• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to the use of aryliodonium and / or arylsulfonium salts of the tetrakis (perfluoro-t-butyloxy) aluminate anion of the following formula (1): as a cationic photoinitiator in the polymerization of cationically polymerizable monomers.
    公开号:AT517626A1
    申请号:T577/2015
    申请日:2015-09-02
    公开日:2017-03-15
    发明作者:Liska Robert；Ing Daniel Bomze Dipl；Krossing Ingo；Knaack Patrick
    申请人:Technische Universität Wien；Albert-Ludwigs-Universität Freiburg；Polymer Competence Center Leoben Gmbh；
    IPC主号:
    专利说明:

    The present invention relates to the use of novel aryliodonium and sulfonium salts as photoinitiators for cationic photopolymerization.
    STATE OF THE ART
    For some years, the use of onium salts as photoinitiators for cationic photopolymerization has proven itself, with iodonium and sulfonium salts among the most common initiators. Such a cationic photoinitiator is also referred to as a photoacid generator or generator, which upon irradiation with (usually ultraviolet) light in an excited state in which then a bond is split homo or heterolytically, followed by other molecules in the reaction mixture, preferably from the cationic monomers to be polymerized, a hydrogen atom is abstracted to form a so-called. Photoacid with the anion of the iodonium or sulfonium cation. The latter is preferably a very strong acid, e.g. a superacid, which in turn protonates a monomer to initiate cationic polymerization. The iodonium or sulfonium cations are therefore usually present in these salts in combination with an anion corresponding to a very strong acid, which should also have low nucleophilicity.
    WO 99/12938 A1 discloses anions of the following formula in which
    Mi represents a transition metal or a group III, IV or V element; p = 1 or 2; Each X is independently O, S or NR5R6;
    R 1 and R 2 are each independently H, halide or C 1-4 -alkyl; Each R3 is independently H, Ci-4-alkyl or C4-2o-aryl; Each R 4 independently is C 1-10 alkyl, C 1-10 alkoxide or C 4-30 aryloxide; R5 and Re are each independently H or Ci-20-alkyl; a and c are each independently an integer from 0 to 3; a + b = 3; c + d = 3; m is an integer from 2 to 8; and n is an integer of 0 to 4; with the proviso that at least one of a and c is not equal to 0.
    As a concrete compound of the huge number of possible combinations, lithium tetrakis (perfluoro-t-butyloxy) aluminate, LiAl (PFTB) 4, is disclosed and synthesized and characterized in Example 17 therein. However, this salt has not been tested for electrical or other properties and therefore represents only one of many actually synthesized examples of the invention there.
    In general, all the anions of the above formula disclosed in WO 99/12938 A1 should be suitable as electrolytes for electrochemical devices due to their good electrical conductivity, it being possible to use as counterion M a metal cation, a phosphonium cation, an ammonium cation or a sulfonium cation.
    Subsequently, by I. Raabe, A. Reisinger and I. Krossing, "Efficient syntheses of Li [Al (ORF) 4], Ag [Al (ORF) 4] (RF = C (CF 3) 3, C (H ) (CF 3) 2, C (CH 3) (CF 3) 2)) and [H (OEt 2) 2] + [Al (OC (CF 3) 3) 4] '", HW Roesky and Dietmar K. Kennepohl (eds), Experiments in Green and Sustainable Chemistry, Wiley VCF, pp. 131-144 (2009), discloses a more efficient production process for lithium tetrakis (perfluoro-t-butyloxy) aluminate.
    The aim of the invention was therefore the development of new photoinitiators, which are characterized by better properties than the known initiators.
    DISCLOSURE OF THE INVENTION
    This object is achieved by the present invention by providing the novel use of aryliodonium and / or arylsulfonium salts of the tetrakis (perfluoro-t-butyl-oxy) aluminate anion of the following formula (I):
    (I) as a cationic photoinitiator in the polymerization of cationically polymerizable monomers.
    In the course of their investigations, the inventors have not only found that the anion of the formula (I) known from WO 99/12938 A1-irrespective of its electrical conductivity-is also suitable for cationic photoinitiators when mixed with common iodonium or sulfonium Combinations is combined, as the inventors had suspected, but surprisingly also found that these new initiators are clearly superior to common cationic iodonium and sulfonium salt photoinitiators in several respects, as the later examples prove.
    In preferred embodiments of the invention, the photoinitiator used is either diphenyliodonium tetrakis (perfluoro-t-butyloxy) aluminate of the following formula (II):
    (II) or phenylthio or 4-diphenylsulfoniophenylthio-substituted triphenylsulphonium tetrakis (perfluoro-t-butyloxy) aluminate of the following formula (III):
    (III) used as a photoinitiator, since these compounds have already delivered excellent results. Nevertheless, it is believed that the advantages attributable to the tetrakis (per-fluoro-t-butyloxy) aluminate anion of formula (I) will be achievable with the other aryliodonium and sulfonium cations commonly used in the art The present invention is not intended to be limited solely to the compounds of the formulas (II) and (III).
    The compound mixture of the unsubstituted triphenylsulfonium cation and the two substituted with phenylthio or 4-Diphenylsulfoniophenylthio variants thereof is evident from the preparation method described in detail later, especially since the reactant triphenylsulfonium only as a mixture of these three substitution variants (in aqueous solution) of Sigma Aldrich in Trade is available and a separation of the three products would be possible only at great expense. Due to the excellent effectiveness of the mixture, such a separation has therefore been omitted so far.
    The cationic polymerization can be carried out according to the present invention in the usual and therefore preferably as a ring-opening polymerization, preferably as mono- or polyfunctional epoxies (oxiranes), thiiranes (episulfides), oxetanes, lactams, lactones, lactide, glycolide, tetrahydrofuran or as cationically polymerizable monomers Mixtures thereof are used, in particular one or more polybasic epoxides, which represent by far the most common cationically polymerized monomers, or as non-cyclic monomers, for example also vinyl ethers.
    The reaction mixture to be polymerized may comprise one or more further components selected from additional initiators, additional monomers, sensitizers, stabilizers, modifiers, regulators, solvents, fillers, dyes, pigments and mixtures thereof, in a manner known per se, to meet the specific requirements to meet the respective polymers.
    In preferred embodiments, the mixture further comprises at least one thermal radical initiator, so that the polymerization reaction can be carried out as a frontal polymerization, as known to the person skilled in the art.
    In a second aspect of the invention, the present invention provides the new substance diphenyliodonium tetrakis (per-fluoro-t-butyloxy) aluminate of the formula (II), which is characterized in more detail in the examples.
    (II)
    BRIEF DESCRIPTION OF THE DRAWINGS
    The figures show comparisons between photo-DSC measurements according to the invention and known initiators, including FIGS. 1 and 2 with respect to tmax, FIGS. 3 and 4 with respect to t95%, and FIGS. 5 and 6 with respect to area, while Figs. 7 and 8 show the recorded DSC curves.
    EXAMPLES
    The present invention will be concretely described by the following examples, which, however, are given only by way of illustration of the practicability of the invention and are not intended to be limiting.
    example 1
    Preparation of diphenyliodonium tetrakis (perfluoro-t-butyloxy) aluminate (II) (DPITTA)
    (II)
    The entire reaction was carried out under argon atmosphere and in the orange light laboratory. Li [Al (OC (CF 3) 3) 4] (1.5622 g, 1.602 mmol, prepared) was initially charged in 35 ml of CH 2 Cl 2, whereby no homogeneous solution could be obtained, iodonium chloride (0.55796 g, 1.762 mmol) was added Suspended 25 ml of CH 2 Cl 2 (DCM) and transferred in the weak countercurrent of argon in the reaction flask. The already turbid solution turned milky white. After 5 h, an additional 20 mL of CH 2 Cl 2 was added to dilute the reaction mixture and the reaction was stirred overnight. The reaction mixture was then transferred to a separatory funnel and extracted 3 times with 40 ml of water. The organic phase was filtered through silica gel and the solvent was evaporated, followed by several hours of drying in a fine vacuum. The product (1634.8 mg, 82% of theory) was obtained as a white solid. 1H-NMR (200 MHz, CD 2 Cl 2) δ (ppm): 7.58-7.70 (m, 2H), 7.79-7.89 (m, 1H), 7.94-8.03 (m, 2H). 13 C-NMR (200 MHz, CD 2 Cl 2) δ (ppm): 111.8 (Cl), 121.7 (q, C (CF 3), J = 291.5 Hz), 134.4 (m), 135.1 (p), 135.5 (0). 27AI NMR (400 MHz, CD 2 Cl 2) δ (ppm): 34.7. TLC: Rt (CH 2 Cl 2) = 0.41 ATR-IR: 1470, 1449, 1351, 1296, 1273, 1239, 1205, 1165, 966, 831, 735, 724, 673, 548, 571, 560, 536 cnr1.
    Mp: 171-174 ° C (CH 2 Cl 2)
    Example 2
    Preparation of triphenylsulfonium tetrakis (perfluoro-t-butyloxy) aluminate, diphenyl- (4-phenylthio) phenylsulfonium tetrakis (perfluoro-t-butyloxy) aluminate and diphenyl-4 - [(4-diphenylsulfonio) phenylthio] phenylsulfonium tetrakis (perfluoro -t-butyloxy) aluminate (III) (TASTTA)
    The entire reaction was carried out under argon atmosphere and in the orange light laboratory. Li [Al (OC (CF 3) 3) 4] (1.588 g, 1.626 mmol) was placed in the flask and treated with 120 ml CH 2 Cl 2, whereby no completely homogeneous solution could be obtained. A 45% solution of triphenylsulfonium chloride in water, which according to the supplier (Sigma Aldrich) contained the three compounds with the substituents R shown above in a molar ratio of 1: 6: 10, was added via syringe through a septum into the flask , The aqueous phase spontaneously turned white and solidified after a short time. After 5 hours 15 ml of water were added, the solid went into solution. The reaction was stirred overnight. The reaction mixture was then transferred to a separatory funnel and extracted 3 times with 40 ml of water. The organic phase was filtered through silica gel and the solvent was evaporated, followed by several hours of drying in a fine vacuum. The product (1490.6 mg, 75% of theory) was obtained as a white solid. 1H-NMR (200 MHz, CD 2 Cl 2) δ (ppm): 7.93-7.82 (m, xH), 7.80-7.70 (m, 2H), 7.69-7.30 (m, 5H).
    An exact assignment was not possible because of the strong overlay. For the same reason, only relative integrals can be specified. 27AI NMR (400 MHz, CD 2 Cl 2) δ (ppm): 34.7. TLC: Rf (CH 2 Cl 2) = 0.76 and 0.42 ATR-IR: 1574, 1478, 1450, 1351, 1296, 1274, 1239, 1208, 1167, 1065, 968, 829, 817, 744, 725, 682, 559, 536 cm'1.
    Mp: 164-167 ° C (CH 2 Cl 2)
    Examples 3 to 6. Comparative Examples 1 to 6
    Reactivity tests of the new compounds as photoinitiators
    The novel compounds of the formula (II), DPITTA, and formula (III), TASTTA, were investigated by means of Photo DSC with two different cationically polymerizable monomers, CE and BADGE, for their reactivity as cationic photoinitiator and that with commonly used initiators, namely (4-octyloxyphenyl) - (phenyl) iodonium hexafluoroantimonate (IOC-8 SBF6), (4-isopropylphenyl) (4'-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate (PFPB) and CYRACURE® UVI 6976 ( see the overleaf illustrations). All work was carried out under light protection (orange light).
    monomers:
    CE BADGE
    initiators:
    For each formulation, 1 mol% of initiator, based on epoxy groups, was weighed out and stirred magnetically at room temperature until complete dissolution. Subsequently, 10 mg of the reaction mixtures were weighed into open aluminum DSC dishes.
    The DSC measurements were performed on a NETSCH DSC 204 F1 Phoenix under nitrogen atmosphere at 50 ° C, irradiation with an Omnicure 2000 mercury vapor lamp with a wavelength filter of 320-500 nm. The intensity of the UV light was 3 W / cm 2, the irradiation time was 5 minutes. All measurements were performed in triplicate and the averaged values are given in the tables below for each monomer.
    Table 1: CE
    Table 2: BADGE
    In it, tmax indicates the time to reach the maximum of heat generation (in s) and is thus a measure of how fast the gel point and thus a high initial strength are reached. Here are short times desirable. t95% is the time (in s) after which 95% of the total heat of reaction has been released, and is thus a measure of the reaction rate (again, low values are advantageous).
    And area is the area under the curve and indicates the heat of reaction released in the polymerization (in J) per gram of the particular formulation. This is therefore a measure of the reaction conversion, which is why the highest possible values should be achieved here.
    For a better overview, the results given in Tables 1 and 2 are also shown graphically for each of the three reaction parameters individually in Figures 1 to 6, i. In Figures 1 and 2, the results for tmax, in Figures 3 and 4 those for% and in Figures 5 and 6 those for area.
    From Figure 1, where the results for tmax are plotted using the monomer CE, it is clear that TASTTA, the initiator of formula (III), requires by far the shortest time to reach maximum heat generation, followed by DPITTA of the formula (II). Examples 3 and 4 according to the invention cut in this respect with 16 s and 11 s, respectively, better than all three initiators according to the prior art (17 s, 37 s, 73 s) - and sometimes even significantly.
    A similar picture is also shown in FIG. 2 for the BADGE monomer: Again, the TASTTA initiator from Example 6 requires the shortest time to reach tmax, in this case, however, with CYRACURE® UVI 6976 from Comparative Example 6 (both 25 s). and just ahead of DPITTA from example 5 (33 s). Significantly longer, in turn, required the two known initiators IOC8 (38 s) and especially PFPB (84 s).
    Figures 3 and 4 show the results for t95% for the two monomers. In the case of CE in FIG. 3, TASTTA from Example 4 according to the invention is again ahead (348 s), closely followed by IOC8 from Comparative Example 1 (350 s) and at a greater distance from DPITTA from Example 3 (504 s), UVI 6976 Comparative Example 3 (509 s) and again PFPB from Comparative Example 4 in the last position (540 s).
    In Fig. 4, however, the conditions are surprisingly completely different. With BADGE as monomer, DPITTA from Example 5 is far ahead (46 s), followed by TASTTA from Example 6 (171 s). Although the best known initiator was also in this case IOC8 from Comparative Example 4, in which it took more than five times as long with 242 s, until 95% of the total heat of reaction were released. Behind it are PFPB with 355 s (Comparative Example 5) and markedly beaten off in this case UVI 6976 from Comparative Example 6 (632 s). Similar to the results for te5% are also those for area, ie the area under the curve, which indicates the released heat of reaction and thus represents a measure of the conversion. As can be seen from FIG. 5, TASTTA from Example 4 precedes CE as the monomer, followed by IOC8 and UVI 6976 by two known initiators, which are still far off before DPITTA and PFPB. In contrast, in Fig. 6 for BADGE, DPITTA of Example 5 is clearly ahead, followed by IOC8, TASTTA and PFPB and finally UVI 6976 far behind.
    Thus, Figs. 1-6 clearly show that for each of the three measured parameters, one embodiment of the invention performs best, often with a large lead.
    Finally, referring to Figures 7 and 8, the two embodiments of the invention are described with the structurally similar known initiators, i. iodonium (FIG. 7) or sulfonium salts (FIG. 8) are compared on the basis of the DSC curves, in which the heat development (in mW / mg) is plotted as a measure of the rate of the polymerization reaction over time (in seconds).
    Both in FIG. 7, where DPITTA is plotted together with the two known iodonium ion-based initiators, IOC8 and PFPB, and in FIG. 8 for the sulfonium initiators TASTTA and UVI 6976, a similar picture appears The polymerization carried out according to the present invention starts much more rapidly and is substantially complete even after a much shorter time than using prior art initiators.
    Thus, Examples 3 to 6 according to the invention impressively confirm the superiority of the present invention over the prior art, which was by no means anticipated prior to the research of the inventors.
    权利要求:
    Claims (9)
    [1]
    1. Use of aryliodonium and / or arylsulfonium salts of the tetrakis (per-fluoro-t-butyloxy) aluminate anion of the following formula (I):

    (I) as a cationic photoinitiator in the polymerization of cationically polymerizable monomers.
    [2]
    2. Use according to claim 1, characterized in that the diphenyl-iodonium-tetrakis (perfluoro-t-butyloxy) aluminate of the following formula (II) is used as a photoinitiator:

    (II)
    [3]
    3. Use according to claim 1, characterized in that optionally substituted with phenylthio or 4-diphenylsulfoniophenylthio triphenylsulfonium tetrakis (perfluoro-t-butyloxy) aluminate of the following formula (III) is used as a photoinitiator:

    (III)
    [4]
    4. Use according to one of claims 1 to 3, characterized in that the cationic polymerization is carried out as a ring-opening polymerization.
    [5]
    5. Use according to claim 4, characterized in that mono- or polyfunctional epoxides (oxiranes), thiiranes (episulfides), oxetanes, lactams, lactones, lactide, glycolide, tetrahydrofuran or mixtures thereof are used as cationically polymerizable monomers.
    [6]
    6. Use according to claim 5, characterized in that one or more polyvalent epoxides is / are used as cationically polymerizable monomers.
    [7]
    7. Use according to one of claims 1 to 6, characterized in that the reaction mixture to be polymerized further comprises one or more components selected from additional initiators, additional monomers, sensitizers, stabilizers, modifiers, regulators, solvents, fillers, dyes, pigments and mixtures including thereof.
    [8]
    8. Use according to claim 7, characterized in that the reaction mixture further comprises at least one thermal-radical initiator and the polymerization reaction is carried out as a frontal polymerization.
    [9]
    9. diphenyliodonium tetrakis (perfluoro-t-butyloxy) aluminate of the following formula (II):

    (II)
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    法律状态:
    2019-03-15| PC| Change of the owner|Owner name: ALBERT-LUDWIGS-UNIVERSITAET FREIBURG, DE Effective date: 20190211 Owner name: TECHNISCHE UNIVERSITAET WIEN, AT Effective date: 20190211 |
    优先权:
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