EP1716206A2 - Supports reactifs pour injection par fusion polymerique - Google Patents

Supports reactifs pour injection par fusion polymerique

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Publication number
EP1716206A2
EP1716206A2 EP05712934A EP05712934A EP1716206A2 EP 1716206 A2 EP1716206 A2 EP 1716206A2 EP 05712934 A EP05712934 A EP 05712934A EP 05712934 A EP05712934 A EP 05712934A EP 1716206 A2 EP1716206 A2 EP 1716206A2
Authority
EP
European Patent Office
Prior art keywords
anhydride
resin
substituted
cyclic
succinic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05712934A
Other languages
German (de)
English (en)
Other versions
EP1716206A4 (fr
Inventor
Jayendra H. Bheda
Banks M. Moore, Iv
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Invista Technologies Sarl
Original Assignee
Invista North America LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/773,490 external-priority patent/US7294671B2/en
Application filed by Invista North America LLC filed Critical Invista North America LLC
Publication of EP1716206A2 publication Critical patent/EP1716206A2/fr
Publication of EP1716206A4 publication Critical patent/EP1716206A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L37/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • C08L73/02—Polyanhydrides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23—Sheet including cover or casing
    • Y10T428/237—Noninterengaged fibered material encased [e.g., mat, batt, etc.]

Definitions

  • the present invention concerns a reactive carrier that forms no by-products during melt injection of polymer into articles such as sheets, films, fibers and containers.
  • the reactive carrier is used to mix additives into the polymer resin. More particularly, the invention relates to the use of one or more cyclic anhydrides or substituted cyclic anhydrides as the reactive carrier.
  • the polymer can be polyester or polyamide.
  • additives are required to improve the functionality of the article.
  • Typical additives are colorants, anti-slip agents, flame retardants, antioxidants, gas barrier agents, ultraviolet (UN) radiation absorbers, acetaldehyde reducing agents, crystallization control agents, fillers and the like.
  • a "masterbatch” approach has been used to mix additives into injection molded polymer articles.
  • the desired additive is dispersed at a relatively highly concentrated level within a carrier polymer.
  • the masterbatch of highly concentrated additive polymer is blended with virgin polymer at the feed throat of the melt extruder.
  • variations in additive levels and the polymer molecular weight can be unacceptable.
  • An alternative method is to use a liquid dispersion of the additive that is pumped at the extruder throat.
  • the liquid carrier must be organic, non-aqueous, soluble in the polymer and have a boiling point greater than the extrusion temperature, i.e. generally above 300° C.
  • Commercial liquid carriers can be obtained from ColorMatrix Corporation, Cleveland, Ohio and designated as ColorMatrix LCPY-1 : 82-89 Series. According to the material safety data sheet (MSDS) from ColorMatrix Corporation, the main named ingredient is refined hydrocarbon oil.
  • liquid carriers can effect the processing of the article and remain in the article. For instance they can cause the extruder screw to slip, plate out on the molds and can be extracted.
  • U.S. Pat. No. 6,342,578 to Huang discloses a polyester with one or more of phthalic anhydride, glutaric anhydride, benzoic anhydride, maleic anhydride or succinic anhydride in an amount sufficient to significantly reduce the caustic stress cracking.
  • the anhydrides reacted with the hydroxyl end groups to forn carboxyl end groups (CEG).
  • cyclic anhydrides and in particular substituted cyclic anhydrides can be used as reactive carriers without foraiing by-products that reduce the molecular weight of the polymer.
  • the present invention relates to the use of a liquid cyclic anhydride at the time it is injected, as a carrier of additives in a polymer that is melt extruder into an article.
  • the invention also comprises a method of injecting a liquid cyclic anhydride containing additives into a melt extrusion process.
  • the anhydride is liquid at the time of injection.
  • Cyclic anhydrides will react with any nucleophilic group, including hydroxyl, carboxyl, primary and secondary amines and amides. This means that they are best suited as reactive carriers in polyesters and polyamides.
  • Suitable cyclic anhydrides are those with a melt point of less than that of the polyester or polyamide. Preferable are cyclic anhydrides with a melt point less than about 160 °C, most preferable are cyclic anhydrides with a melt point of less than 100 °C, and especially suitable are those that are liquid at room temperature (25°C).
  • PET Polyethylene terephthalate
  • ethylene glycol for example, via an esterification reaction, followed by a polycondensation reaction.
  • the reactions can be driven to near completion, yielding PET having up to 3 weight percent of di ethyl ene glycol and other byproducts.
  • PET is meant to include small amounts of byproducts.
  • Conventional continuous production of PET is well known in the art and comprises reacting terephthalic acid and ethylene glycol at a temperature of approximately 200° to 250°C forming monomer and water.
  • the reaction is reversible, the water is continuously removed, driving the reaction to the production of monomers and some oligomers.
  • the monomers and oligomers undergo polycondensation reaction in vacuum conditions at a temperature of approximately 250° to 290°C to fonn polyester having an IV of about 0.4 to 0.6.
  • no catalyst is needed.
  • a catalyst such as an antimony compound or titanium compound is necessary.
  • PET is also made in batch and continuous processes from the reaction of the ester-dimethyl terephthalate and ethylene glycol, at a reaction temperature of approximately 190° to 230°C foraiing alcohol (methanol) and monomer.
  • This esterification reaction is reversible and the alcohol must be continuously removed, driving the reaction to the production of monomer and some oligomer.
  • catalysts such as manganese, zinc, cobalt or other conventional catalyst are employed.
  • the monomer and oligomer undergo a polycondensation reaction at the conditions stated above to fonn polyester or copolyester having an IV of about 0.4 to 0.6.
  • Resins containing up to 20 wt % of the dicarboxylic acid are useful in fonning bottles or jar containers as is known in the art.
  • Suitable diacids may be aliphatic, alicyclic, or aromatic dicarboxylic acids such as isophthalic acid, 1,4- cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid; 2,6-naphthalenedicarboxylic acid, bibenzoic acid, oxalic acid, malonic acid, pimelic acid, suberic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, or mixtures of these and their equivalents. It is often preferred to use a functional acid derivative equivalent such as dimethyl, diethyl,
  • polyester resins may optionally be modified by up to 20 wt % of one or more different diols than ethylene glycol.
  • additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms.
  • diols to be included with ethylene glycol are: diethylene glycol, triethylene glycol, 1,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, propane- 1,3 -diol, butane- 1,4-diol, pentane-l,5-diol, hexane-l,6-diol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(l,4), 2,2,4-trimethylpentane-diol-(l,3), 2-ethylhexanediol-(l,3), 2,2-diethylpropane-diol-(l,3), hexanediol-(l ,3), 1 ,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclocycl
  • Polyamides means polyamides made from the condensation of aliphatic or aromatic diamines with dicarboxylic acids, or the condensation of lactams.
  • the preferred polyamides are nylon 66 and nylon 6.
  • Article means films, sheets for thermoforming, fibers, and injection molded parts in particular preforms for stretch blow molding into containers.
  • the cyclic anhydride carrier containing additives is injected into the melt extrusion process.
  • the injection occurs in the melt piping conducting the molten polymer to the article forming device, such as film or fiber forming machines.
  • the cyclic anhydride carrier containing additives is added at the end of a continuous polymerization process in the transfer pipe between the final reactor and the die that forms the strands that are cooled and chipped.
  • this resin can be solid-state polymerized to a higher molecular weight (IV).
  • the cyclic anhydride liquid carrier containing additives is added into a mixing box at the throat of the extruder of the preform injection molding or extrusion blow molding machine.
  • the liquid carrier has a melting point near or below ambient temperatures. This simplifies the addition of the anhydride into the extruder, as complicated heating systems are not required.
  • the preform is heated to about 100 - 120°C and blown-molded into contour bottle at a stretch ratio of about 12.5.
  • the stretch ratio is the stretch in the radial direction times the stretch in the length (axial) direction.
  • a preform may be stretched about two times its length and stretched about six times is diameter giving a stretch ratio of twelve (2 x 6). Since the bottle size is fixed, different prefonn sizes can be used for obtaining different stretch ratios.
  • the preferred carriers are cyclic anhydrides, selected from the following classes: a) succinic anhydrides
  • R , ⁇ , R , R and R can be hydrogen, alkyl, alkenyl or aryl groups.
  • succinic anhydrides include cy cloalkane and cycloalkene substituents, giving such compounds as hexahydrophthalic anhydride and substituted hexahydrophthalic anhydride:
  • R , 1 , r R> 2 , r R>3 , R D 4 , r R, 5 , R6 , ⁇ R and R can be hydrogen, alkyl, alkenyl or aryl groups.
  • R 1 and R 2 can be hydrogen, alkyl, alkenyl or aryl groups.
  • R 1 and R 2 can be hydrogen, alkyl, alkenyl or aryl groups.
  • cycloalkane and cycloalkene substituents are also included in this class, giving such compounds as 3,4,5,6-tetrahydrophthalic anhydride and substituted tetrahydrophthalic anhydride groups:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 can be hydrogen, alkyl, alkenyl or aryl groups; and substituted l-cyclopentene-l,2-dicarboxylic anhydride:
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be hydrogen, alkyl, alkenyl or aryl groups.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be hydrogen, alkyl, alkenyl or aryl groups.
  • R 1 , R 2 , R 3 and R 4 can be hydrogen, alkyl, alkenyl or aryl groups.
  • R 1 , R 2 , R 3 and R 4 can be hydrogen, alkyl, alkenyl or aryl groups.
  • R , ⁇ , R , R , R , R , R and R can be hydrogen, alkyl, alkenyl or aryl groups.
  • Table 1 summarizes melting point of selected cyclic anhydrides.
  • cyclic anhydride For the process where the cyclic anhydride is added at the preform injection molding stage, low melting points, preferably below 50°C are used.
  • the preferred cyclic anhydrides are the alkenyl succinic anhydrides such as octadecenylsuccinic, hexadecenyl succinic and eicosodecenyl succinic anhydride, or mixtures thereof.
  • Additives according to the present invention are colorants, anti-slip agents, flame retardants, antioxidants, gas (oxygen and carbon dioxide) barrier agents, oxygen scavengers, ultraviolet (UV) radiation absorbers, acetaldehyde reducing agents, crystallization control agents, impact modifiers, catalyst deactivators, melt strength enhancers, anti-static agents, lubricants, chain extenders, nucleating agents, solvents, fillers, and plasticizers.
  • the additives are mixed with the reactive carrier at the required concentration for the functional purpose for which they are used.
  • the preferred reactive carrier level to be injected or mixed with the polymer is about 1 wt-% or less (100 ppm - 10,000ppm). Any additive used with a reactive carrier should not react with the liquid carrier prior to the addition to the polymer.
  • the melting point of the cyclic anhydrides is measured with a hot stage microscope.
  • the hot stage is heated rapidly at first and then adjusted to 2°C/min. during the last 10°C preceding the expected melting point.
  • the melting point is defined as the range from the temperature that melting is first observed to that at which melting is complete.
  • Intrinsic viscosity (IV) of the polymer is deteraiined by mixing 0.2 grams of an amorphous polymer composition with twenty milliliters of dichloroacetic acid at a temperature of 25°C using an Ubbelhode viscometer to determine the relative viscosity (RV). RV is converted to IV using the ISO certificated equation:
  • the haze of the preforms and bottles was measured with a Hunter Lab ColorQuest II instrument.
  • the haze is defined as the percent of diffused light to total transmitted light.
  • the color of the bottle sidewalls was measured with the same instrument, and report in CIE units of L*, a* and b*.
  • This example compares the preferred reactive liquid carrier of US 6,569,991, polyethylene glycol (PEG), to that of the present invention.
  • a standard commercial polyester bottle resin (KoSa 3302, Spartanburg, South Carolina, USA) was used. PEG with a molecular weight of 400 was obtained from Union Carbide, Danbury CT, USA.
  • the cyclic anhydride was alkenyl succinic anhydrides (ASA), a mixture of alkenyl succinic anhydrides from Albemarle Corporation, Richmond, Virginia, U.S.A. that contains 54 % hexadecenyl, 34 % octadecenyl and 10 % eicosodecenyl succinic anhydride
  • the 3302 resin was dried under vacuum at 150° C for 12 hours.
  • the dried resin was blended with the liquid carrier and injected molded into 48 gram prefonns on an Arburg injection molding machine.
  • the ASA liquid carrier had little effect on the color and haze of the prefonn, in contrast to PEG which at a level of 4000 ppm significantly increased the yellowness (b*) and haze.
  • a mixture of ASA containing 5 wt.-% of a fumed silica, Cab-O-sil ⁇ M7D (Cabot Corporation, Boston MA, USA) was prepared by stirring the fumed silica with the ASA liquid.
  • Dried 3302 polyester resin was coated with this mixture by mixing in a bag, and then injected molded into 48 gram preforms on an Arburg injection molding machine.
  • the level of ASA was 4,000 ppm (giving a fumed silica loading of 200 ppm).
  • the coefficient of friction of the 3302 control was 9.3 compared to 0.2 with the anti-slip agent (fumed silica) incorporated into the resin with a cyclic anhydride.
  • Example 2 The procedure of Example 2 was followed with a mixture of 81.2 wt-% ASA and 18.8 wt.-% of an UV absorber, Tinuvin 234 (Ciba Specialty Chemicals, Charlotte NC, USA).
  • the level of ASA was 4,000 ppm giving an UV absorber loading of 900 ppm.
  • the 24 gram preforms were blown into bottles (0.59 liter) on a Cincinnati Milacron stretch blow molding machine.
  • the UV absorbance of the bottle side walls (0.38 mm) was measured.
  • the % transmittance at 370 nm was less than 10% for the UV additive bottle compared to 80% for the 3302 control.
  • Example 3 The procedure of Example 3 was followed using a mixture of 97.5 wt-% ASA and 2.5 wt-% of a blue dye, Polysynthren Blue RBL (Clariant Corporation, Charlotte NC, USA). The mixture was used at a level of 500 ppm. The color and haze of the bottle sidewalls was compared with commercial bottles in which the same concentration of blue dye was added with a hydrocarbon oil carrier, the results are set forth in Table 4. Table 4
  • Example 5 A common additive that is used in polyester bottle resin compositions is a reheat agent. These reheat agents reduce the time it takes for the preform to heat to the stretch blow molding temperature.
  • US Patent No. 5,925,710 discloses the use of graphite as a reheat agent.
  • Example 1 The procedure of Example 1 was followed to prepare a mixture of 99 wt-% ASA and 1 wt.-% graphite (Grafitbergbau Kaiserberg AG, Kaiserberg Austria). The mixture was used at a level of 1,000 ppm to give 10 ppm graphite in the resin.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention se rapporte à un support réactif qui ne forme pas de sous-produits au cours de l'injection par fusion de polymères dans des articles tels que des feuilles, des films, des fibres et des contenants. Ce support réactif permet de mélanger des additifs dans la résine polymérique. Plus précisément, cette invention concerne l'utilisation d'un ou plusieurs anhydrides cycliques ou anhydrides cycliques substitués en tant que support réactif. Le polymère peut être du polyester ou du polyamide. Des anhydrides cycliques convenables possèdent un point de fusion inférieur à celui du polyester ou polyamide, de préférence inférieur à 160 °C environ, idéalement inférieur à 125 °C environ. De préférence, il s'agit d'anhydrides cycliques possédant un point de fusion inférieur à 100 °C environ, ceux qui sont liquides à température ambiante (25°C) étant particulièrement utiles. L'anhydride cyclique peut être choisi dans le groupe anhydride succinique, anhydride succinique substitué, anhydride glutarique, anhydride glutarique substitué, anhydride phthalique, anhydride phthalique substitué, anhydride maléique, anhydride maléique substitué, ou des mélanges d'au moins deux de ces éléments.
EP05712934A 2004-02-06 2005-02-04 Supports reactifs pour injection par fusion polymerique Withdrawn EP1716206A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/773,490 US7294671B2 (en) 2004-02-06 2004-02-06 Reactive carriers for polymer melt injection
PCT/US2005/003685 WO2005076947A2 (fr) 2004-02-06 2005-02-04 Supports reactifs pour injection par fusion polymerique

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EP1716206A2 true EP1716206A2 (fr) 2006-11-02
EP1716206A4 EP1716206A4 (fr) 2008-03-19

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EP05712934A Withdrawn EP1716206A4 (fr) 2004-02-06 2005-02-04 Supports reactifs pour injection par fusion polymerique

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EP (1) EP1716206A4 (fr)
JP (1) JP2007522295A (fr)
BR (1) BRPI0507336A (fr)
CA (1) CA2554228A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP2837647A1 (fr) * 2013-08-16 2015-02-18 BASF Coatings GmbH Dérivés de poly- et diesters à fonction carboxy

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US4361681A (en) * 1980-11-03 1982-11-30 The Goodyear Tire & Rubber Company Polyethylene terephthalate having a reduced acetaldehyde generation rate
US5663029A (en) * 1996-01-24 1997-09-02 Xerox Corporation Electrostatic imaging process
US5693681A (en) * 1994-02-28 1997-12-02 Ciba Specialty Chemicals Corporation Increasing the molecular weight of polyesters
EP0819716A2 (fr) * 1996-07-18 1998-01-21 SINCO ENGINEERING S.p.A. Procédé amélioré pour la production de polyesters
US6342578B1 (en) * 2000-12-06 2002-01-29 Arteva North America S.A.R.L. Copolyester with high carboxyl end groups and a method for making

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JPH0593063A (ja) * 1991-10-01 1993-04-16 Teijin Ltd 末端カルボキシル基量の増加したポリアミドの製造方法
JPH10212345A (ja) * 1997-01-29 1998-08-11 Teijin Ltd 成形性に優れたポリエステルの製造方法

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US5693681A (en) * 1994-02-28 1997-12-02 Ciba Specialty Chemicals Corporation Increasing the molecular weight of polyesters
US5663029A (en) * 1996-01-24 1997-09-02 Xerox Corporation Electrostatic imaging process
EP0819716A2 (fr) * 1996-07-18 1998-01-21 SINCO ENGINEERING S.p.A. Procédé amélioré pour la production de polyesters
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BRPI0507336A (pt) 2007-07-03
CA2554228A1 (fr) 2005-08-25
EP1716206A4 (fr) 2008-03-19
JP2007522295A (ja) 2007-08-09

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