CN114478843B - Method for terminating anionic polymerization - Google Patents
Method for terminating anionic polymerization Download PDFInfo
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- CN114478843B CN114478843B CN202110237203.2A CN202110237203A CN114478843B CN 114478843 B CN114478843 B CN 114478843B CN 202110237203 A CN202110237203 A CN 202110237203A CN 114478843 B CN114478843 B CN 114478843B
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Abstract
The present invention relates to a method for terminating an anionic polymerization reaction, comprising: mixing an organic alkali metal compound with a monomer containing a double bond, and performing anionic polymerization reaction to form a living polymer; and adding a terminator to deactivate the living polymer, wherein the terminator comprises a silicon oxide having silanol groups or lignin having hydroxyl and phenolic groups.
Description
Technical Field
The present disclosure relates to a method of terminating anionic polymerization reactions, and more particularly to a terminator employed therein.
Background
Anionic polymerization is often used to produce polydiene elastomers, styrene-butadiene rubber, thermoplastic elastomers, or the like, and is one of the important polymerization techniques. The polymer is suitable for use in tires, shoe materials, adhesives, sealing materials, or toughening agents, etc.
In general, anionic polymerization uses an initiator and a terminator, and the initiator usually contains an organic alkali metal compound. The terminator can inactivate the active end of the polymer, thus achieving the purpose of terminating the reaction. However, the initiator may cause alkali metal compounds in the product to remain, and the terminator may remain in the product.
In view of the foregoing, there is a need for novel anionic polymerization terminators and metal scavengers that reduce the residual amounts of terminators and alkali metal compounds in polymer solutions or polymer products.
Disclosure of Invention
The object of the present invention is to provide a method for terminating anionic polymerization which substantially overcomes the drawbacks of the prior art and which allows to reduce the residues of terminators and alkali metal compounds in the polymer solution or polymer product.
The method for terminating an anionic polymerization reaction according to one embodiment of the present disclosure includes: mixing an organic alkali metal compound with a monomer containing a double bond, and performing anionic polymerization reaction to form a living polymer (containing an alkali metal); and adding a terminator to deactivate the living polymer, wherein the terminator comprises a silicon oxide having silanol groups or lignin having hydroxyl and phenolic groups.
In some embodiments, the terminating agent forms a complex with the alkali metal of the living polymer.
In some embodiments, the above-described methods further comprise removing the complex, and the method of removing the complex comprises centrifugation, filtration, membrane separation, decantation, sedimentation, extraction, flotation, distillation, or a combination thereof.
In some embodiments, the above method further comprises recovering the complex and acid treating the complex to form a recovered terminator.
In some embodiments, the method further comprises treating the terminator with acid prior to adding the terminator.
In some embodiments, the silicon oxide having silanol groups comprises diatomaceous earth, silica gel, porous silica, or combinations of the foregoing.
In some embodiments, the lignin having hydroxyl groups and phenolic groups comprises alkali lignin, sulfonate lignin, phenolized lignin, or a combination of the foregoing.
In some embodiments, the weight ratio of the terminating agent to the organic alkali metal compound is from 100:0.1 to 100:10, and the weight ratio of the active polymer to the terminating agent is from 100:1 to 100:100.
In some embodiments, the terminating agent is free of protic solvents.
The method for terminating an anionic polymerization reaction according to one embodiment of the present disclosure includes: mixing an organic alkali metal compound with a monomer containing a double bond, and performing anionic polymerization reaction to form a living polymer; and passing the living polymer through a column packed with a terminating agent, wherein the terminating agent comprises a silicon oxide having silanol groups or lignin having hydroxyl and phenolic groups.
In some embodiments, the terminating agent forms a complex with the alkali metal of the living polymer.
In some embodiments, the above method further comprises recovering the complex and acid treating the complex to form a recovered terminator.
In some embodiments, the method further comprises treating the terminating agent with acid prior to passing the living polymer through the terminating agent-filled tubular string.
In some embodiments, the silicon oxide having silanol groups comprises diatomaceous earth, silica gel, porous silica, or combinations of the foregoing.
In some embodiments, the lignin having hydroxyl groups and phenolic groups comprises alkali lignin, sulfonate lignin, phenolized lignin, or a combination of the foregoing.
In some embodiments, the weight ratio of the terminating agent to the organic alkali metal compound is from 100:0.1 to 100:10, and the weight ratio of the active polymer to the terminating agent is from 100:1 to 100:100.
In some embodiments, the step of passing the living polymer through a column filled with a terminating agent deactivates the living polymer without using a protic solvent.
Compared with the prior art, the method for terminating the anionic polymerization reaction can reduce the residual of the terminating agent and the alkali metal compound in the polymer solution or the polymer product.
Detailed Description
In one embodiment, a method for terminating an anionic polymerization reaction includes mixing an organic alkali metal compound with a monomer having a double bond in a reaction tank to perform an anionic polymerization reaction to form a living polymer. The organic alkali metal compound may be an alkyl lithium (such as butyl lithium), an alkyl sodium, or an alkyl potassium. The double bond containing monomers may be conjugated dienes, alkenyl aromatic, or reactive alpha olefins. Conjugated dienes include C 4-12 Such as 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2-methyl-1, 3-pentadiene, 2, 3-dimethyl-1, 3-pentadiene, 2-methyl-3-ethyl-1, 3-pentadiene, and 2-phenyl-1, 3-butadiene. The alkenyl aromatic monomer may be a vinyl-substituted aromatic hydrocarbon such as styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 3, 5-diethylstyrene, 4-cyclohexylstyrene, 2,4, 6-trimethylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 4, 5-dimethyl-1-vinylnaphthalene, 3, 6-di-p-tolyl-1-vinylnaphthalene, or 7-decyl-2-vinylnaphthalene. Other monomers containing double bonds also include: acrylic esters, methacrylic esters, methyl vinyl groupsKetones, vinylidene esters, nitroethylenes, vinylidene dicyano, acrylonitrile, or the like. For example, anionic polymerization of styrene with butadiene as monomer and butyllithium as organoalkali metal compound (e.g., initiator) is as follows:
the product of the reaction is active polymer (lithium metal). The living polymer can continue to react as long as the monomer containing the double bond is added. x, y, and z are the number of repetitions, and the above products may be random copolymers or block copolymers, depending on whether styrene and butadiene are reacted simultaneously or sequentially. The repeat unit corresponding to the number y of repeats is from 1, 3-addition, while the repeat unit corresponding to the number z of repeats is from 1, 2-addition, and the ratio of y to z can be adjusted by the reaction conditions such as temperature. In some embodiments, y=0. In some embodiments, z=0. In other embodiments, both y and z are not 0.
The process described above is followed by the addition of a terminating agent to the reaction tank to deactivate the living polymer. The terminator includes a silicon oxide having silanol groups, or lignin having hydroxyl groups and phenol groups. For example, the silicon oxide having silanol groups includes diatomaceous earth, silica gel, porous silica, or combinations of the foregoing. In another aspect, the lignin having hydroxyl groups and phenolic groups includes alkali lignin, sulfonate lignin, phenolized lignin, or a combination of the foregoing.
In some embodiments, the terminating agent forms a complex with the alkali metal of the living polymer to deactivate the living polymer, i.e., terminate the anionic polymerization reaction. Taking a silicon oxide having a silanol group as an example, the reaction of the silanol group of the silicon oxide with an alkali metal of the living polymer is as follows:
it will be appreciated that the silicon oxide may have a plurality of silanol groups (Si-OH) and thus the resulting complex may also have a plurality of Si-OLi groups. In some embodiments, the above-described methods further comprise removing the complex, and the method of removing the complex comprises centrifugation, filtration, membrane separation, decantation, sedimentation, extraction, flotation, distillation, or a combination thereof. The polymer product after removal of the compound has a low content of residual alkali metals (e.g. less than 5 ppm).
In some embodiments, the above method further comprises recovering the complex and acid treating the complex to form a recovered terminator. The recovered terminator may be used to terminate other batches of anionic polymerization. Alternatively, the terminating agent may be treated acidic prior to adding the terminating agent to the living polymer. The terminator after the acid treatment may have a better alkali metal removing effect than the terminator before the acid treatment.
In some embodiments, the weight ratio of terminator to the organic alkali metal compound is 100:0.1 to 100:10. In some embodiments, the weight ratio of terminator to organo alkali metal compound is 100:0.4 to 100:7, 100:0.7 to 100:4, 100:0.7 to 100:7, 100:0.1 to 100:4, or 100:0.4 to 100:4. If the proportion of the organic alkali metal compound is too low, the molecular weight of the polymerization product becomes too high, resulting in a high viscosity of the reaction solution, and the solid-liquid separation procedure of the terminator and the reaction solution is not easy to be performed. If the proportion of the organic alkali metal compound is too high, it takes longer to terminate the reaction.
In some embodiments, the weight ratio of active polymer to terminator is from 100:1 to 100:100. In some embodiments, the weight ratio of active polymer to terminator is 100:1 to 100:100, 100:1 to 100:50, 100:3 to 100:100, 100:3 to 100:50, or 100:3 to 100:20. If the proportion of the terminator is too low, the living polymer cannot be effectively deactivated. If the proportion of the terminator is too high, the time for the separation procedure increases.
In some embodiments, the terminating agent is free of protic solvents such as alcohols and the like. Therefore, the polymer product does not need an additional step to remove alcohols, so that the experimental step can be simplified and the related cost can be reduced.
In one embodiment, the method for terminating an anionic polymerization reaction includes mixing an organic alkali metal compound with a monomer having a double bond, and performing an anionic polymerization reaction to form a living polymer having an alkali metal. The anionic polymerization to form living polymers is the same as that described above and is not described in detail herein. The living polymer is then passed through a column packed with a terminating agent to deactivate the living polymer. The kind of the terminator is similar to that described above, and is not described here.
In some embodiments, the terminating agent of the packing string forms a complex with the alkali metal of the living polymer, thus eliminating the need for an additional step to remove the alkali metal. The polymer product after passing through the column has a low content of residual alkali metals (e.g. less than 5 ppm). In some embodiments, the above method further comprises recovering the complex and acid treating the complex to form a recovered terminator. In some embodiments, the method further comprises treating the terminating agent with an acid prior to passing the living polymer through the terminating agent-filled tubular column to further improve the effect of the terminating agent in complexing alkali metal.
In some embodiments, the weight ratio of terminator to the organic alkali metal compound is 100:0.1 to 100:10. In some embodiments, the weight ratio of terminator to organo alkali metal compound is 100:0.4 to 100:7, 100:0.7 to 100:4, 100:0.7 to 100:7, 100:0.1 to 100:4, or 100:0.4 to 100:4. If the proportion of the organic alkali metal compound is too low, the molecular weight of the polymerization product becomes too high, resulting in a high viscosity of the reaction solution, and the solid-liquid separation procedure of the terminator and the reaction solution is not easy to be performed. If the proportion of the organic alkali metal compound is too high, it takes longer to terminate the reaction.
The weight ratio of the living polymer to the terminator is 100:1 to 100:100. In some embodiments, the weight ratio of active polymer to terminator is 100:1 to 100:100, 100:1 to 100:50, 100:3 to 100:100, 100:3 to 100:50, or 100:3 to 100:20. If the proportion of the terminator is too low, the living polymer cannot be effectively deactivated. If the proportion of the terminator is too high, the time for the separation procedure increases.
In some embodiments, the step of inactivating the living polymer by passing the living polymer through a column packed with a terminating agent does not use a protic solvent (e.g., an alcohol) or the like. Therefore, the polymer product does not need an additional step to remove alcohols, so that the experimental step can be simplified and the related cost can be reduced.
The foregoing and other objects, features and advantages of the present disclosure will be apparent from the following more particular description of preferred embodiments, as illustrated in the accompanying drawings in which:
examples (example)
Example 1
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Lignin (alkali Lignin, lignin from Sigma-Aldrich) was used as a terminator for the anionic polymerization and a metal remover and a solution of the active polymer was added, wherein the weight ratio of the active polymer to Lignin was 100:5, and wherein the weight ratio of Lignin to n-butyllithium was 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). The polymer solution after filtration was then filtered through a 1 μm pore size filter paper, the solvent was removed, and the polymer was dried in an oven at 100℃for 2 hours, and the lithium metal concentration (2.8 ppm) in the polymer was analyzed by ICP-OES.
Example 2
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer. After 1 hour of reaction, the temperature was lowered, and the polymerization reaction liquid was sampled and observed to be orange-red, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Diatomaceous earth (purchased from Sigma-Ald)rich (richl)545 As a terminator for the anionic polymerization and a metal remover and adding a solution of the active polymer, wherein the weight ratio of the active polymer to the diatomite is 100:5, and the weight ratio of the diatomite to the n-butyllithium is 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). The polymer solution after filtration was then filtered through a 1 μm pore size filter paper, the solvent was removed, and the polymer was dried in an oven at 100℃for 2 hours, and the lithium metal concentration (1.7 ppm) in the polymer was analyzed by ICP-OES.
Example 3
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Silica gel (particle size: 70-230 mesh from Sigma-Aldrich) was used as a terminator for the anionic polymerization reaction and a metal remover and a solution of the active polymer was added, wherein the weight ratio of the active polymer to the Silica gel was 100:5, and wherein the weight ratio of the Silica gel to n-butyllithium was 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). The polymer solution after filtration was then filtered through a 1 μm pore size filter paper, the solvent was removed, and the polymer was dried in an oven at 100℃for 2 hours, and the lithium metal concentration (3.8 ppm) in the polymer was analyzed by ICP-OES.
Comparative example 1
Water-removed cyclohexane (100 ml) was used as a reaction solvent and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Methanol was used as a terminator for the anionic polymerization and a solution of the living polymer was added, wherein the weight ratio of the living polymer to methanol was 100:5, and wherein the weight ratio of methanol to n-butyllithium was 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). The polymer solution after filtration was then filtered through a 1 μm pore size filter paper, the solvent was removed, and the polymer was oven dried at 100℃for 2 hours, and the lithium metal concentration (102 ppm) in the polymer was analyzed by ICP-OES.
Comparative example 2
Water-removed cyclohexane (100 ml) was used as a reaction solvent and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Wood flour (homemade, particle size: 325 mesh) was used as a terminator and metal remover for the anionic polymerization and added to the solution of active polymer, wherein the weight ratio of active polymer to wood flour was 100:5, and wherein the weight ratio of wood flour to n-butyllithium was 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). The polymer solution after filtration was then filtered through a 1 μm pore size filter paper, the solvent was removed, and the polymer was dried in an oven at 100℃for 2 hours, and the lithium metal concentration (16 ppm) in the polymer was analyzed by ICP-OES.
Comparative example 3
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Cellulose (microcrystalline Cellulose available from Sigma-Aldrich) was used as a terminator for the anionic polymerization and a metal remover and a solution of the active polymer was added, wherein the weight ratio of the active polymer to Cellulose was 100:5 and wherein the weight ratio of Cellulose to n-butyllithium was 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). The polymer solution after filtration was then filtered through a 1 μm pore size filter paper, the solvent was removed, and the polymer was dried in an oven at 100℃for 2 hours, and the lithium metal concentration (13 ppm) in the polymer was analyzed by ICP-OES.
Comparative example 4
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Isopropyl alcohol is used as a terminator for the anionic polymerization reaction and is added into a solution of the active polymer, wherein the weight ratio of the active polymer to the isopropyl alcohol is 100:5, and the weight ratio of the isopropyl alcohol to the n-butyllithium is 100:2. After stirring for 10 minutes, a colorless transparent polymer solution was obtained, indicating that the polymerization reaction had terminated (i.e., the living polymer had deactivated). Diatomaceous earth (purchased from Sigma-Aldrich)545)As a metal remover and packing the column, wherein the weight ratio of active polymer to diatomaceous earth is 100:10, and wherein the weight ratio of diatomaceous earth to n-butyllithium is 100:1. The polymer solution containing isopropanol was then passed through a column, the solvent was removed and dried in an oven at 100℃for 2 hours, and the lithium metal concentration (3.4 ppm) in the polymer was analyzed by ICP-OES, whereas the polymer solution contained isopropanol residue, adding to the subsequent solvent separation and purification procedure.
Example 4
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Lignin (alkali Lignin, lignin from Sigma-Aldrich) was taken as a terminator and metal remover for the anionic polymerization and the column was filled with a weight ratio of active polymer to Lignin of 100:10, wherein the weight ratio of Lignin to n-butyllithium was 100:1. The orange-colored living polymer solution was then passed through the column to give a colorless transparent polymer solution indicating that the polymerization reaction had been terminated (i.e., the living polymer was deactivated). After the solvent was removed, the polymer was oven dried at 100deg.C for 2 hours and analyzed for lithium metal concentration (1.3 ppm) by ICP-OES.
The anionic polymerization was again carried out and the orange-colored reactive polymer solution was passed through the column used. After repeating the above step 5 times, the colorless transparent polymer solution obtained in the fifth time was dried in an oven at 100℃for 2 hours after the solvent was removed, and the lithium metal concentration (12 ppm) in the polymer was analyzed by ICP-OES.
Washing the lignin after 5 times with 10% hydrochloric acid and drying to obtain recovered lignin. The column is filled with the recovered lignin. The anionic polymerization was again carried out as described above and the orange-colored active polymer solution was passed through a column filled with recovered lignin to give a colorless transparent polymer solution indicating that the polymerization had been terminated (i.e., the active polymer had been deactivated). After the solvent was removed, the polymer was oven dried at 100deg.C for 2 hours and analyzed for lithium metal concentration (0.9 ppm) by ICP-OES. From the above, it can be seen that the lignin after use can be acid treated to obtain recovered lignin, which can be used again to terminate the anionic polymerization and remove lithium metal.
Example 5
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Diatomaceous earth (purchased from Sigma-Aldrich)545 As terminator for anionic polymerization and metal remover and packing the column, wherein the weight ratio of active polymer to diatomaceous earth is 100:10, wherein the weight ratio of diatomaceous earth to n-butyllithium is 100:1. The orange-colored living polymer solution was then passed through the column to give a colorless transparent polymer solution indicating that the polymerization reaction had been terminated (i.e., the living polymer was deactivated). After the solvent was removed, the polymer was oven dried at 100deg.C for 2 hours and analyzed for lithium metal concentration (0.8 ppm) by ICP-OES.
The anionic polymerization was again carried out and the orange-colored reactive polymer solution was passed through the column used. After repeating the above step 5 times, the colorless transparent polymer solution obtained in the fifth time was dried in an oven at 100℃for 2 hours after the solvent was removed, and the lithium metal concentration (15 ppm) in the polymer was analyzed by ICP-OES.
The diatomaceous earth after 5 uses was washed with 10% hydrochloric acid and dried to obtain recovered diatomaceous earth. The column was packed with recovered diatomaceous earth. The anionic polymerization was again carried out as described above and the orange-colored living polymer solution was passed through a column filled with recovered diatomaceous earth to give a colorless transparent polymer solution indicating that the polymerization had been terminated (i.e., the living polymer had been deactivated). After the solvent was drawn off, the polymer was oven dried at 100℃for 2 hours and analyzed for lithium metal concentration (0.7 ppm) by ICP-OES. From the above, it can be seen that the used diatomaceous earth can be acid treated to give recovered diatomaceous earth, which can be used again to terminate anionic polymerization and remove lithium metal.
Example 6
Water-removed cyclohexane (100 mL) was used as a reaction solvent, and styrene (6 g) and butadiene (4 g) were used as comonomers, and the mixture was stirred uniformly and then heated to 60 ℃. N-butyllithium (0.01 g) was added as an initiator to carry out anionic polymerization of the styrene-butadiene copolymer, and after 1 hour of reaction, the polymerization reaction solution was observed to be orange-red in color by cooling and sampling, indicating that the polymer remained active. After sampling the active polymer solution and removing the solvent, it was dried in an oven at 100℃for 2 hours, and analyzed for lithium metal concentration (122 ppm) by inductively coupled plasma atomic emission spectrometry (ICP-OES). Lignin (alkali Lignin, lignin from Sigma-Aldrich) and Silica gel (Silica gel from Sigma-Aldrich, particle size: 70-230 mesh) were taken as a terminator for the anionic polymerization reaction and a metal remover and the column was filled, the weight ratio of Lignin to Silica gel was 1:1, wherein the weight ratio of the active polymer to the total weight of Lignin plus Silica gel was 100:10, and the weight ratio of Lignin plus Silica gel to n-butyllithium was 100:1. The orange-colored living polymer solution was then passed through the column to give a colorless transparent polymer solution indicating that the polymerization reaction had been terminated (i.e., the living polymer was deactivated). After the solvent was removed, the polymer was oven dried at 100deg.C for 2 hours and analyzed for lithium metal concentration (1.5 ppm) by ICP-OES.
Although the present disclosure has been described with respect to the preferred embodiments, it should be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the disclosure as defined by the appended claims.
Claims (15)
1. A method of terminating an anionic polymerization reaction comprising:
mixing an organic alkali metal compound with a monomer containing a double bond, and performing anionic polymerization reaction to form a living polymer; and
adding a terminator to deactivate the living polymer,
wherein the terminator comprises a silicon oxide having silanol groups or lignin having hydroxyl groups and phenolic groups;
wherein the monomer containing double bond is C 4-12 2-vinylnaphthalene, 3-methylstyrene, 3, 5-diethylstyrene, 4-cyclohexylstyrene, 2,4, 6-trimethylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 4, 5-dimethyl-1-vinylnaphthalene, 3, 6-di-p-tolyl-1-vinylnaphthalene, or 7-decyl-2-vinylnaphthalene;
wherein the weight ratio of the terminator to the organic alkali metal compound is 100:0.1 to 100:10;
wherein the weight ratio of the living polymer to the terminator is 100:1 to 100:100.
2. The method of terminating an anionic polymerization reaction of claim 1, wherein the terminating agent forms a complex with an alkali metal of the living polymer.
3. The method of terminating an anionic polymerization of claim 2, further comprising removing the complex, and the method of removing the complex is centrifugation, filtration, membrane separation, decantation, sedimentation, extraction, flotation, distillation, or a combination thereof.
4. The method of terminating an anionic polymerization reaction of claim 3, further comprising recovering the complex and acid treating the complex to form a recovered terminator.
5. The method of terminating an anionic polymerization reaction of claim 1, further comprising acid treating the terminating agent prior to adding the terminating agent to deactivate the living polymer.
6. The method of terminating an anionic polymerization of claim 1, wherein the silicon oxide having silanol groups is diatomaceous earth, silica gel, porous silica, or a combination thereof.
7. The method of terminating an anionic polymerization reaction of claim 1, wherein the lignin having hydroxyl groups and phenolic groups is alkali lignin, sulfonate lignin, phenolized lignin, or a combination thereof.
8. The method of terminating an anionic polymerization of claim 1, wherein the terminating agent is free of protic solvents.
9. A method of terminating an anionic polymerization reaction comprising:
mixing an organic alkali metal compound with a monomer containing a double bond, and performing anionic polymerization reaction to form a living polymer; and
passing the living polymer through a column packed with a terminating agent to deactivate the living polymer,
wherein the terminator comprises a silicon oxide having silanol groups or lignin having hydroxyl groups and phenolic groups;
wherein the monomer containing double bond is C 4-12 2-vinylnaphthalene, 3-methylstyrene, 3, 5-diethylstyrene, 4-cyclohexylstyrene, 2,4, 6-trimethylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 4, 5-dimethyl-1-vinylnaphthalene, 3, 6-di-p-tolyl-1-vinylnaphthalene, or 7-decyl-2-vinylnaphthalene;
wherein the weight ratio of the terminator to the organic alkali metal compound is 100:0.1 to 100:10;
wherein the weight ratio of the living polymer to the terminator is 100:1 to 100:100.
10. The method of terminating an anionic polymerization reaction of claim 9, wherein the terminating agent forms a complex with an alkali metal of the living polymer.
11. The method of terminating an anionic polymerization reaction of claim 10, further comprising recovering the complex and acid treating the complex to form a recovered terminator.
12. The method of terminating an anionic polymerization reaction of claim 9, further comprising acid treating the terminating agent prior to passing the living polymer through a column filled with the terminating agent.
13. The method of terminating an anionic polymerization of claim 9, wherein the silicon oxide having silanol groups is diatomaceous earth, silica gel, porous silica, or a combination thereof.
14. The method of terminating an anionic polymerization of claim 9, wherein the lignin having hydroxyl groups and phenolic groups is alkali lignin, sulfonate lignin, phenolized lignin, or a combination thereof.
15. The method of terminating an anionic polymerization of claim 9, wherein the step of passing the living polymer through a column filled with the terminating agent deactivates the living polymer without using a protic solvent.
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| US7704676B2 (en) * | 2007-09-04 | 2010-04-27 | Kraton Polymers U.S. Llc | Block copolymers having distinct isoprene and butadiene midblocks, method for making same, and uses for such block copolymers |
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