CN1037908C - Di(mu-bromine) di(3-chlorine-1,2-benzene disulfophenol) dipalladium (II) coordination compound and its preparing method - Google Patents
Di(mu-bromine) di(3-chlorine-1,2-benzene disulfophenol) dipalladium (II) coordination compound and its preparing method Download PDFInfo
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- CN1037908C CN1037908C CN94109062A CN94109062A CN1037908C CN 1037908 C CN1037908 C CN 1037908C CN 94109062 A CN94109062 A CN 94109062A CN 94109062 A CN94109062 A CN 94109062A CN 1037908 C CN1037908 C CN 1037908C
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Abstract
The present invention relates to a di(mu-bromo)di(3-chloro-1, 2-phenyl dithiol) dipalladium complex compound whose structural formula is as shown, wherein the complex compound has good thermostability, weather fastness and good compatibility with polymers. The complex compound can absorb the ultraviolet ray with the wavelength below 400 nm, and has good transmittance for above 400 nm light rays. The complex compound can be used as an ultraviolet ray absorber.
Description
The present invention relates to a kind of palladium coordination compound and its production and use.
O-diphenyl disulfide phenol with different substituents, can with the transition metal coordination, generate metal complex, its general formula is:
In the formula: R=CH
3, n=0～4, M=Ni; R=Cl, n=4, M=Ni; R=Cl, Br, n=1～3, M=Ni, Pd, Pt, A=tetraalkyl ammonium ion.
The distinguishing feature of this metalloid coordination compound is: the near-infrared region presents strong characteristic absorption band [Monatschefte fur Chemie, Vo1.102, PP.308-320 (1971); Journal ofthe.American Chemical Society, Vo1.88, PP.4870～4875 (1966)], Heat stability is good, weathering resistance is strong, (Japanese Patent discloses 135551/1981), what have has good compatibility (US4508655) with polymkeric substance, thereby be used as important near infrared absorbent use, for example, they are mixed with high transparent polymer, the plastic film of making, plate or can be coated with the polymers soln of stain on substrate can be used for preparing the plastic sheeting for farm use of selecting to absorb sunlight, sun glasses, welder's mirror, aircraft windows, the televisor spectral filter, optical filter, semiconductor laser recording materials etc.
Yet, in this class title complex, have because of ligand (R=CH
3, n=0-4) to could obtain through polystep reaction, cause coordination compound to cost an arm and a leg, application is restricted; (R=Cl n=0-4) can economic, preparation easily, but the compatibility of corresponding coordination compound and polymkeric substance is poor, and (Japanese Patent discloses 135463/1981 can not to satisfy the needs that contain high density coordination compound polymer materials for the ligand that has; US4508655).The coordination compound that US4508655 proposes (R=Cl, Br, n=1～3, M=Ni, Pd Pt) had both kept the ligand preparation method easy, and economic characteristics have improved the compatibility of coordination compound and polymkeric substance again, thereby have made range of application more extensive.But US4508655 only discloses the coordination compound of the non-bridging that this class ligand and nickel, palladium, platinum forms.They are mainly used in the near infrared ray that absorbs 850～1140nm as near infrared absorbent, and are relatively poor to the ultraviolet radiation absorption below the 400nm.For example, with metal complex (R=Cl, n=1, M=Ni, A=N (n-C
4H
9) 4): the polyester material of polymethylmethacrylate=0.15: 100, make the thick polyester chips of 1mm and detect, the result shows, the following ultraviolet ray of 400nm still has＜10% see through.Thereby, when the service requirements ultraviolet ray transmissivity is low, or only require and block ultraviolet ray that when allowing 400nm to see through with polished yarn, they are just inapplicable.
Purpose of the present invention is to provide a kind of new halogen to replace diphenyl disulfide phenol metal complex that its structure is different with above-mentioned metal complex and preparation method thereof.Coordination compound of the present invention has kept the ligand preparation method of US4508655 easy, economy, the coordination compound Heat stability is good, weathering resistance is strong, with polymkeric substance good compatibility characteristics are arranged,, make its optical property significantly different again with above-mentioned known coordination compound.Coordination compound of the present invention is strong significantly to the above-mentioned known coordination compound of the ultraviolet specific absorption below the 400nm, and does not have characteristic absorption band at the 400-250nm wave band.Therefore metal complex of the present invention is good uv-absorbing agent, has and the different range of application of above-mentioned known coordination compound.
Technical scheme of the present invention is by the synthetic Benzene Chloride dithiol palladium compound with bridge architecture of preparation technology of the present invention, thereby changes the optical property of coordination square object.
Coordination compound two of the present invention (μ-bromine), two (3-chloro-1,2-diphenyl disulfide phenol) two palladiums (II)-four-n-butyl ammonium, its structural formula is:
Coordination compound of the present invention is by 3-chloro-1,2-diphenyl disulfide phenol and palladium compound, four n-butyl brometo de amonios react under certain condition and obtain, its concrete preparation method is following, and (said in following method " by the suitable metered proportions of chemical reaction " is meant the thoroughness for chemical reaction, central ion, the add-on of ligand and quaternary ammonium salt must satisfy the mol ratio of chemical reaction at least, under the principle of not wasting, the comparable central ion of ligand and quaternary ammonium salt is suitably more excessive).
1, press the suitable metered proportions of chemical reaction with 3-chloro-1,2-diphenyl disulfide phenol is dissolved in from methylene dichloride, in a kind of solvent of selecting in chloroform and the benzene, obtains first kind of solution (A);
2, pressing the suitable metered proportions of chemical reaction will be from PdCl2, PdBr2, K2PdCl4, Pd (NO3) 2 or floating among the Pd (CH3COO) 2 a kind of palladium compound of selecting is dissolved in or is suspended in the monohydroxy-alcohol of 1-4 carbon, obtain second kind of solution (B), to less PdCl2 of solubleness etc., can adding appropriate hydrochloric acid in solution, to make pH value be 1-6, makes its dissolving.
3, stirring joins B solution in the A solution down, under room temperature or reflux temperature, reaction is 1-7 hour under the high degree of agitation, direct chemical is reacted the alcoholic solution G that suitable metered proportions adds four-n-butyl brometo de amonio or this quaternary salt again, perhaps use the pH value of ethanol-sodium hydroxide solution or alcohol sodium solution conditioned reaction system to PH=7-11 earlier, react and add said quaternary ammonium salt again after 2-5 hour, continue reaction 1.5-5 hour, filter, methanol wash leaches thing, drying obtains redness, or the orange solid crude product.
4, with methylene dichloride or chloroform thermosol operation 3 resulting crude products, filter, remove insolubles, add hot methanol in the filtrate it is precipitated out, perhaps directly make the crude product recrystallization with the mixing solutions of methyl alcohol with methylene dichloride or chloroform, obtain pure product.
Coordination compound of the present invention can be used as UV light absorber, in particular as absorbing wavelength is the high UV light absorber of UV transparent rate below the 400mm, and the handy family expenses film of doing can promote plant-growth, improve its output and quality, use condiments, coating, the additive of paint etc., can absorb ultraviolet ray, slow down fading of material, variable color also can be made various UV filter etc.
Compare with prior art, coordination compound of the present invention has following characteristics:
1, has good weathering resistance and thermostability, its is exposed in the sun, in the air, does not all change its structure and optical property.Heating is at 240 ℃, and compound does not decompose, thereby can use in processing below 240 ℃.
2, has the ultraviolet performance of strong absorption, for example, when containing The compounds of this invention 0.1g in 1 liter of chloroformic solution, the following ultraviolet ray of 400nm is blocked fully, the 400-2500nm transmittance is 100%, with The compounds of this invention and polymkeric substance, as the polymethylmethacrylate sheet, just can block the following ultraviolet ray of 400nm (only 380-400nm has＜4% transmittance), visible region transmittance＞70%
3, coordination compound of the present invention and polymkeric substance have good compatibility, when weight ratio is a coordination compound of the present invention: polymethylmethacrylate=1.2, or the coordination compound ratio is when bigger, and it still can crystallization not show to come from polymkeric substance.
Embodiment 1
7.6 part (weight ratio, down with) 3-chloro-1,2-diphenyl disulfide phenol is dissolved in 45 parts of benzene, solution A, 3 parts of palladium chlorides add 130 parts of ethanol and small amount of hydrochloric acid (making PH=1) is placed, and shake frequently, main palladium chloride is molten entirely, solution (B).
Under stirring B solution is joined in the A solution, reacted 1 hour, add 11 parts of four-n-butyl brometo de amonios and 55 parts of alcoholic acid solution again, room temperature, reaction is 5 hours under the high degree of agitation, crosses the crack, and the filtrate decompression distillation is removed most of solvent postcooling and is crossed the crack again.Leach thing and merge, drying at room temperature obtains 8.5 parts of soil Red solid crude product.Crude product with part: the mixing solutions recrystallization of 1 part CHCl3: CH3OH=25.1 obtains pure 46 parts of coffee-like non-crystalline solids, productive rate 56%.
20.5 parts of 3-chloro-1 of embodiment, 2-diphenyl disulfide phenol is dissolved in 16 parts, in the methylene dichloride, stirs full and 40 parts of methanol mixture of 0.3 part of acetic acid of adding down, room temperature, reaction is 4 hours under the high degree of agitation.Add 0.9 part of four-n-butyl brometo de amonio, continue reaction 4 hours.Filter, leach the thing drying, obtain 0.46 part of crude product, following operation is with embodiment 1, at last 0.3 part of pure product, productive rate 47.6%.
30.5 parts of 3-chloro-1 of embodiment, 2 diphenyl disulfide phenol are dissolved in 15 parts of chloroforms, stir down to add 0.3 part of Pd (NO3) 23H2O and 20 parts of methanol mixture, under the reflux temperature, high degree of agitation reaction 7 hours, generation orange precipitation adds 0.8 part of four-n-butyl brometo de amonio, continues reaction 2 hours, filter, methanol wash goes out thing, and drying obtains 0.8 part of soil Red solid crude product.Crude product filters with 26 parts of methylene dichloride thermosols, removes insolubles.Add hot methanol in the filtrate, solid precipitation is come out, cooling, filtration, drying gets 0.21 part of red-brown solid pure product, productive rate 42%.
Embodiment 4
1.7 part 3-chloro-1,2-diphenyl disulfide phenol is dissolved in 14 parts of methylene dichloride, adds the solution of 0.7 part of palladium chloride, 3 parts of ethanol and small amount of hydrochloric acid, and room temperature reaction 2.5 hours adds sodium hydroxide-ethanolic soln, and adjusting PH=11 reacted 4 hours.Add 4 parts of four-n-butyl brometo de amonios again, continue reaction 1.5 hours.Filter, leach thing water successively, washing with alcohol, drying gets 1.1 parts of crude products.According to the method among the embodiment 1,, obtain 0.9 part of coffee-like solid crystal, productive rate 47.3% with CH2Cl2CH3OH=5.3 solution-treated crude product.
Under the reaction conditions that the present invention proposes, the outward appearance of the product that obtains, molten tool, infrared spectra (400-100cm), the ultraviolet-external spectrum (200-1500nm) of closely playing be unanimity all, shows that the product that obtains under the differential responses condition is the palladium coordination compound of bromine bridging dimerization.Analytical results is as follows:
Through the product of n purification process, fusing point 248-250 ℃.Ultimate analysis value (C28H24Cl2S4Br2NPd2): measured value (weight %): C34.72, N1.45, H4,36.Infrared spectra (4000-400Cm, KBr pressed disc method): 3040VC=H; 2960,2930,2872.VC-H1553,1477 phenyl ring skeletal vibrations, 1459 δ CH2; 1390 δ CH2; Three adjacent hydrogen of 773 δ phenyl ring; (500-100cm), paraffin oil process: 331VpdS; 247Vpds; Nuclear magnetic resonance spectrum: (δ PPM, solvent DCl3): 7.1-6.8 (3H, m, phenyl ring proton), 2.94 (2H, broad peak, NCH2), 1.43 (2H, broad peak, NC-CH2), 1.34-1.21 (2H.m, Ncc-CH2), 0.96-0.43 (3H, t, CH3).Heat branch folding: 242 ℃, a small amount of long heavy, 251 ℃, heat absorption rate (fusion), and follow decomposition weightless.In ultraviolet-near infrared spectrum (solvent: CHCl3, concentration 0.1010g/l) wavelength 200-400 and the 400-2500nm scope, transmittance is respectively 0% and 100%.
Embodiment 5
1 part of metal complex of the present invention, 2 parts of polymethylmethacrylates, with 4 parts of methylene dichloride dissolvings, mix or 1 fen Ben Dingming compound, 3 fens polymethylmethacrylates, with methylene dichloride dissolving in 5 fens, stirring was coated to mixture on glass respectively, thickness 0.03mm, treating that it is dry and take the film that generates off one examines, and there is no metal complex and separate out 0 ℃ of temperatures and make the coffee-like polyester chips that certain thickness has the different depths, be blank with the air, detect its transmittance, it the results are shown in Table 1, and table 1 shows that ultraviolet ray is blocked, visible light still keeps better transmittance, thereby can be used for preparing various ultraviolet filtering materials.Table 1
| Palladium complex PMMA (weight ratio) | Print thickness (m m) | Extinction wave band (nm) | Transmittance (T) | Printing opacity waviness (nm) | Transmittance (T%) |
| 0.08∶100 | 1 | 190-400 | ＜4 | 400-900 | ＞75 |
| 0.1∶100 | 1 | 190-400 | 0 | 400-900 | ＞70 |
| 0.15∶100 | 1 | 190-400 | 0 | 400-900 | ＞65 |
| 0.02∶100 | 2.5 | 200-380 | 0 | 380-1000 1000-15000 | ＞80 ＞70 |
| 0.06∶100 | 2.5 | 140-400 | 0 | 400-900 | ＞60 |
| 0.10∶100 | 2.5 | 200-400 | 0 | 400-1000 1000-15000 | ＞50 ＞70 |
Claims (3)
1, two (μ-bromines), two (3-chloro-1,2-diphenyl disulfide phenol) two palladiums (II) coordination compound, its structural formula is:
2, a kind of preparation two (μ-bromine), the method for two (3-chloro-1,2-diphenyl disulfide phenol) two palladiums (II) coordination compound is characterized in that:
2.1 press the chemical reaction metered proportions with 3-chloro-1,2-diphenyl disulfide phenol is dissolved in a kind of solvent of selecting from methylene dichloride, chloroform and cost, obtains a kind of solution (A);
2.2 by the suitable metered proportions of chemical reaction will from PdCl2, PdBr2, K2PdCl4, Pd (NO3) 2, Pd (CH3COO) 2, a kind of palladium compound of selection be dissolved in or be suspended in the monohydroxy-alcohol of 1-4 carbon, obtain second kind.Solution (B), the PdCl2 less to solubleness can add appropriate hydrochloric acid (making pH value is 1-6) in solution, it is dissolved fully;
2.3 stir down B solution is joined in the A solution, under room temperature or backflow and temperature, high degree of agitation reaction 1-7 hour, press the alcoholic solution (C) that the suitable metered proportions of chemical reaction directly adds four-n-butyl brometo de amonio or this quaternary ammonium salt again, perhaps use the pH value of ethanol-sodium hydroxide solution or alcohol sodium solution or alcohol sodium solution conditioned reaction system to 7-11 earlier, react and add said quaternary ammonium salt again after 2-5 hour, continue reaction 1.5-5 hour, filter, methanol wash leaches thing, drying obtains soil Red or orange solid crude product.
2. 4 usefulness methylene dichloride or chloroform thermosol operation 2.3 resulting crude products, filter, remove insolubles, add hot methanol in the filtrate it is precipitated out, perhaps directly make the crude product recrystallization with the mixing solutions of methyl alcohol, thereby obtain pure product with methylene dichloride or chloroform.
3, two (μ-bromines), two (3-chloro-1,2-diphenyl disulfide phenol) two palladiums (II) coordination compound is as UV light absorber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94109062A CN1037908C (en) | 1994-08-04 | 1994-08-04 | Di(mu-bromine) di(3-chlorine-1,2-benzene disulfophenol) dipalladium (II) coordination compound and its preparing method |
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|---|---|---|---|
| CN94109062A CN1037908C (en) | 1994-08-04 | 1994-08-04 | Di(mu-bromine) di(3-chlorine-1,2-benzene disulfophenol) dipalladium (II) coordination compound and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1109467A CN1109467A (en) | 1995-10-04 |
| CN1037908C true CN1037908C (en) | 1998-04-01 |
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| CN94109062A Expired - Fee Related CN1037908C (en) | 1994-08-04 | 1994-08-04 | Di(mu-bromine) di(3-chlorine-1,2-benzene disulfophenol) dipalladium (II) coordination compound and its preparing method |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508655A (en) * | 1981-12-16 | 1985-04-02 | Mitsui Toatsu Chemicals, Inc. | Metal complexes of halogen-substituted o-benzenedithiols |
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1994
- 1994-08-04 CN CN94109062A patent/CN1037908C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508655A (en) * | 1981-12-16 | 1985-04-02 | Mitsui Toatsu Chemicals, Inc. | Metal complexes of halogen-substituted o-benzenedithiols |
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