CN116529281A - Process for producing thermoplastic polyoxazolidone polymers - Google Patents

Process for producing thermoplastic polyoxazolidone polymers Download PDF

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CN116529281A
CN116529281A CN202180080989.XA CN202180080989A CN116529281A CN 116529281 A CN116529281 A CN 116529281A CN 202180080989 A CN202180080989 A CN 202180080989A CN 116529281 A CN116529281 A CN 116529281A
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compound
substituted
unsubstituted
reaction
diisocyanate
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S·莫瓦海德
S·韦斯修斯
D·蒂尔
K·兰默霍尔德
A·沃尔夫
C·盖特勒
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Covestro Deutschland AG
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Covestro Deutschland AG
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Priority claimed from PCT/EP2021/083118 external-priority patent/WO2022117443A1/en
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Abstract

A process for producing a thermoplastic polyoxazolidone comprising copolymerizing a diisocyanate compound with a diepoxide compound in the presence of a catalyst in a solvent, wherein the solvent (E) comprises at least one of a substituted or unsubstituted alkylnitrile, a substituted or unsubstituted alkenylnitrile, a substituted or unsubstituted cycloalkylnitrile, a substituted or unsubstituted arylnitrile, a substituted or unsubstituted alkylcycloalkylnitrile, a substituted or unsubstituted alkylaryl nitrile, a substituted or unsubstituted heterocycloalkyl nitrile, a substituted or unsubstituted heteroalkylnitrile, and a substituted or unsubstituted heteroaryl nitrile, preferably a substituted or unsubstituted arylnitrile. The invention also relates to the thermoplastic polyoxazolidone obtained.

Description

Process for producing thermoplastic polyoxazolidone polymers
A process for producing a thermoplastic polyoxazolidone comprising copolymerizing a diisocyanate compound with a diepoxide compound in the presence of a catalyst in a solvent, wherein the solvent (E) comprises at least one of a substituted or unsubstituted alkylnitrile, a substituted or unsubstituted alkenylnitrile, a substituted or unsubstituted cycloalkylnitrile, a substituted or unsubstituted arylnitrile, a substituted or unsubstituted alkylcycloalkylnitrile, a substituted or unsubstituted alkylaryl nitrile, a substituted or unsubstituted heterocyclylalkylnitrile, a substituted or unsubstituted heteroalkylnitrile and a substituted or unsubstituted heteroarylnitrile, preferably a substituted or unsubstituted arylnitrile. The invention also relates to the thermoplastic polyoxazolidone obtained.
Oxazolidinones are widely used building blocks in pharmaceutical applications and cycloadditions of epoxides and isocyanates appear to be a convenient one-pot synthetic route. Expensive catalysts, reactive polar solvents, long reaction times and low chemoselectivities are common in early reports on oxazolidinone synthesis (m.e. dye and D.Swern, chem.Rev.,67, 197, 1967). Because of these drawbacks, alternative methods for producing oxazolidinones are needed, especially for the use of oxazolidinones as structural motifs in polymer applications.
WO 2019/052991 A1 and WO 2019/052994 A1 disclose a process for producing thermoplastic polyoxazolidinones comprising the copolymerization of a diisocyanate compound with a diepoxide compound and a monofunctional epoxide in the presence of lithium chloride and lithium bromide as catalysts in N-methylpyrrolidone and sulfolane as high-boiling co-solvents.
WO 2020/016276 A1 discloses a process for the production of polyoxazolidinones by bulk polymerization of diisocyanates and diepoxides using ionic liquids as catalysts in the absence of solvents, wherein the reaction temperature is increased during the addition of the diisocyanates. The use of monofunctional epoxides in addition to the diepoxides is not disclosed.
In unpublished patent application EP 20165326 a two-step process for the production of thermoplastic polyoxazolidinones and the resulting products thereof is disclosed, comprising the copolymerization of a diisocyanate compound with a diepoxide compound in the presence of a LiCl-based catalyst and a monofunctional epoxide as chain regulator in a mixture of trichlorobenzene and sulfolane as solvent, wherein the diepoxide compound comprises 2,4 '-isopropylidenediphenol diglycidyl ether (2, 4' badge) and 4,4 '-isopropylidenediphenol diglycidyl ether (4, 4' badge); and wherein the molar ratio of 2,4 '-isopropylidenediphenol diglycidyl ether (2, 4' badge) is from 3 mol% or more to 11 mol% or less. The thermoplastic polyoxazolidone intermediate formed is further reacted with a monofunctional epoxide to form a thermoplastic polyoxazolidone product.
In unpublished patent applications EP 20192497, EP 20192499 and EP 20192501, two-stage processes for the production of thermoplastic polyoxazolidinones and the products obtained thereof are disclosed, which comprise copolymerizing a diisocyanate compound with different diepoxides in the presence of a phosphonium-based catalyst and a monofunctional epoxide as chain regulator in o-dichlorobenzene or 1,2, 4-trichlorobenzene as solvent and in the absence of a high-boiling solvent having a boiling point (at 1 bar (absolute)) of more than 200 ℃. In this two-step process, a thermoplastic polyoxazolidone intermediate is first formed and then further reacted with a monofunctional epoxide to form a thermoplastic polyoxazolidone product.
The object of the present invention was therefore to find an optimized and simple, preferred one-step process for preparing thermoplastic polyoxazolidines which has improved or at least comparable thermal stability and a lower or at least comparable polydispersity compared to the known thermoplastic polyoxazolidines prepared by the polyaddition route. In particular, suitable process conditions should be developed to obtain polyoxazolidone products with high chemical selectivity and reduce the amount of undesired byproducts such as isocyanurates that cause undesired crosslinking of the reaction products and adversely affect thermoplastic properties without adding chain regulators, e.g. monofunctional epoxides and/or without performing multiple reaction steps, e.g. by adding chain regulators in the second step. Thus, process efficiency may be improved by reducing reaction time and/or reducing or avoiding additional reactants, such as monofunctional chain regulators or solvents, without degrading the quality of the resulting thermoplastic polyoxazolidone.
Thus, in combination with a simplified, preferably one-step, preparation process, a high oxazolidone/isocyanurate ratio of the resulting thermoplastic polyoxazolidone product, comparable to or improved over the systems disclosed in the prior art, is desirable to obtain good thermoplastic properties for the subsequent molding process. Furthermore, the improved oxazolidone/isocyanurate ratio and lower polydispersity of the resulting polyoxazolidone compared to the prior art are also of particular interest to the present invention.
Surprisingly, it has been found that this problem can be solved by a process for the production of thermoplastic polyoxazolidinone (1) comprising copolymerizing a diisocyanate compound (a) with a diepoxide compound (B) in the presence of a catalyst (C) in a solvent (E), wherein the solvent (E) comprises at least one of a substituted or unsubstituted alkylnitrile, a substituted or unsubstituted alkenylnitrile, a substituted or unsubstituted cycloalkylnitrile, a substituted or unsubstituted arylnitrile, a substituted or unsubstituted alkylcycloalkylnitrile, a substituted or unsubstituted alkylaryl nitrile, a substituted or unsubstituted heterocycloalkyl nitrile, a substituted or unsubstituted heteroalkylnitrile and a substituted or unsubstituted heteroaryl nitrile, preferably a substituted or unsubstituted arylnitrile.
The term "thermoplastic polyoxazolidone" as used herein is intended to mean a compound containing at least two oxazolidone groups in the molecule. Thermoplastic polyoxazolidinones are obtainable by reaction of diisocyanate compounds with diepoxides.
In one embodiment of the method according to the invention, the copolymerizing comprises:
(i) Placing a solvent (E) and a catalyst (C) in a reactor to provide a mixture (i),
(ii) Placing a diisocyanate compound (A), a diepoxide compound (B) and optionally a compound (D) in a second container to provide a mixture (ii), and
(iii) Adding mixture (ii) to mixture (i).
In a preferred embodiment of the process according to the invention, compound (D) is added in step (ii). The compound (D) acts as a chain regulator for the thermoplastic polyoxazolidone and reduces the polydispersity of the thermoplastic polyoxazolidone (1).
In one embodiment of the invention, the mixture (ii) of step (ii) is added in step (iii) to the mixture (i) of step (i) in a continuous manner.
In an alternative embodiment of the invention, the mixture (ii) of step (ii) is added in step (iii) to the mixture (i) of step (i) in a stepwise manner.
The term "diisocyanate compound (a)" as used herein is intended to mean a diisocyanate compound (i=2) having two isocyanate groups, an isocyanate terminated biuret, an isocyanurate, a uretdione, a urethane and/or an isocyanate terminated prepolymer.
In one embodiment of the process according to the invention, the diisocyanate compound (A) is selected from the group consisting of tetramethylene diisocyanate, hexamethylene Diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2, 4-trimethyl-hexamethylene diisocyanate (THDI), dodecanemethylene diisocyanate, 1, 4-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), dicyclohexylmethane diisocyanate (H12-MDI), diphenylmethane diisocyanate (MDI), 4' -diisocyanato-3, 3' -dimethyldicyclohexylmethane, 4' -diisocyanato-2, 2-dicyclohexylpropane, poly (hexamethylene diisocyanate), octamethylene diisocyanate, toluene-. Alpha.4-diisocyanate, poly (propylene glycol) toluene-2, 4-diisocyanate end-caps, poly (ethylene adipate) toluene-2, 4-diisocyanate end-caps, 2,4, 6-trimethyl-1, 3-dichloro-benzene-diisocyanate, 4-dichloro-1, 4-fluoro-benzo-1-diisocyanate, 4-co-fluoro-1-4-phenylene-diisocyanate, omega-diisocyanate, 1, 4-butane diisocyanate, 1, 8-octane diisocyanate, 1, 3-bis (1-isocyanato-1-methylethyl) benzene, 3' -dimethyl-4, 4' -biphenyl diisocyanate, naphthalene-1, 5-diisocyanate, 1, 3-benzene diisocyanate, 1, 4-benzene diisocyanate, 2, 4-or 2, 5-and 2, 6-Toluene Diisocyanate (TDI) or mixtures of these isomers, 4' -, 2,4' -or 2,2' -diphenylmethane diisocyanate or mixtures of these isomers, 4' -, 2,4' -or 2,2' -diisocyanato-2, 2-diphenylpropane-p-xylene diisocyanate and alpha, alpha ' -tetramethyl-m-or-p-xylene diisocyanate (TMXDI) and at least one compound of the biurets, isocyanurates, urethanes and uretdiones of the abovementioned isocyanates.
The diisocyanate compound (A) is more preferably selected from toluene- α, 4-diisocyanate, poly (propylene glycol) toluene-2, 4-diisocyanate-terminated, 2,4, 6-trimethyl-1, 3-benzene diisocyanate, 4-chloro-6-methyl-1, 3-benzene diisocyanate, 3 '-dimethyl-4, 4' -biphenyl diisocyanate, 4'-, 2,4' -or 2,2 '-diphenylmethane diisocyanate or a mixture of these isomers, 4' -, 2,4 '-or 2,2' -diisocyanato-2, 2-diphenylpropane-p-xylene diisocyanate and α, α, α ', α' -tetramethyl-m-or-p-xylene diisocyanate (TMXDI), diphenylmethane diisocyanate (MDI), naphthalene-1, 5-diisocyanate, 1, 3-benzene diisocyanate, 1, 4-benzene diisocyanate, 2, 4-or 2, 5-and 2, 6-Toluene Diisocyanate (TDI) or a mixture of these isomers.
And the diisocyanate compound (A) is most preferably selected from diphenylmethane diisocyanate (MDI), naphthalene-1, 5-diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-or 2, 5-and 2, 6-Toluene Diisocyanate (TDI) or a mixture of these isomers.
Mixtures of two or more of the above-mentioned diisocyanate compounds (a) may also be used.
The term "diepoxide (B)" as used herein is intended to mean a diepoxide compound having two epoxy groups (f=2).
In a preferred embodiment of the present invention, the bisepoxide (B) is a diglycidyl ether of at least one member selected from the group consisting of resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S diglycidyl ether, 9-bis (4-epoxypropoxyphenyl) fluoride, tetrabromobisphenol-A diglycidyl ether, tetrachlorobisphenol-A diglycidyl ether, tetramethylbisphenol-F diglycidyl ether, tetramethylbisphenol-S diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, 1, 4-cyclohexane diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, vinylcyclohexene diglycidyl ether, dicyclohexyl diglycidyl ether, 1, 4-dihydroxybenzene diglycidyl ether, 3-dihydroxybenzene 3-dihydroxybenzene diglycidyl ether, 3-5-dihydroxybenzene diglycidyl ether, and 3-dihydroxybenzene diglycidyl ether.
The bis-epoxy compound (B) is more preferably selected from the group consisting of resorcinol diglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
The bisepoxide compound (B) is most preferably selected from bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
Mixtures of two or more of the above-mentioned diepoxide compounds (B), two or more of the above-mentioned epoxy-terminated oxazolidone-based prepolymers may also be used. And mixtures of the above-mentioned diepoxide compounds (B) and epoxy-terminated oxazolidone-based prepolymers may also be used.
The molecular weight of the thermoplastic polyoxazolidone obtained depends on the molar ratio of the diepoxide compound (B) relative to the diisocyanate compound (a) and optionally relative to the compound (D).
In one embodiment of the present invention, catalyst (C) comprises at least one of tetraalkylphosphonium halides, tetracycloalkylphosphonium halides, tetraarylphosphonium halides, tetraalkylammonium halides, tetracycloalkylammonium halides and/or tetraarylammonium halides, preferably tetraalkylphosphonium halides, tetracycloalkylphosphonium halides and tetraarylphosphonium halides.
In a preferred embodiment of the present invention, catalyst (C) is at least one compound selected from the group consisting of: tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, tetrapentyl ammonium bromide, tetrahexyl ammonium bromide, tetraheptyl ammonium bromide, tetraoctyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetrapentyl ammonium chloride, tetrahexyl ammonium chloride, tetraheptyl ammonium chloride, tetraoctyl ammonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium iodide, bis (triphenylphosphine) imine chloride, tetraphenyl phosphonium nitrate, tetraphenyl phosphonium carbonate, and a compound represented by formula (I)
[A] n + [Y] n- (I)
Wherein [ A ]] n + Is selected from the group consisting of p-phenol triphenyl-phosphonium; para-phenol triphenyl-ammonium; p-chlorobenzotriphenyl-phosphonium; ethyl-ammonium; methyl trioctyl-ammonium; choline; 1-allyl-3-methyl-imidazolium; 1-butyl-2, 3-dimethyl-imidazolium; 1-butyl-3-methyl-imidazolium; 1, 2-dimethyl-3-propyl-imidazolium; 1, 3-dimethyl-imidazolium; 1-ethyl-3-methyl-imidazolium; 1-hexadecyl-3-methyl-imidazolium; 1-hexyl-3-methyl-imidazolium; 1-methyl-3-octyl-imidazolium; 1-methyl-3-propyl-imidazolium; trihexyltetradecyl-phosphonium; 1-methyl-1-propylpiperidinium; 1-butyl-pyridinium; 1-butyl-3-methyl-pyridinium; 1-Di-4-methyl-pyridinium; 1-butyl-1-methyl-pyrrolidinium; 1-methyl-1-propyl-pyrrolidinium; at least one compound of triethyl sulfonium,
wherein [ Y ]] n- Is selected from bis (trifluoromethyl-sulfonyl) imine; iodide ions; a bromide ion; a chloride ion; dicyandiamide; diethyl phosphate; dihydrogen phosphate; dimethyl phosphate; ethyl sulfate radical; hexafluorophosphate; hydrogen sulfate; nitrate radical; tetrafluoroborate; thiocyanate radical; at least one compound of triflate.
In a more preferred embodiment of the present invention, the catalyst (C) is at least one compound selected from the group consisting of tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, tetrapentyl ammonium bromide, tetrahexyl ammonium bromide, tetraheptyl ammonium bromide, tetraoctyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetrapentyl ammonium chloride, tetrahexyl ammonium chloride, tetraheptyl ammonium chloride, tetraoctyl ammonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium iodide, bis (triphenylphosphine) imine chloride, tetraphenyl phosphonium nitrate, tetraphenyl phosphonium carbonate.
In an even more preferred embodiment of the present invention, catalyst (C) is at least one compound selected from the group consisting of tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium iodide, bis (triphenylphosphine) imine chloride, tetraphenyl phosphonium nitrate and tetraphenyl phosphonium carbonate.
In a most preferred embodiment of the present invention, the catalyst (C) is at least one compound selected from the group consisting of tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide and tetraphenyl phosphonium iodide.
In one embodiment of the process according to the invention, catalyst (C) is present in an amount of from.gtoreq.0.001 to.ltoreq.5.0 wt.%, preferably from.gtoreq.0.005 to.ltoreq.3.0 wt.%, more preferably from.gtoreq.0.08 to.ltoreq.2.0 wt.%, based on the theoretical yield of thermoplastic polyoxazolidone (1).
In one embodiment of the invention, compound (D) is added prior to the copolymerization, and compound (D) is added prior to the copolymerization, wherein compound (D) comprises at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol, and a monofunctional amine, preferably a monofunctional epoxide, wherein compound (D) acts as a chain regulator for the thermoplastic polyoxazolidone and results in a lower polydispersity of the thermoplastic polyoxazolidone (1).
In a further embodiment of the invention, compound (D) is a branched, unbranched aliphatic, cycloaliphatic and/or aromatic monofunctional alcohol.
Suitable monofunctional alcohols are, for example, straight-chain primary alcohols, such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol and n-eicosanol. Suitable branched primary monofunctional alcohols are, for example, isobutanol, isoamyl alcohol, isohexanol, isooctanol, isostearyl alcohol and isopalmitol, 2-ethylhexanol, 3-n-propylheptanol, 2-n-propylheptanol and 3-isopropylheptanol. Suitable secondary monofunctional alcohols are, for example, isopropanol, sec-butanol, sec-amyl alcohol (pentan-2-ol), pentan-3-ol, cyclopentanol, cyclohexanol, zhong Jichun (hex-2-ol), hex-3-ol, zhong Gengchun (hept-2-ol), hept-3-ol, zhong Gui-ol and dec-3-ol. Examples of suitable tertiary monofunctional alcohols are t-butanol and t-amyl alcohol.
Aromatic monofunctional alcohols such as phenol, cresol, thymol, benzyl alcohol and 2-phenylethanol may also be used.
In a further embodiment of the invention, compound (D) is a branched, unbranched aliphatic, cycloaliphatic and/or aromatic monofunctional isocyanate.
Suitable monofunctional isocyanates are, for example, n-hexyl isocyanate, cyclohexyl isocyanate, omega-chlorohexamethylene isocyanate, 2-ethylhexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate (stearyl isocyanate), methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate (octadecyl isocyanate), 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3, 4-trimethylcyclohexyl isocyanate, 3, 5-trimethylcyclohexyl isocyanate, 2-norbornylmethyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate octadecyl isocyanate, 3-butoxypropyl isocyanate, 3- (2-ethylhexyl oxy) -propyl isocyanate, (trimethylsilyl) isocyanate, phenyl isocyanate, o-, m-, p-tolyl isocyanate, chlorophenyl isocyanate (2, 3, 4-isomer), dichlorobenzyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenyl isocyanate (technical mixture and individual isomers), 4-dodecylphenyl isocyanate, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-tert-butylphenyl isocyanate, 1-naphthyl isocyanate.
In one embodiment of the invention, compound (D) is a branched, unbranched aliphatic, cycloaliphatic and/or aromatic monofunctional amine. Specific examples of aliphatic monofunctional amines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine. Examples include amine, octadecylamine, nonadecylamine, eicosylamine (icosamine), heneicosamine (henecosylamine), and docosylamine. Specific examples of the alicyclic monofunctional amine include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2, 3-dimethylcyclohexylamine, 2, 4-dimethylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 3-n-propylcyclohexylamine, 4-n-propylcyclohexylamine, 2-isopropylcyclohexylamine, 3-isopropylcyclohexylamine, 4-isopropylcyclohexylamine, 2-n-butylcyclohexylamine, 3-n-butylcyclohexylamine, 4-n-butylcyclohexylamine (Silamine), 2-isobutylcyclohexylamine, 3-isobutylcyclohexylamine, 4-isobutylcyclohexylamine 2-tert-butylcyclohexylamine, 3-tert-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 2-n-octylcyclohexylamine, 3-n-octylcyclohexylamine, cyclohexylmethylamine, 2-methylcyclohexylmethylamine, 3-methylcyclohexylmethylamine, 4-methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethylcarboxymethyl cyclohexylmethylamine, methoxycyclohexylethylamine, dimethoxycyclohexylethylamine, methylcyclohexylpropylamine and dodecylcyclohexylamine.
Specific examples of the aromatic monofunctional amine include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, o-toluidine, p-toluidine, m-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, cumylamine, 2-N-butylaniline, 3-N-butylaniline, 4-N-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 4-isobutylaniline, 2-sec-butylaniline, 3-sec-butylaniline, 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 2-N-pentylamin, 3-N-pentylamin, 4-N-pentylamin 2-isopentylaniline, 3-isopentylaniline, 4-isopentylaniline, 2-sec-pentylamine, 3-sec-pentylamine, 4-sec-pentylamine, 2-tert-pentylamine, 3-tert-pentylamine, 4-tert-pentylamine, 2-hexylaniline, 3-hexylaniline, 4-hexylaniline, 2-heptylaniline, 3-heptylaniline, 4-heptylaniline, 2-octylaniline, 3-octylaniline, 4-octylaniline, 2-nonylaniline, 3-nonylaniline, 4-nonylaniline, 2-decylaniline, 3-decylaniline, 4-decylaniline, cyclohexylaniline, di-dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-butylaniline, anisole, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, alpha-phenylethylamine, beta-phenylethylamine, methoxyphenylethylamine, dimethoxyphenylethylamine, alpha-phenylpropylamine, beta-phenylpropylamine, gamma-phenylpropylamine, methylphenylpropylamine.
In one embodiment of the present invention, the compound (D) is at least one compound selected from the group consisting of 4-phenyl-1, 3-dioxolan-2-one (styrene carbonate), 1, 3-dioxolan-2-one (ethylene carbonate), 4-methyl-1, 3-dioxolan-2-one (propylene carbonate).
In a preferred embodiment of the invention, compound (D) is at least one compound selected from the group consisting of phenyl glycidyl ether, o-cresol glycidyl ether, m-cresol glycidyl ether, p-cresol glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4, 6-trichlorophenyl glycidyl ether, 2,4, 6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, benzoic acid glycidyl ester, acetic acid glycidyl ester, cyclohexyl formic acid glycidyl ester, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, C10-C18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 1, 2-hexene oxide, C10-C18 alpha-olefin oxide, cyclohexene oxide, monocyclohexene oxide, mono-N-tert-butyl glycidyl ether, 4-phenylglycidyl imine and o-butyl glycidyl ether.
In a preferred embodiment of the invention, the compound (D) is 4-tert-butylphenyl glycidyl ether and/or phenyl glycidyl ether and/or o-cresol glycidyl ether and/or styrene oxide.
In one embodiment of the process according to the invention, compound (D) is present in an amount of from.gtoreq.0.1 to.ltoreq.7.0 wt.%, preferably from.gtoreq.0.2 to.ltoreq.5.0 wt.%, more preferably from.gtoreq.0.5 to.ltoreq.3.0 wt.%, based on the theoretical yield of thermoplastic polyoxazolidone.
Preferably, the molar amount of monofunctional isocyanate, monofunctional epoxide, cyclic carbonate, monofunctional alcohol, monofunctional amine added as compound (D), preferably monofunctional epoxide, meets certain criteria regarding the molar amounts of the bisepoxide compound (B) and the diisocyanate compound (a). The ratio r is defined as the molar amount (n) of the compound (D) according to the following formula (II) D ) Molar amount of the diepoxide (B) (n) Bisepoxides ) And di-differencesMolar amount (n) of cyanate ester compound (A) Diisocyanate (BI) ) Absolute value of difference between
r＝|n D /(n Bisepoxides -n Diisocyanate (BI) )|
It is preferably in the range of from.gtoreq.1.5 to.ltoreq.2.5, more preferably in the range of from.gtoreq.1.9 to.ltoreq.2.1, and particularly preferably in the range of from.gtoreq.1.95 to.ltoreq.2.05. Without being bound by theory, when such amounts of chain regulators are used, all epoxy groups and all isocyanate groups have reacted at the end of the reaction.
The solvent (E) according to the present invention dissolves the diisocyanate compound (a), the diepoxide compound (B) and the thermoplastic polyoxazolidone but does not react with the diisocyanate compound (a), the diepoxide compound (B), the catalyst (C), the compound (D) (if present), the compound (F) (if present), the thermoplastic polyoxazolidone (1) and the thermoplastic polyoxazolidone (2).
It is pointed out that the solvents (E) suitable for the purposes of the present invention can be described using a special relationship, which is described below as satisfying the so-called "Hansen solubility parameter delta D 、δ P And delta H "certain requirements related". The solvent (E) according to the invention is prepared by cohesive energy density delta 2 Characterization, cohesive energy Density delta 2 Is the component delta D 2 (δ D 2 Is a representation of the force of dispersion between the molecules of solvent (E), component delta p 2 (δ P 2 Is a characterization of the intermolecular dipole forces between the molecules of solvent (E) and component delta H 2 (δ H 2 Is a characterization of the hydrogen bonding forces between the molecules of solvent (E)
Wherein: delta 2 ＝δ D 2 +δ P 2 +δ H 2 ；
Wherein at 25℃:
δ D has a pressure of 18.0MPa 0.5 To 20.0MPa 0.5 Is used as a reference to the value of (a),
δ P has a pressure of 8.0MPa 0.5 To 15.0MPa 0.5 And (2) a value of
δ H Has a pressure of 2.5MPa 0.5 To 9.0MPa 0.5 Is a value of (2).
Hansen parameters are physicochemical properties that define the compatibility between materials, e.g., solvents, such as solvent (E), and can be described by three hansen parameters, each typically in MPa 0.5 Measuring, where the parameters are
δ D Describing energy from the dispersive forces between molecules
δ P Describing energy from dipole intermolecular forces between molecules, and
δ H energy from hydrogen bonding between molecules is described. Hansen solubility parameters were developed in their doctor papers by Charles m.hansen in 1967 (Hansen, charles (1967), the Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient and Their Importance in Surface Coating formulation. Copenhagen: danish Technical Press) and are a widely accepted concept in technology and science for predicting whether a material (molecule) will dissolve in another and form a solution (Hansen, charles (2007), hansen Solubility Parameters: a user's handbook, second edition. Boca Raton, fla: CRC Press). An overview of hansen Solubility parameters of different liquids at 25 ℃ can be found in table 16.3 of Zeng et al (Zeng w., du y., xue y., frisch h.l. (2007) solution parameters in Mark j.e. (eds) Physical Properties of Polymers handbook Springer, new York, NY), where the hansen Solubility parameter of o-dichlorobenzene (o-DCB) at 25 ℃ is δ D ：19.2MPa 0.5 、δ P ：6.3MPa 0.5 、δ H ：3.3MPa 0.5 And the hansen solubility parameter of benzonitrile is (δ D ：18.8MPa 0.5 、δ P ：12.0MPa 0.5 、δ H ：3.3MPa 0.5 ). Sulfolane has a hansen solubility parameter delta at 25 DEG C D ：20.3MPa 0.5 、δ P ：18.2MPa 0.5 、δ H ：10.9MPa 0.5 (Hansen, C.Hansen Solubility Parameters: A User's Handbook, second edition; CRC Press: boca Raton, FL, USA, 2012).
In one embodiment of the process according to the invention, the solvent (E) is a single solvent, which means that no mixture comprising at least two solvents is used.
In a preferred embodiment of the process according to the invention, the solvent (E) is one or more compounds, preferably one compound, and is selected from the group consisting of benzonitrile, p-chlorobenzonitrile, p-bromobenzonitrile, p-tolunitrile, p-methoxybenzonitrile, p-tert-butylbenzonitrile, o-chlorobenzonitrile, o-bromobenzonitrile, o-tolunitrile, o-methoxybenzonitrile, m-chlorobenzonitrile, m-tolunitrile, m-methoxybenzonitrile, 2, 3-dichlorobenzonitrile, 2, 4-dichlorobenzonitrile, 2, 5-dichlorobenzonitrile, 2, 6-dichlorobenzonitrile, 3, 4-dichlorobenzonitrile, butyronitrile, isobutyronitrile, valeronitrile, cyclohexane carbonitrile, capronitrile (capronitrile) and pivalonitrile, preferably benzonitrile.
In a most preferred embodiment of the process according to the invention, the solvent (E) comprises benzonitrile.
In one embodiment of the process according to the invention, step (iii), the copolymerization is preferably carried out at a reaction temperature of from.gtoreq.130℃to.ltoreq.280℃preferably at a temperature of from.gtoreq.140℃to.ltoreq.240℃and more preferably at a temperature of from.gtoreq.155℃to.ltoreq.210 ℃. If a temperature below 130 ℃ is set, the reaction is generally very slow and byproducts, such as isocyanurates, are also formed. At temperatures above 280 ℃, the amount of undesirable byproducts increases significantly.
In one embodiment of the process according to the invention, the calculated mass ratio of the sum of diisocyanate compound (a), diepoxide compound (B) and compound (D) to the sum of diisocyanate compound (a), diepoxide compound (B), compound (D) and solvent (E) is from 10 to 90% by weight, preferably from 20 to 85% by weight, and more preferably from 27 to 80% by weight. If this mass ratio is too low, a large amount of solvent (E) needs to be removed, for example by distillation, which causes additional production time and undesirable energy consumption. This results in a more efficient overall process due to energy savings and reduced solvent levels. If the solids content is too high, the viscosity of the copolymerization process is too high to ensure adequate mixing, thus causing mass transfer limitations.
In one embodiment of the process according to the invention, catalyst (C) is present in an amount of from.gtoreq.0.008 to.ltoreq.2.0 wt.% based on the theoretical yield of thermoplastic polyoxazolidone and the reaction temperature of the copolymerization is from.gtoreq.180℃to.ltoreq.210℃. This gives thermoplastic polyoxazolidone (1) with a high oxazolidone/isocyanate ratio and reduced polydispersity.
In one embodiment of the process according to the invention, the copolymerization is carried out for a reaction time of from 1h to 20h, preferably from 1h to 10h, and more preferably from 1h to 6 h.
Another aspect of the invention is a thermoplastic polyoxazolidone (1) obtainable by the process according to one of claims 1 to 11, wherein the thermoplastic polyoxazolidone has a number average molecular weight Mn of from more than or equal to 500 to less than or equal to 500,000g/mol, more preferably from more than or equal to 1,000 to less than or equal to 50,000g/mol, and even more preferably from more than or equal to 5,000 to less than or equal to 25,0000g/mol, as determined by Gel Permeation Chromatography (GPC), wherein GPC is carried out on an Agilent 1100Series instrument with N, N-Dimethylacetamide (DMAC) +LiBr (1.7g.L) -1 ) PSS GRAM analytical column from PSS as eluentEquipped with Refractive Index (RI) detector, wherein the column flow in all measurements was set to 1mL min - 1, wherein for determination of molecular weight, calibration is performed with poly (styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS), and wherein samples are analyzed using PSS WinGPC UniChrom V8.2.2 software.
A further aspect of the invention is a process for producing a thermoplastic polyoxazolidone (2), wherein a thermoplastic polyoxazolidone (1) obtainable by the process according to one of claims 1 to 13 is further reacted with a compound (F) to form a thermoplastic polyoxazolidone (2), wherein the compound (F) comprises at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol and a monofunctional amine, preferably a monofunctional epoxide. The compound (F) acts as a chain regulator for the thermoplastic polyoxazolidone and further enhances the thermal stability of the thermoplastic polyoxazolidone.
Compound (F) is added to the reaction mixture as a chain regulator after the reaction between the diepoxide (B) and the diisocyanate (a) forming the thermoplastic polyoxazolidone (1) has been completed. Without being bound by theory, the terminal, e.g., epoxide groups or terminal isocyanate groups, resulting from the reaction of the diepoxide and diisocyanate will be converted to inert terminal groups by reaction with the modifier. The excess regulator is then removed from the product, for example by extraction, precipitation, distillation, stripping or thin film evaporation.
Suitable monofunctional alcohols are, for example, straight-chain primary alcohols, such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol and n-eicosanol. Suitable branched primary monofunctional alcohols are, for example, isobutanol, isoamyl alcohol, isohexanol, isooctanol, isostearyl alcohol and isopalmitol, 2-ethylhexanol, 3-n-propylheptanol, 2-n-propylheptanol and 3-isopropylheptanol. Suitable secondary monofunctional alcohols are, for example, isopropanol, sec-butanol, sec-amyl alcohol (pentan-2-ol), pentan-3-ol, cyclopentanol, cyclohexanol, zhong Jichun (hex-2-ol), hex-3-ol, zhong Gengchun (hept-2-ol), hept-3-ol, zhong Gui-ol and dec-3-ol. Examples of suitable tertiary monofunctional alcohols are t-butanol and t-amyl alcohol.
Aromatic monofunctional alcohols such as phenol, cresol, thymol, benzyl alcohol and 2-phenylethanol may also be used.
In a further embodiment of the invention, compound (F) is a branched, unbranched aliphatic, cycloaliphatic and/or aromatic monofunctional isocyanate.
Suitable monofunctional isocyanates are, for example, n-hexyl isocyanate, cyclohexyl isocyanate, omega-chlorohexamethylene isocyanate, 2-ethylhexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate (stearyl isocyanate), methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate (octadecyl isocyanate), 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3, 4-trimethylcyclohexyl isocyanate, 3, 5-trimethylcyclohexyl isocyanate, 2-norbornylmethyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate octadecyl isocyanate, 3-butoxypropyl isocyanate, 3- (2-ethylhexyl oxy) -propyl isocyanate, (trimethylsilyl) isocyanate, phenyl isocyanate, o-, m-, p-tolyl isocyanate, chlorophenyl isocyanate (2, 3, 4-isomer), dichlorobenzyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenyl isocyanate (technical mixture and individual isomers), 4-dodecylphenyl isocyanate, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-tert-butylphenyl isocyanate, 1-naphthyl isocyanate.
In one embodiment of the invention, compound (F) is a branched, unbranched aliphatic, cycloaliphatic and/or aromatic monofunctional amine. Specific examples of aliphatic monofunctional amines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine. Examples include amine, octadecylamine, nonadecylamine, eicosylamine, heneicosanylamine, and docosylamine. Specific examples of the alicyclic monofunctional amines include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2, 3-dimethylcyclohexylamine, 2, 4-dimethylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 3-n-propylcyclohexylamine, 4-n-propylcyclohexylamine, 2-isopropylcyclohexylamine, 3-isopropylcyclohexylamine, 4-isopropylcyclohexylamine, 2-n-butylcyclohexylamine, 3-n-butylcyclohexylamine, 4-n-butylcyclohexylsilane, 2-isobutylcyclohexylamine, 3-isobutylcyclohexylamine, 4-isobutylcyclohexylamine, 2-tert-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 2-n-octylcyclohexylamine, 3-n-octylcyclohexylamine, 4-n-octylcyclohexylamine, cyclohexylmethyl amine, 2-methylcyclohexylmethyl amine, 3-methylcyclohexylmethyl amine, 4-methylcyclohexylmethyl amine, dimethylcyclohexylmethyl amine, trimethylcyclohexylamine, methoxycyclohexylmethyl amine, dimethylcyclohexylamine, and dimethylcyclohexylamine.
Specific examples of the aromatic monofunctional amine include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, o-toluidine, p-toluidine, m-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, cumylamine, 2-N-butylaniline, 3-N-butylaniline, 4-N-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 4-isobutylaniline, 2-sec-butylaniline, 3-sec-butylaniline, 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 2-N-pentylamin, 3-N-pentylamin, 4-N-pentylamin 2-isopentylaniline, 3-isopentylaniline, 4-isopentylaniline, 2-sec-pentylamine, 3-sec-pentylamine, 4-sec-pentylamine, 2-tert-pentylamine, 3-tert-pentylamine, 4-tert-pentylamine, 2-hexylaniline, 3-hexylaniline, 4-hexylaniline, 2-heptylaniline, 3-heptylaniline, 4-heptylaniline, 2-octylaniline, 3-octylaniline, 4-octylaniline, 2-nonylaniline, 3-nonylaniline, 4-nonylaniline, 2-decylaniline, 3-decylaniline, 4-decylaniline, cyclohexylaniline, di-dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-butylaniline, anisole, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, alpha-phenylethylamine, beta-phenylethylamine, methoxyphenylethylamine, dimethoxyphenylethylamine, alpha-phenylpropylamine, beta-phenylpropylamine, gamma-phenylpropylamine, methylphenylpropylamine.
In one embodiment of the present invention, the compound (F) is at least one compound selected from the group consisting of 4-phenyl-1, 3-dioxolan-2-one (styrene carbonate), 1, 3-dioxolan-2-one (ethylene carbonate), 4-methyl-1, 3-dioxolan-2-one (propylene carbonate).
In a preferred embodiment of the invention, compound (F) is at least one compound selected from the group consisting of phenyl glycidyl ether, o-cresol glycidyl ether, m-cresol glycidyl ether, p-cresol glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4, 6-trichlorophenyl glycidyl ether, 2,4, 6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, benzoic acid glycidyl ester, acetic acid glycidyl ester, cyclohexyl formic acid glycidyl ester, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, C10-C18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 1, 2-hexene oxide, C10-C18 alpha-olefin oxide, cyclohexene oxide, monocyclohexene oxide, N-tert-butyl glycidyl ether, 4-phthalimide, and o-butyl glycidyl ether.
In a preferred embodiment of the invention, the compound (F) is 4-tert-butylphenyl glycidyl ether and/or phenyl glycidyl ether and/or o-cresol glycidyl ether and/or styrene oxide.
In a preferred embodiment of the present invention, compound (D) and compound (F) are monofunctional epoxides. The use of monofunctional epoxides as compound (D) and compound (F) gives thermoplastic polyoxazolidone (2) with increased oxazolidone/isocyanurate ratio and lower polydispersity.
In a more preferred embodiment of the present invention, compound (D) and compound (F) are 4-tert-butylphenyl glycidyl ether and/or phenyl glycidyl ether and/or o-cresol glycidyl ether and/or styrene oxide.
In one embodiment of the process according to the invention, compound (F) is present in an amount of from.gtoreq.0.1 to.ltoreq.10.0 wt.%, preferably from.gtoreq.0.2 to.ltoreq.8.0 wt.%, more preferably from.gtoreq.0.5 to.ltoreq.7.0 wt.%, based on the theoretical yield of thermoplastic polyoxazolidone.
In one embodiment of the process according to the invention, the reaction of the polyoxazolidone (1) with the compound (F) is carried out at a reaction temperature of from.gtoreq.130℃to.ltoreq.280℃and preferably at a temperature of from.gtoreq.140℃to.ltoreq.240℃and more preferably at a temperature of from.gtoreq.155℃to.ltoreq.210 ℃. If the temperature lower than 130℃is set, the reaction with the compound (F) is very slow. At temperatures above 280 ℃, the amount of undesirable byproducts increases significantly.
In one embodiment of the process according to the invention, the reaction of the polyoxazolidone (1) with the compound (F) is carried out with a reaction time of from 1h to 20h, preferably from 1h to 10h, and more preferably from 1h to 6 h.
In one embodiment, the process according to the invention is carried out in the absence of a solvent (G) having a boiling point above 200℃at 1 bar (absolute). Due to the absence of large amounts of high boiling solvents, negative effects on subsequent extrusion and injection molding processes of thermoplastic polyoxazolidone, such as unwanted foaming, unsuitable viscosity and explosive atmospheres, can be reduced. Thus, the solvents normally necessary for the synthesis of polyoxazolidone should be quantitatively removed, for example to below 1500ppm by distillation methods at elevated temperature and reduced pressure, wherein thermal decomposition of the polyoxazolidone results in a higher polydispersity and poor coloration of the desolvated polyoxazolidone should be minimized to obtain desolvated polyoxazolidone with good thermoplastic properties and improved thermal stability.
Such solvents (G) include, for example, cyclic carbonates such as ethylene carbonate or propylene carbonate, N-methylpyrrolidone (NMP) and sulfolane. The absence of such additional solvent (G) reduces the energy intensive and time consuming removal process, such as distillation, of such high boiling solvents.
In a preferred embodiment of the present invention, benzonitrile is applied as solvent (E) and no solvent (G) is used, such as ethylene carbonate or propylene carbonate, N-methylpyrrolidone (NMP) and sulfolane.
By the method of the inventionThe thermoplastic polyoxazolidone (2) obtained is also an aspect of the invention, wherein the thermoplastic polyoxazolidone (2) is obtainable by the process according to claim 14, wherein the thermoplastic polyoxazolidone has a number average molecular weight Mn of from 500 to 500,000g/mol, more preferably from 1,000 to 50,000g/mol, and even more preferably from 5,000 to 25,0000g/mol, as determined by Gel Permeation Chromatography (GPC), wherein GPC is carried out on an Agilent 1100Series instrument with N, N-Dimethylacetamide (DMAC) +LiBr (1.7g.L) -1 ) PSS GRAM analytical column from PSS as eluentEquipped with Refractive Index (RI) detector, wherein the column flow in all measurements was set to 1mL min -1 Wherein for determination of molecular weight, calibration was performed with poly (styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS), and wherein samples were analyzed using PSS WinGPC UniChrom V8.2.2 software.
The invention further relates to spun fibers comprising the thermoplastic polyoxazolidone (1) and/or thermoplastic polyoxazolidone (2) according to the invention and textiles comprising such spun fibers.
The process according to the invention is suitable for the synthesis of oxazolidinones having useful properties for use as e.g. pharmaceuticals or antimicrobial agents.
The thermoplastic polyoxazolidinones (1) and/or (2) obtainable by the process according to the invention are particularly suitable as polymer building blocks (building blocks) in polyurethane chemistry. For example, an epoxy-capped oligomeric oxazolidone (oligomeric oxazolidone) may be reacted with a polyol or polyamine to form a foam or thermoset. Such epoxy-capped oligomeric oxazolidinones are also useful in preparing composites. Epoxy-terminated oligooxazolidones (oligooxazolidones) can also be reacted with their NCO-terminated counterparts to form high molecular weight thermoplastic polyoxazolidones that can be used as transparent high temperature resistant materials. The high molecular weight thermoplastic polyoxazolidinones obtained by the process according to the invention are particularly suitable as transparent heat-resistant thermoplastic materials.
Conventional additives for these thermoplastics, such as fillers, UV stabilizers, heat stabilizers, antistatic agents and pigments, can also be added in conventional amounts to the thermoplastic polyoxazolidinones according to the invention; mold release properties, flow properties and/or flame retardancy may also optionally be improved by the addition of external mold release agents, flow agents and/or flame retardants (e.g., alkyl and aryl phosphites and phosphates, alkyl-and aryl phosphanes and low molecular weight alkyl and aryl carboxylates, halogen compounds, salts, chalk, quartz powder, glass fibers and carbon fibers, pigments and combinations thereof, such compounds are described, for example, in WO 99/55772, pages 15-25 and corresponding section "Plastics Additives Handbook", editions of Hans Zweifel, 5 th edition 2000,Hanser Publishers,Munich).
The thermoplastic polyoxazolidinones (1) and/or (2) obtained according to the invention have excellent properties in terms of stiffness, hardness and chemical resistance.
They can also be used in polymer blends with other polymers, for example polystyrene, high impact polystyrene (polystyrene modified by rubber used for toughening, usually polybutadiene), copolymers of styrene, such as styrene-acrylonitrile copolymer (SAN), styrene, copolymers of alpha-methylstyrene and acrylonitrile, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-acrylic acid copolymer, SAN modified by grafting rubber used for toughening, such as ABS (acrylonitrile-butadiene-styrene polymer), ASA (acrylonitrile-styrene-acrylate), AES (acrylonitrile-EPDM-styrene), ACS (acrylonitrile-chlorinated polyethylene-styrene) polymers, copolymers of styrene, alpha-methylstyrene and acrylonitrile modified with rubber, such as polybutadiene or EPDM, MBS/MABS (methyl methacrylate-styrene modified with rubber, such as polybutadiene or EPDM), aromatic polyesters, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), aliphatic polyamides such as PA6, PA4,6, PA 11 or PA 12, polylactic acid, aromatic polycarbonates such as those of bisphenol A, copolycarbonates such as those of bisphenol A and bisphenol TMC, polymethyl methacrylate (PMMA), polyvinyl chloride, polyoxymethylene (POM), polyphenylene oxide, polyphenylene sulfide (PPS), polysulfone, polyetherimide (PEI), polyethylene, polypropylene.
They can also be used in combination with the above polymers or other polymers in blends, for example, a blend of polycarbonate and ABS, a blend of polycarbonate and PET, a blend of polycarbonate and PBT, a blend of polycarbonate and ABS and PBT, or a blend of polycarbonate and ABS and PBT.
The properties of the thermoplastic polyoxazolidinones (1) and/or (2) or blends with the above-mentioned polymers or other polymers according to the invention can also be modified by fillers, such as glass fibers, hollow or solid glass spheres, silica (for example fumed silica or precipitated silica), talc, calcium carbonate, titanium dioxide, carbon fibers, carbon black, natural fibers such as straw, flax, cotton or wood fibers.
The thermoplastic polyoxazolidinones (1) and/or (2) can be mixed with any usual plastics additives, such as antioxidants, light stabilizers, impact modifiers, acid scavengers, lubricants, processing aids, antiblocking additives, slip additives, antifogging additives, antistatic additives, antimicrobial agents, chemical blowing agents, colorants, optical brighteners, fillers and reinforcing materials and flame retardant additives.
Suitable impact modifiers are generally high molecular weight elastomeric materials derived from olefins, monovinylaromatic monomers, acrylic and methacrylic acids and their ester derivatives, as well as conjugated dienes. The polymer formed from the conjugated diene may be fully or partially hydrogenated. The elastomeric material may be in the form of a homopolymer or copolymer, including random, block, radial block (radial block), graft, and core-shell copolymers. Combinations of impact modifiers may be used.
One particular type of impact modifier is an elastomer-modified graft copolymer that comprises (i) an elastomeric (i.e., rubbery) polymer substrate having a Tg of less than 10 ℃, more particularly less than-10 ℃, or more particularly from-40 ℃ to-80 ℃, and (ii) a rigid polymer shell grafted onto the elastomeric polymer substrate. Materials suitable for use as the elastomeric phase include, for example, conjugated diene rubbers such as polybutadiene and polyisoprene; copolymers of conjugated dienes with less than 50 weight percent of copolymerizable monomers, for example monovinyl compounds such as styrene, acrylonitrile, n-butyl acrylate or ethyl acrylate; olefin rubbers such as ethylene propylene copolymers (EPR) or ethylene-propylene-diene monomer rubbers (EPDM); ethylene-vinyl acetate rubber; an organic silicon rubber; elastomeric C1-8 alkyl (meth) acrylates; elastomeric copolymers of C1-8 alkyl (meth) acrylates with butadiene and/or styrene; or combinations comprising at least one of the foregoing elastomers. Materials suitable for use as the rigid phase include, for example, monovinylaromatic monomers such as styrene and alpha-methylstyrene, and monovinyl monomers such as acrylonitrile, acrylic acid, methacrylic acid, and C1-C6 esters of acrylic acid and C1-C6 esters of methacrylic acid, especially methyl methacrylate.
Specific exemplary elastomer-modified graft copolymers include those formed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), and styrene-acrylonitrile (SAN).
The impact modifier is typically present in an amount of from 1 to 30 wt%, especially from 3 to 20 wt%, based on the total weight of the polymers in the flame retardant composition (flame retardant composition). Exemplary impact modifiers comprise acrylic polymers in an amount of 2 to 15 wt%, especially 3 to 12 wt%, based on the total weight of the flame retardant composition.
The composition may also comprise a mineral filler. In one embodiment, the mineral filler acts as a synergist. The synergist promotes an improvement in flame retardant properties when added to a flame retardant composition, as compared to a comparative thermoplastic polyoxazolidone composition containing all the same ingredients in the same amounts except the synergist. Examples of mineral fillers are mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar, barite, and the like, or a combination comprising at least one of the foregoing mineral fillers. The mineral filler may have an average particle size of 0.1 to 20 microns, especially 0.5 to 10 microns, and more especially 1 to 3 microns. An exemplary mineral filler is talc having an average particle size of 1 to 3 microns.
The mineral filler is present in an amount of 0.1 to 20 wt%, especially 0.5 to 15 wt%, and more especially 1 to 5 wt%, based on the total weight of the flame retardant composition.
Thermoplastic polyoxazolidinones can also be colored with various soluble organic dyes and with pigment dyes (pigments dyes) which can be organic or inorganic.
Further possible uses of the thermoplastic polyoxazolidinones according to the invention are:
01. housings for electrical appliances (e.g. household appliances, computers, mobile phones, display screens, televisions.), including transparent or translucent housing parts, such as lamp covers.
02. Light guide plate and BLU
03. Optical data storage (CD, DVD, blu-ray disc)
04. Electrical conductors, electrically insulating material for plug housings and plug connectors, carrier material for organic light conductors, chip boxes and Chip carriers (Chip supports), fuse packages
05. Static dissipative/conductive formulations for explosion-proof applications and other applications with respective requirements
06. Optics, diffusers, reflectors, light pipes and housings for LEDs and conventional lighting, such as street lamps, industrial lamps, floodlights, traffic lights
07. Thermally conductive formulations for thermal management applications, such as heat sinks
08. Applications for automobiles and other transportation vehicles (cars, buses, trucks, trains, planes, boats), as glazing, as well as safety glass, light fixtures (e.g., headlamp lenses, tail lights, turn signals, reversing lights, fog lights; collector rings and reflectors), sunroofs and panoramic sunroofs, canopies, railway cars (rail) or cladding of other cabins (cladding), windshields, interior and exterior parts (e.g., instrument covers, consoles, dashboards, mirror housings, radiator grilles, bumpers, spoilers)
EVSE and Battery
10. Metal substitutes in gears, seals, support rings
11. Roof structures (e.g. for gymnasiums, stations, hothouses, greenhouses)
12. Window (including burglary-resisting window and bulletproof window, teller window, and inner barrier of bank)
13. Partition wall
14. Solar panel
15. Medical devices (blood pumps, auto-injector and ambulatory medical syringe pump assemblies, iv set (IV access devices), renal treatment and inhalation devices (e.g., nebulizers, inhalers), sterilizable surgical devices, medical implants, oxygenators, dialyzers,)
16. Food contact applications (kitchen ware, tableware, glassware, glasses, food containers, institutional food trays (institutional food trays), water bottles, water filtration systems)
17. Sports articles, e.g. slalom poles or ski boot buckles
18. Household articles, e.g. kitchen sink and letter box casings
19. Safety applications (glasses, goggles or optical corrective glasses, helmets, goggles, anti-riot gear (helmets and shields), safety panels (safety panels))
20. Sunglasses, swimming goggles and diving mask
21. Sign, display, poster protection
22. Light luggage case
23. Water fitting, pump impeller, and fine hollow fiber for water treatment
24. Industrial pump, valve and seal, connector
25. Film and method for producing the same
26. Gas separation
27. Coating applications (e.g. anti-corrosion paints, powder coatings)
The present application likewise provides shaped articles and moldings and extrudates made from the polymers according to the invention.
Examples
The invention is further described with reference to the following examples, which are not intended to be limiting.
Diisocyanate compound (A)
MDI 4,4' -diphenylmethane diisocyanate 98%, covestro AG, germany
Epoxy compound (B)
BADGE 2- [ [4- [2- [4- (oxiran-2-ylmethoxy) phenyl ] prop-2-yl ] phenoxy ] methyl ] oxirane (bisphenol-A-diglycidyl ether), difunctional epoxide, D.E.R.332 (Dow) was used without any further purification (EEW: 171-175 g/eq.)
Catalyst (C)
TPPCl tetraphenyl phosphonium chloride (Sigma-Aldrich, 98%)
LiCl lithium chloride (Sigma-Aldrich, > 99.9%)
Compounds (D) and (F)
BPGE p-tert-butylphenyl glycidyl ether (ABCR Dr. Braunagel GmbH+Co.KG)
Solvent (E)
o-DCB o-dichlorobenzene (o-DCB) 99% pure, anhydrous, obtained from Sigma-Aldrich, germany
Benzonitrile purity 99%, obtained from Acros Organics, germany
Solvent (G)
Sulfolane Acros Organics,99%
o-DCB, sulfolane, benzonitrile, NMP, MDI, BADGE, TPPCl, liCl and BPGE were used as received without further purification. BADGE and sulfolane are used after melting at 50 ℃, whereas BPGE is stored at 7 ℃.
Characterization of thermoplastic polyoxazolidinones
The average chain length of the thermoplastic polyoxazolidone is controlled by the molar ratio of the diepoxide, diisocyanate and/or compound (D).
The following formula gives the general mathematical formula for calculating the average chain length n in the polymerization product obtained with diisocyanate (A) and diepoxide (B):
n＝(1+q)/(1+q-2pq)(III)
wherein the method comprises the steps ofq＝n x /n y Less than or equal to 1 and x, y=diepoxide (B) or diisocyanate (A)
And conversion p
Whereby n is x And n y The molar amounts of the diepoxide or diisocyanate, respectively.
The average molecular weight M of the thermoplastic polyoxazolidone can be calculated by the formula given below
M＝n*((M A +M B )/2)+(2*M D ) (IV)
Wherein M is A 、M B And M D Is the molar mass of the compounds (A), (B) and (D).
Infrared spectroscopy:
solid state IR analysis was performed on a Bruker ALPHA-P IR spectrometer equipped with a diamond probe. Software OPUS 7.5 is used for data processing. Background spectra were recorded against ambient air. Thereafter, a small sample of thermoplastic polyoxazolidone (2 mg) was applied to the diamond probe and an infrared spectrum recorded, at 4000 to 400cm -1 Within a range of 4cm -1 Averaged over 24 spectra obtained at the resolution of (c).
OXA: PIR ratio is calculated by means of signal height in infrared spectroscopy. Thus, samples from the crude reaction product mixture were analyzed by ATR-IR-spectroscopy. Use of the oxazolidone group at 1753cm -1 Characteristic carbonyl band at 1710cm -1 The signal at that point was used to determine isocyanurate levels. OXA is calculated based on the following formula: PIR ratio:
SEC：
the determination of the number average molecular weight, weight average molecular weight and polydispersity index was performed by Gel Permeation Chromatography (GPC). GPC was performed on an Agilent 1100Series instrument with N, N-Dimethylacetamide (DMAC) +LiBr (1.7g.L) -1 ) PSS GRAM analytical column from PSS as eluentIs provided with a Refractive Index (RI) detector. The column flow rate in all measurements was set to 1mL min -1 . For molecular weight determination, calibration was performed with a poly (styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS). Samples were analyzed using PSS WinGPC UniChrom V8.2.2 software.
Example 1 (comparative):reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using LiCl as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), in o-DCB as solvent (E) and sulfolane as high-boiling cosolvent
LiCl (0.0999 g) and sulfolane (28 ml) were charged to a glass flask (500 ml) under a continuous nitrogen flow and stirred at 175℃for 15 minutes. Subsequently, o-dichlorobenzene (95 ml) was added. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a diglycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and o-dichlorobenzene (85 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, NMP (107 ml) was added to homogenize the reaction mixture and the viscous solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 2 (comparative))：Reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using LiCl as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), in o-DCB as solvent (E)
LiCl (0.0999 g) and o-dichlorobenzene (95 ml) were charged into a glass flask (500 ml) under a continuous nitrogen flow and stirred at 175℃for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a diglycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and o-dichlorobenzene (85 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. In the IR spectrum of the reaction mixture there was an isocyanate band (2260 cm -1 ) Indicating incomplete conversion. Subsequently, the mixture was allowed to cool to ambient temperature. No product isolation was performed since no significant amount of polymerization product was formed.
Example 3 (comparative):reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), in o-DCB as solvent (E)
A glass flask (500 ml) was charged with tetraphenyl phosphonium chloride (TPPCl, 0.8834 g) and o-dichlorobenzene (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and o-dichlorobenzene (77 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition is completed, the reactionStirring was carried out for a further 30 minutes at 175 ℃. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, NMP (107 ml) was added to homogenize the reaction mixture and the viscous solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 4 (comparative):reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C) and p-tert-butylphenyl glycidyl ether (BPGE) as compound (D), in o-DCB as solvent (E)
A glass flask (500 ml) was charged with tetraphenyl phosphonium chloride (TPPCl, 0.8834 g) and o-dichlorobenzene (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and o-dichlorobenzene (77 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, NMP (107 ml) was added to homogenize the reaction mixture and the viscous solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. Washing the product with ethanolWashed, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 5:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), in benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in benzonitrile (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 6:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) added in step (α), no compound (F), benzonitrile as solvent(E) And no solvent (G)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 7:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to the ringAmbient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 8:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C) and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 9:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C) and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Directional glassThe glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (28.3134 g), bisphenol a glycidyl ether (40.1173 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 10 (comparative):reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C) and o-DCB as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and o-DCB (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g) and o-DCB (77 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, NMP (107 ml) was added to the reaction mixture and the mixture was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 11:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B)), tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (F), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in benzonitrile (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 12:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (F), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Two bottles (250 ml) were filled withPhenylmethane diisocyanate (MDI) (28.3134 g), bisphenol a glycidyl ether (40.1173 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in benzonitrile (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 13:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (50 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (40 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in benzonitrile (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By being in the infrared spectrum of the reaction mixture Absence of isocyanate band (2260 cm) -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 14:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (20 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (33 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in benzonitrile (11 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 15:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (25 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (15 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 16:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and benzonitrile (18 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175℃CAnd stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol A glycidyl ether (38.5141 g) and p-tert-butylphenyl glycidyl ether (1.9449 g). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 17 (comparative):reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), and o-DCB as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and o-DCB (31 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and o-DCB (38 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-DCB (8 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. By passing through In the IR spectrum of the reaction mixture, there was no isocyanate band (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, NMP (107 ml) was added to homogenize the reaction mixture and the viscous solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 18:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.4417 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 19:diphenylmethane diisocyanate (MDI) as the reaction of diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B)As catalysts (C), tetraphenylphosphonium chloride (TPPCl), p-tert-butylphenyl glycidyl ether (BPGE) and benzonitrile as solvent (E) are used, respectively
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.2209 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 20:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.1104 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 210 minutes. By reaction in a reaction mixture In the IR spectrum there is no isocyanate band (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 21:reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D), and benzonitrile as solvent (E)
A glass flask (500 ml) was charged with tetraphenylphosphonium chloride (TPPCl, 0.2209 g) and benzonitrile (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 190 ℃ and stirred for 15 minutes. Into a glass bottle (250 ml) were charged diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol a glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and benzonitrile (79 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 190 ℃ for an additional 210 minutes. By the absence of isocyanate bands in the IR spectrum of the reaction mixture (2260 cm -1 ) The reaction was confirmed to be complete. Subsequently, the clear reaction solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
Example 22 (comparative):reaction of diphenylmethane diisocyanate (MDI) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) using tetraphenylphosphonium chloride (TPPCl) as catalyst(C) P-tert-butylphenyl glycidyl ether (BPGE) as compound (D) and as compound (F), and o-DCB as solvent (E)
A glass flask (500 ml) was charged with tetraphenyl phosphonium chloride (TPPCl, 0.2209 g) and o-dichlorobenzene (92 ml) under a continuous nitrogen flow. Subsequently, the mixture was heated to 175 ℃ and stirred for 15 minutes. A glass bottle (250 ml) was charged with diphenylmethane diisocyanate (MDI) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g) and o-dichlorobenzene (77 ml). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 ℃ for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 ml) was added to the reaction solution. After addition, the reaction was stirred at 175 ℃ for an additional 180 minutes. The reaction was confirmed to be complete by the absence of isocyanate band (2260 cm-1) in the infrared spectrum of the reaction mixture. Subsequently, NMP (107 ml) was added to homogenize the reaction mixture and the viscous solution was allowed to cool to ambient temperature. Precipitation of the polymer was performed in ethanol at ambient temperature: thus, the product mixture (about 50 ml) was slowly added to 200 ml of ethanol and triturated with an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160℃for 6 hours.
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Claims (14)

1. A process for producing a thermoplastic polyoxazolidone (1) comprising copolymerizing a diisocyanate compound (a) with a diepoxide compound (B) in the presence of a catalyst (C) in a solvent (E), wherein the solvent (E) comprises at least one of a substituted or unsubstituted alkylnitrile, a substituted or unsubstituted alkenylnitrile, a substituted or unsubstituted cycloalkylnitrile, a substituted or unsubstituted arylnitrile, a substituted or unsubstituted alkylcycloalkylnitrile, a substituted or unsubstituted alkylaryl nitrile, a substituted or unsubstituted heterocycloalkyl nitrile, a substituted or unsubstituted heteroalkylnitrile, and a substituted or unsubstituted heteroaryl nitrile, preferably a substituted or unsubstituted arylnitrile.
2. The process of claim 1, wherein catalyst (C) comprises at least one of a tetraalkylphosphonium halide, a tetracycloalkyl phosphonium halide, a tetraaryl phosphonium halide, a tetraalkyl ammonium halide, a tetracycloalkyl ammonium halide, and/or a tetraaryl ammonium halide, preferably a tetraalkyl phosphonium halide, a tetracycloalkyl phosphonium halide, and a tetraaryl phosphonium halide.
3. The process according to claim 1 or 2, wherein catalyst (C) is at least one compound selected from the group consisting of tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium iodide, bis (triphenylphosphine) imine chloride, tetraphenyl phosphonium nitrate and tetraphenyl phosphonium carbonate, preferably tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide and tetraphenyl phosphonium iodide.
4. A process according to any one of claims 1 to 3, wherein compound (D) is added prior to the copolymerization, wherein compound (D) comprises at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol and a monofunctional amine, preferably a monofunctional epoxide.
5. The method according to any one of claims 1 to 4, wherein the solvent (E) is a single solvent.
6. The process according to any one of claims 1 to 4, wherein the solvent (E) is one or more compounds, preferably one compound, and is selected from the group consisting of benzonitrile, p-chlorobenzonitrile, p-bromobenzonitrile, p-tolunitrile, p-methoxybenzonitrile, p-tert-butylbenzonitrile, o-chlorobenzonitrile, o-bromobenzonitrile, o-tolunitrile, o-methoxybenzonitrile, m-chlorobenzonitrile, m-tolunitrile, m-methoxybenzonitrile, 2, 3-dichlorobenzonitrile, 2, 4-dichlorobenzonitrile, 2, 5-dichlorobenzonitrile, 2, 6-dichlorobenzonitrile, 3, 4-dichlorobenzonitrile, butyronitrile, isobutyronitrile, valeronitrile, cyclohexanecarbonitrile, decanonitrile and pivalonitrile, preferably benzonitrile.
7. The process according to any one of claims 1 to 6, wherein the solvent (E) comprises benzonitrile.
8. The method of any one of claims 1 to 7, wherein the copolymerizing comprises:
(i) Placing the solvent (E) and the catalyst (C) in a reactor to provide a mixture (i),
(ii) Placing the diisocyanate compound (A), the diepoxide compound (B) and optionally the compound (D) in a second container to provide a mixture (ii), and
(iii) Adding the mixture (ii) to the mixture (i).
9. The process according to claim 8, wherein the compound (D) is added in step (ii).
10. The process according to claim 8 or 9, wherein step (iii) is carried out at a reaction temperature of from ≡130 ℃ to ≡280 ℃, preferably at a temperature of from ≡140 ℃ to ≡240 ℃, more preferably at a temperature of from ≡155 ℃ to ≡210 ℃.
11. The method according to any one of claims 1 to 10, wherein the calculated mass ratio of the sum of the diisocyanate compound (a), the diepoxide compound (B) and the compound (D) to the sum of the diisocyanate compound (a), the diepoxide compound (B), the compound (D) and the solvent (E) is 10 to 90 wt%, preferably 20 to 85 wt%, and more preferably 27 to 80 wt%.
12. Thermoplastic polyoxazolidone (1) obtainable by the process according to any of claims 1 to 11, wherein the thermoplastic polyoxazolidone has a concentration of from more than or equal to 500 to less than or equal to 500,000g/mol as determined by Gel Permeation Chromatography (GPC), More preferably from 1.gtoreq.000 to 50,000g/mol, and even more preferably from 5,000 to 25,0000g/mol, wherein GPC is performed on an Agilent 1100Series instrument with N, N-Dimethylacetamide (DMAC) +LiBr (1.7 g.L) -1 ) PSS GRAM analytical column from PSS as eluent ) Equipped with Refractive Index (RI) detector, wherein the column flow in all measurements was set to 1mL min -1 Wherein for determination of molecular weight, calibration was performed with poly (styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS), and wherein samples were analyzed using PSS WinGPC UniChrom V8.2.2 software.
13. A process for producing a thermoplastic polyoxazolidone (2), wherein a thermoplastic polyoxazolidone (1) obtainable by the process according to any of claims 1 to 11 is further reacted with a compound (F) to form the thermoplastic polyoxazolidone (2), wherein the compound (F) comprises at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol and a monofunctional amine, preferably a monofunctional epoxide.
14. Thermoplastic polyoxazolidone (2) obtainable by the process according to claim 13, wherein the thermoplastic polyoxazolidone has a number average molecular weight Mn of from 500 to 500,000g/mol, more preferably from 1,000 to 50,000g/mol, and even more preferably from 5,000 to 25,0000g/mol, as determined by Gel Permeation Chromatography (GPC), wherein GPC is performed on an Agilent 1100Series instrument with N, N-Dimethylacetamide (DMAC) +libr (1.7 g·l) -1 ) PSS GRAM analytical column from PSS as eluent ) Equipped with Refractive Index (RI) detector, wherein the column flow in all measurements was set to 1mL min -1 Wherein for determination of molecular weight, calibration was performed with poly (styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS), and wherein samples were analyzed using PSS WinGPC UniChrom V8.2.2 software.
CN202180080989.XA 2020-12-03 2021-11-26 Process for producing thermoplastic polyoxazolidone polymers Pending CN116529281A (en)

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EP21175834 2021-05-25
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PCT/EP2021/083118 WO2022117443A1 (en) 2020-12-03 2021-11-26 Method for the production of thermoplastic polyoxazolidinone polymers

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