KR101808042B1 - Method of preparing for selective di-styrenated phenol using titanium dioxide solid acid catalyst - Google Patents
Method of preparing for selective di-styrenated phenol using titanium dioxide solid acid catalyst Download PDFInfo
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- KR101808042B1 KR101808042B1 KR1020160067071A KR20160067071A KR101808042B1 KR 101808042 B1 KR101808042 B1 KR 101808042B1 KR 1020160067071 A KR1020160067071 A KR 1020160067071A KR 20160067071 A KR20160067071 A KR 20160067071A KR 101808042 B1 KR101808042 B1 KR 101808042B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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Abstract
The present invention relates to a process for producing di-styrenated phenol, and more particularly, to a process for selectively producing di-styrenated phenol using a titanium dioxide solid acid catalyst at a high yield.
The process for producing di-styrenated phenol according to the present invention shows high reactivity under a titanium dioxide solid acid catalyst, thereby minimizing the amount of unreacted residual materials and greatly increasing the selectivity of di-styrenated phenol have.
Description
The present invention relates to a process for selectively producing di-styrenated phenol, and more particularly, to a process for selectively producing di-styrenated phenol at a high yield when producing styrenated phenol using a titanium dioxide solid acid catalyst .
Plastics are widely used not only for industrial purposes but also for everyday life due to their excellent chemical and physical properties. Such a plastic is rarely used as such, and a small amount of an additive is added to the raw material in accordance with the intended use to supplement its characteristics. Typical examples thereof include an antioxidant to increase the oxidation stability of the raw material . The antioxidant functions to stabilize the plastic by reacting with radicals generated by the oxidation reaction of heat, oxygen, light and the like in the plastic. The antioxidant releases its own hydrogen to stabilize the radical, which itself becomes a radical, which remains in a stable form through a resonance effect or electron rearrangement.
Typical examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants. Particularly, phenol-based antioxidants have excellent thermal stability and are widely used as non-staining antioxidants, unlike amine-based antioxidants.
Examples of the phenolic antioxidant include styrenated phenol (SPs), in which phenol and styrene are alkylated to replace phenol hydrogen with styrene. In general, when styrene is used in an amount of 2 equivalents to phenol, mono-styrenated phenol (MSP), di-styrenated phenol (DSP) in which two styrenes are bonded, and styrene Tri-styrenated phenol (TSP) compound is produced in a weight ratio of MSP: DSP: TSP = 10: 15: 30 to 45: 35: 45, and the unreacted residual phenol There is a problem that an excessive amount of styrene remains.
In Korean Patent No. 10-1111248, styrene-naphthyl phenol is synthesized using a liquid acid catalyst as a homogeneous catalyst. Liquid acid catalysts such as sulfuric acid, nitric acid, phosphoric acid and the like can produce stainned phenol products and cause discoloration due to the violent reaction conditions of high temperature and strong acid, low selectivity, sensitivity to moisture, There is a problem that the reproducibility is low depending on the kind of the substance and the amount of catalyst used. Further, since the catalyst can not be reused and separation of the product from the catalyst is not easy, it can act as an impurity, and therefore a search for a new heterogeneous catalyst is required.
The present invention provides a method for selectively producing di-styrenated phenol which is excellent in thermal stability and discoloration stability and capable of selectively producing di-styrenated phenol I want to.
It is also an object of the present invention to provide a method for selectively producing di-styrenated phenols which can minimize the unreacted residual materials in a simple and economical production process.
The present invention can be represented by the following formula (1), which is a reaction between a phenol compound represented by the following formula (2) and a styrene monomer under a titanium dioxide solid acid catalyst.
[Chemical Formula 1]
(2)
[In the above Chemical Formulas 1 to 2,
R 1 and R 2 are each independently hydrogen, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, cycloalkyl having 3 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms.
The titanium dioxide solid acid catalyst may be a solid acid catalyst in which sulfate ions are supported on the titanium dioxide particles.
The size of the titanium dioxide particles may be 10 to 50 nm.
The styrene monomer may be used in the range of 1.8 to 2.2 mol based on 1 mol of the phenol compound.
The titanium dioxide solid acid catalyst may be used in an amount of 0.5 to 10% by weight based on the mixture of the phenolic compound and the styrene monomer.
The reaction of the phenolic compound with the styrene monomer may be carried out at a temperature ranging from 40 to 140 ° C.
The mixture of the phenolic compound and the styrene monomer may be carried out under an inert gas supply of argon, nitrogen, helium or neon.
The process for the selective preparation of di-styrenated phenols according to the present invention shows a high reactivity under a titanium dioxide solid acid catalyst, thereby minimizing the amount of unreacted residual materials and dramatically increasing the selectivity of the di-styrenated phenol .
In addition, the process for selectively producing di-styrene-substituted phenol according to the present invention can be carried out by a simple process, thereby increasing the industrial efficiency and enabling mass production at a lower cost.
1 illustrates a process for preparing a titanium dioxide solid acid catalyst according to an embodiment of the present invention.
2 shows the results of the conversion of the phenol compound and the styrene monomer and (b) the selectivity of the di-styrenated phenol according to the catalyst content of the embodiment of the present invention.
FIG. 3 shows the results of (a) conversion of phenol compound and styrene monomer and (b) selectivity of di-styrene nitrile phenol according to the reaction temperature of Examples of the present invention.
Hereinafter, the present invention will be described in more detail. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It is also to be understood that the terminology used herein is for the purpose of describing specific examples only and is not intended to be limiting of the invention. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
As shown in FIG. 1, the titanium dioxide solid acid catalyst of the present invention can be prepared by supporting titanium dioxide on sulfuric acid, but is not limited thereto.
(SPs) by reacting phenol with styrene under a titanium dioxide solid acid catalyst prepared therefrom to exhibit high reactivity, thereby minimizing the amount of unreacted residual materials, and can be used for the production of di-styrenated phenol It is possible to remarkably increase selectivity.
The present invention relates to a method for producing styrene-substituted phenol, which comprises reacting phenol with a styrene monomer to simultaneously produce mono-, di-, and tri- styrenated phenols as shown in Reaction Scheme 1 . However, it has been difficult to selectively produce any one of them in the conventional styrene-based phenol manufacturing process. Further, there is a disadvantage that an additional complicated separation process must be performed in order to separate the catalyst and the product.
The styrene-substituted phenol, which includes conventional discolouration and impurities or unreacted residual materials, can be used only as an antioxidant, but the present invention is not limited to the antioxidant of the present invention in a simple process, while minimizing the amount of unreacted residual material However, the present invention has been devised to provide a novel process for selectively producing di-styrenated phenol which can be applied as a surfactant by acting as a hydrophobic surfactant.
[Reaction Scheme 1]
The present invention will be described in detail,
The present invention relates to a method for selectively producing di-styrenated phenol represented by the following formula (1) wherein a phenol compound represented by the following formula (2) is reacted with a styrene monomer under a titanium dioxide solid acid catalyst.
[Chemical Formula 1]
(2)
[In the above Chemical Formulas 1 to 2,
R 1 and R 2 are each independently hydrogen, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, cycloalkyl having 3 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms.
Substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in the present invention include both straight chain and branched forms. &Quot; Cycloalkyl ", alone or as part of another group described in the present invention, refers to a fully saturated and partially unsaturated hydrocarbon ring of 3 to 9 carbon atoms, inclusive of the fused aryl or heteroaryl do.
The term " aryl " as used in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination, in which each ring is optionally substituted by a single or a plurality of ring atoms, preferably containing from 4 to 7, preferably 5 or 6, A fused ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But is not limited thereto.
For example, R 1 and R 2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, Butyl, n-pentyl, i-pentyl, s-pentyl, n-hexyl, i-hexyl, s-hexyl, phenyl, naphthyl or biphenyl.
More preferably the phenolic compound of formula (2) is selected from the group consisting of phenol, m-cresol, p-cresol, o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4- Ethylphenol, p-ethylphenol, on-propylphenol, mn-propylphenol, pn-propylphenol, o-propylphenol, butylphenol, m-butylphenol, pn-butylphenol, o-butylphenol, mi-butylphenol, , m-butylphenol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, Butoxyphenol, p-phenoxyphenol, m-propoxyphenol, p-propoxyphenol, o-butoxyphenol, m-butoxyphenol, p-butoxyphenol and the like.
The titanium dioxide solid acid catalyst according to an exemplary embodiment of the present invention may be a solid acid catalyst in which sulfate ions (SO 4 2- ) are supported on titanium dioxide particles.
The use of the sulfuric acid ion-supported solid titanium dioxide solid acid catalyst proposed in the present invention can provide an effect of maximizing the yield and purity of the di-styrenated phenol (DSP), and the mono-styreneide The generation of phenol (MSP) and tri-styrenated phenol (TSP) can be suppressed as much as possible. Therefore, since the present invention does not use any polymerization terminator that is used for the purpose of inhibiting the production of the polymerization by-product, the purification process due to coloring is not performed, and thus the process simplification effect can be expected.
In addition, the titanium dioxide solid acid catalyst is characterized by being a solid acid catalyst. That is, the reaction time can be greatly shortened by using a liquid acid catalyst in the production of conventional styrenated phenol, unlike the case where a long reaction time is required. In addition, the liquid acid catalyst was forced to generate waste acid and wastewater. However, by using the solid acid catalyst, it is possible to recover the catalyst through a simple filtration process without discharging waste acid and wastewater.
The titanium dioxide particles of the present invention serve as a carrier for dispersing and holding an active material having a catalytic function in a stable manner. Although the carrier is not active, when the catalyst is prepared using only the active material having low thermal stability, the surface area of the active material can be greatly reduced by sintering during the reaction. Accordingly, if the active material is supported on a carrier having excellent thermal stability, the carrier can be stabilized, and the catalyst deactivation due to sintering can be suppressed. In addition, the carrier may increase the mechanical stability of the catalyst, so that the catalyst can be conveniently used to form a suitable catalyst.
The titanium dioxide particles of the present invention do not have an obvious acidity or basicity, but can be strongly acidic when supported by sulfate ions. In this mechanism, since the sulfate ion strongly attracts the electrons, the electron density of the Ti (IV) atom is lowered, resulting in a strong Lewis acid point capable of receiving an electron pair. Therefore, titanium dioxide is very strong in interaction with the active material as a carrier, so that the titanium dioxide solid acid catalyst on which sulfate ions are supported can be used as a catalyst having high activity and stronger acidity than 100% sulfuric acid, And can be easily handled without causing pollution.
The titanium dioxide particle size is 10 to 50 nm, preferably 20 to 30 nm, and the specific surface area of the titanium dioxide particle may be 10 to 100 m 2 / g, preferably 30 to 70 m 2 / g, but is not limited thereto .
When the titanium dioxide particles have a particle size and a specific surface area within the above range, the amount of sulfate ions supported is increased, and the surface area is enlarged, thereby maximizing the operational ability as a catalytically active material.
The catalyst according to an embodiment of the present invention can be prepared by supporting titanium dioxide particles on a sulfuric acid as an active material solution using a carrier. The production method of the catalyst is not specifically limited, but the production method thereof will be described in detail as follows.
First, titanium dioxide particles are added to an aqueous solution of sulfuric acid and stirred for 1 to 6 hours. The sulfate ion can be uniformly supported within the above range, and the loading amount can be easily controlled.
Next, the supported titanium dioxide is filtered, dried at 100 to 150 ° C. for about 10 to 20 hours, and then calcined in an electric furnace at 500 to 700 ° C. for 1 to 6 hours to prepare a titanium dioxide solid acid catalyst carrying sulfate ion .
The drying temperature is preferably from 100 to 150 ° C., because it affects the movement of sulfate ions during drying, so that the water can be gradually evaporated to spread the sulfate ion evenly, and it can be sufficiently supported in the titanium dioxide particles.
At this time, the amount of the sulfate ion to be loaded may be 0.5 to 20% by weight of the titanium dioxide particle as the carrier, but the present invention is not limited thereto.
When sulfuric acid ions within the above range are supported, the action as an acid catalyst is smooth and a large specific surface area can be obtained.
For example, Fourier transform infrared spectroscopy (FT-IR,
The method of selectively producing di-styrene-substituted phenol according to an exemplary embodiment of the present invention is characterized in that a phenol compound and a styrene monomer are mixed and an alkylation reaction is performed in the presence of a titanium dioxide catalyst carrying sulfate ions to selectively form di- .
The reaction mechanism for the alkylation of the phenolic compound of the present invention with the styrene monomer is shown in the following reaction formula (2).
[Reaction Scheme 2]
Specifically, as shown in
Therefore, titanium dioxide is very strong in interaction with the active material as a carrier, so that the titanium dioxide solid acid catalyst on which sulfate ions are supported can be used as a catalyst having high activity and stronger acidity than 100% sulfuric acid, And can be easily handled without causing pollution.
The styrene monomer may be used in an amount of 1.8 to 2.2 mol based on 1 mol of the phenol compound, preferably 2 mol of the styrene monomer per mol of the phenol compound, thereby increasing the selectivity of the di-styrenated phenol desirable.
The di-styrenated phenol of the present invention has a molecular weight and viscosity corresponding to that between the mono-styrenated phenol and the tri-styrenated phenol, and the mono-styrenated phenol and the tri-styrenated phenol It is required to have a minimum content of the surfactant as a surfactant. Therefore, the highly selective di-styrenedione phenol of the present invention can be applied not only as an antioxidant but also as a hydrophobic surfactant, It has applicable advantages.
The content ratio of the titanium dioxide solid acid catalyst carrying the sulfate ion of the present invention may be in the range of 0.5 to 10% by weight based on the mixture of the phenolic compound and the styrene monomer. When used in this range, not only the excellent reactivity but also the reaction time .
The reaction conditions of the di-styrenated phenol according to an embodiment of the present invention will be described in detail. The reaction temperature for the production of the di-styrenated phenol may be 40 to 140 ° C, preferably 60 To 100 < 0 > C, more preferably 70 to 90 < 0 > C for 1 to 6 hours, but is not limited thereto.
The product of the di-styrenedephenol can be obtained by separately filtering it with a catalyst filter or the like without any solvent and an additional process.
The reaction conditions of the di-styrenated phenol are preferably carried out in an inert state, and the mixing of the phenolic compound and the styrene monomer may be carried out under an inert gas supply of argon, nitrogen, helium or neon. When the reaction is carried out under the supply of the inert gas, it is preferable in terms of minimizing unreacted residual materials and reaction by-products.
According to the method for producing styrene-substituted phenol of the present invention, the ratio of di-styrenated phenol in the final product can be made 40 to 60 mol% using a titanium dioxide solid acid catalyst, and unreacted materials can be minimized .
The styrene-butadiene phenol having a high content of highly di-styrene nitrile phenol obtained according to the present invention can be used not only as a high-quality antioxidant for products such as synthetic rubbers and resins, but also as a raw material for surfactants for electronic materials Do.
Hereinafter, a method for selectively preparing di-styrenated phenol using the titanium dioxide solid acid catalyst according to the present invention will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, the unit of the additives not specifically described in the specification may be% by weight.
[Property evaluation method]
Gas Chromatography (GC, HP-6890, Hewlett-Packard) analysis was performed to confirm the composition ratios. The conversion rates of phenolic compounds and styrene monomers, MSP, DSP, and TSP in the alkylation reaction of styrene monomer and phenol compound Were calculated according to the following equations (1) and (2).
- GC analysis conditions
GC; HP-6890 (Hewlett-Packard)
Sampling; 5 [mu] l (30 wt% toluene solution)
Carrier gas; He, 1 ml min -1
Column; Capillary column HP-5
Oven tem. ; 100 ℃ → 10 ℃ / min ↑ → 130 ℃ → 18 ℃ / min ↑ → 300 ℃ (15min Hold)
Injection tem. ; 300 ° C
Detector tem. ; 300 ° C (FID)
Split ratio; 1/50
[Formula 1]
[Formula 2]
[Example 1]
1. Catalyst Preparation
To 500 ml of distilled water was added 5.8 g of 98% sulfuric acid to prepare an aqueous sulfuric acid solution. 20 g of TiO 2 powder (20 to 30 nm, Degussa Co. Ltd, P25) was added to the aqueous sulfuric acid solution by stirring for 3 hours. After filtering to obtain a solid catalyst, it is dried at 110 ° C for 12 hours and then calcined at 600 ° C for 2 hours to prepare a titanium dioxide solid acid catalyst (SO 4 2- / TiO 2 ) carrying sulfate ion.
2. High selective preparation of di-styrenated phenol
After replacing the 100cc Schlenk tube with nitrogen, the reaction temperature was adjusted to 80 ° C using a temperature controller and a thermocouple (Al / Cr). 10 g (0.106 mol) of phenol, 22.0887 g (0.212 mol) of styrene, SO 4 2- / TiO 2 The catalyst was added in an amount of 5 wt% based on the mixture of phenol and styrene and stirred for 6 hours. After stirring, the catalyst was filtered to give the product.
[Example 2]
In Example 1, SO 4 2- / TiO 2 The di-styrenated phenol was obtained in the same manner as in Example 1 except that the catalyst was added in an amount of 0.5 wt% based on the mixture of phenol and styrene.
[Example 3]
In Example 1, SO 4 2- / TiO 2 A di-styrenated phenol was obtained in the same manner as in Example 1 except that the catalyst was added in an amount of 2% by weight based on the mixture of phenol and styrene.
[Example 4]
In Example 1, SO 4 2- / TiO 2 The di-styrenated phenol was obtained in the same manner as in Example 1 except that the catalyst was added in an amount of 10% by weight based on the mixture of phenol and styrene.
[Example 5]
A di-styrenated phenol was obtained in the same manner as in Example 1, except that the temperature of the di-styrenated phenol was adjusted to 40 ° C in Example 1.
[Example 6]
A di-styrenated phenol was obtained in the same manner as in Example 1, except that the temperature of the di-styrenated phenol was adjusted to 60 ° C in Example 1.
[Example 7]
A di-styrenated phenol was obtained in the same manner as in Example 1, except that the temperature of the di-styrenated phenol was adjusted to 100 ° C in Example 1.
[Example 8]
A di-styrenated phenol was obtained in the same manner as in Example 1, except that the temperature of the di-styrenated phenol was adjusted to 140 ° C in Example 1.
[Comparative Example 1]
Example 1 was carried out in the same manner as in Example 1 except that a phosphoric acid catalyst was used instead of the titanium dioxide solid acid catalyst.
[Comparative Example 2]
The procedure of Example 1 was repeated except that the sulfuric acid catalyst was used instead of the titanium dioxide solid acid catalyst in Example 1.
[Comparative Example 3]
Example 1 was carried out in the same manner as in Example 1, except that a nitric acid catalyst was used instead of the titanium dioxide solid acid catalyst.
As shown in Table 1, it was confirmed that the selectivity of the di-styrenated phenols of Examples 1 to 8 was high. Further, as shown in FIG. 2, in Examples 1 to 4, the conversion ratio of the phenol compound and the styrene monomer both approaches nearly 100% as the catalyst content increases. As shown in FIG. 3, in Example 1 and Examples 5 to 8, the conversion ratio of the phenol compound and the styrene monomer both approaches nearly 100% as the reaction temperature increases.
When the selectivity of mono-styrene-butadiene (MSP), di-styrene-naphthophenol (DSP) and tri-styrene-naphthophenol (TSP) was confirmed according to the catalyst contents in Examples 1 to 4, It was confirmed that the selectivity to styrene was high.
The selectivities of mono-styrene-butadiene phenol (MSP), di-styrene-naphthophenol (DSP) and tri-styrene nitrile phenol (TSP) were confirmed according to the reaction temperatures in Example 1 and Examples 5 to 8 , It was confirmed that the degree of selectivity of the di-styrenated phenol was high.
In the comparative example, it was confirmed that the selectivity of di-styrenated phenol was low and the conversion rate was low when sulfuric acid, phosphoric acid, and nitric acid, which are liquid acid catalysts, were used instead of solid acid catalysts. Further, after the reaction was carried out using a liquid acid catalyst, further processing was carried out in order to remove the waste acid, wastewater and byproducts, which was troublesome.
The styrene-based phenol of the present invention can be used as an important raw material for a color filter of an LCD panel and a developer for a thin film transistor (TFT) as a nonionic surfactant. At this time, the developer is used to develop a photosensitizer for forming a pattern on a glass or plastic surface in the manufacturing process of a TFT-LCD, and is generally formed by mixing distilled water, a hydroxide and a surfactant. In this case, the surfactant should be free of residual phenol, and the higher the content of di-styrenedephenol is, the more applicable it is.
Accordingly, the highly selective preparation method of the di-styrenated phenol of the present invention can increase the selectivity of the di-styrenated phenol, and the di-styrenated phenol can play a hydrophobic role of the surfactant and can be applied to a stable surfactant have.
As described above, in the present invention, a method for selectively producing di-styrenated phenol using a titanium dioxide solid acid catalyst has been described through specific embodiments and limited examples. However, the present invention has been made in order to provide a more general understanding of the present invention, The present invention is not limited to the above-described embodiments, and various modifications and changes may be made thereto by those skilled in the art to which the present invention belongs.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (7)
[Chemical Formula 1]
(2)
[In the above Chemical Formulas 1 to 2,
R 1 and R 2 are each independently hydrogen, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, cycloalkyl having 3 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms.
Wherein the titanium dioxide particles have a size of 10 to 50 nm.
Wherein the styrene monomer is used in a range of 1.8 to 2.2 mol based on 1 mol of the phenol compound.
Wherein the titanium dioxide solid acid catalyst is used in the range of 0.5 to 10 wt% based on the mixture of the phenolic compound and the styrene monomer.
Wherein the reaction of the phenolic compound with the styrene monomer is carried out at a temperature in the range of 40 to 140 占 폚.
Wherein the mixture of the phenolic compound and the styrene monomer is carried out under an inert gas supply of argon, nitrogen, helium or neon.
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Non-Patent Citations (2)
| Title |
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| Catalysis Letters, 1995, vol 30, pp. 241-252.* |
| Chemistry Letters, 1999, vol 28(3), pp.231-232 |
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