• 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 organotitroorganic substances, in particular the preparation of titanocenes of total f-ly 1: (R 1) TI / C = CF-CR 2 = CX-CR 2 = CF / 2, where X = -O -) NR 3, R 1-cyclopetadienyl or methylcyclopentadienyl, R 2 = H or F, R 3 = C 1-4 alkyl, N = 1-3, as photoinitiators in photopolymerizable compositions. The goal is to create new, more effective compounds of the specified class. The synthesis is carried out by the reaction of compounds f-ly II and III: (R 1) 2 TICL 2 (II) and LI-C = CF-CR 2 = CX-CR 2 = CF (III), with their molar ratio equal to 1: 2. New photoinitiators are superior to those known 10 times in the concentration used. 1 tab.
    公开号:SU1597105A3
    申请号:SU874203074
    申请日:1987-07-31
    公开日:1990-09-30
    发明作者:Ридикер Мартин；Штайнер Эгинхард；Бейелер Харри；Рембольд Манфред；Ситек Францижек
    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
    (,,
    R
    I
    where is r. - cyclopetadienyl or methylcyclopent adi enyl;
    R - H or F;
    ft - C, -C-alkyl;
    n 1-3,
    which can be used in the quality of photoinitiators in photopolymerizing compositions.
    The purpose of the invention is the synthesis of new photo-injectors, which are more effective than the known ones used for the same purpose.
    Example 1.23 g (1 mol) of finely divided sodium is introduced into 500 ml of monobutyl eLira, diethylene glycol, maintaining the temperature not higher. After the reaction is quenched, the mixture is warmed up and held until the sodium is completely dissolved. The resulting brown solution is added over 1 hour at 40-45 ° C to 233 g (1.16 mol) of chloropentafluorobenzene. The reaction mixture is then heated to and kept at this temperature for 7 hours, then cooled and poured into 1 liter of water and extracted with 1 liter of methylene chloride. The extract is dried, the solvent is removed in a vacuum, the residue is distilled, collecting Fraction 100-104 puz mbar Obtain 280 g (81%) of clear white colored oil - diethylene glycol monobutyl mono- (2,3,5,6 tetra4tor-4-chloro) 6-methyl ester. Found,%: C 48.71; H 5.0i C1 10.2. C, R, .C1F.O f4 - E Calculated,%: C 48.78; H 4.97, F 22.04; C1 10.28. 51.7 g (0.15 mol) of the resulting compound are dissolved in 400 ml of absolute diethyl ether in an argon atmosphere and cooled to, then 103 ml of a 1.6 M solution of butyl lithium in hexane are added dropwise. After 15 minutes, 18.7 g (0.075 mol) of bis (cyclopentadienyl) titanium dichloride was added at the same temperature as a powder. The temperature was slowly raised to 2 hours, the reaction mixture was poured into 1 liter of water, and the portions were extracted with 600 ml of ethyl acetate. The extract is dried underneath, the solvent is removed in vacuo. The residue, a clear orange-red oil, is purified by chromatography on silica gel (hexane-ether). I get 40 g (67%) bis (cyclopentadienyl) -bis 4- (1,4,7-trioxaundec-1-yl) -2,3,5,6 -tetraPterPhenylJ gita. Found,%: C 56.9; H 5.8-, F 18.3, - Ti 5.6. C3 "H44FtO Ti Calculated,%: C 57.29; H 5.57; F 19.08; Ti 6.02. I-NMR spectrum, ppm (CDCls): 6.50 (5H); 4.32 (2H); 3.83; 3.70; 3.5 (6H 3.47, 1.58, - 1.38-, 0.92 (9H). Mass spectrum (, mass number (intensity): 57.4100); 72 (10); 88 (18) ; 101 (20) 145 (20); 193 (14); 321 (2); 341 (1) - 357 (1), 388 (1); 413 (1), 432 (2) V 796 (0, 3). IR spectrum, cm: 2860; 1730 162 1480; 1420; 1080; 950; 830. Example 2. Similarly, from pi ethylene glycol monobutyl mono (2,3,5,6-tetraFluoro-4-chloro) Phenyl ether and bis (methylcyclopentadienyl) titanium dichloride give 59% bis (methylcyclopentadienyl) (G, 4, 7-trio sounde-1-yl) -2,3,5,6 -trtraFluorophenyl-titanium. Found: C 57.7 H 6.0i 17, 9; Ti 4, 9. C, oH ,,, Ti Calculated,%: C 58.26; H 5.87.18, 43-Ti 5.81. H-NMR spectrum, m D (CDCId) 6.52 and 6.28 (4H), 4.35 (2H), 3.85; 3.69, 3.59 (6H); 3.47i 1.57; 1.37- , 0.92 (9B); 1.88 (ЗН). Mass -spectrum (250s), mass number (intensity): 45 (50); 57 (K) 0), 72 (10) 88 (20); 101 (24); 145 (20); 166 (10); 193 (20b 263 (2-) v 279 (1); 281 (1); 311 (l) i 369 (1); 427 (1) j 462 (1) for 534 (1); 550 (1); 628 (1). IR spectrum, CV-: 2860i 1730; 1620; 1480-, 1420; 1240; 1080 950- 830. Example 3. In a similar manner to Example 1, triethylene glycol mono-ethyl mono- (2.3.5 , 6-tetraFluoro-4-chloro) Phenyl ether, t.kip.124-128 C / / 8 mbar. From 54.1 g (0.5 mol) of this ester by reacting with 103 ml of butyl lithium solution and 18.7 g (0.075 mol) bis (cyclopentadienyl) titanedichloride is obtained as in the example bis (cyclopentadienyl) bis-4 (1, 4, 7, 1 O-tetraoxapovecyl) -2,3,5,6-tetraFluoroPhenyltitanium, Bbixon 53%. 5, 1; h- Found: C F 17.4 ;.Ti 5.4, Se8H44Rb 8T1 Calculated,%: C 55.07; F 18.34; Ti 5.78. H-NMR spectrum, ppm . (CDCl) (5H); 4.30 (2H); 3.38; 3.77; 3.57 (YUN); 3.49i 1, 22 (.5H). Mass spectrum (250 C), mass number (intensity ): 45 (100); 72 (30); 73 (54); 89 (10), i 117 (14); 145 (10); 161 (10); 193 (30) - 230 (4); 237 (6); 257 (1); 273 (1); 293 (1); 341 (1} 390 (1), - 429 (1); 502 (1); 522 (1). IR spectrum, CN -: 2860; 1730; 1620; 1480; 1420 1240; 1080; 950,830. Example 4. 130.1 g of difluorophenol (1 mol) are dissolved in 300 ml of dimethylformamide, introduced into the reaction with 200 g of powder, after which 153.1 g of 2-ethoxyethyl bromide are slowly added to this mixture with cooling. . After the addition, the mixture is heated at 60 ° C for 1 hour and then drunk in 1.5 liters of water and. extracted with diethyl ether. The extract is washed with 1N.
    NaOH and water, dried over NajSO4. The solvent is removed in vacuo, the residue is distilled, collecting a fraction of 67 ° C / / 0.03 mbar. Obtain 142.4 g (70.4%) of ethyleneglycol-monoethyl-mono- (2,4-di (1ztor) 4enyl ether.
    C 59.3i H 5.9;
    Found,%: 18.7. .
    10 P f 2 C 59.40 H 5.99; Calculated% F 18.79. To a mixture of 69 ml of a 1.6 M solution of butyl lithium in hexane and 100 ml of absolute diethyl ether, a solution of 14.0 g (0.12 mol) of N, N, N, N-tetramethylethylenediamine in 50 ml of absolute diethyl diethyl ether is added dropwise. ether and stirred pr -25 ° C for 30 minutes Then it is cooled to -75 ° C and a solution of 20.2 g of ethylene glycol-mono-ethanol-mono (2,4-diFluoroPhenyl) ether (0.1 mol) in 50 ml of absolute diethyl ether is added dropwise. After stirring for 20 minutes, 12.5 g of bis (cyclopentadienyl) titanium dichloride (0.05 mol) was added in the form of a fine powder. The temperature of the reaction mixture is slowly raised to room. A yellow-orange suspension is formed. All further procedures are carried out in yellow light. The suspension is treated with 500 ml of ethyl acetate and washed several times with deionized water. The organic phase is separated, suiat over. the solvent is removed under vacuum b, the residue 31.2 g of an orange-brown oil is crystallized from ethanol. Poluchak1T 20.4 g of bis (cyclopentadienyl) -bis 3- (I, 4-dioxahex-1-yl) -2,6-diFluorophenylJ titanium, mp 105-106С. C, 61.7; H 5.5; Found,%: 13.1. Cr.H3-, P, 62.08 N 5.56i Calculated,%: F 13.09. 2980-2880; 1440; IR spectrum, cm 1360; 1300i 1210; 1140; . n-NMR spectrum, ppm (CDC1j): 6.65 and 6.43 (2H); 6.43 (5H); 4.05 (2H); 3.83-3.48 (4H); 1.22 (G). Mass spectrum (), mass number (intensity): 45 (100) -, 73 (40) -, 139 (15) -, 155 (10); 197 (10); 241 (10); 242 (20); 257 (10); 285 (10);
    314 (10); 324 (10); 370 (10) v 398 (4); 507 (3); 580 (0.6).
    Example 5. Analogously to Example 4, 198.8 g (85.6%) of diethylene glycol-monomethyl-non- (2,4-diFluoro) Fekyl ether, t. kip.83-87 s / O, 02 mbar.
    Found,%: C 57.0; H 6.1 S ,, H ,,. 56.90; H 6.08; Calculated,%: 16, 36. To 23.2 g (0.1 mol) of diethylene glycol-monomethyl-mono- (2,4-diFluorophenyl) ether in 50 ml of tetrahydrofuran while 69 ml of a 1.6 M solution of butyl Lithium in hexane (0.11%) are slowly added dropwise. mole). In the flowable suspension, the mixture is diluted by adding dropwise 150 ml of diethyl ether and stirred at -7Ci ° C for 20, then 12.5 g (0.05 mol) of bis (cyclopentadienyl) titanium dichloride are added as a fine powder. The desired product is then isolated in a manner analogous to that described in Example 4, and purified chromatographically on silica gel (eluent hexane, then a mixture of hexane and diethyl ether). Obtain 19.1 g of bis (cyclopentadienyl) -bis-GZ- (1,4, 7 - trioxaoct-1 -yl) -2,6-di topopenyl-Titanium, m.p. 83-85 C. Found,%: C 60.0; H 5.8; F 1 1, 5-, Ti 7.21. C3iK5, F, OjTi Calculated, 7.:C 60.01, H 5.67; F 11.86; Ti 7.48. IR Spectrum, 29- -0-2880 1440; 1360; 1300; 1220; 1,140; 840. CMR spectrum, ppm (CDCl): 6.63 and 6.44 (2H); 6.44 (5H) j 4.10, 3.87, 3.73, 3.58 (8H) -, 3.40 (ЗН). Mass spectrum (, mass number (intensity): 44 (20); 59 (100); 103 (42) -, 129 (10); 161 (10); 163 (10); 197 (10), 207 (10 ), 213 (5); 232 (5); 285 (5); 335 (5) i 344 (2), - 283 (2); 428 (2). Make-up artist 6. The test of the proposed Photo-initiators was exemplified by Photo-hardening mixtures of acryates of the following composition: 50 h of oligourethaneacrylate (Lctylan AI 20); 20 parts of trimethylolpropane triacrylate 15 hours of tripropylene glycol diacrylate
    5 h. N-vinylpyrrolipone, 0.5 h. BYKi K 300 - auxiliary agent. All operations were performed in red or yellow light. The samples mixed with the initiator were applied with a thickness of 100 microns to the Altuminiyun) yolgu (10-15 cm). A 76 micron thick polyester film was placed on the liquid layer and a standard test negative with 21 steps of a wedge was placed on it. A second Foil was placed on top and the laminate thus obtained was fixed on a metal plate. Then, the sample was illuminated with a 5 kW metal-halogen lamp with a 30 cm distance for 10 s. After exposure, the films and masks were removed, the exposed layer was developed in an ethanol bath and then dried at 60 ° C for 5 minutes.
    The test results in comparison with the results of photo-curing in the presence of the well-known Photo-initiator Irgacure 651 (benzyldimethyl-ketal) are given in the table.
    t
    10 10
    0.2 0.2
    权利要求:
    Claims (1)
    [1]
    As can be seen from the data table, the proposed Photoinitiators are superior to the known Photoinitiator, even when using 10 times lower concentration. Invention Formula
    The method of obtaining titanocene General Formula
    i F g
     {EL, T1-nNs0 2CH20) pNz; i; Z - L - D
    2
    F
    where is r,
    cyclopentadienyl or methylcyclopentadietylV
    H or F;
    R.
    C-C, -alkyl;
    1-3.
    P
    characterized in that the compound (P.,) TiCl, where R has the indicated value, is reacted with the compound
    R2
    (СН2СН20) „Кз
    where R, 3 have the indicated values, at a molar ratio of 1: 2, respectively.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH310186|1986-08-01|
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