WO2018219756A1 - Pré-imprégné de polyuréthane, procédé de préparation et applications associés - Google Patents

Pré-imprégné de polyuréthane, procédé de préparation et applications associés Download PDF

Info

Publication number
WO2018219756A1
WO2018219756A1 PCT/EP2018/063569 EP2018063569W WO2018219756A1 WO 2018219756 A1 WO2018219756 A1 WO 2018219756A1 EP 2018063569 W EP2018063569 W EP 2018063569W WO 2018219756 A1 WO2018219756 A1 WO 2018219756A1
Authority
WO
WIPO (PCT)
Prior art keywords
motor vehicle
polyurethane
weight
parts
methyl
Prior art date
Application number
PCT/EP2018/063569
Other languages
English (en)
Inventor
Guobin Sun
Liang Xue
Erika ZHU
Chenxi Zhang
Original Assignee
Covestro Deutschland Ag
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 Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Publication of WO2018219756A1 publication Critical patent/WO2018219756A1/fr

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
    • C08G18/67—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
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more 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
    • C08G18/40—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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • 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
    • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
    • 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
    • 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
    • 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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention belongs to the field of polyurethane composite. Specifically, the present invention relates to a polyurethane prepreg, and a preparation method and applications thereof.
  • VOC Volatile Organic Compounds
  • the process operability of a material is equally important in the field of composite materials. Generally, it is desirable that not only the material be not susceptible to the ambient humidity and temperature, easy to handle, can be stored for long period, and capable of being stored at room temperature for a long time, but also that the processing characteristics of the material endow a certain design freedom and flexibility to the subsequent processors.
  • the unsaturated resin or vinyl ester resin employed in the current compression molding may allow the molding material to be stored at 25 ° C for at least 3 months due to the selection of a curing agent and addition of a polymerization inhibitor, after which period the molding material will become stiff and be difficult to mold.
  • a polymerization inhibitor such as sodium sulfate
  • it will react with polyol immediately upon mixing together uniformly and cure in seconds to hours. This will make the polyurethane molding material unable to flow or stiff, difficult to cut, and also not easily placed into a mold with a certain shape to be pressed into articles with relatively complicated shapes, thus no qualified products can be obtained. Therefore, the polyurethane molding material prepared in accordance with the current method may have a typical storage period of no more than 24 hours, limiting the application of the polyurethane composites in compression molding greatly.
  • the technical problem to be solved by the present invention is to provide a prepreg used to prepare polyurethane composites, which is not susceptible to the ambient humidity and temperature, easy to handle, can be stored for long period, and also endows certain design freedom and flexibility to subsequent processors.
  • a polyurethane prepreg comprising:
  • an isocyanate component comprising one or more organic polyisocyanate(s);
  • Ri is selected from hydrogen, methyl, or ethyl
  • R 2 is selected from alkylenes having 2-6 carbon atoms, 2,2-di(4-phenylene)-propane, 1,4- di(methylene)benzene, l,3-di(methylene)benzene, l,2-di(methylene)benzene
  • n is an integer selected from 1-6;
  • a method for preparing the above prepreg comprising the following steps: allowing the components Al), A2), and A3) to mix under reaction conditions in the absence of long fibers, optionally in the presence of B) the reactive diluent, C) the free radical reaction initiator, D) the reinforcing material, and/or E) the solvent.
  • a polyurethane composite prepared by the method of the present invention is provided.
  • the prepreg of the present invention is heated to 50-100°C or combined with a solvent or diluent (in particular a reactive diluent), its viscosity will be reduced, thus it can flow and can be used to impregnate long fibers (such as glass fiber fabrics, knitting mats, etc.) as required.
  • a solvent or diluent in particular a reactive diluent
  • it is cooled to room temperature to be used or it can be placed into a mold with a certain shape, heated to 150°C, hot-pressed to cure into a final article.
  • the prepreg of the present invention is not susceptible to the ambient humidity and temperature during post-treatment and easy to handle. It is also convenient for subsequent processors to operate since it is not necessarily limited by weather conditions and requires no extra dehumidification renovation to the plant.
  • the prepreg of the present invention can be stored for a long period and may be stored at room temperature for a long time, for example, for 6 months. During the storage period, the polyurethane prepreg can remain in a semi-solid state without substantial changes in physical and chemical properties and will not become stiff. Thus, it can be used to prepare polyurethane composites with superior properties.
  • the subsequent processors may alter the types and amounts of the reinforcing materials as required, thus high design flexibility can be achieved.
  • Fig. 1 is the image of the glass fiber fabric after impregnation with the polyurethane prepreg according to Comparative Example 6.
  • Fig. 2 is the image of the glass fiber fabric after impregnation with the polyurethane prepreg according to Example 5.
  • a polyurethane prepreg comprising:
  • an isocyanate component comprising one or more organic polyisocyanate(s);
  • Ri is selected from hydrogen, methyl, or ethyl
  • R 2 is selected from alkylenes having 2-6 carbon atoms, 2,2-di(4-phenylene)-propane, 1,4- di(methylene)benzene, l,3-di(methylene)benzene, l,2-di(methylene)benzene
  • n is an integer selected from 1-6;
  • the organic polyisocyanate in the Al) isocyanate component comprises an organic diisocyanate, which may be any aliphatic, cycloaliphatic, or aromatic isocyanate known to be used to prepare polyurethane.
  • organic diisocyanate mentions may be made of: 2,2'-,2,4- and 4,4'- diphenyl methane diisocyanate; diphenyl methane diisocyanate homologs with three or more rings
  • polymetric MDI hydrogenated diphenyl methane diisocyanate (HMDI), isophorone diisocyanate (IPDI), the oligomers of isophorone diisocyanate (IPDI); 2,4-toluene diisocyanate (2,4-TDI), 2,6- toluene diisocyanate; tetramethylene diisocyanate, the oligomers of tetramethylene diisocyanate; hexamethylene diisocyanate (HDI), the oligomers of hexamethylene diisocyanate (HDI); naphthalene diisocyanate (NDI); or a compound resulted from the aforementioned organic polyisocyanates with a compound with at least two isocyanate reactive groups or mixtures thereof.
  • HMDI hydrogenated diphenyl methane diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • the organic polyisocyanate comprises an isocyanate based on diphenyl methane diisocyanate, especially that comprising polymetric MDI.
  • the functionality of the organic polyisocyanate is preferably of 1.9-3.5, particularly preferably of 2.0-2.8.
  • the viscosity of the organic polyisocyanate is preferably of 5-700 mPa- s, particularly preferably of 10-300 mPa- s, as measured at 25°C in accordance with DIN 53019-1-3.
  • the organic polyisocyanate may also be used in the form of a polyisocyanate prepolymer.
  • the polyisocyanate prepolymer may be obtained by the reaction between one or more of the aforementioned organic polyisocyanates in excessive amounts and a compound with at least two isocyanate reactive groups at a temperature of 30-100°C, for example, and preferably of about 80°C.
  • the compounds with at least two isocyanate reactive groups are well known to those skilled in the art, which, for example, are described in Kunststoff-Handbuch, Chapter 3.1 ("Kunststoffhandbuch, 7, Polyurethanes", Carl Hanser-Verlag, 3 rd ed., 1993), which is incorporated by reference herein in its entirety.
  • the NCO content of the polyisocyanate prepolymer of the present invention is preferably of 12-33wt. , particularly preferably of 20-32wt. .
  • the organic polyol in the A2) one or more organic polyol(s) has preferably a molecular weight of 280-10000, and the content thereof is 20-50 wt. , preferably of 30-40wt. , based on the weight of the prepolymer.
  • the molecular weight of the organic polyol described herein means number-average molecular weight, which is generally calculated in accordance with the type and amount of raw material used to prepare the organic polyol.
  • the organic polyol has a hydroxyl value of 10-400 mg KOH/g, preferably of 28-350 mg KOH/g; a functionality of 1-4, more preferably of 1.5-3, and most preferably of 1.8-2.5.
  • the organic polyol may be the one commonly used to prepare polyurethane in the art, for example, selected from one or more of: polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, and vegetable oil polyols.
  • the polyether polyol may be prepared by a known process. For example, it may be prepared by reacting an olefin oxide with a starting agent in the presence of a catalyst.
  • the catalyst is preferably, but not limited to, an alkaline hydroxide, an alkaline alkoxide, antimony pentachloride, boron trifluoride etherate, or a mixture thereof.
  • the olefin oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1 ,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or a mixture thereof, particularly preferably ethylene oxide and/or propylene oxide.
  • the starting agent is preferably, but not limited to, a polyhydric compound or a compound with multiple amino groups.
  • the polyhydric compound is preferably, but not limited to, water, ethylene glycol, 1 ,2-propanediol, 1,3-propanediol, diethylene glycol, trimethylolpropane, glycerol, bisphenol A, bisphenol S, or a mixture thereof.
  • the compound with multiple amino groups is preferably, but not limited to, ethanediamine, propanediamine, butanediamine, hexanediamine, diethylenetriamine, toluenediamine, or a mixture thereof.
  • the polyether polyol may be an unsaturated polyether polyol.
  • the polyether carbonate polyol may be prepared by addition of carbon dioxide with alkylene oxide on a starting agent comprising reactive hydrogen in the presence of double metal cyanide as a catalyst.
  • the polyester polyol is prepared by reacting a dicarboxylic acid or a dicarboxylic acid anhydride with a polyol.
  • the dicarboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid containing 2-12 carbon atoms, which is preferably, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, octanedioic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, or a mixture thereof.
  • the dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a mixture thereof.
  • the polyol which reacts with the dicarboxylic acid or dicarboxylic acid anhydride is preferably, but not limited to, ethylene glycol, diethylene glycol, 1 ,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3- methylpropanediol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10- decanediol, glycerol, trimethylolpropane, or a mixture thereof.
  • the polyester polyol further includes a polyester polyol prepared from a lactone.
  • the polyester polyol prepared from a lactone is
  • the polycarbonate diol may be prepared by reacting a diol with a dihydrocarbyl carbonate or a diaryl carbonate or phosgene.
  • the diol is preferably, but not limited to, 1 ,2-propanediol, 1,3- propanediol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxane diol, or a mixture thereof.
  • the dihydrocarbyl carbonate or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.
  • the polyol based on vegetable oil comprises vegetable oils, vegetable oil polyols, or modified products thereof.
  • Vegetable oil is a compound prepared from an unsaturated fatty acid and glycerol or an oil extracted from fruits, seeds, or embryos of a plant, which is preferably, but not limited to, peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, and palm oil.
  • the vegetable oil polyol is a polyol originated with one or more vegetable oils.
  • a starting agent used to synthesize a vegetable oil polyol includes, but not limited to, soybean oil, palm oil, peanut oil, low erucic acid rapesed oil, and castor oil.
  • Hydroxyl groups may be introduced into a starting agent of the vegetable oil polyol via a process such as hydrolysis, oxidation, or transesterification and then the corresponding vegetable oil polyol may be prepared by a process for preparing an organic polyol well known to those skilled in the art.
  • the functionality and hydroxyl value of an organic polyol refer to the average functionality and average hydroxyl value, respectively.
  • the organic polyol is polyether polyol.
  • R2 is selected from ethylene, propylene, butylene, pentylene, 1 -methyl- 1 ,2-ethylene, 2-methyl-l,2-ethylene, l-ethyl-l,2-ethylene, 2-ethyl-l,2-ethylene, l-methyl-l,3-propylene, 2-methyl- 1,3 -propylene, 3-methyl-l,3-propylene, 1- ethyl- 1,3 -propylene, 2-ethyl- 1,3 -propylene, 3-ethyl-l,3-propylene, 1 -methyl- 1,4-butylene, 2- methyl-l,4-butylene, 3-methyl- 1,4-butylene and 4-methyl- 1,4-butylene, 2,2-di(4-phenylene)- propane, 1 ,4-dimethylene benzene, 1,3-dimethylene benzene, or 1 ,2-dimethylene benzene.
  • the compound of formula (I) is selected from one or more of: hydroxy ethyl methylacrylate, hydroxypropyl methylacrylate, hydroxybutyl methylacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate.
  • the compound of formula (I) may be prepared by a method commonly used in the art, for example, by esterification reaction between (meth)acrylic anhydride, (meth)acrylic acid, or (meth)acryloyl halide and HO-(R20) n -H.
  • This method is well known to those skilled in the art and is, for example, described in Handbook of Raw Materials and Addictives for Polyur ethanes, Chapter 3, Liu Yijun, published on April 1, 2005, and Handbook of Polyur ethane Elastomers, Chapter 2, Liu Houjun, published in August, 2012, which are incorporated by reference herein in their entirety.
  • the weight ratio of the component A2) to the component A3) is from 30:70 to
  • the reactive diluent is the one comprising a group that may participate in the curing reaction and is classified into mono-functional active diluent and multi-functional active diluent.
  • a group that participates in the curing reaction is, for example, an alkenyl group. That is to say, the reactive diluent described in the present application is an active dilute comprising ethylenic bonds.
  • the reactive diluent mainly functions to reduce viscosity and/or participate in a subsequent curing reaction.
  • the mono-functional active diluent has only one group that may participate in the curing reaction in each molecule, such as styrene, ⁇ -hydroxyethyl acrylate (HPA), or the compound of formula (I) as defined above.
  • HPA ⁇ -hydroxyethyl acrylate
  • the multi-functional active diluent refers to the one that has two or more groups that may participate in the curing reaction in each molecule, such as 1,6-hexanediol di(meth)acrylate (HDDA).
  • HDDA 1,6-hexanediol di(meth)acrylate
  • the cured film With a monomer containing more functional groups, in addition to an increased reactivity, the cured film will be imparted with a cross-linked structure, which is due to the fact that a mono-functional monomer will only result in a linear polymer after polymerization while a multi-functional monomer may result in a highly cross-linked network.
  • the C) free radical reaction initiator includes, but not limited to, peroxides, persulfides, peroxycarbonates, peroxyboric acids, azo compounds, or other suitable free radical initiators that may initiate curing of a compound comprising ethylenic bonds.
  • Representative examples include, but not limited to, i-butyl peroxy isopropyl carbonate, benzoyl peroxide, i-butyl peroxy-3,5,5-trimethyl hexanoate, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, and the like.
  • thermal initiation may be performed.
  • promoters in the system, such as cobalt compounds or amine compounds, in an amount of 0-5 parts by weight, based on 100 parts by weight of the prepolymer.
  • the reinforcing material does not include the long fibers used to prepare the fiber- reinforced polyurethane composite.
  • the reinforcing material is selected from one or more of fillers, carbon nanotubes, short fibers, and fiber powder.
  • the filler is selected from one or more of: aluminium hydroxide powder, bentonite, flyash, wollastonite, perlite powder, floating bead, calcium carbonate, talc powder, mica powder, porcelain clay, fumed silica, expendable microspheres, diatomaceous earth, pozzuolana, barium sulfate, calcium sulfate, glass microspheres, mountain flour, wood flour, wood chips, bamboo flour, bamboo chips, rice grains, chopped crop straw, chopped broomcorn straw, graphite powder, metal powder, recycled powder of thermosetting composites, and plastic particles or powder.
  • the glass microspheres may be solid or hollow.
  • the solvent may be commonly used organic solvent, such as acetone, butanone, and the like. Those skilled in the art may choose the amount of a solvent such that the system comprising the polyurethane prepreg of the present invention and the solvent has a viscosity suitable for impregnating long fibers (such as glass fiber fabrics) to prepare a prepreg sheet.
  • the prepreg according to the present invention may further comprise one or more addictives selected from the group consisting of: internal release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, antifoaming agents, coupling agents, surface wetting agents, levelling agent, moisture scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, foaming agents, foam stabilizers, foam homogenizers, and free radical reaction suppressants.
  • addictives selected from the group consisting of: internal release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, antifoaming agents, coupling agents, surface wetting agents, levelling agent, moisture scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, foaming agents, foam stabilizers, foam homogenizers, and free radical reaction suppressants.
  • the amounts of the addictives may choose the amounts of the addictives as required, e.g., 0-25 parts by weight, based on 100 parts by weight of the prepolymer.
  • the internal release agent that may be used in the present invention includes any conventional release agent used to produce polyurethane, examples of which include long-chain carboxylic acids, especially fatty acids such as stearic acid, amides of long-chain carboxylic acids such as stearamide, esters of fatty acids, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
  • long-chain carboxylic acids especially fatty acids such as stearic acid, amides of long-chain carboxylic acids such as stearamide, esters of fatty acids, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
  • the flame retardant that may be used in the present invention includes triaryl phosphates, trialkyl phosphates, triaryl phosphates, or trialkyl phosphates containing halogen, melamine, melamine resin, halogenated paraffin, red phosphorus, or mixtures thereof.
  • the moisture scavenger that may be used in the present invention may be molecular sieves.
  • the antifoaming agent may be, for example, polydimethylsiloxane.
  • the coupling agent may be, for example, mono-ethylene oxide, organoamine functionalized trialkoxysilanes, or mixtures thereof.
  • the coupling agent is particularly preferably used to increase the binding strength between a resin matrix and a fiber reinforcing material. Fine particle fillers, such as clay and fumed silica, are commonly used as the thixotropic agents.
  • the free radical reaction suppressants that may be used in the present invention include polymerization inhibitors, polymerization retarders, and the like, such as some phenol, quinine compounds or hindered amine compounds, examples of which include methylhydroquinone, p- methoxyphenol, benzoquinone, polymethyl piperidine derivatives, low valence copper ions, etc.
  • the polyurethane prepreg is in a shape of a sheet, a strip, a ribbon, or a ring.
  • a method for preparing the above polyurethane prepreg comprising the following steps:
  • reaction conditions of an isocyanate group and an isocyanate reactive group are well known to those skilled in the art.
  • the reactants may be allowed to react under an elevated temperature or a lower temperature (such as 10°C).
  • the reaction temperature is preferably no higher than 80°C, and more preferably no higher than 70°C, such as 50-60°C, whereby the reaction between the isocyanate group and the isocyanate reactive group (such as a hydroxyl group) may occur rapidly, while the free radical polymerization reaction via ethylenic bonds will not occur rapidly. Therefore, the above reaction conditions include a temperature of 10°C to 80°C.
  • a catalyst may be used to promote the reaction between the isocyanate group and the isocyanate reactive group, which may be those commonly used in the art to catalyze the reaction between an isocyanate group (NCO) and an isocyanate reactive group (such as a hydroxyl group).
  • a catalyst suitable for a polyurethane reaction is preferably, but not limited to, an amine catalyst, an organometallic catalyst, or a mixture thereof.
  • the amine catalyst is preferably, but not limited to, triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl- ethylenediamine, pentamethyldiethylene-triamine, N,N-methylaniline, ⁇ , ⁇ -dimethylaniline, or a mixture thereof.
  • the organometallic catalyst is preferably, but not limited to, an organotin compound, such as tin (II) acetate, tin (II) octanoate, tin ethylhexanoate, tin laurate, dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin maleate, dioctyl tin diacetate, or a mixture thereof.
  • the catalyst is included in an amount of 0.001-10 wt. , based on the total weight of the isocyanate reactive component (which refers to the organic polyol and the compound of formula (I) in the present invention) being 100 wt.%.
  • the reaction between the isocyanate group and the isocyanate reactive group may be carried out for several hours, e.g., 4 to 8 hours.
  • a free radical polymerization reaction may also occur in minimum amount, as long as it will not render the obtained prepreg too rigid to be used for the subsequent processing.
  • the above Al) isocyanate component, A2) one or more organic polyol(s), and A3) one or more compound(s) of formula (I) are subjected to an addition reaction via a hydroxyl group and an isocyanate group in the absence of long fibers, forming a gel gradually. If the reaction is carried out at a temperature higher than room temperature, the temperature will be lowered to room temperature after gel formation. The obtained polyurethane prepreg is then stored to be used for the subsequent processing.
  • the polyurethane prepreg may be manufactured into a desired shape by a known plastic processing method in the art, e.g., casting, pressing, rolling, or squeezing, and then cured in the presence of long fibers to prepare the polyurethane composite.
  • the polyurethane prepreg may be in a shape of a sheet, a strip, a ribbon, or a ring. Since the hardness of the polyurethane prepreg is not very high, it will be easy to cut the polyurethane prepreg into a desired shape.
  • the polyurethane addition polymerization reaction between the isocyanate group and the isocyanate reactive group (such as a hydroxyl group) therein begins to occur, which may be partially or fully completed, preferably mostly or fully completed.
  • the active ethylenic bonds within the polyurethane prepreg remain stable and no substantial free radical polymerization reaction will occur. Only under certain conditions (such as heating) will the substantial amount of active ethylenic bonds within the polyurethane prepreg be subjected to the free radical polymerization reaction, which allows the polyurethane prepreg to be cross-linked and cured in the presence of long fibers, and thus, results in the polyurethane composite being obtained.
  • Such a stability of the ethylenic bonds ensures a long- term stability of the prepreg and is advantageous for the storage and transportation of the polyurethane prepreg.
  • the prepreg is a mixture having a viscosity of at least 30000 mPa-s (25°C) or a semi-solid state.
  • the prepreg may be stored at a temperature of 5-45°C for over 6 months without substantial changes in physical and chemical properties, while it still can be used to prepare polyurethane composites with superior properties.
  • a method for preparing a polyurethane composite comprising the following steps:
  • the viscosity of the polyurethane prepreg is reduced by heating to melt or adding with solvents or dilutes.
  • the viscosity of the polyurethane prepreg is typically reduced to a degree suitable for impregnating long fibers, e.g., 600mPa- s.
  • the free radical polymerization reaction is the addition polymerization reaction of ethylenic bonds, which may be those in the compound of formula (I) or may be those in the intermediate product of the reaction between the compound of formula (I) and the organic polyisocyanate, excluding those carried by aromatic rings.
  • the curing step (iii) may be carried out at a temperature of 80-300°C, preferably of 100- 250°C, for example, 150°C and under a pressure of 0.1-50 Mpa, for example, lOMpa. Generally, the curing step is carried out in a specific mold according to the shape requirement of the product.
  • the long fibers may be loose fibers, fiber bundles, fiber webs, or fiber fabrics formed through bonding or weaving.
  • the long fibers may be selected from one or more of: glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, and metal fibers.
  • the long fibers are in an amount of 5-95 wt. , preferably of 30-85 wt. , based on the total weight of the polyurethane composite.
  • a polyurethane composite prepared by the method of the present invention is provided.
  • the polyurethane composite is selected from: a motor vehicle fender, a motor vehicle lampshade, a motor vehicle dashboard, a motor vehicle hard roof, a motor vehicle door, a motor vehicle frame, a motor vehicle body shell, a motor vehicle radiator grid plate, a motor vehicle headlamp reflector, a motor vehicle front support, a motor vehicle floor, a motor vehicle seat frame, a motor vehicle air deflector, a motor vehicle radiator cover or bracket, a motor vehicle body guard, a motor vehicle crossbeam, a motor vehicle spoiler, a motor vehicle sun shade, a motor vehicle front and rear bumper, a motor vehicle hood, a motor vehicle decorative panel, a motor vehicle trunk rear liftgate, a motor vehicle interior decoration, an engine valve cover, an engine air inlet manifold, a bottom shell of a fuel tank, a motor vehicle air filter cover, a motor vehicle air director, a motor vehicle gear housing cover
  • HPMA hydroxypropyl methacrylate (HPMA), purchased from Shanghai Pharmaceuticals Holding Co., Ltd.
  • Polyether 1 polyether polyol 1, prepared by using propylene glycol as the starting agent and propylene oxide as the main polymerization component, hydroxyl value: 280, functionality: 2, viscosity: 70 mP- s@25°C, molecular weight: 400.
  • Polyether 2 polyether polyol 2, prepared by using propylene glycol as the starting agent and propylene oxide as the main polymerization component, hydroxyl value: 112, functionality: 2, viscosity: 150 mP- s@25°C, molecular weight: 1000.
  • Polyether 3 polyether polyol 3, prepared by using glycerol as the starting agent and propylene oxide as the main polymerization component, hydroxyl value: 240, functionality: 3, viscosity: 250 mP- s@25°C, molecular weight: 700.
  • Polyether 4 polyether polyol 4, prepared by using glycerol as the starting agent and propylene oxide as the main polymerization component, hydroxyl value: 470, functionality: 3, viscosity: 475 mP- s@25°C, molecular weight: 350.
  • Polyether 5 polyether polyol 5, prepared by using sucrose and propylene glycol as the starting agents and propylene oxide as the main polymerization component, hydroxyl value: 380, functionality: 5.8, viscosity: 11250 mP- s@25°C, molecular weight: 850.
  • Dicumyl peroxide purchased from Syrgis.
  • Benzoyl peroxide purchased from Syrgis.
  • Antifoaming agent 066N, purchased from BYK.
  • Polyisocyanate NCO : 30.5-32.5%, viscosity: 160-240mP.s @25°C, purchased from Covestro Polymer (China) Co., Ltd.
  • Glass fiber fabric uniaxial glass fiber fabric, E-glass UD, EKU1150(0)PU-500, purchased from Chongqing International Composite Materials Co., Ltd.
  • Comparative examples 1-5 and examples 1-4 are preformed as follows. All the components in accordance with Table 1 were mixed except the polyisocyanate, then the polyisocyanate was added to the resulting mixture stepwise and allowed to react at a temperature of 60°C for 8 hours, resulting in the polyurethane prepreg.
  • the obtained polyurethane prepreg was heated to be able to flow, forming a homogenous resin liquid with a low viscosity.
  • a glass fiber fabric was laid on a thin film, and the obtained resin liquid with a low viscosity was poured onto the glass fiber fabric and then another thin film was covered thereon, then the thin films were pressed repeatedly with a rubber roll until the glass fiber fabric was impregnated completely.
  • the finished sheet can be stored at 25 ° C for over 6 months.
  • the upper and bottom thin films were removed, a sheet with a suitable weight was cut out, put into a mold with a desired shape, and hot- press molded for 3-5 minutes at a mold temperature of about 150 ° C and a pressure of lOMPa.
  • Example 1 Example 2 2 3
  • friable substantia friable, bendable, bendable
  • the glass fiber fabric was impregnated immediately after all the components were mixed and then the liquid resin was heated at 60 ° C for another 4 hours to gelatinize gradually before cooled to room temperature again to reach B-stage.
  • Figure 1 is the image of the glass fiber fabric after impregnation with the polyurethane in Comparative Example 6.
  • Prepolymer 4 According to the formulation of Prepolymer 4, all the components were heated at 60 ° C for 4 hours after being mixed to allow the liquid resin to form a gel gradually, then it was cooled to room temperature to reach a state that was not tacky. This gel was then heated to 90 ° C to become a liquid with a low viscosity in order to have a good flowability. It was used to impregnate the glass fiber fabric immediately and then cooled to room temperature (-25 ° C) naturally, reaching B -stage.
  • Figure 2 is the image of the glass fiber fabric after impregnation with the polyurethane prepreg in Example 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un pré-imprégné de polyuréthane, comprenant : A) un prépolymère produit avec les constituants A1), A2) et A3) suivants par la réaction d'addition entre des groupes hydroxyle et des groupes isocyanate en l'absence de fibres longues : A1) un constituant isocyanate, le constituant isocyanate comprenant un ou plusieurs polyisocyanate(s) organique(s) ; A2) un ou plusieurs polyol(s) organique(s), le(s) polyol(s) organique(s) ayant un indice d'hydroxyle de 10 à 400 mg KOH/g et une fonctionnalité de 1 à 4 ; A3) un ou plusieurs composé(s) de formule (I) ; éventuellement, B) des diluants réactifs ; C) un initiateur de réaction radicalaire ; D) un matériau de renforcement ; et/ou E) un solvant. Le pré-imprégné selon la présente invention n'est pas sensible à l'humidité et à la température ambiantes pendant le post-traitement, est facile à manipuler, et peut être stocké pendant une longue période.
PCT/EP2018/063569 2017-05-27 2018-05-23 Pré-imprégné de polyuréthane, procédé de préparation et applications associés WO2018219756A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710421055.3 2017-05-27
CN201710421055.3A CN108929426A (zh) 2017-05-27 2017-05-27 一种聚氨酯预浸料及其制备方法与应用

Publications (1)

Publication Number Publication Date
WO2018219756A1 true WO2018219756A1 (fr) 2018-12-06

Family

ID=62486558

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/063569 WO2018219756A1 (fr) 2017-05-27 2018-05-23 Pré-imprégné de polyuréthane, procédé de préparation et applications associés

Country Status (2)

Country Link
CN (1) CN108929426A (fr)
WO (1) WO2018219756A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110804150A (zh) * 2019-11-14 2020-02-18 江苏雅克科技股份有限公司 三维方向增强型聚氨酯保温材料及其制备方法
WO2020193396A1 (fr) 2019-03-26 2020-10-01 Covestro Intellectual Property Gmbh & Co. Kg Procédé de préparation d'un composite de polyuréthane pultrudé
CN111748073A (zh) * 2019-03-26 2020-10-09 科思创德国股份有限公司 一种制备聚氨酯拉挤复合材料的方法
EP3733729A1 (fr) * 2019-05-02 2020-11-04 Covestro Deutschland AG Procédé de préparation d'un composite de polyuréthane pultrudé
WO2021048334A1 (fr) 2019-09-12 2021-03-18 Basf Se Résines pu composites
CN113501930A (zh) * 2021-06-23 2021-10-15 四川东树新材料有限公司 风电叶片用灌注聚氨酯树脂及其制备方法
WO2023274995A1 (fr) * 2021-06-30 2023-01-05 Covestro Deutschland Ag Composite de polyuréthane
EP4130083A1 (fr) * 2021-08-03 2023-02-08 Covestro Deutschland AG Composition de polyol
WO2023035262A1 (fr) * 2021-09-13 2023-03-16 Dow Global Technologies Llc Compositions de polyuréthane, matériaux composites préparés avec celles-ci et procédés de préparation associés

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776751A (zh) * 2019-01-15 2019-05-21 烟台正海合泰科技股份有限公司 一种汽车发动机舱专用的低密度轻质pu板及其生产工艺
CN112090444B (zh) * 2020-08-17 2023-05-09 杭州电子科技大学 一种生物质热解用高芳构化性能催化剂及其制备方法
CN112776312A (zh) * 2020-12-29 2021-05-11 江苏华曼复合材料科技有限公司 汽车防撞梁及其制造方法
CN115181231B (zh) * 2021-04-02 2024-01-23 上海高铁电气科技有限公司 一种液体组合物和由其制备的预浸料和复合材料
CN114409869B (zh) * 2022-01-12 2023-07-11 万华化学集团股份有限公司 一种多重固化异氰酸酯预聚体及其制备方法和其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772404A (en) * 1971-01-08 1973-11-13 Ici Ltd Resins
JP3821169B2 (ja) * 1996-04-12 2006-09-13 ダイセル・サイテック株式会社 ガラス繊維ヤーンまたは織布のほつれ防止固着剤
WO2013084967A1 (fr) * 2011-12-08 2013-06-13 ディーエイチ・マテリアル株式会社 Composition de résines polymérisables par voie radicalaire, matériau de moulage et article moulé

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5214281B1 (fr) * 1968-07-29 1977-04-20
JP4326247B2 (ja) * 2003-03-31 2009-09-02 三菱重工業株式会社 インフレータブル性を備えた繊維強化プラスチック用プリプレグ及びその製造方法
DE102009001793A1 (de) * 2009-03-24 2010-10-07 Evonik Degussa Gmbh Prepregs und daraus hergestellte Formkörper
CN104177581B (zh) * 2013-05-27 2019-07-30 科思创德国股份有限公司 用于聚氨酯复合材料的聚氨酯组合物
EP3026072A1 (fr) * 2014-11-28 2016-06-01 Evonik Degussa GmbH Procédé destiné à la fabrication de composites

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772404A (en) * 1971-01-08 1973-11-13 Ici Ltd Resins
JP3821169B2 (ja) * 1996-04-12 2006-09-13 ダイセル・サイテック株式会社 ガラス繊維ヤーンまたは織布のほつれ防止固着剤
WO2013084967A1 (fr) * 2011-12-08 2013-06-13 ディーエイチ・マテリアル株式会社 Composition de résines polymérisables par voie radicalaire, matériau de moulage et article moulé

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HOUBEN WEYL: "Methoden der Organischen Chemie", vol. XIV/2, 1963, GEORG THIEME VERLAG, article "Makromolekulare Stoffe", pages: 17
LIU HOUJUN: "Handbook of Polyurethane Elastomers", August 2012
LIU YIJUN: "Handbook of Raw Materials and Addictives for Polyurethanes", 1 April 2005

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020193396A1 (fr) 2019-03-26 2020-10-01 Covestro Intellectual Property Gmbh & Co. Kg Procédé de préparation d'un composite de polyuréthane pultrudé
CN111748073A (zh) * 2019-03-26 2020-10-09 科思创德国股份有限公司 一种制备聚氨酯拉挤复合材料的方法
CN111748073B (zh) * 2019-03-26 2024-06-11 科思创德国股份有限公司 一种制备聚氨酯拉挤复合材料的方法
EP3733729A1 (fr) * 2019-05-02 2020-11-04 Covestro Deutschland AG Procédé de préparation d'un composite de polyuréthane pultrudé
WO2021048334A1 (fr) 2019-09-12 2021-03-18 Basf Se Résines pu composites
CN110804150A (zh) * 2019-11-14 2020-02-18 江苏雅克科技股份有限公司 三维方向增强型聚氨酯保温材料及其制备方法
CN113501930A (zh) * 2021-06-23 2021-10-15 四川东树新材料有限公司 风电叶片用灌注聚氨酯树脂及其制备方法
CN113501930B (zh) * 2021-06-23 2022-04-01 四川东树新材料有限公司 风电叶片用灌注聚氨酯树脂及其制备方法
WO2023274995A1 (fr) * 2021-06-30 2023-01-05 Covestro Deutschland Ag Composite de polyuréthane
EP4130083A1 (fr) * 2021-08-03 2023-02-08 Covestro Deutschland AG Composition de polyol
WO2023035262A1 (fr) * 2021-09-13 2023-03-16 Dow Global Technologies Llc Compositions de polyuréthane, matériaux composites préparés avec celles-ci et procédés de préparation associés

Also Published As

Publication number Publication date
CN108929426A (zh) 2018-12-04

Similar Documents

Publication Publication Date Title
WO2018219756A1 (fr) Pré-imprégné de polyuréthane, procédé de préparation et applications associés
JP6794266B2 (ja) ポリウレタン複合材およびその製造方法
US10683403B2 (en) Polyurethane composite material and process of preparing same
US11512164B2 (en) Composite material comprising a polyurethane-polyacrylate resin matrix
US7763341B2 (en) Filled polymer composite and synthetic building material compositions
CN106751737B (zh) 热固性聚氨酯复合物
CN105778005B (zh) 可自由基聚合的聚氨酯组合物
CN104045806B (zh) 用于制备聚氨酯复合材料的聚氨酯组合物
CN111748073B (zh) 一种制备聚氨酯拉挤复合材料的方法
JPS6048533B2 (ja) ビニルエステルウレタン樹脂を含有する成形用組成物
WO2019193152A1 (fr) Procédé de fabrication d'une résine poly (méth) acrylate de polyuréthane
CN115536808A (zh) 多元醇组合物
CN117651728A (zh) 聚氨酯复合材料
CN113950496A (zh) 一种存储异氰酸酯反应性组分的方法
CN115536798A (zh) 多元醇组合物
CN112440490A (zh) 一种制备涡轮风机叶片主梁/辅梁的方法

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: 18728333

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: 18728333

Country of ref document: EP

Kind code of ref document: A1