WO1990007409A1 - Pellet thermoplastique extrudable - Google Patents

Pellet thermoplastique extrudable Download PDF

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Publication number
WO1990007409A1
WO1990007409A1 PCT/US1989/005750 US8905750W WO9007409A1 WO 1990007409 A1 WO1990007409 A1 WO 1990007409A1 US 8905750 W US8905750 W US 8905750W WO 9007409 A1 WO9007409 A1 WO 9007409A1
Authority
WO
WIPO (PCT)
Prior art keywords
pellet
vinylidene chloride
processing aid
interpolymer
weight percent
Prior art date
Application number
PCT/US1989/005750
Other languages
English (en)
Inventor
Mark J. Hall
Duane F. Foye
Stephen R. Betso
Kun Sup Hyun
Steven R. Jenkins
Donald E. Kirkpatrick
Paul T. Louks
James A. Stevenson
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to BR898907856A priority Critical patent/BR8907856A/pt
Publication of WO1990007409A1 publication Critical patent/WO1990007409A1/fr
Priority to KR1019900701847A priority patent/KR910700131A/ko
Priority claimed from PCT/US1993/006695 external-priority patent/WO1995002629A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/08—PVDC, i.e. polyvinylidene chloride
    • 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
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/08—Homopolymers or copolymers of vinylidene chloride

Definitions

  • the present invention relates to thermoplastic pellets having improved extrusion properties.
  • a variety of useful articles may be formed using thermally sensitive polymers, such as vinylidene chloride interpolymers.
  • thermally sensitive polymers such as vinylidene chloride interpolymers.
  • the practice generally was to extrude the vinylidene chloride interpolymer directly from the powder form in which it is recovered after polymerization. Because of the convenience of shipping and handling, it is desirable to form the vinylidene chloride interpolymer into pellets prior to final extrusion.
  • a first aspect of the invention is a pellet of 0 extrudable thermoplastic material comprising vinylidene chloride interpolymer, characterized in that, it is coated with at least one processing aid in an amount effective to improve the extrudability of the vinylidene _- chloride interpolymer.
  • a second aspect of the invention is a process for improving the extrudability of a pellet of thermoplastic material comprising vinylidene chloride, 0 which process comprises coating the pellet with at least one processing aid.
  • the inventors have discovered that making a pellet of a vinylidene chloride interpolymer having a -,_- processing aid coated on its surface, improves the extrudability of the vinylidene chloride interpolymer.
  • the pellets of the present invention are considered to possess improved extrudability, i.e., less carbonaceous material contamination on the melt processing equipment, e.g., on an extruder screw heel; and a lower mechanical energy to extrude, i.e., amount of energy expended to extrude the interpolymer due to friction and the viscosity of the polymeric composition, than a pellet formed solely from vinylidene chloride interpolymer.
  • vinylene chloride interpolymer encompasses homopolymers, copolymers, terpolymers, etc. of vinylidene chloride.
  • the vinylidene chloride may be copolymerized with another monoethylenically unsaturated monomer.
  • Monoethylenically unsaturated comonomers suitable for copolymerization with vinylidene chloride include vinyl chloride, alkyl acrylates, alkyl methacrylates, acrylic -it-
  • the monoethylenically unsaturated comonomers are desirably selected from the group consisting of vinyl chloride, alkyl acrylates, and alkyl methacrylates; the alkyl acrylates and alkyl methacrylates having from about 1 to about 8 carbon atoms per alkyl group, preferably from about 1 to about 4 carbon atoms per alkyl group.
  • the alkyl acrylates and alkyl methacrylates are most preferably selected from
  • the monomer mixture comprises a vinylidene chloride monomer generally in the range of from about 60
  • the vinylidene chloride interpolymers suitable for use in the present invention are well-known in the prior art.
  • the vinylidene chloride interpolymer is generally formed through an emulsion or suspension polymerization process.
  • pellets refer to particles having a minimum cross-sectional dimension of at * least 1/32 inch (0.8 mm), preferably of at least 1/16 inch (-1.6 mm), and most preferably of at least 1/8 inch (3.2 mm); said pellets suitably have a maximum cross-sectional dimension of at least 1/2 inch (13 mm), beneficially of at least 3/8 inch (10 mm), and preferably of at least 1/4 inch (6 mm).
  • An exemplary method of forming the polymeric composition into pellets includes extruding the polymeric composition through a strand die to form an extruded strand, and chopping the extruded strand into pellets.
  • Other methods include under water cutting, dicing, and die face cutting.
  • processing aid any component which is employed to improve extrusion performance. These include lubricants (e.g., internal and external types), olefinic waxes and oils, and polyolefins.
  • lubricants e.g., internal and external types
  • olefinic waxes and oils e.g., olefinic waxes and oils
  • polyolefins e.g., polyolefins.
  • the rapid migration of the processing aid provides relatively fast functioning compared to conventionally compounded processing aids, which require pellet melting prior to functioning. Consequently, a lower amount of the processing aid is necessary to achieve equivalent effects to the same processing aid blended with the vinylidene chloride interpolymer.
  • the coating is formed by applying the processing aid onto at least a portion of the surface of the vinylidene chloride pellet.
  • the processing aid will be coated on the vinylidene chloride interpolymer surface in an amount of between about 0.001 weight percent to about 2 weight percent, based on the total weight of the pellet.
  • the processing aid will be coated on the vinylidene chloride interpolymer surface in an amount of between about 0.01 weight percent to about 1.5 weight percent, based on the total weight of the pellet.
  • the processing aid will be coated on the vinylidene chloride interpolymer surface in an amount of between about 0.1 weight percent to about 0.7 weight percent, based on the total weight of the pellet.
  • the choice of optimum amounts of processing aids will be dependent upon the processing aid selected, the viscosity of the processing aid, the size of the pellet, and the type and size of the equipment through which the pellet is extruded, and other parameters known to those of ordinary skill in the art.
  • the processing aid will be uniformly coated on the vinylidene chloride interpolymer pellet surface.
  • the thicker the surface coating the more oenefit one will see in terms of decreasing the particulate degradation in the extrudate. If, however, the processing aid is applied in quantities excessive for the processing aid selected, the viscosity of the processing aid, the size of the pellet, and the type and size of the equipment through which the pellet is extruded, then feeding of the pellet into the melt processing equipment may be impaired because of insufficient friction in the feed zone; or the excess amount of processing aid may form globules on the vinylidene chloride interpolymer surface.
  • the processing aids coated on the vinylidene 0 chloride interpolymer surface are those generally used for the conventional melt processing of vinylidene chloride interpolymers in either powder or pellet form.
  • the specific processing aid selected will be a matter of choice for the skilled artisan, depending upon a variety
  • Exemplary factors in selecting a processing aid include melt adhesion requirement.3, fusion delay requirements, viscosity reduction reqjirements, friction reduction, and the rate increase desired for a selected 0 extruder screw rpm.
  • Exemplary processing aids include lubricants, and olefin polymers.
  • the processing aid should be selected to have a sofarticul.f point between _- ambient temperatures and below the processing temperature of the plastic in pellet.
  • Suitable lubricants include :oth internal and external lubricants which improve extrusion performance
  • interpolyr er any of the class _f compounds that increase the ease with which the pol:Tier molecules slip past one another, resulting in reduce i melt viscosity, better flow, and a lower energy to e..zrude for melt
  • the lubricants may perfcrm functions in addition to that mechanism referred to as internal lubrication.
  • external lubricant any of the _- class of compounds that will migrate to the surface of the molten vinylidene chloride interpolymer and form a film between the interpolymer and the heated metal surface of the extruder, mill or other equipment used to process the pellet. This film significantly reduces the 10 tendency of the polymer to adhere to these metal surfaces and degrade.
  • the compositions may perform functions in addition to that mechanism referred to as external lubrication.
  • the lubricants are classified as “external"
  • Exemplary lubricants include fatty acids (e.g., stearic acid); esters (e.g., fatty esters, wax esters,
  • glycerol esters glycol esters, fatty alcohol esters, and the like
  • fatty alcohols e.g., n-stearyl alcohol
  • fatty amides e.g., N,N*- ethylene bis stearamide
  • metallic salts of fatty acids e.g., calcium stearate, 2I - magnesium stearate, and sodium stearate, sodium lauryl sulfate, and the like
  • polyolefin waxes e.g., paraffinic, nonoxidized and oxidized polyethylene and the like
  • olefin polymer includes homopolymers
  • Exemplary ⁇ -monoolefins polymers include polyethylene (e.g., ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene); polypropylene; poly(butene-1) , poly(isobutylene) ; poly(1-pentene) ; poly(1-hexene) ; and poly(1-octene) .
  • polyethylene e.g., ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene
  • polypropylene e.g., poly(butene-1) , poly(isobutylene) ; poly(1-pentene) ; poly(1-hexene) ; and poly(1-octene) .
  • Substituted ⁇ -monoolefins include those wherein the substituents can be halo, alkyl or haloalkyl having from 1 to 12 carbon atoms; carboxylic acid having from 3 to 8 carbon atoms; alkyl or haloalkyl ester of carboxylic acid wherein alkyl or haloalkyl has from 1 to
  • the ⁇ -monoolefins and substituted ⁇ -monoolefins may also be copoly erized with a variety of suitable comonomers such as carboxylic acids having from 3 to 8 carbon atoms (e.g., ethylene vinyl acetate, and ethylene acrylic acid); alkyl or haloalkyl esters of carboxylic acid wherein alkyl or haloalkyl has from 1 to 12 carbon atoms; ⁇ -alkenyls having 2 to 12 atoms; acyls having 1 to 12 carbon atoms; carboxylates having from 1 to 12 carbon atoms; alkoxyls having from 1 to 12 carbon atoms, aryloxys having from 6 to 12 carbon atoms; and ⁇ - onoolefin/ ⁇ -monoolefin copolymers (e.g., ethylene/propylene copolymers).
  • suitable comonomers such as carboxylic acids having from 3 to 8 carbon atoms (
  • the olefin polymers selected are those which lower the mechanical energy to extrude and the frictional coefficient of the polymeric composition,
  • mechanical energy to extrude is the amount of energy expended when extruding the interpolymer. It defines the amount of energy which has been viscously and frictionally dissipated to the polymer during extrusion. A detailed discussion of mechanical energy to extrude is set forth in Principles 5 of Polymer Processing, Tadmor, Z., and Gogos, C, Chapter 12, Wiley and Sons, (1979).
  • the frictional coefficient of the polymeric composition should be at least about 20 10 percent lower than the frictional coefficient of the polymeric composition without the polyolefin.
  • One method of measuring friction is by impinging a sample of known cross-section on a rotating roll. The ratio of the tangent force to the radial impinging force is
  • C0F coefficient of friction
  • Viscosity is the resistance to flow. Viscosity pc is a function of many variables including molecular weights with higher molecular weight polymers having higher viscosities.
  • polystyrene resins are those
  • the processing aid When in powder form, the processing aid may be applied directly to the vinylidene chloride interpolymer surface. Suitable techniques for applying the powder include softening the vinylidene chloride interpolymer surface prior to application of the powder, or by dispersing the powder in a carrier prior to application. When a carrier is employed, the powder may be blended with the carrier and applied concurrently on the vinylidene chloride interpolymer surface, or may be consecutively applied after the carrier is applied on the vinylidene chloride interpolymer surface. Suitable carriers include mineral oil.
  • the processing aid When in solid or wax form, the processing aid may be prepared for coating the solid or wax on the vinylidene chloride interpolymer surface by exposing the solid or wax to a temperature sufficient to cause it to soften and become tacky or liquid. The softened solid or wax may then be applied to the vinylidene chloride interpolymer surface by any suitable means.
  • Exemplary means for applying the lubricant to the vinylidene chloride interpolymer surface are by means of spraying, tumble blending, or by high intensity blending.
  • a particularly preferred technique for applying a processing aid, regardless of its physical form, to the vinylidene chloride interpolymer surface is by using high intensity blending.
  • the pellets are mixed until they are brought to a temperature at least about 10°C, preferably about 5°C, below the temperature at which the processing aid will soften and fuse.
  • the processing aid is then charged in the blender and further mixing of the preheated pellet and processing aid continued until the processing aid fuses on the vinylidene chloride interpolymer surface.
  • Exemplary high intensity blenders include Banbury mixers, Prodex-Henschel mixers, Welex- Papenmeier mixers, and the like.
  • the pellet After being surface coated, the pellet is then melt processed and extruded into any suitable final product.
  • the process of the present invention can be used to form a variety of films or other articles.
  • the pellet may be fabricated into any suitable final product, e.g., a variety of films or other articles.
  • the films and articles are fabricated with conventional coextrusion; e.g, feedblock coextrusion, multimanifold die coextrusion, or combinations of the two; injection molding; coinjection molding; extrusion molding; casting; blowing; blow molding; calendering; and laminating.
  • Exemplary articles include blown and cast, mono and multilayer, films; rigid and flexible containers; rigid and foam sheet; tubes; pipes; rods; fibers; and various profiles.
  • Lamination techniques are particularly suited to produce multi-ply sheets.
  • specific laminating techniques include fusion; i.e., whereby self-sustaining lamina are bonded together by applications of heat and pressure; wet combining, i.e., whereby two or more plies are laminated using a tie coat adhesive, which is applied wet, the liquid driven off, and in one continuous process combining the plies by subsequent pressure lamination; or by heat reactivation, i.e., combining a precoated film with another film by heating, and reactivating the precoat adhesive so that it becomes receptive to bonding after subsequent pressure laminating.
  • Vinylidene chloride interpolymers are particularly suited for fabrication into rigid containers used for the preservation of food, drink, medicine and other perishables. Such containers should have good mechanical properties, as well as low gas permeabilities to, for example, oxygen, carbon dioxide, water vapor, odor bodies or flavor bodies, hydrocarbons or agricultural chemicals.
  • the structures have organic -polymer skin layers laminated on each side of a vinylidene chloride interpolymer barrier layer, with glue layers generally interposed therebetween.
  • PVdC A pellet containing about 96.5 weight percent Pellet of a vinylidene chloride interpolymer; about 1.5 weight percent ethylene vinyl acetate; about 1.2 weight percent tetrasodium, pyrophosphate; and about 0.8 weight percent of epoxidized soybean oil.
  • the vinylidene chloride interpolymer is formed from about 99.8 weight percent of a vinylidene chloride 0 copolymer formed from a monomer mixture comprising 80 weight percent vinylidene chloride and about 20 weight percent vinyl chloride; and about 0.2 weight percent of epoxidized soybean oil.
  • the vinylidene chloride copolymer has a major melting point of 162°C and a weight average molecular weight 5 of 80,000.
  • PA-1 Magnesium stearate commercially available from Mallinckrodt, Inc., under the trade designation magnesium stearate RSN 1-1.
  • PA-2 Sodium lauryl sulfate commercially available from Albright and Wilson, Inc., under the trade designation Empicol LZV/E.
  • PA-3 A poly(ethylene-co-vinyl acetate) containing 28% vinyl acetate, which is commercially available from DuPont de Nemours Chemical Co. c under the trade designation Elvax 3180.
  • PA-4 An oxidized polyethylene commercially available under the trade designation as Allied 629A from Allied Corp.
  • the oxidized polyethylene has a density (ASTM Test D-1505) of 0.93 grams per cubic centimeter @ 20°C, a 0 drop point of 104°C, and a Brookfield Viscosity of 200 cps (mPa-s) ⁇ 140°C.
  • PA-5 A polyethylene wax commercially available from Allied Corp. under the trade designation Allied 617A.
  • the polyethylene wax has a density (ASTM Test D-1505) of 0.91 grams per 5 cubic centimeter, a drop point of 102°C, and a Brookfield Viscosity of 180 cps (mPa-s) @ 140°C.
  • ASTM Test D-1505 a density of 0.91 grams per 5 cubic centimeter
  • a drop point of 102°C a drop point of 102°C
  • Brookfield Viscosity 180 cps (mPa-s) @ 140°C.
  • processing aids are coated on the surface of the PVdC pellets in quantities set forth in Table II. Those processing aids in powder form are coated on the pellet by placing the powder and pellet in a bag and then shaking them. More sophisticated equipment could have been used but was not necessary.
  • Those processing aids in the form of a wax or solid are coated on the pellet using the following method: the pellets are placed in a high speed blender which is commercially available under the trade designation Welex Model 35 from F. H. Papenmeier K. G. Company.
  • the mixer has a diameter of 35 cm, and a nominal capacity of 1 cubic foot (28 dm ⁇ ).
  • the baffle of the mixer is adjusted in the radial direction, the impeller is started and maintained at a tip speed of about 2700 feet per minute (fpm) (825 m/min) .
  • fpm feet per minute
  • various processing aids, coded in Table I are charged in the mixer in quantities set forth in Table II.
  • the pellets and processing aids are blended for a period of about eight minutes and then discharged.
  • the coated pellets are cooled to about 65°C by circulating air having a temperature of 20°C.
  • the pellets are extruded through a 2.5 inch (6.3 cm) extruder having a length to diameter ratio of 21/1.
  • the decomposition of the extruded resin into carbonaceous material is determined by visually inspecting the carbonaceous material on the root of the extruder screw heel. When evaluating the root of the extruder screw heel, pellets are extruded in a continuous process for a period of about 4 hours.
  • the extent * of carbonaceous material formation in the transition section of the extruder screw is qualitatively rated.
  • the carbonaceous material buildup is rated on a scale of 0 to 4 over a continuous range, wherein 0 represents generally no visible carbonaceous material on the surface and 4 represents a layer of carbonaceous material generally completely covering the surface.
  • Pellet pellets as set forth in Table I.
  • Particulate Degradation Product carbonaceous material contamination on the extruder screw heel according to visual inspection, on a scale of 0 to 4.
  • a pellet having the following composition is employed: about 96.5 weight percent of a vinylidene chloride interpolymer; about 1.5 weight percent ethylene vinyl acetate; about 1.2 weight percent tetrasodiuum pyrophosphate; and about 0.8 weight percent of epoxidized soybean oil.
  • the vinylidene chloride interpolymer comprises from about 99.8 weight percent of a vinylidene chloride copolymer and about 0.2 weight percent of epoxidized soybean oil.
  • the vinylidene chloride copolymer is formed from a monomer mixture comprising 94 weight percent vinylidene chloride and about 6 weight percent methyl acrylate and has a major melting point of 165°C and a weight average molecular weight of 90,000.
  • the coated pellets generate a relatively low level of particulate degradation product.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On a amélioré l'extrusion de pellets d'interpolymère de chlorure de vinylidène par revêtement avec au moins un auxiliaire de traitement. On peut citer à titre d'exemple d'auxiliaire de traitement des acides gras, esters, alcools gras, amides gras, sels métalliques d'acides gras, polymères d'oléfines et cires de polyoléfines.
PCT/US1989/005750 1988-12-23 1989-12-18 Pellet thermoplastique extrudable WO1990007409A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR898907856A BR8907856A (pt) 1988-12-23 1989-12-18 Conta termoplastica extrudavel
KR1019900701847A KR910700131A (ko) 1988-12-23 1990-08-22 압출성 열가소성 펠렛

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US25993688A 1988-12-23 1988-12-23
US259,936 1988-12-23
PCT/US1993/006695 WO1995002629A1 (fr) 1988-12-23 1993-07-16 Matieres particulaires thermoplastiques extrudables

Publications (1)

Publication Number Publication Date
WO1990007409A1 true WO1990007409A1 (fr) 1990-07-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/005750 WO1990007409A1 (fr) 1988-12-23 1989-12-18 Pellet thermoplastique extrudable

Country Status (4)

Country Link
JP (1) JPH04502478A (fr)
AU (1) AU640627B2 (fr)
CA (1) CA2006359A1 (fr)
WO (1) WO1990007409A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995002629A1 (fr) * 1988-12-23 1995-01-26 The Dow Chemical Company Matieres particulaires thermoplastiques extrudables

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3355404A (en) * 1965-01-25 1967-11-28 Dow Chemical Co Styrene polymers containing behenic acid as a lubricant
US3669722A (en) * 1969-06-25 1972-06-13 Copolymer Rubber & Chem Corp Free flowing pellets of uncured elastomeric material
US3758656A (en) * 1970-03-25 1973-09-11 Du Pont Ainst excessive cold flow during shipment or storage process for preparing an elastomer which is structurally supported ag
US4079115A (en) * 1974-10-21 1978-03-14 The Dow Chemical Company Process for preparing improved transparent shaped articles from vinylidene chloride polymer compositions modified with a nitrile containing elastomer
US4203880A (en) * 1978-11-13 1980-05-20 M&T Chemicals Inc. Lubricant composition for halogen-containing polymers
US4769289A (en) * 1985-09-13 1988-09-06 The Dow Chemical Company Free-flowing plural extrudates of polar ethylene interpolymers
US4822545A (en) * 1984-06-15 1989-04-18 Exxon Research & Engineering Company Method for making free-flowing coated rubber pellets

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4456689A (en) * 1982-05-17 1984-06-26 Becton Dickinson And Company Competitive protein binding assay using an organosilane-silica gel separation medium
US4668620A (en) * 1984-02-22 1987-05-26 Syntex (U.S.A.) Inc. Reducing background interference activity in enzyme-label immunoassays
US4703001A (en) * 1985-10-23 1987-10-27 Synbiotics, Corporation Immunoassay for the detection of serum analytes using pH dependent chastropic acids

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3355404A (en) * 1965-01-25 1967-11-28 Dow Chemical Co Styrene polymers containing behenic acid as a lubricant
US3669722A (en) * 1969-06-25 1972-06-13 Copolymer Rubber & Chem Corp Free flowing pellets of uncured elastomeric material
US3758656A (en) * 1970-03-25 1973-09-11 Du Pont Ainst excessive cold flow during shipment or storage process for preparing an elastomer which is structurally supported ag
US4079115A (en) * 1974-10-21 1978-03-14 The Dow Chemical Company Process for preparing improved transparent shaped articles from vinylidene chloride polymer compositions modified with a nitrile containing elastomer
US4203880A (en) * 1978-11-13 1980-05-20 M&T Chemicals Inc. Lubricant composition for halogen-containing polymers
US4203880B1 (en) * 1978-11-13 1994-04-26 M & T Chemicals Inc Lubricant composition for halogen-containing polymers
US4822545A (en) * 1984-06-15 1989-04-18 Exxon Research & Engineering Company Method for making free-flowing coated rubber pellets
US4769289A (en) * 1985-09-13 1988-09-06 The Dow Chemical Company Free-flowing plural extrudates of polar ethylene interpolymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995002629A1 (fr) * 1988-12-23 1995-01-26 The Dow Chemical Company Matieres particulaires thermoplastiques extrudables

Also Published As

Publication number Publication date
CA2006359A1 (fr) 1990-06-23
AU640627B2 (en) 1993-09-02
AU4802190A (en) 1990-08-01
JPH04502478A (ja) 1992-05-07

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