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    • 专利摘要:
    phosphonamidate compound, methods of improving the flame resistance of a polymeric material, a substance and a polyurethane foam, polymeric material with improved flame resistance, and method of making a phosphonamidate. The invention relates to a group of novel compounds containing one or more substituted dope (9,10-dihydro-9-oxa-phosphapentren-10-oxide) fragments. The compounds have been found to have good flame retardant properties and also good thermal stability, which makes them particularly suitable as flame retardant additives for various thermoplastic polymers. In particular, they may be incorporated into a polyurethane foam.
    公开号:BR112014002985B1
    申请号:R112014002985-7
    申请日:2012-08-06
    公开日:2019-10-08
    发明作者:Sabyasachi Gaan；Matthias Neisius；Primo Mercoli；Shuyu Liang；Henri Mispreuve；Reinold Näscher
    申请人:EMPA Eidgenössische Materialprüfungs-und Forschungsanstalt；Fritz Nauer Ag；
    IPC主号:
    专利说明:

    [0001] The present invention relates to new phosphonamidate compounds and their use as flame retardant substances.
    Background of the Invention [0002] Currently, polymers based on various organic monomers are present almost everywhere around us. They are also used for the purposes of outdoor as well as indoor uses. For this reason, it is very important to make the majority of these flame retardant polymers to minimize the risk of fire. In the past, most flame retardants were halogenated organic compounds that showed very high efficiency in polymer flame retardancy. These halogenated compounds act by a gas phase mechanism, which means that in the event of a fire they decompose and easily release halogen radicals. These halogen radicals act as a remover to trap H * and OH * reactive radicals so that there is no heat flow to sustain the flame. Nowadays some of these halogen-based flame retardants have been banned because they are not very environmentally friendly. Therefore, there is more than ever the need for new flame retardants that are able to replace and act on halogenates. 1 DOPO (9,10-dihydro - 9 - oxa - phosphaphenanthrene -10-oxide) 2 and some of its derivatives have attracted a lot of attention in the last decade due to their flame retardant properties. 3 It is mainly accepted and investigated in detail that these compounds predominantly act by a gas phase mechanism. 4
    Scheme 1: DOPO and its derivatives
    Petition 870190047929, of 05/22/2019, p. 10/51
    2/37
    Derivative DOPO (9, 10-dihydro-9-oxa-phosphaphenanthrene-10-oxide) [0003] During combustion, they decompose and release fragments containing low molecular weight phosphorus that are capable of sequestering radicals and OH * -. 4a ' 5 .
    [0004] In the literature, there are a number of reports dealing with the synthesis and application of flame retardants of DOPO alkyl derivatives. 3.6 [0005] In addition, there are also several reports dealing with the synthesis and application as flame retardant of DOPO alkoxy derivatives. In contrast to the aforementioned derivatives, one can find some publications dealing with amino-DOPO derivatives. 7, 8 According to the best of the Applicants' knowledge, there are only a few reports that describe the synthesis and characterization of amino-DOPO derivatives. 7h ' k Again the synthesis takes place through a two-step reaction sequence as mentioned before. 8
    Scheme 2: Preparation of amino-DOPO derivatives via a two-step reaction sequence 8
    [0006] Additionally, some DOPO amino-thio derivatives can also be found in the literature 9 . Although DOPO phosphinate derivatives are commonly known as flame retardants for various polymeric systems, DOPO amino derivatives are not well studied as flame retardants. Organophosphorous compounds that contain a PN bond, i.e., phosphoramidates, are known to exhibit superior flame retardant properties, for example, in cellulose. 10 Therefore, it would be interesting to develop DOPO amino derivatives and evaluate them, due to their FR efficacy. There are a few
    3/37 patent documents mentioning the application in flame retardant amino derivatives - DOPO in various compositions of polymeric resins 7 . But the derivatives referred to in these patent documents have not been characterized by appropriate analytical methods. Some amino - DOPO derivatives were also mentioned in EP 1889878 A1 as possible flame retardant structures.
    However, in the aforementioned patent document there is no report on such structures having been prepared, or any method of their elaboration prepared. 11 In addition, there are amino derivatives of DOPO that have been reported as components in organic light-emitting diodes (OLEDs), batteries and azo dyes. 8
    Scheme 3: Amino-DOPO derivatives previously described in the literature
    Flame retardant additive 7a
    Derivative for non-aqueous electrolytes 6a
    Derivative for OLEDs®
    Derivative for azo dyes 8c
    SUMMARY OF THE INVENTION [0007] According to one aspect of the invention, a group of new phosphonamidate compounds is provided, which are particularly contemplated for their flame retardant properties in combination with improved thermal stability and concomitant processability at elevated temperatures such as in a thermoplastic process. Phosphonamidate compounds are
    4/37 selected from the group consisting of:
    - AA-DOPO;
    - BHEA-DOPO;
    - PB-DOPO;
    - PDAB-DOPO;
    - a compound according to formula (I)
    R 1 = H, (C1-8) alkyl, (C1-8) alkoxy, (C1-8) amine, OH, SR (R = H, alkyl), Ometal (I)
    R 2 = H, (C1-8) alkyl, (C1-8) alkoxy, (C1-8) amine, OH, SR (R = H, alkyl), Ometal
    R 3 = H, (C1-8) alkyl, (C1-8) alkoxy, (C1-8) amine, OH, SR (R = H, alkyl), Ometal
    Y = NH, fragment N-DOPO, O, S
    X = NHY, NR (R = alkyl) n = 1-8 m = 1-8
    particularly:
    - TESPA-DOPO, or
    - TMSPA-DOPO;
    - a compound according to Formula (II)
    5/37
    X = O, NR (R = H, alkyl), S
    Y = N-DOPO fragment, CH 2 Z = O, NR (R = H, alkyl), S m = 0-8 n = 0-8
    the DOPO fragment particularly:
    - EAB-DOPO,
    - DEA-DDOPO, or
    - DEA-TDOPO; a compound according to formula (III)
    Y = NR [R = H, alkyl, DOPO fragment, any organophosphorous compound for example, PO (OR) 2 (R = alkyl or aryl) or PO (OR 1 ) R 2 (R 1 = alkyl or aryl, R 2 = alkyl or aryl), COR (R = O-alkyl, NH 2 , NH-alkyl, N- (alkyl) 2 , alkyl or aryl), carbonyl, SiR 3 (R = alkyl, alkoxy)] n = 0-100 and mixtures, particularly:
    - EDAB-DOPO, or
    - TDETA-DOPO,
    - a compound according to formula (IV)
    6/37
    Y = NR [R = H, alkyl, DOPO residue, any organophosphorous compound for example, PO (OR) 2 (R = alkyl or aryl) or PO (OR 1 ) R 2 (R 1 = alkyl or aryl, R 2 = alkyl or aryl), COR (R = O-alkyl, NH 2 , NH-alkyl, N- (alkyl) 2 , alkyl or aryl), carbonyl, S1R3 (R = alkyl, alkoxy)] n = 0-100 and its mixtures, in particular: TEPA-PDOPO.
    [0008] The abbreviations mentioned above will have the meanings as defined unambiguously in the Examples given below. Preferably, Y as referred to in formulas III and IV is NR where R = H, alkyl, DOPO fragment, PO (OR) 2 (R = alkyl or aryl), PO (OR 1 ) R 2 (R 1 = alkyl or aryl , R 2 = alkyl or aryl), COR (R = O-alkyl, NH 2 , NH-alkyl, N- (alkyl) 2 , alkyl or aryl), S1R 3 (R = alkyl, alkoxy). More preferably, it is COR within the definition of Y, R = alkyl or aryl.
    [0009] The compounds of formula (I) represent a wide variety of functionalized silane or siloxane derivatives.
    [0010] The compounds of formula (II) represent a wide variety of multi-DOPO derivatives ”, that is, compounds containing at least two DOPO entities.
    [0011] The compounds of formula (III) and formula (IV) represent another variety of multi-DOPO derivatives that are based on a polyethyleneamine backbone to which they are attached in at least two DOPO entities. The dorsal structure can comprise up to 100 amine units. The compounds of formula III can be obtained by reacting a polyethyleneamine template with an excess of DOPO, which results in a mixture of poly-DOPO amino derivatives. This mixture can generally be considered as an oligomeric mixture that may not be subject to REACH regulations.
    [0012] It is intended that in certain situations AA-DOPO, BHEA-DOPO and / or PDAB-DOPO may desirably be excluded from the group of appropriate phosphonamidate compounds. They can also be deleted individually or
    7/37 in any exchange.
    [0013] In accordance with another aspect of the invention, a method of improving the flame resistance of a polymeric material is provided, comprising the step of adding a first amount of a phosphonamidate according to the present invention, or a mixture thereof , as a flame retardant substance, for a second amount of the polymeric material.
    [0014] According to another aspect of the invention, a polymeric material with improved flame resistance is provided, comprising a flexible polyurethane foam containing an amount of about 1% to about 30%, preferably about 3% to about 25%, particularly about 5%, by weight per 100 parts of polyol of a flame retardant additive selected from among the phosphonamidate of the invention, preferably from the group consisting of
    - EDAB-DOPO,
    - TEPA-PDOPO,
    - a compound of formula (IV) where n = 2-10, preferably 3-10,
    - BHEA-DOPO,
    - DEA-DDOPO, and their mixtures.
    [0015] According to yet another aspect of the invention, a polymeric material with improved flame resistance is provided, comprising the rigid polyurethane foam containing an amount of about 1% to about 30% by weight, preferably about 1% to about 25%, particularly about 3%, by weight per 100 parts of polyol of a flame retardant additive selected from the phosphonamidate of the invention, preferably the group consisting of
    - EDAB-DOPO,
    - ΤΕΡΑ-PDOPO a compound of formula (IV) where n = 2-10, preferably 3-10,
    - BHEA-DOPO,
    - DEA-DDOPO, its mixtures,
    8/37 and optionally also comprising a synergist for example an efficient intumescent carbonized former as expandable graphite and / or an efficient carbonaceous former as pentaerythritol.
    [0016] Other aspects of the invention provide methods of making phosphonamidate compounds using a single reaction step. Specifically, methods of making a phosphonamidate are provided comprising the steps: of dissolving DOPO an amine in a solvent to form the mixture; optionally cool the mixture to below about 20 ° C, 15 ° C, or 10 ° C; -add tetrachloromethane or trichloroisocyanuric acid to the mixture at a rate (i) so that the reaction temperature does not exceed about 30 ° C, or if the mixture has been cooled, (ii) so that the reaction temperature does not exceed about 20 °, 15 ° C or 10 ° C; allowing the mixture to return to about 25 ° C; and stir the mixture. Preferably the solvent is dichloromethane, chloroform, dichloroethane, acetonitrile, THF, 1,4-dioxane or toluene.
    [0017] The invention further provides for the use of a phosphonamidate compound to improve flame resistance, in particular in polyurethane foams.
    [0018] Advantageous embodiments are defined in the dependent claims.
    BRIEF DESCRIPTION OF THE DRAWINGS [0019] The aforementioned and other features and objects of the present invention and the way to achieve them, will become more evident and this invention itself will be better understood by reference to the following description of various embodiments of the present invention , taken in conjunction with the attached drawings, in which are shown:
    [0020] Figures 1 to 10 - total ion chromatograms for a selection of amino-DOPO derivatives showing, as a function of time in minute: total ion chromatogram (top trace), ion sign of radical PO am / z = 47 (middle trace) and ion sign of radical PO 2 am / z = 63 (bottom trace); and [0021] Figure 11 - thermal gravimetric data for a selection of amino-DOPO derivatives showing the percentage of residue as a function
    9/37 temperature in ° C.
    DETAILED DESCRIPTION OF THE INVENTION
    Materials [0022] All reagents and solvents were either reagent-type or were purified by standard methods before use. 9,10-Dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (DOPO) was purchased from Conier Chem & Pharma Co., Ltd and used as received. The amines used were purchased from Aldrich and used as received. CCI4 and Aldrich's trichloroisocyanuric acid (TCCA) and used as chlorinating agents as received.
    Syntheses [0023] Amino-DOPO (phosphonamidates) were synthesized by two synthetic procedures as described here below.
    General procedure A for the preparation of amino-DOPO derivatives (phosphonamidates)
    Scheme 4: General reaction scheme for the preparation of amino-DOPO derivatives via an Atherton-Todd reaction
    HNR 1 R 2
    1.2eq. CCU
    1.1 »q EtjN
    CHjCIj, 0'C-rt over nlght
    [0024] 9,10-dihydro - 9 - oxa -10 - phosphaphenanthrene -10 - oxide (DOPO) (108 g, 500 mmol), triethylamine (79 ml, 566 mmol) and the appropriate amine (240-750 mmol ) were dissolved in 400 ml of an appropriate solvent, for example dichloromethane, chloroform, dichloroethane, acetonitrile, THF, 1,4-dioxane or toluene, stirred and cooled to 0 ° C. After the solution was cooled, tetrachloromethane (59 ml, 600 mmol) is added dropwise at a rate where the reaction temperature does not exceed 10 ° C. After all the tetrachloromethane has been added, the solution is allowed to warm to room temperature and stirring is continued until all the starting material has been consumed (observed with TLC). After the complete conversion of the triethylamine hydrochloride, it is filtered and washed with excess dichloromethane. The resulting clear solution is washed with water (100 ml), dried over Na 2 SO4 and the
    10/37 solvent is evaporated in vacuo. If the resulting product does not have sufficient analytical purity, it is recrystallized from an appropriate solvent.
    General procedure B for the preparation of amino-DOPO derivatives (phosphonamidates):
    Scheme 5: General reaction scheme for the preparation of amino-DOPO using TCCA as a chlorinating agent
    HNR 1 R 2
    0.34 eq TCCA in CH 3 CN
    CHjCIj, 0 'C-rt over nlght
    TCCA- trichloroisocyanuric acid [0025] 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide (DOPO) (108 g, 500 mmol), triethylamine (79 ml, 566 mmol) and the amine (240 - 750mmol) are dissolved in 400 ml of an appropriate solvent, for example dichloromethane, chloroform, dichloroethane, acetonitrile, THF, 1,4 - dioxane or toluene, stirred and cooled to 0 ° C. Then the solution was cooled, a TCCA solution (38.7 g,
    166.7 mmol) in 200 ml of acetonitrile is added dropwise at a rate where the reaction temperature does not exceed 10 ° C. After this solution has been added completely the solution is allowed to warm to room temperature and stirring is continued until all the starting material has been consumed (TLC). After complete conversion, the reaction mixture is filtered to remove triethylamine hydrochloride and cyanuric acid. The resulting clear solution is washed with water (100 ml). The aqueous phase is extracted twice with 100 ml of dichloromethane. The combined organic phases are dried over Na2S04 and the solvent is evaporated in vacuo. If the resulting product does not have sufficient analytical purity, it is recrystallized from an appropriate solvent.
    Analytical data
    Example 1
    11/37
    phosphinine 6-oxide (AA-DOPO)
    Synthesis cycle with a DOPO to amine ratio: 1: 1
    Solvent: CH 2 CI 2
    Yield: 1 9.2g (440mmol, 88%)
    Melting point 95 ° C 1 H- NMR (CDCI 3 ) δ (ppm): 7.88-7.99 (m, 3H), 7.92 (dd, J = 1.7, 7.9 Hz, 1 H), 7.66 (tt, J = 1.3, 8.7, 1 H), 7.48 (ddt, J = 1.0, 3.0, 7.5 Hz, 1 H), 7, 35 (mCI 1 H), 7.207.26 (m, 2H), 5.75-5.86 (m, 1 H), 5.19 (dq, J = 1.4, 17.1 Hz, 1 H) , 5.06 (dq, J = 1.4,
    10.3 Hz, 1 H), 3.39-3.60 (m, 3H), 13 C-NMR (CDCI3) δ (ppm): 149.8, 138.9, 137.0, 132.7, 130.1, 130.0 128.4,
    128.1 127.2, 124.8, 124.2, 123.5, 123.3, 121.9, 44.9.
    31 P-NMR (CDCl3) δ (ppm): 15.9.
    IR (Film) v (cm ' 1 ) = 3179 (m), 2855 (w), 1648 (w), 1592 (w), 1475 (m), 1428 (m), 1222 (s), 1198 (m) , 1152 (m), 1142 (s), 1054 (w), 923 (m), 899 (w), 752 (s), 715 (s).
    MS (ESI) m / z (%) 271 (14), 216 (55), 199 (18), 168 (54), 139 (27), 56 (100).
    12/37
    6 - ((3- (triethoxysilyl) propyl) amino) -6H-dibenzo [c, e] [1,2] oxaphosfinine
    6-oxide (TESPA-DOPO) [0026] One can imagine the preparation of DOPO-amino silane derivatives, choosing different types of silanes or functional siloxanes. In addition, DOPO amino silane or siloxane derivatives can be further hydrolyzed and polymerized to form cross-linked or linear polymers As described for DOPO-phosphinates in the literature. 12
    Synthesis cycle with a DOPO to amine ratio: 1: 1
    Solvent: CH 2 CI 2
    Yield: 7.57g (17.4mmol, 75%)
    Melting point: 85 ° C 1 H-NMR (CDCl3) δ (ppm): 7.86-7.99 (m, 3H), 7.66 (tt, J = 1.2, 8.8, 1 H ), 7.48 (ddt, J = 0.8, 3.1, 7.5 Hz, 1 H), 7.35 (mc, 1 H), 7.19-7.25 (m, 2H), 3.76 (q, J = 6.9 Hz, 6H), 3.41 (mc, 1 H), 2.87 (mc, 2H), 1.59 (m c , 2H), 1.17 (t , J = 6.9 Hz, 9H), 0.59 (mCI 2H).
    13 C-NMR (CDCI3) δ (ppm): 150.1, 137.2, 132.8, 130.3, 130.2 128.2, 125.5, 125.0, 124.3, 123.8 , 123.7, 122.2, 120.7, 58.5, 43.6, 25.1, 18.4, 7.5.
    31 P-NMR (CDCI3) δ (ppm): 15.8.
    IR (Film) v (CDCI3) = 3148 (w), 2939 (w), 2895 (w), 2838 (w), 1597 (w), 1474 (m), 1430 (m), 1274 (w), 1225 (m), 1195 (s), 1149 (m), 1074 (s), 926 (m), 816 (m), 752 (s).
    Example 3
    Bsl1 / O
    6 - {(3- (trimethoxysilyl) propyl) amino) - 6W-dibenzo [c, e] [1,2] oxa phosphinine 6-oxide
    13/37 (TMSPA-DOPO)
    Synthesis cycle with a DOPO to amine ratio: 1: 1
    Solvent: CH 2 CI 2
    Yield: 161 g (370 mmol, 74%)
    Melting point: 85 ° C 1 H-NMR (CDCl3) δ (ppm): 7.86-7.99 (m, 3H), 7.66 (tt, J = 1.2, 8.8, 1 H ), 7.48 (ddt, J = 0.8, 3.1, 7.5 Hz, 1 H), 7.35 (mc, 1 H), 7.19-7.25 (m, 2H), 3.55 (mc, 1 H), 3.49 (s, 9H), 2.87 (mc, 2H), 1.58 (m c , 2H), 0.59 (m c , 2H).
    31 P-NMR (CDCI3) δ (ppm): 15.8
    Example 4
    6- (2 - ((6-oxido-6H-dibenzo [c, e] [1,2] oxafosfinin-6-yl) amino) ethoxy) -6Hdibenzo [c, e] [1,2] oxafosfinine 6-oxide (EAB-DOPO)
    Synthesis cycle with a DOPO to amine ratio: 2: 1
    Solvent: CH 2 CI 2
    Yield: 98.2g (203mmol, 81%)
    Melting point 121 ° C 1 H-NMR (CDCl 3) δ (ppm): 7.85-7.99 (m, 5H), 7.71-7.85 (m, 2H), 7.65 (mc, 1 H), 7.48-7.56 (m, 1 H), 7.32-7.45 (m, 3H), 7.10-7.28 (m, 4H), 4.16 (mc, 2H), 3.51 (m c , 1 H), 3.17 (mo. 2H).
    13 C-NMR (CDCI3) δ (ppm): 149.8, 149.7, 137.2, 137.1, 133.9, 133.1, 130.8,
    130.5, 130.5, 130.4, 130.1, 128.6, 128.4, 125.5, 125.5, 125.1, 124.5, 124.3, 123.8,
    122.6, 122.1, 120.7, 120.3, 120.2, 66.9, 41.4 31 P-NMR (CDCI3) δ (ppm): 15.5 (d, J = 3.5 Hz, 1 P), 11.4.
    IR (Film) v (cm ' 1 ) = 3215 (w), 2879 (w), 1597 (w), 1476 (m), 1430 (m), 1267 (m), 1230 (m), 1204 (s) , 1151 (m), 11 (s), 1029 (m), 989 (m), 911 (s), 749 (s).
    MS (ESI) m / z (%) 489 (100).
    14/37
    6- (bis (2-hydroxyethyl) amino) - (6H-dibenzo [c, e] [1,2] oxaphosphinine 6-oxide (BHEA-
    DOPO)
    6- (((2-hydroxyethyl) (2 - ((6-oxide-6 / - / - dibenzo [c, e] [1,2] oxafosfinin-6-yl) oxy) ethyl) amino) - (6 / - / -dibenzo [c, e] [1,2] oxaphosfinine 6-oxide (DEA-DDOPO)
    6-, 6 '- ((((((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6-yl) azanediyl) bis (ethane-2,1diyl)) bis (oxy)) bis (6 / - / - dibenzo [c, e] [1,2] oxaphosfinine 6-oxide (DEA-TDOPO)
    Synthesis cycle with a DOPO to amine ratio: 1: 1 or 1: 1.5 Solvent: CH2CI2
    Yield: 113.2g (355mmol, 71%)
    HPLC-MS (ESI-MS): BHEA-DOPO retention time 15.2 minutes (319.9 m / z), DEA-DOPO 15.7 minutes (533.9 m / z); Flow 0.25 ml / min, solvent mixture 90:10 H2O + 0.1% formic acid: acetonitrile + 0.1% formic acid for 1 minute, then 0: 100 gradient in 10 minutes, then two more minutes 0: 100, then gradient at 90:10 in two minutes, 5 minutes isocratic at 90:10, Column: Phenomenex® Gemini C18, 110A, 250mm * 2mm * 5pm.
    [0027] DOPO reaction with diethanolamine (DEA) can result in three
    15/37 types of molecules, ie BHEA-DOPO, DEA-DDOPO, DEA-TDOPO. In the synthesis described in the applicants' experiments it leads to BHEA-DOPO and DEADDOPO compounds in the d e1: 3 ratio respectively. One can imagine the preparation of DEATDOPO by varying the reaction conditions. It is also possible to prepare one of the aforementioned compounds, exclusively by optimizing the reaction conditions.
    6-, 6 '- ((((((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6-yl) azanediyl) bis (ethane-2,1-diyl)) bis (oxy) ) bis (6H-dibenzo [c, e] [1,2] oxaphosfinine 6-oxide (DEATDOPO)
    Analytical data for DEA-TDOPO 1 H- NMR (CDCI 3 ) δ (ppm): 7.80-8.05 (m, 9H), 7.65-7.80 (m, 3H), 6.95-7 , 45 (m, 12H), 4.01-4.18 (m, 4H), 3.0-3.21 (m, 4H).
    31 P-NMR (Trifluoroethanol-d3) δ (ppm): 16.9, 10.7.
    MS (ESI) m / z (%) 747 (100).
    6.6 '- (piperazine-1,4-diyl) bis (6H-dibenzo [c, e] [1,2] oxaphosfinine 6-oxide) (PBDOPO)
    Synthesis cycle with a DOPO to amine ratio: 2.5: 1
    Solvent: CHCI3
    Yield: 110.5g (212 mmol, 85%)
    Melting point 320 ° C
    16/37 1 H-NMR (Trifluoroethanol-d3) δ (ppm): 7.91 (mCI 2H), 7.84 (m c , 2H), 7.56-7.66 (m, 4H), 7, 38 (m c , 2H), 7.24 (m c , 2H), 7.12 (m c , 2H), 7.06 (m c , 7.06), 2.99 (m c , 8H), 13 C-NMR (Trifluoroethanol-d3) δ (ppm): 151.2, 139.8, 136.0, 132.6, 131.2,
    130.6, 127.0, 126.1, 123.5, 123.4, 121.9, 121.8, 45.7, 31 P-NMR (Trifluoroethanol-d3) δ (ppm): 19.5.
    IR (Film) v (cm1) = 2856 (w), 1596 (w), 1476 (w), 1428 (w), 1369 (w), 1230 (s), 1205 (m), 1147 (m), 1114 (m), 969 (m), 901 (s), 747 (s), 707 (s).
    MS (ESI) m / z (%) 514 (100).
    Example 9
    6.6 ’- (ethane-1,2 diylbis (azanediyl)) bis (6H-dibenzo [c, e] [1,2] oxaphosphinine 6oxide) (EDAB-DOPO)
    Synthesis cycle with a ratio of -DOPO to amine: 2.5: 1
    Solvent: CHCI 3
    Yield: 102.5g (210mmol, 84%)
    Melting point 267-270 ° C 1 H-NMR (Trifluoroethanol-d3) δ (ppm): 7.65-7.75 (m, 3H), 7.54-763 (m, 2H), 7.40- 7.52 (m, 3H), 7.26-7.33 (m c , 1 H), 6.97-7.19 (m, 5H), 6.81 (dd, J = 1.1, 7 , 9 Hz, 1 H), 7.59 (dd, J = 1.1, 8.0 Hz, 1 H), 2.73-2.91 (m, 2H), 2.58-2.72 ( m, 2H), 13 C-NMR (Trifluoroethanol-d3) δ (ppm): 150.8, 150.5, 139.3, 139.1, 135.8,
    135.7, 132.5, 132.4, 131.4, 131.3, 130.3, 130.2, 126.8, 126.7, 126.1, 125.8, 123.3, 123, 2, 121.8, 121.5, 43.6.43.4, 31 P-NMR (Trifluoroethanol-d3) δ (ppm): 21.4, 20.7.
    IR (Film) v (cm-1) = 3159 (m), 2877 (w), 1598 (w), 1476 (m), 1446 (m), 1196 (s), 1146 (m), 1116 (s) , 922 (s), 747 (s), 711 (m).
    MS (ESI) m / z (%) 488 (100).
    17/37
    Example 10
    6-, 6 '- (1,4-phenylenebis) azanediyl)) bis (6 / - / - dibenzo [c, e] [1,2] oxaphosphinine 6-oxide (PDAB-DOPO)
    Synthesis cycle with a DOPO to amine ratio: 2.5: 1
    Solvent: CHCI3
    Yield: 5.2g (9.7 mmol, 81%)
    Melting point 295 ° C (decomp.) 1 H-NMR (trifluoroethanol-d3) δ (ppm): 7.75-7.90 (m, 4H), 7.51-7.65 (m, 4H),
    7.27 (m c ) 2H), 7.21 (m c , 2H), 7.11 (m c , 2H), 7.01 (d, J = 8.1 Hz, 2H) 6.54 (s , 4H), 31 P-NMR (CDCI 3 ) δ (ppm): 14.9,
    IR (Film) v (cm-1) = 3153 (w), 3093 (w), 2944 (w), 1506 (m), 1477 (m), 1392 (w), 1286 (m), 1196 (s) , 1116 (w), 974 (s), 911 (w), 747 (s).
    MS (ESI) m / z (%) 536 (100).
    Example 11
    θ · - ((3 - ((6-oxide-6 / - / - dibenzo [c, e] [1,2] oxafosfinin-6-yl) (2 - (((6-oxide-6 / - / - dibenzo [c, e] [1,2] oxafosfinin-6-yl) amino) ethyl) amino) propyl) amino) -6 / - / - dibenzo [c, e] [1,2] oxafosfinine 6-oxide TDETA-DOPO
    Synthesis cycle with a DOPO to amine ratio: 3.5: 1
    Solvent: CHCI3
    Yield: 102.5g (210 mmol, 84%)
    18/37
    Melting point 267-270 ° C 1 H- NMR (CDCI 3 ) δ (ppm): 7.65-7.95 (m, 9H), 7.40-7.63 (m, 3H), 6.82 -7.35 (m, 12H), 3.99 (bs, 3H), 3.1-3.25 (m, 4H), 2.98-3.10 (m, 4H), 31 P-NMR ( Trifluoroethanol-d3) δ (ppm): 15.9, 17.8
    MS (ESI) m / z (%) 745 (100).
    Example 12 [0028] As an example for the preparation of multi-DOPO derivatives of tetraethylene pentaamine, an amount of tetraethylene pentaamine was reacted with an excess of DOPO. This reaction resulted in a mixture of polyDOPO amino derivatives that were identified by HPLC-MS. The HPLC-MS data from these mixtures indicate that tetraethyleneepentaamine had 3-5 DOPO attached to various amino groups. This mixture can be considered as an oligomeric mixture that does not pass REACH regulations. Scheme shown below shows the tetraethyleneepentaamine derivative DOPO (TEPA-PDOPO) in which all amino groups were reacted with DOPO.
    6-6-oxide, 6 '- (((((6-oxide-6 / - / - dibenzo [c, e] [1,2] oxafosfinin-6-yl) azanediyl) is (ethane-2,1-diyl )) bis ((2 - ((6-oxide-6 / - / - dibenzo [c, e] [1,2] oxafosfinin-6-yl) amino) tyl) azanediyl)) bis (6H-dibenzo [c, e] [1,2] oxaphosfinine) - (TEPA-PDOPO)
    HPLC-MS: m / z = 1260
    Proof of the gas phase action of amino-DOPO derivatives [0029] DOPO and its phosphinate derivatives have been shown to have a gas phase action. There are analytical data that clearly indicate the formation of a PO * radical that can extinguish the H * and OH * radicals formed during the thermal decomposition of polymers and prevent their oxidation. 4 '' 5 There are no analytical data for the gas phase action of amino-DOPO derivatives. So in this
    19/37 study, the elucidation of the gas phase action of the amino derivatives of DOPO was performed using the direct insertion probe MS. The amino derivatives DOPO were heated from 50 ° C to 450 ° C at a rapid rate of 100 ° C / minute in a quartz capillary in the ionic source of MS and maintained for another 2 minutes and several mass fragments measured. The total ion chromatograph (TIC) was then scanned for PO * (m / z 47) and PO2 (m / z 63). Figures 1 to 10 show the TIC chromatogram for each amino-DOPO derivative.
    [0030] The figures above clearly indicate the gas phase action of amino-DOPO derivatives as they all exhibit release of PO * (m / z 47) and PO2 (m / z 63) at an elevated temperature. In addition, it is also evident that the formation of these active species occurs at different temperatures (indicated by the time of formation), for different derivatives and, thus, could imply different areas of application (ie, different polymeric systems).
    Thermal stability of DOPO derivatives [0031] One of the important objectives of the development of several DOPO derivatives was to improve the thermal stability of DOPO itself. This will guarantee its suitability for use in thermoplastic polymers, which generally require high processing temperatures (200-350 ° C). The thermal decomposition studies of derived DOPO and DOPO are shown in Figure 11.
    [0032] Various transition temperatures and carbonized content of DOPO amino derivatives are further tabulated in Table 1.
    Table 1: TGA data of Amino DOPO derivatives
    Compounds T d1 (° C) T d Max (° C) % Carbonized at 800 ° C DOPO 201 267 2 BHEA-DOPOOEA-DDOPO (1: 3) 284 361 8 EDAB-DOPO 355 415 7 PA-DOPO 235 292 2 AA-DOPO 247 295 3 PB-DOPO 387 433 5 BA-DOPO 289 315/400/462 2 TESPA- DOPO ' 234 135/287/437 28 EAB-DOPO 311 387 2 EA-DOPO 241 293/375 2
    20/37 | TDETA-DOPO | 294 | 385 | 2 |
    T d i: Temperature for 10% weight loss, TdMax- 'Temperature for maximum decomposition rate, * Multiple decomposition stages, bold data indicate main stage of decomposition [0033] It can be seen from figure 11 and in the table 1 that DOPO starts to decompose earlier than 200 ° C and is therefore not very suitable for melt processing of most organic polymers. Most amino-DOPO derivatives are quite stable at this temperature and are therefore more suitable for melt processing at temperatures> 200 ° C. In addition, some derivatives, such as PB-DOPO and EDAB-DOPO, exhibit stability above 300 ° C.
    [0034] No previous studies on DOPO amino derivatives indicate their thermal stability. It can also be seen from the TGA data that TESPA-DOPO has a very interesting thermal behavior. It has a relatively high carbonized content (28%) at 800 ° C and indicates possible hybrid action, that is, combined gas phase and condensed phase action. This type of hybrid flame retardant can find useful applications in special intumescent coatings.
    Water solubility of specific DOPO compounds [0035] These DOPO derivatives are very poorly soluble in water which is exemplarily shown for EDAB-DOPO and TEPA-PDOPO in Table 2.
    Table 2: Water solubility of EDAB-DOPO and TEPA-PDOPO
    Flame Retardant Temperature FR solubility in water mg / L FR solubility in water mmol / L EDAB-DOPO 25 ° C 392.9 0.80 EDAB-DOPO 90 ° C 500.8 1.03 TEPA-PDOPO 25 ° C 15.4 0.01 TEPA-PDOPO 90 ° C 818.1 0.65
    [0036] From Table 2, it can be seen that only small amounts of EDAB-DOPO and TEPA-PDOPO dissolve in water, even when the temperature is increased to 90 ° C.
    [0037] This fact makes these compounds very useful for several applications
    21/37 of flame retardants where a requirement is solubility in any organic solvent and limited solubility in water.
    Application and test procedures [0038] The synthesized compounds were evaluated for flame retardant properties, incorporating them in flexible PU foams.
    [0039] Methods for making flexible polyurethane foams (flexible PU foams) are known in the art and are covered, for example, on pages 163 - 197 of the Plastics Manual, Volume 7, Polyuretanes, Becker / Braun, 1 to . Ed. (1985), published by CaH Hanser Verlag.
    [0040] Conventionally, flexible PU foams can be prepared by reacting a polyol with a multifunctional isocyanate, so that the NCO and OH groups form urethane bonds by an addition reaction, and the polyurethane is foamed with produced carbon dioxide. in situ by isocyanate reaction with water.
    [0041] This conventional process can be carried out as a so-called one-shot process, in which the polyol, isocyanate and water are mixed together so that the polyurethane is formed and foamed in the same step.
    [0042] The flexible polyurethane foams were manufactured according to the formulation mentioned in Table 3 below.
    [0043] The manufacture of foams according to the formulations in Table 3 was performed by manual mixing in the laboratory from 200 grams of polyol. The formulation of the components that participate in the reaction was identical in all cases, except for the addition of flame retardants, where indicated.
    Table 3: Formulation of flexible polyurethane foam (PU)
    Flexible PU foam Ingredients pphp Whole PO polyol 97 Compatibles 3.4 Tin (II) Octanoate 0.25 Catalysts 0.5 Silicone Stabilizer 0.5 H 2 O (total) 1.85 Toluene diisocyanate (TDI) 29.8
    22/37 | Flame retardant (FR) | X |
    X = 1-30%
    Description of ingredients:
    [0044] With respect to the polyol, it can be of any suitable type. Polyether and polyester polyols are typically used in the production of PU foam and in accordance with the present invention. In table 3, the polyol is a polyether polyol. When a polyether polyol is used it is preferably wholly, or predominantly, derived from propylene oxide (PO), although ethylene oxide (EO) can also be used instead, or in addition to PO. However, it is also possible to use polyester polyols or mixtures of polyester and polyester polyols. Suitable polyols can have an OH functionality of 2 to 6, particularly 2 to 4 and can have a molecular weight (MW) in the range of, say, 400-10,000.
    [0045] It is well known in the art to use mixed polyols to vary the reactivity of the system or to provide the desired properties for the resulting PU foam and, with the present invention, as PO derived from the polyether polyol is generally preferred, other polyols and mixtures of polyols can be used as needed.
    [0046] Examples of polyether polyols that can be used according to the invention are described, for example, on pages 44 - 54 and 75 - 78 of the Plastics Manual, Volume 7, Polyuretanes, Becker / Braun, 2 a . Ed., Published by Carl Hanser Verlag.
    [0047] So, for example, polyol can be as follows:
    I. derived from PO and propylene glycol with viscosity (at 25 ° C) of 250-350 mPa.s, number OH 56 ± 3.
    II. derived from EO and PO and trimethylolpropane with viscosity (at 25 ° C) 750 900 mPa.s, number OH 35 ± 2.
    III. derived from PO and trimethylolpropane with viscosity 600-700, number OH 380 ± 25.
    IV. derived from PO and glycerin with viscosity 450-550 and OH number 56 ± 3.
    [0048] All viscosity measurements (in mPa.s) are obtained using
    23/37 a Brookfield viscometer. Unless otherwise noted, viscosity is measured at 25EC. The OH number (hydroxyl number) is a conventional parameter that gives the concentration of OH groups reactive to NCO per unit weight in mg KOH / g.
    Hydroxyl (OH) = 56.1 x functionality x 1,000
    MW polyol [0049] It is also possible to use these polyether polyols, which already contain incorporated catalysts, as for example described in WO 03 / 016373A1. Likewise, it is also possible to use mixtures of the polyether polyols mentioned above.
    [0050] The invention can also be applied to OH-terminated prepolymer foams, natural oil-based polyols (NOP’s), mixtures and / or prepolymers thereof.
    [0051] The polyol described in Table 2 is a triol which is a propylene oxide adduct of glycerin and has a molecular weight of the order of 3000. Commercial examples are Voranol® 3008 (Dow Chemical Company), or DESMOPHEN® 20WB56 ( Bayer).
    [0052] With respect to the multifunctional isocyanate this is preferably a diisocyanate, particularly TDI (toluene diisocyanate), as described in Table 2 However, other multifunctional isocyanates, preferably with a functionality of 2 to 5 can be used alone or in any combination appropriate. Thus, the multifunctional isocyanate, can be any one or more of the following:
    TDI (all mixtures of toluene diisocyanate isomers),
    MDI (diphenyl methylene isocyanate), which can be pure or polymeric versions (so-called aromatic isocyanates).
    [0053] More particularly, the multifunctional isocyanate is a polyisocyanate containing two or more isocyanate groups and commercial or standardized di- and / or triisocyanates are typically used. Examples of suitable ones are aliphatic, cycloaliphatic, arylaliphatic and / or aromatic isocyanates, such as mixtures
    24/37 commercially available 2,4- and 2,6 -isomers of diisocyanatotoluene (= tolylelene diisocyanate TDI), which are marketed under the trade names of CARADATE® T80 (Shell) or VORANATE® T80 and T65 (Dow Chemicals) . 4.4 'diisocyanatodiphenylmethane (= 4.4' - methylenebis (phenylisocyanate); MDI) and mixtures of TDI and MDI, can also be used. It is also possible, however, to use isocyanate prepolymers based on TDI or MDI and polyols. Modified or mixed isocyanates (for example, Bayer's Desmodur ® MT58), can also be used. Examples of aliphatic isocyanates are 1,6 - hexamethylene diisocyanates or triisocyanates, such as Desmodur® N100 or N3300 from Bayer. The isocyanate index can be used from very low (75 or less) to very high (125 or greater) to suit the required hardness or other properties of the foam.
    [0054] Catalysts are well known in the art of PU foams, in particular an amine such as DMEA (dimethyl ethanolamine), DABCO® 33 LV (a tertiary amine from Air Products). Low-emission / reactive amines can also be used as catalysts. Examples include Tegomanin ZE -1 from Evonik or Niax EF 700 from Momentive or NE 400 from Air Products.
    [0055] Metallo-organic compounds, such as, for example, a tin catalyst, for example, KOSMOS 29 (stannous octoate), but other low-emission catalysts, such as Kosmos EF (tin ricinolate), sodium octoate compounds zinc or bismuth can also be used.
    [0056] Silicone stabilizers known in the art, for example, silicone surfactant, such as in the Evonik Tegostab ® range, ie Tegostab B 8232, BF 2370 ... or in the Momentive Niax ® range, ie L 670, L 595.
    [0057] Additional additives, such as compatibilizing agents (ie 9904 from SILBYK Byk Chemie), chain extension agents and / or crosslinking agents, such as diethanolamine, glycerin, sorbitol, as well as additional flame retardants; fillers can also be added to the formulation. These additives and others known in the art in relation to conventional foaming processes can be used in any combination.
    25/37 [0058] Water can be used in any amount appropriate to achieve the desired density (typically 0.1 to 15 pphp, preferably 1 to 5 pphp), also in combination with liquid CO2.
    [0059] For the purpose of comparing the effectiveness of the synthesized aminoDOPO derivatives, Tris (2-chloroisopropyl) phosphate (TCPP), which is a flame retardant commonly used for foams, was taken as the standard FR. It is common in the PU foam industry to use haloalkyl derivatives as flame retardant additives. Recently, the use of some of these derivatives as flame retardants [TCEP (tris (2-chloro-ethyl phosphate)), TDCPP (tri (2,3-dichloropropyl) phosphate) and TCPP)] has either been banned or is being investigated due to its toxicity by environmental agencies. 13 [0060] The resulting foams were dried and aged for 3 hours at 80 ° C. The foams were then tested for flammability according to the Swiss flammability standard (BKZ). It is a vertical firing test for foamed materials with a specific sample size (length: 160 mm, width: 60 mm, thickness: 6 mm, tolerance of ± 10%). For each sample, a flame test (BKZ) was performed in triplicate. If the results were not consistent, each sample was tested 6 times. For the BKZ test, an air-dried sample was placed in an upright position and subjected to flame from the lower front edge by a standard flame. The height of the 20 mm flame has been maintained and must burn constantly with clear contours. The position of the burner was adjusted to 45 °, so that the flame reaches the sample vertically in the middle of the lower front edge. The flame is placed in contact with the foam for 15 seconds and must be placed in such a way that the foam bottom is approximately 4 mm ± 1 mm inside the flame from the tip. The burning test analysis is then performed according to the details presented in Table 4.
    Table 4: BKZ flammability test
    Classification Requirements Flammability degree (class 3) time 5 - 20 s Flammability degree (class 4) firing time> 20 s Flammability degree (class 5) ' The flame does not reach the top level of the support
    26/37 of the sample (150 mm). Duration <20 s [0061] The BKZ firing test was performed according to the procedure given above and the results are given in Table 5.
    Table 5: Fire test in flexible PU foam test - BKZ
    FR Amount Rating 0 DOPO 5% class 5 BHEA-DOPO: DEA-DDOPO (1: 3) 5% class 5 EDAB-DOPO 5% class 5 AA-DOPO 5% class 5 PB-DOPO 5% class 5 TCPP 5% class 5 TDETA-DOPO 5% class 5 TEPA-PDOPO 5% class 5
    a) Classification according to table 1. b) virgin foam does not self-extinguish.
    [0062] These foams were also evaluated for flame retardancy (UL-94 HB test) using standard ASTM D4986 or ISO / DIS 9772.3. The data for this fire test are shown in Table 6 below:
    Table 6: UL-94 HB test
    Samples Burning rate (mm / min) Classification 3 In blank 58 X 5% DOPO 48 HBF 5% AA-DOPO 47 HF-2 5% PB-DOPO 57 HBF 5% EDAB-DOPO 25 HF-1 5% DEA-DOPO: BHEADOPO (3: 1) 52 HF-2 5% TDETA-DOPO not determined HF-1 5% TEPA-PDOPO not determined HF-1 5% TCPP 23 HBF
    a) x = foam does not self-extinguish, HBF = does not have any samples with a burning rate exceeding 40 mm per minute over a period of
    100 mm, or each sample will stop burning before forming the flame or the incandescence reaches the 125 mm gauge mark; HF-2 = foam self-extinguishes within two seconds after the burner has been removed, the foam is damaged <60 mm, after the glowing time is less than 30s, cotton gauge is allowed to be ignited by dripping, HF-1 = foam self-extinguishes within two seconds after the burner has been removed, the foam is
    Damaged 27/37 <60 mm, after the glowing time is less than 30s, cotton indicator is not allowed to be ignited by dripping [0062] All amino-DOPO derivatives have a similar or even better fire performance as compared to TCPP and therefore can be used to replace TCPP as a halogen-free FR system for flexible PU foams. It can also be seen from Table 6 that the amino derivatives DOPO [AA-DOPO, EDAB-DOPO, DEA-DOPO, BHEA-DOPO (3: 1)] have a better flame retardant effect compared to non-DOPO modified. Without being bound by theory, it is contemplated that the improved flame retardancy effect of amino derivatives DOPO may be due to a P-N synergism effect.
    [0063] Other tests were carried out to investigate the effect of this new class of compounds.
    Polyether Foams / EDAB-DOPO [0064] The foams were produced on a commercial standard flexible foam board (Messrs. Hennecke, Germany) in a one-step process (oneshot). In this example, the basic materials (raw materials) were measured according to the formulation directly from the storage containers in a mixing chamber by means of pumps (for example, piston pumps or gears), the mixing chamber being equipped with a stirrer and a discharge pipe.
    [0065] The measurement and mixing of raw materials was done in a manner known in the art. In this example, the temperature of the raw materials was 25 ± 3 ° C.
    [0066] The global production of polyol was 30 kg / min. EDAB-DOPO were pre-dispersed in the polyol before carrying out the one-step process formulation.
    Table 7: Evaluation of EDAB-DOPO in polyether foams.
    1 2 3 4 5 Ref. VA 1812 V06 V01 V02 V16 V14 Polyol OH 56 all PO 100 100 100 100 100 TDI 80/20 26.2 26.2 38.8 26.2 38.8 Water 1.6 1.6 2.8 1.6 2.8
    28/37
    Tegoamin ZE-1 0.5 0.35 0.35 0.5 0.5 Kosmos EF 0.5 0.5 0.5 0.9 0.9 Niax L 595 0.5 0.5 0.5 0.7 0.7 TCPP 0 5 5 0 0 EDAB-DOPO 0 0 0 5 5 Density (Kg / M3) 42.5 47.2 25.47 46.0 30.0 CLD 40% (Kpa) DIN EN ISO 3381/1 3.1 3.5 3.0 2.5 2.6 Air flow (It / m2 / s) DIN EN ISO 9237 7.9 57 500 161 414 BKZ Class (Vertical) X burning 5 X burning 5 5 UL 94 HB test rating (Horizontal) X burning HF2 HF2 HF2 HF2
    Discussion of the results in Table 7:
    [0067] Columns 1 to 3 are not examples of the Invention. 4 and 5 show the effect of EDAB - DOPO. It can be seen that at the same water level (1.6 pphp) EDAB5 DOPO has a positive effect on flammability (Columns 4 and
    1) and works at least as well as TCPP (columns 4 and 2). What is unexpected is that, despite having reactive isocyanate groups (see structure in example 12 page 16) the resulting foam has a more open air flow 161 versus 57 (l / m2 / s) and needs more EF Kosmos, indicating better processability (flexibility in 10 production). In lower density (2.8 pphp of water) ED-AB-DOPO performs better, at least in vertical tests (comparison columns 3 and 5).
    [0068] A proof of the effectiveness of TEPA-PDOP in polyether is given in Table
    8. The work was done on manual mixers
    1 2 3 4 Prepolymer finished in OH OH 30, all PO 100 100 100 100 TDI 80/20 31.9 31.9 31.9 31.9 Water 2.8 2.8 2.8 2.8 Tegoamin ZE-1 0.35 0.35 0.35 0.35 Kosmos EF 0.7 0.7 0.7 0.7 Tegostab B 8232 0.8 0.8 0.8 0.8 Exolit OP 560 0 10 0 0 TEPA-PDOPO 0 0 5 10Density (Kg / M3) 38.5 shrinks 40.6 42 CLD 40% (Kpa) DIN EN ISO 3381/1 7.3 without foam 5.82 5.80 Class BKZ XX 5
    29/37
    (Vertical) burnburnUL 94 HB test rating (Horizontal) X burningHF2 HF1
    [0069] OH-terminated prepolymers are described in WO 2005/108455 (Fritz Nauer Ag) [0070] Exolit OP 560 is a market-leading, reactive, halogen-free flame retardant from Clariant.
    [0071] You can clearly see the improvement in flammability over the blank control. Exolit OP 560 can no longer be processed at 10 pphp, as it closes the foam so much that the cells shrink. The addition of more TEPAPDOPO improves the flammability behavior in both horizontal and vertical tests.
    Evaluation of EDAB-DOPO and ΤΕΡΑ -PDOPO in rigid formulations
    Flame retardant of polyurethane and polyisocyanurate foams:
    [0072] The main method for retarding the rigid foam flame at the moment is the use of additives, although reactive diols are occasionally used where there is a particular requirement. Well-established additives are still TCEP, that is. tris (2-chloroethyl) phosphate, and TCPP, i.e., tris (1-chloro-2propyl) phosphate. The recent need for higher percentages of these additives was due to the use of HFCs or hydrocarbon blowing agents in place of chlorofluorocarbons depleting the ozone layer progressively suppressed.
    [0073] The use of pentanes (cyclopentane, isopentane, n-pentane or mixture) for blowing the foams in place of blowing chlorofluorocarbon, imposes the need for more flame retardants to neutralize the flammability of the blowing agent.
    [0074] Furthermore, it is known that by increasing the isocyanate index to obtain a larger isocyanurate structure, a lower level of flame retardant can be used to satisfy the standard. The higher the content of isocyanurate groups, the greater the carbonized yield on exposure to fire and, therefore, more resistant to flame, but also more fragile (brittle).
    [0075] Blowing agents not depleting the fluorine-containing ozone layer,
    That is, HFCs, may allow less flame retardancy, especially in combination with a high isocyanurate content.
    [0076] Although chloroalkyl phosphates continue to dominate, there is a special interest in Europe in non-halogenated flame retardants.
    [0077] However in the event of a fire, halogenated fire retardant polyurethanes release combustion products that are more toxic than untreated polymer.
    [0078] These are the reasons why current research focuses on the development of halogen-free and non-toxic fire retardants.
    Classification and Fire Performance Testing of Building Materials and Components - DIN 4102:
    [0079] Agreement / compliance with construction inspection regulations can be embodied with the aid of standards generally recognized as standard construction practice.
    [0080] The DIN 4102 standard - Fire Performance of Building Materials and Components - defines in concrete terms the fire protection terminology (fuel and non-fuel) used in the rules and regulations related to the inspection of buildings and fire protection.
    [0081] According to DIN 4102 - Part 1 - construction materials can be classified in class A (non-combustible) or class B (fuel).
    [0082] Due to their organic structures, plastics usually reach only class B.
    [0083] According to DIN 4102 -1 combustible building materials can be classified into the following categories:
    1. B 1 = Low flammability (Brandschacht test)
    2. B 2 = Moderately flammable (small burner test)
    3. B 3 = Highly flammable [0084] The test methods and requirements for combustible and (non-combustible building materials) materials are described in different sections of DIN 4102-1.
    31/37
    Class B2 building materials:
    [0085] Class B2 building materials reach Class B2 if they meet the test requirements given in the following table.
    Samples 4. Flame edge application: five samples 90 mm x 190 mm x original thickness (Max. 80 mm), reference mark 150 mm from the bottom edge5. Flame surface application: five samples 90 mm x 230 mm x original thickness (Max. 80 mm), reference marks 40 mm and 150 mm from the bottom edge Sample position 6. Vertical Ignition source 7. Small flame burner, inclined at 45 °, flame height 20 mm Flame application 8. 15 s Test duration 9. 20 s Continued 10. Conclusions 11. Approved if the flame tip does not reach the reference marks in 20 s on any sample.12. If the filter paper under the sample burns within 20 s after adding a flame, the material is judged to burn with flame droplets.
    Small burner test equipment [0086] The small burner test equipment used in this patent complies with the requirements for tests on the B2 building materials class specified in DIN 4102-1.
    [0087] All flame tests performed within this report are based on application at the edge of the incident flame.
    EDAB-DOPO / TEPA-PDOPO dispersion:
    [0088] EDAB - DOPO respectively ΤΕΡΑ - PDOPO were dispersed in polyol components by means of high speed dispersion, in order to incorporate the extremely fine solid particles in the fluids, to produce colloidal suspensions. The dispersion preparations were carried out (before the addition of the respective blowing agents) at high peripheral speeds (formation of the thread-like effect).
    Equipment used:
    [0089] IKA “Eurostar Power Control” - Vise. 6000 (speed range up to 6000 rpm) with IKA R 1402 Dissolve disc.
    [0090] For the dispersion of EDAB - DOPO, respectively ΤΕΡΑ 32/37
    PDOPO in the polyol component, high intensity ultrasound can be an improved alternative to the use of a rotor - stator mixer.
    [0091] Ultrasonic preparation of solids in liquids has been proven to be more effective than other high shear mixing methods ( 14 ). At appropriate energy levels, ultrasound can achieve a particle size reduction of one or two quantities.
    [0092] Efficiency of highly dispersed submicron particle size flame retardants (0.1 to 1.0 μιτι is discussed by Levchik ( 15 )
    Description of chemicals
    Petol PM 500 - 3F Mannich - Polyether Polyol; OH-No.480 - 520; f = 3.0 - 3.5; aim. 5000-11000 mPa s (25 ° C)
    Rokopol RF- 551 Sorbitol-based rigid polyether polyol; OH-No. 400 - 440; f = about 4.5; aim. 3000 - 5000 mPa s (25 ° C).
    Stepanpol PS-2352 Rigid aromatic polyester polyol (based on o-phthalate-
    diethylene glycol); OH-No. about 240; f = 2.0; aim. 3000 mPa s (25 ° C)
    Dabco DC 193 Rigid foam silicone surfactant Dabco TMR-2 Blocked, amine based trimerization catalyst Polycat 9Polycat 41Polycat 77Kitane 20 AS Tris (dimethyl aminopropyl) amine; blowing catalystTriazine derivative; pentamethyl dipropylene triamine trimerization catalyst: blowing catalyst / gel Emulsifier / compatibilizer for foam blown from pentaneSolkane 365mfc / 227eaflammable HFCs; 227ea = 93: 7; BP. 30 ° C; classified as not Pentane n - Pentane; BP. 36 ° C Desmodur 44 V 20 L PMDI; f = about 2.7; aim. 160 - 240 mPa s (25 ° C) Desmodur 44 V 40 L PMDI; f = about 2.9; aim. 350 - 450 mPa s (25 ° C)
    Test results:
    [0093] The B2-burner tests were performed approximately one week after defoaming.
    33/37
    1. Sandwich. Panel (SP):
    [0094] All samples of sandwich panels prepared were of high macroscopic quality, that is, very fine and regular cell structure. They did not shrink within the shelf life of approximately four to five weeks after preparation.
    [0095] There were no flame drips in exposure to fire.
    Formulations for the production of batch panel (HCF blowing agent 365mfc / 227ea) with TCPP as a flame retardant have been specified as a reference mark.
    [0096] The formulation containing 3.0 parts by weight of 365mfc / 227ea blown EDAB-DOPO (comparing formulation SP-12 with 365mfc / 227ea versus formulation SP-10 with TCPP gave similar results with respect to flame height, and flame extinction, demonstrating the efficiency of EDAB-DOPO in SP formulations.
    Sandwich panel (SP) - Solkane 365 mfc / 227 ea
    SP-10 SP-12 Rokopol RF-551 10.0 10.0 Stepanpol OS 2352 40.0 40.0 TCPP 15.0 0.0 Dabco-TMR-2 2.5 2.5 Polycat 77 0.45 0.45 Polycat 41 0.15 0.15 Dabco DC 193 2.0 2.0 Kitane 20 AS 0.0 0.0 Water 0.50 0.5 EDAB - DOPO 0 3.0 Solkane 365 mfc / 227 ea 10 10.0 index 250 250 Desmodur 44 V 40 L (PMDI; f = about 2.9) 101 101.0
    Foam structure (very fine and regular = very good e.g. e.g. Flame height (cm) 13-14 16-17 flame extinguishes after 15s focusing more x s. x = 0-1 x = 0- 1 Density (kg / cm 3 ) 39.2 41.2
    [0097] HFC 365 mfc / 227 eA was used for sandwich panels in
    34/37 case of batch production while pentane is standard for continuous production.
    [0098] Other works indicate that EDAB - DOPO respectively ΤΕΡΑ PDOPO could need the synergism of an efficient intumescent carbonized former as expandable graphite in combination with an efficient carbonaceous former as pentaerythritol to be efficient in pentane formulations.
    [0099] From the individual point of the project, the application of EDAB - DOPO respectively ΤΕΡΑ - PDOPO in combination with effective intumescent carbonaceous carbonizers, such as expandable graphite and pentaerythritol, has a pronounced effect in reducing smoke from burning the sandwich panel ( compared to the application of TCPP). The quantitative results of the density of concentrated smoke must be obtained from cone calorimetry (CC).
    2. Spray foam (SPF):
    [0100] All the spray foam samples prepared were of high macroscopic quality, ie a very fine and regular cell structure. No shrinkage was noted within the shelf life of approximately four weeks after preparation.
    [0101] There were no drips on fire.
    [0102] Spray foam formulations (blowing agent HFC 365mfc / 227ea) with TCPP as flame retardants have been specified as a reference mark.
    Spray foam (SPF) - Solkane 365 mfc / 227 ea
    Product SPF-11 SPF-17 SPF-18 SPF-19 SPF21 Petol PM 500-3F 43.0 43.0 43.0 43.0 43.0 Stepanpol OS 2352 31.0 31.0 31.0 31.0 31.0 TCPP 10.0 0 0 0 0 Dabco DC 193 3.0 3.0 3.0 3.0 3.0 Dabco TMR 2 2.00 2.0 2.0 2.0 2.0 Polycat 9 0.85 0.85 0.85 0.85 0.85 Polycat 41 0.15 0.15 0.15 0.15 0.15 Water 1.0 1.0 1.0 1.0 1.0 EDAB-DOPO 0 3.0 0 6.0 0
    35/37
    TEPA-PDOPO 0 0 3.0 0 0 Solkane 365 mfc / 227 ea 10.0 10.0 10.0 10.0 10.0 Desmodur 44 V 20 L (PMDI; f = ca, 2.7) 0 0 0 0 0 Desmodur 44 V 40 L (PMDI; f = about 150 150 150 150 150 2.9) index 175 175 175 175 175
    Very fine and regular foam structure = very
    good v.g12.5- vg vg. e.g. v.g · Flame height (cm)Extinguishes the flame after 15s plus x 13.5 14.5-15 15-16 14 <20 sec. x = 1 x = 3 x = 4 x = 1 x = 9 Density (kg / m 3 ) 40 43.1 41.7 41.4 43.7
    [0103] The reference formulation is SPF-11 (TCPP; index 175). It shows surprising results.
    [0104] SPF 11 flame test results were excellent due to the high TCPP content and / or higher PMDI content, which results in a higher PIR content in the foam (and therefore higher carbonized formation on fire exposure) ).
    [0105] Acceptable results with EDAB-DOPO respectively TEPAPDOPO were achieved with formulations SPF -17 to SPF-19 (3.0 respectively, 6.0 parts of EDAB-DOPO, respectively, TEPA-PDOPO. Compare the results against the SPF- blind test 21.
    [0106] It is remarkable and unexpected that the doubling of the amount of EDAB-DOPO, respectively TEPA-PDOPO, does not have a significant effect on the height of the flame and the extinction of the flame.
    Lu, S.-H., Hamerton, I. Progress in Polymer Science 2002 27 (8), 16611712.
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    b) Doering, M. et al. Ger. Often. A7.2010 102009035301 ', c) Buysch, H.J. et al Ger. Often. 1996, 19505352 ', d) Saito T. Patent US 1972 3702878
    a) Shieh, J. Y .; Wang, C.-S. Polymer 2001, 42, 7617; b) Dittric, U .; Just, B .; Doering, M .; Ciesielski, M. US Patent Application Publication 2005, US
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    a) Koenig, A .; Kroke, E. From Polymers for Advanced Technologies 2011, 22, 5; b) Zhao, X. Huaxue Yanjiu Yu Yingyong 2000, 12, 648.
    Schaefer, A., Seibold, S., Lohstroh, W., Walter, O., Doring, M. Journal of Applied Polymer Science 2007, 105 (2), 685-696.
    a) Beletskaya, I.P .; Neganova, E.G .; Veits, Y.A. Russian Journal of Organic Chemistry, 2004, 40,1782; b) Sponton, M .; Lligadas, G .; Ronda, J.C .; Galla. M .; Cadiz, M. Polymer Degradation and Stability 2009, 94, 1693.
    a) Lindner, B .; Kammerer, F .; Kohl, C. PCT International Application 2011, WO 2011000457A120110106 b) Saito, T .; Kim, S.H .; Kim, J.S .; Park, J.H. Jpn. Kokai Tokkyo Koho 2007, JP 2007091606A20070412] c) Yun, K.K .; Kim, Y.C .; Choi, T.K .; Park, LS. Repub. Korea 1999, KR 199102 B1 1999061; d) Wang, C.S .; Hsieh, C.Y .; Lin, C.Y. Jpn. Kokai Tokkyo Koho 2003, JP 2003105058 A 2003040; e) Feng, L .; Tang, A .; Xu, Z .; Li, S. Faming Zhuanil Shenging Gongkai Shuomingshu 2007 CN 100999 145 A 2000707 18; f) Salto, T; Kim, S.H .; Kim, J.S .; Park, J.H Jpn. Kokai Tokkyo Koho 2006, JP 2006328100 A 20061207. g) Kanno, T., Sugata, Y., Yanase, H., Shigehara, K., PCT international application. 2006 WO 2006126393 A1 20061130. h) Kerenyi, A .; Balassa, A .; Kortvelyesi, T .; Lu-danyi, K .; Keglevich, G. Transition Metal Chemistry 2008, 33, 459; i) Keglevich, G., Szelke, H., Kerenyi, A., Kudar, V., Hanusz, M., Simon, K., Imre, T., Ludanyi, K. Tetrahedron Asymmetry 2005 76 (24), 4015 -4021; j) Abrányi-Balogh, P .; Keglevich, G. Synth. Comm. 2011, 41, 1421-1426;
    k) Ujj, V .; Czugler, M .; Schindler, J .; Fogassy, E .; Keglevich, G. Magyar Kemiai Folyoirat, Kemiai Kozlemenyek 2010,116, 31.
    b) Jung, G. C; Hyeon, N .; Park, I. G .; Yoo, J. H .; Hyun, A. R .; Jung, Y. H. Repub. Korean Kongkae Taeho Kongbo 2008, KR 2008091036 A 20081009] a) Hinohara, A .; Hayashi, T .; Nogi, S .; Ikemoto, K .; Saito, T. Jpn. Kokai Tokkyo Koho
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    2009, JP 2009266663 A 20091112] c) Uchida, O., Sato, K. Jpn. Kokai Tokkyo Koho 1998 JP 10203028 A 19980804.
    a) Zich, T .; Artner, J .; Mehofer B .; Doring, M .; Ciesielski, M .; Zwick, G .; Rakotomalala, M. 2011, AT 508468 A1; b) Rakotomalala, M; Wagner, S .; Zevaco, T .; Doring, M. Heterocycles 2011, 83, 743-753
    a) Gaan, S., Rupper, P., Salimova, V. POLYMER DEGRADATION AND STABILITY 2009 94 (7), 1125-1134; b) Deo, Η. T .; Patel, N. K .; Patel, B.K. J. of Engineered Fibers and Fabrics 2008, 3 (4), 23-38. c) Leu, T.-S .; Wang, C.-S. J. of Applied Polymer Science 2004, 92 (1), 410-417. d) Nguyen, C; Kim, J. Polymer Degradation and Stability 2008, 93, 1037-1043. e) Lewin, M. J. of Fire Sciences 1999, 17 (1), 3-19.
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    a) Risk Assessment Report on Tris (2-Chlor-propyl) Phosphate (TCPP), Scientific Committee on Health and Environmental Risks, Environmental Part 2007, EINECS No. 237-158-7. b) Gupta, R. Toxicology of Organophosphate and Carbamate compounds 2006, ISBN: 978-0-12-088523-7, Elsevier Inc. Burlington, Mass.
    Stein, H.N .: The Preparation of Dispersions in Liquids, New York 1995, p.62 f.
    15. Levchik, S.V. jlntoduction to Flame Retardancy and Polymer Flammability, in: Morgan.A.B. and Wilkie.C.A. (Eds.): Flame Retardant Polymer Nanocomposites, Hoboken / NJ 2007, p. 20 ff. (ibid, other references).
    权利要求:
    Claims (20)
    [1]
    1. Phosphonamidate compound characterized selected from the group consisting of:
    AA-DOPO: 6- (allylamino) -6H-dibenzo [c, e] [1,2] oxaphosphinine 6-oxide;
    PB-DOPO: 6.6 '- (piperazine-1,4-diyl) bis (6H-dibenzo [c, e] [1,2] oxaphosphinine 6oxide);
    PDAB-DOPO: 6,6- (1,4-phenylenebis (azanediyl)) bis (6Hdibenzo [c, e] [1,2] oxaphosfinine 6-oxide);
    TMSPA-DOPO: 6 - ((3- (methoxysilyl) propyl) amino) -6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide;
    a compound according to formula (I)

    R 1 = H, (C1-8) alkyl, (C1-8) alkoxy, (C1-8) amine, OH, SR (R = H, alkyl), O-metal
    R 2 = H, (C1-8) alkyl, (C1-8) alkoxy, (C1-8) amine, OH, SR (R = H, alkyl), O-metal
    R 3 = H, (C1-8) alkyl, (C1-8) alkoxy, (C1-8) amine, OH, SR (R = H, alkyl), O-metal
    Y = NH, portion N-DOPO, O, S
    X = NH, NR (R = alkyl) n = 1-8 m = I-8 portion DOPO =

    a compound according to formula (II)
    Petition 870190047929, of 05/22/2019, p. 11/51
    [2]
    11/11

    X = NR (R = H, alkyl),
    Y = N-DOPO portion, CH 2 Z = NR (R = H, alkyl), m = 0-8 n = 0-8 DOPO portion =

    a compound according to formula (III)

    Y = NR [R = H, alkyl, DOPO portion, PO (OR) 2 (R = alkyl or aryl), PO (OR 1 ) R 2 (R 1 = alkyl or aryl, R 2 = alkyl or aryl), COLOR (R = O-alkyl, NH 2 , NH-alkyl, N (alkyl) 2 , alkyl or aryl), carbonyl, SiR 3 (R = alkyl, alkoxy)], n = 0-100 and mixtures thereof, a compound according to formula (IV)
    Petition 870190047929, of 05/22/2019, p. 12/51
    [3]
    3/11

    Υ = NR [R = H, alkyl, DOPO portion, PO (OR) 2 (R = alkyl or aryl), PO (OR 1 ) R 2 (R 1 = alkyl or aryl, R 2 = alkyl or aryl), COLOR (R = O-alkyl, NH2, NH-alkyl, N (alkyl) 2, alkyl or aryl), carbonyl, S1R3 (R = alkyl, alkoxy)], n = 0-100 and mixtures thereof, where AA- DOPO, PB-DOPO, PDAB-DOPO, and TMSPA-DOPO, are defined as follows:

    6- (allylamino) -6Hdibenzo [c, e] [1,2] oxaphosphinine 6oxide (AA-DOPO)

    6.6 '- (piperazine-1,4-diyl) bis (6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide) (PB-DOPO)
    Petition 870190047929, of 05/22/2019, p. 13/51
    [4]
    4/11

    6.6 '- (1,4-phenylenebis (azanediyl)) bis (6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide) (PDAB-DOPO)


    I
    6 - ((3- (trimetoxysilyl) propyl) amino) 6H-dibenzo [c, e] [1,2] oxaphosphinine 6oxide (TMSPA-DOPO).
    2. Phosphonamidate compound according to claim 1, characterized by the fact that the compound is not AA-DOPO or PDAB-DOPO.
    Phosphonamidate compound according to claim 1, characterized by the fact that the compound is according to formula (III) and is EDAB-DOPO defined as:

    6.6 '- (ethane-1,2-dilbis (azanediyl)) bis (6H-dibenzo [c, e] [1,2] oxaphosphinine 6-oxide) (EDAB-DOPO)
    Petition 870190047929, of 05/22/2019, p. 14/51
    [5]
    5/11
    4. Method of improving the flame resistance of a polymeric material, characterized by the fact that it comprises the step of adding a first amount of a phosphonamidate, as defined in claim 1, or a mixture thereof, as a flame retardant substance for a second amount of said polymeric material.
    5. Method according to claim 4, characterized by the fact that said flame retardant substance is selected from the group consisting of:
    AA-DOPO,
    PB-DOPO, EDAB-DOPO
    [6]
    6.6 '- (ethane-1,2-dilbis (azanediyl)) bis (6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide) (EDAB-DOPO)
    DEA-DDOPO, which is a compound according to formula (II),
    HO
    6 - (((2-hydroxyethyl) (2 - (((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) oxy) ethyl) amino) -6H-dibenzo [c, e] [ 1,2] 6-oxide oxafosfinine (DEA-DDOPO) and mixtures thereof.
    Petition 870190047929, of 05/22/2019, p. 15/51
    6/11
    6. Method according to claim 4, characterized by the fact that said flame retardant substance is selected from the group consisting of:
    AA-DOPO,
    EDAB-DOPO

    6.6 '- (ethane-1,2-dilbis (azanediyl)) bis (6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide) (EDAB-DOPO) and
    a mixture comprising DEA-TDOPO, which is a compound according to formula (II), and DEA-DDOPO

    6.6 '- ((((((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) azanediyl) bis (ethane-2,1-diyl) bis) (oxy)) bis ( 6Hdibenzo [c, e] [1,2] oxaphosfinine 6-oxide) (DEA-TDOPO)
    Petition 870190047929, of 05/22/2019, p. 16/51
    [7]
    7/11

    6 - ((hydroxyethyl) (2 - ((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) oxy) ethyl) amino) -6H-dibenzo [c, e] [1, 2] oxafosfinine 6-oxide (DEA-DDOPO)
    Method according to claim 4, characterized in that said flame retardant substance comprises DEA-DDOPO

    6 - (((2-hydroxyethyl) (2 - (((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) oxy) ethyl) amino) -6H-dibenzo [c, e] [ 1.2] 6-oxide oxaphosphinine (DEA-DDOPO)
    [8]
    Method according to claim 4, characterized in that said flame retardant substance is mixed with a polyurethane foam formulation or added to a polyurethane foam as a post-treatment.
    [9]
    Method according to claim 4, characterized in that said flame retardant substance is mixed with a flexible polyurethane foam formulation or added to a flexible polyurethane foam as a post-treatment, wherein the foam Flexible polyurethane or foam formulation is a polyether or polyester flexible polyurethane foam, or a combination thereof.
    Petition 870190047929, of 05/22/2019, p. 17/51
    11/11
    [10]
    10. Polymeric material with improved flame resistance, characterized by the fact that it comprises a flexible polyurethane foam containing an amount of 1% to 30% by weight per 100 parts of polyol of a flame retardant additive selected from a phosphonamidate compound as defined in claim 1.
    [11]
    11. Polymeric material with improved flame resistance, characterized by the fact that it comprises a rigid polyurethane foam containing an amount of 1% to 30% by weight per 100 parts of polyol of a flame retardant additive selected from a phosphonamidate compound as defined in claim 1, and optionally also comprising a synergist.
    [12]
    12. Method of making a phosphonamidate as defined in the claim
    1, characterized by the fact that this method comprises the steps of:
    (a) dissolving DOPO and an amine in a solvent to form a mixture, (b) optionally cooling the mixture below about 10 ° C, (c) adding tetrachloromethane to the mixture at a rate such that (i) the reaction temperature do not exceed about 30 ° C, or if the mixture has been cooled, (ii) such that the reaction temperature does not exceed about 20 ° C, (d) let the mixture return to about 25 ° C, and stir.
    [13]
    13. Method of making a phosphonamidate according to claim 1, characterized by the fact that this method comprises the steps of:
    (a) dissolving DOPO and an amine in a solvent to form a mixture, (b) optionally cooling the mixture below about 10 ° C, (c) adding trichloroisocyanuric acid to the mixture at a rate such that (i) the temperature of reaction does not exceed about 30 ° C, or if the mixture has been cooled, (ii) such that the reaction temperature does not exceed about 20 ° C, (d) let the mixture return to about 25 ° C, and stir.
    [14]
    14. Method of improving the flame resistance of a substance, characterized by the fact that it comprises the addition of the phosphonamidate compound as defined in claim 1 to the substance.
    Petition 870190047929, of 05/22/2019, p. 18/51
    9/11
    [15]
    15. Method of improving the flame resistance of a polyurethane foam, the method characterized by the fact that it comprises the addition of the phosphonamidate compound as defined in claim 1 to the polyurethane foam.
    [16]
    16. Phosphonamidate compound according to claim 1, characterized by the fact that the compound is selected from the group consisting of:
    AA-DOPO: 6- (allylamino) -6H-dibenzo [c, e] [1,2] oxaphosphinine 6-oxide;
    PB-DOPO: 6.6 '- (piperazine-1,4-diyl) bis (6H-dibenzo [c, e] [1,2] oxafosfinine 6oxide); and
    PDAB-DOPO: 6.6 '- (1,4-phenylenebis (azanediyl)) bis (6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide).
    [17]
    17. Phosphonamidate compound according to claim 1, characterized by the fact that the compound is according to formula (I) and is selected from the group consisting of:
    TESPA-DOPO:
    6 - ((3- (triethoxysilyl) propyl) amino) -6Hdibenzo [c, e] [1,2] oxaphosphinine 6-oxide

    TMSPA-DOPO: 6 - ((3- (trimethoxysilyl) propyl) amino) -6H-dibenzo [c, e] [1,2] oxafosfinine 6-oxide.
    [18]
    18. Phosphonamidate compound according to claim 1, characterized by the fact that the compound is according to formula (II) and is selected from the group consisting of:
    EAB-DOPO: 6- (2 - ((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) amino) ethoxy) -6H-dibenzo [c, e] [1,2] oxafosfinine 6-oxide
    Petition 870190047929, of 05/22/2019, p. 19/51
    11/10

    DEA-DDOPO: 6 - ((2-hydroxyethyl) (2 - ((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin6-yl) oxy) ethyl) amino) -6H-dibenzo [c , and] [1,2] oxaphosphinine 6-oxide

    [1,2] oxafosfinin-6yl) azanediyl) bis (ethane-2,1-diyl)) bis (oxy)) bis (6Hdibenzo [c, e] [1,2] oxafosfinine 6-oxide)
    [19]
    19. Phosphonamidate compound according to claim 1, characterized by the fact that the compound is according to formula (III) and is selected from the group consisting of:
    EDAB-DOPO: 6.6 '- (ethane-1,2-dilbis (azanediyl)) bis (6H-dibenzo [c, e] [1,2] oxaphosphinine 6-oxide)
    Petition 870190047929, of 05/22/2019, p. 20/51
    11/11

    TDETA-DOPO: 6 - ((3 - ((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6-yl) (2 - ((6-oxide-6Hdibenzo [c, e] [1 , 2] oxafosfinin-6-yl) amino) ethyl) amino) propyl) amino) -6H-dibenzo [c, e] [1,2] oxafosfinin 6-oxide

    [20]
    20. Phosphonamidate compound according to claim 1, characterized by the fact that the compound is according to formula (IV) and comprises:
    TEPA-PDOPO: 6.6 '- ((((((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) azanediyl) bis (ethane-2,1-diyl)) bis (( 2 - ((6-oxide-6H-dibenzo [c, e] [1,2] oxafosfinin-6yl) amino) ethyl) azanediyl)) bis (6Hdibenzo [c, e] [1,2] oxafosfinine 6-oxide)
    类似技术:
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    PL2557085T3|2015-04-30|
    JP6082393B2|2017-02-15|
    WO2013020696A3|2013-05-10|
    MX2014001547A|2015-03-20|
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    CA2844567C|2018-05-08|
    EP2557085A1|2013-02-13|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-30| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-09-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-08| 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 06/08/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/08/2012, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11176861.0|2011-08-08|
    EP11176861.0A|EP2557085B1|2011-08-08|2011-08-08|Novel phosphonamidates - synthesis and flame retardant applications|
    PCT/EP2012/003354|WO2013020696A2|2011-08-08|2012-08-06|Novel phosphonamidates-synthesis and flame retardant applications|
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