WO2010149733A1 - Système et procédé pour durcir une composition - Google Patents

Système et procédé pour durcir une composition Download PDF

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Publication number
WO2010149733A1
WO2010149733A1 PCT/EP2010/058983 EP2010058983W WO2010149733A1 WO 2010149733 A1 WO2010149733 A1 WO 2010149733A1 EP 2010058983 W EP2010058983 W EP 2010058983W WO 2010149733 A1 WO2010149733 A1 WO 2010149733A1
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WO
WIPO (PCT)
Prior art keywords
gas
oxygen
sink
gas sink
substrate
Prior art date
Application number
PCT/EP2010/058983
Other languages
English (en)
Inventor
David Cranfill
Keith E. Gutowski
Donald H. Campbell
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2010149733A1 publication Critical patent/WO2010149733A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/107—Post-treatment of applied coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/0453—After-treatment
    • B05D3/046—Curing or evaporating the solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0466—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere

Definitions

  • the present invention generally relates to a system and a method for curing a composition on a substrate.
  • the composition comprises an organoborane complex and a radical polymerizable compound.
  • OEM automotive finish coatings and aftermarket refinish automotive coatings are two-part compositions that require physical mixing of two condensed phases. This mixing typically limits control of curing, increases cure times, and makes application of the coatings to complex shapes and sequestered surfaces difficult.
  • the coatings are applied to automobile parts which are then passed through the ovens to cure the coatings.
  • use of the ovens is very energy intensive, expensive, and has an adverse impact on the environment.
  • OEM automobile production facilities the ovens occupy large footprints and are cumbersome to use.
  • This technology includes use of gaseous atmospheres with UV light and irradiation of coatings in gaseous atmospheres.
  • the gaseous atmospheres limit amounts of oxygen that are present during curing thereby limiting oxygen surface inhibition.
  • UV and radiation sources used in this type technology are typically disposed at great distances from the coatings such that incomplete curing is reduced but not eliminated. Since radiation sources typically emit large amounts of heat, it is difficult to bring the radiation sources within the gaseous atmospheres and shorten the distances between the radiation sources and the coatings. The heat from the radiation sources causes strong vortexing in the gaseous atmospheres and contaminates the atmospheres with oxygen, thus negating the benefits of using this technology.
  • the present invention includes a system for curing a composition comprising an organoborane complex and a radical polymerizable compound on a substrate.
  • the system comprises at least one vessel storing the composition comprising the organoborane complex and the radical polymerizable compound and at least one applicator coupled to the vessel for applying the organoborane complex and radical polymerizable compound to the substrate.
  • the system also includes a booth having an inlet, an outlet, and a gas sink disposed below the inlet and the outlet.
  • a conveyor extends through the gas sink for moving the substrate through the gas sink.
  • a gas source is in communication with the gas sink for introducing to the gas sink a displacing gas heavier than oxygen to displace oxygen from the gas sink.
  • a controller is in communication with the gas source for controlling the introduction of the displacing gas to the gas sink to control oxygen surface inhibition as the displacing gas decomplexes the organoborane complex for polymerization of the radical polymerizable compound as the conveyor moves the substrate through the gas sink.
  • the invention also includes a method of curing a composition comprising an organoborane complex and a radical polymerizable compound on a substrate in a gas sink.
  • the method comprises applying the organoborane complex and the radical polymerizable compound to the substrate.
  • the method further includes lowering the substrate into the gas sink from the inlet.
  • the method also comprises introducing a displacing gas selected from the group of carbon dioxide, sulfur dioxide, sulfuric anhydride, and combinations thereof to the gas sink in a greater concentration than in ambient air to displace oxygen from the gas sink to control oxygen surface inhibition as the displacing gas decomplexes the organoborane complex for polymerization of the radical polymerizable compound.
  • the method also includes raising the substrate from the gas sink to the outlet to remove the substrate from the gas sink.
  • the displacing gas being heavier than oxygen, the displacing gas settles in the gas sink.
  • the substrate is simply lowered into the gas sink from the inlet to decomplex the organoborane complex for polymerization of the radical polymerizable compound.
  • the controller controls the introduction of the displacing gas to control the concentration of oxygen in the gas sink to advantageously control oxygen surface inhibition, which can disadvantageously cause incomplete curing of the composition.
  • Decomplexing of the organoborane complex in the gas sink allows for the polymerization of the radical polymerizable compound at room temperature without the need for UV light, curing ovens, etc. This greatly reduces production costs, complexities, and times, decreases a number of synthetic steps required, and increases product yields and concentrations. In addition, this reduces a carbon footprint of the instant invention and saves energy.
  • the organoborane complex also allows the composition to rapidly cure at reduced temperatures and to bond to various substrates, including low energy substrates. This increases production efficiency and speed and further reduces production costs and energy expenditure associated with heating and/or using radiation for curing.
  • Figure 1 is a schematic view of a system for curing a composition wherein the system includes a booth having a gas sink and a gas source in communication with the gas sink;
  • Figure 2 is a schematic view of another embodiment of the system including an applicator for the composition disposed in the gas sink;
  • Figure 3 is a schematic view of another embodiment of the system including doors at the inlet and the outlet of the booth;
  • Figure 4 is a schematic view of another embodiment of the system including a coating composition vessel and applicator.
  • a system for curing a composition 26 on a substrate 22.
  • the composition 26 comprises an organoborane complex and a radical polymerizable compound.
  • the composition 26 is cured in a gas sink 24 that holds a displacing gas 28 and has a concentration of oxygen at a prescribed level.
  • the displacing gas 28 initiates the curing of the composition 26.
  • the displacing gas 28 decomplexes the organoborane complex for polymerization of the radical polymerizable compound.
  • the displacing gas 28 is heavier than oxygen to displace oxygen from the gas sink 24 to achieve the prescribed level of concentration of oxygen in the gas sink 24.
  • the concentration of oxygen is maintained at the prescribed level to limit or prevent oxygen surface inhibition, which disadvantageously causes incomplete curing of the composition 26 on the substrate 22.
  • the organoborane complex is typically an organoborane-amine complex. The organoborane complex, the radical polymerizable compound, and the curing of the composition 26 are described further below.
  • the substrate 22 may be further defined as an automobile component such as a door, hood, roof, panel, etc., and the like.
  • the automobile component can also be an entire automotive body.
  • the substrate 22 is a sheet of organic or inorganic material such as carbon fiber, steel, aluminum, and the like.
  • the substrate 22 may be coated or uncoated, treated or untreated, and combinations of these.
  • the substrate 22 is selected from the group of plastic, metals such as steel, iron, and aluminum, and combinations thereof.
  • the substrate 22 may include steel and/or extruded automobile parts.
  • the substrate 22 is further defined as an automobile component.
  • the substrate 22 includes automotive exterior components, such as automotive body panels, bumpers, fenders, etc.
  • the automotive exterior components may be primed or electrocoated prior to curing the composition 26 thereon.
  • the automotive exterior components may be uncoated prior to curing the composition 26 thereon, in which case the composition 26 may be cured to form an electrocoat layer, or the automotive exterior components may be coated with an electrocoat layer, in which case the composition 26 may be cured to form a primer layer.
  • the instant invention is not limited to the composition 26 being used to form any particular type of layer on the substrate 22. [0019]
  • the composition 26 may be used in any industry.
  • the composition 26 may be used in a variety of applications including, but not limited to, original equipment manufacturing (OEM) "finish” coatings, aftermarket “refinish” coatings, automotive coatings, protective coatings, films, encapsulants, gels, sealants, release coatings, conformal coatings, and combinations thereof. Most typically, the composition 26 is used as an automotive OEM finish coating or as an automotive refinish coating as a primer, basecoat, clearcoat, and/or sealant.
  • OEM original equipment manufacturing
  • the system 20 includes a booth 30 and a conveyor 32 extending through the booth 30.
  • the booth 30 can, for example, be located in a manufacturing plant and can, for example, be further defined as a continuous automotive production line.
  • the automotive production line can be "continuous" in that multiple substrates 22, e.g., exterior automotive components, are arranged sequentially along the conveyor 32 such that the substrates 22 are simultaneously moved to different locations, respectively, in a continuous manner.
  • the booth 30 can be coupled to or directly connected to existing booths capable of performing preparation, application of paint, finishing, assembling, etc.
  • the conveyor 32 can be coupled to or directly connected to existing conveyors in the existing booths.
  • the system 20 can be standalone without departing from the nature of the present invention. While the conveyor 32 is shown in Figures 1-4 as being of the type typically referred to as a chain conveyor 32, it should be appreciated that the conveyor 32 can be of any type without departing from the nature of the present invention.
  • the booth 30 has an inlet 34, an outlet 36, and a gas sink 24 between the inlet 34 and the outlet 36.
  • the inlet 34 is disposed upstream of the gas sink 24 along the conveyor 32 and presents an area for ingress of the substrate 22 to the gas sink 24.
  • the outlet 36 is disposed downstream of the gas sink 24 along the conveyor 32 and presents an area for egress of the substrate 22 from the gas sink 24.
  • the gas sink 24 is typically defined by one or more walls 38 that have a gastight construction. It should be appreciated that the gas sink 24 can be of any shape without departing from the nature of the present invention such as, for example, trapezoidal as shown in Figures 1-4, spherical, cylindrical, etc. As shown in Figures 1-4, one of the walls 38 of the gas sink 24 defines a bottom 40 of the gas sink 24. In any event, the bottom 40 of the gas sink 24 is defined by the lowest vertical portion of the gas sink 24. It should be appreciated that the term "vertical" is used throughout with reference to the earth's gravity. It should also be appreciated that Figures 1-4 are schematic and that walls 38 of the gas sink 24 extend upwardly from the bottom 40 to surround the gas sink 24 vertically.
  • the gas sink 24 is disposed below the inlet 34 and the outlet 36.
  • the walls 38 of the gas sink 24 descend vertically from the inlet 34 to the bottom 40 of the gas sink 24.
  • the walls 38 of the gas sink 24 ascend vertically from the bottom 40 of the gas sink 24 to the outlet 36.
  • the conveyor 32 extends through the gas sink 24 for moving the substrate 22 through the gas sink 24.
  • the conveyor 32 typically extends through the inlet 34 and the outlet 36 to introduce the substrate 22 to the booth 30 through the inlet 34 and to remove the substrate 22 from the booth 30 through the outlet 36.
  • the inlet 34 and the outlet 36 can be any type of structure such that the inlet 34 is disposed above the gas sink 24 for ingress to the gas sink 24 and the outlet 36 is disposed above the gas sink 24 for egress from the gas sink 24.
  • the inlet 34 and the outlet 36 include platforms 42 disposed above the gas sink 24 for supporting the conveyor 32, which extends into and out of the gas sink 24.
  • the booth 30 can include an enclosure 44 covering the gas sink 24 and defining the inlet 34 and the outlet 36.
  • the enclosure 44 typically has a gastight construction to limit and/or prevent the seepage of gas through any seam, e.g., so that the levels of gases in the gas sink 24 can be effectively controlled.
  • the enclosure 44 is typically formed of metal but could be formed of any material capable of creating a gastight construction. It should be appreciated that the booth 30 can be open, i.e., without the enclosure 44, without departing from the nature of the present invention.
  • the inlet 34 and the outlet 36 can be open such that the gas sink 24 is in communication with ambient air through the inlet 34 and the outlet 36 of the booth 30.
  • ambient air is used herein to describe the air at the exterior of the inlet 34 and the outlet 36.
  • the ambient air can be naturally occurring air.
  • the atmosphere surrounding the booth 30 can be controlled such that the ambient air includes varying percentages or additional gases not found in naturally occurring air.
  • the booth 30 can include doors 46 at the inlet 34 and the outlet 36 as shown in Figure 3.
  • the doors 46 open to allow ingress and egress of the substrate 22 and close to seal the booth 30 at the inlet 34 and the outlet 36.
  • the doors 46 can close to create a gastight seal at the inlet 34 and the outlet 36 or alternatively can close to limit the ingress and egress of gases at the inlet 34 and the outlet 36 without creating a gastight seal.
  • the booth 30 can include curtains (not shown) at the inlet 34 and/or outlet 36 that are structured so as to allow the substrate 22 to pass therethrough while limiting the passage of gases therethrough.
  • the booth 30 can include a vent 78.
  • the system 20 includes a gas source 48 in communication with the gas sink 24 for introducing the displacing gas 28 to the gas sink 24.
  • the gas source 48 is a tank that is capable of forcing the displacing gas 28 therefrom such as, for example, a pressurized tank.
  • the gas source 48 is typically in communication with the gas sink 24 with tubing that extends from the gas source 48 to the gas sink 24 to deliver the displacing gas 28 from the gas source 48 to the gas sink 24.
  • the introduction of the displacing gas 28 from the gas source 48 to the gas sink 24 can be manually controlled, a constant flow, selectively controlled with a controller 50 as described further below, or a combination thereof.
  • the system 20 can include a valve 52 in communication with the gas source 48 and the gas sink 24.
  • the valve 52 is can be selectively adjusted to increase or decrease the introduction of the displacing gas 28 from the gas source 48 to the gas sink 24.
  • the controller 50 can be in communication with the valve 52 to selectively adjust the valve 52.
  • the displacing gas 28 is heavier than oxygen. As such, the displacing gas 28 is introduced to the gas sink 24 to force oxygen from the gas sink 24. In addition, as set forth above and described further below, the displacing gas 28 decomplexes the organoborane complex. In one embodiment, the displacing gas 28 is a single type of gas. In this embodiment, the displacing gas is a curing (or a reactive) gas, and may be selected from the group of carbon dioxide, sulfur dioxide, sulfuric anhydride, and combinations thereof.
  • the displacing gas 28 comprises more than one gas where the curing (or reactive) gas is present but there is also a non-reactive (i.e., inert) case that can be present with the curing/reactive gas, with the non-reactive/inert gas is also heavier than oxygen.
  • a non-reactive (i.e., inert) gas is argon.
  • non-reactive/inert gases that are lighter than oxygen such as nitrogen
  • the non-reactive/inert gases that are lighter than oxygen may escape from the gas sink 24 and, therefore, such gases may be circulated into the gas sink 24.
  • the displacing gas 28 is retained in the gas sink 24 because the displacing gas 28 is heavier than air. As such, as the displacing gas 28 is introduced to the gas sink 24, the displacing gas 28 displaces the air and sinks toward the bottom 40 of the gas sink 24. It should be appreciated that devices (not shown) such as fans can be disposed in the gas sink 24 to circulate the displacing gas 28 in the gas sink 24 to uniformly distribute the displacing gas 28 in the gas sink 24.
  • the displacing gas 28 may escape the gas sink 24 as a result of drafts, movement of the substrate 22 through the gas sink 24, etc.
  • the introduction of the displacing gas 28 to the gas sink 24 can be controlled.
  • the introduction of the displacing gas 28 to the gas sink 24 can be controlled to maintain the concentration of oxygen in the gas sink 24 at the prescribed level to control or prevent oxygen surface inhibition as the displacing gas 28 decomplexes the organoborane complex for polymerization of the radical polymerizable compound as the conveyor 32 moves the substrate 22 through the gas sink 24.
  • the prescribed level for concentration of oxygen in the gas sink 24 is preferably from 0.1% to 5.0%, and more preferably from 0.2% to 2.0%, most preferably from 0.2% to 0.8% by weight based on the total weight of all gases in the gas sink 24. It should be appreciated that the prescribed level can be a fixed value, a range of values, or a value or range of values that change based on other conditions.
  • the carbon dioxide used in this invention is typically gaseous but may be a supercritical fluid.
  • the carbon dioxide may originate from dry ice, from the supercritical fluid, or may be extracted from flue gas produced in coal fired power plants.
  • a low pressure gas ( ⁇ 1 bar) produced from combustion of coal may serve as a source of the carbon dioxide.
  • the carbon dioxide is provided from gas tanks that include regulators, as a by-product of an ancillary chemical reaction, as a by-product of a biological process, as a byproduct of a manufacturing operation, from a carbon dioxide generator, as a by-product from combustion of natural gas, as a by-product from gasification of coal, as a by-product of various carbon-containing fuel sources, from flue gas streams, such as abatable flue gas streams, or from combinations thereof.
  • the carbon dioxide used in the instant invention is non-toxic and is not classified as a hazardous air pollutant, thus making this method environmentally friendly and allowing this method to be utilized in large production facilities with minimal emissions and pollution.
  • the carbon dioxide is inexpensive and is readily available from recycling efforts designed to reduce greenhouse gases and environmental pollution.
  • use of the carbon dioxide minimizes oxygen surface inhibition of curing thereby increasing the efficiency of this method.
  • use of the carbon dioxide increases control of curing rate and allows for use of one-component (IK) systems that reduce cure times.
  • the carbon dioxide used in this method can be reclaimed from this method through a thermally reversible reaction, thereby further reducing emissions and pollution.
  • the controller 50 can be used to selectively control the introduction of the displacing gas 28 from the gas source 48 to the gas sink 24.
  • the controller 50 can be in communication with the gas source 48 for controlling the introduction of the displacing gas 28 to the gas sink 24.
  • the controller 50 can be used to maintain the concentration of oxygen in the gas sink 24 at the prescribed level.
  • the controller 50 is typically computerized and includes a memory and a central processing unit.
  • the controller 50 can be programmed to selectively control the introduction of the displacing gas 28. It should be appreciated that the controller 50 can by of any type without departing from the nature of the present invention.
  • the system 20 can include an oxygen sensor 54 disposed in the gas sink
  • oxygen sensor 54 can be of any type without departing from the nature of the present inventions
  • the controller 50 is operatively connected to the oxygen sensor 54 and the gas source 48 for controlling the introduction of the displacing gas 28 based on the measurement of the concentration of oxygen in the gas sink 24.
  • the controller 50 communicates with the oxygen sensor 54 and the valve 52 to control the introduction of displacing gas 28 to the gas sink 24 as described herein.
  • the valve 52 is controlled by the controller 50 for introducing the displacing gas 28 to the gas sink 24.
  • the controller 50 receives oxygen concentration measurements from the oxygen sensor 54.
  • the controller 50 determines that the concentration of oxygen in the gas sink 24 is above the prescribed level
  • the controller 50 directs the valve 52 to open to introduce additional displacing gas 28 to the gas sink 24 to displace oxygen.
  • the controller 50 determines that the concentration of oxygen in the gas sink 24 is at or below the prescribed level based on measurements from the oxygen sensor 54, the controller 50 directs the valve 52 to close.
  • the system 20 can include an oxygen source 56 to increase the concentration of oxygen in the gas sink 24 when it is determined that an increased concentration of oxygen is advantageous.
  • the concentration of oxygen in the gas sink 24 affects the curing of the composition 26.
  • an increased concentration of oxygen could be advantageous in a number of scenarios including changing conditions that affect the curing of the composition 26, inadvertent addition of too much displacing gas 28, etc.
  • the oxygen source 56 is in communication with the gas sink 24 for introducing oxygen to the gas sink 24.
  • the oxygen source 56 is a tank that is capable of forcing the oxygen therefrom such as, for example, a pressurized tank.
  • the oxygen source 56 is typically in communication with the gas sink 24 with tubing that extends from the oxygen source 56 to the gas sink 24 to deliver oxygen from the oxygen source 56 to the gas sink 24.
  • the controller 50 can be in communication with the oxygen source 56 to control the introduction of oxygen to the gas sink 24.
  • the system 20 can include an oxygen source valve 80 to in communication with the controller 50.
  • the controller 50 can direct the oxygen source valve 80 to open to introduce oxygen to the gas sink 24 when the controller 50 determines that the concentration of oxygen is below the prescribed level, for example, based on measurements from the oxygen sensor 54.
  • the controller 50 can direct the oxygen source valve 80 to close when the controller 50 determines that the concentration of oxygen is at the prescribed level.
  • the system 20 can also include a carbon dioxide sensor 58 disposed in the gas sink 24 and in communication with the controller 50.
  • the carbon dioxide sensor 58 measures the concentration of carbon dioxide in the gas sink 24.
  • the controller 50 can increase or decrease the introduction of displacing gas 28 to the gas sink 24 based at least partly on the concentration of carbon dioxide in the gas sink 24.
  • the system 20 can also include a humidity sensor 60 disposed in the gas sink 24 and in communication with the controller 50.
  • the humidity sensor 60 measures the humidity in the gas sink 24.
  • the humidity in the gas sink 24 can, for example, affect the curing of the composition 26 and the humidity, oxygen concentration, and/or displacing gas concentration in the gas sink 24 can be independently changed to compensate accordingly.
  • the system 20 includes at least one vessel 62 storing the organoborane complex and the radical polymerizable compound.
  • the vessel 62 is a single source with the organoborane complex and the radical polymerizable compound stored together therein.
  • the vessel 62 could be further defined as two or more vessels such that the organoborane complex and the radical polymerizable compound are stored separate from each other. As described below, the organoborane complex and the radical polymerizable compound are applied from the vessel 62 to the substrate 22.
  • composition 26 can be that described in United States Patent
  • the composition 26 may be water-borne or solvent-borne and may be used as a one component (IK) or two component (2K) system. . Typically, the composition is solvent-borne and is a IK system.
  • the composition 26 is typically applied to a substrate 22 and cured to form a film. In one embodiment, the composition 26 is a 2K system and includes two components that are reactive with each other, e.g.
  • one component may include the radical polymerizable compound as set forth above and another component may include a cross-linking agent or other compound without which curing the 2K system could not be adequately achieved.
  • the 2K system includes a cross-linking agent in one component and the radical polymerizable compound in the other component.
  • the composition 26 is a IK system and includes the radical polymerizable compound.
  • the composition 26 that is a IK system includes the radical polymerizable compound, with adequate curing achieve in the absence of mixing with a second component as is required in 2K systems.
  • the coating composition that is a is a
  • IK system may include more than one radical polymerizable compound, and may include a cross-linking agent and/or catalyst.
  • the IK and/or 2K systems may include hindered amine light stabilizers (HALS), UVA packages, flow additives, wetting agents, pigments, cross-linkers, catalysts, and the like.
  • HALS hindered amine light stabilizers
  • UVA packages may include hindered amine light stabilizers (HALS), UVA packages, flow additives, wetting agents, pigments, cross-linkers, catalysts, and the like.
  • the radical polymerizable compound is present in the composition 26.
  • the radical polymerizable compound may also include one or more alkynyl groups, i.e., C ⁇ C groups
  • the radical polymerizable compound may be selected from the group of monomers, dimers, oligomers, pre -polymers, polymers, co-polymers, block polymers, star polymers, graft polymers, random co-polymers, and combinations thereof, so long as the radical polymerizable compound is still able to be radically polymerized.
  • the radical polymerizable compound is a monomer.
  • the radical polymerizable compound is partially polymerized and is an oligomer or a polymer, but still retains an ability to be further polymerized.
  • the radical polymerizable compound is selected from the group of mono- and poly- unsaturated glycerols or phospholipids, phosphor diesters, peptides, nucleosides, nucleotides, and combinations thereof, having at least one radically polymerizable functional group.
  • the radical polymerizable compound is selected from the group of acrylates, carbamates, epoxides, and combinations thereof.
  • Suitable non-limiting examples of carbamates and epoxides are those having at least one radically polymerizable functional group and typically one or more functional groups selected from the group of esters, ethers, ketones, aldehydes, carboxylic acids, amides and ureas, acrylics, sulfur groups, phosphorous groups, and combinations thereof.
  • the carbamates may include aliphatic, cycloaliphatic, and aromatic groups and may have linear or branched structures with various functionalities including, but not limited to, branched hydrocarbon functionality, hydroxyl functionality, carboxylate functionality, carbamate functionality, and/or ester functionality.
  • the radical polymerizable compound is selected from the group of ⁇ , ⁇ - unsaturated aliphatic compounds, vinyl esters, substituted styrenes, esters of methacrylic acid, esters of acrylic acid, and combinations thereof.
  • suitable ⁇ , ⁇ -unsaturated aliphatic compounds include, but are not limited to, 1-octene, 1-hexene, 1-decene, and combinations thereof.
  • suitable vinyl esters and styrenes include vinyl acetate, styrene, ⁇ -methylstyrene, p-methylstyrene, and combinations thereof.
  • the radical polymerizable compound is selected from the group of acrylates, halogen substituted acrylates, alkenoates, carbonates, phthalates, acetates, itaconates, and combinations thereof.
  • Suitable examples of acrylates include, but are not limited to, butyl acrylate, t-butyl acrylate, isobornyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, octyl acrylate, isocyanate containing acrylates such as isocyanatoacrylate, and combinations thereof.
  • the radical polymerizable compound is selected from the group of diacrylates, triacrylates, polyacrylates, urethane acrylates, unsaturated polyesters, and combinations thereof.
  • di-, tri-, and poly- acrylates include, but are not limited to, hexanediol diacrylate, tripropyleneglycol diacrylate, trimethylolpropane triacrylate, alkoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and combinations thereof.
  • Suitable non-limiting examples of urethane acrylates include Ebercryl
  • the radical polymerizable compound is further defined as a mixture of an OH-acrylic resin and a dipentaerythritol penta/hexa acrylate.
  • the radical polymerizable compound is selected from the group of unsaturated acrylic and methacrylic ester resins, functional acrylic and methacrylic ester monomers, and combinations thereof.
  • the radical polymerizable compound is selected from the group of butyleneglycol diacrylate, butylene glycol dimethylacrylate, 2- ethylhexylacrylate, 2-ethylhexylmethacrylate, 2 -hydroxy ethylacrylate, 2 -hydroxy ethyl methacrylate, methylacrylate, methylmethacrylate, neopentylglycol diacrylate, neopentylglycoldimethacrylate, glycidyl acrylate, glycidyl methacrylate, allyl acrylate, allyl methacrylate, stearyl acrylate, stearyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone acrylate, perfiuorobutyl acrylate, perfluorobutyl methacrylate, IH
  • Suitable acrylates include acrylamides and methacrylamides such as N-isopropyl acrylamide and N,N-dimethylacrylamide.
  • the radical polymerizable compound is selected from the group of alkylene glycol dialkylacrylate, alkylene glycol diacrylate, and combinations thereof. Most typically, the radical polymerizable compound is an acrylate or methacrylate.
  • the radical polymerizable compound may include compounds including acryloxyalkyl groups such as an acryloxypropyl group, methacryloxyalkyl groups such as a methacryloxypropyl group, and/or unsaturated organic groups including, but not limited to, alkenyl groups having 2-12 carbon atoms including vinyl, allyl, butenyl, and hexenyl groups, alkynyl groups having 2-12 carbon atoms including ethynyl, propynyl, and butynyl groups, and combinations thereof.
  • acryloxyalkyl groups such as an acryloxypropyl group
  • methacryloxyalkyl groups such as a methacryloxypropyl group
  • unsaturated organic groups including, but not limited to, alkenyl groups having 2-12 carbon atoms including vinyl, allyl, butenyl, and hexenyl groups, alkynyl groups having 2-12 carbon atoms including ethynyl, propynyl,
  • the unsaturated organic groups may include radical polymerizable groups in oligomeric and/or polymeric polyethers including an allyloxypoly(oxyalkylene) group, halogen substituted analogs thereof, and combinations thereof.
  • the radical polymerizable compound includes a compound formed by copolymerizing organic compounds having polymeric backbones with the radical polymerizable compound such that there is an average of at least one free radical polymerizable group per copolymer.
  • Suitable organic compounds include, but are not limited to, hydrocarbon based polymers such as polyisobutylene, polybutadienes, polyisoprenes, polyolefins such as polyethylene, polypropylene and polyethylene polypropylene copolymers, polystyrenes, styrene butadiene, and acrylonitrile butadiene styrene, polyacrylates, polyethers such as polyethylene oxide and polypropyleneoxide, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides, polycarbonates, polyimides, polyureas, polymethacrylates, partially fluorinated or perfluorinated polymers such as polytetrafluoroethylene, fluorinated rubbers, terminally unsaturated hydrocarbons, olefins, polyolefins, and combinations thereof.
  • hydrocarbon based polymers such as polyisobutylene, polybutadienes, polyisoprenes, poly
  • the composition 26 may also include the second, a third, or more than three radical polymerizable compounds.
  • the second, third, and any additional radical polymerizable compounds may be the same or different from the radical polymerizable compound described above.
  • the radical polymerizable compound is typically present in the composition 26 in an amount of from 20 to 99, alternatively in an amount of from 50 to 99, alternatively in an amount of from 60 to 99, alternatively in an amount of from 80 to 99, percent by weight based on the total weight of the composition 26.
  • the radical polymerizable compound is present in an amount of from 50 to 80 parts by weight per 100 parts by weight of the composition 26.
  • 20 parts by weight of the composition 26 typically includes a solvent.
  • the organoborane initiator typically includes tri-functional boranes which have the general structure:
  • each of R 1 - R 3 independently has 1 to 20 carbon atoms and wherein each of R 1 - R independently include one of a hydrogen atom, a cycloalkyl group, a linear or branched alkyl group having from 1 to 12 carbon atoms in a backbone, an aliphatic group, and aromatic group, an alkylaryl group, an alkylene group capable of functioning as a covalent bridge to the boron, and halogen substituted homologues thereof, such that at least one of R , R , and R includes one or more carbon atoms, and is covalently bonded to boron.
  • the organoborane complex is the organoborane-amine complex
  • any amine known in the art may be used to form the organoborane-amine complex and serve as a "bound" amine.
  • the amine used to form the organoborane-amine complex may be a primary, secondary, or tertiary amine.
  • the amine includes at least one of an alkyl group, an alkoxy group, an amidine group, an ureido group, and combinations thereof.
  • Particularly suitable amines include, but are not limited to, 1,3 propane diamine, 1,6- hexanediamine, methoxypropylamine, pyridine, isophorone diamine, amine functional compounds including at least one amine functional group such as 3-aminopropyl, 6- aminohexyl, 11 -aminoundecyl, 3-(N-allylamino)propyl, N-(2-aminoethyl)-3-aminopropyl, aminomethyl, N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethylpyridine, and combinations thereof.
  • 1,3 propane diamine 1,6- hexanediamine
  • methoxypropylamine pyridine
  • isophorone diamine amine functional compounds including at least one amine functional group such as 3-aminopropyl, 6- aminohexyl, 11 -aminoundecyl, 3-(N-allyla
  • the amine is selected from the group of propylamine, hexylamine, benzylamine, heptylamine, methoxypropylamine, 2-methyl amino ethanol, cysteamine, and combinations thereof.
  • the amine is a diamine. In another embodiment, the amine is a monoamine.
  • the instant invention can utilize any organoborane-amine complex known in the art and is not limited to those embodiments described above or set forth below.
  • the organoborane- amine complex is formed from dialkylboranes, trialkylboranes, and the like.
  • the organoborane initiator may be complexed with the amine and simultaneously bonded to another atom and/or blocking group. These other atoms and/or blocking groups may be any known in the art including carbon compounds, halogenated compounds, transition metal compounds, and the like.
  • the organoborane-amine complex is capable of initiating polymerization or cross-linking of the radical polymerizable compound after dissociation of the organoborane initiator from the amine.
  • the organoborane-amine complex typically has the formula:
  • each of R 4 -R 6 may be any such that the amine is any described above and is a primary, secondary, or tertiary amine.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is independently selected from the group of a hydrogen atom, an alkyl group, an alkoxy group, an arylalkyl group, an alkylene group, halogenated homologs thereof, and combinations thereof.
  • each of R 4 -R 6 may independently be nitrogen and/or sulfur functional.
  • R 4 , R 5 , and/or R 6 are diamine functional.
  • Suitable non-limiting examples of the organoborane-amine complex include N,N-diethyl aniline borane (DEANB) as a neat liquid, pyridine borane (PYB) as a neat liquid, a 50 wt% solution pyridine borane (PYB) in pyridine, tert-butylamine borane (TBAB) as a powder, triethylamine borane (TEAB) as a neat liquid, triethylborane-l ,3-diaminopropane complex (TEB-DAP) as a neat liquid, trimethylamine borane (TMAB) as a powder, and combinations thereof.
  • DEANB N,N-diethyl aniline borane
  • PYB pyridine borane
  • TBAB tert-butylamine borane
  • TEAB triethylamine borane
  • TAB-DAP triethylborane-l ,3
  • the organoborane-amine complex is selected from the group of tri-n-butylborane diaminopropane (TnBB-DAP), tri-sec-butylborane methoxypropylamine (TsBB-MOPA), tri-n-butylborane methoxypropylamine (TnBB-MOPA), triethylborane cysteamine (TEB-CA or TEB-cysteamine), tri-n-butylborane cysteamine (TnBB- CA), triethylborane diaminopropane (TEB-DAP), tri-sec-butylborane diaminopropane (TsBB- DAP), and combinations thereof.
  • the organoborane-amine complex has the following formula: R3BH2NCH2CH2CH2NH2BR3, wherein each R may independently have
  • 1 to 20 carbon atoms may independently be a hydrogen atom, a cycloalkyl group, a linear or branched alkyl group having from 1 to 12 carbon atoms in a backbone, an aliphatic group, and aromatic group, an alkylaryl group, an alkylene group capable of functioning as a covalent bridge to the boron, and halogen substituted homologues thereof.
  • organoborane-amine complexes set forth above can be used to act in concerted fashion with other organoborane-amine complexes that act through different decomplexing mechanisms than are described herein.
  • the organoborane-amine complex may be used in any amount to form the composition 26.
  • the organoborane-amine complex is used in an amount equivalent to of from 0.01 to 95, more typically of from 0.1 to 80, even more typically of from 0.1 to 30, still more typically of from 1 to 20, even more typically of from 1 to 15, and most typically of from
  • the amounts of the organoborane-amine complex depend upon a molecular weight and functionality of the organoborane-amine complex and the presence of other components in the composition 26 such as fillers.
  • the composition 26 may also include an optional amine.
  • This optional amine is different from the amine of the organoborane-amine complex in that the optional amine is not part of the organoborane-amine complex.
  • the optional amine may be chemically identical to the amine that is part of the organoborane-amine complex.
  • the optional amine may be different from the amine that is part of the organoborane-amine complex.
  • the optional amine is added to promote the reaction that forms the carbamic zwitterion. In other words, the optional amine may react with carbon dioxide to form the zwitterion, as described in greater detail below.
  • the optional amine is not included in the composition 26 if the amine of the organoborane-amine complex is di-, tri-, or poly- amine functional. However, even if the amine of the organoborane-amine complex is di-, tri-, or poly- amine functional, the optional amine may still be included.
  • the optional amine is typically a primary amine but may be a secondary amine or a combination of primary and/or secondary amines. In one embodiment, the optional amine is ammonia.
  • the optional amine is selected from the group of ammonia, methylamine, ethanolamine or 2-aminoethanol, propylamine, 2 -propylamine, trisamine, dimethylamine, methylethanolamine or 2-(methylamino)ethanol, hexylamine, heptylamine, benzylamine, methoxypropylamine, cysteamine, aziridine, azetidine, pyrrolidone, piperidine, trimethylamine, dimethylethanolamine (DMEA) or 2-(dimethylamino)ethanol, and combinations thereof.
  • DMEA dimethylethanolamine
  • 2-(dimethylamino)ethanol 2-(dimethylamino)ethanol
  • the optional amine is included in the composition 26 in an amount sufficient to provide sufficient "free amine groups" in the composition such that a molar ratio of at least 1 :1 of free amine to organoborane -bound amine groups is achieved. "Free amine groups" are described in further detail below.
  • the optional amine is included in the composition 26 in an amount of from 5 to 30 weight percent of the organoborane-amine complex to achieve the desired molar ratio.
  • the optional amine is include in various stoichiometric ratios to the carbon dioxide, e.g. 1:2, 1 :3, 1 :4, 1 :5, etc. Typically, a stoichiometric excess of carbon dioxide is preferred.
  • a sub-stoichiometric ratio of optional and/or free amine to the organoborane-amine complex can be utilized.
  • the composition including sub-stoichiometric ratios of optional and/or free amine to the organoborane-amine complex e.g. using RNH 2 )BRs
  • the sub-stoichiometric ratio of optional and/or free amine to the organoborane-amine complex is from 0.5: 1 to 1:1.
  • the sub-stoichiometric ratio of optional and/or free amine to the organoborane- amine complex is from 0.6-0.85:1. In still another embodiment, the sub-stoichiometric ratio of optional and/or free amine to the organoborane-amine complex is from 0.7 to 0.8: 1. Also, it is to be understood that the organoborane-amine complex and optional and/or free amines of these embodiments are not particularly limited and may be any suitable in the art.
  • the composition 26 may also include one or more additives.
  • the one or more additives may be selected from the group consisting of leveling agents, solvents, surfactants, fillers, stabilizers, solvents, plasticizers, defoaming agents, wetting additives, catalysts, rheology controlling agents, pigments, photosynergists, adhesion promoters, pigment dispersants, flow aids, acid functional polymers, additive polymers, catalysts, and combinations thereof.
  • suitable surfactants include Surfynol® Surfactants commercially available from Air Products and
  • plasticizers include Coroc® Acrylic Plasticizer Resins commercially available from Cook Composites and Polymers of St. Louis, MO.
  • free amine groups refers to any amine group that is both (1) available for further reaction and (2) not coordinately bonded (e.g., through a dative or coordinate covalent bond) to the organoborane initiator.
  • the free amine group may be a primary and/or secondary amine, or may be ammonia, as described above. Typically, the free amine group is a primary amine.
  • the free amine groups are found in the organoborane-amine complex when the amine of the complex is di-, tri- tetra-, or poly- functional.
  • the amine of the organoborane-amine complex may include a first amine group that is coordinately bonded to the organoborane initiator and also include one or more additional amine groups that are not coordinately bonded. These additional amine groups can serve as the free amine groups described above.
  • the optional amine may be the source of the free amine groups.
  • both the amine of the organoborane-amine complex and the optional amine may be the source of the free amine groups.
  • the system 20 includes at least one applicator 64 coupled to the vessel 62 for applying the organoborane complex and radical polymerizable compound to the substrate 22.
  • tubing connects the vessel 62 to the at least one applicator 64 to deliver the organoborane complex and the radical polymerizable compound to the applicator 64.
  • the at least one applicator 64 is typically further defined as at least one organoborane complex applicator and at least one radical polymerizable compound applicator 68.
  • both the organoborane complex and the radical polymerizable compound could be applied to the substrate 22 together through a single applicator.
  • the at least one applicator 64 can be disposed upstream of the gas sink 24 along the conveyor 32, as shown in Figure 1, to apply the organoborane complex and the radical polymerizable compound to the substrate 22 prior to the introduction of the substrate 22 to the gas sink 24.
  • the at least one applicator 64 can be disposed in the gas sink 24, as shown in Figures 2 and 4, to apply the organoborane complex and the radical polymerizable compound to the substrate 22 while the substrate 22 is in the gas sink 24.
  • the application of the composition 26 to the substrate 22 includes any application method known in the art. Suitable application methods include, but are not limited to, spray coating, dip coating, roll coating, curtain coating, electrostatic spraying, and combinations thereof.
  • the organoborane complex and the radical polymerizable compound are applied to the substrate 22 via electrostatic spraying for extrusion coating.
  • the system 20 typically includes a coating composition vessel 70 storing a coating composition 72 and a second applicator 74 coupled to the coating composition vessel 70 for applying the coating composition 72 on the substrate 22 in addition to the composition 26 comprising the organoborane complex and the radial polymerizable component.
  • the coating composition 72 can be, for example, electrocoating, primer, base coat, clear coat, etc.
  • the second applicator 74 can be disposed before the gas sink 24 along the conveyor 32 to apply the coating composition 72 before the substrate 22 is introduced to gas sink 24, in the gas sink 24 to apply the coating composition 72 when the substrate 22 is in the gas sink 24, or after the gas sink 24 along the conveyor 32 to apply the coating composition 72 after the substrate 22 is removed from the gas sink 24.
  • Oxygen in the coating composition 72 can affect the curing of the composition 26.
  • the system 20 can include a second oxygen sensor 76 disposed in the coating composition vessel 70 for measuring the concentration of oxygen in the coating composition 72.
  • the controller 50 can be in communication with the second oxygen sensor 76. The controller 50 can control the introduction of the displacing gas 28 to the gas sink 24 based on the measurement of the concentration of oxygen in the gas sink 24 and the measurement of the concentration of oxygen in the coating composition 72.
  • the present invention also includes a method of curing the composition 26 comprising the organoborane complex and the radical polymerizable compound on the substrate 22 in the gas sink 24.
  • the method includes applying the organoborane complex and the radical polymerizable compound to the substrate 22.
  • the application of the organoborane complex and the radical polymerizable compound can be accomplished with the at least one applicator 64 upstream of the gas sink 24 along the conveyor 32 or in the gas sink 24.
  • the method further includes introducing the substrate 22 to the gas sink 24 before or after the application of the organoborane complex and the radical polymerizable compound to the substrate 22. Specifically, the method includes lowering the substrate 22 into the gas sink 24 from the inlet 34 and raising the substrate 22 from the gas sink 24 through the outlet 36. The method includes moving the conveyor 32 holding the substrate 22 through the gas sink 24. [0071] The method also includes introducing the displacing gas 28 to the gas sink
  • the displacing gas 28 is introduced to the gas sink 24 to control oxygen surface inhibition as the displacing gas 28 decomplexes the organoborane complex for polymerization of the radical polymerizable compound.
  • the method further includes measuring the concentration of oxygen in the gas sink 24.
  • the concentration of oxygen in the gas sink 24 is typically measured with the oxygen sensor 54, which is in communication with the controller 50.
  • the method includes controlling the introduction of the displacing gas 28 based on the measurement of the concentration of oxygen in the gas sink 24.
  • the controller 50 directs the valve 52 to open to increase the introduction of the displacing gas 28 when the concentration of oxygen in the gas sink 24 exceeds a prescribed level.
  • the controller 50 directs the valve 52 to close to decrease the introduction of the displacing gas 28 when the concentration of oxygen is below the prescribed level.
  • the method can further include applying the coating composition 72 from the coating composition vessel 70 to the substrate 22 at a location exterior to the gas sink 24.
  • the coating composition 72 is applied from the coating composition vessel 70 to the substrate 22 before the substrate 22 is introduced into the gas sink 24, in the gas sink 24, or after the substrate 22 is introduced to the gas sink 24.
  • the method can also include measuring the concentration of oxygen in the gas sink 24 and measuring the concentration of oxygen in coating composition vessel 70 to determine the concentration of oxygen in the coating composition 72. Further, the method can include controlling the introduction of the displacing gas 28 based on the measurement of the concentration of oxygen in the gas sink 24 and the measurement of the concentration of oxygen in the coating composition 72. Specifically, controlling the introduction of the displacing gas 28 is further defined as increasing the introduction of the displacing gas 28 when a combined measurement of the concentration of oxygen in the gas sink 24 and the measurement of the concentration of oxygen in the coating composition 72 exceeds the prescribed level.
  • the decomplexing of the organoborane complex can be initiated prior to applying the composition 26 to the substrate 22 or can be initiated after the composition 26 is applied on the substrate 22.
  • the decomplexing of the organoborane complex can be initiated prior to applying the composition 26 to the substrate 22 in the configuration where the at least one applicator 64 for the organoborane complex and the radical polymerizable compound is disposed in the gas sink 24 such that the decomplexing of the organoborane complex is initiated as the organoborane complex travels through the displacing gas 28 to the substrate 22.
  • the decomplexing of the organoborane complex can be initiated after the composition 26 is applied on the substrate 22 when the organoborane complex is applied to the substrate 22 prior to the introduction of the substrate 22 the gas sink 24 such that the decomplexing of the organoborane complex is initiated when the substrate 22 is introduced into the gas sink 24.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention porte sur un système pour durcir une composition, lequel système comprend une cabine ayant une entrée, une sortie et une évacuation de gaz. La composition comprend un complexe organoborane et un composé polymérisable radical, et est appliquée à un substrat. Le système comprend un transporteur s'étendant à travers l'évacuation de gaz pour déplacer le substrat à travers l'évacuation de gaz. Une source de gaz est en communication avec l'évacuation de gaz pour introduire dans l'évacuation de gaz un gaz en déplacement. Le gaz en déplacement est plus lourd que l'oxygène, de façon à déplacer l'oxygène à partir de l'évacuation de gaz. Un dispositif de commande est en communication avec la source de gaz pour commander l'introduction du gaz en déplacement vers l'évacuation de gaz. L'introduction du gaz en déplacement est commandée de façon à commander une inhibition de surface d'oxygène lorsque le gaz en déplacement décomplexe le complexe organoborane pour la polymérisation du composé polymérisable radical lorsque le transporteur déplace le substrat à travers l'évacuation de gaz.
PCT/EP2010/058983 2009-06-26 2010-06-24 Système et procédé pour durcir une composition WO2010149733A1 (fr)

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US8647716B2 (en) 2009-06-26 2014-02-11 Basf Se Method of dissociating an organoborane-amine complex
US8652578B2 (en) 2009-06-26 2014-02-18 Basf Se Method of forming a cured coating composition on an automobile component
US8653183B2 (en) 2009-06-26 2014-02-18 Basf Se Method of curing a coating composition comprising a radical curable compound and an organoborane-amine complex
EP3144072A1 (fr) * 2015-09-17 2017-03-22 Henkel AG & Co. KGaA Distributeur, kit et procédé pour appliquer un activateur pour un composant durcissable à base de cyanoacrylate
EP3144073A1 (fr) * 2015-09-17 2017-03-22 Henkel AG & Co. KGaA Distributeur, kit et procédé pour appliquer un activateur pour un matériau durcissable
US9757898B2 (en) 2014-08-18 2017-09-12 Lord Corporation Method for low temperature bonding of elastomers

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CN109051793A (zh) * 2018-07-31 2018-12-21 中山易必固新材料科技有限公司 一种下沉式二氧化碳气体保护输送管

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WO2008085234A1 (fr) * 2007-01-09 2008-07-17 Dow Corning Corporation Procédé de formation de films et films formés par le procédé

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8647716B2 (en) 2009-06-26 2014-02-11 Basf Se Method of dissociating an organoborane-amine complex
US8652578B2 (en) 2009-06-26 2014-02-18 Basf Se Method of forming a cured coating composition on an automobile component
US8653183B2 (en) 2009-06-26 2014-02-18 Basf Se Method of curing a coating composition comprising a radical curable compound and an organoborane-amine complex
US9757898B2 (en) 2014-08-18 2017-09-12 Lord Corporation Method for low temperature bonding of elastomers
EP3144072A1 (fr) * 2015-09-17 2017-03-22 Henkel AG & Co. KGaA Distributeur, kit et procédé pour appliquer un activateur pour un composant durcissable à base de cyanoacrylate
EP3144073A1 (fr) * 2015-09-17 2017-03-22 Henkel AG & Co. KGaA Distributeur, kit et procédé pour appliquer un activateur pour un matériau durcissable

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