WO2021202876A1 - Composition de prépolymère de polyuréthane comprenant un benzoate d'alkyle - Google Patents

Composition de prépolymère de polyuréthane comprenant un benzoate d'alkyle Download PDF

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Publication number
WO2021202876A1
WO2021202876A1 PCT/US2021/025384 US2021025384W WO2021202876A1 WO 2021202876 A1 WO2021202876 A1 WO 2021202876A1 US 2021025384 W US2021025384 W US 2021025384W WO 2021202876 A1 WO2021202876 A1 WO 2021202876A1
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polyurethane prepolymer
prepolymer composition
composition according
diisocyanate
alkyl benzoate
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PCT/US2021/025384
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English (en)
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Thomas Peter
Johnathon CRIBB
Rebecca Nicholson
Tyler Ryan
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Lanxess Corporation
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Publication of WO2021202876A1 publication Critical patent/WO2021202876A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic 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
    • C08G18/28—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
    • C08G18/4825—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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids

Definitions

  • Polyurethane prepolvmer composition comprising an alkyl benzoate
  • the present invention relates to a polyurethane prepolymer composition
  • a polyurethane prepolymer composition comprising at least one alkyl benzoate as well as cured polyurethane made thereof and the use of alkyl benzoate as plasticizers in polyurethanes mixed, cast and cured at room temperature.
  • the viscosity of the individual components and the viscosity of the mixed system are critical metrics that impact the usability of such cast urethane systems. If the viscosity is too high, the system may be difficult to mix, and the mixed system may not easily flow into a cast mold. Lowering the viscosity of a cast urethane system can be achieved through the choice of the polyol backbone or higher amounts of free polyisocyanate monomer content. However, application requirements and health and safety issues limit these options, especially when the prepolymer is intended to be a low free (LF) product comprising only low amounts of free polyisocyanate monomer.
  • LF free
  • Another option for the polyurethane prepolymer composition formulator is to lower the viscosity through the addition of a diluent, generally a plasticizer. Adding a plasticizer to a urethane composition will lower viscosity; However, adding a plasticizer has a negative effect on the physical properties of the cured polyurethane elastomer.
  • the challenge for the polyurethane prepolymer composition formulator is to only add enough plasticizer to the polyurethane prepolymer composition to ensure ease of use but not so much as to significantly lower the physical properties.
  • a possible solution to such an issue would be to use a low molecular weight solvent to accomplish better plasticizing efficiency. This is often not a viable approach, as the solvent may cause leaching and the odor imparted by the solvent is highly undesirable.
  • WO-A-2019/089237 discloses viscosity reducers for sprayable polyurethane compositions, such as triethylphosphate (TEP), tris(1-chloro-2-propyl phosphate) (TCPP), diisononyl adipate (Plastomoll® DNA), phthalate plasticizers (Palatinol®), and trimethyl pentanyl diisobutyrate (TXIB).
  • TEP triethylphosphate
  • TCPP tris(1-chloro-2-propyl phosphate)
  • TCPP diisononyl adipate
  • Plastomoll® DNA diisononyl adipate
  • phthalate plasticizers Palatinol®
  • TXIB trimethyl pentanyl diisobutyrate
  • US-A-2016/0312090 discloses an adhesive comprising polyurethane prepolymers and plasticizers such as tris(2-ethylhexyl) trimellitate (TOTM), phthalate free C1-C20 alkylsulphonic acid ester with phenol (such as Mesamoll®), benzoate ester, biobased plasticizers such as bio succinic acid or soy based plasticizers.
  • plasticizers such as tris(2-ethylhexyl) trimellitate (TOTM), phthalate free C1-C20 alkylsulphonic acid ester with phenol (such as Mesamoll®), benzoate ester, biobased plasticizers such as bio succinic acid or soy based plasticizers.
  • EP-A-1846492 discloses the use of Cg to Cn alkyl benzoates as plasticizers for polyvinyl chloride in combination with other plasticizers. The use of such alkyl plasticizers for cast polyurethanes is not disclosed.
  • US-A-4365051 discloses a polyurethane polymer prepared from 4,4’-MDI and caprolactone/diethylene glycol polyester polyol and various diamino alkyl benzoates.
  • the diamino alkylbenzoates work as a curative in these compositions. Since the isocyanate monomers are not removed from the composition, it is believed that they are still present in the composition.
  • CN104302685 discloses a polyurethane polymer prepared from polyether or polyester polyols and isocyanate, and plasticizers like dibasic ether (DBE) and triethyl phosphate in an amount of 11-30 wt%. Isononyl benzoate is disclosed in a list of suitable plasticizers. Since the isocyanate monomers are not removed from the composition, it is believed that they are still present in the composition.
  • DBE dibasic ether
  • Isononyl benzoate is disclosed in a list of suitable plasticizers. Since the isocyanate monomers are not removed from the composition, it is believed that they are still present in the composition.
  • US-A-2015/167263 discloses a polyurethane polymer prepared from polyether polyol and IPDI.
  • the prepolymer is mixed with HDI-trimer and plasticizer in an amount of 15-50 wt%. Since the isocyanate monomers are not removed from the composition, they are still present in a relatively high amount in the composition.
  • EP-A-2103648 discloses a polyurethane polymer prepared from PPG and IPDI. Isononyl benzoate is used as plasticizer in one of the examples. Since the isocyanate monomers are not removed from the composition, they are still present in a relatively high amount in the composition.
  • plasticized polyurethane prepolymer compositions which are of low viscosity, preferably at room temperature, which have low volatility (e.g. low odor), which are not compromised on physical properties [compared to non-plasticized polyurethane prepolymer compositions], which are preferably color stable, which comprise preferably low amounts of free polyisocyanate monomer and contain as little plasticizer as possible.
  • polyurethane prepolymer compositions comprising at least one polyurethane prepolymer (obtained by the reaction of at least one polyisocyanate and at least one polyol) and at least one alkyl benzoate, in particular a monoester of benzoic acid and isodecyl alcohol, as a plasticizer achieves the same viscosities as common polyurethane plasticizers such as phthalate at significantly lower amounts and that the physical properties of the cured polyurethanes are even better compared to polyurethanes comprising common polyurethane plasticizers.
  • Embodiments of the present invention exhibit a number of advantages over the prior art.
  • Polyurethane prepolymers of the present invention are formed from the reaction of at least one polyisocyanate and at least one polyol, wherein the at least one polyisocyanate is used in an amount such that NCO groups are present in molar excess relative to the hydroxyl groups of the at least one polyol to obtain a polyurethane prepolymer with free NCO groups, such as an NCO-terminated PU prepolymer.
  • a polyurethane prepolymer with free NCO groups such as an NCO-terminated PU prepolymer.
  • polyisocyanate as used herein, is defined as a molecule having two or more isocyanate (NCO) groups, such as di- and poly-functional isocyanates, e.g. tri- and tetra- functional isocyanates, including oligomers, polymers and blocked isocyanates.
  • NCO isocyanate
  • the present invention is not limited to a particular polyisocyanate. Any polyisocyanate having two or more isocyanate groups, is suitable for use in preparing the polyurethane prepolymers of the present invention. Obviously, no attempt is made here to provide an exhaustive list of possible polyisocyanate suitable for the practice of the present invention.
  • Suitable polyisocyanates of the present invention include aliphatic polyisocyanates, cycloaliphatic polyisocyanates, polycyclic polyisocyanates, aromatic polyisocyanates and aliphatic-aromatic diisocyanates.
  • the at least one polyisocyanate to prepare the polyurethane prepolymer of the present invention comprises a diisocyanate.
  • Diisocyanate monomer is understood to mean a hydrocarbon compound of low molar mass (of less than 700 g/mol) having two isocyanate groups.
  • Suitable diisocyanates of the present invention include aliphatic diisocyanates, cycloaliphatic diisocyanates, polycyclic diisocyanates, aromatic diisocyanates and aliphatic-aromatic diisocyanates.
  • “Aromatic diisocyanate monomer” is understood to mean a diisocyanate monomer as defined above, in which one of the NCO groups is connected via a covalent bond to a carbon atom forming part of an aromatic hydrocarbon ring, such as a phenyl group.
  • Suitable aromatic diisocyanates of the present invention include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), phenylene diisocyanate (PDI), tolidine diisocyanate (TODI), diphenyl diisocyanate (DPDI), dibenzyl diisocyanate, naphthalene diisocyanate (NDI), anthracene diisocyanate, benzophenone diisocyanate, xylene diisocyanate (XDI), and combinations thereof.
  • MDI diphenylmethane diisocyanate
  • TDI toluene diisocyanate
  • PDI phenylene diisocyanate
  • TODI tolidine diisocyanate
  • DPDI diphenyl diisocyanate
  • NDI naphthalene diisocyanate
  • XDI xylene diisocyanate
  • Preferred aromatic diisocyanate monomers suitable in the practice of the present invention include 2,4’-methylene-bis-(phenyl isocyanate) (2,4’-MDI) and 4,4’-methylene- bis-(phenyl isocyanate) (4,4’-MDI), 2,2-diphenylpropane-4,4’-diisocyanate, toluene-2, 4- diisocyanate (2,4-TDI; CAS: 584-84-9), toluene-2, 6-diisocyanate (2,6-TDI; CAS: 91-08-7), para-phenylene diisocyanate (PPDI), tolidine diisocyanate, naphthalene-1 ,4-diisocyanate, naphthalene-1 ,5-diisocyanate, stilbene-4,4'-diisocyanate, diphenyl-4, 4'-diisocyanate, benzophenone-4,4'-diis
  • Suitable aliphatic and cycloaliphatic diisocyanates of the present invention include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanates (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, tetracene diisocyanate, isophorone diisocyanate (IPDI), cyclohexyl diisocyanates (CHDI), 2, 4, 4-trimethyl-1 ,6-hexane diisocyanate (TMDI), methylene bis(p-cyclohexyl isocyanate) (H12MDI), xylene diisocyanate (XDI), L-lysine ethyl ester diisocyanate (
  • Preferred aliphatic diisocyanate monomer suitable in the practice of the present invention include 1 ,3-trimethylene diisocyanate, propylene-1 ,2-diisocyanate, tetramethylene-1 ,4- diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethylhevamethylene diisocyanate, 2,4,4-trimethylheyamethylene diisocyanate, 1 ,9-nonamethylene diisocyanate, 1 ,10-decamethylene diisocyanate, dodecane-1 ,12-diisocyanate, isophorone diisocyanate, cyclobutane-1 ,3-diisocyanate, 1 ,3-cyclopentyl diisocyanate, 1 ,4’-cyclohexyl diisocyanate, 4,4’-dicyclohexylmethane diisocyanate, m-xylene diisocyanate, 2,2
  • the at least one polyisocyanate is selected from a group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanates (HDI), para-phenylene diisocyanate (PPDI) and methylene bis(p-cyclohexyl isocyanate) (H12MDI).
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanates
  • PPDI para-phenylene diisocyanate
  • H12MDI methylene bis(p-cyclohexyl isocyanate
  • the at least one polyisocyanate is toluene diisocyanate (TDI).
  • the present invention is not limited to a particular polyol.
  • Such polyols are well known in the art and more than one may be used.
  • a polyol suitable for the present invention used in the preparation of the present polyurethane prepolymer may be selected from any polyol known in the art.
  • Polyols include compounds having more than one hydroxyl groups.
  • polyols suitable for the present invention comprise diols, triols, and/or higher average hydroxyl functionality.
  • the average hydroxyl functionality can range from 2 to 8, preferably 2 to 3 and more preferably from 2 to 2.5. The formation of such polyols is well known in the art.
  • diols are preferred over triols or polyols with higher hydroxyl functionality.
  • the polyol comprises at least one polyester polyol, at least one polyether polyol, at least one polycaprolactone polyol, at least one polycarbonate polyol or combinations thereof.
  • polyester polyol as used herein means a polyol having ester linkages.
  • a polyester polyol suitable for the present invention for making a polyurethane prepolymer is a polyol having a backbone derived mainly from a polycarboxylate and a poly alcohol, e.g., a majority of the ester linkages in the backbone are derived from a polycarboxylate and a polyol, such as found in polyethylene adipate) glycol:
  • the hydrocarbon chain of the polyol can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups and can be either linear or branched.
  • Some polyester polyols also employ caprolactone and dimerized unsaturated fatty acids in their manufacture.
  • polyester polyols include poly(adipate) glycol, poly(hexamethylene adipate) glycol, polyethylene adipate) glycol (PEAG), poly(diethylene adipate) glycol, poly(ethylene/propylene adipate) glycol, poly(trimethylolpropane/hexamethylene adipate) glycol, poly(ethylene/butylene adipate) glycol, poly(butylene adipate) glycol, poly(hexamethylene/neopentyl adipate) glycol, poly(butylene/hexamethylene adipate) glycol (PBHAG), poly(neopentyl adipate) glycol, ortho-phthalate-1 ,6-hexanediol, and combinations, compolymers (including block and random copolymers) and terpolymers thereof.
  • PAG poly(diethylene adipate) glycol
  • poly(ethylene/propylene adipate) glycol
  • Suitable polyester polyols may be produced by polycondensation.
  • polyester polyols are prepared by conventional methods using a combination of diacids (dibasic acids) and polyols that are known in the art.
  • polyester polyols include the reaction products of diacids such as adipic acid, glutaric acid, succinic acid, azelaic, sebacic, or phthalic or isophtalic acid with diols such as ethylene glycol, 1 ,2- propylene glycol, 1 ,3 propane diol, 1 ,4-butane diol (BDO), 1 ,3 butanediol, 1 ,6-hexane diol, diethylene glycol, polyethylene glycol, polypropylene glycols, or polytetramethylene ether glycol.
  • diacids such as adipic acid, glutaric acid, succinic acid, azelaic, sebacic, or phthalic or isophtalic acid
  • diols such as ethylene glycol, 1 ,2-
  • polyether polyol as used herein means a polyalkylene ether polyol represented by the general formula HO(RO)nH, wherein R is an alkylene radical and n is an integer large enough that the polyether polyol has a number average molecular weight of at least 250 g/mol.
  • polyalkylene ether polyols are well-known components of polyurethane products and can be prepared by the polymerization of cyclic ethers such as alkylene oxides and glycols, dihydroxyethers, and the like by known methods.
  • polyether polyols include polyethylene glycol (PPG), polypropylene glycol (PPG), polyhexamethylene glycol (PHMG), polyoctamethylene glycol (POMG), polyceamethylene glycol (PDMG), copolymers from propylene oxide and ethylene oxide (PPG-EO glycol), poly(tetramethylene ether) glycol (PTMEG or PTMG; also known as polytetrahydrofuran (PTHF)), mixed ether diols, such as poly ethylene propylene glycol copolymer diols, and the like.
  • PPG polyethylene glycol
  • PPG polypropylene glycol
  • PHMG polyhexamethylene glycol
  • POMG polyoctamethylene glycol
  • PDMG polyceamethylene glycol
  • PPG-EO glycol poly(tetramethylene ether) glycol
  • PTMEG or PTMG also known as polytetrahydrofuran (PTHF)
  • mixed ether diols such
  • the at least one polyol is selected from the group consisting of PPG and PTMEG. In a more preferred embodiment, the at least one polyol is PPG.
  • a “polylactone polyol” suitable for the present invention for making a polyurethane prepolymer is a polyol having a backbone derived mainly from a hydroxycarboxylic acid or lactone.
  • Suitable polylactone polyols include those made by polycondensation of, e.g., a caprolactone such as e-caprolactone, and the like, often initiated by a small polyol such as ethylene glycol.
  • polycaprolactone polyols include, but are not limited to, 1 ,6- hexanediol-initiated polycaprolactone, diethylene glycol initiated polycaprolactone, trimethylol propane initiated polycaprolactone, neopentyl glycol initiated polycaprolactone, 1 ,4-butanediol-initiated polycaprolactone, and combinations thereof.
  • the hydrocarbon chain can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.
  • a “polycarbonate polyol” suitable for the present invention for making a polyurethane prepolymer is a polyol having a backbone comprising mainly carbonate linkages, -O- (CO)-O-, as opposed to carboxylate linkages, -0-(CO)-R wherein R is a hydrogen or an organic radical bound to the carbonyl by a C-C bond .
  • Polycarbonate polyols can be prepared by reaction of glycols, e.g., 1 ,6-hexylene glycol and the like, with organic carbonates, e.g., diphenyl carbonate, diethyl carbonate, or ethylene carbonate and the like.
  • suitable polyols of the present invention are poly(hexamethylene carbonate) (PHMC) diol or Poly(1 ,6-hexyl-1 ,2-ethyl carbonate) (PHEC) diol.
  • Suitable polycarbonates include, but are not limited to, polyphthalate carbonate.
  • the hydrocarbon chain can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.
  • the at least one polyurethane prepolymer of the present invention, further comprising free polyisocyanate monomers is a “low free monomer” polyurethane prepolymer (also known as “low free”, “LF” or “low isocyanate”).
  • “low free monomer” polyurethane prepolymer also known as “low free”, “LF” or “low isocyanate”.
  • the amount of free polyisocyanate in the polyurethane prepolymer composition may be at a reduced level, e.g., the polyurethane prepolymer composition may be a "low free" polyisocyanate prepolymer mixture, e.g., free polyisocyanate levels of less than 25 wt.%, less than 10 wt.%, less than 5 wt.%, less than 3 wt.%, less than 1 wt.%, less than 0.5 wt.% or less than 0.1 wt.%.
  • free diisocyanate in the polyurethane prepolymer composition may be removed by distillation as is known in the art.
  • the amount of free diisocyanate in the prepolymer mixture is at a reduced level, e.g., less than 10 wt.%, and in many embodiments the prepolymer mixture is a low free diisocyanate prepolymer mixture having free diisocyanate amounts of less than 5 wt.%, less than 3 wt.%, less than 1 wt.%, less than 0.5 wt.% or less than 0.1 wt.%.
  • Such low free monomer prepolymers and methods for their preparation are also known in the art.
  • NCO prepolymers In the case of the low-monomer-content NCO prepolymers, a typical structure is composed of the reaction product of two isocyanates A and of a polyol B, therefore being ABA. Because of the large excess of isocyanate (high index) in relation to polyol, the probability of formation of larger units, such as ABABA, is very small. These low- monomer-content NCO prepolymers comprise only ABA units. In contrast, NCO prepolymers that do not comprise low monomer content (also termed batch prepolymers or non-thin-layer prepolymers) have a distribution of ABA, ABABA, ABABABA, etc., and also comprise free isocyanate A.
  • Residual monomer contents in polyurethane prepolymer compositions and polyurethanes can be disadvantageous for different reasons.
  • Some systems are processed at elevated temperatures (e.g. hot melt adhesives at 100-170°C), a temperature range at which monomeric diisocyanates have a considerable vapor pressure.
  • Alkyl benzoate (benzoic acid monoester) (Plasticizer)
  • the polyurethane prepolymer composition of the present invention comprises at least one alkyl benzoate.
  • the at least one alkyl benzoate is an unsubstituted alkyl benzoate.
  • the at least one alkyl benzoate is a compound according to the following formula (I)
  • R1 is a linear or branched Cg-Cn alkyl.
  • the at least one alkyl benzoate is isodecyl benzoate (also named 8-methlynoyl benzoate) CAS Nr.: 120657-54-7 as illustrated in formula (II)
  • Isodecyl benzoate of the present invention is available as BenzoflexTM 131 from Eastman Chemical Company or JayflexTM MB10 from ExxonMobil Chemical.
  • the total plasticizer content of the polyurethane prepolymer composition is made up of the Cg benzoate and/or Cm benzoate and/or Cn benzoate.
  • the total plasticizer content may be made up of one or more Cg-Cn benzoates only.
  • additional plasticizers such as phthalate esters, alkyl adipate or trialkyl isobutyrate might be present.
  • phthalate esters that are optionally used as additional plasticizers with Cg to C11 alkyl benzoate(s) in accordance with the present invention include diisobutyl phthalate, butyl benzyl phthalate, diisoheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisooctyl phthalate, diisoheptyl phthalate, di-2-ethyl hexyl phthalate (DEHP), diisononyl phthalate, di-2-propyl heptyl phthalate and diisodecyl phthalate.
  • DEHP diisononyl phthalate
  • di-2-propyl heptyl phthalate and diisodecyl phthalate diisodecyl phthalate.
  • Typical commercial materials include the JayflexTM plasticizers, JayflexTM 77 (DIHP), JayflexTM DINP and JayflexTM DIDP available from ExxonMobil Chemical and the Palatinol plasticizers marketed by BASF and Vestinol plasticizers from Oxeno.
  • Examples of preferred additional plasticizers include JayflexTM DINA (di-isononyl adipate; available from ExxonMobil Chemical), di-2-ethyl hexyl terephthalate, di-2-propyl heptyl phthalate or diisodecyl phthalate.
  • JayflexTM DINA di-isononyl adipate; available from ExxonMobil Chemical
  • di-2-ethyl hexyl terephthalate di-2-propyl heptyl phthalate or diisodecyl phthalate.
  • the ratio of alkyl benzoate to additional plasticizer is 1 :1 to 10:1 .
  • the at least onepolyurethane prepolymer is present from 60 wt.% to 95 wt.%, preferably 70 wt.% to 90 wt.%, based on the total weight of the polyurethane prepolymer composition.
  • the at least one alkyl benzoate is present from 5 wt.% to 40 wt.%, preferably from 10 wt.% to 30 wt.%, based on the total weight of the polyurethane prepolymer composition.
  • the polyurethane prepolymer composition of the present invention does not comprise additional plasticizer.
  • the present invention further relates to a curable polyurethane prepolymer composition
  • a curable polyurethane prepolymer composition comprising
  • Curatives also called curing agents, coupling agents, cross linking agents or chain extenders, are well known in the art and include various polyols or polyamines.
  • Common curatives include C1-12 alkylene diols such as ethylene glycol, 1 ,3-propanediol,
  • ether diols such as diethylene glycol; dipropylene glycol, dibutylene glycol, triethylene glycol and the like; hydroquinone-bis-hydroxyalkyl ethers such as hydroquinone-bis-hydroxyethyl ether (HQEE), diethylene glycol etc.; and diamines including ethylene diamine, hexamethylene diamine, isophorone diamine, xylylene diamine, methylenedianiline (MDA), naphthalene-1 ,5-diamine, ortho, meta, and para-
  • the at least one curative is a polyol.
  • the polyol curative may include ethylene glycol; polyethylene glycol; propylene glycol; polypropylene glycol; lower molecular weight polytetramethylene ether glycol; 1 ,3- bis(2-hydroxyethoxy)benzene; 1 ,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene; 1 ,3-bis-12-[2- (2-hydroxyethoxy)ethoxy]ethoxy)benzene; 1 ,4-butanediol; 1 ,5-pentanediol; 1 ,6- hexanediol; resorcinol-bis(2-hydroxyethyl)ether; hydroquinone-di(2-hydroxyethyl)ether; trimethylol propane, and combinations thereof.
  • the at least one curative is a polyamine.
  • the polyamine curative may include 3,5-dimethylthio-2,4-toluenediamine (DMTDA ) and isomers thereof, 3, 5-diethyltoluene-2, 4-diamine and isomers thereof, 1 ,3- propanediol-bis-(4-aminobenzoate), 4,4'-bis-(sec-butylamino)-diphenylmethane, 1 ,4-bis- (sec-butylamino)-benzene, 4,4'-methylene-bis-(2-chloroaniline), 4,4'-methylene-bis-(3- chloro-2,6-diethylaniline), trimethylene glycol-di-p-aminobenzoate, polytetramethyleneoxide-di-p-aminobenzoate, N,N'-dialkyldiamino diphenyl methane,
  • DMTDA 3,5-dimethylthio
  • the at least one curative comprises an aromatic diamine, including a methylenedianiline, toluene diamine, xylylene diamine, phenylene diamine, and the like; specific examples include, 4,4'-methylenedianiline (MDA), 4,4'-ethylene-bis- 2,6 diethyl aniline (MDEA) ortho, meta, and para-phenylene diamines, toluene-2, 4- diamine, 4,4'-methylene-bis(3-chloroaniline) (MBCA), 4,4'-methylene-bis(3-chloro-2,6- diethylaniline) (MCDEA), diethyl toluene diamine (DETDA), 3,5-dimethylthio-2,4- toluenediamine (DMTDA), isobutyl-3, 5-diamino-4-chlorobenzoate, and trimethylene glycol di-p-amino-benzoate.
  • MDA 4,4'-methylenedianiline
  • the at least one curative of the curable polyurethane prepolymer composition is a polyol and more preferably an ethylene oxide-capped polypropylene oxide) (EO-PPG).
  • EO-PPG ethylene oxide-capped polypropylene oxide
  • the at least one curative is present from 1 wt.% to 50 wt.%, preferably 10 wt.% to 50 wt.%, based on the total weight of the curable polyurethane prepolymer composition.
  • the present invention further relates to a process for producing curable polyurethane prepolymer compositions, comprising the step of: contacting the at least one polyurethane prepolymer of the present invention, the at least one alkyl benzoate of the present invention and at least one curative.
  • the at least one polyurethane prepolymer, the at least one alkyl benzoate and the at least one curative can be combined in any order or in any manner.
  • the at least one curative can be mixed with the polyurethane prepolymer composition, e.g. adding the at least one curative to the at least one polyurethane prepolymer and the at least one alkyl benzoate or adding the at least one polyurethane prepolymer and the at least one alkyl benzoate to the at least one curative.
  • a meter-mix machine may be used to meter and mix the three components simultaneously and continuously and allow continuous filling of molds to obtain higher productivity.
  • the process comprises the step of adding the at least one curative to the polyurethane prepolymer composition of the present invention. In another embodiment, the process comprises the step of adding the polyurethane prepolymer composition of the present invention to the at least one curative.
  • the at least one curative is present from 1 wt.% to 50 wt.%, preferably 10 wt.% to 50 wt.%, based on the total weight of the curable polyurethane prepolymer composition.
  • the curable polyurethane prepolymer composition comprises a catalyst (d).
  • the present invention is not limited to a particular catalyst.
  • catalysts suitable for the present invention are trialkylamines, diazabicyclooctane, tin dioctoate, dibutyltin dilaurate, N-alkylmorpholine, lead octoate, zinc octoate, calcium octoate, magnesium octoate, the corresponding naphthenates, and p-nitrophenolate.
  • the catalyst is a solution of triethylene diamine in dipropylene glycol.
  • the catalyst (d) speeds up certain reactions in the chain extension (i.e. curing) of polyurethanes.
  • the catalysts include a range of amines and metal salts.
  • the at least one catalyst is present in an amount of 0.0001 to 1 parts per 100 parts polyurethane prepolymer composition, preferably 0.005 to 0.5 parts per 100 parts polyurethane prepolymer composition.
  • Polyurethanes of the present invention are obtained by reacting the polyurethane prepolymer composition and the curative of the present invention (such process being known as “casting” or “curing”).
  • the curing of the polyurethane prepolymer composition with the at least one curative typically progresses in a mold. In a preferred embodiment, the curing occurs at a temperature of 10°C to 40°C, more preferably at room temperature. Curing of the curable polyurethane prepolymer composition with the curative imparts a network structure to the polyurethanes.
  • the polyurethane formed in the mold is demolded and, optionally, postcured with additional heat and time so as to fully realize the physical properties of the polyurethane’s elastomeric network structure.
  • Polyurethane articles can be casted in various ways, including, but not limiting to, open casting, compression molding, centrifugal molding, liquid injection molding, reaction injection molding, Ribbon Flow® rotational casting (moldless), spraying, rotational molding, vacuum casting, transfer molding, pressure casting, solvent casting and troweling.
  • the polyurethane (polyurethane elastomer) of the present invention can be formed into numerous useful articles by various means known such as coating, casting and milling processes.
  • a molded product of the polyurethane elastomer composition may be optionally further subjected to secondary crosslinking under the conditions of 100°C to 150°C for 5 h to 24h after being molded.
  • the polyurethane comprises the reaction product of at least one polyurethane prepolymer composition according to the present invention, free polyisocyanate monomer and at least one curative, wherein the amount of free polyisocyanate monomer is below 0.1 wt.% and wherein the at least one alkyl benzoate is isodecyl benzoate.
  • the invention is particularly useful in the production of cast polyurethanes at room temperature.
  • the present invention relates to the use of an alkyl benzoate as plasticizer for the production of cast polyurethanes at room temperature, preferably for the production of cast polyurethanes based on at least one polyurethane prepolymer with an amount of free polyisocyanates of below 0.1 wt.% based on the total weight of the polyurethane prepolymer.
  • an alkyl benzoate as plasticizer for the production of cast polyurethanes at room temperature, preferably for the production of cast polyurethanes based on at least one polyurethane prepolymer with an amount of free polyisocyanates of below 0.1 wt.% based on the total weight of the polyurethane prepolymer.
  • CAS Chemical Abstracts Service
  • DEG diethylene glycol
  • DINP diisononyl phthalate
  • the abbreviation ⁇ 300 means Ethacure® 300.
  • EO-PPG ethylene oxide-capped polypropylene glycol.
  • h or “hrs” means hours.
  • mPa * s means millipascal-second.
  • MW means average molecular weight
  • % NCO means content of free isocyanate groups.
  • PPG polypropylene glycol
  • the abbreviation "PU” means polyurethane.
  • the abbreviation “S 160” means Santicizer® 160.
  • S 278 means Santicizer® 278.
  • TPI toluene diisocyanate
  • Polyurethane prepolvmer components TDI 80:20 mixture of toluene-2, 4-diisocyanate (CAS No. 584-84-9) and toluene-2, 6-diisocyanate (CAS No. 91-08-7) (commercially available at Covestro)
  • DIDP diisodecyl phthalate CAS No. 26761-40-0; (commercially available from ExxonMobil)
  • BenzoflexTM 9-88 SG dipropylene glycol dibenzonate CAS No. 27138-31-4
  • Ethacure® 300 curative mixture of dimethyl thio-toluene diamine and monomethyl thio-toluene diamine (commercially available from Albemarle)
  • Niax * A33 catalyst 33 weight % solution of triethylene diamine in dipropylene glycol; (commercially available from Momentive Performance Materials)
  • Free NCO content (% NCO) Free NCO content can be determined by a procedure similar to that described in ASTM D1638-70, but employing tetrahydrofuran as the solvent.
  • Viscosity was measured according to D4878.
  • Hardness Hardness of cured polymer samples was measured using a Type A durometer (Pacific Transducer, Model 306L) according to ASTM 2240-85.
  • Die-C tear strength was tested according to ASTM D-624 (Die-C Tear).
  • Trouser tear strength was tested according to ASTM D1938 (Trouser Tear).
  • compression set buttons were tested according to ASTM D-395 Method B. Compression set measures the ability of an elastomer to retain its elastic properties during prolong action of compressive forces. The lower the compression set the better the elastomer retains its elastic properties (less permanent deformation or viscous flow). Low compression set is important in applications such as seals, machinery mount and vibration dampening.
  • LF TDI-PPG-425 polyurethane prepolymer was prepared by reacting 4073.4 g PPG-425 with excess TDI at temperatures in the range of 60°C to 100°C. The reaction mixture was held at the reaction temperature for 3 hours with agitation. Unreacted TDI monomer was then removed by a wiped film evaporator.
  • Polyurethane prepolymer 1 was prepared by reacting 3429.8 g PPG-1000 and 643.8 g DEG with excess TDI at temperatures in the range of 60°C to 100°C. The reaction mixture was held at the reaction temperature for 3 hours with agitation. Unreacted TDI monomer was then removed by a wiped film evaporator.
  • Polyurethane prepolymer 2 was prepared by reacting 6902.3 g PPG-2000 and 269.7 g PPG-4000 with excess TDI at temperatures in the range of 60°C to 100°C. The reaction mixture was held at the reaction temperature for 6 hours with agitation. Unreacted TDI monomer was then removed by a wiped film evaporator.
  • a prepolymer dilution is made by weighing out the appropriate amount of prepolymer into a mixing vessel, followed by the appropriate amount of plasticizer. This mixing vessel is then placed into a vortex mixer and mixed at 1900 RPM for approximately 30 seconds. This mixing process is repeated until the plasticizer has been completely incorporated. If the viscosities of the prepolymer and plasticizer are exceedingly different, it is often helpful to first mix the two by hand and then utilize the vortex mixer.
  • the viscosity of the polyurethane prepolvmer dilution After a prepolymer dilution has been made, the viscosity of the dilution at room temperature is measured. To do this, a Brookfield RV Viscometer equipped with an S27 spindle and Thermosel is employed. The Thermosel that has had a disposable measurement sleeve inserted is set to a temperature of 25°C and allowed to equilibrate at this temperature, prior to making a measurement. Once equilibrated, 10 mL of a plasticizer dilution are then placed into the disposable sleeve, using a disposable syringe, and the Brookfield Viscometer is then lowered into the measurement position.
  • the viscometer is then turned on, and the rotations per minute (RPM) of the spindle are adjusted such that the torque reading on the viscometer is between 20% and 80% of full scale.
  • the experimental setup is allowed to come to a steady-state, before recording the viscosity, approximately 30 minutes.
  • MB10 is a more efficient plasticizer than the other tested plasticizers, as the viscosity of the polyurethane prepolymer composition is the lowest when the same amounts of plasticizers are used.
  • the efficiency of the MB10 plasticizer is in particular remarkable at low amounts of only 10-15 wt.% plasticizer based on the total weight of the polyurethane prepolymer composition.
  • Table 3 shows the physical properties of cast polyurethanes PU 1 to PU 3 with various plasticizers.
  • the inventive polyurethane PU 1 comprising MB10 as plasticizer, has comparable physical properties to polyurethane PU 2, comprising DINP, although the amount of plasticizer is in PU 1 much lower (18 wt.% of the polyurethane prepolymer composition) compared to PU 2 (30 wt.% of the polyurethane prepolymer composition). PU 1 also shows better trouser tear than PU 2.
  • the inventive polyurethane PU 1 comprising MB10 as plasticizer, has better physical properties than polyurethane PU 3, comprising TXIB when the same amount of plasticizer is used in both polyurethanes (18 wt.% of the polyurethane prepolymer composition).
  • the inventive polyurethane PU 1 shows no leaching, low odor and low discoloration.

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

Abstract

La présente invention concerne une composition de prépolymère de polyuréthane comprenant au moins un benzoate d'alkyle ainsi qu'un polyuréthane durci obtenu à partir de celle-ci et l'utilisation de benzoate d'alkyle en tant que plastifiants dans des polyuréthanes mélangés, coulés et durcis à température ambiante.
PCT/US2021/025384 2020-04-01 2021-04-01 Composition de prépolymère de polyuréthane comprenant un benzoate d'alkyle WO2021202876A1 (fr)

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Cited By (1)

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WO2023247096A1 (fr) 2022-06-20 2023-12-28 Filoform B.V. Procédé d'étanchéification d'une jonction ou d'une terminaison de câble électrique avec une composition de résine de polyuréthane à plusieurs composants électriquement isolante

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EP1846492A1 (fr) 2005-01-18 2007-10-24 ExxonMobil Chemical Patents Inc. Compositions de plastifiant ameliorees
EP2103648A1 (fr) 2008-03-20 2009-09-23 Sika Technology AG Composition durcissant à l'humidité ayant une bonne stabilité de stockage et une perte de volume réduite
CN104302685A (zh) 2012-05-25 2015-01-21 亨茨曼国际有限公司 聚氨酯灌浆组合物
US20150167263A1 (en) 2012-05-29 2015-06-18 3M Innovative Properties Company Pavement marking compositions
US20160312090A1 (en) 2015-04-24 2016-10-27 Illinois Tool Works, Inc. Primer-less two component polyurethane adhesive
WO2019089237A1 (fr) 2017-10-31 2019-05-09 Basf Se Compositions de polyuréthane avec faible exposition à un contenu d'isocyanate mdi monomère libre pendant une application par pulvérisation
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EP1846492A1 (fr) 2005-01-18 2007-10-24 ExxonMobil Chemical Patents Inc. Compositions de plastifiant ameliorees
EP2103648A1 (fr) 2008-03-20 2009-09-23 Sika Technology AG Composition durcissant à l'humidité ayant une bonne stabilité de stockage et une perte de volume réduite
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US20150167263A1 (en) 2012-05-29 2015-06-18 3M Innovative Properties Company Pavement marking compositions
US20160312090A1 (en) 2015-04-24 2016-10-27 Illinois Tool Works, Inc. Primer-less two component polyurethane adhesive
WO2019089237A1 (fr) 2017-10-31 2019-05-09 Basf Se Compositions de polyuréthane avec faible exposition à un contenu d'isocyanate mdi monomère libre pendant une application par pulvérisation
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WO2023247096A1 (fr) 2022-06-20 2023-12-28 Filoform B.V. Procédé d'étanchéification d'une jonction ou d'une terminaison de câble électrique avec une composition de résine de polyuréthane à plusieurs composants électriquement isolante
NL2032226B1 (en) * 2022-06-20 2024-01-08 Filoform Bv A method for sealing an electrical cable joint or termination with an electrically-insulating multicomponent polyurethane resin composition

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