard PLA.
• the heat deflection temperature (HDT) according to ASTM D648 of the PLA 50/50 blend may be 320 to 333 °F as compared to 212 to 300 °F for highly crystalline PLLA and 130 to 140 °F for standard PLA. Maximum effects are observed in temperature stability when this 50-50 blend is used, but lower concentrations of PDLA (e.g., a reduction 3-10%) may be used,
• the polylactide blend composition may further comprise impact modifiers.
• the composition can further include impact modifier(s), with the proviso that the additives are selected so as to not significantly adversely affect the desired properties of the composition.
• Suitable impact modifiers may be high molecular weight elastomeric materials derived from olefins, mono vinyl aromatic monomers, acrylic and methacrylic acids and their ester derivatives, as well as conjugated dienes.
• the polycarbonate blend composition formed from conjugated dienes can be fully or partially hydrogenated.
• the elastomeric materials can be in the form of homopolymers or copolymers, including random, block, radial block, graft, and core-shell copolymers. Combinations of impact modifiers may be used.
• a specific type of impact modifier may be an elastomer-modified graft copolymer comprising (i) an elastomeric (i.e., rubbery) polymer substrate having a Tg less than about 10°C, less than about 0°C, less than about -10°C, or between about -40°C to -80°C, and (ii) a rigid polymer grafted to the elastomeric polymer substrate.
• Materials suitable for use as the elastomeric phase include, for example, conjugated diene rubbers, for example polybutadiene and polyisoprene; copolymers of a conjugated diene with less than about 50 wt % of a copolymerizable monomer, for example a monovinylic compound such as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate; olefin rubbers such as ethylene propylene copolymers (EPR) or ethylene-propylene-diene monomer rubbers (EPDM); ethylene-vinyl acetate rubbers; silicone rubbers; elastomeric C 1-8 alkyl(meth)acrylates; elastomeric copolymers of C 1-8
• conjugated diene rubbers for example polybutadiene and polyisoprene
• alkyl(meth)acrylates with butadiene and/or styrene or combinations comprising at least one of the foregoing elastomers.
• Materials suitable for use as the rigid phase include, for example, monovinyl aromatic monomers such as styrene and alpha-methyl styrene, and monovinylic monomers such as acrylonitrile, acrylic acid, methacrylic acid, and the Ci-C 6 esters of acrylic acid and methacrylic acid, specifically methyl methacrylate.
• Specific impact modifiers include styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene- styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), and styrene-acrylonitrile (SAN).
• SBS styrene-butadiene-styrene
• SBR styrene-butadiene rubber
• SEBS styrene-ethylene-butadiene-styrene
• ABS acrylonitrile-butadiene- styrene
• AES acrylonitrile
• Exemplary elastomer-modified graft copolymers include those formed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene- isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), and styrene-acrylonitrile (SAN).
• SBS styrene-butadiene-styrene
• SBR styrene-butadiene rubber
• SEBS styrene-ethylene-butadiene-styrene
• ABS acrylonitrile-butadiene-
• MBS may be derived from the following monomers:
• the MBS impact modifier may be paraloid BPM 520, which is available from Dow Plastics Additives.
• the impact modifier may contain from 40% to 50% rubber content, 50% to 60% rubber content, 60% to 70% rubber content, 70% to 75% rubber content, 70% to 80% rubber content, 80% to 90% rubber content, or 90% to 99% rubber content.
• Paraloid BPM 520 may contain between 70% and 75% rubber content (soft phase).
• the rubber content (soft phase) may represent the content of butadiene.
• SEBS may be a linear triblockcopolymer based on styrene and ethylene/butylene. Each copolymer chain may consist of three blocks: a middle block that is a random ethylene/butylene copolymer surrounded by two blocks of polystyrene.
• the SEBS may be styrene-b-(ethylene-co- butylene)-b-styrene polymer.
• Impact modifiers may be present in amounts of 1 to 30 parts by weight, based on 100 parts by weight of copolycarbonate, and any additional polymer. Impact modifiers may include MBS and SBS.
• the polylactide blend composition may further comprise a UV stabilizer for improved performance in UV stabilization.
• UV stabilizers disperse UV radiation energy.
• UV stabilizers may be hydroxybenzophenones, hydroxyphenyl benzotriazoles, cyanoacrylates, oxanilides, and hydroxyphenyl triazines.
• UV stabilizers may include, but are not limited to, poly[(6-morphilino-s-triazine-2,4-diyl) [2,2,6, 6-tetramethyl-4-piperidyl) imino]- hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino], 2-hydroxy-4-octyloxybenzophenone (Uvinul®3008), 6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenyl (Uvinul® 3026), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol (Uvinul®3027), 2-(2H- benzotriazo
• the polylactide blend composition may comprise one or more UV stabilizers, including Cyasorb 5411, Cyasorb UV-3638, Uvinul 3030, and/or Tinuvin 234.
• Certain monophenolic UV absorbers which can also be used as capping agents, can be utilized as one or more additives; for example, 4-substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2- hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-l,3,5-triazines and their derivatives, and the like.
• the polylactide blend composition may further comprise colorants such as pigment and/or dye additives.
• Useful pigments may include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines,
• Pigment Red 101 Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or combinations comprising at least one of the foregoing pigments.
• Pigments are generally used in amounts of 0.01 to 10 parts by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition.
• Exemplary dyes are generally organic materials and include, for example, coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes;
• scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C 2 -s) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes;
• carbostyryl dyes ; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti- stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; lumin
• the polylactide blend composition may further comprise flame retardants.
• flame retardants Various types of flame retardants can also be utilized as additives.
• the flame retardant additives include, for example, flame retardant salts such as alkali metal salts of perfluorinated Ci_i6 alkyl sulfonates such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, potassium
• KSS diphenylsulfone sulfonate
• NATS sodium benzene sulfonate
• Rimar salt and KSS and NATS are particularly useful in the polyphenylsulfone sulfonate (KSS), and the like, sodium benzene sulfon
• the flame-retardants may be selected from at least one of the following: alkali metal salts of perfluorinated C 1-16 alkyl sulfonates; potassium perfluorobutane sulfonate; potassium perfluoroctane sulfonate; tetraethylammonium perfluorohexane sulfonate; and potassium diphenylsulfone sulfonate.
• the flame retardant is not a bromine or chlorine containing composition.
• the flame retardant additives may include organic compounds that include phosphorus, bromine, and/or chlorine.
• Non-brominated and non-chlorinated phosphorus-containing flame retardants can be used in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus-nitrogen bonds.
• exemplary aromatic phosphates include, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'- trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2- ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2- chloroethyl diphenyl phosphate, p-tolyl bis
• Di- or poly-functional aromatic phosphorus-containing compounds are also useful as additives, for example, compounds of the formulas below:
• polyfunctional aromatic phosphorus-containing compounds include resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol- A, respectively, their oligomeric and polymeric counterparts, and the like.
• RDP resorcinol tetraphenyl diphosphate
• the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol- A, respectively, their oligomeric and polymeric counterparts, and the like.
• Exemplary flame retardant additives containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl) phosphine oxide.
• additive may have formula (25):
• R is a C1-C36 alkylene, alkylidene or cycloaliphatic linkage, e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, or the like; or an oxygen ether, carbonyl, amine, or a sulfur-containing linkage, e.g., sulfide, sulfoxide, sulfone, or the like.
• R can also consist of two or more alkylene or alkylidene linkages connected by such groups as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, or the like.
• Ar and Ar' in formula (25) are each independently mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, or the like.
• Y is an organic, inorganic, or organometallic radical, for example (1) halogen, e.g., chlorine, bromine, iodine, fluorine or (2) ether groups of the general formula OB, wherein B is a monovalent hydrocarbon group similar to X or (3) monovalent hydrocarbon groups of the type represented by R or (4) other substituents, e.g., nitro, cyano, and the like, said substituents being essentially inert provided that there is greater than or equal to one, specifically greater than or equal to two, halogen atoms per aryl nucleus.
• Ar and Ar' may further have one or more hydroxyl substituents.
• each X is independently a monovalent hydrocarbon group, for example an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, decyl, or the like; an aryl group such as phenyl, naphthyl, biphenyl, xylyl, tolyl, or the like; an aralkyl group such as benzyl, ethylphenyl, or the like; or a cycloaliphatic group such as cyclopentyl, cyclohexyl, or the like.
• the monovalent hydrocarbon group can itself contain inert substituents.
• Each d is independently 1 to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar'.
• Each e is independently 0 to a maximum equivalent to the number of replaceable hydrogens on R.
• Each a, b, and c is independently a whole number, including 0. When b is not 0, neither a nor c can be 0.
• hydroxyl and Y substituents on the aromatic groups, Ar and Ar' can be varied in the ortho, meta or para positions on the aromatic rings and the groups can be in any possible geometric relationship with respect to one another.
• polymeric or oligomeric flame retardants derived from mono or dihydroxy derivatives of formula (25) are: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2- chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; l,l-bis-(4-iodophenyl)-ethane; 1,2- bis-(2,6-dichlorophenyl)-ethane; l,l-bis-(2-chloro-4-iodophenyl)ethane; l,l-bis-(2-chloro-4- methylphenyl)-ethane; l,l-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)- ethane; 2,6-bis-(4,6-dichloronaphthyl)-
• biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1 ,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'- dichlorobiphenyl as well as decabromo diphenyl oxide, and the like.
• Another useful class of flame retardant is the class of cyclic siloxanes having the general formula (R 2 SiO)y wherein R is a monovalent hydrocarbon or fluorinated hydrocarbon having from 1 to 18 carbon atoms and y is a number from 3 to 12.
• fluorinated hydrocarbon include, but are not limited to, 3-fluoropropyl, 3,3,3-trifluoropropyl, 5,5,5,4,4,3,3- heptafluoropentyl, fluorophenyl, difluorophenyl and trifluorotolyl.
• Suitable cyclic siloxanes include, but are not limited to, octamethylcyclotetrasiloxane, 1,2,3,4-tetramethyl- 1 ,2, 3 ,4-tetravinylcyclotetrasiloxane, 1 ,2,3 ,4-tetramethyl- 1 ,2, 3 ,4-tetraphenylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octapropylcyclotetrasiloxane, octabutylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
• eicosamethylcyclodecasiloxane octaphenylcyclotetrasiloxane, and the like.
• a particularly useful cyclic siloxane is octaphenylcyclotetrasiloxane.
• the foregoing flame retardant additives are generally present in amounts of 0.01 to 10 wt %, more specifically 0.02 to 5 wt %, based on 100 parts by weight of the polymer component of the thermoplastic composition.
• the herein described polycarbonates and blends can include various additives ordinarily incorporated in polycarbonate compositions, with the proviso that the additives are selected so as to not significantly adversely affect the desired properties of the polycarbonate, such as transparency. Combinations of additives can be used. Such additives can be mixed at a suitable time during the mixing of the components for forming the polycarbonate and/or blend.
• the polylactide blend composition may further comprise heat stabilizers.
• heat stabilizer additives include, for example, organophosphites such as triphenyl phosphite, tris- (2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like; phosphonates such as dimethylbenzene phosphonate or the like, phosphates such as trimethyl phosphate, or the like, or combinations comprising at least one of the foregoing heat stabilizers.
• Heat stabilizers are generally used in amounts of 0.0001 to 1 part by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition. (5) Plasticizers, Lubricants, Mold Release Agents
• the polylactide blend composition may further comprise plasticizers, lubricants, and mold release agents.
• Mold release agent MRA
• phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris-
• polyethylene glycol polymers polypropylene glycol polymers, poly(ethylene glycol-co- propylene glycol) copolymers, or a combination comprising at least one of the foregoing glycol polymers, e.g., methyl stearate and polyethylene-polypropylene glycol copolymer in a suitable solvent; waxes such as beeswax, montan wax, paraffin wax, or the like.
• Such materials are generally used in amounts of 0.001 to 1 part by weight, specifically 0.01 to 0.75 part by weight, more specifically 0.1 to 0.5 part by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition.
• the polylactide blend composition may further comprise other fillers or reinforcing agents.
• Possible fillers or reinforcing agents include, for example, silicates and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica sand, or the like; boron powders such as boron-nitride powder, boron-silicate powders, or the like; oxides such as Ti0 2 , aluminum oxide, magnesium oxide, or the like; calcium sulfate (as its anhydride, dihydrate or trihydrate); calcium carbonates such as chalk, limestone, marble, synthetic precipitated calcium carbonates, or the like; talc, including fibrous, modular, needle shaped, lamellar talc, or the like; wollastonite; surface-treated wollastonite; glass spheres such as hollow and solid glass spheres, silicate spheres, cenospheres,
• additional fillers and reinforcing agents such as mica, clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous earth, carbon black, or the like; or combinations comprising at least one of the foregoing fillers or reinforcing agents.
• the fillers and reinforcing agents can be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polycarbonate polymeric matrix.
• the reinforcing fillers can be provided in the form of monofilament or multifilament fibers and can be used individually or in combination with other types of fiber, through, for example, co- weaving or core/sheath, side-by-side, orange- type or matrix and fibril constructions, or by other methods known to one skilled in the art of fiber manufacture.
• Exemplary co-woven structures include, for example, glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or the like.
• Fibrous fillers can be supplied in the form of, for example, 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. Fillers are generally used in amounts of 0 to 80 parts by weight, based on 100 parts by weight of the polymer component of the composition.
• the polylactide blend composition may further comprise an antioxidant additive.
• antioxidant additives include, for example, organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite ("IRGAFOS 168" or "1-168"), bis(2,4-di-t- butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like;
• organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite ("IRGAFOS 168" or "1-168"), bis(2,4-di-t- butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like;
• alkylated monophenols or polyphenols alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, or the like; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones;
• hydroxylated thiodiphenyl ethers alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5- di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearyl thiopropionate,
• Antioxidants are generally used in amounts of 0.0001 to 1 part by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition (excluding any filler).
• the polylactide blend composition may further comprise an antistatic agent.
• monomeric antistatic agents may include glycerol monostearate, glycerol distearate, glycerol tristearate, ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylarylsulfates, alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such as sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, quaternary ammonium salts, quaternary ammonium resins, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, or the like, or combinations comprising at least one of the foregoing monomeric antistatic agents.
• Exemplary polymeric antistatic agents may include certain polyesteramides polyether- polyamide (polyetheramide) block copolymers, polyetheresteramide block copolymers, polyetheresters, or polyurethanes, each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
• polyetheramide polyether- polyamide
• polyetheresteramide block copolymers polyetheresters
• polyurethanes each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
• Such polymeric antistatic agents are commercially available, for example PELESTAT® 6321 (Sanyo) or PEBAX® MH1657 (Atofina), IRGASTAT® P18 and P22 (Ciba-Geigy).
• antistatic agents are inherently conducting polymers such as polyaniline (commercially available as PANIPOL®EB from Panipol), polypyrrole and polythiophene (commercially available from Bayer), which retain some of their intrinsic conductivity after melt processing at elevated temperatures.
• Carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or a combination comprising at least one of the foregoing may be used in a polymeric resin containing chemical antistatic agents to render the composition electrostatically dissipative.
• Antistatic agents are generally used in amounts of 0.0001 to 5 parts by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition.
• the polylactide blend composition may further comprise a blowing agent.
• Foam may be a useful blowing agent.
• Low boiling halohydrocarbons and those that generate carbon dioxide may be used as blowing agents.
• Blowing agents may be used that are solid at room temperature and when heated to temperatures higher than their decomposition temperature, generate gases such as nitrogen, carbon dioxide, and ammonia gas, such as azodicarbonamide, metal salts of azodicarbonamide, 4,4' oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammonium carbonate, or the like, or combinations comprising at least one of the foregoing blowing agents.
• Blowing agents may be used in amounts of 0.01 to 20 parts by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition.
• the polylactide blend composition may further comprise anti-drip agents.
• the anti-drip agent may be a fibril forming or non-fibril forming fluoropolymer such as
• PTFE polytetrafluoroethylene
• the anti-drip agent can be encapsulated by a rigid copolymer as described above, for example styrene-acrylonitrile copolymer (SAN).
• SAN styrene-acrylonitrile copolymer
• TSAN PTFE encapsulated in SAN
• Encapsulated fluoropolymers can be made by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example an aqueous dispersion.
• TSAN can provide significant advantages over PTFE, in that TSAN can be more readily dispersed in the composition.
• An exemplary TSAN can comprise 50 wt.% PTFE and 50 wt.% SAN, based on the total weight of the encapsulated fluoropolymer.
• the SAN can comprise, for example, 75 wt.% styrene and 25 wt.% acrylonitrile based on the total weight of the copolymer.
• the fluoropolymer can be pre-blended in some manner with a second polymer, such as for, example, an aromatic polycarbonate or SAN to form an agglomerated material for use as an anti-drip agent. Either method can be used to produce an encapsulated fluoropolymer.
• Antidrip agents are generally used in amounts of 0.1 to 5 percent by weight, based on 100 parts by weight of the polymer component of the thermoplastic composition.
• the polylactide blend composition may further comprise radiation stabilizers.
• the radiation stabilizer may be a gamma-radiation stabilizer.
• Exemplary gamma-radiation stabilizers include alkylene polyols such as ethylene glycol, propylene glycol, 1,3 -propanediol, 1,2- butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4- pentanediol, 1 ,4-hexandiol, and the like; cycloalkylene polyols such as 1 ,2-cyclopentanediol, 1,2-cyclohexanediol, and the like; branched alkylenepolyols such as 2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well as
• Unsaturated alkenols are also useful, examples of which include 4-methyl-4-penten-2-ol, 3-methyl-penten-3- ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl-4-penten-2-ol, and 9 to decen-l-ol, as well as tertiary alcohols that have at least one hydroxy substituted tertiary carbon, for example 2-methyl-2,4- pentanediol (hexylene glycol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone, 2-phenyl-2- butanol, and the like, and cyclic tertiary alcohols such as 1 -hydroxy- 1-methyl-cyclohexane.
• hydroxymethyl aromatic compounds that have hydroxy substitution on a saturated carbon attached to an unsaturated carbon in an aromatic ring can also be used.
• the hydroxy- substituted saturated carbon can be a methylol group (-CH 2 OH) or it can be a member of a more complex hydrocarbon group such as -CR 4 HOH or -CR 4 2 OH wherein R 4 is a complex or a simple hydrocarbon.
• Specific hydroxy methyl aromatic compounds include benzhydrol, 1,3- benzenedimethanol, benzyl alcohol, 4-benzyloxy benzyl alcohol and benzyl benzyl alcohol.
• 2- Methyl-2,4-pentanediol, polyethylene glycol, and polypropylene glycol are often used for gamma-radiation stabilization.
• Gamma-radiation stabilizing compounds are typically used in amounts of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer component of the thermoplastic composition.
• the polylactide blend composition can be manufactured by various methods.
• the polycarbonate, epoxy resin and glass may be first blended in a high speed
• HENSCHEL-Mixer® Other low shear processes, including but not limited to hand mixing, can also accomplish this blending.
• the blend may then be fed into the throat of a single or twin- screw extruder via a hopper.
• at least one of the components can be incorporated into the composition by feeding directly into the extruder at the throat and/or downstream through a side-stuffer.
• Additives can also be compounded into a master-batch with a desired polymeric resin and fed into the extruder.
• the extruder is generally operated at a temperature higher than that necessary to cause the composition to flow.
• the extrudate is immediately quenched in a water batch and pelletized.
• the pellets, so prepared, when cutting the extrudate can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.
• the polylactide blend composition may be formed, shaped, molded or injection molded into an article.
• the article formed from the composition may have a impact value of 45 kJ/m , 50 kJ/m 2 , 55 kJ/m 2 , 60 kJ/m 2 , 65 kJ/m 2 , 70 kJ/m 2 , 75 kJ/m 2 , 80 kJ/m 2 , 85 kJ/m 2 , or 90 kJ/m 2 at 23°C according to ISO 180m, or may have an impact strength average of greater than 60 kJ/m , greater than 65 kJ/m 2 , greater than 70 kJ/m 2 , greater than 75 kJ/m 2 , greater than 80 kJ/m 2 , greater than 85 kJ/m 2 , greater than 90 kJ/m 2 , greater than 100 kJ/m 2 , or greater than 110 kJ/m 2 at 23 °C according to ISO 180 wherein
• polylactide compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding, and
• thermoforming to form articles such as, for example, various components for cell phones and cell phone covers, components for computer housings, computer housings and business machine housings such as housings for monitors, handheld electronic device housings such as computer or business machine housings, housings for hand-held devices, components for light fixtures or home appliances, components for medical applications or devices, or components for interior or exterior components of an automobile, and the like.
• the article may have a biocontent according to ASTM-D6866 of at least 25 weight %, at least 30 weight %, at least 35 weight %, at least 40 weight %, at least 45 weight %, at least 50 weight %, at least 55 weight %, at least 60 weight %, at least 65 weight %, at least 70 weight %, at least 75 weight %, at least 80 weight %, at least 85 weight %, or at least 90 weight %.
• the article may be produced by a manufacturing process.
• the process may comprise the steps of (a) providing a blended copolymer comprising (i) one or more polycarbonates as described above wherein at least one of the polycarbonates has at least some structural units derived from isosorbide, (ii) polylactide polymer and (iii) an impact modifier as described above.
• the blended copolymer from step (a) is then (b) melted (a) between 200-400°C , 225-350°C , 250-310°C, or 270-290°C in an extruder.
• the blended copolymer of step (b) is then (c) extruded, and (d) the blended copolymer is isolated or chopped.
• the article of manufacture may further be produced by the steps of (e) drying the blended copolymer of (d) wherein the article has a melt volume rate of 7.50 5kg/5minutes at 265°C according to ILOl 133, or 2.50
• a blended composition can comprise: (a) one or more polycarbonates wherein at least one of the polycarbonates is formed from a reaction between isosorbide, bisphenol A, a C36 diol, and a carbonate source; (b) one or more polylactide polymers having the following structural unit wherein n is between 1000 and 3000
• the composition has an overall biocontent of at least 50% according to ASTM D6866 and a notched izod impact value of at least 48 kJ/m 2 at 23°C.
• a blended composition can comprise: (a) one or more polycarbonates wherein at least one of the polycarbonates contains at least one structural unit
• Ri is an isosorbide unit and R2-R9 are independently selected from at least one of the following: a hydrogen, a halogen, a Ci-C 6 alkyl, a methoxy, an ethoxy, and an alkyl ester; (b) one or more polylactide polymers having the following structural unit wherein n is between 1000 and 3000
• the composition has an overall biocontent of at least 50% according to ASTM D6866 and a notched izod impact value of at least 48 kJ/m 2 at 23°C.
• the reaction in (a) is a melt polymerization reaction or an interfacial phase transfer reaction; and/or (iii) the impact modifier is at least one of styrene-butadiene-styrene (SBS), styrene- butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile- butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene- styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), styrene-acrylonitrile (SAN), or Paraloid BPM 520; and/or (iv) the impact modifier is Paraloid BPM 520; and/or (v) the composition has a notched izod impact value of at least 20 kJ/m at
• Ri is an isosorbide unit and R2-R9 are independently selected from at least one of the following: a hydrogen, a halogen, a Ci-C 6 alkyl, a methoxy, an ethoxy, and an alkyl ester.
• the article can have an overall biocontent of greater than 35% according to ASTM D6866.
• the article can be a computer or business machine housing, a housing for a hand-held electronic device, a component of a lighting fixture or home appliance, a component of a medical application or device, or a component of an interior or exterior component of an automobile.
• the present invention has multiple aspects, illustrated by the following non-limiting examples.
• An impact modified isosorbide PC copolymer blend was synthesized as shown below.
• the blend contains an isosorbide-containing polycarbonate, PLA, and the impact modifier paraloid BPM-520.
• the paraloid BPM-520 is a copolymer of methyl methacrylate, butadiene and styrene. This impact modifier contains 70-75% rubber as a soft phase.
• Paraloid BPM-520 is commercially available from Dow Chemical Company under the tradename PARALOIDTM BPM-520.
• the isosorbide-PC copolymer has the following three structural units and characteristics shown in Table 1. CH 3
• the isosorbide-PC copolymer also had a Tg of ⁇ 115°C and an MVR of 25 cc/minute when measured at 245°C (5 kg load/5 minute res time).
• the isosorbide-containing polycarbonates were made by a melt process as disclosed in U.S. Patent Application Publication No. 2011/0160422, which is hereby incorporated by reference in its entirety.
• the polycarbonates were made in melt by adding 101-103% of carbonate precursor (bis(methylsalicyl)carbonate (BMSC)) to the total of 100 mol % of dihydroxy and acid functional monomers.
• BMSC bis(methylsalicyl)carbonate
• a 200 liter stainless steel stirred tank reactor was charged with BMSC, isosorbide, bisphenol A, and C36 diol. No catalyst was added to the reactor. The reactor was then evacuated and purged with nitrogen three times to remove residual oxygen and then put to a constant pressure of 800 mbar.
• the temperature was increased to 130 °C in order to melt and to dissolve the monomers.
• the temperature was then reduced to 100 °C.
• the monomer mixture was then pumped to a plug flow reactor (PFR).
• PFR plug flow reactor
• the PFR is operated at 180 °C-200 °C and a pressure of 4-5 bar.
• the oligomer out of the PFR is transferred to a flash devolatilisation system.
• the flash devolatilization system consists of a pre-heater and a flash vessel.
• the pre- heater is operated at approximately 240 °C and 200 mbar
• the flash vessel is operated at 190 °C and 180 mbar.
• Under the flash vessel there is a melt pump which transfers the material to the extruder.
• the reaction mixture was reactively extruded at a 250-rpm screw speed.
• the extruder barrels were set to 270 °C and the die was set to 280 °C.
• the extruder was equipped with five forward vacuum vents and one back-vent.
• the extruder has one vacuum system called hi-vac, all the vents are connected to this system and have a vacuum of ⁇ 1 mbar.
• the methyl salicylate byproduct was removed via devolatilization through these vents. Collected at the end of the extruder through a die were molten strands of polymer that were solidified through a water bath and pelletized.
• the polycarbonate was extruded using the conditions described below on a twin screw extruder. During extrusion, 0.02% weight percent of a 45 weight percent H 3 PO 3 solution in water was added to stabilize the polymer and minimize degradation. 0.3 weight percent PETS was added as a mold release agent. Weight percents are based on the total weight of the composition. No other additives and/or colorants were used. Materials were extruded on a twin screw extruder using the following settings:
• Formulation 1 contains 10 wt % of a siloxane-based polycarbonate
• Formulation 3 contains 10 wt % of a terpolymer (Lotador)
• Formulation 4 contains 10 wt % of Paraloid BPM 520 impact modifier. While the Formulations that contained either the terpolymer or siloxane-based PC showed improved room temperature impact performance or no improvement, respectively, only Formulation 4, which contained the Paraloid
• BPM 520 impact modifier exhibited retention of impact performance at -20°C.
• all blends that contain between 10% and 30% PLA have notched izod impact values of between 48 and 53 kJ/m at room temperature (23°C), at least 20% ductility at -20°C, and at least an impact strength of 20 kJ/m at -20°C.
• the blends that contain between 10% and 30% PLA, with isosorbide, and between 9 and 15% of Paraloid BPM 520 have a Vicat Softening Temperature ("VST") of between 70°C and 87°C.
• VST Vicat Softening Temperature
• the MVR values of these blends vary from between 15 to 55 gm/cc as measured at 260°C/2.16 Kg load with a dwell time of 4 minutes.
• the blends having 75 wt % of isosorbide, 10 wt % of PLA, and 15 wt % of the Paraloid BPM 520 impact modifier had 100% ductility at -20°C, while the formulations that contain the Elvaloy PTW impact modifier, which is a terpolymer from Dow Chemical Co., fail to retain sufficient impact values at -20°C. Compare Run 1 and Run 9 with Runs 11-13 from Table 4.

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