Main preparation method of tetrakis triphenylphosphine platinum_Kain Industrial Additive

Background and overview^[1]

Platinum has superior performance and is widely used. For example, in the jewelry industry, platinum is mainly used as decorations and handicrafts; in the chemical industry, platinum is used to manufacture advanced chemical vessels, platinum crucibles, electrodes and accelerate chemical reactions. A catalyst for speed; Platinum-iridium alloy is the material used to make fountain pen tips. Especially in the automobile industry, platinum plays an irreplaceable role in exhaust gas treatment and other aspects, and its consumption accounts for almost half of the industrial use of platinum. Platinum compounds such as cisplatin, carboplatin, and oxaliplatin are a class of very effective anticancer drugs. Catalytic reactions involving precious metals are of great significance to chemical industry. Platinum, as an important catalytic material, has been widely used in petrochemical industry, pharmaceutical chemical industry, fine chemical industry, environmental protection and other fields. The reactions of addition and petroleum catalytic reforming play an irreplaceable role. Metal-platinum-organophosphine complexes are widely used in homogeneous catalysis. Tetrakis(triphenylphosphine)platinum(0) was first reported by Ugo, R.; Cariati, F. and La Monica, G. in Journal of the Chemical Society (1958), 2323. They reported hydrazine hydrate in a solution containing three The product was obtained by reducing bis(triphenylphosphine)platinum dichloride in an ethanol solution of phenylphosphine. Afterwards, they improved the method in Inorganic Syntheses (1968), 11, 105-8. Dissolve K2PtCl4 in ethanol and heat to 65°C , adding triphenylphosphine and KOH for reduction to obtain Pt(PPh3)4, with a yield of 79%. In summary, the method for synthesizing tetrakis(triphenylphosphine)platinum(0) has a yield of only about 80% in actual scale-up production. The main reason is that the solvent DMF dissolves part of the product. When alcohol and alkali are used as reducing agents, it is difficult to completely remove the strong alkali in post-processing, which not only reduces the purity of tetrakis(triphenylphosphine)platinum(0), but also greatly shortens the shelf life and easily deteriorates. Bis(triphenylphosphine)platinum dichloride is obtained by the reaction of platinum inorganic salt and triphenylphosphine. However, in order to simplify and shorten the reaction, it is not easy to use triphenylphosphine platinum chloride as the raw material. .

Preparation^[1]

A method for synthesizing tetrakis(triphenylphosphine)platinum(0) that can reduce costs, shorten reaction time, improve product purity, and simplify operating procedures. The technical solution adopted is: the method for synthesizing tetrakis (triphenylphosphine) platinum (0), which method is: mixing platinum precursor and triphenylphosphine with dimethyl sulfoxide in proportion, under nitrogen protection Heat to 130-150°C for dissolution. After 0.5-1 hour of heat preservation and dissolution reaction, after the platinum precursor and triphenylphosphine are completely dissolved, cool down to about 100-120°C, and then add 80% hydrazine hydrate reducing agent dropwise for reduction. After the reduction reaction for 0.5-1 hour, the reaction solution with a large amount of yellow precipitate was cooled to room temperature, filtered under a nitrogen atmosphere, washed with ethanol and petroleum ether, and dried under vacuum to obtain a yellow powder - tetrakis (triphenylphosphine) platinum. (0)Finished product;

Apply^[2-3]

Tetrakis(triphenylphosphine)platinum(0), as an important platinum-organophosphine complex, is mainly used for hydrosilylation of olefins, carbon-silicon bond cleavage, silicone rubber vulcanization, carbonylation, hydrogenation, and olefin isomerization. , a catalyst for reactions such as the oxidation of organic mercury compounds, and is also used as a raw material for the preparation of many platinum compounds.

1) Used to prepare an environmentally friendly additive for natural gas welding and cutting gas. The additive is composed of at least one of ethanol, 2-hexanol, 2-hexanone, limonene, organic platinum and C5-C7 isoparaffins. It is composed of one, and the weight percentage of each component is: ethanol 5%-10%, 2-hexanol 5%-10%, 2-hexanone 5%-10%, limonene 10%-15%, organic platinum 0.02 %-0.08%, the remainder is at least one of C5-C7 isoparaffins, and the organic platinum is selected from the group consisting of tetrakis triphenylphosphine platinum, triphenylphosphine platinum chloride, and diaminocyclohexane platinum oxalate. , at least one of dinitrile phenyl platinum dichloride and ethylenediamine platinum. The invention can significantly reduce the use cost of natural gas welding and cutting gas and is harmless to the environment, so it is worthy of promotion and application in existing corresponding occasions.

2) Preparation of macrocyclic modified dendrimer supported Pd-Pt bimetallic nanoparticle catalyst. The preparation method is to first use a fifteen-membered triene nitrogen heterocycle to modify polypropylene imine to synthesize a new type of macrocyclic modified dendrimer (Gn-M) with different generations of surface-grafted fifteen-membered triene nitrogen heterocycles. Then Pd-Pt was prepared by ligand exchange method using tetrakis (triphenylphosphine) platinum ((PPh3) 4Pt) and tetrakis (triphenylphosphine) palladium ((PPh3) 4Pd) as precursors and Gn-M as carrier. Bimetallic nanoparticle catalysts (DSNs) supported by modified dendrimers in different proportions were applied to the catalytic hydrogenation of nitrile butadiene rubber (NBR). The catalyst prepared by the invention not only has excellent catalytic activity and selectivity, but also has efficient recyclability and recycling.