CN112645981A - Phosphine compound and production process thereof - Google Patents

Phosphine compound and production process thereof Download PDF

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Publication number
CN112645981A
CN112645981A CN202011391198.2A CN202011391198A CN112645981A CN 112645981 A CN112645981 A CN 112645981A CN 202011391198 A CN202011391198 A CN 202011391198A CN 112645981 A CN112645981 A CN 112645981A
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catalyst
stirring
graphene oxide
carrying
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CN112645981B (en
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鲍远志
翁世兵
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Lu'an Koreda New Materials Co ltd
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Lu'an Koreda New Materials Co ltd
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    • C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract

The invention discloses a phosphine compound and a production process thereof, and a catalyst is prepared in the preparation process, the catalyst is prepared by carrying out ultrasonic treatment on graphene oxide and carbon fibers to enable the carbon fibers to be embedded in grooves on the surface of the graphene oxide, then adding 1-hydroxybenzotriazole to enable carboxyl on the surface of the graphene oxide to react with amino on the surface of the aminated carbon fibers, further fixing the graphene oxide and the carbon fibers, dissolving zinc chloride, ferric chloride and nickel chloride in deionized water, and carrying out ultrasonic treatment to enable zinc, iron and metal ions to be fixed on the surface of the carbon fibers so as to prepare the catalyst, the catalyst is composed of multiple metals with reducibility, the carrier has reducibility, can be fully contacted with the reactants to increase the reaction rate, and is easy to recover, the recovered catalyst can be treated by nickel potassium borohydride, and the preparation cost is greatly reduced and the resource waste is reduced by reusing the catalyst.

Description

Phosphine compound and production process thereof
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a phosphine compound and a production process thereof.
Background
The powder coating is a solid coating which does not contain solvent and volatile matter, has the advantages of harmlessness, environmental protection, high efficiency, low price and the like, and in recent years, along with the continuous increase of environmental protection strength at home and abroad and the continuous improvement of environmental protection consciousness of users, the demand on the powder coating in various fields is more and more urgent, the powder coating is widely applied in the fields of automobiles, pipelines, household appliances, furniture, aluminum profiles and the like at present, and the phosphonized matter is a common catalyst in the powder coating.
The existing phosphine production process needs to use a large amount of catalysts in the preparation process, so that the production cost is increased, the catalysts cannot be recycled, and the resource waste is serious.
Disclosure of Invention
The invention aims to provide a phosphine compound and a production process thereof.
The technical problems to be solved by the invention are as follows:
the existing phosphine production process needs to use a large amount of catalysts in the preparation process, so that the production cost is increased, the catalysts cannot be recycled, and the resource waste is serious.
The purpose of the invention can be realized by the following technical scheme:
a phosphonized compound, which is prepared by the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, reactants and tetrahydrofuran into a reaction kettle, stirring for 20-30min at the rotation speed of 200-300r/min and the temperature of 0-3 ℃, adding a catalyst, heating to the temperature of 70-80 ℃, and carrying out reflux reaction for 3-8h to obtain the phosphide.
Further, the molar ratio of the phosphorus trichloride to the sublimed sulfur to the aluminum trichloride to the reactants is 1:1:3:3, the reactants are one of aromatic hydrocarbon or Grignard reagent, the Grignard reagent is obtained by reacting halogenated hydrocarbon with metal magnesium, the halogenated hydrocarbon is one of halogenated cycloalkane and halogenated alkane, and the amount of the catalyst is 50-60% of the mass of the phosphorus trichloride.
Further, the catalyst is prepared by the following steps:
step A1: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5-10min under the condition that the rotating speed is 200-300r/min, heating to 70-80 ℃, carrying out reflux stirring for 4-6h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dispersing carbon fibers in deionized water, adding ethanol, stirring uniformly, adding gamma-aminopropyltriethoxysilane, introducing nitrogen for protection, stirring at the rotation speed of 300-500r/min and the temperature of 70-80 ℃ for 10-15h, filtering to remove filtrate, and drying a filter cake to obtain the aminated carbon fibers;
step A3: dispersing the graphene oxide prepared in the step A1 in deionized water, adding the aminated carbon fiber prepared in the step A2, carrying out ultrasonic treatment for 5-10min under the condition that the frequency is 3-5MHz, adding 1-hydroxybenzotriazole, continuing ultrasonic treatment for 1-1.5h, filtering to remove filtrate, and drying a filter cake to prepare a carrier;
step A4: adding zinc chloride, ferric chloride, nickel chloride and deionized water into a reaction kettle, stirring until the zinc chloride, the ferric chloride and the nickel chloride are completely dissolved, adding the carrier prepared in the step A3, stirring for 30-40min under the condition that the rotating speed is 300-plus-500 r/min, carrying out ultrasonic treatment for 5-10min under the condition that the frequency is 8-10MHz, filtering to remove filtrate, and drying a filter cake under the condition that the temperature is 120-plus-150 ℃ in nitrogen to prepare the catalyst.
Further, the dosage ratio of the graphene and the hydrogen peroxide in the step A1 is 5g:30-50mL, and the mass fraction of the hydrogen peroxide is 30-35%.
Further, the using amount of the ethanol in the step A2 is 8-10% of the mass of the deionized water, and the using amount of the gamma-aminopropyltriethoxysilane is 10-15% of the mass of the carbon fiber.
Further, the mass ratio of the graphene oxide to the aminated carbon fiber in the step A3 is 2:1-1.2, and the amount of the 1-hydroxybenzotriazole is 30-50% of the mass of the graphene oxide.
Furthermore, the dosage ratio of the zinc chloride, the ferric chloride, the nickel chloride, the deionized water and the carrier in the step A4 is 1g:1g:10mL:3 g.
A production process of a phosphine compound specifically comprises the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, reactants and tetrahydrofuran into a reaction kettle, stirring for 20-30min at the rotation speed of 200-300r/min and the temperature of 0-3 ℃, adding a catalyst, heating to the temperature of 70-80 ℃, and carrying out reflux reaction for 3-8h to obtain the phosphide.
The invention has the beneficial effects that: the invention adopts phosphorus trichloride and sublimed sulfur as raw materials in the process of preparing phosphine, reduces the production cost compared with the prior art, and prepares a catalyst in the process of preparing phosphine, the catalyst firstly takes graphene as a raw material, hydrogen peroxide is used for oxidation to ensure that the surface of the graphene contains a large amount of active carboxyl, then carbon fiber is treated by gamma-aminopropyltriethoxysilane, the gamma-aminopropyltriethoxysilane is firstly hydrolyzed to ensure that self-siloxane is hydrolyzed to form silanol, and then the silanol reacts with active hydroxyl on the surface of the carbon fiber to ensure that amino is grafted on the surface of the carbon fiber to prepare aminated carbon fiber, the graphene oxide and the carbon fiber are subjected to ultrasonic treatment to ensure that the carbon fiber is embedded in a groove on the surface of the graphene oxide, and then 1-hydroxybenzotriazole is added to ensure that the carboxyl on the surface of the graphene oxide reacts with the amino on the surface of the aminated carbon fiber, the catalyst is composed of multiple metals with reducibility, the reduction effect is good, the carrier has reducibility, the carrier can be fully contacted with reactants to increase the reaction rate, and the catalyst is easy to recover, and the recovered catalyst can be reused after being treated by potassium borohydride, so that the preparation cost is greatly reduced, and the resource waste is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A phosphonized compound, which is prepared by the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, benzene and tetrahydrofuran into a reaction kettle, stirring for 20min at the rotation speed of 200r/min and the temperature of 0 ℃, adding a catalyst, heating to the temperature of 70 ℃, and carrying out reflux reaction for 3h to obtain the triphenylphosphine.
The catalyst is prepared by the following steps:
step A1: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5min at the rotation speed of 200r/min, heating to 70 ℃, carrying out reflux stirring for 4h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dispersing carbon fibers in deionized water, adding ethanol, stirring uniformly, adding gamma-aminopropyltriethoxysilane, introducing nitrogen for protection, stirring at the rotation speed of 300r/min and the temperature of 70 ℃ for 10 hours, filtering to remove filtrate, and drying a filter cake to obtain aminated carbon fibers;
step A3: dispersing the graphene oxide prepared in the step A1 in deionized water, adding the aminated carbon fiber prepared in the step A2, carrying out ultrasonic treatment for 5min under the condition of 3MHz frequency, adding 1-hydroxybenzotriazole, continuing ultrasonic treatment for 1h, filtering to remove filtrate, and drying a filter cake to prepare a carrier;
step A4: adding zinc chloride, ferric chloride, nickel chloride and deionized water into a reaction kettle, stirring until the zinc chloride, the ferric chloride and the nickel chloride are completely dissolved, adding the carrier prepared in the step A3, stirring for 30min under the condition that the rotating speed is 300r/min, carrying out ultrasonic treatment for 5min under the condition that the frequency is 8MHz, filtering to remove filtrate, and drying a filter cake under the condition of nitrogen at the temperature of 120 ℃ to obtain the catalyst.
Example 2
A phosphonized compound, which is prepared by the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, n-butyl magnesium bromide and tetrahydrofuran into a reaction kettle, stirring for 20min at the rotation speed of 200r/min and the temperature of 3 ℃, adding a catalyst, heating to the temperature of 80 ℃, and carrying out reflux reaction for 3h to obtain tributyl phosphine.
The catalyst is prepared by the following steps:
step A1: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 10min at a rotation speed of 200r/min, heating to 70 ℃, carrying out reflux stirring for 6h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dispersing carbon fibers in deionized water, adding ethanol, stirring uniformly, adding gamma-aminopropyltriethoxysilane, introducing nitrogen for protection, stirring at the rotation speed of 300r/min and the temperature of 80 ℃ for 10 hours, filtering to remove filtrate, and drying a filter cake to obtain aminated carbon fibers;
step A3: dispersing the graphene oxide prepared in the step A1 in deionized water, adding the aminated carbon fiber prepared in the step A2, carrying out ultrasonic treatment for 10min under the condition of 3MHz frequency, adding 1-hydroxybenzotriazole, continuing ultrasonic treatment for 1h, filtering to remove filtrate, and drying a filter cake to prepare a carrier;
step A4: adding zinc chloride, ferric chloride, nickel chloride and deionized water into a reaction kettle, stirring until the zinc chloride, the ferric chloride and the nickel chloride are completely dissolved, adding the carrier prepared in the step A3, stirring for 30min under the condition that the rotating speed is 500r/min, carrying out ultrasonic treatment for 5min under the condition that the frequency is 10MHz, filtering to remove filtrate, and drying a filter cake under the condition of nitrogen at the temperature of 150 ℃ to obtain the catalyst.
Example 3
A phosphonized compound, which is prepared by the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, cyclopentyl magnesium bromide and tetrahydrofuran into a reaction kettle, stirring for 30min at the rotation speed of 300r/min and the temperature of 0 ℃, adding a catalyst, heating to the temperature of 70 ℃, and performing reflux reaction for 8h to obtain tricyclopentylphosphine.
The catalyst is prepared by the following steps:
step A1: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5min at the rotation speed of 300r/min, heating to 80 ℃, carrying out reflux stirring for 4h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dispersing carbon fibers in deionized water, adding ethanol, stirring uniformly, adding gamma-aminopropyltriethoxysilane, introducing nitrogen for protection, stirring at the rotation speed of 500r/min and the temperature of 70 ℃ for 15 hours, filtering to remove filtrate, and drying a filter cake to obtain aminated carbon fibers;
step A3: dispersing the graphene oxide prepared in the step A1 in deionized water, adding the aminated carbon fiber prepared in the step A2, carrying out ultrasonic treatment for 10min under the condition of 3MHz frequency, adding 1-hydroxybenzotriazole, continuing ultrasonic treatment for 1h, filtering to remove filtrate, and drying a filter cake to prepare a carrier;
step A4: adding zinc chloride, ferric chloride, nickel chloride and deionized water into a reaction kettle, stirring until the zinc chloride, the ferric chloride and the nickel chloride are completely dissolved, adding the carrier prepared in the step A3, stirring for 30min under the condition that the rotating speed is 500r/min, carrying out ultrasonic treatment for 5min under the condition that the frequency is 10MHz, filtering to remove filtrate, and drying a filter cake under the condition of nitrogen at the temperature of 120 ℃ to obtain the catalyst.
Comparative example 1
Compared with the embodiment 1, the iron powder is used for replacing the catalyst, and the specific steps are as follows:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, benzene and tetrahydrofuran into a reaction kettle, stirring for 20min at the rotation speed of 200r/min and the temperature of 0 ℃, adding iron powder, heating to the temperature of 70 ℃, and carrying out reflux reaction for 10h to obtain the triphenylphosphine.
Comparative example 2
Compared with the embodiment 1, the method for preparing the zinc oxide catalyst by the comparative example has the following specific steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, benzene and tetrahydrofuran into a reaction kettle, stirring for 20min at the rotation speed of 200r/min and the temperature of 0 ℃, adding zinc powder, heating to the temperature of 70 ℃, and performing reflux reaction for 10h to obtain the triphenylphosphine.
Comparative example 3
The comparative example is a common phosphine preparation process in the market.
The preparation time was compared with the preparation processes of examples 1 to 4 and comparative examples 1 to 3, and the yields of the prepared phosphides were compared, with the results shown in table 1 below;
TABLE 1
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Preparation time 3.5h 3.5h 8.5h 10.5h 10.5h ＞12h
Yield of 96.53％ 97.28％ 96.42％ 88.26％ 89.15％ 89.34％
From table 1 above, it can be seen that the processes for preparing phosphides according to examples 1 to 3 have a preparation time of 3.5 to 8.5 hours and a phosphide yield of 96.42 to 97.28%, the process for preparing a phosphide according to comparative example 1 has a preparation time of 10.5 hours and a phosphide yield of 88.26%, the process for preparing a phosphide according to comparative example 2 has a preparation time of 10.5 hours and a phosphide yield of 89.15%, and the process for preparing a phosphide according to comparative example 3 has a preparation time of more than 12 hours and a phosphide yield of 89.34%, which indicates that the present invention has advantages of high yield and high efficiency.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (8)

1. A phosphonized compound characterized by: the method comprises the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, reactants and tetrahydrofuran into a reaction kettle, stirring for 20-30min at the rotation speed of 200-300r/min and the temperature of 0-3 ℃, adding a catalyst, heating to the temperature of 70-80 ℃, and carrying out reflux reaction for 3-8h to obtain the phosphide.
2. The phosphine compound according to claim 1, wherein: the phosphorus trichloride, the sublimed sulfur, the aluminum trichloride and the reactants are used in a molar ratio of 1:1:3:3, the reactants are aromatic hydrocarbon or Grignard reagent, the Grignard reagent is obtained by reacting halohydrocarbon with metal magnesium, the halohydrocarbon is halocycloalkane or haloalkane, and the catalyst is used in an amount of 50-60% of the mass of the phosphorus trichloride.
3. The phosphine compound according to claim 1, wherein: the catalyst is prepared by the following steps:
step A1: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5-10min under the condition that the rotating speed is 200-300r/min, heating to 70-80 ℃, carrying out reflux stirring for 4-6h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dispersing carbon fibers in deionized water, adding ethanol, stirring uniformly, adding gamma-aminopropyltriethoxysilane, introducing nitrogen for protection, stirring at the rotation speed of 300-500r/min and the temperature of 70-80 ℃ for 10-15h, filtering to remove filtrate, and drying a filter cake to obtain the aminated carbon fibers;
step A3: dispersing the graphene oxide prepared in the step A1 in deionized water, adding the aminated carbon fiber prepared in the step A2, carrying out ultrasonic treatment for 5-10min under the condition that the frequency is 3-5MHz, adding 1-hydroxybenzotriazole, continuing ultrasonic treatment for 1-1.5h, filtering to remove filtrate, and drying a filter cake to prepare a carrier;
step A4: adding zinc chloride, ferric chloride, nickel chloride and deionized water into a reaction kettle, stirring until the zinc chloride, the ferric chloride and the nickel chloride are completely dissolved, adding the carrier prepared in the step A3, stirring for 30-40min under the condition that the rotating speed is 300-plus-500 r/min, carrying out ultrasonic treatment for 5-10min under the condition that the frequency is 8-10MHz, filtering to remove filtrate, and drying a filter cake under the condition that the temperature is 120-plus-150 ℃ in nitrogen to prepare the catalyst.
4. The phosphine compound according to claim 3, wherein: the dosage ratio of the graphene and the hydrogen peroxide in the step A1 is 5g:30-50mL, and the mass fraction of the hydrogen peroxide is 30-35%.
5. The phosphine compound according to claim 3, wherein: the using amount of the ethanol in the step A2 is 8-10% of the mass of the deionized water, and the using amount of the gamma-aminopropyl triethoxysilane is 10-15% of the mass of the carbon fiber.
6. The phosphine compound according to claim 3, wherein: the mass ratio of the graphene oxide to the aminated carbon fiber in the step A3 is 2:1-1.2, and the mass of the 1-hydroxybenzotriazole is 30-50% of the mass of the graphene oxide.
7. The phosphine compound according to claim 3, wherein: the using amount ratio of the zinc chloride, the ferric chloride, the nickel chloride, the deionized water and the carrier in the step A4 is 1g:1g:10mL:3 g.
8. The process according to claim 3, wherein: the method specifically comprises the following steps:
adding phosphorus trichloride, sublimed sulfur, aluminum trichloride, reactants and tetrahydrofuran into a reaction kettle, stirring for 20-30min at the rotation speed of 200-300r/min and the temperature of 0-3 ℃, adding a catalyst, heating to the temperature of 70-80 ℃, and carrying out reflux reaction for 3-8h to obtain the phosphide.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073584A (en) * 2013-01-16 2013-05-01 湖北兴发化工集团股份有限公司 Method for preparing triphenylphosphine
CN104841465A (en) * 2015-05-08 2015-08-19 中国石油大学(华东) Load type nickel phosphide catalyst and pre-phosphating preparation method thereof
CN111825715A (en) * 2020-07-16 2020-10-27 江苏富比亚化学品有限公司 Synthesis method of triphenylphosphine derivative tri- (R-phenyl) phosphine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073584A (en) * 2013-01-16 2013-05-01 湖北兴发化工集团股份有限公司 Method for preparing triphenylphosphine
CN104841465A (en) * 2015-05-08 2015-08-19 中国石油大学(华东) Load type nickel phosphide catalyst and pre-phosphating preparation method thereof
CN111825715A (en) * 2020-07-16 2020-10-27 江苏富比亚化学品有限公司 Synthesis method of triphenylphosphine derivative tri- (R-phenyl) phosphine

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