WO2019038722A1 - Composition de polyurée comprenant un capteur d'eau et un constituant hydroxyle et procédé - Google Patents

Composition de polyurée comprenant un capteur d'eau et un constituant hydroxyle et procédé Download PDF

Info

Publication number
WO2019038722A1
WO2019038722A1 PCT/IB2018/056406 IB2018056406W WO2019038722A1 WO 2019038722 A1 WO2019038722 A1 WO 2019038722A1 IB 2018056406 W IB2018056406 W IB 2018056406W WO 2019038722 A1 WO2019038722 A1 WO 2019038722A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
hydroxyl component
hydroxyl
water
water scavenger
Prior art date
Application number
PCT/IB2018/056406
Other languages
English (en)
Inventor
Chad M. AMB
Saswata CHAKRABORTY
Zai-Ming Qiu
Alexander J. KUGEL
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Publication of WO2019038722A1 publication Critical patent/WO2019038722A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L55/00—Devices or appurtenances for use in, or in connection with, pipes or pipe systems
    • F16L55/16—Devices for covering leaks in pipes or hoses, e.g. hose-menders
    • F16L55/162—Devices for covering leaks in pipes or hoses, e.g. hose-menders from inside the pipe
    • F16L55/165—Devices for covering leaks in pipes or hoses, e.g. hose-menders from inside the pipe a pipe or flexible liner being inserted in the damaged section
    • F16L55/1656—Devices for covering leaks in pipes or hoses, e.g. hose-menders from inside the pipe a pipe or flexible liner being inserted in the damaged section materials for flexible liners
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • Trenchless methods for structural renovation of drinking water pipelines include the pipe in pipe method, pipe bursting method, and polyethylene thin wall lining method. As described in U.S. Patent No. 7,189,429, these methods are disadvantaged by their inability to deal with multiple bends in a pipeline and the fact that lateral connection pipes to customers' premises are disconnected and then reinstated after execution of the renovation process.
  • compositions have been described that are suitable to form a coating on the internal surface of a drinking water pipeline. See for example US 2013/0116379 and US2015/0104652.
  • Components of polyurea coating compositions such as polyisocyanates and especially polyamines typically contain very small concentrations of water that can accelerate the reaction resulting is fast cure rates, as evident by the gel time. However, the concentration of water is very inconsistent, which in turn can result in wide variation in the rate of cure.
  • the water By removing the water from the first and/or second part, the water is no longer a "variable" with respect to the rate of cure.
  • the cure rate By adding a specified amount of a hydroxyl component, the cure rate can be accelerated in a controlled manner, such that the cure rate is consistent for each "batch" of the two-part composition.
  • a method of forming a coating on a surface of a pipeline comprises the steps of: a) providing a polyurea coating composition comprising a first part comprising at least one polyisocyanate, and a second part comprising at least one poly amine; and b) combining the first part and the second part to form a liquid mixture; wherein the first part, second part, or liquid mixture further comprises 0.5 wt.-% to 5 wt.-% of water scavenger(s); and 0.05 to 10 wt.-% of hydroxyl component(s) comprising one or more reactive hydroxyl groups; c) applying the liquid mixture to internal surfaces of the pipeline; and d) allowing the mixture to set forming a cured coating.
  • a method of controlling the reaction rate of a polyurea coating composition comprising a) providing a polyurea coating composition comprising a first part comprising at least one polyisocyanate; and a second part comprising at least one polyamine; and b) combining the first part and the second part to form a liquid mixture wherein the first part, second part, or liquid mixture further comprises 0.5 wt.-% to 5 wt.-% water scavenger; and 0.05 to 10 wt.-% of a hydroxyl component comprising one or more reactive hydroxyl groups.
  • polyurea coating compositions comprising a) a first part comprising at least one polyisocyanate, and b) a second part comprising at least one polyamine.
  • the first part and/or second part further comprises water scavenger and 0.05 wt.-% to 10 wt.-% of a hydroxyl component comprising one or more reactive hydroxyl groups.
  • the composition further comprises a third part comprising 0.05 to 10 wt.-% of a hydroxyl component comprising one or more reactive hydroxyl groups.
  • FIG. 1 depicts a perspective view of a pipe comprising a coating of a caliper of at least 5 mm.
  • FIG. 2 depicts a perspective view of a pipe comprising a coating not having a caliper of at least 5 mm.
  • the present invention provides a polyurea composition, typically comprising at least two-parts.
  • the polyurea composition is suitable for applying to internal pipeline surfaces so as to form an impervious lining suitable for contact with drinking water.
  • the composition is particularly useful as an "in-situ" applied lining for refurbishment of existing drinking water pipelines.
  • the first part of the two-part coating composition generally comprises at least one polyisocyanate and the second part comprises at least one polyamine.
  • the coating composition comprises the reaction product of such first and second components.
  • the reacted coating comprises urea groups (- R-C(O)- R-).
  • polyureas Polymers containing urea groups are often referred to as polyureas.
  • the two-part coating composition comprises other isocyanate reactive or amine reactive components
  • the reacted coating may comprise other groups as well.
  • the coating composition may optionally comprise a filler.
  • polyurea compositions suitable for applying to internal pipeline surfaces often contain a filler in order that the composition can be applied at a caliper of at least 5 mm in a single pass.
  • the amount of residual water in the polyurea coating composition can vary depending on the components.
  • Organic components typically have no greater than 1.0, 0.5, or 0.25 wt.-% of water. However, fillers may have a higher water content.
  • the residual water content is typically no greater than 2, 1.5, or 1 wt.% of the total polyurea coating composition.
  • the first part, second part, or both the first and second part comprise a water scavenger, otherwise known as a drying agent.
  • Drying agents are typically grouped into three classes.
  • a first class of drying agents reversibly react with water. This first group varies in their drying ability with the temperature, depending on the vapor pressure of the hydrate that is formed. Examples of such drying agents include for example anhydrous sodium sulfate, magnesium sulfate or calcium chloride.
  • Anhydrous magnesium sulfate is described as forming MgS04 7 ⁇ 2 0 below 48°C in the presence of water and thus has a fairly large capacity to reversibly react with water.
  • anhydrous MgS0 4 was not found to be an effective drying agent at ambient temperature. Further, for embodiments wherein the composition is heated at the time of application, such heating can cause the hydrate to release water due to the reversibility of such reaction.
  • a second class of drying agents irreversibly react with water.
  • This class of drying agents includes alkali metals, metal hydrides and calcium carbide. Such irreversible reactions disadvantageously produce a by-product. For example, alkali metals and hydride form hydrogen gas. Further, drying agents of this class often react with hydroxyl groups in general and thus react not only with water, but also with the hydroxyl component.
  • a third class of drying agent are non-reactive with water (e.g., trap water), such as molecular sieves. Molecular sieves are non-reactive in general and thus are also non- reactive with the components (e.g. polyisocyanates, polyamines, hydroxyl component) of the polyurea coating composition.
  • Molecular sieves are types of adsorbents composed of crystalline zeolites (sodium, potassium, and calcium aluminosilicates). When such crystalline zeolites are heated, water of hydration is removed, leaving holes of molecular dimensions in the crystal lattices. These holes are of uniform size and allow the passage of small molecules into the crystals, but not the passage of large ones. The pore size of these sieves can be modified (within limits) by varying the cations built into the lattices.
  • the first part and/or second part, or liquid mixture comprises a water adsorbing molecular sieve.
  • Type 4A sieves generally comprise crystalline sodium aluminosilicate with a pore size of about 4 angstroms. This sieve size is suitable for adsorbing water.
  • Type 3 A sieves comprises potassium aluminosilicate with a pore size of about 3 angstroms. Type 3 A are the most selective type of molecular sieves for water adsorption.
  • Molecular sieves are commercially available from various suppliers. For example, a Type 3 A molecular sieve is available from Zeochem LLC, as "PURMOL 3 ST". Such material is described as having a primary crystal size of 4.6 microns and a typical particle size of 24 microns.
  • the water adsorbing sieve has a water adsorption capacity of at least 5, 10, 15, or 20% w/w at 50% relative humidity at 20°C in 24 hours. In otherwords, 1 gram of water adsorbing sieve may absorb 0.05, 0.10, 0.15, or 0.2 grams of water at such conditions.
  • the molecular sieve comprises crystalline sodium aluminosilicate and/or potassium aluminosilicate at a high level of purity (e.g. at least 95%, 96%, 97%, 98%, or 99%)
  • the molecular sieve has a pore size of 3-4 angstroms.
  • the molecular sieve may comprise a small amount (e.g. less than 5, 4, 3, 2, or 1 wt- %) of sieve or pores having a smaller and/or larger pore size.
  • the molecular sieve may have an average pore size greater than 2.5 or 3 angstroms (e.g.
  • the molecular sieve does not adsorb the hydroxyl component.
  • the addition of the water adsorbing molecular sieve generally reduces the reaction rate by removing the residual water.
  • the gel time of the polyurea composition without the drying agent, but containing residual water was about 25 seconds.
  • the addition of molecular sieve can increase the gel time to greater than 75 seconds.
  • the addition of the molecular sieve alone can increase the gel time by 1.5X, 2X, 2.5X, or 3X.
  • the gel time can be determined according to the test method described in the examples.
  • the amount of drying agent can vary depending on the amount of residual water in the first and/or second parts of the polyurea composition.
  • the minimal amount of drying agent can be determined by adding incremental amounts of (e.g. water adsorbing molecular sieve) drying agent until the reaction rate (e.g. gel time) no longer decreases. In typical embodiments, the amount of drying agent will be in slight excess of the minimum.
  • the amount of drying agent is typically at least 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 wt.-% of the total coating
  • the amount of drying agent is no greater than 5, 4.5, 4, 3.5, 3.0 or 2.5 wt.-% of the total coating composition.
  • the polyurea coating composition further comprises an (e.g. organic) component comprising one or more reactive hydroxyl groups.
  • the hydroxyl component is typically a liquid at 25°C or at the application temperature of the polyurea coating composition.
  • the hydroxyl component is a solid that is soluble with the second part.
  • the term "reactive" refers to a hydroxyl group that is not sterically hindered.
  • hindered phenols such as BHT (butylated hydroxytoluene, depicted below) contains a hindered hydroxyl group (e.g. hindered phenols).
  • the reactivity of the hydroxyl group is hindered in view of the branched (e.g. C 4 ) alkyl substituents.
  • the branched (e.g. C 4 ) alkyl substituents as typically bonded to adjacent carbon atoms relative to the carbon atom bonded to the hydroxyl group.
  • reactive does not necessarily require the hydroxyl group to be reactive enough to form urethane linkages in the presence of isocyanates at the time scales that gelling occurs in polyurea reactions, as it has been shown that urethane formation can be up to 1,000X slower than polyurea formation using secondary aliphatic amines.
  • nonylphenol molecular weight 220 g/mol.
  • reactive does not necessarily require the hydroxyl group to be reactive enough to form urethane linkages in the presence of isocyanates at the time scales that gelling occurs in polyurea reactions, as it has been shown that urethane formation can be up to ⁇ , ⁇ slower than polyurea formation using secondary aliphatic amines.
  • the component comprising one or more reactive hydroxyl groups typically comprises at least two, three, or four carbon atoms.
  • the hydroxyl component is larger than the pore size of the water adsorbing molecular sieve, the hydroxyl component is not affected by any excess molecular sieve (i.e. in an amount greater than required to adsorb residual water) that may be present in the coating composition.
  • the hydroxyl component is an aliphatic or aromatic alcohol.
  • Such alcohols typically having the general formula:
  • R is alkyl, aryl, alkaryl, or ary alkyl.
  • the number of carbon atoms of R typically ranges from 2 to 30. In some embodiments, the number of carbon atoms is no greater than 20, 19, 18, 17, 16, or 15 carbon atoms.
  • the alkyl group can be linear, cyclic, or branched, provided the hydroxyl group is reactive as previously described. Suitable examples include for example ethanol, 4-sec butyl phenol, and nonylphenol.
  • the hydroxyl component is an aliphatic or aromatic polyol.
  • such polyols have the general formula:
  • R 15 is a multivalent atom (e.g. carbon or nitrogen) or an organic moiety having a valence of at least two
  • L is a covalent bond or divalent organic linking group
  • n typically averages from 2 to 4.
  • the number of carbon atoms of R 15 typically ranges from 2 to 30, and n typically averages from 2 to 4. In some embodiments, the number of carbon atoms is no greater than 20, 19, 18, 17, 16, or 15 carbon atoms.
  • L is a covalent bond and R 15 is alkylene, arylene, alkarylene, or aryalkylene.
  • the polyol is aliphatic. In other embodiments, L is a C1-C4 alkylene group.
  • Representative polyol compounds include for example 1,2 propylene glycol; 1,2,6 hexanetriol, as well as ethylene glycol and glycerol depicted as follows.
  • R 15 is alkylene and L is a C1-C4 alkylene group, such as in the case of trimethylol propane.
  • R 15 is nitrogen and L is a C1-C4 alkylene group, such as in the case of triethanolamine.
  • R 15 is carbon and L is a C1-C4 alkylene group, such as in the case of pentaerythritol.
  • the hydroxyl component is a poly ether polyol.
  • the polyether polyols have the same general formula as depicted above wherein L is an ether group, such a polypropylene oxide.
  • L is an ether group, such a polypropylene oxide.
  • the number of hydroxyl groups of polyether polyols, i.e. n, can range up to 7, 8, 9, or 10.
  • CARPOL GSP-370 is reported as having a functionality of 7.
  • linear polyether (i.e. polypropylene oxide) polyols typically have the general formula: wherein m is typically no greater than 20 or 25.
  • m typically no greater than 20 or 25.
  • the hydroxyl component e.g. alcohol, polyol
  • the hydroxyl component is aliphatic and therefore lacks aromatic moieties.
  • the hydroxyl component when the hydroxyl component is a polyether polyol, the hydroxyl component can have a higher molecular weight than the previously described compounds.
  • the molecular weight can range up to 1000 or 1500 g/mol.
  • the molecular weight per hydroxyl group can range up to 500, 550, 600, 650, 700, or 750 g/per hydroxyl group.
  • the previously described alcohols, and polyol compounds typically have a molecular weight per hydroxyl group of less than 500 g/per hydroxyl group.
  • the hydroxyl component is less likely to affect any other (e.g. mechanical) properties of the polyurea.
  • the molecular weight per hydroxyl group of the hydroxyl component is less than 500, 450, 400, 350, or 300 g/hydroxyl group.
  • the molecular weight per hydroxyl group of the hydroxyl component is less than 250, 200, 150, or 100 g/hydroxyl group.
  • the molecular weight per hydroxyl group of the hydroxyl component is typically at least 30, such as in the case of glycerol.
  • the amount of hydroxyl component depends of the molecular weight per hydroxyl group (i.e. equivalent weight). For example, when 0.07 wt.-% (based on the total composition) of glycerol is added to the second part (comprising at least one polyamine), the hydroxyl equivalents per 100 g of the second part was about 0.0023. However, 1.16 wt.-% of a polymeric polyether polyol, such as "VORANOL 220-110N", was needed to provide the same amount of hydroxyl equivalents per 100 g (0.0023).
  • the amount of hydroxyl component also depends on the desired reaction rate. For example, when 0.07 wt.-% (based on the total composition) of glycerol is added to the second part (comprising at least one polyamine and molecular sieve) the gel time decreased from about 80 seconds to about 30 seconds. However, for a gel time of 50 seconds, less of this hydroxyl component would be used.
  • One of ordinary skill in the art can plot the concentration of a particular hydroxyl component as a function of gel time to control the gel time based on the concentration added.
  • the amount of hydroxyl component is typically at least 0.05, 0.06, 0.07, 0.08 0.09, 0.10 wt.-% of the total coating composition.
  • the amount of hydroxyl component is typically no greater than 10, 9, 8, 7, 6, or 5 wt.-% of the total coating composition.
  • the hydroxyl component is sufficiently reactive such that no greater than 5 wt.-% of the hydroxyl component reduces the gel time by at least 50%, 60, 70%), 80%), 90%), or greater.
  • this statement alone is not intended to limit the concentration of hydroxyl component, but rather specify the reactivity of the hydroxyl component.
  • the polyurea composition containing water scavenger has a gel time of 100 seconds
  • the gel time is reduced to 50 seconds with no greater than 5 wt- %> of the hydroxyl component.
  • the gel time is reduced by at least 50%> with no greater than 4.5, 4, 3.5, 3, 2.5, 2, 1.5 or 1 wt.-%> of the hydroxyl component based on the total composition. Reducing the gel time with the minimal amount of hydroxyl component can favorably have substantially no effect on the other (e.g. mechanical) properties of the polyurea composition, such as tensile strength.
  • the gel time of the polyurea coating composition further comprising the water scavenger and hydroxyl component is less than 200, 175, 150, 125, 100, 75, or 50 second according to the Gel Time test method described in the examples. In some embodiments, the gel time is less than 45, 40, 35, 30, 25, or 20 second.
  • One example of a less favored hydroxyl component has the following structure, wherein Z is -CH2OH and n is 1, commercially available from Eastman Chemical as the trade designation "ABITOL E”.
  • the low reactivity may be due to this compound having more than one cyclic structure.
  • Such cyclic (e.g. hexyl) rings share a common side thereby constraining the rotation of the ring structures.
  • These structural features result in this material having a relatively high viscosity in comparison to other materials of similar molecular weight.
  • ABITOL E is reported to have a melt viscosity of 6500 centipoise (cP) a 50°C. The viscosity of such material may reduce its mobility within the composition, thereby reducing its reactivity.
  • the organic hydroxyl component has a viscosity less than 6000, 5500, 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, or 1000 centipoise at 50°C.
  • the bulky cyclic structure and methyl substituent near the hydroxyl group may contribute to some degree of steric hindrance.
  • the (e.g. molecular sieve) water scavenger and organic hydroxyl components can be added to the polyurea composition in various manners.
  • the polyurea coating composition is provided with the water scavenger(s) and the hydroxyl component(s) contained within the first and/or second part.
  • the polyurea coating composition is commercially available containing both the water scavenger(s) and the hydroxyl component(s). This may be characterized as having the water scavenger(s) and the hydroxyl component(s) "pre-added" to the (e.g. two-part) polyurea coating composition.
  • the reactive polyurea coating composition comprises a) a first part comprising at least one polyisocyanate, and b) a second part comprising at least one poly amine, wherein the first part and/or second part further comprises water scavenger(s) and hydroxyl component(s) comprising one or more reactive hydroxyl groups. More typically, the polyurea coating composition is provided with the water scavenger(s) and the hydroxyl component(s) contained within the second part.
  • the first part may also contain water scavenger(s).
  • the hydroxyl component can be added to the first (e.g. polyisocyanate) part, doing so result in the first part has a limited shelf life.
  • the polyurea coating composition may be provided with the water scavenger(s) contained within the first and/or second part, but not contain the hydroxyl component(s) in the second part.
  • the hydroxyl component(s) is added to the second part prior to combining the first and second part or during combining the first part and the second part. This may be characterized as having the water scavenger(s) pre-added and the hydroxyl component(s) "post-added".
  • the reactive polyurea coating composition comprises a) a first part comprising at least one polyisocyanate, and b) a second part comprising at least one polyamine, wherein the first part and/or second part further comprises water scavenger; and c) a third part comprising a hydroxyl component comprising one or more reactive hydroxyl groups.
  • the polyurea coating composition is provided without the water scavenger(s) and without the hydroxyl component(s). Both the water scavenger(s) and hydroxyl component(s) are (e.g. sequentially) added to the second part prior to combining the first and second part or during combining the first part and the second part. This may be characterized as having the water scavenger(s) and the hydroxyl component(s) "post-added" to the (e.g. two-part) polyurea coating composition.
  • the reactive components such as the polyisocyanate and polyamine can be characterized based on their functionality. Functionality may be calculated by dividing the molecular weight by the equivalent weight.
  • the equivalent weight of isocyanate end groups can be determined by titration procedures such as, for example ASTM D 2572-97.
  • the equivalent weight of amine end groups can be determined by titration procedures such as, for example ASTM D 2074-92. In the case of polyisocyanates, the average
  • functionality is the average number of isocyanate (-NCO) groups of a polyisocyanate.
  • polyamines the average functionality is the average number of amine groups of a polyamine.
  • the functionality is typically reported by the supplier. For example, Covestro, Leverkusen, Germany, reports the average functionality of their
  • polyisocyanates An average functionality is often reported when the material comprises a mixture of compounds. However, when the material is substantially a single compound, the material may be reported as difunctional (e.g. diamine) or trifunctional (e.g. triamine).
  • the first part of the two-part coating comprises one or more polyisocyanates.
  • Polyisocyanate refers to any organic compound that has two or more reactive isocyanate (-NCO) groups in a single molecule such as diisocyanates, triisocyanates, tetraisocyanates, etc., and mixtures thereof. Cyclic and/or linear polyisocyanate molecules may be usefully employed.
  • the polyisocyanate(s) of the isocyanate component are preferably aliphatic. In typical embodiments, the (e.g. aliphatic) polyisocyanates are selected such that the total composition is substantially free of isocyanate monomer (e.g. less than 0.5%).
  • Suitable aliphatic polyisocyanates include derivatives of hexamethylene-1,6- diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate; and 4,4'-dicyclohexylmethane diisocyanate.
  • reaction products or prepolymers of aliphatic polyisocyanates may be utilized.
  • the first part generally comprises at least one aliphatic polyisocyanate.
  • Such aliphatic polyisocyanate typically comprises one or more derivatives of hexamethylene- 1,6-diisocyanate (HDI).
  • the aliphatic polyisocyanate is a derivative of isophorone diisocyanate.
  • the aliphatic polyisocyanate may comprise an uretdione, biuret, and/or isocyanurate of HDI.
  • the first part comprises at least one solvent-free aliphatic polyisocyanate(s) that is substantially free of isocyanate (HDI) monomer, i.e. less than 0.5 % and more preferably no greater than 0.3 % as measured according to DIN EN ISO 10 283.
  • HDI isocyanate
  • Various solvent-free aliphatic polyisocyanate(s) are available.
  • One type of HDI uretdione polyisocyanate reported to have an isocyanate content of 21.8 and a viscosity of 150 mPa s at 23°C is available from Covestro under the trade designation "DESMODUR N 3400".
  • Another HDI polyisocyanate is a trimer, reported to have a viscosity of about
  • DESMODUR N 3600 1200 mPa- s at 23°C is available from Covestro under the trade designation "DESMODUR N 3600". Such polyisocyanates typically have an isocyanate content of 20-25%.
  • Another polyisocyanate is an aliphatic prepolymer resin comprising ether groups, based on HDI is available from Covestro under the trade designation "DESMODUR XP 2599”.
  • Yet another aliphatic HDI polyisocyanate is a trimer is available from Covestro under the trade designation "DESMODUR N3800”. This material has an NCO content of 11% and a viscosity of 6,000 mPa- s at 23°C.
  • HDI polyisocyanate is a trimer is available from Covestro under the trade designation "DESMODUR N3300”. This material has an NCO content of 21.8% and a viscosity of 3,000 mPa- s at 23°C.
  • DESMODUR N3300 is available from Covestro under the trade designation "DESMODUR N3300”. This material has an NCO content of 21.8% and a viscosity of 3,000 mPa- s at 23°C.
  • DESMODUR XP2838 This material has an NCO content of 20% and a viscosity of 3,000 mPa s at 23°C.
  • One type of HDI biuret polyisocyanate is available from Covestro under the trade designation
  • the first part comprises a single aliphatic polyisocyanate based on hexamethylene-l,6-diisocyanate (HDI).
  • the first part may comprise 100 wt-% of a single aliphatic polyisocyanate based on hexamethylene-1,6- diisocyanate (HDI).
  • the single aliphatic polyisocyanate has a viscosity of no greater than 1,500 mPa s at 23°C and a functionality ranging from about 2.8 to 3.5, such as "DESMODUR N 3600".
  • the first part further comprises additives, as will subsequently be described, such that the first part comprises less than 100 wt-% of polyisocyanate.
  • the first part comprises a mixture of aliphatic
  • the first part comprises a first aliphatic polyisocyanate having a viscosity of no greater than 1,500 mPa s at 23°C and a functionality ranging from about 2.8 to 3.5, such as
  • the second aliphatic polyisocyanate has an average functionality of at least 3.6, 3.7, 3.8, 3.9, or 4.0 and typically no greater than 4, 5, or 6. In some embodiments, the second aliphatic
  • the polyisocyanate may have a higher viscosity than the first polyisocyanate.
  • the second aliphatic polyisocyanate has a viscosity of at least 1,600; 1,700; 1,800; or 1,900 mPa s at 23°C and typically no greater than 5,000; 4,500; 4,000; 3,500; or 3,000 mPa- s at 23°C, such as "DESMODUR XP 2599".
  • the amount of first aliphatic polyisocyanate is typically at least 70, 75, or 80 wt.% and in some embodiments at least 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95 wt.% or greater of the first part.
  • the amount of second aliphatic polyisocyanate is typically at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 wt.% or greater of the first part.
  • mixtures of aliphatic polyisocyanates based on hexamethylene-1,6- diisocyanate (HDI) can be used.
  • the mixtures comprise three or four different polyisocyanates.
  • the first part is substantially free of other "amine reactive resin(s)" (i.e. a resin containing functional groups capable of reacting with primary or secondary amines).
  • the first part is typically free of aromatic amine reactive resins.
  • the first part may also be free of epoxy functional compounds and compounds containing unsaturated carbon-carbon bonds capable of undergoing "Michael Addition" with polyamines (e.g. monomeric or oligomeric polyacrylates).
  • the first part may optionally comprise non-reactive resins or the composition may be free of non-reactive resins.
  • the second part of the two-part coating comprises one or more polyamines.
  • polyamine refers to compounds having at least two amine groups, each containing at least one active hydrogen (N-H group) selected from primary amine or secondary amine.
  • the second component comprises or consists solely of one or more (e.g. secondary) polyamines.
  • the amine component comprises at least one aliphatic cyclic secondary polyamine (e.g. diamine).
  • aliphatic cyclic secondary polyamine e.g. diamine
  • aspartic ester amines react with isocyanates to form urea- diester linkages.
  • urea-diester linkages are reportedly unstable, typically forming the hydantoin and an alcohol as a by-product. Hydantoin formation can cause dimensional changes of the polymer.
  • the amine component comprises at least one aliphatic cyclic secondary polyamine (e.g. diamine) that is not an aspartic ester amine. Therefore, such polyamine comprises secondary amine substituents, yet the polyamine lacks ester groups and specifically diester moieties.
  • the second part comprises one or more aliphatic cyclic secondary diamines that comprise two, optionally substituted, hexyl groups bonded by a bridging group.
  • Each of the hexyl rings comprise a secondary amine substituent.
  • the aliphatic cyclic secondary diamine typically has the general structure:
  • Ri and R2 are independently linear or branched alkyl groups, having 1 to 10 carbon atoms. Ri and R2 are typically the same alkyl group. Representative alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The symbol "S" in the center of the hexyl rings indicates that these cyclic groups are saturated.
  • the preferred Ri and R2 contain at least three carbons, and the butyl group is particularly favored, such as a sec-butyl group.
  • R3, R4, R5 and R 6 are independently hydrogen or a linear or branched alkyl group containing 1 to 5 carbon atoms.
  • R3, and R 4 are typically the same alkyl group.
  • R5 and R 6 are hydrogen.
  • R3, and R 4 are methyl or hydrogen.
  • the substituents are represented such that the alkylamino group may be placed anywhere on the ring relative to the CR5R6 group. Further, the R3 and R 4 substituents may occupy any position relative to the alkylamino groups. In some embodiments, the alkylamino groups are at the 4,4'-positions relative to the CR5R6 bridge. Further, the R3 and R 4 substituents typically occupy the 3- and 3'-positions.
  • aliphatic cyclic secondary diamines having this structure include:
  • the second part comprises one or more aliphatic cyclic secondary diamines that comprise a single hexyl ring.
  • the aliphatic cyclic secondary diamine typically has the general structure:
  • R 7 and Rs are independently linear or branched alkyl groups, having 1 to 10 carbon atoms or an alkylene group terminating with a -CN group.
  • R7 and Rs are typically the same group.
  • Representative alkyl groups include the same as those described above for Ri and R2.
  • R 7 and Rs are alkyl groups having at least three carbons, such as isopropyl.
  • R 7 and Rs are short chain (e.g. Cl- C4) alkylene groups, such as ethylene, terminating with a -CN group.
  • R9, Rio and R11 are independently hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • R9, Rio and R11 are typically the same alkyl group.
  • R9, Rio and R11 are methyl or hydrogen.
  • R9, Rio and R11 are methyl groups.
  • the substituents are represented such that the alkylamino group may be placed anywhere on the ring relative to the -NRs group. In some embodiments, the alkylamino group is 2 or 3 positions away from the -NRs. The preferred alkylamine group is two positions away from the -NRs group on the cyclohexyl ring.
  • the aliphatic cyclic secondary diamine is prepared by the reaction product of (1 equivalent of) isophorone diamine and (2 equivalents of) a Michael acceptor group that reduces the nucleophilicity of the resulting secondary amine groups.
  • Representative Michael acceptors include acrylonitrile and ⁇ , ⁇ -unsaturated carbonyl compounds, with acrylonitrile typically preferred.
  • the alkylene group between the terminal -CN group and the amine group has at least two carbon atoms.
  • aliphatic cyclic secondary polyamines having this structure include:
  • the i socyanate-reactive component of the second part may include a single aliphatic cyclic secondary diamine comprising two hexyl rings bonded by a bridging group, such as a species according to Formula 1.
  • the i socyanate-reactive component of the second part comprises two or more aliphatic cyclic secondary diamines comprising two hexyl rings bonded by a bridging group, such as two or more species according to Formula 1.
  • the isocyanate-reactive component of the second part may include a single aliphatic cyclic secondary diamine comprising a single hexyl ring, such as a species according to Formula 2.
  • the isocyanate-reactive component of the second part comprises two or more aliphatic cyclic secondary diamines comprising a single hexyl ring, such as two or more species according to Formula 2.
  • the isocyanate-reactive component of the second part may include at least one aliphatic cyclic secondary diamine comprising two hexyl rings bonded by a bridging group (e.g. a specie or species according to Formula 1) and at least one aliphatic cyclic secondary diamine comprising a single hexyl ring (e.g. a specie or species according to Formula 2).
  • the second part typically comprises at least 20, 21, 22, 23, 24 or 25 wt.-% of aliphatic cyclic secondary polyamine(s) (e.g. diamine(s)). In some embodiments, the second part comprises at least 30, 35, 40, 45 or 50 wt.-% of aliphatic cyclic secondary polyamine(s) (e.g. diamine(s)). The amount of aliphatic cyclic aliphatic cyclic secondary polyamine(s) (e.g. diamine(s)) can range up to 100%. However, in typical embodiments, the second part further comprises a polyether polyamine and fillers, such as a thixotrope.
  • the amount of aliphatic cyclic secondary polyamine(s) is less than 100%.
  • the second part comprises up to 70, 75, 80, 85, 90, or 95 wt.-% of aliphatic cyclic secondary polyamine(s) (e.g. diamine(s)).
  • the liquid mixture of the first and second part further comprises a polyether component.
  • the polyether component may be an isocyanate functional polyether, such as DESMODUR XP 2599.
  • the polyether component may also be an isocyanate-functional prepolymer, where an alcohol or amine functional polyether is added to a large molar excess of isocyanate compound.
  • the polyether component may also be an amine- functional prepolymer, where an isocyanate functional polyether is added to a large molar excess of polyamine.
  • the polyether component comprises one or more amine functional polyethers, such as the JEFF AMINE series of polyether amines.
  • amine functional polyethers include for example amine-terminated polypropylene oxide, amine-terminated polyethylene oxide (PEG), amine-terminated polytetram ethylene oxide, etc.
  • the polyether amines may be either primary or secondary and are available in various molecular weights and functionality. In typical embodiments, the molecular weight is at least 100, 150, or 200 g/mol. In typical embodiments, the molecular weight is no greater than about 10,000; 9,000; 8,000; 7,000; 6,000 or 5,000 g/mol.
  • polyether amines include the following:
  • the polyether component is amine functional polyether(s) or a combination of at least one isocyanate functional polyether and at least one amine functional polyether.
  • the first and/or second part comprises one or more polyether components such that the polyether content of the total composition (i.e. liquid mixture of first and second part) is at least 1, 1.5, 2, or 2.5 wt.%. In some embodiments, the total polyether content is at least 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 8, 9.5 or 10 wt.-%. In other embodiments, the total polyether content is at least 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5 or 15 wt.-%. In some embodiments, the polyether content of the total composition (i.e. liquid mixture of first and second part) is preferably less than 25, 24, 23, 22 or 21 wt.-%. When the second part consists of aliphatic cyclic secondary diamine comprising a single hexyl ring, the concentration of polyether amine is typically no greater than 15, 14, 13, 12, 11, or 10 wt.-%.
  • the inclusion of one or more polyether components can increase the elongation while maintaining a calculated 50 year tensile creep rupture strength of at least 8, 9, or 10 MPa as described in US patent application serial no. 62/527508; incorporated herein by reference.
  • the calculated 50 year creep rupture strength refers to the value obtained according to the test method described in US patent application serial no. 62/527508. Such test method is believed to correspond with the value obtained when determining the 50 year creep rupture tensile strength according to ASTM D-2990-17, using the same sample conditioning method described in the examples and keeping the sample specimens saturated throughout the test.
  • composition when a composition exhibits a calculated 50 year creep rupture tensile strength of at least 10 MPa according to such test method it will also exhibit a calculated 50 year creep rupture tensile strength of at least 10 MPa according to ASTM D-2990-17.
  • the difference between the average values obtained by these methods is generally within the statistical standard deviation of such tests, meaning the average values are statistically the same.
  • the calculated 50 year creep rupture tensile strength is at least 11, 12, 13, 14, 15, or 16 MPa. In typical embodiments, the calculated 50 year creep rupture tensile strength is no greater than 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, or 17 MPa. In some embodiments, the elongation is at least 4, 5, 6, or 7%. In typical embodiments, the elongation is no greater than 25% or 20% and in some embodiments, no greater than 19, 18, 17, 16 or 15%.
  • the aliphatic cyclic secondary polyamine e.g. diamine
  • one or more secondary aliphatic polyamine including other cycloaliphatic polyamines
  • the other secondary aliphatic polyamine may include aspartic acid ester, such as described in
  • Preferred aspartic ester amines have the following formula:
  • Rms an aliphatic group (preferably, having 1-20 carbon atoms), which can be branched, unbranched, or cyclic. More preferably, R12 is selected from the group of divalent hydrocarbon groups obtained by the removal of the amino groups from 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- and 2,4,4-trimethyl-l,6- diaminohexane, l-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 4,4'-diamino- dicyclohexyl methane or 3,3-dimethyl-4,4'-diamino-dicyclohexyl methane.
  • R12 preferably comprises a dicyclohexyl methane group or a branched C4 to C12 group.
  • R13 is typically independently a lower alkyl group (having 1-4 carbon atoms).
  • Suitable aspartic acid esters are commercially available from Bayer Corp. under the trade designations "DESMOPHEN H 1420", “DESMOPHEN NH 1520" and
  • DESMOPHEN NH 1220 is substantially composed of the following compound Formula 4;
  • aspartic acid esters according to Formula 3, wherein R 12 is a branched or unbranched group lacking cyclic structures and having less than 12, 10, 8, or 6 carbon atoms, such as depicted in Formula 4, is typically preferred for faster film set times of 2 to 5 minutes.
  • the inclusion of an aspartic acid ester according to Formula 3, wherein R 12 comprises unsubstituted cyclic structures can be employed to extend the film set time to 5 to 10 minutes.
  • R 12 comprises substituted cyclic structures, (e.g. Formula III of US
  • the second part may further comprise acyclic aliphatic linear or branched polyamines (i.e. that lacks a cyclic group).
  • One suitable commercially available aliphatic acyclic secondary diamine includes the following:
  • the other aliphatic secondary diamine components are utilized at a lower concentration than the aliphatic cyclic secondary diamine (e.g. of Formula 1 and/or 2).
  • concentration of such other aliphatic secondary diamine is typically no greater than 40, 35, 30, 25, 20, 15, 10 or 5 wt.-% of the polyamines of the second part or less than 25, 20, 15, 10, or 5 wt.-% of the total coating composition.
  • the optional other amine components are chosen to dissolve in the liquid aliphatic cyclic secondary diamine (e.g. of Formula 1 and/or 2).
  • the total composition (i.e. first and second part) is substantially free of aromatic components, such that the composition meets the NSF/ANSI Standard. In some embodiments, the total composition typically comprises less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 wt.-% of aromatic components.
  • the average functionality (favg) of the reactive components (e.g. polyisocyanates, polyamines, etc.) of the total composition can be calculated using Equation 1, where Ni is the number of moles of a given reactant, and is the functionality of that reactant.
  • the functionality of the reactant can be obtained by division of the molecular weight of the reactant by the equivalent weight of the reactant. It is appreciated that fillers (inclusive of pigments, thixotropes, and desiccants (i.e. molecular sieves or other solid drying agents described above), and other additives are not reactive components and are excluded for the calculation of favg.
  • the average functionality is at least 2.30, 2.31, 2.32, 2.33, 2.34, 2.35, 2.36, 2.37, 2.38, 2.39, or 2.40. In other embodiments, the average functionality is at least 2.41, 2,42, 2.43, 2.44, 2.45, 2.46, 2.47, 2.48, 2.49, or 2.50. In typical, embodiments, the average functionality is less than 2.65, 2.64, 2.63, 2.62, 2.61, or 2.60.
  • the above functionality is achieved utilizing one or more polyisocyantes each having a functionality greater than 2.
  • the above polyisocyantes each having a functionality greater than 2.
  • functionality can also be achieved by utilizing a polyisocyanate having a functionality of 2 in combination with a second polyisocyante having a functionality greater than 2.
  • the first and/or second part may comprise a filler.
  • a filler is a solid, insoluble particulate material often employed to add bulk volume or to extend the pigment capabilities without impairing the reactive chemistry of the coating mixture.
  • Many fillers are natural inorganic minerals such as talc, clay (e.g. kaolin), calcium carbonate (e.g. whiting), dolomite (calcium magnesium carbonate), and siliceous fillers including silica (e.g. particle size greater than 1 micron).
  • Pigments such as titanium dioxide
  • molecular sieves e.g. aluminosilicate
  • inorganic thixotropes such as fumed silica
  • thixotropes comprise an organic material such as polyamides, waxes, castor oil derivatives, and others, as described for example in US 4,923,909 and US 5,164,433. These may be soluble and/or semisoluble in the resin and are not considered "fillers”.
  • fillers include ceramic microspheres, hollow polymeric microspheres such as those available from Akzo Nobel, Duluth, GA, (under the trade designation "EXPANCEL 551 DE”), and hollow glass microspheres (such as those commercially available from 3M Company, St. Paul, MN, under the trade designation "K37”). Hollow glass microspheres are particularly advantageous because they demonstrate excellent thermal stability and a minimal impact on dispersion viscosity and density.
  • Other fillers can be solid insoluble particulates comprised of insoluble organic matter. Exemplary fillers of this type could include nylon, polyethylene, polypropylene, polyamides, etc.
  • the filler may further comprise a surface treatment compound.
  • the surface treatment compound may be non-reactive with respect to the reactive components (e.g. amine(s) and isocyanate) of the first and second part.
  • the reactive components e.g. amine(s) and isocyanate
  • polydimethylsiloxane as can be present as a surface treatment compound on the fumed silica thixotrope, is an example of a non-reactive surface treatment compound.
  • the composition typically comprises thixotrope filler, other fillers, or a combination thereof.
  • Thixotropes often can provide a suitable viscosity at lower concentrations than other types of filler and therefore can be advantageous for reducing the filler concentration.
  • pipe 100 illustrates the polyurea coating composition 150, as described herein, having a caliper of at least 5 mm.
  • pipe 200 illustrates the polyurea coating composition (250 and 260) not having a caliper of at least 5 mm.
  • the coating sags such that portion 250 may have a thickness greater than 5 mm.
  • portions 260 have a caliper significantly less than 5 mm.
  • Filler is preferably employed in the coating composition (i.e. liquid mixture of first and second part) at a concentration no greater than 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% by volume.
  • the second part comprises at least 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 wt.-%> or greater of thixotrope in order that a coating of sufficient caliper can be applied in a single pass.
  • the concentration of thixotrope in the second part is typically no greater than 30 wt.-%>.
  • the first part may also comprise thixotrope.
  • the concentration of thixotrope in the first part can be less than the second part depending on the viscosity (e.g. molecular weight) of polyisocyanate(s).
  • the amount of thixotrope in the first part is the same range as just described for the second part.
  • the second part comprises up to 1, 1.5, 2, 2.5, or 3 wt.-%> of thixotrope.
  • the amount of thixotrope employed in the coating composition i.e. liquid mixture of first and second part
  • the concentration of thixotrope employed in the coating composition is no greater than 30, 25, 20, 15% or 10 wt.-%.
  • the first and/or second part may comprise various additives as are known in the art, provided the inclusion of such is permitted with the requirements of the NSF/ANSI Standard. For example, dispersing and grinding aids, defoamers, etc., can be added to improve the manufacturability, the properties during application, and/or the shelf life.
  • the stoichiometry of the polyurea reaction is based on a ratio of equivalents of isocyanate (e.g. modified isocyanate and excess isocyanate) of the first component to equivalents of amine of the second component.
  • the first and second components are reacted at a stoichiometric ratio of at least about 1 : 1.
  • the isocyanate is employed in slight excess, such that the first part is combined with the second part at a ratio of 1.1 to 1.4 equivalents isocyanate to amine.
  • the first and second part are formulated such that the stoichiometric ratio is obtained at a volume ratio of 1 : 1.
  • volume ratios can be employed, typically ranging from 1 :3 to 3 :2.
  • the weight percent of each of the components in the total coating composition i.e. liquid mixture of first and second part
  • the density of the component Typical amounts of each of the components in the total coating composition are set forth in the following table. Other specific amounts can be derived from the wt.-% of the part as previously described and the density of a particular component as described in Table 1 of the examples.
  • the first and second parts are preferably each liquids at temperatures ranging from 5°C to 25°C, 30°C, 35°C, or 40°C.
  • both the first part and the second part are substantially free of any volatile solvent. That is to say, solidification of the system applied to the pipeline interior is not necessitated by drying or evaporation of solvent from either part of the system.
  • the coating composition has a useful shelf life of at least 6 months, more preferably, at least one year, and most preferably, at least two years.
  • the coating compositions described herein are particularly suitable for water distribution pipes, typically having a diameter > 3 inches (7.6 cm) up to about 36 inches (91 cm). It is generally desired that the cured coating has sufficient long term strength (i.e. 50 year creep rupture tensile strength) and ductility (i.e. flexibility as characterized by elongation at break) to remain continuous in the event of a subsequent circumferential fracture of a partially deteriorated (e.g. cast iron) pipe, such that the cured coating continues to provide a water impervious barrier between the flowing water and internal surfaces of the pipe.
  • the following table describes typical and preferred properties of cured coating compositions for water distribution pipes as determined by the test methods described in US patent application serial no. 62/527508.
  • the coating compositions described herein advantageously provide these desired properties while complying with NSF/ANSI Standard 61-2008, (i.e. the standard for the United States) and are also believed to comply with Regulation 31 of the Water Supply (Water Quality) Regulations (i.e. the standard for the United Kingdom).
  • the coating composition is typically applied directly to the internal surfaces of a pipe without a primer layer applied to the surface. This can be done using various spray coating techniques.
  • the amine component and the isocyanate component are applied using a spraying apparatus that allows the components to combine immediately prior to exiting the apparatus.
  • the first and second parts of the system are fed independently, e.g. by flexible hoses, to a spraying apparatus capable of being propelled through an existing pipeline to be renovated.
  • a remote-controlled vehicle such as described in US 2006/0112996, may enter the pipeline to convey the spraying apparatus through the pipeline.
  • the apparatus preferably heats the two parts of the system prior to application to the pipeline interior and mixes the two parts immediately before applying the mixture to the interior surface of the pipeline.
  • the mixture of the two parts cures on the interior surface of the pipeline to form a (e.g. monolithic) water impervious lining.
  • a (e.g. monolithic) water impervious lining may be formed when the pipeline is initially laid, or after a period of use when the pipeline itself begins to deteriorate.
  • the pipeline is typically buried underground at the time the coating composition is applied.
  • the liquid mixture can be applied at various thickness.
  • the coating is present at a caliper ranging from about 1 to 15 mm. Multiple coating layers can be applied to obtain the desired caliper.
  • the composition described herein can be applied at a caliper of at least 5 mm in a single pass forming a cured continuous lining.
  • a heated airless spray apparatus such as a centrifugal spinning head
  • an airless, impingement mixing spray system is employed and generally includes the following components: a proportioning section which meters the two components and increases the pressure to above about 1500 psi (10.34 MPa); a heating section to raise the temperatures of the two components (preferably, independently) to control viscosity; and an impingement spray gun which combines the two components and allows mixing just prior to atomization.
  • the liquid mixture e.g. coating composition
  • an impingement spray gun which combines the two components and allows mixing just prior to atomization.
  • the liquid mixture e.g. coating composition
  • an impingement spray gun which combines the two components and allows mixing just prior to atomization.
  • the first and second part typically each have a (Brookfield) viscosity ranging from about 5,000 centipoise (cps) to about 60,000 cps (using spindle 6 with a spindle speed of 20 revolutions per minute (RPM)) at the temperature at which the liquid mixture is applied.
  • the temperature at which the liquid mixture is applied typically ranges from about 15°C to 50°C.
  • Viscosity behavior of each of the two components is important for two-part spray- coating processes. With impingement mixing, the two parts should be as close as possible in viscosity at high shear rates to allow adequate mixing and even cure.
  • the plural component static mix/spray system appears to be more forgiving of viscosity differences between the two components. Characterization of viscosities as functions of shear rate and temperature can help with decisions as to starting points for temperatures and pressures of the coatings in the two part spray equipment lines.
  • 110N polyol is a propylene glycol Co., Midland, initiated, MI
  • CARPOL GSP-370 is a 1.12 Carpenter Co., glycerin/sucrose initiated Richmond, VA polyether polyol with a nominal
  • ABITOL E ABITOL E Resin is a high 1.008 Eastman
  • EAAC400-01-10-01 400 milliliter (mL) 1 to 1 Cartridge Assembly Kit available from Ellsworth Adhesives, Germantown, WI).
  • Resin formulations of the first and second part were separately blended using either a Flacktek SPEEDMIXER DAC 400 FVC mixer (Flacktek Inc., Landrum, SC) at 2500 revolutions per minute (RPM) for 2 minutes in a Flacktek MAX 100 cup (controls CT-1 to CT-3 and example EX-1) or a 3 horse power (FIP), high dispersion Ross Mixer (Charles Ross and Son Company, St. Charles, IL) equipped with a vacuum attachment (all other examples). Liquid formulation components were charged into a mixing vessel equipped with a Cowles mixing blade and vacuum was applied to the mixing vessel. The components mixed for 15 minutes at 1200 (RPM). The first and second part compositions were then loaded into opposite sides of the two-part cartridges.
  • RPM revolutions per minute
  • the cartridges were dispensed at 40°C for controls CT-1 to CT-3 and example EX- 1. All other examples were dispensed at room temperature.
  • Each sample was dispensed using a pneumatic cartridge dispenser through a 32 element static mixer (Sulzer Mixpac Static Mixer MCQ 08-32T, BrandyWine Materials, LLC, Burlington, MA).
  • the materials were injected into a closed polytetrafluoroethylene (PTFE) mold (ASTM D638-08 Type IV dogbone, ⁇ 2 mm thickness).
  • PTFE polytetrafluoroethylene
  • the parts were then demolded and stored in a desiccator for greater than 7 days prior to testing. Tags/molding excess on the samples were sanded smooth using 400 grit sandpaper.
  • a 4 inch x 4 inch x 2 millimeter (mm) (10 cm x 10 cm x 2 mm) deep coating was made using a mold with a stainless steel spatula as a drawdown bar.
  • the temperature of the coating was measured using a V&A VA6530 infrared thermometer. The maximum temperature observed was recorded.
  • Samples were stored for at least thirty days in a desiccator prior to taking measurements.
  • Tensile strength and elongation were measured from the molded samples according to ASTM D-638-14 using either a MTS 880 servohydraulic load frame (MTS, Eden Prairie, MN) or a Sintech 10/D electromechanical load frame. Strain was measured by means of an extensometer with 25.4 mm gage length for both load frames. Test control and data acquisition was performed using TestWorks 4.0 software (MTS Corp., Eden Prairie, MN).
  • Cartridges (Sulzer Mixpac EAAC400-01-10-01) filled with the first part and the second part of resin formulations were heated to 40 °C and dispensed using a variable speed screw driven plunger apparatus. Plunger speeds were set to 18 inches/min (46 cm/min).
  • the blended resin is dispensed through a static mixer (Sulzer statomix MC-18) into a centrifugal spinning cone head, the spinning cone is placed onto a translational stage that moves within the pipe interior at a fixed speed.
  • the volumetric rate of the resin in the spinning cone is determined to coincide with the translational speed of the spinning cone relative to the interior of the pipe, thus it is possible to achieve a determined coating thickness.
  • the translational speed was set to approximately 12 inches/min (30.5 cm/min), thus targeting a thickness of 8.3 mm.
  • Post-lining coating measurements were taken by cutting cross-sections of the coated pipes using a band saw and measuring with a ruler. All inventive, control, and comparative examples were generated using the general procedure described above. The values described are weight percent for each side of the two-part formulations. All formulations were dispensed using 1 : 1 volume ratio cartridges.
  • Weight percents in the tables below are of the total composition (liquid mixture of first and second part)
  • Example 12 was sprayed on a 6" PVC pipe according to the general method for spraying formulations on PVC pipes as described above. A caliper of 8 mm was obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des procédés de régulation de la vitesse de réaction d'une composition de revêtement à base de polyurée consistant à : a) fournir une composition de revêtement à base de polyurée comprenant une première partie comprenant au moins un polyisocyanate ; et une seconde partie comprenant au moins une polyamine ; et b) combiner la première partie et la seconde partie de sorte à former un mélange liquide ; la première partie, la seconde partie ou le mélange liquide comprenant en outre de 0,5 % en poids à 5 % en poids de soufre et de 0,05 à 10 % en poids % d'un constituant hydroxyle comprenant un ou plusieurs groupes hydroxyle réactifs. Dans un mode de réalisation, le procédé est utilisé pour former un revêtement sur une surface d'un pipeline par application du mélange liquide sur des surfaces internes du pipeline et par prise du mélange de sorte à former un revêtement durci. L'invention concerne également des compositions de revêtement à base de polyurée.
PCT/IB2018/056406 2017-08-25 2018-08-23 Composition de polyurée comprenant un capteur d'eau et un constituant hydroxyle et procédé WO2019038722A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762550095P 2017-08-25 2017-08-25
US62/550,095 2017-08-25

Publications (1)

Publication Number Publication Date
WO2019038722A1 true WO2019038722A1 (fr) 2019-02-28

Family

ID=65439803

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2018/056406 WO2019038722A1 (fr) 2017-08-25 2018-08-23 Composition de polyurée comprenant un capteur d'eau et un constituant hydroxyle et procédé

Country Status (1)

Country Link
WO (1) WO2019038722A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030047836A1 (en) * 2001-08-31 2003-03-13 Stephen Rickner Method for making a polyurea-polyurethane composite structure substantially free of volatile organic compounds
US20030049458A1 (en) * 2001-08-31 2003-03-13 Stephen Rickner Polyurea-polyurethane composite structure substantially free of volatile organic compounds
US20100311890A1 (en) * 2009-06-05 2010-12-09 Ppg Industries Ohio, Inc. Curable compositions that form a low modulus polyurea
US20130261270A1 (en) * 2010-12-17 2013-10-03 Sika Technology Ag Polyamines having secondary aliphatic amino groups
US20150104652A1 (en) * 2012-06-15 2015-04-16 3M Innovative Properties Company Curable polyurea forming composition, method of making, and composite article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030047836A1 (en) * 2001-08-31 2003-03-13 Stephen Rickner Method for making a polyurea-polyurethane composite structure substantially free of volatile organic compounds
US20030049458A1 (en) * 2001-08-31 2003-03-13 Stephen Rickner Polyurea-polyurethane composite structure substantially free of volatile organic compounds
US20100311890A1 (en) * 2009-06-05 2010-12-09 Ppg Industries Ohio, Inc. Curable compositions that form a low modulus polyurea
US20130261270A1 (en) * 2010-12-17 2013-10-03 Sika Technology Ag Polyamines having secondary aliphatic amino groups
US20150104652A1 (en) * 2012-06-15 2015-04-16 3M Innovative Properties Company Curable polyurea forming composition, method of making, and composite article

Similar Documents

Publication Publication Date Title
US9908146B2 (en) Composition comprising cyclic secondary amine and methods of coating drinking water pipelines
JP5193047B2 (ja) アルジミンを含む化合物を含有する湿分硬化ポリウレタン組成物
JP4242834B2 (ja) ポリアルジミンを含有するポリウレタン組成物
EP2861684B1 (fr) Composition durcissible formant de polyurée, son procédé de préparation et article composite
KR102220540B1 (ko) 장쇄 알디민을 포함하는, 지붕용의 액체 도포식 방수막
US20200354504A1 (en) Polyaspartic compositions
KR20120030045A (ko) 음용수 파이프라인을 코팅하기에 적합한 방법 및 조성물
KR102243167B1 (ko) 옥사졸리딘 및 알디민을 포함하는 액체 도포 방수막
JP2012506937A (ja) α−シランを含み、アニソトロピー材料特性を有するポリウレタン組成物
CN113227301B (zh) 由环氧树脂和聚氨酯制成的组合物
JP5319454B2 (ja) 混合多脂環式アミン（ｍｐｃａ）及びｍｐｃａアルキレート
US11827788B2 (en) Faster cure polyaspartic resins for faster physical property development in coatings
WO2019038722A1 (fr) Composition de polyurée comprenant un capteur d'eau et un constituant hydroxyle et procédé
WO2019038721A1 (fr) Composition de polyurée comprenant un constituant hydroxyle et procédés
WO2019003190A1 (fr) Composition dotée d'une résistance à la rupture en fluage et méthodes de revêtement de canalisations d'eau potable
WO2019087081A1 (fr) Composition de polyurée comprenant une charge et un composé silane réactif et procédés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18847671

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18847671

Country of ref document: EP

Kind code of ref document: A1