CN116003796B - Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination - Google Patents
Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of polysulfone resin, and particularly relates to a method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps: polymerization reaction: adding bisphenol A, 4' -dichloro diphenyl sulfone, a salifying agent and a water diversion agent into a polar aprotic solvent, introducing a protective gas, heating to perform salifying reaction, continuously heating to perform nucleophilic polycondensation reaction, adding an organic borate-diphenyl bisphenol potassium initiator when the polymer grows to a certain molecular weight, and continuously reacting and stirring until torque is not increased any more to obtain polysulfone resin polymer; and (5) post-treating to obtain polysulfone resin. The nucleophilic polycondensation-anionic ring-opening polymerization combined preparation method of polysulfone resin provided by the invention has the advantages that the content of cyclic dimer in the obtained polysulfone resin is low, and the application of downstream products is facilitated.
Description
Technical Field
The invention belongs to the technical field of preparation of polysulfone resin, and particularly relates to a method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization.
Background
Polysulfone resin (PSU) is amorphous special engineering plastic, and has good oxidation resistance, mechanical property and thermal stability due to containing sulfonyl, isopropyl and benzene ring, and has certain toughness due to the existence of ether bond, and is widely applied to the fields of high-end medical treatment, electronic products, water treatment, aerospace and the like due to the excellent characteristics.
The main method for synthesizing polysulfone resin is a one-step method, bisphenol A and 4, 4-dichloro diphenyl sulfone monomer are subjected to salification and nucleophilic substitution polycondensation in the presence of an alkaline nucleophilic reagent, the alkaline nucleophilic reagent is usually potassium carbonate, the solvent is N-methyl pyrrolidone, water, ethanol or methanol is used as a precipitant after polymerization is finished, and polysulfone is separated from a polymer solution in the precipitant. The polysulfone is purified, dried, granulated and packaged. Due to the existence of flexible isopropyl in bisphenol A monomer molecules during polymerization, the bisphenol A monomer is polymerized with 4, 4-dichloro diphenyl sulfone to form a linear dimer, and then the linear dimer is easy to bite back into a chlorine end group to form a cyclic dimer, and the structural formula is shown as formula I.
I is a kind of
In the polysulfone material synthesized by the traditional polymerization process, the content of the cyclic dimer is 1.7-2.5wt%, the structure of the cyclic dimer is regular, the melting point can reach 520 ℃, the common injection molding temperature of polysulfone is about 320 ℃, the melting point of the cyclic dimer can not be reached, and the crystal point is easy to form in an injection molding piece to influence the appearance of a product; meanwhile, the solubility of the cyclic dimer in NMP (N-methylpyrrolidone) is low, the cyclic dimer is slowly separated out from a solvent system during storage and is difficult to clean when being adhered to the wall of a container, so that a membrane manufacturer spends a great deal of effort in cleaning, and in the spinning process of a hollow fiber membrane, the separated cyclic dimer can cause the blockage of a filter port of a membrane making machine, so that the production efficiency is greatly influenced.
Therefore, reducing the cyclic dimer content is an important direction of polysulfone improvement, which is of great importance for advancing polysulfone applications.
Aiming at the problem of overhigh cyclic dimer content in polysulfone resin, the prior art adopts a mode of replacing bisphenol A with rigid monomers to reduce the cyclic dimer content, but the change of monomer properties often leads to great change of solubility of the polysulfone resin in film formation, the film formation performance is also greatly different, and downstream film-making manufacturers need to carry out obvious process change.
CN114409900a discloses a preparation method of polysulfone with low cyclic dimer content, in which an organic ammonium fluoride catalyst with high solubility is added in the polymerization process, so that the polymerization speed is increased, and when the molecular weight is increased to a certain extent, the system is diluted, so that the molecular weight is further increased. However, before the molecular weight of the diluted polymerization system further increases, cyclic dimer has formed, and the dilution environment easily causes the cyclic dimer content to rise, affecting the effect of lowering the final cyclic dimer content, and the final cyclic dimer content is still high, reaching 1.1%.
CN1443762a discloses a synthesis method of aromatic cyclic oligomer, which uses friedel-crafts acylation reaction, lewis acid such as anhydrous aluminum trichloride is used as catalyst, lewis base such as N-methyl pyrrolidone is used as cocatalyst, so that cyclizing yield reaches 90%, and the specific cyclic structure and low melt viscosity of the aromatic cyclic oligomer can be used for melt ring-opening polymerization under the initiation of anion initiator, so as to obtain high-performance linear polyaryletherketone (sulfone).
CN101519399a discloses an aromatic cyclic polyether ketone oligomer and a preparation method thereof, and utilizes friedel-crafts electrophilic reaction to synthesize cyclic prepolymers of commercial, semi-crystalline and high-performance polymers PEEK and PEK, namely aromatic cyclic polyether ketone oligomer, by taking carbon tetrachloride, substituted aromatic hydrocarbon monomers and the like as raw materials.
In the two patents, diphenyl bisphenol potassium is used as an initiator to initiate ring-opening polymerization of a cyclic oligomer to prepare a high molecular weight aromatic polymer, but the temperature of the ring-opening polymerization is up to 300-350 ℃, and the aromatic polymer can only be polymerized in a molten state, and the product is easy to be partially decomposed or excessively crosslinked in a nitrogen atmosphere, so that the aromatic polymer has a darker color.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects existing in the prior art, and provide a method for preparing polysulfone resin by combining nucleophilic polycondensation and anionic ring-opening polymerization, wherein the obtained polysulfone resin has low cyclic dimer content, has no influence on yellowness index, and is beneficial to application of downstream appearance part products.
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Polymerization reaction: adding bisphenol A, 4' -dichloro diphenyl sulfone, a salifying agent and a water diversion agent into a polar aprotic solvent, introducing a protective gas, heating to 120-150 ℃, preserving heat for 2-8 hours to perform salifying reaction, continuously heating to 160-210 ℃, preserving heat to perform nucleophilic polycondensation reaction, adding an organic borate-diphenyl bisphenol potassium initiator when the polymer grows to a certain number average molecular weight, and continuously reacting until stirring torque is not increased any more, thus obtaining polysulfone resin polymer liquid;
(2) Post-treatment: cooling, crushing, filtering, washing and drying the polysulfone resin polymerization liquid to obtain polysulfone resin.
When the number average molecular weight of the polymer is increased to 20000-40000g/mol, adding an organic borate-biphenol potassium initiator.
The polar aprotic solvent is one or more of dimethyl sulfoxide, sulfolane, N-dimethylacetamide and N-methylpyrrolidone.
The water-splitting agent is one or more of toluene, dimethylbenzene, mesitylene, o-trimethylbenzene, m-trimethylbenzene, ethylbenzene and meta-ethylbenzene.
The salt forming agent is one or more of potassium bicarbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium carbonate and sodium carbonate.
The synthesis steps of the organic borate-diphenyl bisphenol potassium initiator are as follows: mixing diphenyl bisphenol potassium and organic boric acid ester, dissolving in a reaction solvent, adding a catalyst, introducing nitrogen, heating and stirring for 5-30min, stopping the reaction, cooling the solution, stirring and separating out, washing and drying to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator. The molar ratio of the diphenyl bisphenol potassium to the organic borate is 1 (1-1.4), and the reaction temperature is 60-90 ℃. The precipitation of the organic borate-diphenyl bisphenol potassium initiator product is carried out by stirring at 0-5 ℃, washing for multiple times by 1.5-3.5 times by using a washing solvent, and vacuum drying at 80-100 ℃ for 2-4h. The reaction solvent is one of tertiary butanol, glycerol, toluene and N, N-dimethylformamide. The washing solvent is one of ethanol, methanol, acetone and ethyl acetate. The catalyst is one of potassium methoxide, potassium tert-butoxide and potassium ethoxide.
The mass molar ratio of bisphenol A to 4,4' -dichlorodiphenyl sulfone to the salifying agent is 1 (0.85-1) to 1.05-3.
The addition amount of the organic borate-biphenol potassium initiator is 1.7-2.7% of the theoretical polysulfone resin product mass.
The ratio of the total mass of bisphenol A and 4,4' -dichlorodiphenyl sulfone to the mass of the polar aprotic solvent is 1 (2.5-5).
The addition amount of the water diversion agent is 20-40% of the volume of the polar aprotic solvent.
Specifically, the method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mole ratio of 1 (1-1.4), dissolving in reaction solvent tert-butyl alcohol, glycerol, toluene or N, N-dimethylformamide, adding catalyst potassium methoxide, tert-butyl alcohol potassium or potassium ethoxide, introducing nitrogen gas, heating to 60-90 ℃ and stirring for 5-30min, cooling to 0-5 ℃ after stopping reaction, stirring and separating out until no new crystal is formed, washing 3 times by using 1.5-3.5 times of washing solvent, and vacuum drying for 2-4h at 80-100 ℃ to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator. The synthesis reaction formula is:
。
(2) Polymerization reaction: adding a polar aprotic solvent into a 100L polymerization reaction kettle, then adding bisphenol A (BPA), 4' -dichloro diphenyl sulfone (DCDPS), a salifying agent and a water splitting agent, after nitrogen replacement for a plurality of times, introducing nitrogen to normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, heating to 120-150 ℃ for carrying out water reaction for 2-8h, heating to 160-210 ℃ after evaporating out a whole water agent, continuing to carry out heat preservation reaction until the number average molecular weight of the polymer reaches 20000-40000g/mol, adding an organic borate-diphenyl bisphenol potassium initiator for continuous polymerization, and obtaining polysulfone resin polymerization liquid after the stirring torque is no longer increased.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
According to the nucleophilic polycondensation-anionic ring-opening polymerization combined preparation method of polysulfone resin, an initiator formed by organic borate and biphenol potassium is added in the later stage of nucleophilic substitution solution polymerization, as cyclic dimer has larger ring tension and has certain ring opening tendency, phenoxy anions attack sulfone activated aryl ether bonds of cyclic oligomer to open the ring to form new phenoxy end groups and continuously initiate ring opening of the cyclic oligomer, and introduced biphenol potassium monomers enter an oligomer molecular chain, the molecular rigidity is strong, the biphenol potassium monomers are not easy to rotate, the oligomer after ring opening is not easy to form rings for the second time, so that the content of the cyclic oligomer in a polymerization solution is reduced, and the dimer content in the prepared polysulfone resin can be as low as below 0.5%. The anion ring opening process of the nucleophile and cyclic dimer of the present invention is as follows:
。
according to the method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization, sulfonyl and two adjacent benzene rings form a high conjugated structure, the strong electron-withdrawing property of the sulfonyl has the tendency of attracting electrons to the adjacent benzene rings, so that the number of benzene ring electrons is insufficient, namely one side of ether bond sulfonyl is activated and is more easily attacked by nucleophilic reagent to break, but the nucleophilicity of the individual biphenyl bisphenol potassium is insufficient, ring opening can be initiated only by the higher temperature, the earlier patent reports are carried out in a molten state of 300 ℃ or more, the boron atoms have stronger nucleophilicity, the strong nucleophilic reagent is formed after the bonding with the phenoxy anions, a dimer with larger ring tension is preferentially attacked, the C-O on the benzene ring on one side of the ring dimer contains the sulfonyl is broken, the other end of the ether bond after breaking forms a new phenoxy anion, the free phenoxy anions in the system attack the boron atoms of the electron-withdrawing again, and the organic boric acid ester is eliminated, so that a polysulfone dimer ring-opening product with biphenyl bisphenol potassium end group is obtained, and the probability of the biphenol potassium is greatly reduced because the biphenol unit is not easy to rotate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The nucleophilic polycondensation-anionic ring-opening polymerization combined preparation method of polysulfone resin does not introduce other monomers, does not change the basic structure of polysulfone, has small addition amount, does not influence the physicochemical property of polysulfone, greatly reduces the change of polysulfone property compared with the technology of replacing bisphenol A with other rigid bisphenol monomers in the initial stage, and does not need to change the preparation parameters of downstream clients.
(2) According to the nucleophilic polycondensation-anionic ring-opening polymerization combined preparation method of polysulfone resin, due to the existence of ring tension of the cyclodimer, the initiator only directionally initiates the anionic ring-opening reaction of the cyclodimer, so that the initiator is used as an anionic initiator for ring-opening polymerization, and a rigid chain end group after ring opening is provided, the probability of re-cyclization of a linear oligomer after ring opening is greatly reduced, and the linear oligomer is re-polymerized to a main chain, so that the molecular weight distribution of a final product is narrowed. When the molecular weight of polysulfone is increased to a certain extent, an organic borate-biphenol potassium initiator is added into the system, so that the linear polymer with a certain molecular weight has high stability, the main chain of the product cannot be broken due to attack of the initiator, the polymerization time is not prolonged, and the yellowness index of the product is not affected.
(3) The solution nucleophilic polycondensation stage for preparing polysulfone resin has low cyclic dimer content, only contains 1.7-2.5%, and the added organic borate and biphenol potassium form strong nucleophilic reagent, so that the solution can carry out anion ring opening under the solution condition and at 160-200 ℃; however, the existing anionic ring opening of the cyclic oligomer by using potassium biphenol alone needs to be performed in a molten state of 300 ℃ or higher.
Detailed Description
In order to facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. The raw materials used were all from commercial products.
Example 1
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mol ratio of 1:1.1, dissolving in a reaction solvent tert-butyl alcohol, adding catalyst potassium methoxide, heating to 60 ℃ by nitrogen, stirring for 30min, cooling to 0 ℃ after stopping the reaction, stirring and separating out to be free of new crystals, washing 3 times by using ethanol with the concentration of 1.5 times, and vacuum drying for 4h at 80 ℃ to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator.
(2) Polymerization reaction: into a 100L polymerization reactor was charged 60.480kg of N, N-Dimethylacetamide (DMAC), followed by bisphenol A (BPA, 6084.34 g), 4' -dichlorodiphenyl sulfone (DCDPS, 7278.89 g), potassium carbonate (K) 2 CO 3 3866.67 g) and 12.160kg of dimethylbenzene, introducing nitrogen into the reactor to react under normal pressure after nitrogen is replaced for three times, performing nitrogen protection in the whole polymerization reaction, heating to 145 ℃ to react with water for 4 hours, evaporating all dimethylbenzene, heating to 165 ℃, continuing to perform heat preservation reaction until the number average molecular weight of the polymer reaches 28027g/mol, adding 190.70g of the organic borate-biphenyl bisphenol potassium initiator to continue polymerization, and obtaining polysulfone resin polymerization liquid after the stirring torque is not increased.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
Example 2
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mol ratio of 1:1.1, dissolving a reaction solvent glycerol, adding a catalyst potassium tert-butoxide, introducing nitrogen, heating to 70 ℃, stirring for 25min, cooling to 2 ℃ after stopping the reaction, stirring and separating out the solution until no new crystal exists, washing 3 times with 2.5 times of methanol, and vacuum drying at 90 ℃ for 3h to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator.
(2) Polymerization reaction: into a 100L polymerization reactor was charged 31.474kg of N-methylpyrrolidone (NMP), followed by bisphenol A (BPA, 6084.34 g), 4' -dichlorodiphenyl sulfone (DCDPS, 6505.33 g), sodium carbonate (Na 2 CO 3 2966.07 g), toluene 6.29kg, nitrogenAfter three times of gas displacement, introducing nitrogen to normal pressure for reaction, performing nitrogen protection in the whole polymerization reaction, heating to 120 ℃ for reaction with water for 3 hours, heating to 190 ℃ after all toluene is distilled off, continuing to perform heat preservation reaction until the number average molecular weight of the polymer reaches 30491g/mol, adding 180.45g of the organic borate-biphenol potassium initiator for continuous polymerization, and obtaining polysulfone resin polymerization liquid after the stirring torque is not increased any more.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
Example 3
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mol ratio of 1:1.2, dissolving reaction solvent toluene, adding catalyst potassium ethoxide, heating to 80 ℃ by nitrogen, stirring for 15min, cooling to 5 ℃ after stopping the reaction, stirring and separating out to have no new crystal, washing 3 times by using 1.5 times of acetone, and vacuum drying for 2h at 100 ℃ to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator.
(2) Polymerization reaction: into a 100L polymerization reactor was charged sulfolane 64.479kg, followed by bisphenol A (BPA, 6084.34 g), 4' -dichlorodiphenyl sulfone (DCDPS, 6811.47 g), cesium carbonate (Cs) 2 CO 3 26051.08 g), ethylbenzene 19.343kg, nitrogen is introduced into the reactor to react under normal pressure after three times of nitrogen replacement, nitrogen protection is carried out in the whole polymerization reaction, the temperature is raised to 140 ℃ to carry out water reaction for 2 hours, the temperature is raised to 210 ℃ after all ethylbenzene is distilled off, the heat preservation reaction is continued until the polymer number average molecular weight reaches 31380g/mol, 199.45g of the organic borate-biphenyl bisphenol potassium initiator is added to continue polymerization, and the stirring torque is not increased any more during the reaction, thus obtaining polysulfone resin polymer.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
Example 4
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mol ratio of 1:1.4, dissolving into a reaction solvent N, N-dimethylformamide, adding catalyst potassium methoxide, heating to 75 ℃ by nitrogen, stirring for 15min, cooling the solution after stopping the reaction to 3 ℃, stirring and separating out until no new crystal exists, washing 3 times by using ethyl acetate which is 2.5 times, and vacuum drying for 2h at 100 ℃ to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator.
(2) Polymerization reaction: into a 100L polymerization reactor was charged 45.938kg of dimethyl sulfoxide, followed by bisphenol A (BPA, 6084.34 g), 4' -dichlorodiphenyl sulfone (DCDPS, 7041.07 g), potassium bicarbonate (KHCO) 3 6404.11 g), 13.781kg of mesitylene, nitrogen is introduced into the reactor to react under normal pressure after three times of nitrogen replacement, nitrogen protection is carried out in the whole polymerization reaction, the temperature is raised to 150 ℃ to carry out water reaction for 4 hours, the temperature is raised to 170 ℃ after all mesitylene is distilled off, the heat preservation reaction is continued until the polymer number average molecular weight reaches 35211g/mol, 217.02g of the organic borate-biphenyl bisphenol potassium initiator is added to continue polymerization, and the stirring torque is not increased any more during the reaction, thus obtaining the polysulfone resin polymer liquid.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
Example 5
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mol ratio of 1:1.1, dissolving in a reaction solvent tert-butyl alcohol, adding catalyst potassium methoxide, heating to 85 ℃ by nitrogen gas, stirring for 10min, cooling to 0 ℃ after stopping the reaction, stirring and separating out until no new crystal exists, washing 3 times by 3.5 times of ethanol, and vacuum drying for 4h at 80 ℃ to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator.
(2) Polymerization reaction: into a 100L polymerization reactor was charged 46.742kg of N, N-Dimethylacetamide (DMAC), followed by bisphenol A (BPA, 6084.34 g), 4' -dichlorodiphenyl sulfone (DCDPS, 7270.67 g), sodium bicarbonate (NaHCO) 3 5373.64 g) and 18.697kg of dimethylbenzene, introducing nitrogen into the reactor to react under normal pressure after nitrogen is replaced for three times, performing nitrogen protection in the whole polymerization reaction, heating to 145 ℃ to react with water for 4 hours, steaming out all dimethylbenzene, heating to 165 ℃, continuing to perform heat preservation reaction until the number average molecular weight of the polymer reaches 27000g/mol, adding 280.13g of the organic borate-biphenyl bisphenol potassium initiator to continue polymerization, and obtaining polysulfone resin polymerization liquid after the stirring torque is not increased any more.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
Example 6
The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination comprises the following steps:
(1) Synthesizing an organic borate-diphenyl bisphenol potassium initiator: mixing diphenyl bisphenol potassium and organic boric acid ester according to the mol ratio of 1:1.3, dissolving in a reaction solvent tert-butyl alcohol, adding catalyst potassium methoxide, heating to 90 ℃ by nitrogen gas, stirring for 5min, cooling to 5 ℃ after stopping the reaction, stirring and separating out to be free of new crystals, washing 3 times by using ethanol with the concentration of 1.5 times, and vacuum drying for 4h at 80 ℃ to obtain the organic boric acid ester-diphenyl bisphenol potassium initiator.
(2) Polymerization reaction: into a 100L polymerization reactor was charged 53.420kg of N, N-Dimethylacetamide (DMAC), followed by bisphenol A (BPA, 6084.34 g), 4' -dichlorodiphenyl sulfone (DCDPS, 7270.67 g), potassium carbonate (K) 2 CO 3 7367.09 g), 21.368kg of dimethylbenzene, nitrogen is introduced into the reactor to react under normal pressure after the nitrogen is replaced for three times, the whole polymerization is carried out under nitrogen protection, the temperature is raised to 145 ℃ to react with water for 4 hours, the temperature is raised to 165 ℃ after all dimethylbenzene is distilled off, the heat preservation reaction is continued until the number average molecular weight of the polymer reaches 40000g/mol, and the catalyst is added291.33g of the organoborate-biphenol potassium initiator is continuously polymerized, and the stirring torque is not increased any more after the reaction, so as to obtain polysulfone resin polymerization liquid.
(3) Post-treatment: pouring polysulfone resin polymerization liquid into cold water for cooling precipitation, mechanically crushing into powder, boiling for many times with high temperature water, filtering and drying to obtain polysulfone resin, namely white powder product.
Comparative example 1
In this comparative example, an organic borate-potassium biphenol initiator was not added during the reaction, and the other conditions were the same as in example 1 to prepare a polysulfone resin.
Comparative example 2
The initiator added in this comparative example was 107.27g of potassium biphenol, and the other conditions were the same as in example 1 to prepare a polysulfone resin.
Comparative example 3
In this comparative example, when the number average molecular weight of the polymer in the reaction vessel was 15000g/mol, an initiator organoborate-biphenol potassium was added and polymerization was continued for 7 hours, under the same conditions as in example 1, to obtain a polysulfone resin.
Comparative example 4
In this comparative example, when the number average molecular weight of the polymer in the reaction vessel was 45000g/mol, an initiator organoborate-biphenol potassium was added and polymerization was continued for 1 hour, under the same conditions as in example 1, to obtain a polysulfone resin.
The following procedure was adopted for the number average molecular weight measurement during the preparation of polysulfone resin polymer solutions of examples 1-6 and comparative examples 1-4 above.
Polymer number average molecular weight central test
In order to quickly obtain molecular weight data and avoid adverse effects of inorganic salt in the polymerization liquid on the chromatographic column, an ultraviolet spectrophotometry is adopted to calculate the number average molecular weight of the polymer in the polymerization process.
And (3) diluting the trace polymerization solution in NMP, adding a proper amount of acetic acid to enable the pH value of the solution to be 4-6, adding ethanol to enable polysulfone resin to be separated out, rapidly drying, dissolving the powdery polysulfone resin in THF to prepare a uniform solution of 20-40mg/100mL, detecting the end group content by an ultraviolet spectrophotometer, and further calculating the number average molecular weight.
The polysulfone resins prepared in examples 1 to 6 and comparative examples 1 to 4 above were subjected to the following respective parameter tests, and the test results are shown in Table 1.
1. Gel Permeation Chromatography (GPC) test molecular weight
Test instrument: watersE2695 gel chromatograph, equipped with UV detector (wavelength 254 nm).
Test conditions: the flow rate was 1mL/min and the column temperature was 40 ℃.
Sample preparation: the sample to be tested was dissolved in THF to prepare a 1% solution, which was filtered through a filter.
The integration method comprises the following steps: the relative molecular weight was determined using polystyrene standards as standard curves, and the cyclic dimer content was determined using an area normalization method.
2. Yellowness index test
The yellowness index of polysulfone was measured by a yellowness index tester and a polysulfone 2mm coupon was prepared as follows: polysulfone particles were injection molded at a melt temperature of 330℃and a mold temperature of 180℃and cut into 2mm thick plaques.
TABLE 1
As can be seen from the examination of the results of the above examples and comparative examples, comparing the data of comparative example 1 with the data of examples 1 to 6, the content of cyclic dimer in the product was significantly increased from 0.32% to a high level of 2.51% without adding the initiator organoborate-biphenol potassium during the polymerization, indicating that the initiator organoborate-biphenol potassium initiates the ring-opening polymerization of the cyclic dimer content after the formation of the cyclic dimer, resulting in a significant decrease in the content.
The potassium biphenol initiator in comparative example 2 was not reduced in cyclic dimer content in the product relative to comparative example 1, indicating that potassium biphenol initiator alone was unable to ring-open cyclic dimer in solution at temperatures below 300 ℃.
The addition of initiator at lower molecular weight polymers in comparative example 3, without a decrease in the polymerization rate relative to comparative example 1, slows down and the molecular weight of the final product is lower, indicating that premature addition of initiator would result in cleavage of the lower molecular weight linear polysulfone molecular chain moiety, affecting the polymerization process, and the final product yellowness index increased to 41, widening the molecular weight distribution.
The addition of the initiator at a higher molecular weight of the polymer in comparative example 4, although having a somewhat reduced cyclic dimer content as compared with comparative example 1, did not reach the level of example 1 because the viscosity of the polymerization system increased after the higher molecular weight, and the added initiator was difficult to collide with the cyclic dimer effectively, resulting in a reduced effect.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (8)
1. A method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination is characterized in that: the method comprises the following steps:
(1) Polymerization reaction: adding bisphenol A, 4' -dichloro diphenyl sulfone, a salifying agent and a water diversion agent into a polar aprotic solvent, introducing a protective gas, heating to 120-150 ℃, preserving heat for 2-8 hours to carry out salifying reaction, continuously heating to 160-210 ℃, preserving heat to carry out nucleophilic polycondensation reaction, adding an organic borate-diphenyl bisphenol potassium initiator when the polymer grows to 20000-40000g/mol number average molecular weight, and continuously reacting until stirring torque is not increased any more, thus obtaining polysulfone resin polymer liquid;
(2) Post-treatment: cooling, crushing, filtering, washing and drying the polysulfone resin polymerization liquid to obtain polysulfone resin;
the synthesis steps of the organic borate-diphenyl bisphenol potassium initiator are as follows: mixing diphenyl bisphenol potassium and organic boric acid ester, dissolving in a reaction solvent, adding a catalyst, introducing nitrogen, heating and stirring for 5-30min, stopping the reaction, cooling the solution, stirring and separating out, washing and drying to obtain an organic boric acid ester-diphenyl bisphenol potassium initiator; the molar ratio of the biphenol potassium to the organic borate is 1 (1-1.4), and the reaction temperature is 60-90 ℃; the precipitation of the organic borate-diphenyl bisphenol potassium initiator product is carried out by stirring at 0-5 ℃, washing for multiple times by 1.5-3.5 times by using a washing solvent, and vacuum drying for 2-4h at 80-100 ℃; the reaction solvent is one of tertiary butanol, glycerol, toluene and N, N-dimethylformamide; the washing solvent is one of ethanol, methanol, acetone and ethyl acetate; the catalyst is one of potassium methoxide, potassium tert-butoxide and potassium ethoxide; the synthesis reaction formula is:
2. the method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the addition amount of the organic borate-biphenol potassium initiator is 1.7-2.7% of the theoretical polysulfone resin product mass.
3. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the polar aprotic solvent is one or more of dimethyl sulfoxide, sulfolane, N-dimethylacetamide and N-methylpyrrolidone.
4. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the water-splitting agent is one or more of toluene, dimethylbenzene, mesitylene, o-trimethylbenzene, m-trimethylbenzene and ethylbenzene.
5. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the salt forming agent is one or more of potassium bicarbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium carbonate and sodium carbonate.
6. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the mol ratio of bisphenol A, 4' -dichloro diphenyl sulfone and salifying agent is 1 (0.85-1) to 1.05-3.
7. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the ratio of the total mass of bisphenol A and 4,4' -dichlorodiphenyl sulfone to the mass of the polar aprotic solvent is 1 (2.5-5).
8. The method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring opening polymerization combination according to claim 1, wherein: the addition amount of the water diversion agent is 20-40% of the volume of the polar aprotic solvent.
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