Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/18—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
  • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
  • B65D85/84—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for corrosive chemicals
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S220/00—Receptacles
  • Y10S220/913—Ventilated container

Definitions

• the present invention relates to (i) a packaged formulation comprising a compound liable to exothermic decomposition, (ii) the storage and/or transport of said formulation, and (iii) methods for producing and modifying polymers using said packaged formulation.
• organic peroxides are generally stored and transported in containers containing the peroxide diluted with one or more liquids, e.g. in the form of a suspension, emulsion, or solution.
• Aqueous peroxide emulsions or suspensions are generally considered safe formulations, because the peroxide is dispersed in the water phase, which is well suited for the removal of the heat of decomposing peroxide molecules, e.g. by convection and/or evaporation.
• Peroxide formulations containing organic diluents are regarded far more dangerous.
• Containers for the storage and/or transport of large volumes of non-aqueous peroxide mixtures are generally made of steel that can withstand the pressures exerted upon explosion. Conventional plastic tanks have not been regarded suitable for such mixtures because of their easy fragmentation.
• the present invention therefore relates to a packaged formulation comprising a compound liable to exothermic decomposition and optionally one or more organic diluents, said formulation being packaged in a container with a volume of at least 250 litre provided with a vent to release gases and made from a thermoplastic material having a Vicat B softening temperature not higher than
• the formulation contains at least one compound liable to exothermic decomposition and no diluent. That is: no organic diluent but also no aqueous diluent, wherein "no diluent" is defined as less than 1 wt%, preferably less than 0.5 wt% of diluent.
• no diluent is defined as less than 1 wt%, preferably less than 0.5 wt% of diluent.
• it is essential that the Vicat B softening temperature of the thermoplastic material is not higher than the run-away temperature of the compound liable to exothermic decomposition. This run- away temperature is defined as the Self Accelerating Decomposition Temperature (SADT) plus 40 0 C.
• SADT Self Accelerating Decomposition Temperature
• the SADT is the lowest temperature at which self-accelerating decomposition may occur with a packaged substance and is measured according to UN test H.4. In practice, the run-away does not start before the temperature is more than 40 0 C above the SADT. That is why in this specification the run-away temperature is defined as SADT+40°C.
• the Vicat B softening temperature of the thermoplastic material is preferably at least 0 0 C, more preferably at least 10°C, even more preferably at least 20°C, and most preferably at least 30 0 C below the run-away temperature of the compound liable to exothermic decomposition.
• the formulation contains an organic diluent.
• the Vicat B softening temperature of the thermoplastic material is not higher than the boiling temperature of at least 50 wt% of the total weight of diluent. If a pure diluent is used, the boiling temperature is defined as the boiling point of this diluent at normal pressure.
• the boiling temperature is defined as the lowest limit of the boiling range of said mixture at normal pressure. If the diluent consist of an azeotropic mixture of liquid compounds, the boiling temperature is defined as the boiling point of the azeotrope at normal pressure. If the mixture of liquid compounds forming the diluent has individual boiling points or boiling ranges at normal pressure, this mixture has more than one boiling temperature.
• At least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt%, and most preferably at least 90 wt% of the total weight of diluent present in the formulation must have a boiling temperature at least equal, but preferably higher than the Vicat B softening temperature of the thermoplastic material.
• the Vicat B softening temperature is measured in accordance with ASTM D1525-00.
• the walls of the container have an average thickness in the range 0.5- 5.0 mm, more preferably 0.5-3.5 mm, and most preferably 0.5-2.5 mm.
• Such relatively thin walls allow relatively quick softening of the walls when the temperature of the formulation rises above the softening temperature.
• the bursting pressure of the container is preferably between 0.5 and 4.0 bar, more preferably between 0.5 and 3.0 bar, and most preferably between 0.5 and 2.0 bar. This bursting pressure is determined by filling the container with water and raising the water pressure until the container bursts.
• thermoplastic materials that - depending on the boiling temperature of the diluent and the run-away temperature of the compound liable to exothermic decomposition - might be suitable for constituting the container, are High Density Polyethylene (HDPE; Vicat B softening temperature: approx. 70°C), Polypropylene (PP; Vicat B softening temperature: approx. 90°C), Poly Vinyl Chloride (PVC; Vicat B softening temperature: approx. 85°C); Low Density Polyethylene (LDPE; Vicat B softening temperature: approx. 55°C); Linear Low Density Polyethylene (LLDPE; Vicat B softening temperature: approx.
• HDPE High Density Polyethylene
• PP Polypropylene
• PVC Poly Vinyl Chloride
• LDPE Low Density Polyethylene
• LDPE Vicat B softening temperature: approx. 55°C
• LLDPE Linear Low Density Polyethylene
• Styrene Acrylonitril (SAN; Vicat B softening temperature: approx. 100 0 C); Acrylonitril Butadiene Styrene (ABS; Vicat B softening temperature: approx. 100 0 C); Poly Methyl Methacrylate (PMMA; Vicat B softening temperature: approx. 100 0 C); Poly Styrene (PS; Vicat B softening temperature: approx. 95°C).
• Acrylonitril Styrene Acrylate (ASA; Vicat B softening temperature: approx. 95°C); Thermoplastic Starch Polymer (TPS; Vicat B softening temperature: approx.
• thermoplastic material may also consist of a co- or terpolymer of two or more of the above-mentioned thermoplastic materials.
• the preferred thermoplastic material is HDPE.
• organic diluents that, depending on the thermoplastic material, might be suitable for use in the formulation are aliphatic hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons, such as ethers, epoxides, and esters.
• Examples of preferred diluents are isododecane (boiling range: 175-195°C), mineral oils (generally boil above 200 0 C), n-paraffinic oils (generally boil above 110 0 C), odorless mineral spirit (generally boil above 110°C), iso-parafinnic oils (generally boil above 110 0 C), white oils (generally boil above 200°C), toluene (generally boiling point: 110°C), ethyl benzene (boiling point: 136°C), xylene (boiling range: 138-144°C), isopropyl benzene (boiling range: 152-154°C) diisopropyl benzene (boiling range: 203-210 0 C), kerosene (boiling range: 175- 325°C), diesel fuel, pthalates (generally boil above 230 0 C) and adipates (generally boil above 230
• the diluent may also be a mixture of any two or more of above mentioned compounds.
• the most preferred organic diluents are isododecane and mineral oil.
• the organic diluent either dissolves the compound liable to exothermic decomposition (in case the compound is solid) or dilutes said compound to form a homogeneous liquid (in case the compound is liquid).
• the organic diluent and the liquid compound liable to exothermic decomposition form, together with water as additional diluent, an emulsion.
• the diluent is also known as phlegmatiser.
• thermoplastic material and organic diluent are HDPE and isododecane, and HDPE and mineral oil.
• Examples of compounds liable to exothermic decomposition are organic peroxides and azo-initiators.
• azo-initiators examples include 2,2'-azodi(isobutyronitrile), 2,2'- azodi(2- methylbutyronitrile, and 1 ,1 '-azobis(1 -cylcohexanenitrile).
• the compound liable to exothermic decomposition is preferably an organic peroxide.
• Any organic peroxide can be used in the second Main Embodiment - i.e. in formulations containing organic diluent - including hydroperoxides, ketone peroxides, peroxyacids, dialkylperoxides, thoxepans, peroxyesters, peroxycarbonates, diacylperoxides, peroxydicarbonates, peroxyketals, cyclic ketone peroxides, mixed peroxides (containing two different peroxygen-beahng moieties in one molecule), and mixtures of two or more of these peroxides.
• organic diluent - including hydroperoxides, ketone peroxides, peroxyacids, dialkylperoxides, thoxepans, peroxyesters, peroxycarbonates, diacylperoxides, peroxydicarbonates, peroxyketals, cyclic ketone peroxides, mixed peroxides (containing two different peroxygen-
• organic peroxide can be oligomehc or polymeric in nature, it is preferred that they comprise one, two or three peroxygen bonds per molecule.
• (di)peroxyesters such as 1 ,1 ,4,4-tetramethylbutyl-1 ,4-di(peroxy-2- methylpropanoate), tert-butyl peroxyneodecanoate, tert-amyl peroxy- neodecanoate, 1 ,1 ,3,3-tetramethylbutyl peroxyneodecanoate, 1 ,1 -dimethyl-3- hydroxybutyl-1 -peroxyneodecanoate, cumyl peroxyneodecanoate, tert- butylperoxy neoheptanoate, tert-amylperoxy neoheptanoate, 1 ,1 ,3,3-tetramethyl butyl-1 -peroxy neoheptanoate, 1 ,1-dimethyl-3-hydroxy butyl -1-peroxy neoheptanoate, tert-butyl
• - peroxycarbonates such as tert-butylperoxy isopropylcarbonate, tert- butylperoxy 2-ethylhexyl carbonate, tert-amylperoxy 2-ethylhexyl carbonate, and tert-butylperoxy stearyl carbonate
• hydroperoxides such as isopropylcumyl hydroperoxide, 1 ,1 ,3,3- tetramethylbutyl hydroperoxide, cumyl hydroperoxide, and tert-amyl hydroperoxide
• - ketone peroxides such as methyl ethyl ketone peroxide, 2,4 pentanedione peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, and di(i-hydroxycyclohexyl) peroxide.
• peroxides examples include di-tert-amyl peroxide, tert-butyl cumyl hydroperoxide, and di-tert- butyl peroxide.
• the packaged formulation according to the present invention preferably contains the compound liable to exothermic decomposition in an amount of 10 to 100 wt%, more preferably 10 to 95 wt%, even more preferably 20 to 80 wt%, and most preferably 30 to 70 wt%.
• the organic diluent is preferably present in an amount of 0 to 90 wt%, more preferably 5 to 90 wt%, even more 20 to 80 wt%, and most preferably 30 to 70 wt%.
• the formulation may further contain other ingredients, such suspending or emulsifying agents, e.g polyvinylalcohol. It should be noted that the formulation may also contain water in addition to organic diluent and compound liable to exothermic decomposition - thereby forming an emulsion - but the formulation is preferably non-aqueous.
• the container has a volume of at least 250 litres, preferably at least 600 litres, more preferably at least 800 litres, and most preferably at least about 1 ,000 litres.
• the container volume preferably is not more than 20,000 litres, more preferably not more than 10,000 litres.
• the container must have a vent to release gases formed in the container.
• the required size of this opening depends on, e.g., the volume of the container and the type and concentration of the compound liable to exothermic decomposition that is present in the container.
• This vent can have the form of a membrane, a breather, a pressure release valve, or any other form that allows release of gases form the container.
• the container is constructed as disclosed in WO 2008/020000; that is: it has a spout opening, a neck along the periphery of the spout opening, and a venting cover comprising a body plate to cover the spout opening, the body plate having a vent opening and having arranged along its periphery a flange with an inner peripheral surface provided with fastening means to cooperate with corresponding fastening means on the outer face of the neck, wherein the vent opening is covered by a gas permeable filter, characterized in that the gas permeable filter is a sheet fixed between the fastening means of the neck and the flange.
• This sheet can for example be a foil of a plastic material.
• the thickness of the sheet can be for instance between about 5 micrometres and about 0.5 mm, e.g. between about 10 micrometres and about 0.1 mm.
• the sheet can be perforated.
• the pore diameter of the perforations can for instance be between about 10 micrometres and about 2 mm, e.g., between about 0.1 mm and about 1.5 mm.
• the venting cover can for example be a screw cap.
• the aforementioned fastening means can be formed by an outer screw thread on the outer face of the neck of the spout opening and a corresponding inner screw thread on the venting cover flange.
• the vent opening in the venting cover is provided with a pop-off cap.
• the vent opening can be surrounded by a neck closely fitting into a peripheral flange of the pop-off cap, wherein the mutually facing sides of the neck and the flange are profiled to form a releasable snap joint.
• This profiling can include mutually cooperating beads and recesses as commonly used in the field of snap joint technology. This allows dimensioning of the snap joint in such a way that it will pop off at a certain pre-determined overpressure, e.g., a pressure in the range of 0.1 - 0.5 bar or higher, by selecting a material with suitable flexibility and optimizing the dimensions of the beads and the recesses.
• the vent cover can for example have a diameter of 10-30 cm, e.g., about 15 cm.
• the pop-off cap can for example have a diameter of about 5-12 cm, e.g. about 7 cm.
• other dimensions for the venting cover and/or the pop-off cap, if present, may also be used, if so desired.
• the invention further relates to a method for producing a polymer by means of a radical polymerisation process using organic peroxide as a source of free radicals, which method involves transporting a packaged peroxide formulation according to the invention to a polymerisation unit and introducing the peroxide formulation into the polymerisation process.
• Examples of such polymerisation processes are processes to make polyvinyl chloride, copolymers of vinyl chloride, poly(meth)acrylate (co)polymers, etc.
• the process is a styrene suspension (co)polymehsation process or a high-pressure ethylene (co)polymerisation process.
• Comonomers that may be used in the (co)polymehsation process of ethylene are of the conventional type and include alkenes, such as propene, (cyclo)hexene and (cyclo)octene, and vinyl acetate.
• Comonomers that may be used in the (co)polymerisation process of styrene are of the conventional type and include divinyl benzene.
• the amount of peroxide used in these conventional (co)polymehsation processes will vary, depending on the polymerisation temperature, the capacity for removing the heat of polymerisation, the kind(s) of monomer(s) used, and the applied pressure. Usually, from 0.001-25 wt% of peroxide, based on the total weight of the monomers, is employed. Preferably, from 0.001-15 wt% of peroxide is employed.
• the invention also relates to a process for modifying a (co)polymer - such as in cross-linking, grafting, and controlled degradation processes, e.g. the formation of polypropylene with another molecular weight and/or molecular weight distribution - by transporting a packaged peroxide formulation according to the invention to a polymer modification unit and introducing the peroxide formulation into the process.
• a process for modifying a (co)polymer - such as in cross-linking, grafting, and controlled degradation processes, e.g. the formation of polypropylene with another molecular weight and/or molecular weight distribution - by transporting a packaged peroxide formulation according to the invention to a polymer modification unit and introducing the peroxide formulation into the process.
• TBPP wt% t-butyl peroxypivalate
• a low heating rate i.e. 0.12 °C/min
• the test was performed in a Total Containment Tank under nitrogen atmosphere. Approximately 4h45' after start, the IBC started to bulge on top.
• the pressure in the IBC increased further and caused the cap covering the vent opening to pop-off slowly at approx. 0.1 barg.
• the double-layered plastic sheet beneath it ruptured at 0.4 barg.
• the temperature inside the container then rose quickly to approximately 180 0 C; a lot of smoke and vapours were formed.
• the product deflagrated at a rate of approx. 6.2 mm/min.
• Example 1 was repeated, except that the IBC was filled with 900 litres of 50 wt% di-(3,5,5-trimethyl hexanoyl) peroxide (DTMHP) in isododecane.
• the packaged formulation was heated with a rate of 0.14°C/min. Approximately 4h46' after start, the IBC started to slightly bulge at the top. After the temperature inside the container reached 76°C, the pressure in the IBC increased further and caused the cap covering the vent opening to pop-off slowly at approx. 0.1 barg. The double-layered plastic sheet beneath it ruptured at 0.4 barg. The temperature rose quickly to approx. 188°C; a lot of smoke and vapours were formed.
• DTMHP di-(3,5,5-trimethyl hexanoyl) peroxide
• Example 1 was repeated, except that the heating rate was 0.10 °C/min and the peroxide formulation was circulated via a centrifugal pump.
• This test served to simulate a worse case scenario of homogeneous decomposition.
• the temperature rose gradually and after approx. 11 h the IBC started to slightly bulge at the top.
• the pressure in the IBC increased further and caused the cap to pop-off slowly at approx. 0.1 barg.
• the double-layered plastic sheet ruptured at 0.2 barg.
• a homogeneous runaway resulted in a fast temperature rise to max. 180 0 C; a lot of smoke and vapours were formed.
• Example 3 was repeated with 50 wt% of t-butylperoxy-2-ethylhexanoate (TBPEH) isododecane. A heating rate of 0.23 °C/min was applied.
• TPEH t-butylperoxy-2-ethylhexanoate

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
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• General Chemical & Material Sciences (AREA)
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