• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    ISOCIANATE-FREE METHOD FOR THE PREPARATION OF POLY (CARBONATE-URETANE) OR POLY (ESTER-URETANE). The present invention discloses a method for the preparation of poly (carbonate-urethane) or poly (ester-urethane) without isocyanate.
    公开号:BR112013000857B1
    申请号:R112013000857-1
    申请日:2011-06-21
    公开日:2021-01-12
    发明作者:Sophie Guillaume；Marion Helou；Jean-François Carpentier；Martine Slawinski
    申请人:Total Research & Technology Feluy；Centre National De La Recherche Scientifique (Crs)；
    IPC主号:
    专利说明:

    [0001] The present invention discloses a method for the preparation of poly (carbonatourethane) or poly (ester-urethane) without isocyanate. DESCRIPTION OF RELATED TECHNIQUE
    [0002] Polyurethanes (PUs) are widely used as paints, coatings, foams, adhesives, packaging in numerous fields, such as the automotive and consumer industries or household goods and in construction engineering or medicine as revealed, for example, in Krol (P. Krol , Prog. Mater. Sci., 2007, 52, 915-1015), or in Szycher (M. Szycher, Szycher Handbook of polyurethanes; CRC press: Boca Raton, FL, 1999) or in Matsumura et al. (S. Matsumura, Y. Soeda, K. Toshima Appl. Microbiol. Biotechnol. 2006, 70, 12-20) or in Jayakumar et al. (R. Jayakumar, S. Nanjundan, M. Prabaharan, React. Fund. Polym. 2006, 66, 299-314). In fact, the chemical, thermal or mechanical performances and properties of PUs cover a wide range that is adapted by the nature of the reagents used and the methods of preparation, including both synthetic and processing methods. PUs are potential and reliable substitutes for derivatives of petrochemical polymers. Taking into account their large production volumes, as they are among the five main polymeric materials, the valorization of renewable resources in their synthesis is currently of great concern.
    [0003] PUs are generally prepared by polyaddition of multifunctional diisocyanates and polyols or terminal hydroxyl groups. PUs are thus multi-block copolymers of type (A-B) n, including alternating hard and soft sequences. The flexible and soft segments most commonly arise from polyether, polyester or polycarbonate diols. The rigid and hard segments most often consist of short-chain diisocyanates that confer physical cross-linking through hydrogen bonds thus bringing the melting temperature Tm higher than polyesters or aliphatic polycarbonates. Macrodiols are biocompatible and biodegradable and are currently easily derived from biomass. Isocyanates, obtained from phosgene, on the contrary, raise serious toxic issues. Many efforts have therefore been devoted, therefore, to minimizing the amount of diisocyanates involved in the preparation of PU or even better to develop phosgene and isocyanate-free approaches to PUs in order to improve their biodegradation and chemical recycling. These various approaches and concerns were revealed, for example, in Rokicki and Piotrowska (G. Rokicki, A. Piotrowska Polymer 2002, 43, 2927-2935) or in Petrovic (ZS Petrovic, Polymer Reviews, 2008,48, 109-155) or in Rokicki and Wojciechowski (G. Rokicki, C. Wojciechowski J. Appl. Polym. Sci. 1990, 41, 647- 659) or in Hojabri and Kong (L. Hojabri, X. Kong, SS Narine Macromolecules, 2009, 10 , 884-891) or in Gomez and Varela (RV Gomez, O. Varela, Macromolecules, 2009, 42, 8112-8117) or in Williams et al. (C.K. Williams et al. Polym. Rev. 2008, 48, 1-10) or in Tomita et al. (H. Tomita, F. Sanda, T. Endo, J. Polym. Sci A Polym. Chem. 2001, 39, 3678-3685; H. Tomita, F. Sanda, T. Endo J. Polym. Sci A Polym. Chem. 2001, 39, 860-867; H. Tomita, F. Sanda, T. Endo J. Polym. Sci. A Polym. Chem. 2001, 39, 851-859; H. Tomita, F. Sanda, T. Endo, Macromolecules. 2001, 34, 7601-7607; H. Tomita, F. Sanda, T. Endo, J. Polym. Sci A Polym. Chem. 2001, 39, 4091-4100; H. Tomita, F. Sanda, T. Endo, J. Polym. Sci A Polym. Chem. 2001, 39, 162-168), or in Ochiai et al. (B. Ochiai, Y. Satoh, T. Endo, J. Polym. Sci A Polym. Chem. 2007, 45, 3408-3414; B. Ochiai, J. Nakayama, M. Mashiko, T. Nagasawa, Y. Kanedo , T. Endo, J. Polym. Sci. A Polym. Chem. 2005, 43, 5899-5905; B. Ochiai, Y. Satoh, T. Endo, Green Chem. 2005, 7, 765-767; B. Ochiai , S. Inoue, T. Endo, J. Polym. Sci A Polym. Chem. 2005, 43, 6282-6286) or in Kihara et al. (N. Kihara, Endo J. Polym. Sci. A Polym. Chem. 1993, 31, 2765-2773; N. Kihara, Endo J. Polym. Sci. A Polym. Chem. 1993, 31, 2765-2773; N Kihara, Y. Kushida, Endo J. Polym. Sci. A Polym. Chem. 1996, 34, 2173-2179) or in Steblyanko et al. (A. Steblyanko, W. Choi, F. Sanda, T. Endo, J. Polym. Sci A Polym. Chem. 2000, 38, 2375-2380).
    [0004] Some attempts have been made, however, to use another route. The five, six or seven-membered (di) carbonates are known to undergo a polyaddition reaction with nucleophiles such as diamines (aminolysis) leading to the formation of various polyhydroxyurethanes (PHUs) without releasing any volatile by-products as revealed, for example, in Nederberg et al. (F. Nederberg, E. Appel, JPK Tan, SH Kim, K. Fukushima, J. Sly, R. Miller, RM Waymouth, YY Yang, JL Hedrick, Biomacromolecules, 2009, 10, 1460-1468) or in Goodwin et al. (AP Goodwin, SS Lam, JMJ Frechet, J. Am. Chem. Soc. 2007, 129, 6994-6995) or in Ekin and Webster (A. Ekin, DC Webster, Macromolecules, 2006, 39, 8659-8668; L Ubaghs, N. Fricke, H. Keul, H. Hocker Macromol. Rapid Commun. 2004, 25, 517-521) or in Clements (JH Clements, Ind. Eng. Chem. Res. 2003, 42, 663-674) . These PHUs are characterized by pendant hydroxy groups that favor high water absorption and provide crosslinking sites as well as graft opportunities for additional useful functionalized segments. Five-membered carbonates, due to their stable ring structure, polymerize open less easily than five, six or seven membered congeners as described in Rokicki (G. Rokicki, Prog. Polym. Sci. 2000, 25, 259-342) . They exhibit similarly slower reactivity to amines than six- and seven-membered cyclic carbonates. The PHUs obtained by this method have low numerical average molecular weight Mn of less than 30 kDa, therefore much lower than that of commercial PUs.
    [0005] Poly (carbonate-urethane) s (PCUs) without pending hydroxy groups have recently received some attention, although much less than poly (ester-urethane) and poly (etherurethane). Such PCUs are generally derived from soft carbonate segments of very low molar mass reacted with diisocyanates.
    [0006] Soeda et al. (Y. Soeda, K. Toshima, S. Matsumara Macromol. Biosci., 2004, 4, 721-728) reported the synthesis of PCU without the NCO reagent. This first involved the formation of a diurethanediol having a molar mass of 320 g / mol by opening TMC ring with hexamethylenediamine, followed by its polycondensation reaction with diethyl carbonate using a lipase together with anisole and molecular sieves. In this procedure, both the soft segments and the hard units remained very short, and shorter than the length obtained when using the diisocyanate route which is typically 1,000 g / mol to less than 12,000 g / mol. In addition, the reaction conditions required heating for three days at a temperature of 110 ° C. The process provides a mixture of PTMCUs having a numerical average molecular weight Mn of less than 20,000 g / mol and having three types of chain ends as identified by MALDI-ToF-MS. The yield was 90% after purification.
    [0007] The modulation of the length of the soft block remains, however in need of optimization.
    [0008] It is, therefore, highly desirable to develop efficient and alternative synthetic routes for PCUs, which would combine an ecological approach, especially free of isocyanates, with the possibility of reaching high molar mass PCUs with macrocarbonate segments of adjustable length and with a well-defined structure. SUMMARY OF THE INVENTION
    [0009] It is an object of the present invention to provide a synthetic route for polyurethane that does not use isocyanates.
    [0010] It is also an objective of the present invention to elaborate a method allowing to control the length of the soft blocks.
    [0011] It is another objective of the present invention to value renewable resources.
    [0012] It is yet another object of the present invention to provide a method for the preparation of PCUs or polyester urethanes (PEUs) that are environmentally friendly.
    [0013] In accordance with the present invention, the foregoing objectives are realized as described in the independent claims. Preferred embodiments are described in the dependent claims. BRIEF DESCRIPTION OF THE DRAWINGS
    [0014] Figure 1 represents typical 1H NMR spectra for PTMC- (OH) 2, PTMC- (COOH) 2, and PTMC- (CH2DMC) 2 (300 MHz, CDCI3, 20 ° C) Figure 2 represents a typical Fourier transform infrared spectrum (ATR-FTIR, Shimadzu apparatus) of a PTMCHU expressed as% Transmittance versus cm-1. Figure 3 represents a typical 1H NMR spectrum of a PTMCHU. Figure 4 represents a typical differential scanning calorimetry analysis of a PTMCHU (Setaram apparatus, heating rate 10 ° C / min). It represents the heat flow expressed in mW as a function of the temperature expressed in ° C. DETAILED DESCRIPTION
    [0015] a) polimerização imortal de abertura de anel de um primeiro carbonato cíclico de 5, 6 ou 7 membros ou éster cíclico, suportando ou não os grupos funcionais, na presença de um primeiro sistema catalítico e um ou mais dióis ou polióis agindo como co-iniciadores e agentes de transferência de cadeia; b) modificação química dos grupos hidroxila de extremidade da cadeia em grupos carboxílicos na presença de um segundo sistema catalítico; c) reação de acoplamento com pelo menos 2 equivalentes de um segundo carbonato cíclico de 5, 6 ou 7 membros, suportando pelo menos um grupo funcional permitindo o acoplamento com a porção carboxílica, na presença de um terceiro sistema catalítico; d) poliadição de uma diamina ou uma poliamina via o anel aberto do segundo carbonato cíclico de 5, 6 ou 7 membros terminal da etapa c); e) obtenção de poli(carbonato-uretano) ou poli(éster-uretano) Consequently, the present invention discloses the process for the preparation of poly (carbonate-urethane) (PCU) or poly (ester-urethane) (PEU) which comprises the steps of: a) immortal ring-opening polymerization of a first 5, 6 or 7-membered cyclic carbonate or cyclic ester, supporting or not the functional groups, in the presence of a first catalytic system and one or more diols or polyols acting as co-initiators and chain transfer agents; b) chemical modification of hydroxyl groups at the end of the chain into carboxylic groups in the presence of a second catalytic system; c) coupling reaction with at least 2 equivalents of a second 5, 6 or 7-membered cyclic carbonate, supporting at least one functional group allowing coupling with the carboxyl portion, in the presence of a third catalytic system; d) polyaddition of a diamine or a polyamine via the open ring of the second 5, 6 or 7 membered cyclic carbonate terminal of step c); e) obtaining poly (carbonate-urethane) or poly (ester-urethane)
    [0016] This method is exemplified schematically in scheme 1 for cyclic carbonates using trimethylene carbonate (TMC) to construct the soft polycarbonate blocks and glycerol carbonate (DMC-CH2OH) as the binding reagent.
    [0017] The immortal ring-opening polymerization of cyclic carbonate or cyclic ester from step a) has been described extensively by the same inventors in co-pending orders EP-A-2096132, EP-A-2151465, EP-09290655.1 and PCT / EP2010 / 055797 and in various publications (M. Helou, O. Miserque, J.-M. Brusson, J.-F. Carpentier, SM Guillaume, Chem. Eur. J. 2008, 14, 8772-8775; M. Helou, O. Miserque, J.-M. Brusson, J.-F. Carpentier, SM Guillaume, Adv. Synth. Cat. 2009, 351, 1312-1324; M. Helou, O. Miserque, J.-M. Brusson, J. - F. Carpentier, SM Guillaume, Macromol.Rapid Commun. 2009, 30, 2128-2135; M. Helou, O. Miserque, J.-M. Brusson, J.-F. Carpentier, SM Guillaume, Chem. Cat. Chem. 2010, 2, 306-313; J.-F. Carpentier, C. Guillaume, S. Guillaume, M. Helou, V. Poirier, Y. Sarazin, J. Chem. Soc. Dalton Trans. 2010, in press ; M. Helou, O. Miserque, J.-M. Brusson, J.-F. Carpentier, SM Guillaume, Chem. Cat. Chem. 2010, 2, 306-313; V. Poirier, J.-F. Carpentier , Y. Sarazin, Dalton Trans. 2009 , 9820-9827; C. Guillaume, J.-F. Carpentier, S. M. Guillaume, Polymer 2009, 50, 5909-5917).
    [0018] 'Immortal' ring-opening polymerization (iROP) is particularly attractive when compared to “classic” ROP in which the protic source that is used in large excess as a chain transfer agent allows the growth of a large number of chain polymer by catalytic center. Since the transfer reactions are fast and reversible, the amount of catalytic species needed in iROP is truly catalytic versus both the monomer and the polymer. It can be as low as 10 ppm of metallic or organic catalyst. Any question of toxicity in relation to the quantity of the catalytic system, used in truly low quantities, is, therefore, hardly relevant, since the polymers are practically free of catalyst residues. Such processes allowed the polymerization by opening an immortal trimethylcarbonate (TMC), β-butyrolactone or lactide ring, where they remained fully controlled. They provided well-defined polymers in terms of macromolecular characteristics (molar mass, molar mass distribution, terminal group fidelity). In addition, the polymers had high molar masses. These ring opening polymerizations were carried out in the presence of metal salts, organometallic or organic catalytic systems with very high activities and productivity.
    [0019] found, for example, in EP-A-2,096,132. They can be selected from metal complexes of formula MRn in which M is a Group 1, 2, 3 metal (including from the lanthanide series, in this document referred to as Ln), 8, 12 or 13 of the periodic table, in which each R is independently selected from hydrogen, hydrocarbyl radical having 1 to 12 carbon atoms, alkoxide group OR * where R * is linear or branched hydrocarbyl having 1 to 12 carbon atoms, amide group NR ** 2 in that R ** is of the general formula YR # 3 where Y is Si or C and each R # is independently selected from hydrogen or hydrocarbon radical having from 1 to 12 carbon atoms, borohydride or halide group, and where n is the valence of M.
    [0020] Preferably, M is Mg (ll), Ca (ll), Y (lll), Fe (ll), Fe (lll), Zn (ll), Al (lll), or Bi (lll) Preferably each R is independently selected from an amide group such as N (SiMe3) 2, N (SiHMe2) 2, an OR 'alkoxide group such as OiPr, OMe, OCH2Ph, or a borohydride group (BH4).
    [0021] More preferably, it is a β-diiminate (BDI) ZnN (SiMe3) 2 amide-zinc, or a (LO) ZnR compound where LO is a multidentate phenolate linker as disclosed, for example, in WO / EP2010 / 055797, and R is Et or N (SiMe3) 2, or a Lewis acid metal salt such as a triflate compound M (OSO2CF3) n with M = Al or Bi as disclosed in EP-A-2,151,465.
    [0022] It can also be selected from an organocatalyst as disclosed in co-pending application EP-09290655.1. Preferred organocatalyst precursors are preferably selected from 4-dimethylaminopyridine (DMAP) or 1,5,7-triazobicyclo- [4,4,0] dec-5-ene (TBD) or tert-butylimino-1,3 - dimethylperhydro-1,3,2-diazaphosphine (BEMP). Most preferably, it is BEMP.
    [0023] Diol or polyol is used in excess and acts as a initiator and transfer agent. It can be selected from any polyol of the general formula R (OH) n where n is equal to 2 or more and R is a linear, branched, aliphatic or aromatic hydrocarbon having up to 20 carbon atoms, or any combination thereof. More preferably, it is 1,3- and / or 1,2-propanediol and / or glycerol and / or pentaerythritol. These polyols can be derived from bio-resources.
    [0024] The carbonate or ester monomer to diol / polyol ratio can be varied in the range of 10,000: 1 to 10: 1; preferably, it is in the range of 1,000: 1 to 100: 1. The monomer to catalyst ratio can be varied in the range of 1,000,000: 1 to 100: 1; preferably, it is 500,000: 1 to 10,000: 1.
    [0025] The chemical modification of the hydroxy terminal groups of the chain into carboxylic terminal groups of step b) is performed in the presence of a second catalytic system. It is described, for example, in Yu and Zhuo (F. Yu, R. Zhuo, Polymer J. 2003, 8, 671-676) or in Lee et al. (S.-H. Lee, S. H. Kim, Y.-K. Han, Y. H. Kim J. Polym. Sci. A Polym. Chem, 2001, 39, 973-985) or in Jeon et al. (O. Jeon, S.-H. Lee, S. H. Kim, Y. M. Lee, Y. H. Kim Macromolecules, 2003, 36, 5585-5592). It can be carried out by reacting the polycarbonate or polyester obtained in step a) with any suitable anhydride, optionally in an inert solvent selected, for example, from 2-methyl tetrahydrofuran, furan, 1,4-dioxane, or any aromatic or aliphatic hydrocarbon . The second catalytic system can be selected from any suitable catalyst traditionally used for opening an anhydride with an alcohol. For example, it can be pyridine or a mixture of triethylamine and 4-dimethylaminopyridine (DMAP), loaded in amounts of 0.1 to 5% with respect to the polymer formed in step a). The reaction is carried out at a temperature of 0 to 80 ° C, preferably from 15 to 50 ° C and more preferably at room temperature for a period of time from 1 hour to 2 days, preferably from 2 to 24 hours.
    [0026] The coupling reaction of step c) is carried out in the presence of a third catalytic system. It is carried out by reacting at least 2 equivalents of a second 5, 6, or 7-membered cyclic carbonate, supporting at least one functional group allowing coupling with the carboxyl moiety, optionally in the presence of a coupling agent such as dicyclohexylcarbodiimide (DCC) and a suitable catalyst such as, for example, pyridine or DMAP or N-hydroxybenzotriazole (HOBt) loaded in quantities of 0.1 to 5% with respect to the functional cyclic carbonate, optionally in an inert solvent selected, for example, from 2 -methyl tetrahydrofuran, furan, dichloromethane or any aromatic or aliphatic hydrocarbon. The reaction can be carried out at room temperature for a period of 24 hours.
    [0027] The polyaddition reaction d) is carried out by adding to the compound obtained in step c) a diamine or a polyamine of the general formula R (NH2) n where n is equal to 2 or more and R is a linear, branched, aliphatic or aromatic hydrocarbon having from 1 to 12 carbon atoms, or any combination thereof. Preferably, it can be 1,6-hexamethylenediamine. Optionally, the amine may contain a functional group that will provide functions pending in the main chain. This functional group can be used for several purposes. Non-limiting examples include: a) vinyl functions that can promote additional copolymerization with other monomers; b) nitroxide functions that can promote controlled radical polymerization, c) fluorinated tail. The NH2 / cyclic carbonate ratio can be varied from 0.5 to 5; more preferably it is 0.8 to 1.5. This ratio affects the average molecular weight of the PCUs or PEUs eventually recovered. For the preparation of high molecular weight PCUs or PEUs, the NH2 / cyclic carbonate ratio is preferably close to 1. The polyaddition reaction d) can optionally be carried out in an inert solvent selected, for example, from 2-methyl tetrahydrofuran, furan, 1,4-dioxane, or any aromatic or aliphatic hydrocarbon. The reaction is carried out at a temperature ranging from 20 ° C to 250 ° C. Higher temperatures favor the formation of higher molecular weight products.
    [0028] The present invention also covers poly (carbonate-urethane) or poly (esterurethane) obtained by the method described above in this document. They are characterized by the flexible polycarbonate segments being long and that the length of the segments can be monitored by the ring opening polymerization conditions. The long soft polycarbonate segments typically have Mn molecular weights ranging from 10,000 to 250,000 g / mol, preferably between 50,000 and 100,000 g / mol. EXAMPLES.
    [0029] Global TMC iROP (1.10 g, 10.8 mmol) was performed at a temperature of 60 ° C using a catalytic system based on zinc amide β-diiminate, ((BDIlPr) Zn (N (SiMe3) 2 ( 7 mg, 0.0108 mmol) and 1,3-propanediol (15.8 μL, 0.218 mmol) as a co-initiator and as a chain transfer agent. 1.05 g of α, ω-dihydroxy telekelic PTMCs, PTMC- (OH) 2 as seen in Scheme 1 with a yield of 100% It had a numerical average molecular weight Mn of 5,060 g.mol-1 and a polydispersity index PI defined as the Mw / Mn ratio of the average molecular weight by weight Mw over the numerical average molecular weight Mn of 1.21.
    [0030] The chemical modification of the hydroxyl groups at the end of the chain into carboxylic groups was then carried out as previously reported for polycarbonates as well as polyesters by Yu and Zhuo (F. Yu, R. Zhuo, Polymer J. 2003, 8, 671-676) or by Lee et al. (S.-H. Lee, S. H. Kim, Y.-K. Han, Y. H. Kim J. Polym. Sci, A Polym. Chem, 2001, 39, 973- 985) or by Jeon et al. (O. Jeon, S.-H. Lee, S. H. Kim, Y. M. Lee, Y. H. Kim Macromolecules, 2003, 36, 5585-5592). The reaction of PTMC- (OH) 2 above (1.05 g, 0.207 mmol) with succinic anhydride (41.5 mg, 0.415 mmol) was performed on 1,4-dioxane (5 mL) using triethylamine (58 μL, 0.415 mmol) and 4-dimethylaminopyridine (DMAP) (51 mg, 0.415 mmol) as a catalyst for 24h at room temperature. 1.05 g of PTMC- (COOH) 2 was provided in 100% yield and the molecular characteristics of the polymer were Mn = 6 120 g.mol-1 and Mw / Mn = 1.43.
    [0031] Figure 1 shows the 1H NMR spectra of the dihydroxy precursor PTMC- (OH) 2 and the parent α, ω-telekelic dicarboxylate PTMC- (COOH) 2. The signal corresponding to the terminal methylene proton in PTMC-OH2 at δ = 3.75 ppm completely disappeared while that of the new methylene group in the α position of the carboxyl function resulting from the open ring of the anhydride then appeared at δ = 2.64 ppm together with the OH group corresponding to δ = 5.62 ppm. Such data show the quantitative functionalization of PTMC by the carboxylic units.
    [0032] Coupling of PTMC- (COOH) 2 (1.00 g, 0.163 mmol) with the five-membered glycerol carbonate (4-hydroxylmethyl-1,3-dioxolan-2-one; DMC-CH2OH) (39 mg, 0.327 mmol) was then carried out at room temperature in the presence of N, N'-dicyclohexylcarbodiimide (DCC) (77 mg, 0.327 mmol) and DMAP (10 mg, 0.327 mmol) as a catalyst in CH2Cl2 (5 mL) for a period of time 24h as revealed for example, in Nederberg et al. (F. Nederberg, V. Trang, R. C. Pratt, A. F. Mason, C. W. Frank, R. M. Waymouth, J. L. Hedrick Biomacromolecules, 2007, 8, 3294-3297) or in Mespouille et al. (L. Mespouille, O. Coulembier, D. Paneva, P. Degee, I. Rashkov, P. Dubois, J. Polym. Sci. A Polym. Chem. 2008, 46, 4997-5013) or in Takizawa et al. (K. Takizawa, C. Tang, C. J. Hawker, J. Am. Chem. Soc. 2008, 130, 1718-1726) or in Li et al. (H. Li, R. Jerome, P. Lecomte Macromolecules, 2008, 41, 650-654). 1.0 g PTMC- (CH2DMC) 2 was provided in 100% yield. This esterification of hydroxy terminal groups was quantitative, as demonstrated by the 1H NMR analysis shown in Figure 1. The characteristic signals of the hydroxy group of C (O) OH terminal units at δ = 5.62 ppm disappeared completely in favor of the signals corresponding to the new cyclic carbonate (CH2C (O) OCH2CHCH2), at δ = 4.36, 4.58, 4.92 ppm, respectively. The resonance of the methylene group (CH2C (O) OCH2DMC at δ = 2.69 ppm was maintained. The molar mass of the PTMCs as determined from these spectra were respectively from MnNMR = 2410 g / mol to PTMC- (OH) 2, 3810 g / mol for PTMC- (COOH) 2, and 5100 g / mol for PTMC- (CH2DMC) 2). These values were in good agreement with those determined by size exclusion chromatography in THF, which were respectively MnSEC = 2500 g / mol for PTMC- (OH) 2, 4000 g / mol for PTMC- (COOH) 2, and 5050 g / mol for PTMC- (CH2DMC) 2). The polydispersity index values for PTMCs were 1.32 for PTMC- (OH) 2, 1.24 for PTMC- (COOH) 2, and 1.31 for PTMC- (CH2DMC) 2, respectively. These polydispersions remained restricted throughout the various manipulations, thus demonstrating the efficiency of the procedures to react selectively with the terminal functions without deteriorating the carbonate main chain.
    [0033] The polyaddition reaction of PTMC- (CH2DMC) 2 (1.00 g, 0.172 mmol) with 1,6-hexamethylenediamine (10 mg, 0.862 mmol) was carried out in CH2Cl2 (4 mL) at a temperature of 70 ° C over over a period of 5 days (scheme 1). 0.9 g of product was supplied in 82% yield. The determination of the PTMCU molar mass by SEC in DMF showed a unimodal and symmetrical peak (MnSEC = 68100 g / mol, Mw / Mn = 1.2), clearly shifted to a higher molar mass than the PTMC- (CH2DMC) reagent 2 . As evidenced by 1H NMR spectroscopy, the resulting polyaddition in PTMCHUs exhibiting either primary or secondary hydroxy groups, also corresponding to the DMC acyl oxygen opening site. The chemical structure of the PTMCHUs was also examined by FTIR as represented in Figure 2. The spectrum exhibited the characteristic vibrations of the urethane and carbonate groups. The most significant bands corresponded to the stretching vibrations of the carbonyl group in the carbonate and urethane at νC = O = 1750 cm-1, and of the amide in the urethane at νC-N = 1550 cm-1, νN-H = 400 cm-1. Also illustrative of the carbonate segments were the peaks at ν = 2933 and 2861 cm-1 attributed to the C-H elongation along with the 789 cm-1 bands corresponding to the O = C-O ester fold. In addition, a broad peak at ν = 3466 cm-1 in overlap with the N-H elongation corresponded to the O-H elongation. All of these observations supported the formation of PTMCHUs from PTMC- (CH2DMC) 2. Figure 3 represents a typical 1H NMR spectrum of a PTMCHU and Figure 4 represents a typical differential scanning calorimetry analysis of a PTMCHU (Setaram apparatus, heating rate 10 ° C / min).
    权利要求:
    Claims (15)
    [0001]
    Process for the preparation of poly (carbonate-urethane) or poly (ester-urethane) characterized by comprising the steps of: a) immortal ring-opening polymerization of a first 5, 6 or 7-membered cyclic carbonate or a cyclic ester or diester, whether or not they support the functional groups, in the presence of a first catalytic system and in the presence of one or more diols or polyols both acting as co-initiators and chain transfer agents; b) chemical modification of hydroxyl groups at the end of the chain into carboxylic groups in the presence of a second catalytic system; c) coupling reaction with at least 2 equivalents of a second 5, 6 or 7-membered cyclic carbonate, supporting at least one functional group allowing coupling with the carboxyl portion, in the presence of a third catalytic system; d) polyaddition of a diamine or a polyamine via the open ring of the second 5, 6 or 7 membered cyclic carbonate terminal of step c); e) obtaining poly (carbonate-urethane) or poly (ester-urethane)
    [0002]
    Process according to claim 1, characterized in that the immortal ring-opening polymerization of step a) is carried out in the presence of a first catalytic system selected from an organometallic compound, or (LO) ZnR where LO is a phenolate ligand multidentate and R is Et or N (SiMe3) 2, or a Lewis acid metal salt, or an organocatalyst in which organocatalyst precursors are selected from 4-dimethylaminopyridine (DMAP) or 1,5,7 -triazobicyclo- [4,4,0] dec-5-ene (TBD) or tert-butylimino-1,3-dimethylperhydro-1,3,2-diazaphosphine (BEMP).
    [0003]
    Process according to claim 2, characterized in that the first catalytic system is selected from amine zinc β-diiminate (BDI) ZnN (SiMe3) 2, or from a triflate compound M (OSO2CF3) n with M = Al or Bi .
    [0004]
    Process according to any one of claims 1 to 3, characterized in that the diol or polyol is of the general formula R (OH) n where n is equal to 2 or more and R is a linear, branched, aliphatic or aromatic hydrocarbon having up to 20 carbon atoms, or any combination thereof.
    [0005]
    Process according to any one of claims 1 to 4, characterized in that the monomer / catalyst ratio varies between 1,000,000: 1 and 100: 1.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the monomer / diol or polyol ratio varies between 10,000: 1 and 10: 1.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that the chemical modification of step b) is carried out by reacting the polycarbonate or polyester obtained in step a) with an anhydride, optionally in the presence of an inert solvent.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the second catalyst system is a suitable catalyst for opening an anhydride with an alcohol, selected from pyridine or a mixture of triethylamine and 4-dimethylaminopyridine (DMAP).
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the coupling reaction of step c) is carried out in the presence of a third catalyst selected from pyridine or DMAP, optionally in the presence of a coupling agent such as dicyclohexylcarbodiimide ( DCC).
    [0010]
    Process according to claim 9, characterized in that the third catalyst is loaded in an amount of 0.1 to 5% in relation to the functional cyclic carbonate.
    [0011]
    Process according to any one of claims 1 to 10, characterized in that the polyaddition of step d) is carried out with a diamine or a polyamine of the general formula R (NH2) n where n is equal to 2 or more and R is a linear hydrocarbil , branched, aliphatic or aromatic having up to 12 carbon atoms, or a combination thereof.
    [0012]
    Process according to claim 11, characterized in that the NH2 / cyclic carbonate ratio varies between 0.5 and 5.
    [0013]
    Process according to any one of claims 1 to 12, characterized in that the polymer chain length is determined by the NH2 / cyclic carbonate ratio.
    [0014]
    Process according to any of claims 1 to 13, characterized in that the length of the polymer chain increases with increasing temperature of the polyaddition reaction.
    [0015]
    Poly (carbonate-urethane) or poly (ester-urethane) obtained by the process according to any one of the preceding claims, characterized in that the flexible polycarbonate segments have molecular weights Mn varying between 10,000 and 250 g / mol and that the length of the segments can be monitored by ring opening polymerization conditions.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-07-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10290398|2010-07-15|
    EP10290398.6|2010-07-15|
    PCT/EP2011/060300|WO2012007254A1|2010-07-15|2011-06-21|Isocyanate-free method for preparing poly or poly|
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