WO1996011228A1 - Article en polymere vinylique moule par injection - Google Patents

Article en polymere vinylique moule par injection Download PDF

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Publication number
WO1996011228A1
WO1996011228A1 PCT/US1995/012280 US9512280W WO9611228A1 WO 1996011228 A1 WO1996011228 A1 WO 1996011228A1 US 9512280 W US9512280 W US 9512280W WO 9611228 A1 WO9611228 A1 WO 9611228A1
Authority
WO
WIPO (PCT)
Prior art keywords
stearate
injection molded
vinyl polymer
molded article
tin
Prior art date
Application number
PCT/US1995/012280
Other languages
English (en)
Inventor
Robert Arthur Lindner
Levente Lajos Koller
Original Assignee
Alliedsignal Inc.
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
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Publication of WO1996011228A1 publication Critical patent/WO1996011228A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present invention relates to an injection molded vinyl polymer article.
  • Rigid vinyl polymer compositions such as polyvinyl chloride compositions, are utilized for producing a variety of structural articles.
  • Lubricants are typically added to vinyl polymers to facilitate the melt processing of the structural articles produced.
  • Lubricants are generally classified as external or internal lubricants.
  • An external lubricant provides a lubricating layer between the plastic melt and the metallic surfaces of the processing equipment. The external lubricant serves to coat the individual particles of the polymeric resin and inhibits their adherence to the metallic surfaces.
  • an internal lubricant reduces the effective melt viscosity of the vinyl polymer at the processing temperatures in order to improve its flow properties c ring processing as well as to promote fusion.
  • Vinyl polymer compositions may be formed into articles by extrusion. Extrusion involves forcing a heat-softened polymer material through an orifice or die to produce rods or pipe.
  • U.S. Patent 4,203,880 teaches that melt strength is important for extrudable compositions because it determines the extent to which the diameter of a rod or pipe can be reduced uniformly in the absence of breaks and other defects.
  • Patent 4,203,880 teaches that a tin stabilized polyvinyl chloride having a lubricant package cor rising oxidized polyethylene wax and a known external lubricant such as paraffin oils, paraffin waxes, liquid and solid hydrocarbons, unoxidized polyethylene waxes, montan ester waxes, lead stearate, mineral oil, 1 2-h ⁇ droxystearic acid, ethylene bis-stearamide, and glycol esters of fatty acids that contain 10 to 20 or more carbon atoms has improved melt strength for extrusion.
  • a tin stabilized polyvinyl chloride having a lubricant package cor rising oxidized polyethylene wax and a known external lubricant such as paraffin oils, paraffin waxes, liquid and solid hydrocarbons, unoxidized polyethylene waxes, montan ester waxes, lead stearate, mineral oil, 1 2-h ⁇ droxystearic acid, ethylene bis-stearamide, and glycol esters of fatty
  • Vinyl polymer compositions may also be formed into articles by injection molding.
  • Injection molding involves heating a polymer molding powder or granules in an enclosed cylinder to a suitable temperature. A piston then pushes the softened polymer through a nozzle along runners into a cool mold to produce pipe fitting.
  • An injection molded article having good splay resistance is desirable. Splay is caused by an imbalance in the ratio of internal lubricant to external lubricant such that too much external lubricant is present.
  • Rigid extrusion compounds are made from considerably higher molecular weight materials and thus, are far more viscous materials than molding compounds.
  • Plastics Additives Handbook. 317-319 (1985) teaches injection molded articles formed from lead or barium/cadmium stabilized polyvinyl chloride compositions having montanic acid ester as a lubricant.
  • the reference does not teach that tin stabilized polyvinyl chloride compositions may be injection molded or that oxidized polyethylene wax may be used as a lubricant for injection molded polyvinyl chloride compositions.
  • an injection molded article comprising tin stabilized vinyl polymer composition having oxidized polyethylene wax as a lubricant has improved splay resistance.
  • the present invention provides an injection molded article comprising: (a) vinyl polymer; (b) an effective amount for stabilizing the vinyl polymer of tin stabilizer and metallic stearate; and (c) an effective amount for lubricating the vinyl polymer of polyethylene having a Brookfield viscosity at a temperature of 1 50°C of between about 1 ,000 and about 100,000 centipoises and an acid number as determined by standardized titration of KOH of between about 1 and about 40.
  • the present invention also provides a method of improving splay resistance in an injection molded article comprising the steps of: (a) adding, to vinyl polymer stabilized with tin stabilizer and metallic stearate, an effective amount for lubricating the stabilized vinyl polymer of polyethylene having a Brookfield viscosity at a temperature of 150°C of between about 1 ,000 and about 100,000 centipoises and an acid number as determined by standardized titration of KOH of between about 1 and about 40; and (b) injection molding the composition resulting from step (a).
  • Vinyl polymers useful in the present invention include polyvinyl chloride and polymerized forms of vinyl acetate, vinyl chloride-vinyl acetate copolymers, vinylidene halides such as vinylidene chloride vinyl pyridine, vinyl carbazole styrene, vinylbenzene, acrylic esters such as methyl acryiate, ethyl acryiate, or methylmethacrylate as well as acrylonitrile.
  • the preferred vinyl polymer is polyvinyl chloride which includes both homopolymers of vinyl chloride and both copolymers and terpolymers of vinyl chloride with comonomers such as vinyl acetate, vinyl formate, alkyl vinyl ethers, ethylene, propylene, butylene, vinylidene chloride, alkyl acrylates and methacrylates, alkyl maleates, and alkyl fumarates.
  • comonomers such as vinyl acetate, vinyl formate, alkyl vinyl ethers, ethylene, propylene, butylene, vinylidene chloride, alkyl acrylates and methacrylates, alkyl maleates, and alkyl fumarates.
  • at least 80% and more preferably 00% of the monomer to be polymerized will be a vinyl chloride monomer.
  • Vinyl polymers useful in the present invention are commercially available.
  • Tin stabilizers useful in the present invention include tin maleates, tin thioglycolates, and methyl tin. Preferred tin stabilizers are octyltin thioglycolates and methyl tin. Tin stabilizers useful in the present invention are commercially available. Other useful tin stabilizers are disclosed in U.S. Patent 4,203,880 which is incorporated herein by reference.
  • metallic soaps such as metallic stearates are also added.
  • Preferred metallic stearates include cadmium stearate, manganese stearate, cesium stearate, lead stearate, lithium stearate, strontium stearate, sodium stearate, calcium stearate, barium stearate, and magnesium stearate.
  • the more preferred metallic stearates are lead stearate, calcium stearate, and barium stearate.
  • the most preferred metallic stearate is calcium stearate.
  • Metallic stearates useful in the present invention are commercially available.
  • an effective amount for stabilizing the vinyl polymer of the tin stabilizer and metallic stearate is used.
  • the tin stabilizer and metallic stearate are present in an amount of about 0.25 to about 5 parts by weight per 100 parts of vinyl polymer.
  • the ratio of tin stabilizer to metallic stearate is about 1 : 10 to about 10:1 .
  • the polyethylene of the present invention has a Brookfield viscosity at a temperature of 150°C of between about 1000 and about 100000 centipoises and an acid number as determined by standardized titration of KOH of between about 1 and about 40.
  • Suitable polyethylenes may be characterized as oxidized high density homopolymers of ethylene, copolymers containing acrylates and ethylene, terpolymers containing acrylates, esters, and ethylene.
  • oxidized high density homopolymers of ethylene are used.
  • These polyethylenes have been oxidized to an acid number as determined by a standardized titration of KOH of more preferably between about 1 and about 30, and most preferably between about 1 and about 20.
  • These polyethylenes typically have a density as determined by ASTM D-1505 in the range of about 0.85 to about 1 .05, more preferably in the range of about 0.98 to about 1 .05, and most preferably in the range of about 0.98 tc ibout 1.00.
  • These oxidized polyethylenes exhibit a Broo ⁇ f ield viscosity at a temperature of 150°C of more preferably in the range of between about 2000 and about 90000 centipoises and most preferably in the range of between about 8000 and about 90000 centipoises.
  • Suitable oxidized polyethylenes are available from AlliedSignal Inc., Morristown, New Jersey. Preferred oxidized polyethylenes are listed in the following Table: Oxidized Acid Number Density Brookfield Polyethylene (mgKOH/ (grams/cc) Viscosity gram) (cps at
  • the more preferred oxidized polyethylenes are A-C ® 307A and A-C ® 316A oxidized polyethylenes.
  • the most preferred oxidized polyethylene is A-C ® 316A oxidized polyethylene.
  • oxidized polyethylenes as well as others which are useful in the practice of the present invention may be obtained by oxidizing polyethylenes with air or oxygen by convention procedures. Suitable methods are described in U.S. Patents 3,060,163 and 3,322,71 1 which are incorporated herein by reference. As those skilled in the art know, the oxidation results in the scission of the polymer and the formation of acid groups. In addition to the formation of acid groups on the polymer chain, esters, aldehydes, ketones, hydroxides, and peroxides are also found in various quantities along the polymer chains.
  • the melt viscosity of the vinyl polymer composition may be too high or the fusion time may be too short.
  • An extremely short fusion time is undesirable for extrudable compositions because this may result in prolonged exposure of the polymer melt to elevated temperatures which results in premature degradation.
  • a condition referred to as "plate out" may occur.
  • the excess lubricant rises to the surface of the vinyl polymer composition and remains in contact with the heated wall of the equipment for a sufficient time to become charred.
  • the char is either carried along with the molten polymer causing discoloration, or the char may form deposits along the inner wall, thereby altering the shape of the injection molded article.
  • an effective amount for lubricating the vinyl polymer of oxidized polyethylene is used.
  • the oxidized polyethylene is present in an amount of about 0.01 to about 10 parts by weight per 100 parts of vinyl polymer.
  • the oxidized polyethylene is present preferably in an amount of about 0.05 to about 5 parts by weight per 100 parts of vinyl polymer, more preferably in an amount of about 0.05 to about 1 part by weight per 00 parts of vinyl polymer, and most preferably in an amount of about 0.1 to about 1 part by weight per 100 parts of vinyl polymer.
  • the present compositions may contain one or more additives conventionally employed in moldable polymer compositions.
  • additives include fillers such as alkaline earth metal carbonates, pigments such as titanium dioxide, antioxidants such as stericaliy hindered phenols or bis-phenols, impact modifiers such as methyl methacrylate-butadiene-styrene terpolymers, and adsorbents such as the alkaline earth metal silicates and diatomaceous earth if the composition contains a significant amount of liquid ingredients.
  • the present injection molded article is useful as rigid polyvinyl chloride pipe fitting.
  • the lubricants used were A-C® 307A and A-C ? 316A oxidized polyethylenes which are commercially available from AHiedSignal Inc., Morristown, New Jersey, United States of America.
  • the properties of these oxidized polyethylenes are as follows:
  • the resin used was K58-60 polyvinyl chloride and the filler used was finely ground coated CaCO ⁇ .
  • the pigment used was Titanox 2101 Ti ⁇ 2 and the tin stabilizer used was AdvastabTM 181 methyl tin.
  • the co-stabilizer used was calcium stearate and the internal lubricant was Lubol 330 and Loxiol G30 ester.
  • composition was injection molded by a Kawaguchi 25 ton machine.
  • the splay rating for the Comparative and each Example was determined by observation of ASTM step chip and rated by a panel of ten observers.
  • the splay rating scale runs from 0 (poor ) to 10 (excellent). The results are in the following Table.
  • the splay rating is an average of the ten observations.
  • the improved splay rating indicates the improved integrity of the injection molded part resulting in fewer inservice breakages due to pressure causing ruptures along the splay fissures.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne un article moulé par injection, constitué d'une matière comprenant: (a) un polymère vinylique, (b) une quantité de stabilisateur à base d'étain et de stéarate métallique efficace pour stabiliser le polymère vinylique; (c) une quantité, efficace pour lubrifier le polymère vinylique, d'un polyéthylène présentant une viscosité de Brookfield, à une température de 150 °C, comprise entre environ 1000 et 100000 centipoises, ainsi qu'un indice d'acidité, déterminé par titrage normalisé de KOH, compris entre environ 1 et environ 40. Ledit article moulé par injection présente un indice d'évasement amélioré et peut être utilisé comme raccord de tuyaux.
PCT/US1995/012280 1994-10-07 1995-09-22 Article en polymere vinylique moule par injection WO1996011228A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32046794A 1994-10-07 1994-10-07
US08/320,467 1994-10-07

Publications (1)

Publication Number Publication Date
WO1996011228A1 true WO1996011228A1 (fr) 1996-04-18

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PCT/US1995/012280 WO1996011228A1 (fr) 1994-10-07 1995-09-22 Article en polymere vinylique moule par injection

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072855A1 (fr) * 2000-03-29 2001-10-04 Clariant Gmbh Utilisation de cires de polyolefine dans le traitement de matieres plastiques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862066A (en) * 1971-05-26 1975-01-21 Universal Pvc Resins Method for making rigid vinyl chloride polymer compounds
US4081413A (en) * 1974-04-29 1978-03-28 Hooker Chemicals & Plastics Corporation Polyvinyl chloride compositions
US4500665A (en) * 1983-06-27 1985-02-19 Argus Chemical Corporation Codispersed particulate lubricant stabilizer compositions for synthetic resins
US4544694A (en) * 1982-12-27 1985-10-01 American Hoechst Corporation Extrusion lubricant composition and process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862066A (en) * 1971-05-26 1975-01-21 Universal Pvc Resins Method for making rigid vinyl chloride polymer compounds
US4081413A (en) * 1974-04-29 1978-03-28 Hooker Chemicals & Plastics Corporation Polyvinyl chloride compositions
US4544694A (en) * 1982-12-27 1985-10-01 American Hoechst Corporation Extrusion lubricant composition and process
US4500665A (en) * 1983-06-27 1985-02-19 Argus Chemical Corporation Codispersed particulate lubricant stabilizer compositions for synthetic resins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072855A1 (fr) * 2000-03-29 2001-10-04 Clariant Gmbh Utilisation de cires de polyolefine dans le traitement de matieres plastiques
US7192909B2 (en) 2000-03-29 2007-03-20 Clariant Produkte (Deutschland) Gmbh Use of polyolefin waxes in the field of plastics processing

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