WO2016128380A1 - Process for the synthesis of polyoxazolidinone compounds with high stability - Google Patents
Process for the synthesis of polyoxazolidinone compounds with high stability Download PDFInfo
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- WO2016128380A1 WO2016128380A1 PCT/EP2016/052689 EP2016052689W WO2016128380A1 WO 2016128380 A1 WO2016128380 A1 WO 2016128380A1 EP 2016052689 W EP2016052689 W EP 2016052689W WO 2016128380 A1 WO2016128380 A1 WO 2016128380A1
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- methylene
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- phenylene
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
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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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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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
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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- 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
- C08G18/71—Monoisocyanates or monoisothiocyanates
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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
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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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
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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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
Definitions
- the present invention relates to polyoxazolidinone compounds, a method for the production of polyoxazolidinone compounds, comprising the step of reacting a biscarbamate compound with a bisepoxide compound in the presence of a mono-carbamate, a mono-isocyanate and/or a mono- epoxide compound as chain regulator and a suitable base having a pKb value of ⁇ 9 as catalyst.
- the invention further relates to the use of polyoxazolidinone compounds with high thermal stability.
- Oxazolidinones are widely used structural motifs in pharmaceutical applications and the cycloaddition of epoxides and isocyanates seems to be a convenient one-pot synthetic route to it. Expensive catalysts, reactive polar solvents, long reaction times and low chemoselectivities are common in early reports for the synthesis of oxazolidinones (M. E. Dyen and D. Swern, Chem. Rev., 67, 197, 1967). Due to these disadvantages there was the need for alternative methods for the production of oxazolidinones especially for application of oxazolidinones as structural motif in polymer applications.
- EP 0 530 812 Al discloses the preparation of thermosetting resinous compositions by the reaction of the mono-functional ethyl carbamate with mono- or poly-functional epoxides at a reaction temperature of 130 °C.
- the formed oxazolidinone moiety is a terminal and/or pendant group, which reacts in situ with amines to form polymeric urea repeating units in a thermosetting polymer.
- the oxazolidinone intermediate comprises an N-H functional group, which reduces the thermal and chemical stability of the oxazolidinone intermediate.
- the thermosetting polymer formed in the reaction with amines does not soften or melt.
- European Patent Application No. 1219261 1.7 relates to a method for the production of oxazolidinone and polyoxazolidinone compounds, comprising the step of reacting an isocyanate compound with an epoxide compound in the presence of a Lewis acid catalyst.
- An antimony catalyst (PruSbBr) was used as Lewis acidic catalyst, which has certain toxicity.
- the isocyanate has to be synthesised in a preceding step and requires additional safety measures due to the high reactivity of isocyanates.
- a mixture of the 5 -oxazolidinone and 4 -oxazolidinone regioisomers was obtained, which gives a less defined product mixture.
- the reaction of biscarbamates with bisepoxides in the presence of a base has not been disclosed in this patent application.
- the paper .1. Polym. Sci. 4 (1966) 751 -760 discloses polyoxazolidinones prepared from bisurethanes (biscarbamates) and bisepoxides. Although a high catalyst concentration of 18 mol% was used, long reaction times of 5-30 h were required. The polymers precipitated before a high molecular weight was reached and gradually decomposed at 250-300°C. The homo-polymerisation of the epoxide was observed as side reaction. The use of a chain regulator has not been disclosed. Objective of the present invention was therefore to identify polyoxazolidinones having a higher thermostability than the already known polyoxazolidinones and which are useful as thermoplastic material. Furthermore a method for the preparation of these highly thermostable polyoxazolidinones, which avoids the use of free isocyanates, the use of toxic Lewis acid catalysts and the use of high catalyst concentrations, is an objective of the present invention.
- polyoxazolidinone compounds prepared in the presence of a mono- carbamate, a mono-isocyanate and/or a mono-epoxide compound have a high thermal stability.
- inventive polyoxazolidinone compounds may be prepared by the reaction of biscarbamates and bisepoxides in the presence of a compound comprising a mono-carbamate group, a mono- isocyanate group and/or a mono-epoxide group and a base having a pKb-value of ⁇ 9.
- the polyoxazolidinones prepared according to the invention exhibit a high thermal stability. These compounds have a decomposition temperature up to 392°C.
- R l ', R2, R2 ' , R3, R3 ' . R4, R5 and R6 have the meanings given further below.
- thermostability of the polyoxazolidinones can be characterized by thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC) as described below in the methods.
- polyoxazolidinone compound is meant to denote compounds containing at least two oxazolidinone groups in the molecule according to formula (I), (II) and/or (III) as described above.
- the polyoxazolidinone compounds are obtainable by the reaction of a biscarbamate with a bisepoxide.
- X represents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene optionally substituted with heteroatoms containing groups, cyclohexylene, phenylene, diphenylene, dimethyl phenylene optionally comprising heteroatoms, 2-methylpentamethylene, 2,2,4-trimethyl-hexamethylene, dodecanemethylene, 1 ,2 -cyclohexylene, 1 ,3-cyclohexylene, 1 ,4-cyclohexylene, 5-(l-methylene- ( 1 ,3 ,3-trimethylcyclohexane)), all regioisomers of methylene biscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis-(3,3'-dimethylcyclohexanel ,4-diyl), propane-2,2- diyl)bis(cyclohe
- Y represents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, polyethylene, polyethyleneglycol, 1 ,2- cyclohexylene, 1 ,3-cyclohexylene, 1 ,4-cyclohexylene, 1,2-phenylene, 1 ,3 -phenylene, 1 ,4- phenylene, 1 ,2-tolylene, 1 ,3-tolylene, 1,4-tolylene, 4,4'-methylenebis(4, 1 -phenylene), 4,4'- methylenebis(cyclohexane-4, 1 -diyl), 4 ,4'-(propane-2,2-diyl)bis(4,l -phenylene), propane-2,2-diyl- bis(cyclohexane-4, 1 -diyl) or Y can be represented by formula IV "
- Y' is represented by methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, polyethylene, polyethyleneglycol, 1 ,2-cyclohexylene, 1 ,3-cyclohexylene, 1 ,4-cyclohexylene, 1,2-phenylene, 1,3- phenylene, 1,4-phenylene, 1 ,2-tolylene, 1 ,3-tolylene, 1 ,4-tolylene, 4,4'-methylenebis(4, 1 - phenylene), 4,4'-methylenebis(cyclohexane-4, 1 -diyl), 4,4'-(propane-2,2-diyl)bis(4, 1 -phenylene), propane-2,2-diyl-bis(cyclohexane-4, 1 -diyl), or 4,4'-(3,3,5-trimethylcyclohexyliden)bis
- ZZ represents methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, ⁇ -chlorohexamethylene, n-heptyl, n-octyl, iso-octyl, 2 -ethyl hexyl, 2-norbornyl methyl, nonyl, 2,3 ,4-trimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, stearyl, 3-butoxypropyl, 3-(2- ethylhexyloxy)-propyl, 6-chloro
- benzyl, phenyl, ortho-, meta-, para-to ⁇ y ⁇ , dimethylphenyl, 4-cyclohexylphenyl and ortho-, meta-, para -methoxyphenyl preferably benzyl, phenyl, ortho-, meta-, para-to ⁇ y ⁇ , dimethylphenyl, 4-cyclohexylphenyl and ortho-, meta-, para -methoxyphenyl .
- a mixture of two or more of the aforementioned ZZ substituents can also be used.
- R3 ', R4, R5, R6 independent of one another represent hydrogen, chloride, bromide, fluoride, methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, 2 -butyl, tert-butyl, hexyl, methoxy, ethoxy, butoxy, phenyl, methoxyphenyl, chlorophenyl, bromophenyl, nitrophenyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and most preferably hydrogen.
- Another subject-matter of the invention is a method for the production of polyoxazolidinone compounds comprising the reaction of at least one biscarbamate with at least one bisepoxide, characterized in that the reaction takes place in the presence of
- a compound comprising a mono-carbamate group, a mono-isocyanate group and/or a mono-epoxide group preferably a compound comprising a mono-carbamate group and/or a mono-epoxide group, and
- the method for the production of polyoxazolidinone compounds comprises the reaction of at least one diisocyanate compound with at least one bisepoxide compound, characterized in that the reaction takes place in the presence of
- a compound comprising a mono-carbamate group, a mono-isocyanate group and/or a mono-epoxide group preferably a compound comprising a mono-isocyanate group and/or a mono-epoxide group, and
- Biscarbamates within the scope of the invention are compounds containing two carbamate groups in the molecule, preferably compounds of the formula (V) below:
- R7 and R7' independently of one another represent a linear or branched CI - C 22 alkyl group optionally containing heteroatoms a mono- or poly-substituted C6 - C18 aryl group optionally containing heteroatoms, or a saturated or unsaturated 4- to 7-membered ring or polycyclic system optionally containing heteroatoms or a group of formula (VI)
- R8 and R9 independently from each other represent a CI C4 alkyl group or a C6-C10 aryl group of are members of an alicyclic C5-C12 ring.
- R7 and R7 " are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, all isomers of pentyl and hexyl, phenyl, tolyl, naphthyl, trifluoromethyl, 2,2,2 -trifluoroethyl, pentafluoroethyl, 1,1,1 ,3,3,3 -hexafluoro -2 -propyl, more preferably methyl, ethyl, isopropyl, n-butyl and 2-butyl.
- suitable biscarbamate compounds of the above formula are compounds selected from the group consisting of N,N '-tetram ethylene biscarbamate, A r , V'-hexamethylene biscarbamate, N,N'-(2-methylpentamethylene) biscarbamate, iV,A r '-2,2,4-trimethyl-hexamethylene biscarbamate, N,N ' -dodecanemethylene biscarbamate, N,N'-cyclohexane-l ,4- biscarbamate, N,N '-isophorone biscarbamate, A r ,A r '-(4,4'-methylenebis(cyclohexane-4, 1 -diyl)biscarbamate, i ⁇ , A r '-diphenylmethane biscarbamate, iV,A r '-(4,4'-methylenebis(2-methylcyclohexane-4, 1 -diyl))
- Biscarbamates can be obtained from the corresponding diisocyanates by reaction with the corresponding alcohol.
- the reaction of the diisocyanate with the alcohol can be performed in the same reactor as the polymerisation reaction or in a separate reactor.
- Diisocyanates within the scope of the invention are compounds containing two or more isocyanate groups in the molecule.
- diisocyanate compounds are tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2 ,2 ,4-trimethylhexam ethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1 ,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,3,5- trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'- diisocyanatodicyclohexylmethane (i1 ⁇ 2-MDI), 4,4'-diisocyanato-3 ,3 '-dimethyldicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, poly
- Preferred diisocyanates are hexamethylene diisocyanate (HDI), 3 -isocyanatomethyl-3 ,3,5 - trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'- diisocyanatodicyclohexylmethane (H12-MDI), 2.4- or 2,5- or 2,6-diisocyanatotoluene (TDI) or mixtures of these isomers, 4,4'-, 2,4'- or 2,2'-diisocyanatodiphenylmethane (MDI) or mixtures of these isomers.
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- H12-MDI 4,4'- diisocyanatodicyclohexylmethane
- TDI 2,5- or 2,6-diisocyanatototoluene
- MDI 4,
- a mixture of two or more of the aforementioned diisocyanates can also be used.
- Bisepoxides within the scope of the invention are compounds containing two epoxy groups in the molecule, preferably compounds of the formula (VII) below:
- Preferred substituted bisepoxide compounds of the above formula are bisepoxide compounds, in which Y represents C1-C22 linear or branched alkoxy group. C5 - C22 cycloalkoxy, C6 - CI 8 aroxy substituent.
- Preferred cycloaliphatic bisepoxides are selected from the group vinylcyclohexene dioxide, dicyclopentadiene dioxide, 3 ,4-epoxy-cyclohexyl-6-methyl 3 ,4-epoxycyclohexylcarboxylate, limonene dioxide.
- More preferred bisepoxide compounds of the above formula (VII) are bisepoxide compounds selected from the group consisting of resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butandiol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S digylcidyl ether, 9,9-bis(4-glycidyloxy phenyl)fluorine, tetrabromo bisphenol-A diglycidyl ether, tetrachloro bisphenol-A diglycidyl ether, tetramethyl bisphenol-A diglycidyl ether, tetramethyl bisphenol-F diglycidyl ether, tetramethyl bisphenol-S diglycidy
- the compounds comprising a mono-carbamate group, a mono-epoxide group and/or a mono- isocyanate group are also denoted as "chain regulator" according to the invention.
- chain regulator Compounds comprising a mono-carbamate and/or a mono-epoxide group are preferred compounds according to the invention.
- Compounds comprising a mono-carbamate group within the scope of the invention are compounds containing one carbamate group in the molecule, preferably compounds of the formula (VIII):
- ZZ represents a I -C22 linear or branched alkyl group, optionally comprising heteroatoms and/or optionally substituted with a heteroatom containing group; C5-C22 cycloalkyl group, optionally comprising heteroatoms; C6- CI 8 aryl group, optionally comprising heteroatoms; and/or optionally substituted with a heteroatom containing group;
- R7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, fert-butyl, all isomers of pentyl and hexyl, phenyl, tolyl, naphthyl, trifluoromethyl, 2,2,2 -trifluoroethyl, pentafluoroethyl, 1,1,1 ,3,3,3 -hexafluoro -2 -propyl, more preferably methyl, ethyl, isopropyl, n-butyl and 2-butyl.
- Suitable mono-carbamate compounds of the above formula (VIII) are for example compounds selected from the group consisting of N-phenyl carbamate, N-(o-tolyl) carbamate, A r -(p-tolyl) carbamate, N-(4-chlorophenyl) carbamate, A r -(1 -naphthyl) carbamate, N-(2-naphthyl) carbamate, N-cyclohexyl carbamate, iV-methyl carbamate, N- ethyl carbamate, N-(n-propyl) carbamate, N- isopropyl carbamate, N-butyl carbamate, N-pentyl carbamate N-hexyl carbamate and/or N-octyl carbamate, preferably iV-(p-tolyi) carbamate.
- Mono-carbamates can also be obtained from the corresponding mono-isocyanates by reaction with the corresponding alcohol.
- the reaction of the mono-carbamate with the alcohol can be performed in the same reactor as the polymerisation reaction or in a separate reactor.
- Compounds comprising a mono-epoxide group within the scope of the invention are compounds comprising one epoxy group in the molecule, preferably compounds of the formula (IX):
- R5 and R6 have the above meaning.
- Suitable mono-epoxide compounds of the formula (IX) are compounds selected from the group consisting of phenyl glycidyl ether, o-kresyl glycidyl ether, m-kresyl glycidyl ether, p-kresyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, 1 -naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2 ,4 , 6-tribromopheny 1 glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, glycid
- Compounds comprising a mono-isocyanate group within the scope of the invention are compounds containing one isocyanate group in the molecule, preferably compounds of the formula (X):
- ZZ has the above meaning.
- ZZ represents a C 1 -C22 linear or branched alkyl group, optionally comprising heteroatoms and/or optionally substituted with a heteroatom containing group; C5-C22 cycloalkyl group, optionally comprising heteroatoms; C6- CI 8 aryl group, optionally comprising heteroatoms; and/or optionally substituted with a heteroatom containing group;
- Preferred mono-isocyanate compounds of the above formula (X) are n-hexylisocyanate, cyclohexyl isocyanate, ⁇ -chlorohexamethylene isocyanate, 2 -ethyl hexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, stearyl isocyanate, methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3 ,3 ,5 -trimethylcyclohexyl isocyanatate, 2-norbornyl methyl isocyanate, decyl isocyanate, dodecyl isocyanate, t
- a mixture of at least one compound comprising a mono-carbamate group and at least one compound comprising a mono-epoxide group is used.
- Suitable bases are compounds, wherein the atom which is able to abstract an acidic proton from another organic compound is part of conjugated system and/or an aromatic ring.
- Examples for such bases are 1 , 8 -diazabicyclo [5.4.0]undec-7-ene (DBU), 1 ,4-diazabicyclo [2.2.2]octane (DABCO), 1 , 5 -diazabicy clo [4.3.0]non-5-ene (DBN), triazabicyclodecene (TBD).
- 6-(dibutylamino)- 1,8- diazabicyclo[5.4.0]undec-7-ene and imidazoles such as 1 ,2-dimethylimidazole, l -benzyl-2- phenylimidazole, 1 -benzyl-2-methylimidazole, 2 -undecylimidazole, 2 -heptadecylimidazole, 2- ethyl-4-methylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 1 -cyanoethyl-2- methylimidazole and 2-phenylimidazole.
- imidazoles such as 1 ,2-dimethylimidazole, l -benzyl-2- phenylimidazole, 1 -benzyl-2-methylimidazole, 2 -undecylimidazole, 2 -heptadecylimidazole, 2-
- Suitable bases are sterically hindered bases.
- sterically hindered base is meant to denote a base compound, whereby the atom which is able to abstract an acidic proton from another organic compound is surrounded by sterically demanding groups.
- Examples for sterically hindered bases are as diisopropylamine, N ,N-diisopropylethylamine (DiPEA), 2,2,6,6-tetramethylpiperidine (TMP) and tetrakis [tris(dimethylamino)- phosphorany lidenamino ]-pho sphonium chloride.
- Preferred bases with a base strength p3 ⁇ 4 of ⁇ 5.3 in the process according to the invention are compounds selected from the group consisting of l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4- diazabicyclo [2.2.2]octane (DABCO), 1 ,5 -diazabicyclo [4.3.0]non-5 -ene (DBN), triazabicyclodecene (TBD) and tetrakis [tris(dimethylamino)-phosphoranylidenamino]- phosphonium chloride.
- DBU l,8-diazabicyclo[5.4.0]undec-7-ene
- DABCO 1,4- diazabicyclo [2.2.2]octane
- DBN 1,4- diazabicyclo [2.2.2]octane
- DBN 1,4- diazabicyclo [2.2.2]octane
- DBN 1,
- the base catalyst is present in an amount of > 0.001 to ⁇ 5.0 weight-%, preferably in an amount of > 0.01 to ⁇ 1.0 weight-%, more preferred > 0.05 to ⁇ 0.5 weight-%, based on the theoretical yield of polyoxazolidinone.
- the molecular weight of the obtained polyoxazolidinone is determined by the molar ratio of the bisepoxide compound relative to biscarbamate compound and optionally relative to chain regulator.
- the molar ratio of bisepoxide compound to biscarbamate compound is preferably in the range from 1 :2 to 2:1, more preferably in the range from 45:55 to 2:1 and even more preferably in the range 49.5:50.5 to 50.5:49.5.
- a mono- carbamate is employed as chain regulator.
- a mono-epoxide is employed as chain regulator.
- the molar amount of mono-epoxide and mono-carbamate compound added as chain regulator fulfils certain criteria with respect to the molar amount of bisepoxide and biscarbamate.
- the ratio r is defined as the absolute value of the molar amount of chain regulator (n reg uiator) divided by the difference between the molar amount of bisepoxide (nbisepoxide) and the molar amount of biscarbamate (nbiscarbamate) according to the following formula (XI)
- r I n reg ulator / (nbisepoxide " nbiscarbamate)
- all epoxide groups and all carbamate groups will have reacted at the end of the reaction, when such an amount of chain regulator is being used.
- the chain regulator preferably a compound comprising a mono-epoxide group and/or a compound comprising a mono-carbamate group, may be added to the reaction mixture at the beginning of the polymerisation reaction.
- the chain regulator may also be added during the reaction or after the reaction of bisepoxide and biscarbamate has been completed.
- the mono-epoxide and/or mono-carbamate compound may be added in portions at different times of the reaction.
- the mono-epoxide and/or mono-carbamate compound is added at the beginning or during the polymerisation reaction of the bisepoxide and the biscarbamate.
- an excess of a mono-epoxide and/or a mono-carbamate compound is added as chain regulator to the reaction mixture after the reaction between bisepoxide and biscarbamate has been completed.
- the terminal epoxide groups or the terminal carbamate groups resulting from the reaction of the bisepoxide and the biscarbamate will be converted to inert end groups by reaction with the regulator.
- the excess amount of regulator is subsequently removed from the product, e.g., by extraction, precipitation, distillation, stripping or thin film evaporation.
- the reaction is advantageously carried out at a temperature of >100 to ⁇ 300°C, preferably of >120 to ⁇ 270°C, more preferably of >140 to ⁇ 250°C. If temperatures below 100°C are set, the reaction is generally very slow. At temperatures above 300°C, the amount of undesirable secondary products increases considerably.
- the reaction is carried out under a reduced pressure (absolute) of >10 mbar to ⁇ 1000 mbar, preferably >20 mbar to ⁇ 800 mbar, most preferably from >50 mbar to ⁇ 500 mbar.
- the reaction mixture is stripped by passing a stream of inert gas, such as nitrogen, argon through the reaction mixture.
- inert gas such as nitrogen, argon
- the reaction may be performed in the presence of solvent or in absence of a solvent. Preferred is the reaction in the presence of a polar solvent and most preferably in the presence of an aprotic polar solvent.
- Suitable solvents are for example polar organic solvents such as linear or branched alkanes or mixtures of alkanes, toluene, xylene and the isomeric xylene mixtures, mesitylene, mono or polysubstituted halogenated aromatic solvents or halogenated alkane solvents, for example chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, tetrachloroethane, linear or cyclic ether such as tetrahy dro furane (THF) or methyl-teri-butylether (MTBE), linear or cyclic ester, or polar aprotic solvents such as 1 ,4-dioxane, acetonitrile, iV ⁇ V-dimethylformamide (DMF), A ⁇ -dimethy lac etamide (DMAc), dimethylsulfoxid (DMSO), cyclic carbonate, such as
- the reaction of the bisepoxide with the biscarbamate may be carried out in a continuous process, in a batch process or in a semi-batch process.
- the process is carried out continuously. That means in this continuous process the bisepoxide, biscarbamate, regulator, base as catalyst and, if applicable, a solvent are continuously added whereas a part of the reaction mixture is continuously removed from the reactor.
- a residence-time reactor may be added after the continuously reactor in order to complete the reaction.
- the process is carried out as a batch process.
- this batch process the bisepoxide, the biscarbamate, the regulator, the catalyst and, if applicable, a solvent are charged in a reactor and the reaction runs until full conversion is obtained.
- the regulator can be added during the reaction or after the reaction between bisepoxide and biscarbamate has been completed.
- a semi-batch process is preferred.
- the bisepoxide is preferably mixed with a catalyst and optionally a solvent and/or a regulator in a reactor and the biscarbamate and possibly regulator are continuously added to the reaction as pure material or in solution.
- the added amount of biscarbamate is calculated so that the desired molecular weight is achieved.
- the biscarbamate is charged in the reactor along with the catalyst and optionally a regulator and/or solvents while the bisepoxide and possibly regulator are continuously added to the reaction mixture as a pure substance or in solution.
- the biscarbamate compound is added to the bisepoxide compound in a continuous or step-wise manner with two or more individual addition steps in the step-wise addition.
- the biscarbamate compound is added continuously or in the aforementioned step-wise manner.
- the biscarbamate compound is added via a pump, dripping funnel or other continuous or semi-continuous devices where the biscarbamate is brought into the reaction mixture in slow manner.
- the reaction should be essentially complete shortly after the end of the addition of the biscarbamate compound.
- the reaction time for the polymerisation is for example 0.05 to 120 hours, preferably 0.5 to 48 hours, more preferred 1 to 24 hours.
- the reaction time is the time wherein the bisepoxide, the biscarbamate, the chain regulator, the base catalyst and if applicable a solvent are in direct contact at the reaction temperature.
- the precise content of epoxide and carbamate groups in the bisepoxide, biscarbamate, monoepoxide and bisepoxide compound are determined before the polymerisation reaction. This can be achieved, e.g., by measuring the epoxide number according to German standard norm DI EN 1877-1 and by confirming the purity of the carbamate compounds by ' ' H NMR.
- the molecular weight of the polyoxazolidinone is preferentially > 000 to ⁇ 000 ⁇ 00 g/mol, more preferred > 2 ⁇ 00 to ⁇ 100 ⁇ 00 g/mol and even more preferred > 10 ⁇ 00 to ⁇ 50 ⁇ 00 g/mol.
- the molecular weight of the polyoxazolidinone may be calculated, e.g., by end-group analysis based on ! H-NMR spectroscopy.
- the number average molecular weights M n is preferentially > 500 to ⁇ 500 ⁇ 00 g/mol, more preferred > 1 ⁇ 00 to ⁇ 50 ⁇ 00 g/mol and even more preferred > 5 '000 to ⁇ 25 ⁇ 0 g/mol.
- GPC gel permeation chromatography
- Polyoxazolidmones obtained by the method according to the invention are thermally mouldable at elevated temperatures and are suitable for any field where thermoplastic materials are employed. Polyoxazolidmones are particularly suitable for applications, where transparent, light- coloured and/or high temperature-stable materials are required. Thermoplastic polyoxazolidmones can, thus, be employed, e.g., in skylights, roofing, curtain walls, office dividers, swimming pool enclosures, greenhouses, displays and signage.
- TDC O O '-Dimethyl-toluene-2,4-dicarbamate, difunctional carbamate, prepared by reaction of toluene-2,4-diisocyanate with methanol
- the 10 ml Schlenk tube used in the examples was a glass tube with an internal height of 10.5 cm and an internal diameter of 1.6 cm. Close to the top, the Schlenk tube was fitted with three side arms. The lower part of the Schlenk tube was inserted into an electric heating jacket (510 Watt maximum heating power). A cylindrical magnetic stirring bar (PTFE, 10 mm long and 6 mm in diameter) was placed inside of the Schlenk tube. One opening of the Schlenk tube was connected to a water-cooled condenser. The alcohol evolved during the reaction was collected in a receiver flask cooled with ice. One opening of the Schlenk tube was closed with a plug. Two arms of the Schlenk tube were closed with rubber septa.
- a temperature probe (1 mm diameter and 15 cm length) was inserted through one of the septa in such a way that the tip became immersed in the reaction mixture once the Schlenk tube was charged with reagents.
- a gentle Argon- flow was established by passing Argon through a long needle, which was inserted through the second septum, into the lower part of the Schlenk tube. The Argon was released through a second needle.
- the oxazolidinone product was obtained as detailed below and analysed with IR and NMR spectroscopy, HPLC chromatography as well as for its colour.
- the amount of base is stated in weight-% relative to the theoretical yield of polyoxazolidinone.
- Solid state IR analyses were performed on a Bruker ALPHA-P I R spectrometer equipped with a diamond probe head.
- the software OPUS 6.5 was used for data treatment.
- a background spectrum was recorded against ambient air.
- a small sample of the polyoxazolidinone (2 milligrams) was applied to the diamond probe and the IR spectrum recorded averaging over 32 spectra obtained in the range of 4000 to 400 cm '1 with a resolution of 4 cm " '.
- the average chain length of the polyoxazolidinones was controlled by the molar ratio of bisepoxide, biscarbamate and/or chain regulator.
- n 1 / [ ⁇ (nbisepoxide) / (nbiscarbamate) ⁇ - 1]
- nbisepoxide is the molar amount of bisepoxide and nbiscarbamate is the molar amount of biscarbamate.
- n 1 / [ ⁇ (nbiscarbamate) / (nbisepoxide) ⁇ 1]
- ⁇ biscarbamate IS the molar amount of biscarbamate and nbisepoxide is the molar amount of bisepoxide.
- the ratio r defined as the absolute value of the molar amount of chain regulator (nreguiator) to the difference between the molar amount of bisepoxide (nbisepoxide) and the molar amount of biscarbamate (nbiscarbamate) according to formula (VIII) was 2.
- the weight average molecular weight (M w ) and the number of repeating units in the synthesized polyoxazolidinone were calculated by end-group analysis based on ! H-NMR spectroscopy.
- the stability of the polyoxazolidinones was characterised by thermogravimetric analysis (TGA).
- TGA thermogravimetric analysis
- the measurements were performed on a Mettler Toledo TGA/DSC 1.
- the sample (6 to 20 mg) was heated from 25 °C to 600 °C with a heating rate of 10 K/min and the relative weight loss followed in dependence of temperature.
- the software STAR 6 SW 1 1.00 was used.
- decomposition temperature (Td) the onset point of the si nuisancedal weight loss curve is stated.
- the glass transition point was recorded on a Mettler Toledo DSC 1.
- the sample (4 to 10 mg) was heated from 25 °C to 250 °C with a heating rate of 10 K/min.
- the software STAR 6 SW 1 1.00 was used for data analysis.
- For determination of the glass transition temperature a tangential analysis method was used. The midpoint of the intersection point between the tangent at low temperature and the tangent in the mid temperature range and the intersection point between the tangent in the mid temperature range and the tangent at high temperature is stated.
- Example 1 Oligomer ization of 0,0 '-Dimethyl-4,4 '-methylendiphenyl-1,1 '-dicarhamate (MDC) and 4,4'-isopropylidenediphenol diglycidyl ether (BADGE) with 4-tert-butylphenyl glycidyl ether (BPGE) as chain regulator using 1, 8-diazabicyclo[5.4. OJundec- 7-ene (DBU) as catalyst
- a 50 mL Schlenk tube was charged with MDC (6.33 g, 20.14 mmol) and BADGE (3.45 g, 10.13 mmol), closed and inertised with argon. Then, the Schlenk tube was charged with NMP (30 ml). The mixture was stirred (400 rpm) and heated to 180°C. DBU (16.5 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidinone) was added. Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture. After 120 min, half of the reaction mixture was removed. To the reaction mixture left, 4-tert-butylphenyl glycidyl ether ( 5.2, 23.30 mmol) was added. After another 60 min, the reaction mixture was allowed to cool to room temperature.
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with methanol, dried under vacuum and analysed. In the solid state I R spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1746 cm "1 .
- the polyoxazolidinone compound was thermally stable until 389°C.
- the glass transition temperature was 127°C.
- Example 2 Oligomerization of 0,0 '-dimethyl-4,4 '-methylendiphenyl-1 , 1 '- dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the absence of a chain regulator to a carbamate terminated polyoxazolidmone using 1,8-diazabicyclo [5.4.0] undec- 7-ene (DBU) as catalyst
- MDC 0,0 '-dimethyl-4,4 '-methylendiphenyl-1 , 1 '- dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the absence of a chain regulator to a carbamate terminated polyoxazolidmone using 1,8-diazabicyclo [5.4.0] undec- 7-ene (DBU) as catalyst
- DBU 1,8-diazabicyclo [5.4.0] undec- 7
- the Schlenk tube was charged with NMP (30 ml). The mixture was stirred (400 rpm) and heated to 180°C. DBU (16.5 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidinone) was added. Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture. After 120 min, half of the reaction mixture was removed. After 120 min, half of the reaction mixture was removed and allowed to cool to room temperature.
- DBU 16.5 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidinone
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with methanol, dried under vacuum and analysed.
- the polyoxazolidinone compound was thermally stable until 372°C.
- the glass transition temperature was 189°C.
- the AT g value was 41° C.
- Example 3 Oligomerization of O, O '-dimethyl-4,4 ' -methylendiphenyl-l , I '-dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of O-methyl-4- methylphenyl carbamate (MFC) as chain regulator using 1, 8-diazabicyclo[5.4.
- OJundec- 7-ene (DBU) as catalyst A 50 mL Schlenk tube was charged with MDC (3.16 g, 10.05 mmol) and BADGE (6.85 g, 20.12 mmol), closed and inertised with argon.
- the Schlenk tube was charged with NMP (30 ml). The mixture was stirred (400 rpm) and heated to 180°C. DBU (16.5 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidinone) was added. Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture. After 120 min, half of the reaction mixture was removed. To the reaction mixture left, O-methyl-4- methylphenyl carbamate (2.00g, 12.13 mmol) was added. After another 60 min, the reaction mixture was allowed to cool to room temperature.
- DBU 16.5 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidinone
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with methanol, dried under vacuum and analysed.
- the polyoxazolidinone compound was thermally stable until 381 °C.
- the glass transition temperature was 112°C.
- the AT g value was 0° C.
- Example 4 Oligomerization of 0,0 '-dimethyl-4,4 '-methylendiphenyl-1 , 1 '- dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the absence of a chain regulator to an epoxide terminated polyoxazolidinone using 1, 8-diazabicyclo[5.4. OJundec- 7- ene (DBU) as catalyst
- a 50 mL Schlenk tube was charged with MDC (3.16 g, 10.05 mmol) and BADGE (6.85 g, 20.12 mmol), closed and inertised with argon. Then, the Schlenk tube was charged with NMP (30 ml). The mixture was stirred (400 rpm) and heated to 180°C. DBU (16.5 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidinone) was added. Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture. After 120 min, half of the reaction mixture was removed and allowed to cool to room temperature. Analysis of the reaction mixture by ' ' H NMR spectroscopy showed complete conversion of the carbamate groups.
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with methanol, dried under vacuum and analysed.
- the polyoxazolidinone compound was thermally stable until 392°C.
- the glass transition temperature was 128°C.
- the AT g value was 26° C.
- Comparison Table 1 Comparison of the results of Examples 1, 2, 3 and 4
- comparison example 1 A comparison of examples 1 with comparison example 2 and a comparison of examples 3 with comparison example 4 shows that the polyoxazolidinone products obtained with the use of a chain regulator according to this invention (examples 1 and 3) have a higher thermal stability compared to a polyoxazolidinone product obtained without the use of a chain regulator (comparison examples 2 and 4).
- Example 5 Polymerization of O, O '-dimethyl-4,4 '-methylendiphenyl-1, 1 ' -dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of 4-tert-butylphenyl glycidyl ether (BPGE) as chain regulator using l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as catalyst
- the weight average molecular weight Mw was 28446 g/mol with a polydispersity of 3.7.
- the polyoxazolidinone compound was thermally stable until 375°C.
- Example 6 Polymerization of 0, 0 '-dimethyl-toluene-2,4-dicarbamate (TDC) and 4,4'- isopropylidenediphenol diglycidyl ether (BADGE) in the presence of 4-tert-butylphenyl giycidyl ether (BPGE) as chain regulator
- TDC 1, 0 '-dimethyl-toluene-2,4-dicarbamate
- BADGE 4,4'- isopropylidenediphenol diglycidyl ether
- BPGE 4-tert-butylphenyl giycidyl ether
- the weight average molecular weight M w was 92814 g/mol with a polydispersity of 6.6.
- the polyoxazolidinone compound was thermally stable until 381 °C.
- the glass transition temperature was 173.5°C.
- Example 7 Polymerization of O, O '-dimethyl-4,4 ' -methylendiphenyl-l , I ' -dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of 4-tert-butylphenyl giycidyl ether as chain regulator using 1, 4-diazabicyclo[2.2.2 ] octane (DAB CO) as catalyst
- MDC 2-.00 g, 6.36 mmol
- BADGE 1-.98 g, 5.81 mmol
- the mixture was stirred (400 rpm) and heated to 180°C.
- DBU (12.8 mg, 1 mol% relative to biscarbamate, 0.32 weight- % relative to polyoxazolidmone) was added.
- Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture.
- 4-teri-butylphenyl glycidyl ether (0.5 ml, 2.3 mmol) was added. After another 90 min, the reaction mixture was allowed to cool to room temperature.
- the polyoxazolidmone was precipitated with methanol, collected by filtration, washed with diethylether, dried under vacuum and analysed. In the solid state ! R spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm "1 .
- the weight average molecular weight M w was 21168 g/mol with a polydispersity of 3.7.
- the polyoxazolidmone compound was thermally stable until 392°C.
- the glass transition temperature was 153°C.
- Example 8 Polymerization of O, O '-dimethyl-toluene-2,4-dicarbamate ⁇ , ⁇ '- Dimethyl-4,4 '-methylendipheny!-1 , ⁇ -dicarbamate (TDC) and 4,4'-isopropylidenediphenol digiycidyl ether (BADGE) in the presence of tetraphenylantimony bromide (SbPh ⁇ Br) as catalyst
- Example 9 ( ' Comparison ' ): Polymerization of O, O '-dimethyl-toluene-2,4-dicarbamate (TDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the absence of a base as catalyst
- a 25 mL Schlenk tube was charged with TDC (1.99 g. 8.4 mmol) and BADGE (2.60 g, 7.63 mmol), closed and inertised with argon. Then, the Schlenk tube was charged with NMP (18 ml). The mixture was stirred (400 rpm) and heated to 180°C. Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture. After 180 min, the reaction mixture was allowed to cool to room temperature.
- Examples 5 and 7 demonstrate that the polyoxazolidinone product according to the invention can be obtained by using different base catalysts.
- a comparison of examples 5 and 7 with comparison examples 8 and 9 shows that the polyoxazolidinone product is obtained only in the presence of a base (examples 5 and 7), while no polyoxazolidinone product is obtained in the absence of a base (comparison examples 8 and 9).
- Example 10 Polymerization of O, O '-dimethyl-4,4 '-methylendiphenyl- 1 , 1 '-dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of 4-tert-butylphenyl glycidyl ether (BPGE) as chain regulator using l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as catalyst to a polyoxazolidinone with 100 repetition units
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with diethylether, dried under vacuum and analysed. In the solid state I R spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm "1 .
- the weight average molecular weight M w was 65585 g/mol with a polydispersity of 6.7.
- the polyoxazolidinone compound was thermally stable until 376°C.
- Example 11 Polymerization of O, O '-dimethyl-4,4 '-methylendiphenyl- 1 , 1 '-dicarbamate (MDC) and resorcinol diglycidyl ether (RDE) in the presence of 4-tert-butylphenyl glycidyi ether (BPGE) as chain regulator using 1, 8-diazabicyclo[5.4. OJundec- 7-ene (DBU) as catalyst
- a 100 mL Schlenk tube was charged with MDC (6.91 g, 22 mmol) and RDE (4.45 g, 20 mmol), closed and inertised with argon. Then, the Schlenk tube was charged with NMP (45 ml). The mixture was stirred (400 rpm) and heated to 180°C. DBU (33.5 mg, 1 mol% relative to biscarbamate, 0.31 weight- % relative to polyoxazolidinone) was added. Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture. After 300 min, 4-tert-butylphenyl glycidyi ether (1 ml, 4.6 mmol) was added. After another 60 min, the reaction mixture was allowed to cool to room temperature.
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with methanol, dried under vacuum and analysed. In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm "1 .
- the weight average molecular weight M w was 31665 g/mol with a polydispersity of 4.9.
- the polyoxazolidinone compound was thermally stable until 352 °C.
- the glass transition temperature was 142.3 °C.
- Example 12 Polymerization of O, O ' -dimethyl-4,4 ' -methylendiphenyl- 1, 1 '-dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of O-methyl-4- methylphenyl carbamate (MPC) as chain regulator using l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as catalyst
- MDC O-methyl-4- methylphenyl carbamate
- DBU l,8-diazabicyclo[5.4.0]undec-7-ene
- the mixture was stirred (400 rpm) and heated to 180°C.
- DBU 27.4 mg, 1 mol% relative to biscarbamate, 0.35 weight- % relative to polyoxazolidmone
- Argon was bubbled through the reaction mixture by immersing the long metal needle into the reaction mixture.
- 4-ferf-butyiphenyl glycidyl ether (lOOmg, 0.7 mmol) was added. After another 60 min, the reaction mixture was allowed to cool to room temperature.
- the weight average molecular weight M w was 33029 g/mol with a polydispersity of 4.1.
- the polyoxazolidmone compound was thermally stable until 370°C.
- the glass transition temperature was 163.0°C.
- Examples 5 and 10 show that polyoxazolidinones varying in molecular weight can be obtained.
- Examples 5, 6 and 11 demonstrate that different combinations of biscarbamates and bisepoxides can be used to obtain polyoxazolidmone products according to this invention.
- Examples 5 and 12 demonstrate that a monoepoxide (Example 5) and a monocarbamate (Example 12) can be used as chain regulator to obtain polyoxazolidmone products according to this invention.
- Example 13 Polymerization of O, O '-dimethyl-4,4 '-methylendiphenyl- 1 , 1 '-dicarbamate (MDC) and 4, 4 '-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of 4-tert-hutylphenyl glycidyl ether (BPGE) as chain regulator using l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as catalyst and dimethylacetamide (DMAc) as solvent
- the polyoxazolidinone was precipitated with methanol, collected by filtration, washed with diethylether, dried under vacuum and analysed.
- the weight average molecular weight M w was 9336 g/mol with a polydispersity of 2.5.
- the polyoxazolidinone compound was thermally stable until 371 °C.
- the glass transition temperature was 166°C.
- Examples 5 and 13 show that also different solvents can be used to obtain polyoxazolidinone products according to this invention.
- Example 14 Polymerization of 2, 4-toluenediisocyanate (TDI) and 4,4'-isopropylidenediphenol diglycidyl ether (BADGE) in the presence of 4-tolylisocyanate as chain regulator using tetraphenylphosphonium bromide (PPh ⁇ Br) as catalyst and N-methylpyrrolidinone (NMP) as solvent
- the reaction was performed in a 300 ml stainless steel autoclave from the company PARR instruments, equipped with a 4-blade stirrer and a stirring power of 90 W.
- the reactor was charged with bisepoxide 1 (15.0 g, 44.1 mmol) and catalyst PPh.iBr (194 mg, 0.46 mmol) and subsequently flushed with Argon.
- After addition of 40 ml of dry NMP the reactor was sealed and the mixture was heated to 200 °C under rapid stirring (1000 rpm). After reaching 200°C, a solution of 2,4- tolyldiisocyanate (7.52 g, 42.85 mmol) in 15 ml dry NMP was added with an HPLC pump (10 ml pump head) over 3 h.
- the weight average molecular weight M w was 19013 g/mol with a polydispersity of 3.1.
- the polyoxazolidinone compound was thermally stable until 370°C.
- the glass transition temperature was 160°C.
- Examples 6 and 14 show that also different synthesis routes can be used to obtain polyoxazolidinone products according to this invention.
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EP16703330.7A EP3256508B1 (en) | 2015-02-13 | 2016-02-09 | Process for the synthesis of polyoxazolidinone compounds with high stability |
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WO2019073034A1 (en) | 2017-10-13 | 2019-04-18 | Covestro Deutschland Ag | Method for producing a cross-linkable polymer with the formation of oxazolidinones |
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WO2020089107A2 (en) | 2018-10-30 | 2020-05-07 | Covestro Deutschland Ag | Method for the production of thermoplastic polyoxazolidinone polymers |
JP2020535273A (en) * | 2017-09-29 | 2020-12-03 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Thermoplastic polyoxazolidone from diisocyanate and diglycidyl ether derivatives of 2-phenyl-1,3-propanediol |
WO2021191068A1 (en) | 2020-03-24 | 2021-09-30 | Covestro Deutschland Ag | Method for the production of thermoplastic polyoxazolidinones |
EP3960786A1 (en) | 2020-08-24 | 2022-03-02 | Covestro Deutschland AG | Method for the production of a thermoplastic polyoxyzolidinone |
WO2022043127A1 (en) | 2020-08-24 | 2022-03-03 | Covestro Deutschland Ag | Method for the production of a thermoplastic polyoxazolidinone |
WO2022043126A1 (en) | 2020-08-24 | 2022-03-03 | Covestro Deutschland Ag | Method for the production of a thermoplastic polyoxazolidinone |
WO2022043125A1 (en) | 2020-08-24 | 2022-03-03 | Covestro Deutschland Ag | Method for the production of a thermoplastic polyoxazolidinone |
EP4194475A1 (en) | 2021-12-13 | 2023-06-14 | Covestro Deutschland AG | Process for the production of a thermoplastic polyoxazolidinone |
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EP3647335A1 (en) * | 2018-10-30 | 2020-05-06 | Covestro Deutschland AG | Method for the production of thermoplastic polyoxazolidinone polymers |
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Also Published As
Publication number | Publication date |
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JP2018507932A (en) | 2018-03-22 |
JP6698095B2 (en) | 2020-05-27 |
CN107207700A (en) | 2017-09-26 |
ES2731925T3 (en) | 2019-11-19 |
US20180022871A1 (en) | 2018-01-25 |
US10385167B2 (en) | 2019-08-20 |
KR20170118067A (en) | 2017-10-24 |
CN107207700B (en) | 2021-04-27 |
EP3256508B1 (en) | 2019-03-27 |
EP3256508A1 (en) | 2017-12-20 |
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