Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters

Definitions

• This invention relates to linear saturated polyester compositions. More particularly, the invention is directed to a linear saturated polyester composition containing at least one ester of an ethoxylated aromatic alcohol.
• Molding formulations based on linear saturated polyesters, such as polyethylene terephthalate, should result in a molded product having good physical properties including flexural strength, modulus, tensile strength, and impact properties.
• the molding compound should have good molding properties, including a melt flow index for sufficient flow into the mold, good mold release properties and good surface finish appearance.
• the molded article should be crystalline and warp resistant.
• T cc is a measurement to determine at what temperature crystals first appear upon cooling from the melt.
• T ch is a measurement which indicates the temperature at which crystallization is no longer occurring upon cooling. It has been found that mold appearance and mold release properties can be related to T ch .
• T ch is determined by measuring the temperature at which crystals appear upon heating an amorphous piece of polyester.
• T cc and and T ch can be measured using a Differential Scanning Calorimeter.
• a variety of additives are disclosed in the art for use with linear saturated polyester compositions. Two important classes of additives include nucleators and plasticizers. Plasticizers include a variety of low molecular weight esters such as those disclosed in U.S. Patent Nos. 4,223,125 and 4,435,546. These patents describe the use of esters of alcohols having up to 20 carbon atoms and preferably having a carbon bond to ester bond ratio of between 4 and 15, inclusive of the carbonyl atom.
• nucleating agents in crystallizable polymers, such as linear saturated polyesters of aromatic dicarboxylic acids.
• U.S. Patent Nos. 3,435,093; 3,516,957; and 3,639,527 disclose various approaches .to molding thermoplastic compositions of linear saturated polyesters of aromatic dicarboxylic acids, and are particularly applicable to polyethylene terephthalate. These patents generally disclose the use of salts of hydrocarbon and polymeric carboxylic acids as nucleating agents for linear saturated polyesters.
• Great Britain Patent No. 1,315,699 discloses the use of low molecular weight sodium, lithium or barium salts of mono- or polycarboxylic acids used with solid, inert inorganic substances.
• the present invention is a compos ition comprising a linear saturated polyester and from 0.5 to 30 percent by weight of the polyester of at least one ester of an ethoxylated aromatic alcohol, preferably ethoxylated Risphenol A.
• the ester has a molecular weight of from 500 to about 1,500.
• the ethyxolated aromatic alcohol has the formula
• R is the same or different hydrocarbon radicals of from 2 to 4 carbon atoms
• n can be the same or a different integer of from 2 to 15.
• R 1 is an aromatic diradical preferably derived from an aromatic dialcohol, most preferably bisphenol A.
• Ethoxylated bisphenol A has the formula
• the acid is a carboxylic acid of from 1 to 25 and preferably 3 to 10 carbon atoms, and from 1 to 10 carboxyl groups.
• the acid is alphatic and has from 3 to 10 carbon atoms and one carboxyl group.
• composition of the present invention preferably contains a nucleating agent and optionally filler or reinforcing material, an impact modifier, an epoxy compound, and other conventional additives such as antioxidants, colorants, flame retardants and the like.
• the present invention is a composition
• a composition comprising a linear saturated polyester, and from 0.5 to 30, preferably 1.0 to 10, and more preferably 1.5 to 8, and most preferably 1.5 to 5 percent by weight of the polyester of at least one ester of an ethoxylated aromatic alcohol and wherein the ethoxylated aromatic alcohol has the formula
• R is the same or different hydrocarbon radicals of from 2 to 4 carbon atoms, and n can be the same or a different integer of from 2 to 15.
• R 1 is an aromatic radical, preferably derived from an aromatic dialcohol, most preferably bisphenol A.
• the ethoxylated alcohol has greater than 20 carbon atoms and preferably 25 to 50 carbon atoms.
• the alcohol is esterified with an acid which is a carboxylic acid of from 1 to 25 carbon atoms, preferably 3 to 10 carbon atoms.
• the acid is preferably an alphatic acid.
• the acid has from 1 to 3 carboxyl groups and preferably 1 to 2 carboxyl groups with one carboxyl group most preferred.
• the ester formed has a molecular weight of from 500 to 1500 preferably 700 to about 1,200, and more preferably 800 to 1,000.
• the preferred ethoxylated aromatic alcohol are derived from aromatic dialcohols having from at least six carbon atoms and preferably from 6 to about 15 carbon atoms.
• the aromatic portion of the aromatic dialcohol can contain substituents groups which do not make the plasticizer ineffective. Such groups could include hydrocarbons such as methyl groups, ester groups, halogen containing groups and the like.
• Preferred aromatic dialcohols include bisphenol A, resorcinol, dihydroxynapthalene (i.e., 2,6 dihydroxynapthalene), and biphenol, with bisphenol A being most preferred.
• the ethoxylated bisphenol A has the formula
• R is -CH 2 CH 2 - and n is 5.
• the carboxylic acid has from 1 to 25 and preferably from 3 to 10 carbon atoms and preferably from 1 to 3, and most preferably one carboxyl group.
• the most preferred carboxylic acid is an aliphatic carboxylic acid with from 3 to 10 carbon atoms and 1 carboxyl group.
• Useful acids include, but are not limited to, acetic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinolic acid, 2-ethyl butyric acid, tall oil acids, fatty acids, and the like.
• the most preferred acid is 2-ethylhexanoic acid.
• Di- and tri-carboxylic acids which are useful include adipic acid, azelyic acid, citric acid, fumaric acid, maleic acid, glutaric acid, succinic acid, tartaric acid, and sebacic acid.
• the above list of acids is illustrative rather than limiting.
• a preferred ester of the present composition is di- 2-ethylhexoate of an ethoxylated Bisphenol A having the formula:
• the composition of the present invention includes linear, saturated polyesters of aromatic dicarboxylic acids.
• the preferred linear saturated polyesters include polyethylene terephthalate, polybutylene terephthalate, and poly(1,4-cyclohexane dimethylene terephthalate), and mixtures thereof.
• Polyethylene terephthalate is the most preferred due its ability to be molded at low molding temperatures.
• the polyethylene terephthalate has an intrinsic viscosity range between about 0.3 and about 1.20, with a preferred intrinsic viscosity range between about 0.4 and 0.7.
• Intrinsic viscosity is obtained by extrapolation of viscosity values to zero concentration of solutions of poly(ethylene terephthalate) in a 60 to 40 weight/volume ratio of phenol and tetrachloroethane. The measurements are normalized to 25°C.
• the preferred polyethylene terephthalate melts between about 250°C and 275°C.
• the polyethylene terephthalate can contain minor amounts, up to 10%, of other comonomers such as 1,4- cyclohexyldimethyldiol, butylenediol, neopentyldiol, diethylene glycol, or glutaric acid.
• the ester of the present invention acts as plasticizer in that they lower the T ch thereby allowing crystallization to take place as the polyester composition cools to lower temperatures.
• the plasticizing effect has been found to improve mold release properties and molded appearance of molded polyester, preferably polyethylene terephthalate articles.
• T ch is the temperature at which crystal formation occurs upon heating an amorphous piece of polyester.
• T ch is measured as the maximum of the peak of the curve formed when the amorphous polyester is heated in a Differential Scanning Colorimeter (DSC). Typically the polymer is heated at 10°C/minute.
• DSC Differential Scanning Colorimeter
• the T ch for pure polyethylene terephthalate (0.5 intrinsic viscosity) is approximately 125°C- 130°C. It is desirable to lower this value as much as possible for the best mold release and molded article release properties.
• the T ch is preferably not greater than about 110°C. It has been decreased to about 94°C using 5 percent, based on the weight of the polyethylene terephthalate, of the present invention.
• the composition of the present invention preferably contains nucleating agents in combinat ion wi th the polyester and plasticizer.
• the most useful nucleating agent is at least one compound containing a sodium cation or a potassium cation.
• the nucleating agent is preferably the sodium salt of a carboxylic acid, which is most preferably a hydrocarbon carboxylic acid.
• Useful nucleating agents include the sodium or potassium salts of hydrocarbon acids containing from 3 to at least
• the hydrocarbon acids can be aromatic or aliphatic acids.
• Preferred nucleating agents include the sodium salts of a carboxyl containing organic polymer. Such a polymer can contain one or more sodium neutralized carboxyl group.
• Preferred polymeric sodium salts include copolymer acids which are the copolymers of an ⁇ -olefin and an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid.
• the copolymer molecule can include additional materials including esters and other substituents.
• the ⁇ -olefin is preferably ethylene.
• the concentration of ethylene in the copolymer is at least 50 mol percent and preferably from 80 to 95 percent by weight.
• the ⁇ , ⁇ - ethyleneically unsaturated carboxylic acid can be a monocarboxylic acid, or have more than one carboxylic group.
• the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid which can be copolymerized, with the ⁇ -alpha olefin preferably has 3 to 8 carbon atoms.
• examples of such acids include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and monoesters of other dicarboxylic acids, such as methyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogen fumarate, and maleic anhydride which is considered to behave like an acid and be an acid in the present invention.
• Useful copolymer salts include those disclosed in U.S. Patent No. 4,412,040 and U.S. Patent No.
• Preferred nucleators are the sodium salts of copolymers of ethylene and ⁇ , ⁇ ethylenically unsaturated carboxylic acids having a number average molecular weight of from 500 to 6000 as described in U.S. Patent No. 4,412,040. These salts are preferably neutralized from 50 to 100%.
• nucleating agents which are of the type described in U.S. Patent No. 4,357,268 hereby incorporated by reference. These include sodium or potassium salts of dimer acids, trimer acids, or mixtures of the two.
• the dimer acid has at least 36 carbon atoms and 2 carboxyl groups and the trimer acid has at least 54 carbon atoms and 3 carboxyl groups.
• the definition of dimer acid is a high molecular weight dibasic acid, which is liquid (viscous), stable, resistant to high temperatures. It is produced by the dimerization of unsaturated fatty acids, at mid-molecule and usually contains 36 carbon atoms. Trimer acids, which usually contain 3 carboxyl groups and 54 carbon atoms are similarly prepared.
• the temperature at which crystal formation occurs is indicated by T cc .
• the T cc is measured using a Differential Scanning Calorimeter which measures the heat evolved versus temperature. Between 5 and 10 milligrams of sample is prepared. The sample can be made in the form of a compression molded film which is vacuum dried or as a pellet which is hammered flat. The sample is placed in the Differential Scanning Calorimeter and heated to 280°C where it is held for two minutes. The sample is cooled at 10°C per minute. The T cc is the temperature at which the crystallization takes place. The T cc is approximately 195°C to 200°C for polyethylene terephthalate having an intrinsic viscosity normalized to about 0.50.
• the T cc is preferably at least 205°C, and more preferably at least 210°C.
• the preferred polyethylene terephthalate composition should have as high a T cc as possible and as low a T ch as possible, allowing crystal formation and growth over the widest possible temperature range.
• the T ch is preferably not greater than about 110°C. Therefore, the temperature range over which crystallization can occur is from about 220°C to about at least as low as 110°C during cooling of the composition of the present invention.
• the range for pure polyethylene terephthalate is about 195°C to 125°C.
• the composition can optionally contain other additives such as inert nucleating agents (i.e., talc), filler or reinforcing materials, impact modifiers, epoxies, antioxidants, colorants, flame retardants, and the like. Any suitable filler and/or reinforcing agent can be used.
• the fillers may optionally be treated with various coupling agents or adhesion promotors as is known to those skilled in the art. Such fillers may be selected from a wide variety of minerals, metals, metal oxides, siliceous materials, metal salts, and materials thereof.
• fillers examples include glass fibers, alumina, feldspar, asbestos, talc, calcium carbonates, clay, carbon black, quartz, novaculite and other forms of silica, kaolinite, bentonite, garnet, mica, saponite, etc.
• the foregoing recited fillers are illustrative only and are not meant to limit the scope of the fillers that can be utilized in this invention.
• the most preferred filler is glass fibers.
• the composition preferably includes impact modifiers known for use in polyester compositions.
• Preferred input modifiers are ethylene copolymers and terpolymers having carboxylic acids or derivatives.
• copolymers of ethylene and carboxylic acids, their esters or salts can be used as impact modifiers. Included among those impact modifiers are the following copolymers: ethylene-acrylic acid, ethylene-methacrylic acid, ethylene-ethyl aerylate, ethylene-vinyl acetate, and mixtures thereof.
• Useful impact modifiers include copolymers of ⁇ -olefins and the metal salts of carboxylic acids and particularly the sodium and potassium salts. These compolymer salts both nucleate and improve impact resistance. There can be used-up to about 30 percent, and preferably from about 2 percent and about 10 percent of the impact modifier, based on the weight of the poly(ethylene terephthalate).
• the composition can contain up to about 5 percent based on the weight of the polyethylene terephthalate, of a polyepoxide.
• a polyepoxide is epoxy cresol novolac resins of the type produced by Ciba-Geigy Corporation, and include ECN TM 1234, 1273 and 1299, and those formed from bisphenol-A and glycidyl ether.
• a preferred polyepoxide is an epoxy formed from bisphenol- A and glycidyl ether.
• polyepoxide formed from a diglycidyl ether and bisphenol A having a molecular weight of from about 1500 to 4000 and most preferably about 2000.
• the polyepoxides act as chain extenders and help compensate for polyethylene terephthalate chains broken by hydrolysis.
• a preferred filled composition comprises polyethylene terephthalate, from 30% to 90 percent glass fibers and 2% to 8% of the ester of the present invention from, 0.6 to about 3 percent of a polyepoxide and from about 0.1 to about 10 percent of a sodium carboxylate salt as described above. The percents are based on the we ight of the polyethylene terphthalate.
• the use of the ester of the present invention results in the polylinear saturated polyester, such as polyethylene terephthalate, molding composition which can be injection molded into water heated molds as temperatures as low as 76.7°C (170°F). As the mold temperature increases, there is an improvement in molded article appearance.
• the ester of the present invention, the carboxylate salt and polyethylene terephthalate are melt blended. In the most preferred embodiment, they can be melt blended in an extruder at a temperature above the melt temperature of the polyester. In a preferred embodiment, the components are melt blended at a temperature between 260°C (500°F) and 316°C (600°F) in an extruder.
• the polyethylene terephthalate composition of the present invention can be formed by blending the components together by any convenient means to obtain an intimate blend. Neither temperature nor pressure are critical.
• the polyethylene terephthalate can be mixed dry in a suitable blender or tumbler with the other components and the mixture melt extruded. The exudate can be chopped. If desired, a reinforcing or filing agent can be omitted initially and added after the first melt, and the resulting mixture can be melt extruded. It has been observed that the composition can be uniformly extruder blended. Uniform blends were made when all the ingredients were fed into the throat of the extruder.
• composition of the present invention is particularly useful to make injection molded articles.
• IV intrinsic viscosity
• the fiberglass used was 1/8 inch long short glass fibers made by Pittsburgh Plate Glass as PPG 3540.
• the epoxy compound used in the compositions was a diglycidyl ether of Bisphenol A sold by Ciba-Geigy as Araldite 7074.
• the ethylene acryclic acid (EAA) copolymer used was manufactured by Dow Chemical Corporation as Dow EAA- 445 which is described as having 8 percent by weight acrylic acid and a melt index of 5.5g/10 min.
• the ethylene ethyl acrylate copolymer (EEA) used was made by Union Carbide as Bakelite ® flexible ethylene copolymer DPD-6169 which is described as having a melt index of 6g/min and an ethyl acrylate content of 18 weight percent.
• EMA ethylene methyl acrylate copolymer
• Irganox ® 1010 which is tetrakis [methylene 3-(3,5 di-tertiary butyl 4 hydroxyphenyl) proprionate] methane made by Ciba-Geigy, was used as an antixoidant.
• a processing aid S-160 which is butyl benzyl phthalate made by Monsanto Corporation was used to prevent powder/pellet separation prior to extrusion.
• a dimer acid was used which was 100% sodium neutralized with sodium cation.
• the dimer acid is sold by Emery Corp. as Empol ® 1024.
• the dimer salt was used as a preblend (PB) contained 0.6% dimer acid sold, 0.6% EEA, 2.8% EAA, and 0.1% S-160.
• the nucleator was the sodium salt of ethylene methacrylic acid sold by the DuPont Company as Surlyn ® 8920. Unless otherwise indicated, the compositions were made by melt extruding using a 2 1/2" Egan single screw extruder having a 40 L/D ratio.
• Zones 1-7 were Zone 1-500°F/Zone 2-540°F/Zone 3- 530°F/Zones 4-7 -525°F with the die at 540°F.
• the fiberglass was fed into Zone 2 and a vacuum of 10 inches was applied to Zone 3.
• Differential Scanning Calorimeter (DSC) values were measured in accordance with the above-described procedure. Between a 5 and 10 milligram sample is prepared. The sample is made in the form of a film which is vacuum dried. The sample is placed in the DSC and heated at 10°C/min. to 280oC where it is held for 2 minutes. The sample is cooled at 10°C per minuted. The T cc appears as the peak in the cooling branch of the curve. Tg is the glass transition temperature of the composition.
• T ch is measured using similar sample preparation. The sample was melted and then quenched to assure that the sample was substantially amorphous. The sample was heated at 10°C per minute and a crystallization curve forms when crystallization takes place. The T ch was the temperature at the peak of the curve.
• the volatility was measured as percentage weight loss upon heating at the indicated temperature. Mold surface ratings are based on visual appearance ratings of 1 to 10 with 1 being the best and 10 being the worst.
• plasticizer "P” made by C. P. Hall and which is the di-2-ethyhexoate of ethoxylated Bisphenol A having a molecular weight of 876 and the formula
• the plasticizer used was polyethylene glycol di-2-ethylhexoate (PE diester) having a molecular weight of 652 and sold by C. P. Hall as Tegmer 809.
• PE triester aliphatic ethoxylated triester
• Example 1 illustrates a composition using plasticizer P compared to PE triester. The composition and results are summarized in Table 1.
• 1 PB is a preblend of sodium dimer salt, EEA and EAA.
• Examples 2-5 are a comparison of PET compositions melt blended using a 1 inch single screw extruder having a 25 L/D ratio. The extruder was run at barrel temperature of about 540°F.
• the plasticizer P used in Example 5 was the same ester of ethoxylated bisphenol A but from a different batch than the plasticizer used in Examples 2-4 to check lot to lot variation.
• the plasticizer in Comparatives 2 and 3 used the PE diester (MW-652) as described above.
• Table 2 The compositions and test results are summarized in Table 2 below.
• Example 6 In Example 6 and Comparatives 4 and 5 the short glass fiber was fed into the throat of the extruder. Volatility was measured in an oven at a vacuum of 27-28 inches of mercury at the indicated time and temperature,
• the plasticizer P of the present invention resulted in a composition which was generally comparable in physical properties with compositions containing the PE diester (Comp. 4) and the PE triester (Comp. 5) .
• the composition with the PE diester had the Best surface appearance.
• the composition of Ex. 6 and Comp. 5 had similar volatility results with Comp. 5 being slightly better.
• Comp. 4 had the poorest volatility.
• Examples 7-12 illustrate preferred compositions using a low molecular weight sodium ionomer salt as a nucleator. There was variation in the amount of neutralization with sodium cations of a low molecular weight ethylene acrylic acid copolymer sold as A-C ® 120 by Allied Corp. (NaAC) which was neutralized to the precent indicated .
• Example 12 contained 1.2 weight percent of a masterbatch (MB) which was made from 80 parts of PET, 20 parts of sodium stearate (SST), and 40 parts of EMA. Results are summarized in Table 4 below:
• Examples 13 to 19 were extruded as above except that the fiberglass, and the additives were added at Zone 2 followed by the addition of plasticizer downstream from the other additives fed into Zone 2 of the extruder.
• the PET hot was heated and dried at 275°F and added in the throat.
• Table 6 The compositions evaluated and results are summarized in Table 6 below:
• Examples 20-21 illustrate and impact modified version using an Acryloid ® KM-330 shell/core impact modifier produced by Rohm and Haas. This is believed to have a polybutylacrylate core and a polymethylmethacrylate shell.
• the compositions evaluated and results are summarized in Table 7.
• the plasticizer of the present invention is a significantly less volatile plasticizer than the esters of difunetional polyethylene oxides as used in Comparative 2.
• the plasticizer of the present invention is preferred over the PE triester as used in Comparative 1 because it is believed that it is more compatible and therefore is easier to melt blend into a uniform composition.
• the plasticizier of the present invention had satisfactory molded surface appearance and was easily moldable.

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• 1987
  • 1987-10-01 JP JP62506420A patent/JP2582827B2/ja not_active Expired - Lifetime
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  • 1987-10-01 EP EP87906967A patent/EP0334847A1/de not_active Ceased
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