[go: up one dir, main page]

WO2025007334A1 - Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation - Google Patents

Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation Download PDF

Info

Publication number
WO2025007334A1
WO2025007334A1 PCT/CN2023/106028 CN2023106028W WO2025007334A1 WO 2025007334 A1 WO2025007334 A1 WO 2025007334A1 CN 2023106028 W CN2023106028 W CN 2023106028W WO 2025007334 A1 WO2025007334 A1 WO 2025007334A1
Authority
WO
WIPO (PCT)
Prior art keywords
isocyanate
lewis acid
polyol
composite
polyether polyol
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/CN2023/106028
Other languages
English (en)
Inventor
Abhishek DHYANI
An Nguyen KAGA
Thomas Willumstad
Masayuki Suzuki
Wang Yun
Hongjie HAN
Sun GANG
Enrico BAGGIO
Paolo Diena
Richard Keaton
Guido Bramante
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to PCT/CN2023/106028 priority Critical patent/WO2025007334A1/fr
Publication of WO2025007334A1 publication Critical patent/WO2025007334A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/521—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/525—Component parts, details or accessories; Auxiliary operations
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having 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
    • C08G18/28—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
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having 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
    • C08G18/28—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
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • Embodiments relate to polyurethane and polyurethane/ (methacrylate) hybrid compositions used in the fabrication of polyurethane composites and reinforced materials having improved mechanical properties.
  • Polyurethane (PU) formulations may be manufactured into reinforced composites by a variety of fabrication processes, which include processes such as pultrusion, infusion and filament winding.
  • Pultrusion is a continuous manufacturing process to make fiber reinforced polymer composite profiles with constant cross-sectional area, which are often used in structural applications.
  • Infusion is a process where the PU resin is brought into contact with and impregnated into fibers by application of vacuum, and it is applied for manufacturing articles such as wind blades.
  • Filament winding is instead typically applied to manufacturing items such as pipes or closed end structures (pressure vessels or tanks) in a process that involves winding filaments, pre-impregnated with resin, over a rotating mandrel.
  • embodiments of the present disclosure include methods of forming a composite comprising: preparing a reacting mixture by combining: an isocyanate component; and an isocyanate-reactive component that includes at least one Lewis acid catalyzed polyether polyol having a percent by weight (wt%) of 90 wt%or more polypropylene oxide, a primary hydroxy concentration of at least 30 wt%, a functionality of at least 2, an OH number in the range of 100 mg KOH/g to 800 mg KOH/g, and an average acetal content of at least 0.05 wt%; and combining the reacting mixture with one or more reinforcing materials.
  • wt% percent by weight
  • Embodiments relate to two component polyurethane and polyurethane/ (meth) acrylate hybrid compositions for use in composite manufacture that include Lewis acid catalyzed polyether polyols produced by polymerization in the presence of a perfluoroalkyl-substituted arylborane catalyst.
  • Polymer-forming composition include an isocyanate component and an isocyanate reactive component that includes at least Lewis acid catalyzed polyether polyol.
  • Lewis acid catalyzed polyether polyols disclosed herein may have a percent by weight (wt%) of 90 wt%or more polypropylene oxide, a primary hydroxy concentration of at least 30 wt%, a functionality of at least 2, an OH number in the range of 100 mg KOH/g to 800 mg KOH/g, and an average acetal content of at least 0.05 wt%.
  • Methods also include the formation of a composite that include combining the components in the presence of a reinforcement material using a suitable process such as infusion, pultrusion, or filament winding.
  • a Lewis acid polymerization catalyst e.g., perfluoroalkyl-substituted arylborane catalysts
  • the use of a Lewis acid polymerization catalyst to produce polyether polyols may improve polyol reactivity with the isocyanate component, particularly for polypropylene oxide based (or containing) polyether polyols, by increasing the percentage of primary hydroxyl groups. Increased concentrations of primary hydroxyl groups are associated with faster cure times and improved appearance of the final product. Comparative formulations that include concentrations of polyethylene oxide to increase the percentage of primary OH terminal functional groups, producing some decrease in demold time during manufacture.
  • the Lewis acid catalyst may be an arylborane catalyst that has at least one fluoro/chloro or fluoroalkyl-substituted phenyl group, which may allow for improvements in the yield of the reaction.
  • the polymerization catalyst may be fed into the reactor in an amount greater than 0 and less than or equal to 0.005 (e.g., greater than 0.0001, less than or equal to 0.003, less than or equal to 0.001, etc. ) molar equivalents per mole of the initiator feed into the reactor.
  • the Lewis acid catalyst may be active at a lower temperature range (e.g., from 60 °C-110 °C) .
  • functional group or functional polymer group it is meant a molecule that contains at least one of the following: water, an alcohol, an alkoxy (examples include a linear or branched ether and a cyclic ether) , a ketone, an ester, an organosiloxane, an amine, a phosphine, an oxime, and substituted analogs thereof.
  • Each of the alcohol, linear or branched ether, cyclic ether, ketone, ester, alkoxy, organosiloxane, and oxime may include from 2-20 carbon atoms, from 2-12 carbon atoms, from 2-8 carbon atoms, and/or from 3-6 carbon atoms.
  • Anthraquinone curing indicators may be added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 0.001 wt%to 0.15 wt%, 0.001 wt%to 0.10 wt%, or 0.01 wt%to 0.05 wt%.
  • Methods of the present disclosure may include the formation of composite articles and materials by any suitable method.
  • composite part are prepared by combining isocyanate and isocyanate-reactive compounds to form a reactive mixture that is then combined with a reinforcement material.
  • Suitable reinforcement materials include any one or more of glass fibers, e-glass fibers, carbon nanotubes, carbon fibers, polyester fibers, natural fibers, glass fibers, aramid fibers, nylon fibers, mineral fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, metal fibers, and the like.
  • Methods of composite formation may include vacuum assisted resin transfer molding (VARTM, also known as infusion) , pultrusion, filament winding or braiding, reinforced reaction injection molding (RRIM) , structural reaction injection molding (SRIM) , resin transfer molding (RTM) , cured-in-place pipe applications, reactive extrusion, and other reactive processing techniques.
  • VARTM vacuum assisted resin transfer molding
  • RRIM reinforced reaction injection molding
  • SRIM structural reaction injection molding
  • RTM resin transfer molding
  • cured-in-place pipe applications reactive extrusion, and other reactive processing techniques.
  • Reactive processing techniques can include the production of a composite in a single step, such as polymeric material formation and reinforcement that occur in the same step or cycle.
  • a pultrusion process may include drawing pre-selected reinforcement materials, such as fiberglass roving, mat or cloth, through a resin bath in which the reinforcement material is thoroughly impregnated with a toughened PU or PU/ (meth) acrylate hybrid composition.
  • the wet-out fiber may then be formed to the desired geometric shape and pulled into a heated steel die.
  • curing of the toughened composition is initiated by controlling the temperature within the die.
  • the laminate solidifies in the shape of the die, as it is continuously pulled by the pultrusion machine.
  • Compositions and methods have been discussed with respect to examples of polyurethane composites produced by infusion or pultrusion, however, it is envisioned that polyurethane composites may be produced by any suitable method without departing from the scope of this disclosure.
  • a cured article prepared from the curable resin composition can be used to produce composites, articles, coatings, adhesives, inks, encapsulations, or castings.
  • the composites can be used in applications such as, for example, wind turbines (e.g., spar caps, wind blades) , boat hulls, truck bed covers, automobile trim and exterior panels, pipe, tanks, window liners, seawalls, pressure vessels, composite ladders and the like.
  • formulation components and properties have been disclosed individually, it is envisioned that component elements (e.g., compounds in isocyanate or isocyanate-reactive components) may be included, excluded, or combined in any manner or subcombination utilizing any of the above concentration ranges and nested subranges therein. Further, that the recited formulation properties may be similarly achieved through various combinations of the recited components within the recited ranges.
  • component elements e.g., compounds in isocyanate or isocyanate-reactive components
  • Table 1 provides the materials used in the following examples.
  • polyurethane compositions were prepared to analyze the properties of inventive and comparative samples containing polypropylene oxide-based polyols.
  • inventive samples I1-I3 were formulated with Lewis acid-catalyzed PO-based polyol at three different loading levels, from 20 parts to 55 parts, and results were contrasted with comparative formulations (C1-C3) formulated with Polyol 2 (having the same OH number and functionality, but prepared by KOH catalysis) .
  • Formulations are shown in Table 2.
  • samples were generally prepared by mixing the respective components of the isocyanate-reactive component using a DAC 600.1 FVZ-K speedmixer until evenly dispersed. The isocyanate component was then combined in the specified ratio and mixed. The mixture was poured into the appropriate mold and the mold was transferred to an oven at 100°C for 90 minutes. The plaques were then demolded and the test specimen shapes were water jet-cut accordingly.
  • Viscosity rise was measured on a Brookfield DV-II+ Pro viscometer. For each samples, the isocyanate and isocyanate-reactive components were mixed as per Table 5 at 2350 RPM for 15 seconds to ensure same sample temperature each time. 10-10.5 grams of the mixture (depending on the mix ratio) was poured into a disposable chamber (HT-2DB-100) , and then dropped into a Thermosel (Brookfield Engineering) . The temperature of the Thermosel was maintained at an isothermal 26 °C. The disposable spindle (SC4-27) was then used to measure the viscosity rise with time.
  • DMA Dynamic Mechanical Analysis
  • RAS-G2 Advanced Rheometric Expansion System
  • a rectangular sample from the foams prepared in metal mold at 3 mm thickness were punched (45 mm length and 12.8 mm width) .
  • the temperature was increased from -70 °C to 200 °C at a ramp rate of 3 °C/min.
  • the frequency of testing was 1 Hz and axial force of 0.098 N with 0.05%strain at a data collection interval of 30 sec per point.
  • the major output identified from the characterization were the storage modulus in shear mode (G’) and Tan ⁇ .
  • Tensile modulus, Elongation at break, Ultimate tensile strength The elongation at break (%) , ultimate tensile strength (MPa) and tensile modulus (MPa) were all obtained using ASTM D1708 standard on MTS machine. The cured samples of 3 mm thickness post molding (and min 2 days of ageing at ASTM conditions) to test. The microtensile samples were punched in a dog-bone shape.
  • IZOD impact test Samples were molded into 45mm length and 12.7mm width and 3mm thickness. The samples were notched at a notch length of 2.54 mm at the center of the sample. For notching, the CEAST Notchvis automatic notcher (POR-TL-090) was used. The Model 92T with the Model 892 Impact Display System was used to measure impact resistance in accordance with ASTM D256 (Method for Determining the Izod Pendulum Impact Resistance of Plastics) at 23°C and 50%relative humidity.
  • ASTM D256 Method for Determining the Izod Pendulum Impact Resistance of Plastics
  • I1-I3 feature a better reactivity profile (the reactivity is faster) , with an impact that is proportional to the amount of Lewis acid catalyzed polyol in the formulation.
  • the open time remains acceptable, as the mix viscosity is ⁇ 1000 cPs after 10 minutes, and the inventive samples exhibit unexpectedly improved polymer properties that include higher glass transition temperature, modulus, elongation, and tensile strength.
  • the compatibility/miscibility of various isocyanate-reactive component formulations were tested by combining the formulation components as shown in Tables 4 and 5 according to the methods described in Example 1. Following combination, the formulations were sealed in glass vials and left to sit on a horizontal surface at room temperature for a period 1 week. Samples were inspected visually for phase separation and discoloration.
  • formulations incorporated various concentrations of polyol 2 (C4-C6) , polyol 4 (C7-C9) , and the Lewis acid-catalyzed polyol (I4-I6) .
  • the ratio of polyol 1 and polyol 3 was kept about constant in all formulations.
  • isocyanate-reactive components prepared using a primary polyol component of Lewis acid-catalyzed polyol were stable, with no visual phase separation nor discoloration/color change at 20wt%loading, at 40 %loading and at 55 %loading.
  • samples C7-C9 formulated with polyol 4 (a glycerine initiated polyol, all EO) at 20wt%, 40 wt%, and 55 wt%loading displayed phase separation few days after preparation.
  • the extent of the phase separation was estimated of about 15%by volume or higher depending on the polyol loading.
  • the presence of phase separation represents a problem for a formulated resin to be used in composite application.
  • the samples also displayed progressive discoloration and turned slightly yellow with time, indicating unwanted side reactions.
  • the phase separation is believed to be due to the poor compatibility of the all EO polyol with the other formulation ingredients.
  • phase separation limits its usefulness in composite-forming applications.
  • Example 3 Compact composite formulations designed for infusion applications
  • hybrid polyurethane/acrylate formulations were prepared as compact composites and various performance parameters were measured. Polymer samples were prepared substantially as described in Example 1. Formulations and results are shown in Table 6.
  • Tensile and impact properties 1. After chemicals temperature is at 25C, 100g isocyanate and 100g formulated polyol added in 1000ml Speedmixer cup. The mixture will be mixed by Speedmixer at 1500rpm for 1min. 2. Remove the bubble in PU resin by vacuum, then pour the resin into steel mold. The dimension of the mold cavity is 20 cm x 20cm x 0.4cm 3 . The resin will gel and cure in the mold following the cure cycles: 2 hours at 50°C + 6 hours at 70°C. 4. Demolding to get casting plate for test. 5. The test specimen was machined according to ISO527 and ISO179 from cured casting plate. 6. Carry out test and record related mechanical properties.
  • Impact properties test condition ISO 179, Impact speed: 2.9m/s, Impact energy: 4J.
  • I7 containing the Lewis acid-catalyzed polyol exhibits a relatively longer open time over C10 followed by a faster cure.
  • Table 6 also shows that the Lewis acid-catalyzed polyol unexpectedly leads to the formation of polymer with improved mechanical properties compared to polyol 2 both in strength and in elongation. It is desirable that formulations for composite fabrication techniques such as infusion or pultrusion have longer open times and slow viscosity buildup are preferred for enabling fiber wetting and rheology during processing. Moreover, after the gelling reaction initiates, it is important that the formulation cure quickly, have excellent final mechanical properties, good wetting performance, and no bubble formation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mathematical Physics (AREA)
  • Physics & Mathematics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Des procédés selon l'invention peuvent comprendre la préparation d'un mélange réactionnel par combinaison : d'un composant isocyanate ; et d'un composant réactif à l'isocyanate qui comprend au moins un polyol de polyéther catalysé par acide de Lewis ayant un pourcentage en poids (% en poids) égal ou supérieur à 90 % en poids d'oxyde de polypropylène, une concentration en hydroxy primaire d'au moins 30 % en poids, une fonctionnalité d'au moins 2, un indice OH dans la plage de 100 mg KOH/g à 800 mg KOH/g et une teneur moyenne en acétal d'au moins 0,05 % en poids ; et la combinaison du mélange réactionnel avec un ou plusieurs matériaux de renforcement.
PCT/CN2023/106028 2023-07-06 2023-07-06 Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation Pending WO2025007334A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/106028 WO2025007334A1 (fr) 2023-07-06 2023-07-06 Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/106028 WO2025007334A1 (fr) 2023-07-06 2023-07-06 Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation

Publications (1)

Publication Number Publication Date
WO2025007334A1 true WO2025007334A1 (fr) 2025-01-09

Family

ID=87863470

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/106028 Pending WO2025007334A1 (fr) 2023-07-06 2023-07-06 Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation

Country Status (1)

Country Link
WO (1) WO2025007334A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6169124B1 (en) * 1996-12-13 2001-01-02 Basf Aktiengesellschaft Inner parting agents for producing self-parting moldings made of polyisocyanate polyaddition products
WO2008105843A1 (fr) * 2007-02-26 2008-09-04 Bayer Materialscience Llc Mousse hybride de polychlorure de vinyle/polyuréthanne à propriétés de combustion améliorées
WO2011137011A1 (fr) * 2010-04-29 2011-11-03 Dow Global Technologies Llc Polyols hybrides de polyester-polyéther
WO2019055725A1 (fr) 2017-09-14 2019-03-21 Northwestern University Procédé de fabrication de polyols
WO2019055727A1 (fr) 2017-09-14 2019-03-21 Dow Global Technologies Llc Procédé de préparation de polyols
WO2020068493A1 (fr) * 2018-09-28 2020-04-02 Dow Global Technologies Llc Polyuréthanes et procédé de fabrication de polyuréthanes
US20220064365A1 (en) * 2018-12-20 2022-03-03 Basf Se Compact polyurethane

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6169124B1 (en) * 1996-12-13 2001-01-02 Basf Aktiengesellschaft Inner parting agents for producing self-parting moldings made of polyisocyanate polyaddition products
WO2008105843A1 (fr) * 2007-02-26 2008-09-04 Bayer Materialscience Llc Mousse hybride de polychlorure de vinyle/polyuréthanne à propriétés de combustion améliorées
WO2011137011A1 (fr) * 2010-04-29 2011-11-03 Dow Global Technologies Llc Polyols hybrides de polyester-polyéther
WO2019055725A1 (fr) 2017-09-14 2019-03-21 Northwestern University Procédé de fabrication de polyols
WO2019055727A1 (fr) 2017-09-14 2019-03-21 Dow Global Technologies Llc Procédé de préparation de polyols
WO2020068493A1 (fr) * 2018-09-28 2020-04-02 Dow Global Technologies Llc Polyuréthanes et procédé de fabrication de polyuréthanes
US20220064365A1 (en) * 2018-12-20 2022-03-03 Basf Se Compact polyurethane

Similar Documents

Publication Publication Date Title
US9856357B2 (en) Polyurethane resin composition and polyurethane composite prepared from the same
EP3013880B1 (fr) Préparations à base de polyuréthane obtenues par extrusion par étirage pour la production d'articles présentant une meilleure adhésion de revêtement et articles produits avec ces préparations
US4076660A (en) Non-elastomeric rapid-setting polyurethanes
KR102344130B1 (ko) 폴리우레탄에 기초한 인발성형된 제품의 제조 방법
EP3898747B1 (fr) Polyuréthane compact
CN114207032A (zh) 聚氨酯组合物、用所述聚氨酯组合物制备的产品和所述产品的制备方法
JP7023237B2 (ja) 繊維複合構成部品の製造方法
JP6527886B2 (ja) 発泡が減少した多相ポリウレタン組成物
CN111171268B (zh) 一种耐热聚氨酯软质泡沫及其制备方法
JP7746546B2 (ja) ポリウレタン組成物、これを用いて調製したコンポジット材料及びその調製方法
EP3733729A1 (fr) Procédé de préparation d'un composite de polyuréthane pultrudé
WO2025007334A1 (fr) Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation
CN109642006A (zh) 具有耐高温性的聚氨酯材料
WO2025007333A1 (fr) Composites formés à l'aide de polyols polymérisés par acide de lewis et leurs procédés de préparation
EP3947508A1 (fr) Procédé de préparation d'un composite de polyuréthane pultrudé
WO2024182217A1 (fr) Polyuréthane à tg élevée pour hp-rtm
JP7465947B2 (ja) ポリウレタン組成物、それを用いて調製された製品およびその調製方法
CN115667348A (zh) 聚氨酯形成体系、包含聚氨酯形成体系和纤维增强材料的复合材料及其生产方法和用途
KR20210019036A (ko) 이소시아네이트 프리폴리머, 습기 경화형 폴리우레탄 및 이를 포함하는 친환경 접착제 조성물
JP7753198B2 (ja) Ｐｕ複合樹脂
WO2024182229A1 (fr) Résines de polyisocyanurate de polyuréthane pour pultrusion de composites de fibres continues présentant une conservation stable et longue
WO2025093350A1 (fr) Catalyseur thermolatent pour la préparation de polyuréthane
EP3854830A1 (fr) Formulations de polyuréthane aux propriétés d'écoulement améliorées et pièces moulées en polyuréthane fabriquées à partir de celles-ci
WO2021222192A1 (fr) Compositions de polyuréthane

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: 23762139

Country of ref document: EP

Kind code of ref document: A1