WO2020000366A1

WO2020000366A1 - Method for preparing hydrocarbyl phosphine halide and reactor therefor

Info

Publication number: WO2020000366A1
Application number: PCT/CN2018/093672
Authority: WO
Inventors: 邹应全; 焦红军; 郑朝俊; 田传文; 庞玉莲; 何长云; 何长华
Original assignee: 湖北固润科技股份有限公司
Priority date: 2018-06-29
Filing date: 2018-06-29
Publication date: 2020-01-02
Also published as: BR112020026755A2; MY194553A

Abstract

The present invention relates to a method for preparing compounds of the following formulae (I) and (II), wherein X is a halogen, and R is hydrocarbyl, and a reactor specifically used for performing the method. The method comprises reacting yellow phosphorus with a compound of formula (III) in the reactor in the absence of a catalyst, characterized in that, in the reactor, the material of the surface in contact with the reaction space is a nickel-based alloy as a corrosion resistant alloy, or the reactor is entirely made of the nickel-based alloy as a corrosion resistant alloy in the thickness direction of the wall of the whole reactor. Since the present invention uses the nickel-based alloy, which is used as a corrosion resistant alloy, as the material for the reactor and accessories thereof, an improved corrosion prevention effect, compared to existing reactors and accessories thereof, can be achieved, and moreover, the cost is acceptable, and thus the method can be achieved in on industrial scale.

Description

Method for preparing hydrocarbyl phosphine halide and reactor used for the method

Technical field

The invention relates to a method for directly synthesizing a hydrocarbyl halophosphine under the condition of no catalyst, and a reactor specially used for implementing the method.

Background technique

Diphenylphosphine chloride and phenyldichlorophosphine are important monomers for the synthesis of various organic phosphorus compounds. They are also intermediates for the preparation of pesticides, plasticizers, phosphorus flame retardants, and ultraviolet photoinitiators. The demand is vast.

The conventional method for preparing phenylphosphine dichloride is to use benzene and phosphorus trichloride to heat up the reaction for 2-6 hours in the presence of anhydrous aluminum trichloride catalyst. The liquid organic phase was separated at a reduced temperature, and excess benzene and phosphorus trichloride were distilled off under reduced pressure in order. Finally, the product was distilled under reduced pressure to obtain the product phenylphosphine dichloride. In this method, aluminum trichloride and phenylphosphine dichloride will form a complex and lose their activity. Therefore, it is necessary to add aluminum trichloride in an equimolar amount or more with benzene. This not only consumes a large amount of catalyst, but also generates a large amount of solid waste, which seriously pollutes the environment. Since the aluminum trichloride cannot be separated by hydrolysis or acid hydrolysis like other Friedel-Crafts reactions after the reaction, the desired product cannot be directly distilled from the reaction mixture. The product can be separated after adding decomplexing agents such as phosphorus oxychloride, phosphorus pentoxide, and pyridine, but the disadvantage is that a large amount of aluminum trichloride complex solid waste is generated, which is difficult to handle and has high environmental pressure. .

The synthesis of diphenylphosphine chloride is basically similar to that of phenylphosphine dichloride. The conventional method is also obtained by using excess benzene and phosphorus trichloride in the presence of an anhydrous aluminum trichloride catalyst at high temperature. Its disadvantage is that it will generate a large amount of complex solid waste of aluminum trichloride, which has great environmental pressure (see http://www.docin.com/p-1372117195.html).

Many researches and patented technologies around the separation of products have proposed the use of various decomplexing agents. Organic decomplexing agents include phosphorus trichloride, phosphorus pentoxide, pyridine organic bases, ethyl acetate, β-chlorotriethyl phosphate, and dioxane. The inorganic salt decomplexing agent is ground sodium chloride or potassium chloride. However, these methods will bring a large amount of solid waste that is difficult to handle. In addition, there are reports of using ionic liquids to synthesize phenylphosphine dichloride and diphenylphosphine chloride, but there are also problems that a large amount of solid waste is difficult to handle (Wang Zhongwei, Zhang Zhaoju, Liu Shangyi, et al., Fine and Specialty Chemicals, 2014 (10): 29-35).

Chinese patent application CN201110426418.5 discloses that benzene, phosphorus trichloride and aluminum trichloride are mixed vigorously and heated to 140-150 ° C for reaction; after the reaction is completed, the temperature is lowered to room temperature, and the decomplexing agent β-chlorophosphoric acid is added dropwise. Triethyl ester; the lower decomplexer layer was separated, and the upper organic layer was distilled under reduced pressure to obtain diphenylphosphine chloride.

Chinese patent application CN201210473945.6 discloses a method for synthesizing diphenylphosphine chloride. It uses a Lewis acid room temperature ionic liquid to catalyze the reaction of benzene and phosphorus trichloride to synthesize diphenylphosphine chloride. The method uses phosphorus trichloride and excess benzene as raw materials, and reacts under the action of a Lewis acid ionic liquid. After the reaction, the reaction liquid is divided into two layers, one is an ionic liquid layer, and the other is a mixed liquid layer. After direct liquid separation, the ionic liquid layer is extracted, and the extract and the mixed liquid layer are combined, and the pressure distillation and vacuum distillation are respectively performed to obtain the target product, diphenylphosphine chloride and by-product phenylphosphine dichloride. Ionic liquids are often recovered by removing the impurities under reduced pressure and reduced pressure.

Chinese patent application CN201310099065.1 proposes a synthetic method of phenylphosphine dichloride. Benzene and phosphorus trichloride are used as raw materials, and sodium chloride and aluminum trichloride are simultaneously added as catalysts to obtain phenylphosphine dichloride, a mixed solution of benzene and phosphorus trichloride, and a solid residue. The solid residue is treated with an extractant, mixed with the mixed liquid, and often distilled under reduced pressure to obtain pure phenylphosphine dichloride. The catalyst AlCl ₃ · XNaCl complex can be recycled.

The above methods all use benzene and phosphorus trichloride as raw materials and use aluminum trichloride as a catalyst. The focus of the solution is on the subsequent treatment of the aluminum trichloride complex. However, these methods, without exception, generate a large amount of solid waste that is difficult to handle and affects the environment.

The German company HOECHST proposed in US5587517 that triphenylphosphine and phosphorus trichloride are reacted at a high temperature above 350 ° C to form phenylphosphine dichloride and a small amount of diphenylphosphine chloride. 2051 grams of phosphorus trichloride and 816 grams of triphenylphosphine were put in to produce 1284 grams of phenylphosphine dichloride and a small amount of diphenylphosphine chloride. Due to the high price of triphenylphosphine, this method has no economic value in industry.

US patent US3734958 discloses that chlorobenzene and yellow phosphorus are used as raw materials in the presence of phenylphosphine dichloride to raise the temperature to 340 ° C in a tantalum autoclave to react for 4 hours, and then discharged after cooling to obtain phosphorus trichloride, chlorobenzene, A mixture of phenyldichlorophosphine and diphenylphosphine chloride, often under pressure distillation and vacuum distillation to obtain the product-diphenylphosphine chloride. Phosphorus trichloride, phenylphosphine dichloride, and diphenylphosphine chloride are very corrosive. Tantalum materials have Certain corrosion resistance, however, tantalum is expensive and cannot be industrialized, and the slightly cheaper tantalum-based alloy cannot achieve effective corrosion protection.

Since US 3734958 discloses the above-mentioned method for directly synthesizing diphenylphosphine chloride without catalyst, people have been trying to find the industrialization of this method, but no suitable reactor material has been found, resulting in the method has not been industrialized. For example, according to the reaction environment to which the existing corrosion-resistant materials are adapted, after selecting the corresponding materials to make the reactor, the corrosion resistance is not as good as expected.

Therefore, there is still a need to find a reactor and its accessories suitable for implementing the method disclosed in US 3734958. The reactor and its accessories are not only sufficiently resistant to corrosion, but also reasonable in cost and capable of industrial production.

Summary of the invention

In view of the above-mentioned state of the art, the inventors of the present invention have conducted extensive and in-depth studies on the materials of reactors and fittings for directly synthesizing hydrocarbon-based phosphine halide from yellow phosphorus and halogenated hydrocarbons as raw materials in the absence of a catalyst, It is hoped to find a special corrosion-resistant reactor and its accessories that can overcome the above-mentioned disadvantages of the prior art. The inventors of the present invention have unexpectedly discovered that a nickel-based alloy as a corrosion-resistant alloy has a prominent anticorrosive effect on the reaction raw materials and reaction products of the above reaction at the same time, and a reactor made of the corrosion-resistant alloy and its accessories can be effectively implemented. Method for directly synthesizing hydrocarbyl phosphine halide from yellow phosphorus and halogenated hydrocarbon as raw materials. The present invention has been completed based on the foregoing findings.

Therefore, an object of the present invention is to provide a method for synthesizing a hydrocarbon-based phosphine halide in a next step without catalyst in the presence of yellow phosphorus and a halogenated hydrocarbon as raw materials. This method uses a nickel-based alloy as a corrosion resistant alloy as the material of the reactor and its accessories, so that it can achieve an improved anticorrosive effect than the existing reactor and its accessories, and the cost is acceptable, so that the foregoing can be implemented on an industrial scale. method.

Another object of the present invention is to provide a reactor that specifically implements the preparation method of the present invention. The reactor uses a nickel-based alloy as a corrosion-resistant alloy as the material of the reactor, so that it can achieve improved corrosion protection than the existing reactor. Effect, so that the aforementioned method can be implemented on an industrial scale.

Yet another object of the present invention is to provide the use of a nickel-based alloy as a corrosion resistant alloy in the manufacture of the reactor of the present invention and its accessories.

The technical solution to achieve the above-mentioned objective of the present invention can be summarized as follows:

1. A method for preparing compounds of formula (I) and formula (II) below,

among them

X is halogen, preferably chlorine or bromine, and when two X are present in the same molecule, X may be the same or different, and

R is a hydrocarbon group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. When two R exist in the same molecule, R may be the same or different.

Including reacting yellow phosphorus with a compound of formula (III) in a reactor in the absence of a catalyst,

X-R

(III)

Where X and R are each as defined for formula (I) and formula (II),

It is characterized in that the material of the surface in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. production.

2. The method according to item 1, wherein the nickel-based alloy as the corrosion resistant alloy is one or more alloys selected from the group consisting of:

1) Ni-Cu based alloy, which contains 20-30% by weight Cu and 70-80% Ni based on its total weight;

2) Ni-Mo based alloy, which contains 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight;

3) a Ni-Cr based alloy comprising 50 to 65% by weight of Ni and 15% by weight or more of Cr, preferably 25% by weight or more of Cr, more preferably 35 to 50% by weight of Cr based on its total weight; and

4) other nickel-based corrosion-resistant alloys selected from the group consisting of Ni-Si alloys, which comprise 70-85% by weight of Ni and 3-10% by weight of Si, and Ni-Cr-Si alloys based on their total weight, It is a D-205 alloy, which contains 20% by weight of Cr, 5% by weight of Si, and 65% by weight of Ni based on its total weight.

3. The method according to item 1, wherein the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of a Monel (Monel) alloy (e.g. Monel

And Monel K500), Inconel (e.g. Inconel)

Inconel

And Inconel

), Incoloy (Incoloy) alloy

And Incoloy

) And Hastelloy alloys (e.g. Hastelloy

Hastelloy

And Hastelloy

).

4. The method according to any one of items 1-3, wherein the inner wall of the pipe in contact with the reaction raw material or the reaction product or the pipe is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the wall thickness direction, and / or The valve in contact with the reaction raw material or reaction product or those surfaces of the valve in contact with the reaction raw material or reaction product are made of a nickel-based alloy as a corrosion resistant alloy.

5. The method according to any one of items 1-4, wherein R is the same or different, and each independently represents a straight-chain or branched alkyl group containing 1 to 20, preferably 1 to 8 carbon atoms (such as Methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl and octyl), C ₆ -C ₁₀ aryl, preferably C ₆ -C ₈ aryl (eg phenyl, o-toluene Radicals, m-tolyl and p-tolyl), and C ₆ -C ₁₀ aralkyl, preferably C ₆ -C ₈ aralkyl (such as benzyl).

6. The method according to any one of items 1-5, wherein the feed molar ratio of yellow phosphorus to the compound of formula (III) is 1: 6-1: 12, preferably 1: 6-1: 10, more preferably 1: 6-1: 8.

7. The method according to any one of items 1-6, wherein the reaction of yellow phosphorus with a compound of formula (III) is as one or more compounds selected from compounds of formula (I), (II) and (IV) Carried out in the presence of a co-solvent, preferably in the presence of a compound of formula (I) and / or (II) as a co-solvent,

Wherein R is as defined for the compounds of formula (I) and formula (II); preferably, the amount of the co-solvent is 1-50% by weight, preferably 5-30% by weight, based on the total weight of yellow phosphorus and the compound of formula (III).

8. The method according to any one of items 1 to 7, wherein X is chlorine and R in each formula is phenyl or tolyl.

9. The method according to any one of items 1-8, wherein the reaction is carried out at a temperature of 200-800 ° C, preferably 200-600 ° C, more preferably 300-500 ° C, particularly preferably 300-400 ° C; and / or The reaction pressure is an autogenous pressure, for example, the reaction is performed at a gauge pressure of 0.01-8.0 MPa, preferably 0.01-6.0 MPa, more preferably 0.05-5.0 MPa; and / or, the reaction time is 2-10 h, preferably 2-6 h.

10. A reactor for carrying out the method according to any one of items 1-9, the reactor being a kettle reactor comprising: 1) a stirrer, 2) a kettle lid, and 3) a kettle body, 4) heating devices located outside and / or inside the reaction kettle, and 5) cooling devices located outside and / or inside the reaction kettle, wherein the kettle lid and optionally the upper part of the kettle are provided with openings, the kettle The chamber formed by connecting the cover to the kettle body constitutes the reaction space of the reactor, and is characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor reacts throughout the reaction. The thickness direction of the vessel wall is entirely made of a nickel-based alloy as a corrosion resistant alloy, and the volume of the reaction kettle is preferably 300L-5000L.

11. The reactor according to item 10, wherein the kettle cover is a flange cover, and the flange cover is connected to the kettle body through a flange plate.

12. The reactor according to item 10 or 11, wherein the nickel-based alloy as the corrosion resistant alloy is one or more alloys selected from the group consisting of:

4) other nickel-based corrosion-resistant alloys selected from the group consisting of Ni-Si alloys, which comprise 70-85% by weight of Ni and 3-10% by weight of Si, and Ni-Cr-Si alloys based on their total weight, It is a D-205 alloy, which contains 20% by weight of Cr, 5% by weight of Si and 65% by weight of Ni based on its total weight.

13. The reactor according to any one of items 10-12, wherein the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of a Monel (Monel) alloy (e.g. Monel

Monel K500), Inconel alloy (e.g. Inconel

Inconel

), Incoloy (Incoloy) alloy

Incoloy

) And Hastelloy alloys (e.g. Hastelloy

Hastelloy

).

14. Use of a nickel-based alloy as a corrosion-resistant alloy in the manufacture of a reactor according to any one of items 10-12 and its accessories such as pipes and valves.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a nickel-based alloy Hastelloy

And Monel

Photographs of the respective hanging pieces after being corroded in the gas phase.

Figure 2 shows the nickel-based alloy Hastelloy

And Monel

Photographs of the respective hanging pieces after being corroded in the liquid phase.

FIG. 3 is a photo of each hanging piece of tantalum, tantalum alloy Ta-2.5W and titanium-palladium alloy TA9 after being corroded in a gas phase.

FIG. 4 is a photo of each hanging piece of tantalum, tantalum alloy Ta-2.5W and titanium-palladium alloy TA9 after being corroded in a liquid phase.

detailed description

According to one aspect of the present invention, there is provided a method for preparing compounds of formula (I) and formula (II) below,

among them

X is halogen. When two X exist in the same molecule, X may be the same or different, and

R is a hydrocarbon group. When two R exist in the same molecule, R may be the same or different.

X-R

(III)

Where X and R are each as defined for formula (I) and formula (II),

It is characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall .

In the process of the present invention, the reaction of yellow phosphorus with a compound of formula (III) to obtain a compound of formula (I) and formula (II) in the absence of a catalyst is known per se, as described in US Pat. No. 3,734,958. This document is incorporated herein by reference in its entirety.

Since the reaction of yellow phosphorus with compounds of formula (III) to obtain compounds of formula (I) and formula (II) does not use any catalyst and is completed in one step, the reaction is sometimes referred to as "direct synthesis".

The variables X and R in formula (III) will be correspondingly transferred to the compounds of formula (I) and formula (II) after the reaction. Therefore, the definition of variables X and R in formula (III) is the same as that of formula (I) and formula ( II) The corresponding definitions in the compounds have a corresponding relationship. If two compounds of formula (I) in which R is different from each other are to be prepared, two compounds of formula (III) in which R are different from each other can be introduced. If two compounds of formula (II) in which X are different from each other are to be prepared, two compounds of formula (III) in which X are different from each other can be introduced.

In one embodiment of the method of the invention, all R in the compound of formula (I) are the same, and / or all X in the compound of formula (II) are the same.

In the compounds of formulae (I), (II) and (III), X is halogen, preferably chlorine or bromine. When two X are present in the same molecule, X may be the same or different.

In the compounds of formulae (I), (II) and (III), R is a hydrocarbon group. When two R exist in the same molecule, R may be the same or different. Preferably, R is the same or different, and each is independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group. When R is an aliphatic hydrocarbon group, it may be the same or different, and each independently represents a linear or branched alkyl group containing 1-20, preferably 1-8 carbon atoms, such as methyl, ethyl, propyl Base, butyl, isobutyl, tert-butyl, pentyl and octyl. When R is an aromatic hydrocarbon group, it may be the same or different, and each independently represents a C ₆ -C ₁₀ aryl group, preferably a C ₆ -C ₈ aryl group, such as phenyl, o-tolyl, m-tolyl, and p-toluene And C ₆ -C ₁₀ aralkyl, preferably C ₆ -C ₈ aralkyl, such as benzyl.

In a particularly preferred embodiment of the method of the invention, X is chlorine and R in each formula is phenyl or tolyl.

The reaction of yellow phosphorus with the compound of the formula (III) in the absence of a catalyst to obtain the compounds of the formula (I) and the formula (II) is conventional and can be carried out under conventional reaction conditions.

The reaction of yellow phosphorus with the compound of formula (III) can be advantageously carried out in the presence of a co-solvent. Yellow phosphorus is solid at normal temperature, and the co-solvent can dissolve the yellow phosphorus. As co-solvents, it is advantageous to use one or more compounds selected from the compounds of formulae (I), (II) and (IV) as described above,

Where R is as defined for the compounds of formula (I) and formula (II). For example, the co-solvent may be selected from a combination of one or more of triphenylphosphine, diphenylphosphine chloride, and phenyldichlorophosphine, especially when the compound to be prepared is diphenylphosphine chloride and phenyl Phosphine dichloride. The amount of the co-solvent is not particularly limited as long as the yellow phosphorus raw material used can be dissolved. Preferably, the amount of co-solvent is 1-50% by weight, preferably 5-30% by weight, based on the total weight of yellow phosphorus and the compound of formula (III).

It should be noted that although the method of the present invention can be carried out in the presence of one or more compounds selected from compounds of formulae (I), (II) and (IV) as cosolvents, the variables X and R is consistent with the corresponding variables X and R in the compounds of formula (I) and formula (II) to be prepared. For example, in order to prepare phenylphosphine dichloride and diphenylphosphine chloride, the selected co-solvent is preferably one or more of triphenylphosphine, phenylphosphine dichloride and diphenylphosphine chloride. Especially phenylphosphine chloride and / or diphenylphosphine chloride. This can reduce the cost of separating the components after the reaction is complete.

In the reaction of the method of the present invention, the amount of each reactant is conventional. Generally speaking, the molar ratio of yellow phosphorus (chemical formula P4) to the compound of formula (III) is 1: 6-1: 12, preferably 1: 6-1: 10, and more preferably 1: 6-1: 8.

In the reaction of the method of the present invention, the reaction temperature is conventional, and the reaction can be performed at a temperature of 200-800 ° C, preferably 200-600 ° C, more preferably 300-500 ° C, and particularly preferably 300-400 ° C. The reaction pressure is also conventional and is usually carried out under autogenous pressure. The reaction can be performed at a gauge pressure of 0.01 to 8.0 MPa, preferably 0.01 to 6.0 MPa, and more preferably 0.05 to 5.0 MPa. The reaction time is also conventional, and the reaction usually lasts 2-10 h, preferably 2-6 h. Whether the reaction is complete can be judged by sampling and detecting yellow phosphorus.

After the reaction is complete, a reaction mixture is obtained comprising compounds of formula (I) and formula (II), optionally unreacted white phosphorus, optional compound of formula (III), and optional co-solvent. In order to obtain the desired compounds of formula (I) and formula (II), the reaction mixture needs to be worked up. This workup is conventional as long as the compounds of formula (I) and formula (II) can be separated. To this end, the reaction mixture obtained by the reaction is usually cooled to room temperature, and then transferred to a distillation kettle, and separated by distillation, such as first atmospheric distillation and then rectification under reduced pressure, to obtain compounds of formula (I) and formula (II).

Phosphorus trichloride, phenylphosphine dichloride and diphenylphosphine chloride are highly corrosive. An important feature of the method of the present invention is that the material used for the surface in contact with the reaction space in the reactor of the method of the present invention is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely in the direction of the thickness of the entire reactor wall Made of a nickel-based alloy as a corrosion resistant alloy.

The prior art has various corrosion resistant material recommendations for various corrosive work or operating environments. As metal anti-corrosive materials, there are mainly iron-based alloys, such as corrosion-resistant stainless steel. Active metals also have good anti-corrosion capabilities, typically represented by Ti, Zr, and Ta. The reactor taught in US 3734958 is a tantalum autoclave. However, the present inventors have found that when a tantalum autoclave is used to prepare a hydrocarbon-based phosphine halide, although it has a certain degree of corrosion resistance, when used in an industrial scale preparation, its corrosion resistance and durability are not enough, and the cost is high Therefore, the industrialized production of hydrocarbyl phosphine halide cannot be achieved.

The inventors have found that if the surface in the reactor that is in contact with the reaction space or even the entire thickness of the reactor wall is made of a nickel-based alloy as a corrosion-resistant alloy, the corrosion resistance of the reactor thus constructed is greatly improved, which is sufficient Corrosion resistance, and its price is far lower than tantalum materials, which provides a feasible reaction equipment for the industrialization of hydrocarbyl phosphine halide.

In the method of the present invention, the material of the surface in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of nickel as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. Base alloy. In the present invention, the reaction space of a reactor has the meaning commonly understood by those skilled in the art. For example, taking a reaction kettle as an example, the reaction space refers to a three-dimensional space enclosed by the lid of the reaction kettle and the kettle body. In the present invention, the reactor may be made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. Alternatively, for cost, strength, or other considerations, only those surfaces in the reactor that are in contact with the reaction space may be made of a nickel-based alloy as a corrosion resistant alloy. As for the thickness of these surfaces, it can be determined through routine tests according to the actual operating conditions and the design life of the reactor.

Nickel-based alloys, which are corrosion-resistant alloys, generally contain more than 30% by weight of Ni, and common Ni-based alloys have a Ni content of more than 50% by weight. Because nickel-based alloys have superior high-temperature mechanical strength and corrosion resistance, they are collectively called superalloys with iron-based alloys and cobalt-based alloys.

In one embodiment of the present invention, the nickel-based alloy as the corrosion resistant alloy may be selected from one or more of the following groups:

1) Ni-Cu based alloy, which contains 20-30% by weight of Cu and 70-80% of Ni based on its total weight. Ni-Cu series alloys are represented by Monel (Monel) alloys. Monel alloys have many of the advantages of Ni and Cu and can maintain a permanent metallic luster in the atmosphere. Monel alloy is mainly used for corrosion-resistant parts and equipment under high temperature and load. As an example of a Monel alloy, mention may be made of Monel

And Monel K500.

2) A Ni-Mo-based alloy containing 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight. The addition of molybdenum in this type of alloy greatly improves the corrosion resistance, strength, and high-temperature processability of nickel-based (solid solution). Adding more than 15% Mo to Ni can make the alloy have a high resistance to oxidizing acids. Studies have shown that Ni-Mo alloys containing about 28% Mo can withstand hydrochloric acid corrosion at any temperature and concentration under normal pressure, and can also withstand corrosion by sulfuric acid, acetic acid, phosphoric acid, formic acid, and hydrogen chloride gas. The Ni-Mo corrosion resistant alloy includes a Hastelloy alloy. As an example of the Hastelloy alloy, mention may be made of Hastelloy

Hastelloy

And Hastelloy

3) A Ni-Cr-based alloy containing 50 to 65% by weight of Ni and 15% by weight or more of Cr, preferably 25% by weight or more of Cr, and more preferably 35 to 50% by weight of Cr, based on its total weight. The addition of chromium to such alloys significantly increases the resistance of nickel to oxidative acids, salts, and high-temperature oxidation, sulfur, and vanadium. Containing 15% by weight of Cr can passivate Ni in dilute sulfuric acid; containing more than 25% by weight of Cr can passivate in aerated nitric acid; if corrosion resistance is required in hot concentrated nitric acid, 35-50% by weight of chromium. Typical Ni-Cr corrosion resistant alloys include Inconel and Incoloy. Mention may be made of Inconel as an example of the Inconel alloy

Inconel

And Inconel

Inconel

Not only resistant to high temperature oxidation, but also used in aqueous solution, especially strong oxidizing aqueous solution, it can be used in room temperature sulfuric acid, phosphoric acid, low concentration of hydrochloric acid, hydrofluoric acid and other environments. Excellent performance, widely used in chemical industry, nuclear power industry, etc. As an example of the Incoloy alloy, mention may be made of Incoloy

And Incoloy

4) Other nickel-based corrosion resistant alloys. For example, Ni-Si alloys (70-85% by weight of Ni and 3-10% by weight of Si) are resistant to oxidation, sulfuric acid (arbitrary concentration and boiling point temperature), organic acids and salts. There is also Ni-Cr-Si alloy D-205 alloy, in which Cr accounts for 20% by weight, Si accounts for 5% by weight, and Ni accounts for 65% by weight. This alloy is mainly used in the environment where superoxide substances exist.

In a preferred embodiment of the method of the present invention, the inner wall of the pipe that is in contact with the reaction raw material or reaction product or the pipe is entirely made of a nickel-based alloy as a corrosion resistant alloy in the wall thickness direction. In another preferred embodiment of the method of the invention, the valve in contact with the reaction raw material or reaction product or those surfaces of the valve in contact with the reaction raw material or reaction product are made of a nickel-based alloy as a corrosion resistant alloy.

Since the materials of the surface of the reactor and optional reaction accessories of the present invention that are in contact with the reaction raw material or reaction product are sufficiently resistant to corrosion caused by the reaction raw material or reaction product of the present invention, the method of the present invention can not only be performed in a laboratory, but also It can also realize industrialization and large-scale production. The reactor according to the present invention may be designed to have a volume of 300L-5000L, that is, the volume of the internal space of the reaction kettle is 300L-5000L.

According to another aspect of the present invention, there is provided a reactor for carrying out the method of the present invention. The reactor is a kettle reactor and includes: 1) a stirrer, 2) a kettle lid, and 3) a kettle body, 4 ) Heating devices located outside and / or inside the reaction kettle, and 5) cooling devices located outside and / or inside the reaction kettle, wherein the kettle lid of the reaction kettle and optionally, the upper part of the kettle body is provided with openings, the kettle lid The chamber connected to the kettle body constitutes the reaction space of the reactor, and is characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is in the entire reactor The wall thickness direction is made entirely of a nickel-based alloy as a corrosion resistant alloy.

The reactor of the present invention is provided with a stirrer for stirring the materials inside the reactor evenly. Any stirrer that can achieve the function of stirring or agitation can be used, including mechanical stirrers, magnetic stirrers, etc. In consideration of the toxicity and corrosivity of the reaction raw materials and products, the reactor needs to be kept in a sealed state, and the stirrer is preferably a magnetic stirrer. The kettle-type reaction kettle at this time becomes a magnetic reaction kettle. In order to achieve the regulation of the stirring rate, the stirrer usually has a motor reducer. The stirrer is usually fixed on the lid of the kettle, and the magnetic piece of the stirrer or the stirring blade or the stirring belt is located in the reactor.

The kettle lid can be flat or project outward. In order to better seal the reaction space of the reactor, the kettle cover is preferably a flange cover, and the flange cover is connected to the kettle body through a flange plate. Accordingly, the agitator is fixed on the flange cover. At this time, the reactor includes a flange cover, a flange plate and a kettle body from top to bottom. The flange cover is connected with the kettle body through a flange to form a closed chamber, which constitutes a reaction space of the reactor. For the purpose of feeding, discharging, sampling measurement and maintenance, in addition to the opening for setting the stirrer, the kettle lid may also have other openings, such as manholes, inlet and outlet holes. Similarly, the upper part of the reactor body can also be perforated, for example for feeding and discharging, sampling and testing. According to the invention, the reaction kettle is preferably a vertical reactor.

The reactions involved in the process of the invention are generally carried out at elevated temperatures. To this end, the reactor needs to be equipped with heating devices and cooling devices. As the heating means of the reactor, it is located outside and / or inside the reactor, preferably outside. As a cooling device for the reactor, it is located outside and / or inside the reactor, preferably outside. The heating device can be heated by a molten salt electric heater or a far-infrared heating plate. The cooling device can be cooled by air cooling or circulating water.

Regarding the material of the reactor of the present invention, it is applicable to the material description of the reactor involved in the method of the present invention, which is not repeated here. Since the contact surface between the reactor and the stream of the invention or the entire reactor is made of a specific corrosion-resistant alloy, the industrial production of the method of the invention can be realized. In one embodiment of the reactor of the present invention, the working volume of the reactor is 300L-5000L.

According to a final aspect of the invention, there is provided the use of a nickel-based alloy as a corrosion resistant alloy in the manufacture of the reactor of the invention and its accessories. The description of the nickel-based alloy as the corrosion-resistant alloy is applicable to the material description of the reactor involved in the method of the present invention, and is not repeated here. The fittings of the reactor include all pipes and valves in contact with the reaction raw materials or reaction products.

The method and reactor of the present invention have very important practical significance for the industrialized production of hydrocarbyl phosphine halide. At present, there is no such industrial production technology at home and abroad. The present invention successfully realizes the industrialized production of hydrocarbyl phosphine halide in a green and environmentally friendly manner. Advantages of the invention include:

1. The catalyst-free direct synthesis of hydrocarbon-based phosphine halide (especially phenylphosphine dichloride) production process is green and environmentally friendly, and no waste gas, waste liquid, waste residue is generated, which meets the needs of modern green environmental protection chemical production.

2.Using a nickel-based alloy as a corrosion-resistant alloy as the material of the reactor and its accessories or as the material of the material contact surface of the reactor, it has obtained excellent corrosion resistance and can successfully achieve industrialization of 300-5000L per batch produce.

Examples

The present invention is described in detail below with reference to examples and comparative examples, but the scope of the present invention is not limited to these.

In this specification, unless otherwise stated, all "parts" refer to parts by weight.

In each embodiment of the present invention, the yellow phosphorus used was purchased from Yunnan Huofa Phosphate Co., Ltd. with a purity of 95%; chlorobenzene was purchased from Wuhan Fengyao Tonghui Chemical Co., Ltd. with a purity of 98%.

Examples 1-10 and Comparative Examples 1-6: Corrosion resistance of various corrosion-resistant metals

Each corrosion-resistant metal is made into two identical metal pendants, and the size of the pendant is × 10cm × 10cm × 0.3cm or 10cm × 3cm × 0.3cm or 10cm × Φ0.2cm wire. Two pendants of each corrosion-resistant metal were placed in the gas phase of a 5 L closed-pressure axe containing a mixture of 20% by weight of phosphorus trichloride, 40% by weight of phenylphosphine dichloride, and 40% by weight of diphenylphosphine chloride. In the liquid phase, the test temperature is 500 ° C, the pressure (gauge pressure) is 0.5 MPa, and the test is continued for 10 hours. After the test time, remove the pendant to take a picture and weigh it to evaluate the anti-corrosion effect.

The tested corrosion-resistant metals include: pure tantalum metal sheet, tantalum alloy Ta-2.5W, pure metal zirconium sheet, Zr702 zirconium plate, titanium molybdenum nickel alloy TA10 and titanium palladium alloy TA9.

Figure 1 shows the nickel-based alloy Hastelloy

And Monel

Photographs of the respective hanging pieces after being corroded in the gas phase, of which Figure 1 (a) is Hastelloy

Alloy, Figure 1 (b) is Monel

alloy.

Figure 2 shows the nickel-based alloy Hastelloy

And Monel

Photographs of the respective hanging pieces after being corroded in the liquid phase, of which Figure 2 (a) is Hastelloy

Alloy, Figure 2 (b) is Monel

alloy.

Fig. 3 shows a photo of each hanging piece of tantalum, tantalum alloy Ta-2.5W, and titanium-palladium alloy TA9 after being corroded in the gas phase. Fig. 3 (a) is tantalum, and Fig. 3 (b) is tantalum alloy Ta-2.5. W, and FIG. 3 (c) is a titanium-palladium alloy TA9.

Figure 4 shows the photos of the tantalum, tantalum alloy Ta-2.5W, and titanium-palladium alloy TA9 after corrosion in the liquid phase. Figure 4 (a) is tantalum, and Figure 4 (b) is tantalum alloy Ta-2.5. W, and FIG. 4 (c) is a titanium-palladium alloy TA9.

The weight loss before and after corrosion is used to calculate the corrosion rate of each pendant, that is, the percentage of the weight that is eroded and the original weight before corrosion. The corrosion resistance results of each corrosion resistant metal are summarized in Table 1 below.

Table 1

Example 11: Production in a 500L reactor

35 kg (0.282 kmol) of yellow phosphorus, 200 kg (1.777 kmol) of chlorobenzene, and 20 kg (0.112 kmol) of phenylphosphine dichloride were put into a 500L closed autoclave, which was developed by Hastelloy

Made of alloy. The temperature was raised to 300 ° C, and after reacting for 3 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, and unreacted chlorobenzene was distilled off under normal pressure distillation, and then distilled under reduced pressure to produce diphenylphosphine chloride 100. Kilograms (0.453 kmol), and 127.6 kg (0.713 kmol) of phenylphosphine dichloride.

Example 12: Production in a 300L reactor

20 kg (0.161 kmol) of yellow phosphorus, 150 kg (1.333 kmol) of chlorobenzene, and 20 kg (0.076 kmol) of triphenylphosphine were put into a 500L closed autoclave, which was made of Monel K500. The temperature was raised to 330 ° C, and after reacting for 5 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, and the unreacted chlorobenzene was distilled off at normal pressure for recovery and use, and then subjected to vacuum distillation to produce diphenyl chloride. 60 kg (0.272 kmol) of phosphine, and 73.4 kg (0.410 kmol) of phenylphosphine dichloride.

Example 13: Production in a 500L reactor

40 kg (0.323 kmol) of yellow phosphorus, 236 kg (2.097 kmol) of chlorobenzene, and 30 kg (0.168 kmol) of phenylphosphine dichloride were put into a 500L closed autoclave, which was made by Inconel

production. The temperature was raised to 360 ° C, and after reacting for 3 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, the chlorobenzene was distilled off at normal pressure, and then distilled under reduced pressure to yield 134.1 kg (0.608 kmol ), And phenyl phosphine dichloride 152.30 kg (0.851 kmol).

Example 14: Production in a 500L reactor

40 kg (0.323 kmol) of yellow phosphorus, 280 kg (2.488 kmol) of chlorobenzene, and 40 kg (0.181 kmol) of diphenylphosphine chloride were put into a 500L closed autoclave, which was developed by Hastelloy

production. The temperature was raised to 350 ° C, and after reacting for 3 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, and unreacted chlorobenzene was distilled off at normal pressure, and distilled under reduced pressure to produce 120 kg of diphenylphosphine chloride. (0.544 kmol), and 152.6 kg (0.853 kmol) of phenylphosphine dichloride.

Example 15: Production in a 1000L reactor

80 kg (0.646 kmol) of yellow phosphorus, 600 kg (5.330 kmol) of chlorobenzene, and 50 kg (0.279 kmol) of phenylphosphine dichloride were put into a 1000L closed autoclave, which was manufactured by Incoloy

production. The temperature was raised to 380 ° C, and after reacting for 4 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, and subjected to distillation under reduced pressure to produce 219.5 kg (0.995 kmol) of diphenylphosphine chloride and phenyldichloro 300 kg (1.676 kmol) of phosphine.

Example 16: Production in a 1000L reactor

100 kg (0.807 kmol) of yellow phosphorus, 600 kg (5.330 kmol) of chlorobenzene, and 80 kg (0.305 kmol) of triphenylphosphine were put into a 1000 L closed autoclave, which was made of Monel K500. The temperature was raised to 400 ° C, and after reacting for 4 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, and subjected to vacuum distillation to produce 355 kg (1.609 kmol) of diphenylphosphine chloride and phenyl dichloride. Phosphine phosphide 310 kg (1.732 kmol).

Example 17: Production in a 5000L reactor

500 kg (4.036 kmol) of yellow phosphorus, 3,000 kg (26.652 kmol) of chlorobenzene, and 300 kg (1.144 kmol) of triphenylphosphine were put into a 5000L closed autoclave, which was made by Inconel

production. The temperature was raised to 430 ° C, and after reacting for 10 hours under autogenous pressure, the reaction kettle was cooled to room temperature, discharged, the unreacted chlorobenzene was distilled off at normal pressure, and then distilled under reduced pressure to produce 1881 kg of diphenylphosphine chloride (8.525 kmol), and 1500 kg (8.380 kmol) of phenylphosphine dichloride.

Example 18: Production in a 5000L reactor

500 kg (4.036 kmol) of yellow phosphorus, 2800 kg (24.875 kmol) of chlorobenzene, and 300 kg (1.360 kmol) of diphenylphosphine chloride were put into a 5000L closed autoclave. The autoclave was made by Inconel

production. The temperature was raised to 380 ° C, and after reacting for 8 hours under autogenous pressure, the reaction kettle was cooled to room temperature and discharged. The unreacted chlorobenzene was distilled off at normal pressure and distilled under reduced pressure to produce 1789 kg of diphenylphosphine chloride. (8.108 kmol), and 1600 kg (8.939 kmol) of phenylphosphine dichloride.

Claims

A method for preparing compounds of formula (I) and formula (II) below,

among them

X is halogen, preferably chlorine or bromine, and when two X are present in the same molecule, X may be the same or different, and

R is a hydrocarbon group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. When two R exist in the same molecule, R may be the same or different.

Including reacting yellow phosphorus with a compound of formula (III) in a reactor in the absence of a catalyst,

Where X and R are each as defined for formula (I) and formula (II),

It is characterized in that the material of the surface in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. production.
The method according to claim 1, wherein said nickel-based alloy as a corrosion resistant alloy is one or more alloys selected from the group consisting of:

1) Ni-Cu based alloy, which contains 20-30% by weight Cu and 70-80% Ni based on its total weight;

2) Ni-Mo based alloy, which contains 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight;

3) a Ni-Cr based alloy comprising 50 to 65% by weight of Ni and 15% by weight or more of Cr, preferably 25% by weight or more of Cr, more preferably 35 to 50% by weight of Cr based on its total weight; and

4) other nickel-based corrosion-resistant alloys selected from the group consisting of Ni-Si alloys, which comprise 70-85% by weight of Ni and 3-10% by weight of Si, and Ni-Cr-Si alloys based on their total weight, It is a D-205 alloy, which contains 20% by weight of Cr, 5% by weight of Si, and 65% by weight of Ni based on its total weight.
The method according to claim 1, wherein said nickel-based alloy is one or more nickel-based alloys selected from the group consisting of: a Monel alloy (e.g.,
And Monel K500), Inconel alloy (e.g.
with
), Incoloy alloy
with
And Hastelloy alloys (e.g.

with
).
The method according to any one of claims 1 to 3, wherein the inner wall of the pipe in contact with the reaction raw material or the reaction product or the pipe is entirely made of a nickel-based alloy as a corrosion resistant alloy in the wall thickness direction, and / or, and The valve in which the reaction raw material or the reaction product contacts or those surfaces of the valve which are in contact with the reaction raw material or the reaction product are made of a nickel-based alloy as a corrosion resistant alloy.
The method according to any one of claims 1 to 4, wherein R is the same or different, and each independently represents a straight-chain or branched alkyl group containing 1 to 20, preferably 1 to 8 carbon atoms (e.g. methyl , Ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl and octyl), C 6 -C 10 aryl, preferably C 6 -C 8 aryl (e.g. phenyl, o-tolyl, M-tolyl and p-tolyl), and C 6 -C 10 aralkyl, preferably C 6 -C 8 aralkyl (such as benzyl).
The method according to any one of claims 1-5, wherein the molar ratio of yellow phosphorus to the compound of formula (III) is 1: 6-1: 12, preferably 1: 6-1: 10, more preferably 1: 6- 1: 8.
A method according to any one of claims 1 to 6, wherein the reaction of yellow phosphorus with a compound of formula (III) is as a cosolvent in one or more compounds selected from compounds of formula (I), (II) and (IV) In the presence, preferably in the presence of a compound of formula (I) and / or (II) as a co-solvent,

Wherein R is as defined for the compounds of formula (I) and formula (II); preferably, the amount of the co-solvent is 1-50% by weight, preferably 5-30% by weight, based on the total weight of yellow phosphorus and the compound of formula (III).
A process according to any one of claims 1 to 7, wherein X is chlorine and R in each formula is phenyl or tolyl.
Process according to any one of claims 1 to 8, wherein the reaction is carried out at a temperature of 200-800 ° C, preferably 200-600 ° C, more preferably 300-500 ° C, particularly preferably 300-400 ° C; and / or, the reaction The pressure is an autogenous pressure, for example, the reaction is performed at a gauge pressure of 0.01-8.0 MPa, preferably 0.01-6.0 MPa, more preferably 0.05-5.0 MPa; and / or, the reaction time is 2-10 h, preferably 2-6 h.
A reactor for carrying out the method according to any one of claims 1-9, the reactor being a kettle reactor comprising: 1) a stirrer, 2) a kettle lid, and 3) a kettle body, 4) Heating devices located outside and / or inside the reaction kettle, and 5) cooling devices located outside and / or inside the reaction kettle, wherein the kettle lid and optionally the upper part of the kettle body are provided with openings, the kettle lid and The chamber formed by the connection of the kettle body constitutes the reaction space of the reactor, and is characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion resistant alloy, or the reactor is on the entire reactor wall All in the thickness direction are made of a nickel-based alloy as a corrosion resistant alloy, and the volume of the reaction kettle is preferably 300L-5000L.
The reactor according to claim 10, wherein the kettle cover is a flange cover, and the flange cover is connected to the kettle body through a flange plate.
The reactor according to claim 10 or 11, wherein said nickel-based alloy as a corrosion resistant alloy is one or more alloys selected from the group consisting of:

1) Ni-Cu based alloy, which contains 20-30% by weight Cu and 70-80% Ni based on its total weight;

2) Ni-Mo based alloy, which contains 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight;

3) a Ni-Cr based alloy comprising 50 to 65% by weight of Ni and 15% by weight or more of Cr, preferably 25% by weight or more of Cr, more preferably 35 to 50% by weight of Cr based on its total weight; and

4) other nickel-based corrosion-resistant alloys selected from the group consisting of Ni-Si alloys, which comprise 70-85% by weight of Ni and 3-10% by weight of Si, and Ni-Cr-Si alloys based on their total weight, It is a D-205 alloy, which contains 20% by weight of Cr, 5% by weight of Si and 65% by weight of Ni based on its total weight.
A reactor according to any one of claims 10-12, wherein said nickel-based alloy is one or more nickel-based alloys selected from the group consisting of: Monel (Monel)
Monel K500), Inconel alloy (e.g.

), Incoloy alloy
And Hastelloy alloys (e.g.
).
Use of a nickel-based alloy as a corrosion-resistant alloy in the manufacture of a reactor according to any one of claims 10-13 and its fittings such as pipes and valves.