CN113912796B - Method for removing residual catalyst in unsaturated polymer hydrogenation reaction - Google Patents

Method for removing residual catalyst in unsaturated polymer hydrogenation reaction Download PDF

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CN113912796B
CN113912796B CN202010651214.0A CN202010651214A CN113912796B CN 113912796 B CN113912796 B CN 113912796B CN 202010651214 A CN202010651214 A CN 202010651214A CN 113912796 B CN113912796 B CN 113912796B
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陈二中
张娇
燕晓宇
卢俊典
刘歌
于胜楠
李嵬
刘晓杰
朱思琪
孙梦垚
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Shenyang Research Institute of Chemical Industry Co Ltd
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    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/08—Removal of catalyst residues
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F8/04—Reduction, e.g. hydrogenation
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to the technical field of polymer post-treatment, in particular to a method for removing a residual metal catalyst in an unsaturated polymer hydrogenation reaction. And (3) adding an oxidant into the hydrogenated unsaturated polymer glue solution for oxidation, and adding a phosphate-alkali mixed solution to form a precipitate after oxidation, so as to remove the metal of the residual catalyst in the unsaturated polymer hydrogenation reaction. The invention realizes the removal of residual metal ions in the hydrogenated glue solution by adding the phosphate-alkali solution into the glue solution, remarkably improves the appearance and oxidation resistance of the product, has simple and easy operation steps, generates less waste residues and water, and is suitable for industrial production.

Description

Method for removing residual catalyst in unsaturated polymer hydrogenation reaction
Technical Field
The invention relates to the technical field of polymer post-treatment, in particular to a method for removing a residual metal catalyst in an unsaturated polymer hydrogenation reaction.
Background
Some polymers, such as styrene-butadiene block copolymers (SBS), block copolymers of Styrene and Isoprene (SIS), styrene-isoprene-butadiene copolymers (SIBR), and the like, are chemically active due to the presence of unsaturated double bonds in their molecular structure, and in order to improve their thermal stability, photostability, oxidation resistance and aging resistance, hydrogenation is generally used to saturate the unsaturated structure, thereby improving their environmental stability. The polymer is hydrogenated at a certain temperature and pressure by using heavy metal as a catalyst to saturate double bonds, wherein a nickel/aluminum catalytic hydrogenation system is widely applied to hydrogenation reaction of the polymer due to the advantages of high selectivity, low price, high hydrogenation efficiency and the like. The residual metal catalyst is remained in the polymer, which can affect the appearance and physical and chemical properties of the polymer, and limit the application range of the polymer.
The nickel hydrogenation catalyst is removed by the water solution extraction method and the precipitation method in industry. U.S. patent No. 3780138 discloses a method for removing residual nickel aluminum ions by adding an oxidizing agent to a hydrogenated gum solution and then adding an aqueous citric acid solution containing a low fatty alcohol as an extractant, wherein the aqueous citric acid solution containing metal ions is recycled through ion resin exchange. The method has lower inorganic acid corrosiveness than the traditional aqueous solution and low equipment strength requirement, but has high cost, large water consumption and great difficulty in recycling citric acid and sewage discharge treatment.
US4595749 discloses a process for removing residual metal ions from hydrogenated polymers by directly adding an oxidizing agent and a dibasic acid to a polymer dope containing a hydrogenation catalyst to form a precipitate. The method has high removal efficiency, but has long time for forming the precipitate, the precipitate is not easy to separate, and the dibasic acid solvent limits the circulation of the polymer solvent. Furthermore, the physical and chemical properties of the glue solution are affected by the residual dibasic acid, and an industrial step of alkali washing neutralization is required to be added.
U.S. Pat. No. 4, 3793306 and U.S. Pat. No. 3, 3793307 disclose a method for removing residual catalyst by adding an aqueous solution containing ammonium phosphate and an oxidizing agent to a gum solution, and adding sufficient water to deactivate the residual catalyst followed by the aqueous solution of ammonium phosphate and the oxidizing agent. Compared with the method of adding ammonium phosphate aqueous solution singly, the method has better effect of removing the residual catalyst, but the method has the defects of incomplete removal of metal ions with high polymer viscosity, complex process, difficult separation and the like.
Chinese patent CN 102875702B discloses a method for removing metals from a polymer by adding an organic base to the polymer, by adding an organic base to the gum solution, then adding an oxidizing agent, and finally washing with water and centrifuging to remove the residual metal catalyst. The method has higher removal efficiency, but has complex operation and high cost and price of the organic alkali raw material.
Chinese patent CN 109734828A discloses a method for removing residual metal catalyst after unsaturated polymer hydrogenation, which comprises adding alkali liquor into polymer glue solution, mixing uniformly, adding oxidant for oxidation reaction, washing with deionized water, standing for layering, and coagulating and drying to obtain the product. In the method, alkali liquor is added first and then oxidant is added, the oxidant is quickly decomposed and oxidized incompletely, the addition of the alkali liquor is easy to cause emulsification of the polymer after hydrogenation, and the color of the polymer changes from black to grey; after the glue solution is emulsified, the transparent glue solution turns white, the viscosity is increased, the centrifugal separation difficulty is increased, the separation is difficult, and the quick decomposition of the catalytic oxidant is easy, so that the nickel-aluminum is not up to the standard, and the industrial reaction is difficult to control; and the method requires a large amount of deionized water to wash alkali liquor, and the wastewater is large.
In the method for removing the residual metal catalyst after the hydrogenation of the unsaturated polymer, the aqueous solution extraction method has the technical problems of high equipment strength requirement, large water consumption and complex cyclic treatment process; insoluble metal precipitate is not easy to form and separate in the dibasic acid precipitation method, residual acid in the product affects physical and chemical properties, the step of alkali washing neutralization is required to be added, and the process is complex; although the phosphate precipitation method has low requirements on equipment, the method is simple and easy to implement, but the metal ions in the high-viscosity polymer are not thoroughly removed; while the organic alkali precipitation method has high removal efficiency, the method has the defects of easy emulsification of glue solution, difficult multiphase separation, high raw material cost and the like.
Disclosure of Invention
The invention provides a novel method for removing residual catalyst in unsaturated polymer hydrogenation reaction in order to make up for the defects existing in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for removing residual catalyst in unsaturated polymer hydrogenation reaction includes such steps as adding oxidant to hydrogenated unsaturated polymer colloid solution for oxidization, adding phosphate-alkali mixed solution to form deposit, and removing residual catalyst.
And after the precipitate is formed, centrifuging the system, precipitating the supernatant with alcohol, and drying to test the content of metal ions and the oxidation resistance of the product.
Further, adding an oxidant into the hydrogenated unsaturated polymer glue solution, stirring and oxidizing for 10-60min (preferably for 20-40 min) at 20-80 ℃ (preferably at 40-70 ℃), adding a phosphate-alkali mixed solution after oxidation at 20-80 ℃ (preferably at 40-70 ℃), stirring and reacting for 20-60min (preferably for 30-50 min) at normal pressure to form a precipitate, and further removing the metal of the residual catalyst in the unsaturated polymer hydrogenation reaction.
The volume ratio of the phosphate-alkali solution to the glue solution is 1:10-20.
The phosphate-alkali solution is one or more of sodium phosphate-sodium hydroxide, sodium phosphate-ammonia water and ammonium phosphate-ammonia water; wherein the molar ratio of phosphate to base is 1:0.1-1, preferably 1:0.5-1.
The oxidant is hydrogen peroxide; the dosage of the adhesive is 2-10mL/100mL, and the preferable dosage is 3-8mL/100 mL.
The stirring conditions in the oxidation reaction and the reaction process of adding the mixed solution are that the stirring rotation speed is 200-1500rpm/min, and the rotation speed is 400-800rpm/min.
The unsaturated polymer is one or more of styrene-butadiene block copolymer (SBS), block copolymer of Styrene and Isoprene (SIS) and styrene-isoprene-butadiene copolymer (SIBR); the metal catalyst used in the hydrogenation reaction is one or more of nickel and aluminum.
The invention has the advantages that:
according to the invention, the oxidant is added into the glue solution, and then the phosphate-alkali solution is added, so that the removal of residual metal ions in the hydrogenated glue solution is realized in one step, and the appearance and oxidation resistance of the product are obviously improved; under the condition of larger viscosity of the glue solution, the method can also remove the nickel content of the catalyst in the unsaturated polymer hydrogenation reaction system to below 10 ppm; the method has the advantages of simple and easy operation steps, less waste water amount of the generated waste residues, energy consumption conservation, easy recovery of the solvent according to the common method, no need of alkali washing neutralization, high removal efficiency and low cost, and is suitable for industrial production.
Detailed Description
The following examples are intended to further illustrate the invention, but not to limit it. The embodiments described below are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention adopts a method of adding a phosphate-alkali mixed solution into the oxidized glue solution for the first time to realize the removal of nickel-aluminum ions in the hydrogenated glue solution. By adding a little excessive hydrogen peroxide solution into the glue solution, the residual nickel and aluminum catalysts are fully oxidized into nickel aluminum ions, and most hydrogen peroxide is reacted, so that the amount of the oxidant contacted with the phosphate-alkali solution is reduced, and the reaction is more controllable and safer. And then adding phosphate and simultaneously adding alkali liquor, on one hand, nickel and aluminum ions generated by oxidation are promoted to fully react with the phosphate to generate insoluble phosphate precipitate by promoting the pH change of the glue liquor, and on the other hand, the alkali liquor reacts with the nickel and aluminum ions to generate more insoluble precipitate, so that the removal efficiency is remarkably improved. Conversely, the addition of phosphate reduces the addition amount of the independent alkali addition, avoids the emulsification of the glue solution and is beneficial to the separation of the glue solution and the sediment. In addition, compared with the widely applied oxidant and diacid removal method, the method does not need to additionally increase alkali washing neutralization, does not damage the oxidation resistance of the product, and has simple steps.
Example 1
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 25mL of sodium phosphate-sodium hydroxide solution was added after 30min of oxidation, with a molar ratio of sodium phosphate to sodium hydroxide of 1:0.5. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. Testing a dry glue sample by adopting a plasma emission spectrum, wherein the residual nickel content is 8ppm, and the residual aluminum content is 9ppm; the induction period of the dry gel sample for the antioxidant test is 17.47min.
Example 2
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 After 30min of oxidation, 25mL of sodium phosphate-sodium hydroxide solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:0.5. Cooling the glue solution to room temperature, separating with a centrifuge at 3000rpm/min, and centrifugingAnd (5) precipitating the supernatant with ethanol for 10min, and drying in vacuum to obtain a dry gel sample. The dry gel sample was tested by plasma emission spectroscopy for a residual nickel content of 5ppm and a residual aluminum content of 7ppm. The induction period of the antioxidant test was 18.14min.
Example 3
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 25mL, oxidized for 30min, and 50mL of sodium phosphate-sodium hydroxide solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:1. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for 2ppm residual nickel and 3ppm residual aluminum. The induction period of the antioxidant test was 18.84min.
Example 4
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for feedingAnd (3) carrying out catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 After 30min of oxidation, 50mL of sodium phosphate-sodium hydroxide solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:0.5. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for a residual nickel content of 4ppm and a residual aluminum content of 6ppm. The induction period of the antioxidant test was 18.35min.
Example 5
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 40 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 After 30min of oxidation, 50mL of sodium phosphate-sodium hydroxide solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:0.5. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for 8ppm residual nickel and 10ppm residual aluminum. The induction period of the antioxidant test was 18.22min.
Example 6
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 25mL of sodium phosphate-ammonia solution (50 mL) was added after 30min of oxidation, and the molar ratio of sodium phosphate to ammonia was 1:0.5. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for a residual nickel content of 6ppm and a residual aluminum content of 9ppm. The induction period of the antioxidant test was 18.71min.
Example 7
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 25mL of ammonium phosphate-ammonia solution (50 mL) was added after 30min of oxidation, and the molar ratio of ammonium phosphate to ammonia was 1:0.5. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. Testing dry glue sample and residue by adopting plasma emission spectrumNickel content 8ppm and residual aluminum content 9ppm. The induction period of the antioxidant test is 18.68min
Example 8
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, the concentration is 15% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 After 30min of oxidation, 37.5mL of sodium phosphate-sodium hydroxide aqueous solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:1. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for a residual nickel content of 9ppm and a residual aluminum content of 12ppm. The induction period of the antioxidant test is 17.68min
Example 9
The base gum before hydrogenation is SIS copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and the triblock copolymer is synthesized by using n-butyllithium as an initiator and styrene and isoprene as polymerization monomers. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.05gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.0MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.4% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of the glue solution is addedH 2 O 2 25mL, oxidized for 30min, and 50mL of sodium phosphate-sodium hydroxide solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:1. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for 8ppm residual nickel and 8ppm residual aluminum.
Example 10
The base gum before hydrogenation is SBS copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and the triblock copolymer is synthesized by using n-butyllithium as an initiator and styrene and butadiene as polymerization monomers. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.05gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.0MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.2% as measured by the iodometry method.
Transferring the hydrogenated glue solution of the unsaturated polymer to a stirring kettle for catalyst removal treatment, wherein the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 25mL, oxidized for 30min, and 50mL of sodium phosphate-sodium hydroxide solution was added, with a molar ratio of sodium phosphate to sodium hydroxide of 1:1. Cooling the glue solution to room temperature, separating by a centrifugal machine, centrifuging at 3000rpm/min for 10min, precipitating the supernatant with ethanol, and vacuum drying to obtain a dry glue sample. The dry gel sample was tested by plasma emission spectroscopy for a residual nickel content of 6ppm and a residual aluminum content of 7ppm. Comparative example 1
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method. Transferring the hydrogenated glue solution of the unsaturated polymer to stirringThe catalyst removal treatment is carried out in the mixing kettle, and the treatment conditions are as follows: taking 500mL of hydrogenated glue solution, wherein the concentration is 10% (wt), the reaction temperature is 60 ℃, the rotating speed is 600rpm/min, the normal pressure is adopted, and 30% (wt) of H is added 2 O 2 25mL, after 30min of oxidation, sodium phosphate-sodium hydroxide solution was not added. Cooling the glue solution to room temperature, separating with a centrifuge at 3000rpm/min, centrifuging for 10min, precipitating the supernatant with ethanol, and vacuum drying. The plasma emission spectrum is used for testing a dry gel sample, the residual nickel content of the blank control sample is 100ppm, the residual aluminum content is 185ppm, and the induction period of the dry gel sample is 10.13min.
The above embodiments show that the invention can realize the technical effect of removing the residual metal catalyst by adding the oxidant and the phosphate-alkali solution into the hydrogenated polymer glue solution, can obviously improve the appearance and oxidation resistance of the product, has simple and easy operation steps, generates little waste residue and water, and is suitable for industrial production.

Claims (7)

1. A method for removing residual catalyst in unsaturated polymer hydrogenation reaction is characterized in that oxidant is added into hydrogenated unsaturated polymer glue solution for oxidation, and then phosphate-alkali mixed solution is added after oxidation to form precipitate, so that metal of residual catalyst in unsaturated polymer hydrogenation reaction is removed;
and after the precipitate is formed, centrifuging the system, precipitating the supernatant with alcohol, and drying to test the content of metal ions and the oxidation resistance of the product.
2. The method of claim 1, wherein: adding an oxidant into the hydrogenated unsaturated polymer glue solution, stirring and oxidizing for 10-60min at 20-80 ℃ under normal pressure to perform oxidation reaction, adding a phosphate-alkali mixed solution after oxidation, stirring and reacting for 20-60min at 20-80 ℃ under normal pressure to form a precipitate, and further removing the metal of the residual catalyst in the unsaturated polymer hydrogenation reaction.
3. A method according to any one of claims 1-2, characterized in that: the volume ratio of the phosphate-alkali solution to the glue solution is 1:10-20.
4. A method according to claim 3, wherein: the phosphate-alkali solution is one or more of sodium phosphate-sodium hydroxide, sodium phosphate-ammonia water and ammonium phosphate-ammonia water; wherein the molar ratio of the phosphate to the alkali is 1:0.1-1.
5. A method according to any one of claims 1-2, characterized in that: the oxidant is hydrogen peroxide; the dosage is 2-10mL/100mL glue solution.
6. The method of claim 2, wherein: the stirring conditions in the oxidation reaction and the reaction process of adding the mixed solution are that the stirring rotation speed is 200-1500rpm/min.
7. The method of claim 1, wherein: the unsaturated polymer is one or more of styrene-butadiene block copolymer (SBS), block copolymer of Styrene and Isoprene (SIS) and styrene-isoprene-butadiene copolymer (SIBR); the metal catalyst used in the hydrogenation reaction is one or more of nickel and aluminum.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531448A (en) * 1968-11-06 1970-09-29 Phillips Petroleum Co Process for removal of hydrogenation catalyst from hyrogenated polymers
US3793306A (en) * 1973-01-03 1974-02-19 Phillips Petroleum Co Process for removal of catalyst residues
US4671866A (en) * 1986-02-26 1987-06-09 Phillips Petroleum Company Hydrodemetallization of oils
CN1508158A (en) * 2002-12-17 2004-06-30 中国石油化工股份有限公司北京燕山分 Method for removing residue catalyst after polymer hydrogenation using electrostatic separation technology
CN105642304A (en) * 2014-12-04 2016-06-08 中国石油化工股份有限公司 Preparation method of hydrodemetallization catalyst
CN109734828A (en) * 2018-12-25 2019-05-10 山东玉皇化工有限公司 A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531448A (en) * 1968-11-06 1970-09-29 Phillips Petroleum Co Process for removal of hydrogenation catalyst from hyrogenated polymers
US3793306A (en) * 1973-01-03 1974-02-19 Phillips Petroleum Co Process for removal of catalyst residues
US4671866A (en) * 1986-02-26 1987-06-09 Phillips Petroleum Company Hydrodemetallization of oils
CN1508158A (en) * 2002-12-17 2004-06-30 中国石油化工股份有限公司北京燕山分 Method for removing residue catalyst after polymer hydrogenation using electrostatic separation technology
CN105642304A (en) * 2014-12-04 2016-06-08 中国石油化工股份有限公司 Preparation method of hydrodemetallization catalyst
CN109734828A (en) * 2018-12-25 2019-05-10 山东玉皇化工有限公司 A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst

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