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WO2018167220A1 - Prépolymère de polyuréthane à terminaisons hydroxyle et son procédé de préparation - Google Patents

Prépolymère de polyuréthane à terminaisons hydroxyle et son procédé de préparation Download PDF

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Publication number
WO2018167220A1
WO2018167220A1 PCT/EP2018/056555 EP2018056555W WO2018167220A1 WO 2018167220 A1 WO2018167220 A1 WO 2018167220A1 EP 2018056555 W EP2018056555 W EP 2018056555W WO 2018167220 A1 WO2018167220 A1 WO 2018167220A1
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WO
WIPO (PCT)
Prior art keywords
diisocyanate
hydroxyl
polyurethane prepolymer
terminated polyurethane
polyols
Prior art date
Application number
PCT/EP2018/056555
Other languages
English (en)
Inventor
Liang Xue
Jianwu GAO
Chenxi Zhang
Original Assignee
Covestro Deutschland Ag
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Filing date
Publication date
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Publication of WO2018167220A1 publication Critical patent/WO2018167220A1/fr

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
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    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/04—Aerosol, e.g. polyurethane foam spray
    • 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
    • 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
    • C08J2375/06—Polyurethanes from polyesters
    • 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

Definitions

  • the present invention belongs to polyurethane field. Specifically, it relates to a hy- droxyl-terminated polyurethane prepolymer, preparation method thereof and use thereof for synthesizing polyisocyanurate foam.
  • Polyurethane foam for spray application has excellent thermal insulation property, moulding property and adhesion with substrates. With the state and the society have more and more requirements for energy conservation and low carbon, polyurethane foam materials for spray application are enjoying increasingly wide applications in the field of building insulation.
  • the Chinese national document No. 65 ⁇ Notice on Further Specifying Relevant Requirements for Fire Supervision and Management of External Insulation Materials for Civil Buildings> and document No. 46 the notice of printing and distributing ⁇ Interim Provisions on External Insulation Systems for Civil Buildings and Exterior Decorations Fire Protection> have regulated the materials used on the wall to meet the lowest requirement of Rating B2 fire retardancy. Therefore, the key point in developing polyurethane foam for spray application is to increase the fire retardant property thereof and control the cost of high fire retardancy spraying foam.
  • the patent CN200910186702.2 (CN101724254A) discloses a high efficiency non- halogen fire retardant rigid polyurethane foam and preparation method thereof.
  • the high fire retardancy of this rigid polyurethane foam is achieved by adding inorganic fire retardant, red phosphorus and organic fire retardant, dimethyl methylphosphate (DMMP for abbreviation).
  • DMMP dimethyl methylphosphate
  • This method is capable of producing foam with better fire retardancy, however, the addition of inorganic particles makes it difficult to mix, and the storage stability of the system and dimensional stability of the foam will be adversely affected to some extent after addition of DMMP, limiting its production and use in large scale.
  • the patent CN201210196201.4 discloses a polyurethane insulation material for spray application obtained by a blowing technique with a system using DMMP as fire retardant.
  • the dimensional stability of the foam prepared by this technique is good, however, the fire retardant rating is low and can merely meet the usage requirement of Rating E in GB8624-2006.
  • the patent CN 103073986 B discloses a high fire retardancy polyurethane foam material for spray application, and preparation method thereof.
  • the foam for spray application has overcome such problems as foam shrinkage, poor dimensional stability and low fire retardancy by introducing a compounded system comprising Br-P composite fire retardant polyether polyol, Mannich polyether polyol and polyester polyol.
  • problems for the fire retardant polyether polyol employed such as expensive cost and limited source.
  • polyisocyanurate foam Compared to PUR, due to the difference in structure, polyisocyanurate foam has high efficiency fire retardancy, good heat resistance and processing properties.
  • preparation of the polyisocyanurate foam requires much more excessive amount of isocyanate relative to hydroxyl groups so as to produce polyisocyanurate ring by trimerization of isocyanate itself.
  • the patent CN 105940032 A discloses a fire redardant and insulating polyurethane or carbamate-modified polyisocyanurate foam, which has good foam properties and processing characteristics, and has minimal amount of fire redardant.
  • isocyanate index refers to the molar ratio of NCO groups present in the foam formulation relative to reactive hydrogen atoms, given as percentage.
  • the technical problem to be solved by the present invention is to provide a fire retardant polyisocyanurate foam for spray application which can be prepared with a spray machine with a A/B ratio of 1 : 1 and shows relatively good physical and mechanical properties, as well as relatively high oxygen index.
  • the above technical problem is solved by the following technical solutions.
  • hydroxyl- terminated polyurethane prepolymer which is the reaction product of the following raw materials:
  • polymeric polyols selected from polyether polyols and polyester pol- yols
  • hydroxyl-terminated polyurethane prepolymer which is the reaction product of the following raw materials:
  • a polyisocyanu- rate foam which is obtained by the reaction of the following component A and component B:
  • Component A comprising:
  • Component B which is one or more polyisocyanates.
  • component A i) mixing a) the above hydroxyl-terminated polyurethane prepolymer, b) optionally, one or more polymeric polyols, c) one or more foam stabilizers, d) one or more cata- lysts, and e) one or more blowing agents and stirring, to give component A as a uniform mixture;
  • component B one or more polyisocyanates with component A to give a reaction mixture
  • the present invention has prepared a hydroxyl-terminated polyurethane prepolymer with fire retardant elements by adding the fire retardant elements such as halogen and/or phosphorus to raw materials.
  • the hydroxyl-terminated polyurethane prepolymer of the present invention can be used to prepare fire retardant polyisocyanurate foam for spray application with a spray machine with A/B ratio of 1 : 1.
  • the polyisocyanurate foam prepared according to the present invention is superior in thermal insulation property, adhesive property, compression strength and dimensional stability, has a low cost, good fire retardant effect, and is able to achieve a balance between fire retardant property, mechanical property and cost.
  • hydroxyl- terminated polyurethane prepolymer which is the reaction product of the following raw materials:
  • polymeric polyols selected from polyether polyols and polyester pol- yols
  • the polyether polyol has a functionality preferably of 2-8, in particular preferably of 2-4 and a hydroxyl value preferably of 35-800 mg KOH/g, in particular preferably of 35-400 mg KOH/g.
  • the hydroxyl value may be determined according to DIN EN ISO 53240-2:2007- 1 1.
  • the polyether polyols are preferably selected from polyether polyols started with saccharides (e.g., glucose, sucrose), pentaerythritol, sorbitol, trimethylolpropane, glycerol, toluene diamine, ethylenediamine, ethylene glycol, propylene glycol or water.
  • the polyether polyol comprises halogenated polyether polyol and non-halogenated polyether polyol.
  • the halogenated polyether polyol is a halogen-containing polyether polyol, i.e., the polyether polyol containing halogen and preferably started with saccharide (glucose, sucrose), pentaerythritol, sorbitol, trimethylolpropane, glycerol, toluene diamine, ethylenediamine, ethylene glycol, propylene glycol or water.
  • the halogen is selected from CI and Br.
  • the halogen is present in the halogenated polyether polyol in an amount of 35-60 wt%, relative to the weight of the halogenated polyether polyol.
  • the halogenated polyether polyol preferably further contains phosphorus, i.e., it is preferably halogen-phosphorus composite fire retardant polyether polyol.
  • the halogen and phosphorus are present in the halogen-phosphorus composite fire retardant polyether polyol in an amount of 15-40 wt% for the halogen and 1-7 wt% for the phosphorus, respectively, both based on the total weight of the halo- gen-phosphorus composite fire retardant polyether polyol.
  • the halogen-phosphorus composite fire retardant polyether polyol has a functionality preferably of 2-6, particularly preferably of 2-4 and a hydroxyl value preferably of 200-800 mg KOH/g, particularly preferably of 200-400 mg KOH/g.
  • the non-halogenated polyether polyol is the polyether polyol free of halogen, i.e., the polyether polyol free of halogen and preferably started with saccharides (glucose, sucrose), pentaerythritol, sorbitol, trimethylolpropane, glycerol, toluene diamine, eth- ylenediamine, ethylene glycol, propylene glycol or water.
  • saccharides glucose, sucrose
  • pentaerythritol sorbitol
  • trimethylolpropane glycerol
  • toluene diamine eth- ylenediamine
  • ethylene glycol propylene glycol or water.
  • polyester polyol is formed by condensation of acid and/or acid anhydride with polyol, with the acid and acid anhydride preferably being selected from o-phthalic acid, m-phthalic acid, p-phthalic acid, adipic acid, glutaric acid and succinic acid and the acid anhydrides of said acids, and the polyol preferably being selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol and sorbitol.
  • the polyester polyol preferably has a functionality of 2-3 and a hydroxyl value of 200-400 mg KOH/g.
  • the polyester polyol is in particular preferably prepared from terephthalic acid and ethylene glycol as raw materials.
  • the polymeric polyol comprises halogenated polyether polyol. In one embodiment, the polymeric polyol comprises halogen-phosphorus composite fire retardant polyether polyol.
  • the polymeric polyol is halogenated polyether polyol.
  • the polymeric polyol is halogen-phosphorus composite fire retardant polyether polyol.
  • the polymeric polyol comprises halogen-phosphorus composite fire retardant polyether polyol and polyester polyol.
  • the polymeric polyol comprises halogen-phosphorus composite fire retardant polyether polyol, polyester polyol and non-halogenated polyether polyol.
  • the polymeric polyol is present in the hydroxyl-terminated polyurethane prepolymer in an amount of 1-60 pbw, preferably of 5-55 pbw, and particularly preferably of 10- 55 pbw.
  • the phosphate is preferably selected from tris(polyoxyalkylene) phosphate, tris(polyoxyalkylene) phosphite, tris(dipropylene glycol)phosphate (commonly known as P430), dimethyl methyl phosphonate (DMMP), dimethyl propyl phospho- nate (DMPP), diethyl ethyl phosphonate (DEEP), triethyl phosphate (TEP), tricresyl phosphate (TPP) etc. Particularly preferable is triethyl phosphate (TEP).
  • the phosphate is present in the hydroxyl-terminated polyurethane prepolymer in an amount of 5-60 pbw, preferably of 10-50 pbw, particularly preferably of 15-40 pbw, and more particularly preferably of 30-40 pbw.
  • the phosphate can both play a role in fire retarding and reducing viscosity in the pre- sent invention.
  • the polyisocyanate is preferably selected from 4,4-methylenebis(2,6- diethylphenylisocyanate), tetramethylene 1 ,4-diisocyanate, hexamethylene diisocya- nate (HDI), dodecyl 1 ,2-diisocyanate, cyclobutane- l,3-diisocyanate, cyclohexane- 1,3- diisocyanate, cyclohexane- 1 ,4-diisocyanate, l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane, hexahydrotoluene-2,4-diisocyanate, hexahydrophenyl- 1,3-diisocyanate, hexahydrophenyl- 1 ,4-diisocyanate, perhydro-diphenylmethane 2,4- diisocyan
  • the polyisocyanate is in particular preferably the mixture of 4,4'-, 2,4'- and 2,2'- diphenylmethane diisocyanate, most preferably which has the 2,4'-diphenylmethane diisocyanate content of more than 50% and the NCO content of 33%.
  • the polyisocyanate is present in the hydroxyl-terminated polyurethane prepolymer in an amount of 5-60 pbw, preferably of 10-50 pbw, and particularly preferably of 15-40 pbw.
  • the amount of the polyisocyanate may be determined by those skilled in the art according to target hydroxyl value of reaction product, hydroxyl value, type and amount of the polyol used.
  • the mixing in step i) may be carried out as follows: mixing a) one or more polymeric polyols with b) one or more phosphates, and dehydrating at 1 10°C- 130°C and under vacuum to remove moisture therein, then introducing N 2 , reducing the temperature to 70-80°C, followed by adding c) one or more polyisocyanates and stirring.
  • the vacuum pressure is preferably 0.5 mbar to 1 mbar.
  • step ii) is preferably carried out at 70-80°C for 2-3 h.
  • a hydroxyl- terminated polyurethane prepolymer which is the reaction product of the following raw materials:
  • halogenated polyether polyol is defined as above.
  • the halogenated polyether polyol is preferably the halogen-phosphorus composite fire retardant polyether polyol defined as above.
  • the polyisocyanate is defined as above.
  • the one or more polymeric polyols further comprise the polyester polyol and/or non-halogenated polyether polyol as defined above.
  • the polymeric polyol is present in the hydroxyl-terminated polyurethane prepolymer in an amount of 1-60 pbw, preferably of 5-55 pbw, and particularly preferably of 10- 55 pbw.
  • the polyisocyanate is present in the hydroxyl-terminated polyurethane prepolymer in an amount of 5-60 pbw, preferably of 10-50 pbw, particularly preferably of 15-40 pbw, and more particularly preferably of 30-40 pbw.
  • step i) is carried out as follows: dehydrating a) one or more polymeric polyols at 1 10°C- 130°C and under vacuum to remove moisture therein, then introducing N2 , reducing the temperature to 70-80°C, followed by adding b) one or more pol- yisocyanates and stirring.
  • the vacuum pressure is preferably 0.5 mbar to 1 mbar.
  • step ii) is preferably carried out at 70-80°C for 2-3 h.
  • polyisocyanu- rate foam which is obtained by the reaction of component A and component B:
  • Component A comprising:
  • Component B which is one or more polyisocyanates.
  • the hydroxyl-terminated polyurethane prepolymer is present in component A in an amount of 40- 100 pbw, preferably of 50-95 pbw, particularly preferably of 70-95 pbw, and most preferably 70-93 pbw.
  • the polymeric polyol used in component A is selected from the polyether polyols and polyester polyols described for the hydroxyl-terminated polyurethane prepolymer.
  • the polymeric polyol is used in component A in an amount of 0-40 pbw, preferably of 5-30 pbw, and particularly of 5-20 pbw.
  • the foam stabilizer used in component A is a material that promotes the formation of regular foam structure during foam forming.
  • foam stabilizers such as siloxane-oxyalkylene copolymers and other organic polysiloxanes
  • fatty alcohol oxo alcohol
  • fatty amine alkylphenol, dialkylphenol, alkylcresol, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidine, bisphenol A, alkylated bisphenol A, alkoxylated products of polyvinyl alcohol, and alkoxylated products of condensates of formaldehyde and alkylphenol, formaldehyde and dialkylphenol, formaldehyde and alkylcresol, formaldehyde and alkylresorcinol, as well as a mixture of two or more of such foam stabilizers.
  • the foam stabilizer is present in component A in an amount of 1 -10 pbw, preferably of 1 -5 pbw, and particularly of 1 -3 pbw.
  • Non-limiting examples used as the catalyst in component A include tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethyl diamino diethyl ether, bis(dimethylaminopropyl)urea, N-methylmorpholine or N-ethylmorpholine, N- cyclohexylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ ' -tetramethyl ethylene diamine, ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethyl butanediamine, ⁇ , ⁇ , ⁇ ', ⁇ ' -tetramethyl hexane- l,6-diamine, pen
  • octane, l,4-diazabicyclo[2. 2. 2]octane(Dabco), and alkanolamine compounds such as triethanolamine, triisopro- panolamine, N-methyldiethanolamine and N-ethyldiethanolamine, dimethylaminoeth- anol, 2-(N,N-dimethylaminoethoxy)ethanol, ⁇ , ⁇ ', ⁇ "- tris(dialkylaminoalkyl)hexahydro-s-triazine such as ⁇ , ⁇ ', ⁇ "- tris(dimethylaminopropyl)hexahydro-s-triazine, and triethylenediamine.
  • alkanolamine compounds such as triethanolamine, triisopro- panolamine, N-methyldiethanolamine and N-ethyldiethanolamine, dimethylaminoeth- anol, 2-(N,N-dimethylaminoethoxy)
  • Metal salts such as ferrous (II) chloride, zinc chloride and lead octoate are also suitable, and tin salts such as tin dioctoate, tin diethyl hexanoate and dibutyltin dilaurate, and particu- larly mixtures of tertiary amines and organic tin salts are preferred.
  • tin salts such as tin dioctoate, tin diethyl hexanoate and dibutyltin dilaurate, and particu- larly mixtures of tertiary amines and organic tin salts are preferred.
  • potassium acetate and potassium octoate are capable to effectively increase the conversion rate of the trimerization of isocyanates, making foam post-cure better.
  • the catalyst is present in component A in an amount of 1 - 15 pbw, preferably of 1 -10 pbw, and particularly preferably of 3-9 pb
  • the blowing agent used in component A may be selected from those known to be used to prepare polyurethane foam, including chemical and/or physical blowing agents.
  • the chemical blowing agent refers to compound that produces gaseous product through reacting with isocyanate.
  • examples of such compounds include water or car- boxylic acids.
  • the physical blowing agent refers to liquid that is inert to polyisocyanate and has a boiling point of less than 100°C, preferably of less than 50 °C under atmospheric pressure, and which evaporates under the condition of exothermic addition polymerization.
  • useful physical blowing agent include alkanes such as heptane, hexane, n-pentane and isopentane; cycloalkanes such as cyclopentane and cyclohex- ane; ethers such as furan, dimethyl ether and diethyl ether; ketones such as acetone and methyl ethyl ketone; alkyl carboxylates such as methyl formate, dimethyl oxalate and ethyl acetate; and halogenated hydrocarbons such as dichloromethane, dichloro- fluoromethane, difmoromethane, trifluoromethane, difluoroethane, tetrafluoroe
  • blowing agent comprises substituted or unsubstituted hydrocarbon such as alkanes or cycloalkanes.
  • blowing agent A mixture of n-pentane and iso-pentane, as well as a mixture of n-butane, isobutane and propane are particularly preferable as blowing agent.
  • the blowing agent is present in component A in an amount of 5-40 pbw, preferably of 10-35 pbw, and particularly preferably of 15-35 pbw.
  • Suitable polyisocyanate used in component B in the present invention may be those known in the art to be used to prepare rigid polyurethane or carbamate-modified poly- isocyanurate foam, and particularly aromatic polyisocyanates such as diphenylme- thane diisocyanate and oligomers thereof, toluene diisocyanate, 1 ,5-naphthylene diisocyanate and 1 ,4-diisocyanatobenzene, such as diphenylmethane diisocyanates in 2,4'-, 2,2'- and 4,4'-isomers thereof and mixtures thereof, mixtures of diphenylme- thane diisocyanate (MDI) and oligomers thereof (known as "crude product” in the art) or polymeric MDI with an isocyanate functionality of more than 2 (polymethylene polyphenylene polyisocyanate), and toluene diisocyanates in 2,4- to 2,6-isomers thereof and
  • organic polyisocyanate that may be mentioned include aliphatic diisocyanate such as isophorone diisocyanate, 1 ,6- diisocyanatohexane and 4,4'-diisocyanatodicyclohexylmethane.
  • the volume of polyisocyanate in component B is required to be the same as that of component A, and the amount of the polyisocyanate in component B can be determined according to the volume of component A.
  • component A i) mixing a) the above hydroxyl-terminated polyurethane prepolymer, b) optionally, one or more polymeric polyols, c) one or more foam stabilizers, d) one or more catalysts and e) one or more blowing agents and stirring, to give component A as a uniform mixture;
  • Component A and component B are preferably maintained at a temperature of 35- 40°C prior to mixing.
  • Heat Conductivity is measured in accordance with DIN-52612-2: 1984-06.
  • Percentage of Closed Cell Foam is measured in accordance with ASTMD2856-94. Compression strength is measured in accordance with DIN-53421 : 1984-06.
  • Foam Dimensional Stability is measured in accordance with GB881 1 -1988.
  • Oxygen Index is measured in accordance with GB/T 2406.2-2009. The following raw materials are used in the examples:
  • Foam Stabilizer siloxane-oxyalkylene copolymer surfactant Niax ® Silicone L- 6920, Momentive Performance Materials Inc.
  • Catalyst 4 N,N',N"-tri(dimethylaminopropyl) hexahydrotriazine (POLY- CAT ® 41, Evonik Specialty Chemicals Co., Ltd.)
  • the polyisocyanurate foams were prepared according to the formulations in Table 2 using the hydroxyl-terminated polyurethane prepolymers obtained from Examples 1-4.
  • the hydroxyl-terminated polyurethane prepolymer, optional polymeric polyol and foam stabilizer (siloxane-oxyalkylene copolymer surfactant), blowing agent, catalyst, optional fire retardant were mixed and stirred, to give component A as a uniform mixture.
  • Component A was added to the feed tank for component A in the spray machine comprising feed tank for component A and feed tank for component B, transfer pump for component A and transfer pump for component B, proportioning pump for component A and proportioning pump for component B, hose for component A and hose for component B, mixing chamber, with transfer pump for component A were connected to hose for component A via proportioning pump for component A, and transfer pump for component B were connected to hose for component B via proportioning pump for component B, and hose for component A and hose for component B were both connected to the mixing chamber.
  • Component B polyisocyanate was added to the feed tank for component B in the spray machine.
  • the proportionality coefficient of proportioning pump A and proportioning pump B was set to 1 : 1.
  • Component A in feed tank for component A in the spray machine was delivered to proportioning pump for component A through transfer pump for component A, and then it was pumped through hose for component A to the mixing chamber of the spray machine by pressurizing proportioning pump for component A;
  • component B in feed tank for component B in the spray machine was delivered to proportioning pump for component B through transfer pump for component B, and then it was pumped through hose for component B to the mixing chamber of the spray machine by pressurizing proportioning pump for component B;
  • component A and com- ponent B were mixed in the mixing chamber with the temperature of proportioning pump for component A and proportioning pump for component B, hose for component A and hose for component B all set to 35 ⁇ 40 °C.
  • the mixture was sprayed onto the surface of the workpiece to be sprayed by the high pressure gas delivered to the mixing chamber, thus completing the spray moulding for preparing the polyisocyanurate foam.
  • the polyisocyanurate foam was prepared using a high ratio of A/B according to the formulation in Table 2.
  • the comparative example was carried out referring to example 5-8, with the exception that the hydroxyl-terminated polyurethane prepolymer is absent from component A.
  • Table 2 Raw materials used for preparation of polyisocyanurate foams and properties of the resulted polyisocyanurate foams
  • the isocyanates/polyol blend (B/A) ratio can be brought to 1 : 1 by employing the hydroxyl- terminated polyurethane prepolymer to prepare polyisocyanurate foam and this rigid polyisocyanurate foam has comparable foam physical and fire retardant properties to those from the conventional system with an isocyanates/polyol blend (B/A) ratio of other than 1 : 1 (for example a 1 : 1.36 system).
  • the compression strength (parallel and perpendicular) of the polyisocyanurate foams obtained in the Examples 5-8 is improved in view of Comparative Example 9.
  • foam with the comparable fire retardant property was obtained, while conventional device with A/B ratio of 1 : 1 on the market can be used, thus the complexity and cost were reduced substantially during the practical production and the fire retardant property of the product can be improved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne le domaine du polyuréthane et concerne des prépolymères de polyuréthane à terminaisons hydroxyle et leur utilisation dans la synthèse de mousse de polyisocyanurate ignifuge. Le prépolymère de polyuréthane à terminaisons hydroxyle est le produit de réaction des matières premières suivantes : a) un ou plusieurs polyols polymères, choisis parmi les polyols de polyéther et les polyols de polyester ; b) un ou plusieurs phosphates ; et c) un ou plusieurs polyisocyanates. Le prépolymère de polyuréthane à terminaisons hydroxyle est utile dans la préparation de polyisocyanurate et la mousse de polyisocyanurate obtenue est supérieure dans ses propriétés d'isolation thermique, ses propriétés adhésives, la résistance à la compression et la stabilité dimensionnelle, tout en étant plus économique et en présentant un excellent effet ignifugeant.
PCT/EP2018/056555 2017-03-15 2018-03-15 Prépolymère de polyuréthane à terminaisons hydroxyle et son procédé de préparation WO2018167220A1 (fr)

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CN111848900A (zh) * 2020-08-07 2020-10-30 宁波耀众模塑科技有限公司 一种聚氨酯发泡产品的阻燃配方
CN112079987A (zh) * 2020-09-29 2020-12-15 江苏登科聚氨酯材料有限公司 一种本体阻燃热塑性聚氨酯弹性体及其制备方法
WO2023278257A1 (fr) * 2021-06-29 2023-01-05 Covestro Llc Compositions réactives à l'isocyanate à teneur en hfo, compositions de formation de mousse de polyuréthane associées, et mousses de polyuréthane appliquées par pulvérisation
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