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WO2024011531A1 - Composites hybrides de polyuréthane-acrylate contenant des capteurs d'humidité d'oxazolidine et leurs procédés de préparation - Google Patents

Composites hybrides de polyuréthane-acrylate contenant des capteurs d'humidité d'oxazolidine et leurs procédés de préparation Download PDF

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Publication number
WO2024011531A1
WO2024011531A1 PCT/CN2022/105796 CN2022105796W WO2024011531A1 WO 2024011531 A1 WO2024011531 A1 WO 2024011531A1 CN 2022105796 W CN2022105796 W CN 2022105796W WO 2024011531 A1 WO2024011531 A1 WO 2024011531A1
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WIPO (PCT)
Prior art keywords
polyurethane acrylate
acrylate hybrid
isocyanate
group
hybrid composition
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Ceased
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PCT/CN2022/105796
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English (en)
Inventor
Nan Wang
Kunpeng GUO
Gang Sun
Hongjie HAN
Shaoguang Feng
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Priority to PCT/CN2022/105796 priority Critical patent/WO2024011531A1/fr
Priority to CN202280097789.XA priority patent/CN119486882A/zh
Publication of WO2024011531A1 publication Critical patent/WO2024011531A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
    • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
    • 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
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • 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
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
    • 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
    • C08G18/4829—Polyethers containing at least three 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

  • Embodiments relate to polyurethane acrylate hybrid compositions containing oxazolidine moisture scavengers.
  • Polyurethane (PU) hybrid resin systems containing acrylic monomers have wide applicability and provide a range of cure times, low heat release, good surface quality, toughness, and fatigue resistance.
  • PU acrylate hybrid systems may be used in several fields including composite materials manufacturing processes requiring long open time, such as vacuum infusion or pultrusion for the manufacturing of articles for window frames, home appliances, furniture, and wind turbine blades. While PU acrylate hybrid materials have certain advantages, they also have drawbacks: in particular, moisture control is difficult because moisture may be present not only in the PU formulation, but also in the various other components of the composite, such as core materials, fiber reinforced materials, and flow media. The presence of moisture produces unwanted byproducts with the isocyanate components, leading to several physical and mechanical defects. The increased costs associated with dehydration and humidity controls can reduce the advantages of such materials.
  • Embodiments disclosed herein include polyurethane acrylate hybrid compositions, including a reaction product of: an isocyanate component including one or more isocyanate compounds and one or more initiators; and an isocyanate-reactive component including: one or more polyether polyols and/or polyester polyols; one or more hydroxy functional acrylate monomers according to formula:
  • R 1 is selected from hydrogen, methyl or ethyl
  • R 2 is selected from alkylene groups having 2-6 carbon atoms, 2, 2-bis (4-phenylene) propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene, and n is an integer selected from 1-6; and one or more moisture scavengers according to the formula:
  • R 1 is a hydrogen, methyl group, a branched or straight chain alkyl or alkanol group, or forms a 4 to 7 member cycle with R 2 ;
  • R 2 , R 3 , R 4 and R 6 are, individually, a hydrogen atom, a methyl or group, a straight chain or branched chain alkyl or alkanol group, a cyclic alkyl, or an aryl group;
  • R 5 is a methyl or methylol group, or a branched chain or straight chain alkyl or alkanol group;
  • R 7 is a hydrogen atom, a straight chain or branched chain alkyl or alkanol group, a cyclic alkyl group, a carbonyl group, or an aryl group.
  • Embodiments relate to PU acrylate hybrid systems containing moisture scavengers to reduce moisture sensitivity and improve appearance and mechanical properties of articles formed therefrom.
  • PU acrylate hybrid systems include one or more oxazolidine-based moisture scavengers that can be combined with isocyanate-reactive components and sequester residual moisture.
  • oxazolidine-based moisture scavengers react with moisture to generate amine-and hydroxyl-containing species that can then react with one or more isocyanate components, such as diisocyanates, polyisocyanates, or polyurethane prepolymers. Side reactions with the moisture scavenger thus prevents the formation of carbon dioxide from the reaction between isocyanate and water.
  • PU acrylate hybrid compositions may be generated by reacting an isocyanate component with an isocyanate-reactive component containing one or more moisture scavengers.
  • Isocyanate components can include at least one compound having an isocyanate group.
  • the isocyanate component may include one or more isocyanates and polyisocyanates having an average of at least 2.0 isocyanate groups per molecule.
  • the isocyanate components may contain moieties that are aliphatic, cycloaliphatic, alicyclic, arylaliphatic, aromatic, and/or derivatives thereof.
  • the isocyanate components contains moieties where the NCO group is directly attached to an aromatic ring.
  • Examples of compounds suitable for use in isocyanate components include monomeric methylene diphenyl diisocyanate (MDI) , modified MDI, oligomeric MDI, polymeric MDI, toluene 2, 4-/2, 6-diisocyanate (TDI) , and the like.
  • Isocyanates may have an average isocyanate functionality from 2 to 5, 2.2 to 5, or 2.2 to 4.
  • the isocyanate can have an isocyanate equivalent weight (EW) in a range of 75 g/eq to 250 g/eq, 80 g/eq to 200 g/eq, or 80 to 175 g/eq.
  • EW isocyanate equivalent weight
  • the isocyanate component may include one or more prepolymers formed by reaction of a polyisocyanate compound and a polyol, including, for example, the reaction of 4, 4’-MDI and tripropylene glycol, or a reaction of ethylene oxide capped propoxylated glycerine and 4, 4’-MDI.
  • Prepolymers may have an NCO content of 5 wt%to 30 wt%, 10 wt%to 25 wt%, or 15 wt%to 25 wt%.
  • An isocyanate component may include a prepolymer at a percent by weight (wt%) in a range of 5 wt%to 70 wt%, 10 wt%to 65 wt%, or from 15 wt%to 60 wt%.
  • Isocyanate-reactive components may include a polyol blend containing one or more polyether polyols and/or polyester polyols at a percent by weight of the blend (wt%) in a range of 35 wt%and 75 wt%, and one or more hydroxy functionalized (meth) acrylates in a range of 35 wt%and 75 wt%.
  • wt% percent by weight of the blend
  • meth hydroxy functionalized
  • Isocyanate-reactive components may include one or more polyether polyols prepared by polyaddition of alkylene oxides such as propylene oxide and/or ethylene oxide onto polyhydroxy functional starter compounds in the presence of catalysts known in the art.
  • Polyether polyols may be prepared from a starter compound and one or more alkylene oxides, for example, ethylene oxide, butylene oxide, and/or propylene oxide.
  • Starter compounds may include molecules having 2 to 8 hydroxyl groups per molecule such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, l, 4-butanediol, l, 6-hexanediol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol, sugars and sugar alcohols such as sucrose and sorbitol, and the like
  • Polyether polyols may have an average hydroxyl number (OH number) as determined according to ASTM D4274-21 in a range of 100 mg KOH/g to 500 mg KOH/g, 150 mg KOH/g to 450 mg KOH/g, or 200 mg KOH/g to 450 mg KOH/g.
  • OH number average hydroxyl number
  • Polyester polyols disclosed herein include reaction products one or more carboxylic diacids and a polyol having a with OH functionality 2 to 4.
  • Suitable carboxylic acids may include aromatic diacids or anhydrides and C4 to C12 aliphatic diacids.
  • Suitable polyols for the formation of polyesters include one or more alkylene glycols or polyalkylene glycols having a hydroxy functionality of 2 to 4, such as ethylene glycol, 1, 2-or 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, glycerine, and the like.
  • Example polyester polyols include polyesters of phthalic anhydride and diethylene glycol, and polyesters of a C4 to C12 diacid such as succinic acid or adipic acid and diethylene glycol.
  • Polyester polyols may have an average hydroxyl number (OH number) as determined according to ASTM D4274-21 in a range of 100 mg KOH/g to 500 mg KOH/g, 150 mg KOH/g to 450 mg KOH/g, or 200 mg KOH/g to 450 mg KOH/g.
  • OH number average hydroxyl number
  • Isocyanate-reactive components may include one or more polyester polyols at a percent by weight (wt%) ranging from 10 wt%to 40 wt%, from 15 wt%to 35 wt%, or from 15 wt%to 30 wt%.
  • the isocyanate-reactive component may include one or more hydroxy functional (meth) acrylate monomers that react with the isocyanate component and/or polymerize in the presence of a free radical initiator to produce a PU acrylate hybrid composition.
  • Hydroxy functional (meth) acrylate monomers may have the general structure:
  • R1 is selected from hydrogen, methyl or ethyl
  • R2 is selected from alkylene groups having 2-6 carbon atoms, 2, 2-bis (4-phenylene) propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene
  • n is an integer selected from 1-6.
  • Hydroxy functional (meth) acrylate monomers may include hydroxy C1-10 alkyl (meth) acrylate monomers, such as hydroxyethyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate monomer, and the like.
  • Hydroxy functional (meth) acrylates may be added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 15 wt%to 40 wt%, from 20 wt%to 38 wt%, from 25 wt%to 35 wt%, or from 27 wt%to 32 wt%.
  • the isocyanate-reactive component includes one or more moisture scavengers containing oxazolidine rings, oxazolidine derivatives, and combinations of any other type of moisture scavenger with oxazolidines or their derivatives.
  • Moisture scavengers include compounds described by the formula:
  • R 1 is a hydrogen, methyl group, a branched or straight chain alkyl or alkanol group, or forms a 4 to 7 member cycle with R 2 ;
  • R 2 , R 3 , R 4 and R 6 are, individually, a hydrogen atom, a methyl or group, a straight chain or branched chain alkyl or alkanol group, a cyclic alkyl, or an aryl group;
  • R 5 is a methyl or methylol group, or a branched chain or straight chain alkyl or alkanol group;
  • R 7 is a hydrogen atom, a straight chain or branched chain alkyl or alkanol group, a cyclic alkyl group, a carbonyl group, or an aryl group.
  • Moisture scavengers may be added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 0.05 wt%to 15 wt%, 0.1 wt%to 10 wt%, or 1 wt%to 10 wt%.
  • Polyurethane acrylate hybrid compositions may include one or more initiators (e.g., free radical initiators) added to the isocyanate component.
  • the initiator includes but is not limited to peroxides, persulfides, peroxycarbonates, peroxyboric acid, azo compounds or other suitable radical initiators that can initiate curing of a double bond-containing compound. Suitable initiators include azo compound or peroxide.
  • the azo compound can be 2, 2-azobisisobutyronitrile (AIBN) ;
  • the peroxide can be selected from the group consisting of tert-butyl peroxybenzoate, butyl 4, 4-di (tert-butylperoxy) valerate, di-tert-amyl peroxide, dicumyl peroxide, di (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (tert-butylperoxyl) hexane, tert-butyl cumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxyl) hexyne-3, di-tert-butyl peroxide, 3, 6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, isopropylcumyl hydroperoxide, 1, 1, 3, 3-tetramethylbutyl hydroperoxide, cum
  • Polyurethane acrylate hybrid compositions may include an initiator at a percent by weight (wt%) that is larger than zero, including at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt%, and at most 6.0 wt%, at most 5.0 wt%, or at most 4.0 wt%.
  • wt% percent by weight
  • Isocyanate-reactive components may include one or more accelerators, including metal salts, such as cobalt salts and zinc salts that catalyze radical polymerization reactions. Accelerators may be added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 0 wt%to 0.15 wt%, 0.001 wt%to 0.10 wt%, or 0.01 wt%to 0.05 wt%.
  • Catalysts for promoting PU reactions may also be added, including amine catalysts, organometallic catalysts or a mixture thereof.
  • Amine catalysts may include one or more of triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, N-methylaniline, N, N-dimethylaniline, and the like.
  • Organometallic catalysts may include an organotin compound, e.g.
  • Catalysts may be added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 0 wt%to 0.15 wt%, 0.001 wt%to 0.10 wt%, or 0.01 wt%to 0.05 wt%.
  • the isocyanate-reactive component may also contain one or more additives including blowing agents, surfactants, crosslinkers, plasticizers, fillers, smoke suppressants, fragrances, reinforcements, dyes, colorants, pigments, preservatives, odor masks, physical blowing agents, chemical blowing agents, flame retardants, internal mold release agents, biocides, antioxidants, UV stabilizers, antistatic agents, thixotropic agents, adhesion promoters, cell openers, and the like.
  • additives including blowing agents, surfactants, crosslinkers, plasticizers, fillers, smoke suppressants, fragrances, reinforcements, dyes, colorants, pigments, preservatives, odor masks, physical blowing agents, chemical blowing agents, flame retardants, internal mold release agents, biocides, antioxidants, UV stabilizers, antistatic agents, thixotropic agents, adhesion promoters, cell openers, and the like.
  • PU acrylate hybrid compositions may include one or more silicone or organic defoamers added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 0.05 wt%to 5 wt%, 0.1 wt%to 1.5 wt%, or 0.1 wt%to 1 wt%.
  • PU acrylate hybrid compositions may be used in any suitable process for developing articles and composites, including molding, injection, vacuum infusion, pultrusion, and the like.
  • PU acrylate hybrid compositions may be prepared by combining the isocyanate component and the isocyanate-reactive component to form a mixture; processing the mixture in a mold to produce a molded article; and demolding the molded article.
  • PU acrylate hybrid compositions may be used to prepare a molded composite part.
  • the polyurethane-poly (meth) acrylate reactive composition is mixed with a reinforcement material or injected into the reinforcement material, e.g., by vacuum assisted resin transfer molding (VARTM) and /or resin transfer molding (RTM) .
  • Suitable reinforcement materials include any one or more of glass fibers, carbon nanotubes, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, metal fibers, and the like.
  • Composite articles prepared using the inventive PU acrylate hybrid compositions may include one or more reinforcement materials at a percent by weight (wt%) in a range of 1 wt%to 90 wt%, 30 wt%to 90 wt%, 50 wt%to 85 wt%, or 50 wt%to 80 wt%.
  • Composite articles prepared using the inventive PU acrylate hybrid compositions may further include one or more core materials that facilitates the molding and weight reduction of a composite material.
  • Core materials may include polystyrene foams, polyester PET foams, polyimide PMI foams, polyvinyl chloride foam, metal foams, celluloses, woods such as balsa wood, and the like.
  • Polyurethane acrylate hybrid compositions may produce articles and composites having excellent mechanical properties, e.g. a high thermal deformation temperature, high tensile and flexural strength, high resistance to fatigue, high ductility, and low shrinkage rate.
  • Articles and composites may be used in the manufacture of wind generator blades, wind generator nacelle housings, watercraft propeller blades, hulls, interior and exterior automobile decorative parts, automobile bodies, radomes, machinery structural members, decorative parts and structural members for architectures and bridges, and the like.
  • Table 1 provides the materials used in the following examples.
  • Example 1 Properties of clear cast polyurethane acrylate hybrid compositions
  • the clarity of a cast inventive samples (IS1) containing a moisture scavenger is assayed against a comparative sample (CS2) formulated with no moisture scavenger.
  • Samples were prepared by blending formulation components in the proportions specified in Table 2, with all units in grams unless otherwise specified. Sample volumes were prepared at 200 gram scale and blended by speed mixer. The obtained liquid resin was degassed for 6 minutes and cast to 4.5 mm thickness in a flat sheet mold. Samples were cured in a 70 °C oven for 6 hours until fully cured.
  • Samples were then demolded and visually inspected for clarity.
  • Sample CS1 exhibited a distinct haze and numerous bubble defects.
  • IS1 exhibited high transparency and no visible bubbles or defects.
  • laminates are prepared containing one or more PU acrylate hybrid layers.
  • Four layers of uni-direction glass fiber fabrics (1200gsm, 0°) with length-width of 500-500 mm were laid on a mold, followed by a piece of release film with length-width of 500-500mm, a third layer containing peel ply, and a third layer of flow mesh.
  • An injection hose with a length of 300 mm was obtained by cutting and secured next to the flow mesh by two loops of adhesive sealing strips around each layer laid in the mold. The layers were then sealed with two layers of vacuum bag film.
  • a vacuum pump was connected to the injection hose and the system was depressurized to 0 to 20 mbar, while degassed PU acrylate hybrid compositions from Example 1 (CS1 or IS1) were injected directly. Injection was followed by curing at 70°C for 6 hours, then demolding. Auxiliary materials such as peel plies and flow meshes were then removed and the resulting laminate was cut into specimens based on the corresponding testing standards.
  • the oxazolidine-based moisture scavenger improved appearance and mechanical quality.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions hybrides d'acrylate de polyuréthane comprenant un produit de réaction de : un composant isocyanate comprenant un ou plusieurs composés isocyanates et un ou plusieurs initiateurs ; et un composant réactif à l'isocyanate contenant un ou plusieurs polyols de polyéther et/ou polyols de polyester ; un ou plusieurs monomères d'acrylate à fonctionnalité hydroxy ; et un ou plusieurs capteurs d'humidité.
PCT/CN2022/105796 2022-07-14 2022-07-14 Composites hybrides de polyuréthane-acrylate contenant des capteurs d'humidité d'oxazolidine et leurs procédés de préparation Ceased WO2024011531A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2022/105796 WO2024011531A1 (fr) 2022-07-14 2022-07-14 Composites hybrides de polyuréthane-acrylate contenant des capteurs d'humidité d'oxazolidine et leurs procédés de préparation
CN202280097789.XA CN119486882A (zh) 2022-07-14 2022-07-14 含有噁唑烷水分清除剂的聚氨酯丙烯酸酯混合复合物及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/105796 WO2024011531A1 (fr) 2022-07-14 2022-07-14 Composites hybrides de polyuréthane-acrylate contenant des capteurs d'humidité d'oxazolidine et leurs procédés de préparation

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WO2024011531A1 true WO2024011531A1 (fr) 2024-01-18

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PCT/CN2022/105796 Ceased WO2024011531A1 (fr) 2022-07-14 2022-07-14 Composites hybrides de polyuréthane-acrylate contenant des capteurs d'humidité d'oxazolidine et leurs procédés de préparation

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CN (1) CN119486882A (fr)
WO (1) WO2024011531A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070225443A1 (en) * 2005-11-30 2007-09-27 Ashland Licensing And Intellectual Property Llc Prepregs and cured in place solid surfaces prepared therefrom
US20210061942A1 (en) * 2017-09-12 2021-03-04 Covestro Deutschland Ag Composite material comprising a polyurethane-polyacrylate resin matrix
CN110791251B (zh) * 2019-10-30 2021-11-26 广东普赛达密封粘胶有限公司 一种丙烯酸酯改性聚氨酯密封胶及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070225443A1 (en) * 2005-11-30 2007-09-27 Ashland Licensing And Intellectual Property Llc Prepregs and cured in place solid surfaces prepared therefrom
US20210061942A1 (en) * 2017-09-12 2021-03-04 Covestro Deutschland Ag Composite material comprising a polyurethane-polyacrylate resin matrix
CN110791251B (zh) * 2019-10-30 2021-11-26 广东普赛达密封粘胶有限公司 一种丙烯酸酯改性聚氨酯密封胶及其制备方法

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