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WO1996003460A1 - Polymeres vinyliques rigides plus faciles a utiliser en fabrication - Google Patents

Polymeres vinyliques rigides plus faciles a utiliser en fabrication Download PDF

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Publication number
WO1996003460A1
WO1996003460A1 PCT/US1995/008997 US9508997W WO9603460A1 WO 1996003460 A1 WO1996003460 A1 WO 1996003460A1 US 9508997 W US9508997 W US 9508997W WO 9603460 A1 WO9603460 A1 WO 9603460A1
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WO
WIPO (PCT)
Prior art keywords
composition
polyethylene
vinyl polymer
acid number
fusion
Prior art date
Application number
PCT/US1995/008997
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English (en)
Inventor
Robert Arthur Linder
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 WO1996003460A1 publication Critical patent/WO1996003460A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation

Definitions

  • the present invention relates to external lubricant compositions for rigid vinyl polymers and more particularly, to external lubricant compositions for rigid polyvinyl chloride.
  • Rigid vinyl polymer compositions such as polyvinyl chloride compositions, are utilized for producing a variety of structural articles such as plastic pipe, siding, containers, and sheets. These rigid compositions are substantially unplasticized.
  • tin compounds such as organotin mercaptides and organotin sulfides and basic lead compounds such as tribasic lead sulfate, dibasic lead phosphite, or dibasic lead phosphite sulfite are used.
  • basic lead compounds such as tribasic lead sulfate, dibasic lead phosphite, or dibasic lead phosphite sulfite are used.
  • metal soaps such as neutral or basic lead stearate and/or calcium stearate are added.
  • Lubricants are also added to vinyl polymers to facilitate the extrusion or other 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 may coat the individual particles of the polymeric resin and inhibits their adherence to each other or fusion.
  • an internal lubricant reduces the effective melt viscosity of the vinyl polymer at the processing temperatures in order to improve its flow properties during processing and exhibits little adverse effect on fusion.
  • An internal lubricant is generally needed only for thin extrusions such as films and thin-walled pipe or in complicated extrusions such as window or door linear profiles.
  • Suitable rigid polyvinyl chloride pipe formulations include compositions such as:
  • A-C ® 629A (oxidized O to 1 polyethylene wax, acid number of 16, Brookfield viscosity at
  • the first and third formulations above are undesirable because the unoxidized homopolymer polyethylene wax having a Brookfield viscosity at 140°C of 180 or 200 centipoises delays fusion and thus, increases fusion time. Additionally, the unoxidized homopolymer polyethylene wax serves as more of a fusion control rather than an external lubricant and thus, it is necessary to add an additional external lubricant such as oxidized polyethylene wax having a Brookfield viscosity at 140°C of 200 centipoises or stearic acid to the composition. Although the first and third formulations above have good lubricity, the fusion times are too long. Additionally, stearic acid has a low melting point which means that it evaporates during normal processing conditions.
  • the second formulation above is undesirable because a processing aid is used which increases the cost of the final composition. Also, the presence of an acrylic processing aid in the final product may cause high viscosity and poor flow.
  • U.S. Patent 4,203,880 discloses tin stabilized polyvinyl chloride having a lubricant package comprising 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, 12-hydroxystearic acid, and ethylene bis-stearamide and cites two articles which teach the preceding known external lubricants: lllmann, "Waxes as Lubricants in Plastics Processing", SPE Journal. 71 (June 1967) and King et al., "Characterization of Lubricants for Polyvinyl Chloride", Polvmer Engineering and Science 1 2(2). 1 12 (March 1972).
  • the reference teaches that an oxidized polyethylene having a melt viscosity of 200 centipoises and an acid number of 16 undesirably increases fusion time.
  • Polyvinyl chloride systems which provide processing latitude are extremely attractive to polyvinyl chloride processors. Because the components of a polyvinyl chloride formulation and the weight percentages thereof are selected in order to provide desired final polyvinyl chloride properties, any system which allows a processor to vary the weight percentage of a component such as the external lubricant present without dramatically affecting processing conditions such as fusion time would be advantageous.
  • the present external lubricant composition for stabilized vinyl polymer comprises: an effective amount for lubricating the vinyl polymer of polyethylene having a Brookfield viscosity at a temperature of 140°C of about 205 to about 345 centipoises and an acid number as determined by standardized titration of KOH of between about 5 and about 9.
  • the present invention also provides a composition
  • a composition comprising: (a) vinyl polymer; (b) an effective amount for stabilizing the vinyl polymer of stabilizer; and (c) an effective amount for lubricating the vinyl polymer of polyethylene having a Brookfield viscosity at a temperature of 140°C of about 205 to about 345 centipoises and an acid number as determined by standardized titration of KOH of between about 5 and about 9.
  • 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 acrylate, ethyl acrylate, 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 100% of the monomer to be polymerized will be a vinyl chloride monomer.
  • Vinyl polymers useful in the present invention are commercially available.
  • Stabilizers useful in the present invention include antimony thioglycolates and tin stabilizers such as organotin mercaptides, organotin sulfides, tin maleates, and tin thioglycolates such as butyltin thioglycolates and octylin thioglycolates.
  • 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.
  • Lead stabilizers useful in the present invention include tribasic lead sulfate, tetrabasic lead sulfate, dibasic lead phosphite, dibasic lead phosphite sulfite, and lead phthalate.
  • the preferred lead stabilizer is tribasic lead sulfate. Lead stabilizers useful in the present invention are commercially available.
  • metallic soaps such as metallic stearates are also added.
  • Preferred metallic stearates include cadium 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 lead stearate.
  • Metallic stearates useful in the present invention are commercially available.
  • an effective amount for stabilizing the vinyl polymer of the lead or tin stabilizer and metallic stearate is used.
  • the lead or 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 lead or 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 140°C of less than about 1000 and an acid number as determined by standardized titration of KOH of between about 5 and about 9.
  • Suitable polyethylenes may be characterized as oxidized low density homopolymers of ethylene, copolymers containing acrylates and ethylene, terpolymers containing acrylates, esters, and ethylene.
  • oxidized low density homopolymers of ethylene are used.
  • polyethylenes which have been oxidized to an acid number as determined by a standardized titration of KOH of preferably between about 6 and about 9 have minimal variation in fusion time as the weight percent of the polyethylene varies and also good stability and metal release properties and most preferably, to an acid number of about 7 to about 9.
  • polyethylenes which have been oxidized to an acid number as determined by a standardized titration of KOH of preferably between about 5 and about 6 have good plate-out resistance.
  • polyethylenes have a density as determined by ASTM D-1505 preferably in the range of about 0.90 to about 0.94 and more preferably in the range of about 0.92 to about 0.93. These oxidized polyethylenes exhibit a Brookfield viscosity at a temperature of 140°C of preferably in the range of between about 240 and about 340 centipoises.
  • 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 conventional 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 foun in various quantities along the polymer chains. If too little lubricant is present in the final vinyl polymer composition, the melt viscosity of the vinyl polymer composition may be too high or the fusion time may be too short.
  • 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 extruder, mill, or calendar roll 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 or in the die of an extruder, thereby altering the shape of the extruder 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 5 parts by weight per 100 parts of vinyl polymer.
  • the oxidized polyethylene is present preferably in an amount of about 0.05 to about 2 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 100 parts of vinyl polymer, and most preferably in an amount of about 0.1 to about 0.5 part by weight per 100 parts of vinyl polymer.
  • the present compositions may contain one or more additives conventionally employed in moldable or extrudable polymer compositions.
  • additives include fillers such as alkaline earth metal carbonates, pigments such as titanium dioxide, antioxidants such as sterically 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 vinyl compositions to which the present external lubricants are added are rigid which means that they contain essentially no plasticizer. Such vinyl resins are useful in the production of rigid articles, principally rigid pipe, siding, containers, and sheets.
  • a typical torque rheometer curve provides one skilled in the art with information as to melting, fusion, flow, and crosslinking in the processing of the polymer tested. This procedure is set forth in ASTM D 2538-88 - "Standard Practice for Fusion of Poly(Vinyl ChlorideMPVC) Compounds Using a Torque Rheometer".
  • the most generally used rheometer is the Brabender Plasticorder which essentially consists of an oil-heated roller mixing head driven by a variable speed motor equipped with means to measure the torque developed in the head. The machine is fitted with a mixing head equipped with a melt thermocouple.
  • a polyvinyl chloride powder blend for example, an accurately weighed quantity of the blend is charged into the mixing head with the aid of a quick-loading chute.
  • a graph of the torque against time is produced and the point when fusion is complete is shown by an initial peak in torque.
  • the dynamic heat stability is measured in minutes from the start of the graph until the decomposition point which is marked by a rise in torque.
  • the difference between the maximum fusion time at 0.1 part by weight of oxidized polyethylene and the minimum fusion time at 0.8 part by weight of oxidized polyethylene is at least 2 minutes.
  • the effect of the present external lubricants for polyvinyl chloride pipe compounds was determined utilizing a Brabender Plasticorder at 1 90°C jacket temperature, at 60 RPM, and sample size of 40xSPG.
  • Each composition was prepared by blending in a Henschel mixer for 10 minutes at 3800 RPM and for an additional 10 minutes at 2600 RPM.
  • the fusion time and fusion and equilibrium torque were determined from the plastogram and are recorded below.
  • the stability measurements were done by Brabender Plasticorder.
  • the present lubricants used had an acid number of 5.4 or 8.6 as determined by standardized titration of KOH.
  • Titanox 2071 Titanium Dioxide NL Industries Pigment
  • the polyethylene used had an acid number of 0.
  • the difference between the fusion time at 0.1 part per hundred of oxidized polyethylene and the fusion time at 0.75 part per hundred of oxidized polyethylene is 2.8 minutes.
  • the polyethylene used had an acid number of 0.9.
  • the difference between the fusion time at 0.1 part per hundred of oxidized polyethylene and the fusion time at 0.75 part per hundred of oxidized polyethylene is 2.6 minutes.
  • the polyethylene used had an acid number of 3.4.
  • the difference between the fusion time at 0.1 part per hundred of oxidized polyethylene and the fusion time at 0.75 part per hundred of oxidized polyethylene is 1 .1 minutes.
  • the polyethylene used had an acid number of 5.4.
  • the difference between the fusion time at 0.1 part per hundred of oxidized polyethylene and the fusion time at 0.75 part per hundred of oxidized polyethylene is 1 .1 minutes.
  • the polyethylene used had an acid number of 8.6.
  • the difference between the fusion time at 0.1 part per hundred of oxidized polyethylene and the fusion time at 0.75 part per hundred of oxidized polyethylene is 0.4 minutes.
  • the polyethylene used had an acid number of 16.
  • the difference between the fusion time at 0.1 part per hundred of oxidized polyethylene and the fusion time at 0.75 part per hundred of oxidized polyethylene is 0.5 minutes.
  • Titanox 2071 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
  • Lubol 262 1.5 1.4 1.25 1.0 0.75 -- 0.25 0
  • Titanox 2071 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
  • Lubol 262 1.5 1.4 1.25 1.0 0.75 — 0.25 0
  • Fusion Torque 2300 2250 2150 1850 1800 — 1600 1850 (meter-gram)
  • Titanox 2071 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
  • Lubol 262 1.5 1.4 1.25 1.0 0.75 — 0.25 0
  • Fusion Torque 2400 2350 2300 2200 2100 — 2200 2200 (meter-grams)
  • Titanox 2071 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.
  • Lubol 262 1.5 1.4 1.25 1.0 0.75 -- 0.25 0
  • Fusion Torque 3000 2950 — 2800 — — ⁇ (meter-grams)
  • Titanox 2071 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.
  • Comparatives GG through LL and Example 1 7 the compositions were prepared and evaluated as follows.
  • the apparatus consisted of a two-roll mill.
  • the back and front roll temperatures were 370°C.
  • the back roll speed was 23 revolutions per minute while the front roll speed was 1 8.5 revolutions per minute.
  • the mill gap was 40 mils.
  • composition was prepared in an intensive mixer and aged overnight. A 180 gram sample was then weighed, added to the mill, and allowed to band. When banding occurred, the block was started and excess compound not in the nip was taken off and discarded. Every 5 minutes, a sample was taken and mounted. Any excess cut off while taking the sample was returned to the mill and mixed in for 1 minute. When the compound bonded to the mill-roll surface, the test was terminated.
  • EBS is ethylene bis-stearamide.

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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)

Abstract

La présente invention concerne une composition de lubrifiant externe pour un polymère vinylique. Le lubrifiant externe donne davantage de latitude en fabrication et il consiste en un polyéthylène, utilisé en une quantité appropriée pour lubrifier le polymère vinylique. Ce polyéthylène a une viscosité selon Brookfield à la température de 140 °C entre environ 205 et environ 345 centipoises et un indice d'acidité déterminé par le titrage usuel par du KOH entre environ 5 et environ 9. Les compositions de polymère vinylique rigide sont utiles pour des éléments structuraux tels que des conduites, des revêtements muraux, des récipients, et des plaques.
PCT/US1995/008997 1994-07-22 1995-07-18 Polymeres vinyliques rigides plus faciles a utiliser en fabrication WO1996003460A1 (fr)

Applications Claiming Priority (2)

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US27946394A 1994-07-22 1994-07-22
US08/279,463 1994-07-22

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011455A1 (fr) * 1978-11-13 1980-05-28 M & T Chemicals, Inc. Composition pour lubrifier des polymères halogénés et composition de polymère halogéné contenant ledit lubrifiant
US4218353A (en) * 1976-11-18 1980-08-19 Allied Chemical Corporation External lubricant compositions for rigid vinyl polymers
EP0345928A1 (fr) * 1988-04-25 1989-12-13 Morton International, Inc. Compositions lubrifiantes pour PVC
US5426144A (en) * 1993-08-11 1995-06-20 Alliedsignal Inc. External lubricant and stabilizer compositions for rigid vinyl polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4218353A (en) * 1976-11-18 1980-08-19 Allied Chemical Corporation External lubricant compositions for rigid vinyl polymers
EP0011455A1 (fr) * 1978-11-13 1980-05-28 M & T Chemicals, Inc. Composition pour lubrifier des polymères halogénés et composition de polymère halogéné contenant ledit lubrifiant
EP0345928A1 (fr) * 1988-04-25 1989-12-13 Morton International, Inc. Compositions lubrifiantes pour PVC
US5426144A (en) * 1993-08-11 1995-06-20 Alliedsignal Inc. External lubricant and stabilizer compositions for rigid vinyl polymers

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