WO2010100083A1 - Procédé de préparation de particules d'epdm fluides - Google Patents

Procédé de préparation de particules d'epdm fluides Download PDF

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Publication number
WO2010100083A1
WO2010100083A1 PCT/EP2010/052456 EP2010052456W WO2010100083A1 WO 2010100083 A1 WO2010100083 A1 WO 2010100083A1 EP 2010052456 W EP2010052456 W EP 2010052456W WO 2010100083 A1 WO2010100083 A1 WO 2010100083A1
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Prior art keywords
copolymer
pellets
melt
free flowing
pellet
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PCT/EP2010/052456
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English (en)
Inventor
Patric Meessen
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Dsm Ip Assets B.V.
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Publication of WO2010100083A1 publication Critical patent/WO2010100083A1/fr

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    • 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
    • C08J3/12—Powdering or granulating
    • C08J3/124—Treatment for improving the free-flowing characteristics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers

Definitions

  • the invention is related to a method for producing pellets of a non- crystalline olefinic copolymer, said copolymer having a melt flow index greater than 2 and to free flowing pellets of a non-crystalline olefinic copolymer.
  • elastomers are tacky or exhibit cold flow in their green or uncured state. As a consequence, these materials cannot be transported in bulk as free flowing pellets but must be shipped in bales. This practice requires that the ultimate elastomer processor must be equipped to cut up or mill the bales. The necessary equipment is generally large scale, expensive equipment. Additionally, the bales cannot be readily preblended with other materials. The necessity for baling results in high handling and shipping costs. In order to facilitate handling and processing of elastomers, it has been considered desirable to produce elastomer pellets. Generally, however, elastomer pellets exhibit "blocking" or cold flow characteristics which result in solidification into a solid mass after a short storage time, especially at elevated temperatures.
  • the elastomer By blending the elastomer with a crystalline type polymer such as polyethylene, polypropylene, copolymers of ethylene and propylene, polyesters or polyamides, it has been possible to produce free flowing elastomer containing pellets. However, the elastomer content of the pellet must be less than about 65%. The product is, of course, not suitable for use in all elastomer applications. Such processes and products have been described in US 6,184,297 and US 6,077,906.
  • Another coating approach to the problem has been the coating of elastomer pellets with emulsions containing a tack free coating material. Coating is accomplished either by dipping pellets into the emulsion or spraying the emulsion onto the pellets. In either case the emulsion coating must be dried, and where the emulsion contains a solvent the solvent must be recovered. Drying and solvent recovery requirements result in increased costs.
  • melt-coating methods for producing free-flowing elastomer pellets have also been suggested. According to U.S. Pat. No. 3,669,772 to Bishop, coating can be accomplished by using a die, similar to wire coating die, into which a strand of rubber to be coated is fed simultaneous with melt coating material. A continuous melt coated strand of rubber issues from the coextrusion die outlet, is cooled in a liquid cooling bath, and is subsequently pelletized. This melt-coating method not only adds significantly to rubber manufacturing costs, but has limitations from the standpoint of efficiently producing large quantities of coated pellets.
  • a rubber pellet composition comprising an elastomer and plastic insoluble in the elastomer can be caused to coat itself with a plastic skin by control of composition, extrusion conditions and die temperature.
  • U.S. Pat. No. 4,622,193 to Hazelton describes an elastomer-plastic blend, extruded at a temperature above the melting point of the plastic, and pelletized as it exits from a die, the die having a temperature gradient across the die from inlet to outlet, the gradient being such that the die outlet temperature is substantially lower than the extrusion melt temperature (die inlet temperature), resulting in a pellet coated with a skin of plastic.
  • a disadvantage of above-mentioned methods is that non-rubbery materials are mixed into the rubber, which may lead to blooming and, or deterioration of properties of the final product.
  • the invention is a method for producing free flowing pellets of an olefinic copolymer with a crystallinity at 23°C below 1 wt% measured by DSC according to ASTM E793 using HDPE as an external standard, said copolymer having a melt flow index measured according to ISO1 133 at 190 0 C, 2160 g greater than 2 g/10min characterized in that the method consists in grafting from 0.5 to 5 wt% ethylenically unsaturated carboxylic acid material onto said copolymer backbone to form an acylated olefin copolymer, melt-extruding the resulting mixture and cooling, solidifying and pelletizing the resulting melt-extrudate, storing the resulting pellets for at least one week.
  • the invention provides a free flowing pellet comprising an olefinic copolymer with a crystallinity at 23°C below 1 wt% measured by DSC according to ASTM E793 using HDPE as an external standard, said copolymer having a melt flow index measured according to ISO1133 at 190 0 C, 2160 g greater than 2 g/10min, characterized in that the copolymer comprises from 0.5 to 5 wt% ethylenically unsaturated carboxylic acid material.
  • the invention is a method for producing free flowing pellets of a noncrystalline olefinic copolymer.
  • the non-crystalline nature of the olefinic copolymer is defined by a crystallinity below 1 wt% measured by DSC according to ASTM E793 and using HDPE as an external standard. A crystallinity of less than 1 wt% is generally experienced by the absence of an endo- or exothermic crystallization in DSC measurements. In general and in the present application such materials are also addressed as amorphous or non-crystalline polymers.
  • a typical category of non-crystalline olefinic polymer are ethylene- higher alpha-olefin copolymers, especially ethylene propylene copolymers that may consist of from about 30 to 60 wt% ethylene and from about 70 to 40 wt% propylene, cyclic or higher alpha-olefin.
  • the preferred copolymers for practice of this invention are comprised of from 40 to 55 wt% ethylene and 60 to 45 wt% propylene.
  • Hydrogenated random and block copolymers of a vinyl aromatic compound and a conjugated diene, or mixtures of conjugated dienes are also suitable substrates for use in the present invention.
  • hydrogenated random and block copolymers of isoprene-butadiene, styrene-isoprene or styrene-butadiene are preferred.
  • the melt-index of the copolymers of the invention is the melt-index of the processed and pelletized copolymer compound. This viscosity is independent from the viscosity of the initial copolymer subjected to the melt processing since the described modification technology can lead to polymer degradation and cross-lining that will affect final viscosity.
  • the melt-index of the copolymer of the invention is measured in accordance with ISO1133 is more than 2 g/10 min (190 0 C, 2160 g), preferably more than 4 g/10 min.
  • Melt index is a common and simple to measure polymer characteristic, especially in production environment and is most often a leading and reliable quality control parameter.
  • correlation between melt index and more scientific methods such as molecular weight values determined by size exclusion chromatography are readily available.
  • An indicative number average molecular weight, Mn, that can be determined by gel permeation chromatography of the copolymer subject to the present invention is between 700 and 60,000 g/mol, preferably between about 3,000 and about 55,000 g/mol, more preferably between about 10,000 and about 50,000 g/mol.
  • a molecular weight distribution, M w /M n , of the polymer substrates of the present invention can be obtained that is less than 15, preferably 1.0 to 10.
  • the preferred olefinic copolymer substrate employed in the method of the present invention is derived from polymerizable C 2 to C 2 3 olefins.
  • Such copolymers are typically produced from ethylene, propylene, 1-butene, 2-butene, isobutene, cyclopentene, 1-hexene, 1-octene or norbornene.
  • Preferred polymers for use in the present invention are copolymers of ethylene and one or more C 3 to C 23 olefins. Copolymers of ethylene and propylene are most preferred. Other olefins suitable in place of propylene to form the copolymer or to be used in combination with ethylene and propylene to form a terpolymer include 1- butene, 1-pentene, cyclopentene, 1-hexene, 1-octene, norbornene, and styrene; also alpha, omega -diolefins such as 1 ,5-hexadiene, 1 ,6-heptadiene, 1 ,7-octadiene, etc., also branched chain alpha-olefins such as 4-methylbutene-1 , 5-methylpentene-1 and 6-methylheptene-1 and mixtures thereof.
  • the ethylene-olefin copolymers may contain minor amounts of other olefinic monomers such as conjugated or nonconjugated dienes.
  • the polymerization reaction used to form the ethylene-olefin copolymer substrate is generally carried out in the presence of a conventional Ziegler-Natta or metallocene catalyst system.
  • the polymerization medium is not specific and can include solution, slurry, or gas phase processes, as known to those skilled in the art.
  • the solvent may be any suitable inert hydrocarbon solvent that is liquid under reaction conditions for polymerization of olefins; examples of satisfactory hydrocarbon solvents include straight chain paraffins having from 5 to 8 carbon atoms, with hexane being preferred.
  • Aromatic hydrocarbons preferably aromatic hydrocarbon having a single benzene nucleus, such as benzene, toluene and the like; and saturated cyclic hydrocarbons having boiling point ranges approximating those of the straight chain paraffinic hydrocarbons and aromatic hydrocarbons described above, are particularly suitable.
  • the solvent selected may be a mixture of one or more of the foregoing hydrocarbons.
  • the liquid phase for polymerization is preferably liquid propylene. It is desirable that the polymerization medium be free of substances that will interfere with the catalyst components.
  • a first step of the method of the invention consists in grafting from 0.5 to 5 wt% ethylenically unsaturated carboxylic acid material onto said copolymer backbone to form an acylated olefin copolymer.
  • carboxylic reactants which are suitable for grafting onto the ethylene copolymer contain at least one ethylenic bond and at least one, preferably two, carboxylic acid or its anhydride groups, or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis.
  • the carboxylic reactants are selected from the group consisting of acrylic, methacrylic, cinnamic, crotonic, and maleic, fumaric, and itaconic reactants of the general formula: o
  • R is an alkyl group having from 0-4 carbon atoms
  • X and X' are the same or different and are independently selected from the group consisting of -OH, -O- hydrocarbyl, -0-M + wherein M + represents one equivalent of metal, ammonium or amine cation, -NH 2 , -Cl, -Br, and together X and X' can be -O- so as to form the anhydride
  • Y and Y' are the same or different and are independently selected from the group consisting of hydrogen, branched or straight chain alkyls having 1-12 carbon atoms, a halogen atom, or an organo anhydride, ketone, or heterocyclic group having 2-12 carbon atoms.
  • the maleic or fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these.
  • Maleic anhydride is generally preferred due to its commercial availability and ease of reaction.
  • the carboxylic reactant is grafted onto the prescribed polymer backbone in an amount of from about 0.5 to about 5 wt% of carboxylic reactant per 100 wt% of the polymer backbone, preferably, at least 1 wt%. More preferably, at least 2 wt%.
  • the grafting reaction to form the acylated olefin copolymers is generally carried out with the aid of a free-radical initiator either in solution or in bulk, as in an extruder or intensive mixing device.
  • a free-radical initiator either in solution or in bulk, as in an extruder or intensive mixing device.
  • the polymerization is carried out in hexane solution, it is economically convenient to carry out the grafting reaction in hexane as described in U.S. Pat. Nos. 4,340,689, 4,670,515 and 4,948,842.
  • the resulting polymer intermediate is characterized by having carboxylic acid acylating functionality randomly within its structure.
  • the olefin copolymer is fed to rubber or plastic processing equipment such as an extruder, intensive mixer or masticator, heated to a temperature of 150 to 400 ° C. and the ethylenically unsaturated carboxylic acid reagent and free-radical initiator are separately co-fed to the molten polymer to effect grafting.
  • the reaction is carried out optionally with mixing conditions to effect shearing and grafting of the ethylene copolymers according to U.S. Pat. No. 5,075,383, incorporated herein by reference.
  • the processing equipment might be purged with nitrogen to prevent oxidation of the polymer and to aid in venting unreacted reagents and byproducts of the grafting reaction.
  • the residence time in the processing equipment is sufficient to provide for the desired degree of acylation and polymer degradation and to allow for purification of the acylated copolymer via venting.
  • the free-radical initiators which may be used to graft the ethylenically unsaturated carboxylic acid material to the polymer backbone include peroxides, hydroperoxides, peresters, and also azo compounds and decompose thermally within the grafting temperature range to provide free radicals.
  • free- radical initiators are azobutyronitrile, dicumyl peroxide, 2,5-dimethylhexane-2,5-bis- tertiarybutyl peroxide and 2,5-dimethyl-hex-3-yne-2,5-bis-tertiary-butyl peroxide, bis- tertiary-butyl peroxide, 3,3,5,7,7-pentamethyl 1 ,2,4-trioxepane and 3,6,9-triethyl-3,6,9- trimethyl-1 ,4,7-triperoxonane.
  • the initiator is used in an amount of between about 0.005% and about 1% by weight based on the weight of the reaction mixture.
  • the acylated olefin copolymer is extruded, cooled, solidified and pelletized.
  • a typical but not limiting way to perform the peptization under the scope of the invention is to process the acylated melt through a pressure building zone in an extruder to force the polymer through a die at a typical temperature between 100 and 300 0 C to be cut by an underwater pelletizer.
  • Other exit media such as a turbulator, a strand bath or a gear pump may be used.
  • an underwater pelletizer is preferred. Temperature of the cooling water will be typically maintained between 10 and 60 0 C. More preferred the temperature will be between 15 and 35°C.
  • the pelletize material will have a defined residence time in the cooling medium to allow sufficient heat exchange between the cooling medium and the polymeric material.
  • a typical residence time will be between 15 seconds and 5 minutes before being separated and dried from the cooling water by cyclone and drier technology.
  • Longer residence times will require increased dimensioning of the cooling system with the benefit of an improved cooling result or the possibility to work with a higher temperature of the cooling medium.
  • Shorter cooling times will require higher turbulent flows and reduced temperature of the cooling medium to achieve acceptable final pellet temperature with the benefit of a smaller cooling system.
  • the resulting pellets are stored for at least one week.
  • the storage can take place at room temperature in bags, bales or boxes.
  • a conditioned environment consisting of heating or cooling to specific temperatures and maintaining specific humidity levels can be applied.
  • the pellets are stored in bales for at least one week, and subsequently de-lumped by a mechanical force into free flowing pellets.
  • a typical de-lumping process consists of a grinder large enough to accept feeding of entire bales of the original material with sufficient air flow to remove heat generated by the grinding process.
  • the pellets are recovered after pneumatic transport via a cyclone and repackaged in bags or the original boxes. Dusting agents can be applied before, during or after the grinding process.
  • the conditioned pellets are dusted with a partitioning agent either during de-lumping of the bales or thereafter in a suitable dusting equipment.
  • a partitioning agent i.e. dusting agents
  • This process might be extended with other mechanical treatments such as a continuous or batch operated tumbling device to allow homogeneous distribution of the dusting agent.
  • Many kinds of partitioning agents i.e. dusting agents, can be applied.
  • Commercial calcium stearate, aluminum silicate or magnesium silicate powders are examples of such a partitioning agent.
  • Specific additives designed for partitioning and characterized by their high surface area such as fumed silicas are other examples of suited partitioning agents.
  • the dusting agent may be a single dusting agent or a combination of more than one type of dusting agents.
  • Typical partitioning agents are metal salts of organic aliphatic acids like calcium stearate powder, talc, calcium carbonate, clay, and crystalline polyolefin powders, like low or high density polyethylene, polypropylene, ethylene-vinylacetate copolymers as well as amorphous synthetic compounds such as fumed silica or furnace black.
  • a free flowing pellet of the current invention only a minimum amount of dusting is necessary to avoid pellets bounding together.
  • the level of dusting agent required will be a further function of the specific surface of the particulate rubber and additive.
  • the level of dusting may be from a lower level of 0.01 , or 0.05 wt% to an upper level of 0.2, or 0.5, or 2 wt%.
  • Addition of the dusting agent can be performed on a continuous basis before, during or after grinding.
  • the dusting agent can be added batch wise, under the condition of allowing substantial residence time and back mixing for a homogeneous distribution of the additive throughout the pellets.
  • the dusting device can be selected from a number of commercial dusting devices, including, for example, Kason Vibratory Conveyor, Hirshel mixer, Rotary Tumbler, roller mixer, or any vibratory or screw conveyors.
  • the dusting device is selected to achieve uniform distribution and coating of dust on pellets. Also, the particle sizes of the dusts could have an impact on how much dusting agent will be used. Typical dust size varies from 1 to 100 microns. However, dust particle sizes could be as large as 500 to 1000 microns. Generally, the finer the dust particle, the lower the dust level needed to avoid that pellets stick together.
  • the invention further relates to a free flowing pellet comprising a noncrystalline olefinic copolymer, said copolymer having a melt flow index greater than 2, wherein the copolymer comprises from 0.5 to 5 wt% ethylenically unsaturated carboxylic acid material grafted onto said copolymer backbone.
  • the pellet according to the invention preferably comprises a copolymer with a glass transition temperature of less than 20 0 C as determined by standard DSC analysis.
  • the pellet of the invention preferably comprises a copolymer with a maximum gel level of 0.5 wt% determined via solubilization and filtration from a solution.
  • a maleic anhydride modified ethylene propylene copolymer THF is used at room temperature.
  • a storage friability test has been developed consisting of a 10 cm diameter and 10 cm high aluminum cylinder that can be removed sideway by opening along the vertical axis.
  • the cylinder is filled with the granulate and subjected to storage conditions by applying a weight representing single bag or entire pallet stacking height for a defined time and temperature.
  • This test simulates the flow behavior of the bottom fraction of material stored in individual boxes or bags, stacked up to 1.5 meter respectively.
  • the constraint is released, the time required for the pellets to crumble is monitored. If after one hour no crumbling occurred, the pellet made cylinder is manipulated with increasing force. Failure of the flow behavior consists of a cylinder of material that can be lifted by hand without disintegration.
  • Di-tert-butyl peroxide (Akzo Nobel, Trigonox B) as a 30 wt% solution in mineral oil was fed at a combined rate of 0.4% of the rubber throughput. Screw speed was 250 rpm to reach a reaction melt temperature of 201 °C. Degassing of unreacted product was done via a vent zone at a vacuum of 200 mbar. Final compression of the melt in the extruder head gave a final melt temperature of 298°C.
  • the rubber melt exiting the extruder was fed to an under water pelletizer system including a pelletizing head with a star knife assembly and water recirculation system with heat exchanger. The pellets were cooled for an average of 1 minute in the 18°C water stream of the under water peptization system before being collected at a pellet temperature of 27°C.
  • the obtained maleic anhydride grafted rubber was a clear light yellow rubber with a melt flow index (MFI) of 4.9 g/10 min (190 0 C, 216O g), a gel level of 0.05 wt% and a maleic anhydride functional level measured by IR method of 1.93 wt% (conversion 77%).
  • MFI melt flow index
  • the freshly recovered material shows a tendency to agglomerate such that the pelletized product is recovered as bales. This is in line with the polymer analysis, which does not suggest that a stable pellet is possible at all.
  • the generated pellets were free flowing.
  • the so obtained free flowing material was subjected to the storage friability test by simulating compressing of the pellets by a pallet height (1.5 meter) of its own weight at 35°C. Upon release of the constraint, the compressed pellets crumbled readily upon touch.
  • the ground material was dusted with 0.5 wt% of Aerosil
  • pelletized rubber was a clear nearly colorless rubber with a melt flow index (MFI) of 2.3 g/10 min (190 0 C, 216O g), a gel level of less that 0.01 (detection limit) and a maleic anhydride functional level measured by IR method of less than 0.05 wt% (detection limit).
  • MFI melt flow index
  • the freshly recovered material shows an extreme tendency to agglomerate such that the pelletized product is recovered as solid bales.

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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)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de fabrication de granulés d'un copolymère oléfinique ayant une cristallinité à 23 °C inférieure à 1 % en poids, mesurée par DSC selon ASTM E793 en utilisant l'HDPE en tant qu'étalon externe, ledit copolymère ayant un indice de fluidité mesuré selon ISO 1133 à 190 °C, 2 160 g, supérieur à 2 g/10 min. Le procédé selon l'invention consiste à greffer 0,5 à 5 % en poids d'un matériau acide carboxylique éthyléniquement insaturé sur le squelette dudit copolymère pour former un copolymère oléfinique acylé, à extruder à l'état fondu le mélange résultant et à refroidir, solidifier et granuler l'extrudat fondu résultant, à stocker les granulés résultants pendant au moins une semaine. L'invention concerne également des granulés fluides qui comprennent un copolymère oléfinique ayant une cristallinité à 23 °C inférieure à 1 % en poids, mesurée par DSC selon ASTM E793 en utilisant l'HDPE en tant qu'étalon externe, ledit copolymère ayant un indice de fluidité mesuré selon ISO 1133 à 190 °C, 2 160 g, supérieur à 2 g/10 min, caractérisé en ce que le copolymère comprend 0,5 à 5 % en poids d'un matériau acide carboxylique éthyléniquement insaturé.
PCT/EP2010/052456 2009-03-04 2010-02-26 Procédé de préparation de particules d'epdm fluides WO2010100083A1 (fr)

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Cited By (1)

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WO2014152726A1 (fr) * 2013-03-15 2014-09-25 Dow Global Technologies Llc Système et traitement de conditionnement d'epdm

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US6077906A (en) 1998-03-11 2000-06-20 Thiruvengada; Seshan Nylon modifiers hauling enhanced flow properties
US6184297B1 (en) 1992-11-19 2001-02-06 Mitsui Chemicals Inc Ethylene copolymer composition
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GB928120A (en) 1960-09-14 1963-06-06 Exxon Research Engineering Co Coated polymer pellets
US3927166A (en) 1969-04-11 1975-12-16 Chiba Fine Chemical Co Ltd Method for pelletizing compositions comprising a non-crystalline olefinic polymer or copolymer, and a surfactant
US3669772A (en) 1970-07-02 1972-06-13 American Optical Corp Method for producing flexible image transporting fiber optic conduit
US3932368A (en) 1973-11-21 1976-01-13 Eastman Kodak Company Powder coating composition comprising a particulate form of a carboxylated polyolefin
US4340689A (en) 1979-09-17 1982-07-20 Copolymer Rubber & Chemical Corporation Method of grafting EPM and EPDM polymers
US4451614A (en) 1981-08-19 1984-05-29 Chemische Werke Huels, Ag Process for the production of pourable, tack-free vinyl chloride graft polymers
US4670515A (en) 1983-08-15 1987-06-02 Copolymer Rubber & Chemical Corp. Grafted and cross-linked epm
US4622193A (en) 1984-06-15 1986-11-11 Exxon Research & Engineering Co. Method for making free flowing coated rubber pellets
US4948842A (en) 1985-01-11 1990-08-14 Copolymer Rubber And Chemical Corporation Polyesters having improved impact strength
US4927888A (en) 1986-09-05 1990-05-22 The Dow Chemical Company Maleic anhydride graft copolymers having low yellowness index and films containing the same
US5075383A (en) 1990-04-11 1991-12-24 Texaco Inc. Dispersant and antioxidant additive and lubricating oil composition containing same
US6184297B1 (en) 1992-11-19 2001-02-06 Mitsui Chemicals Inc Ethylene copolymer composition
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US6077906A (en) 1998-03-11 2000-06-20 Thiruvengada; Seshan Nylon modifiers hauling enhanced flow properties
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014152726A1 (fr) * 2013-03-15 2014-09-25 Dow Global Technologies Llc Système et traitement de conditionnement d'epdm
CN105008435A (zh) * 2013-03-15 2015-10-28 陶氏环球技术有限责任公司 Epdm包装系统和方法
KR20150131032A (ko) * 2013-03-15 2015-11-24 다우 글로벌 테크놀로지스 엘엘씨 Epdm 포장 시스템 및 방법
US10329071B2 (en) 2013-03-15 2019-06-25 Dow Global Technologies Llc EPDM packaging system and process
CN105008435B (zh) * 2013-03-15 2020-03-13 陶氏环球技术有限责任公司 Epdm包装系统和方法
KR102233615B1 (ko) 2013-03-15 2021-03-30 다우 글로벌 테크놀로지스 엘엘씨 Epdm 포장 시스템 및 방법
US11421085B2 (en) 2013-03-15 2022-08-23 Dow Global Technologies Llc EPDM packaging system and process

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