• 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 titanocenes, in particular to the preparation of titanocenes of total f-ly, g RJ R (R, -O ^^ i - (^ NU) z ^ ".. ^ R5 R- * where RI-H, CH3, (CH ) s51; R2, Hz. R4, Rs - independently of each other mean: H, C1 ^ C7 alkyl, C2-C5 alkenyl, C2H40CH3, 'CH2M (CH3) 2, CH2M (| C2H40CHz) 2. CH ^ -NQo,; CeHs; 2-fu.ryl, 8XH3) 3, the pyrrole ring may be in the meta- or ortho-position to the Ti-C bond, which are used as photoinitiators for optical initiation of unsaturated compounds The goal is to create a new method of obtaining new titanocenes with a higher a Synthesis is carried out by the reaction of the corresponding titanocene dichlorides with a lithium difluoro-aromatic derivative. The obtained target products accelerate the curing by 300--400% and reduce the illumination time by 50-75%, which in turn leads to an improvement in the quality of photopolymers. LG
    公开号:SU1713438A3
    申请号:SU884356932
    申请日:1988-11-30
    公开日:1992-02-15
    发明作者:Хюзлер Ринальдо；Клингерт Бернд；Рембольд Манфред；Стайнер Эгинхард
    申请人:Циба-Гейги, Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing new titanocenes of the general formula
    (", (one)
    where CH3, (CH3) s31; R2, R3, R4. R5 is independently from each other H, C1-C7-alkyl, C2-C5 alkenyl, CH2CH20CH3, CH2M (CH3) 2.
    CH2N (CH2CH20CH3) 2.CHj-NQo; SbH5. ABOUT
    51 (SNS) h. and the pyrrole ring may be in the meta or para position to the Ti-C bond.
    The compounds passed according to the invention can be used.
    as photo initiators for light-initiating polymerization of unsaturated compounds.
    The purpose of the invention is to develop a method for producing new photoinitiators in a series of titanocenes with higher activity leading to an increase in the rate of curing of unsaturated compounds. : Preparation of intermediate.
    Examples 1-7.1 mol of 2,4-difluoroaniline and 1 mol of diketone (see Table 1) are heated for 1 hour in 1 liter of ethanol to reflux temperature. At the end of the reaction (control using thin-layer chromatography)
    the mixture is completely evaporated in vacuo and the residue is recrystallized from ethanol.
    Additional data are presented in table.1.
    Example 8.1 A mol of the compound according to Example 1 is formulated with POCl3 / dimethylformamide.
    The product obtained is reacted with PPSHCCHS), I (potassium butylate in tetrahyronofuran as solvent).
    The remaining data are presented in table.1.
    EXAMPLE 9.1 mol of the compound according to example 1 is reacted with CP350351 (CH3) 3.
    The data presented in Table. one.
    PRI me R 10. 129 g of 2,4-difluoroaniline and 136.1 g of 2,5-dimethoxytetrahydrofuran are heated in an autoclave for. 2 h to 260 ° C. After cooling, the reaction product is distilled with water vapor. The distillate is shaken with petroleum ether, the organic phase is separated, dried over sodium sulfate and evaporated in vacuo. 167 g of an almost colorless oil are obtained, which crystallizes after a short time.
    The data presented in Table. one.
    Example 11 To a solution of 0.1 mol of 1- (2,4-difluorophenyl) -2,5-dimethylpyrrole (product of example 1) was added dropwise a solution consisting of 18 g of 40% dystilamine in water (0.16 mol dimethylamine), 13.7 g of 35% formalin solution (0.16 mol of formaldehyde) and 15 ml of glacial acetic acid. The resulting suspension is stirred at room temperature until chromatographic analysis shows the end of the reaction. The basic pH is adjusted with a dilute sodium hydroxide solution, the product is added to the ether and washed with water. The crude product remaining after evaporation of the solution can be used for the next step or purified further by distillation.
    The remaining data are presented in Table. 2
    Examples 12-21. The compounds are prepared by the methods indicated in Example 11.
    The adducts used, molar equivalents, and reaction temperatures are listed in table. 2
    Examples ry 22 and 23. 0.26 mol specified in table. 3 pyrrole aldehyde, obtained as a result of the formylation of the corresponding pyrrole using POCl3 / dimethylformamide, is mixed in 400 ml of dry diethyl ether CO, 05 mol
    U AIH4 and the suspension are heated to reflux until thin layer chromatography indicates no adduct. After hydrolysis with an aqueous solution of magnesium sulfate, the ether phase is dried and evaporated, while the corresponding alcohol (hydroxymethylpyrrole) remains. It is mixed with a suspension of 0.2 mol of NaH in 100 ml of dry
    0 diethyl ether until three-layer chromatography shows the absence of alcohol. After that, 0.3 mol of methyl iodide is added and stirring is continued overnight. After washing with water, the ethereal solution is dried and evaporated. Crude methoxymethylpyrrole is purified by column chromatography (silica gel hexane - ethyl acetate).
    The remaining data is presented in
    0 tab. 3
    Example 24. 0.1 mol of aminomethylpyrrole from Example 11 is dissolved in 20 ml of ethanol and mixed with 0.1 mol of methyl iodide while cooling. After 30 min
    5, the salt is filtered off, washed with ethanol and 0.14 mol of CaHsONa in ethanol is added to the solution. The suspension is heated 4 days to reflux and then poured into water. The product is extracted
    0 diethyl ether and purified by chromatography on silica gel (hexane - ethyl acetate 9: 1).
    The remaining data are presented in table.3.
    5 Preparation of titanocenes.
    Examples 25-35. In the atmosphere of argon corresponding to the table. 4 amounts of the fluoro-aromatic compound are dissolved in an appropriate solvent, at -70 ° C, the corresponding amount of 1,6-mol of a solution of butyl lithium in hexane is added dropwise and stirred for 1 hour at -70 ° C. Immediately after this, the specified amount is added.
    5 Titanocene dichloride portions, the reaction mixture is slowly heated to room temperature and the reaction is stirred at room temperature for another 3 hours. After that, it is completely evaporated in a vacuum, the residue is extracted with dichloromethane or chloroform and the extracts are filtered, the filtrate is evaporated again and the remaining residue is purified as indicated in the table. five.
    Products have a color ranging from yellow-orange to red-orange. All products are cryallic, stable without light and not sensitive to air.
    In the above table 1-9 Cp means
    cyclopentadienyl and Me - methyl. Chromatographic purification was carried out on a Woelnh alumina neutral (A120) aluminum column or silica gel 60 (Merck) (SlOa) column. Example 36.44.7 g of N-2,4-Diptophenylpyrrole was dissolved in 750 ml of absolute diethyl ether and cooled to -75 ° C. Under a nitrogen atmosphere, 170 ml of a 15% hexane butyl lithium solution was added dropwise. . After stirring for 1 hour at -75 ° C, 31.1 g of titanocene dichloride are added. After cooling is stopped and the room temperature is reached, the orange suspension is added to 2 l of ethyl acetate, washed 3 times with water, dried over sodium sulfate and evaporated on a rotary evaporator. 73.5 g of an orange gum is obtained. The orange gum is stirred in 250 ml of ethanol overnight and crystallization occurs. After filtering and washing with a small amount of ethanol, 53.7 g of light orange crystals are obtained with a mp. 165-166 ° C. The output of 80.4%. For analysis, the product can be recrystallized from ethanol. Examples 37-43. Experiments were performed as described in examples 25-35. The remaining data are presented in Table. 4 and 5. PRI me R 44. Photo hardening of a mixture of acrylates. Get fototerapia composition by mixing the following components. Solid content 150.30 g of script 540 (30% solution in acetone) copolymer of polystyrene and maleic anhydride (Monsanto) 45.1 g of 48.30 g of trimethry triacrylate 48, 3 g of lolpropane 6.60 g of polyethylacrylate 6, 6 g of leneglycol 0.08 g of crystal violet 100.0 g 205.28 g. This composition is mixed in portions with those indicated in the table below. 6 amounts of photoinitiator or mixture of initiators. In the case of a mixture of initiators, we are talking about solutions of a titanocen e liquid initiator consisting of a 1: 1 mixture of hydroxycyclohexylphenyl ketone and benzophenone. All operations are performed in red or yellow light. Samples mixed with an initiator are deposited with a thickness of 150 / gm onto an aluminum film of 200 and m (10 x 15 cm). The solvent is removed by heating to 15 minutes in a conventional drying chamber. A polyester film with a thickness of 76 mm is applied to the liquid layer and a standardized test negative with 21 steps of different optical thickness (optical face) is applied to it. A second polyester film is laid on top and the laminate thus obtained is fixed on a metal plate. The sample is then illuminated with a 5 kW metal halide lamp at a distance of 30 cm during the first test row of 20 s and in the second test row of 40 s. After illumination, the films and masks are removed, the illuminated layer is developed 120 seconds in an ultrasonic bath with the proprietor A and immediately after that at 60 ° C for 15 minutes in a convection drying chamber it is dried. The sensitivity of the initiator system used is characterized by indicating the last glue-free graphic wedge stage. What is the higher the number of steps, the higher the sensitivity of the system. Increasing by two steps means approximately doubling the cure rate. The results are shown in Table. 6. Producer A contains 15 g of sodium metasilicate 9H20 .0.16 gCON, 3 g of polyethylene glycol 6000; 0.5 g of levulinic acid and 1000 g of deionized water. PRI me R 45. Photo hardening of a mixture of acrylates. A photocurable formulation was prepared by mixing the following components 37.64 g of SR 444 sartomer (pentaerythritol triacrylate (Sartomer Company, Westchester) 10.76 g of cyme 301 hexamethoxymethylamine (cyanamide) 47.30 g of carbosete 525 (thermoplastic acrylate with carboxyl groups (B. F. Goodrich) 4.30 g of polyvinylpyrrolidone (GAF) 100.00 g of this mixture 0.50 g of irgalite green 319.00 g of methylene chloride 30.00 g of methanol 450.00 g
    This composition is mixed in portions with those indicated in the table below. 7 amounts of titanocene. All operations are performed in red or yellow light.
    The samples mixed with the initiator are applied with a thickness of 200 jU m to an aluminum film with a thickness of 200 flm (Qt 15 cm). The solvent is removed by heating to 60 ° C for 15 minutes in a conventional drying chamber. A 76 / m thick polyester film is applied to the liquid layer and a standardized test negative with 21 steps of various optical wedges is applied to it. A second polyester film is applied to it and the laminate thus obtained is fixed on a metal plate. The sample is then illuminated with a 5 kW metal halide lamp at a distance of 30 cm, namely in the first test row of 20 s and in the second test row of 40 s. After illumination, the films and masks are removed, the remaining layer is developed in the ultra-light bath 240 with Proponent A and immediately thereafter dried at 60 ° C for 15 minutes in a convection drying chamber. The sensitivity of the applied system of initiators is characterized by a decree, not the last glue-free graphic wedge stage. The higher the number of steps, the more sensitive the system. An increase of two degrees means, at this time, approximately doubling of the curing rate.
    The results are shown in Table. one.
    Example 46. Comparison of the reactivity of some pyrrole derivatives and polyespher derivatives upon photo curing of a mixture of acrylates. A photo-curable composition is used and tested in accordance with Example 44. The lighting time in the first series of tests is 10 seconds, in the second 20 seconds, and in the third 40 seconds. The amount of the photoinitiator tested, based on the photocurable composition, is 0.3%. As compounds according to the proposed method, compounds of the formula
    Gp
    where Ri is cyclopentadiene (Example 36) (Ai)
    R2 trimethylsilyl cyclopentadiene (A2)
    The compounds according to the conventional method are used as compounds of the formula
     Ti,
    where is Ri
    cyclopentadiene
    R -O-0- (CH2CH201z-CH2CHNz (B,)
    F
    and correspondingly
    RI trimethylsilylcyclopentadiene
    F f
    Rj - o-tcHzCHjO -c H / (Vg)
    F f
    The results are presented in table. 8. PRI me R 47. Comparison of the reactivity of some pyrrole derivatives and polyespher derivatives in the photo curing of a mixture of acrylates. A photo-curable composition was used and the test was carried out in accordance with Example 45. The lighting time and test compounds are as described in Example 46.
    The results are presented in table. 9.
    Thus, as can be seen from the presented examples, titanocenes obtained in accordance with the invention, due to higher activity, have the ability to accelerate the curing of polymerized materials by 300-400% and accordingly reduce the lighting time by 50-75%, which in turn leads to an improvement product quality because
    with longer illumination, the image clarity in photopolymers deteriorates under the action of scattered light.
    权利要求:
    Claims (1)
    [1]
    Claims, method for producing titanocenes of general formula
    . RS G where R1-H, CH3. (SNS) s51; R2-R5 - independently of each other And, C1-C7-alkyl, C2-C5-alkenyl, CH2CH20CH3,
    CH2N (CH3) 2, CH2N (CH2CH20CH3) 2, CHj-NQo,
    /
    SbH5. -O 5 (SNZ) s, and pyrrole ring
    may be in the meta or para position for the Ti-C bond, characterized in that 50 that 1 mol of the compound is treated with 2 mol
    V R2 R,
    55
    with the subsequent selection of the target product. L: T 33 34 35 I :: I: L :::; ::::::::: IL ::::; :::: I C HR CHR CH-I- Chromatography, V4 decomposition as in the example 100 Y CH - P 28 Qf zac from diethyl / lovy ether, .. pentane NG- / Cp CHC Recrystalline I decomposition 100 oVrNLj diethyl ester syphyls) c CpH C-y-CHj Washing with 130 N san San Continued -Tab. 5 5 3 Recrystallized
    38Ср. 39Ср itO Ср 42Ср 43МеС СНз, /. (cH3) 2 but ° СН; V2: Recrystallization from hex / NfCH2CH20CH02 ° “to an AB 70 / gnc recrystalline 3 vt / - 3 from I / hexane /.T / 1. - / N О СН - - After washing with hexane 197-200 3 j /, 7 chokes (CHOoN / Г. М (СНз), Recrystallized - 175 h., /. / 2 quenching from CHgCl I / hexane (1 Р chromatography 100-105 ,, / h, / F, xrycrystalline from CHgCl p V / Chromatography 85 I ethyl acetate / hexane / hexane
    Table 6
    Table 7
    Table 8
    Table 9
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    同族专利:
    公开号 | 公开日
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    EP0318894A2|1989-06-07|
    RU1792538C|1993-01-30|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH468387|1987-12-01|
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