A dihydric hydroxyl poly(arylene ether) and a method for making the same
By using acidic water washing wastewater from the production of thermosetting capped polyarylene ethers to wash the hydroxyl-terminated polyarylene ethers, the problem of amine residues was solved, the glass transition temperature and thermal properties of the product were improved, and resource utilization was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANTONG XINGCHEN SYNTHETIC MATERIAL CO LTD
- Filing Date
- 2024-12-26
- Publication Date
- 2026-06-26
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer materials technology, and in particular to a double-hydroxyl-terminated polyarylene ether and its preparation method. Background Technology
[0002] Polyarylene ethers (also known as polyphenylene ethers) are one of the five major general-purpose engineering plastics, widely used in electronics, automobiles, home appliances, office equipment, and industrial machinery. In recent years, with the rapid development of communication technology, 5G communication technology has been widely adopted globally. 5G communication is a high-frequency communication technology, and it places high demands on the electrical and thermal properties of materials.
[0003] A common process for preparing polyphenylene ether (PPE) involves the condensation of at least one monovalent phenol in the presence of oxygen and a catalyst containing a metal amine complex. After adding a chelating agent to convert the catalyst metal into a soluble metal complex, standard extraction techniques are used to remove the catalyst metal from the polymer solution. However, this process cannot avoid leaving residual amines in the organic phase. These amine residues give PPE a pungent odor, affecting its quality and commonly causing yellowing and darkening of the final product during downstream processing. Related technologies typically use water washing to remove amines during PPE preparation; however, the residual amines in the solution after adding the chelating agent have low solubility in water and cannot be removed by ordinary water washing. Summary of the Invention
[0004] This invention provides a hydroxyl-terminated polyarylene ether and its preparation method, which solves the problem that residual amines in existing hydroxyl-terminated polyarylene ether solutions cannot be effectively removed.
[0005] According to a first aspect of the present invention, the present invention provides a method for preparing a dihydroxyl-terminated polyarylene ether, comprising the following steps: A monomer solution containing 2,6-dimethylphenol and tetramethylbisphenol was prepared using toluene as a solvent; The monomer solution and oxidant are placed in an organic solution and polymerized under the action of a catalyst. After the polymerization reaction is completed, an aqueous chelating agent is added to quench the reaction, resulting in a solution of dihydroxyl-terminated polyarylene ether. The solution of the double-hydroxyl-terminated polyarylene ether was washed with the washing wastewater from the production of thermosetting end-capped polyarylene ether. After the washed material is allowed to stand, the upper organic phase is taken and separated to obtain the double-hydroxyl-terminated polyarylene ether.
[0006] During the experimental process of this invention, it was discovered that the large amount of washing wastewater generated during the production of thermosetting end-capped polyarylene ethers is acidic. Due to the raw materials used in the production of hydroxyl-terminated polyarylene ethers, volatile substances with odors inevitably remain, generally amines. These amines have high boiling points and poor water solubility. The acidic washing wastewater can react with these amines, removing them. This not only removes odorous amines but also saves on wastewater treatment steps, achieving resource utilization. Furthermore, this invention unexpectedly discovered that using the large amount of washing wastewater generated during the production of thermosetting end-capped polyarylene ethers to wash the hydroxyl-terminated polyarylene ethers can reduce the impurity content of the hydroxyl-terminated polyarylene ethers, thereby increasing the glass transition temperature and ultimately improving the thermal properties of the hydroxyl-terminated polyarylene ethers.
[0007] Furthermore, the weight ratio of the washing wastewater from the production of thermosetting end-capped polyaryl ethers to the dihydroxyl-terminated polyaryl ether solution is 1:5 to 1:12, preferably 1:6 to 1:8. Under these weight ratio conditions, amine substances can be removed more effectively, and the glass transition temperature of the dihydroxyl-terminated polyaryl ether can be increased more effectively, thereby improving its thermal properties.
[0008] Furthermore, the pH value of the washing wastewater used in the production of thermosetting end-capped polyarylene ethers is 2 to 6.
[0009] Preferably, the washing wastewater from the production of thermosetting-terminated polyarylene ethers includes organic acid and toluene, wherein the organic acid accounts for 1-2% of the total mass of the washing wastewater from the production of thermosetting-terminated polyarylene ethers, and the toluene accounts for less than 1% by weight of the total mass of the washing wastewater from the production of thermosetting-terminated polyarylene ethers, preferably 0.1-0.2%.
[0010] Limiting the proportion of organic acids in the washing wastewater from the production of thermosetting end-capped polyarylene ethers is more conducive to removing amines from the dihydroxyl-terminated polyarylene ether solution. Limiting the proportion of toluene in the washing wastewater from the production of thermosetting end-capped polyarylene ethers is more conducive to stabilizing the content of organic acids in the washing wastewater and ensuring the washing effect.
[0011] Furthermore, the organic acid can be one or both of methacrylic acid and acrylic acid. In some specific embodiments, the organic acid is methacrylic acid.
[0012] Furthermore, the COD value of the washing wastewater from the production of thermosetting end-capped polyarylene ethers is 5000~500000ppm, preferably 50000~100000ppm. Experiments have shown that using the washing wastewater from the production of thermosetting end-capped polyarylene ethers under the above COD value conditions to wash the hydroxyl-terminated polyarylene ethers is more conducive to increasing the glass transition temperature of the hydroxyl-terminated polyarylene ethers.
[0013] Furthermore, the washing temperature of the dihydroxyl-terminated polyarylene ether solution with the washing wastewater from the production of thermosetting end-capped polyarylene ethers is 40-70°C, preferably 50-60°C. By limiting the washing temperature within a reasonable range, amine substances in the dihydroxyl-terminated polyarylene ether solution can be removed more effectively.
[0014] Furthermore, the washing of the dihydroxyl-terminated polyarylene ether solution with the washing wastewater from the production of thermosetting end-capped polyarylene ethers involves a stirring speed of 70-90 rpm and a stirring time of 5-60 min, preferably 10-15 min. By limiting the stirring speed and time within a reasonable range, amines in the dihydroxyl-terminated polyarylene ether solution can be removed more effectively. If the stirring speed is too low or the stirring time is too short, a good washing effect will not be achieved; if the stirring speed is too high or the stirring time is too long, emulsification may occur, resulting in incomplete separation of the organic and aqueous phases, ultimately leading to a decrease in yield.
[0015] Furthermore, the settling time is 5-60 minutes, preferably 20-30 minutes. Limiting the settling time to a reasonable range is more conducive to separating the dihydroxyl-terminated polyarylene ether solution.
[0016] Preferably, the separation method includes one or more of the following: anti-solvent method, devolatile matter extrusion, thin-film evaporation, or flash evaporation to remove volatile matter. Using the above separation method can more effectively extract dihydroxyl-terminated polyarylene ethers from dihydroxyl-terminated polyarylene ether solutions.
[0017] Furthermore, in the monomer solution, the molar ratio of 2,6-dimethylphenol to tetramethylbisphenol is 1:1 to 20:1, preferably 10:1 to 15:1. Limiting the molar ratio of 2,6-dimethylphenol to tetramethylbisphenol to a reasonable range is more conducive to improving the efficiency of the polymerization reaction and obtaining the target product.
[0018] Furthermore, the catalyst is a copper-amine catalyst. Using a suitable type of catalyst is more conducive to improving the efficiency of the polymerization reaction and obtaining the target product.
[0019] The good solvent for the dihydroxyl-terminated polyarylene ether can be conventionally selected in the art, such as one or more organic solvents such as benzene, toluene, xylene, chloroform, and tetrahydrofuran. Preferably, the organic solvent is toluene.
[0020] Furthermore, the oxidant is oxygen.
[0021] Furthermore, the amount of catalyst used is 1 to 10% of the weight of the 2,6-dimethylphenol, preferably 2 to 6%. Limiting the amount of catalyst within a reasonable range is more conducive to improving the efficiency of the polymerization reaction and obtaining the target product.
[0022] Further, the chelating agent aqueous solution is an aqueous solution of sodium ethylenediaminetetraacetic acid; even further, the chelating agent aqueous solution is an aqueous solution of sodium ethylenediaminetetraacetic acid with a mass fraction of 10-20%.
[0023] Furthermore, the polymerization reaction is carried out at a temperature of 35-45°C under inert gas conditions. Limiting the temperature and atmospheric conditions of the polymerization reaction is beneficial for improving its efficiency.
[0024] According to a second aspect of the present invention, the present invention also provides a hydroxyl-terminated polyarylene ether having a glass transition temperature of 155-158°C. Such a glass transition temperature of the hydroxyl-terminated polyarylene ether can improve the heat resistance of multilayer boards and enhance the adhesion between copper foil and resin.
[0025] The bihydroxyl-terminated polyarylene ether has the structure shown in Formula 1: (Equation 1); In Equation 1, m and p are both integers 0 or greater than 1, n is either 0 or 1, and m and p cannot be 0 at the same time, and n cannot be 0 alone; m+p is 5-50; R1-R8 are independently selected from hydrogen atoms, alkyl groups, halogens, haloalkanes, or alkoxy groups; Y has the structure shown in Equation 2: (Formula 2); In Formula 2, X1-X8 are each independently selected from hydrogen atoms or saturated or unsaturated alkyl groups with 1 to 8 carbon atoms, such as methyl, ethyl, allyl, etc.
[0026] W indicates a single bond or ethylene. Alkyl groups with 1 to 4 carbon atoms, such as methylene.
[0027] In some specific embodiments, the double-hydroxyl-terminated polyarylene ether of the present invention has the following structure: (Equation 3).
[0028] In Formula 3, W is an alkyl group with 1-4 carbon atoms, and m+p ranges from 5-50. Preferably, W is... Methylene, ethylene, etc.
[0029] Furthermore, the above-mentioned thermosetting end-capped polyarylene ether has the following structure: (Equation 4).
[0030] In Equation 4, m and p are both integers 0 or greater than 1, n is either 0 or 1, and m and p cannot be 0 at the same time, nor can n be 0 alone. The range of m+p is 5-50.
[0031] R1-R8 are independently selected from hydrogen atoms, alkyl groups, halogens, haloalkanes, or alkoxy groups.
[0032] The Y in the above structure typically has the following structure: (Equation 5).
[0033] In Formula 5, X1-X8 are independently selected from hydrogen atoms or saturated or unsaturated alkyl groups with 1 to 8 carbon atoms, such as methyl, ethyl, or allyl. W represents a single bond or an alkyl group with 1 to 4 carbon atoms. Preferably, W represents ethylene. Or methylene, etc.
[0034] Typically, the thermosetting end-capped polyarylene ether has the following structure: (Formula 6).
[0035] In Formula 6, W is an alkyl group with 1-4 C atoms, and m+p ranges from 5 to 50.
[0036] In Equation 6, W is Methylene, ethylene, etc.
[0037] The present invention discloses a method for preparing dihydroxyl-terminated polyarylene ethers by using a large amount of washing wastewater generated during the production of thermosetting end-capped polyarylene ethers to wash the dihydroxyl-terminated polyarylene ethers. This method can not only effectively remove odorous amine substances, but also save wastewater treatment steps, achieve the effect of resource utilization, and increase the glass transition temperature of dihydroxyl-terminated polyarylene ethers, thereby improving the thermal properties of dihydroxyl-terminated polyarylene ethers. Detailed Implementation
[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0039] Unless otherwise specified, the techniques or conditions described in the examples are as described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.
[0040] The test methods and instruments used in the following examples and comparative examples are as follows: (1) Differential scanning calorimeter: TA Company, DSC25.
[0041] (2) High performance liquid chromatograph: Thermo, UltiMate 3000 (3) Elemental analyzer: Elementar, Vario EL Cube The bi-hydroxyl-terminated polyarylene ethers of the following embodiments of the present invention have the following structures: W indicates , m+p is 5-50.
[0042] Thermosetting end-capped polyarylene ethers have the following structures: W indicates , m+p is 5-50.
[0043] The process for producing thermosetting end-capped polyarylene ethers includes the following steps: (1) dissolving the bihydroxyl-terminated polyphenylene ether in toluene; (2) adding modified small molecule methacrylic anhydride to the solution obtained in step (1) and performing an esterification reaction under alkaline conditions; (3) washing with deionized water after the reaction is completed; (4) separating the organic phase after water washing in step (3) by antisolvent method and drying to obtain the final product. The wastewater used in the following examples and comparative examples for the production of thermosetting-terminated polyarylene ethers was derived from the wastewater after washing in step (3) of the above-mentioned process for producing thermosetting-terminated polyarylene ethers. The components of the wastewater used for the production of thermosetting-terminated polyarylene ethers were detected using a Thermo UltiMate 3000 high-performance liquid chromatograph. The chromatographic conditions were: C18 column (150×3mm, 3μm), flow rate of 0.3 mL / min, column temperature of 35℃, injection volume of 20μL, and a UV-Vis detector with a detection wavelength of 270 nm.
[0044] Example 1 This embodiment provides a method for preparing a double-hydroxyl-terminated polyarylene ether, comprising the following steps: 1) Using toluene as a solvent, prepare 30 kg of monomer solution containing 17 kg of 2,6-dimethylphenol (DMP) and 2.9 kg of tetramethylbisphenol A (TMBPA).
[0045] 2) Add 10 kg of monomer solution, 300 kg of toluene, and 0.4 kg of copper amine catalyst to the reactor and stir until homogeneous.
[0046] 3) Continuously add the remaining monomer solution, introduce oxygen into the bottom of the reactor, and simultaneously introduce nitrogen into the upper gas phase space of the reactor. Control the reactor temperature at 35-45 ℃.
[0047] 4) After polymerization, 0.3 kg of sodium EDTA salt (10% aqueous solution) was added to quench the reaction and obtain a solution of polyarylene ether with hydroxyl-terminated ends.
[0048] 5) Add 50 kg of the washing wastewater from the production of thermosetting-terminated polyarylene ethers to wash the hydroxyl-terminated polyarylene ether solution. The washing temperature is 50℃, and the mixture is stirred for 10 min at 80 rpm. The washing wastewater from the production of thermosetting-terminated polyarylene ethers has a COD value of 61200 ppm and a pH value of 4. The washing wastewater from the production of thermosetting-terminated polyarylene ethers contains 1.2% methacrylic acid by weight, 0.1% toluene by weight, and the remainder is water.
[0049] 6) After standing for 30 minutes, take the upper organic phase to obtain a toluene solution of dihydroxyl-terminated polyarylene ether; use a devolatile fraction extrusion separation method to obtain dihydroxyl-terminated polyarylene ether.
[0050] The yield of the dihydroxyl-terminated polyarylene ether in this embodiment was 87%, the Tg was 155.72 °C, and the N element content was 0.08 wt%.
[0051] Example 2 This embodiment provides a method for preparing a hydroxyl-terminated polyarylene ether, which differs from Example 1 in that the wastewater used for producing the thermosetting-terminated polyarylene ether has a COD value of 153,400 ppm and a pH value of 3. The wastewater contains 1.5% methacrylic acid and 0.2% toluene by weight, with the remainder being water. All other operating conditions remain unchanged.
[0052] The yield of the dihydroxyl-terminated polyarylene ether in this embodiment was 86%, the Tg was 157.27 °C, and the N element content was 0.06 wt%.
[0053] Example 3 This embodiment provides a method for preparing a hydroxyl-terminated polyarylene ether. The difference from Example 1 is that the amount of water used for washing wastewater in the production of thermosetting end-capped polyarylene ether is adjusted to 30 kg, while the other operating conditions remain unchanged.
[0054] The yield of the dihydroxyl-terminated polyarylene ether in this embodiment was 88%, the Tg was 154.16 °C, and the N element content was 0.09 wt%.
[0055] Example 4 This embodiment provides a method for preparing a dihydroxyl-terminated polyarylene ether, which differs from Example 1 in that TMBPA is replaced with TMBPF, while the other operating conditions remain unchanged.
[0056] The yield of the dihydroxyl-terminated polyarylene ether in this embodiment is 85%, the Tg is 156.01℃, and the N element content is 0.08wt%.
[0057] Example 5 This embodiment provides a method for preparing a double-hydroxyl-terminated polyarylene ether, which differs from Example 1 in that the washing temperature is 60°C, the stirring time is 15 min, and the rotation speed is 90 rpm.
[0058] The yield of the dihydroxyl-terminated polyarylene ether in this embodiment was 83%, the Tg was 155.13℃, and the N element content was 0.08wt%.
[0059] Comparative Example 1 This comparative example provides a method for preparing a hydroxyl-terminated polyarylene ether. The difference from Example 1 is that the water washing wastewater used in the production of thermosetting end-capped polyarylene ether is replaced with deionized water, while the other operating conditions remain unchanged.
[0060] The yield of the bihydroxyl-terminated polyarylene ether in this comparative example was 87%, the Tg was 148.13℃, and the N element content was 0.18wt%.
[0061] Comparative Example 2 This comparative example provides a method for preparing a hydroxyl-terminated polyarylene ether. The difference from Example 4 is that the water washing wastewater used in the production of thermosetting end-capped polyarylene ether is replaced with deionized water, while the other operating conditions remain unchanged.
[0062] The yield of the bihydroxyl-terminated polyarylene ether in this comparative example was 86%, the Tg was 147.26℃, and the N element content was 0.19wt%.
[0063] Comparative Example 3 This comparative example provides a method for preparing a hydroxyl-terminated polyarylene ether. The difference from Example 1 is that the COD value of the washing wastewater for producing thermosetting-terminated polyarylene ether is 2000 ppm, and the weight percentage of methacrylic acid in the washing wastewater for producing thermosetting-terminated polyarylene ether is 0.2%, the weight percentage of toluene is 0.02%, and the remainder is water.
[0064] The yield of the dihydroxyl-terminated polyarylene ether in this comparative example was 86%, the Tg was 149.51℃, and the N element content was 0.15wt%.
[0065] Comparative Example 4 This comparative example provides a method for preparing a bihydroxyl-terminated polyarylene ether. The difference from Example 1 is that the washing temperature is 30°C, the stirring time is 120 min, and the rotation speed is 50 rpm.
[0066] The yield of the bihydroxyl-terminated polyarylene ether in this comparative example was 76%, the Tg was 148.74℃, and the N element content was 0.14wt%.
[0067] As can be seen from the results of Examples 1 and 1, and Examples 4 and 2, the present invention utilizes the washing wastewater from the production of thermosetting-terminated polyarylene ethers in the preparation of dihydroxyl-terminated polyarylene ethers. This not only eliminates the need for wastewater treatment in the production of thermosetting-terminated polyarylene ethers, reducing energy consumption, but also further reduces the impurity content of dihydroxyl-terminated polyarylene ethers. Unexpectedly, it also increases the glass transition temperature of dihydroxyl-terminated polyarylene ethers, thereby improving their thermal properties. Furthermore, as can be seen from the results of Examples 1 and 3, the COD value, methacrylic acid content, and toluene content of the washing wastewater from the production of thermosetting-terminated polyarylene ethers affect the washing effect. If the COD value, methacrylic acid content, and toluene content in the washing wastewater are too low, the increase in the glass transition temperature of dihydroxyl-terminated polyarylene ethers is not significant, and the removal effect on impurities is also not significant. As can be seen from the results of Example 1 and Comparative Example 4, the control of washing temperature, stirring time and stirring speed during the washing process is also very important. Under the washing temperature, stirring time and stirring speed selected in this invention, the yield of the double-hydroxyl-terminated polyarylene ether is high, the glass transition temperature is significantly increased, and the impurity removal effect is obvious.
[0068] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A process for the preparation of a dihydric hydroxy poly(arylene ether) characterized by, Includes the following steps: A monomer solution containing 2,6-dimethylphenol and tetramethylbisphenol was prepared using toluene as a solvent; The monomer solution and oxidant are placed in an organic solution and polymerized under the action of a catalyst. After the polymerization reaction is completed, an aqueous chelating agent is added to quench the reaction, resulting in a solution of dihydroxyl-terminated polyarylene ether. The solution of the double-hydroxyl-terminated polyarylene ether was washed with the washing wastewater from the production of thermosetting end-capped polyarylene ether. After the washed material is allowed to stand, the upper organic phase is taken and separated to obtain the double-hydroxyl-terminated polyarylene ether.
2. The production method according to claim 1, characterized by, The weight ratio of the washing wastewater from the production of thermosetting end-capped polyarylene ethers to the dihydroxyl-terminated polyarylene ether solution is 1:(5~12), preferably 1:(6~8).
3. The production method according to claim 1 or 2, characterized by, The washing wastewater from the production of thermosetting end-capped polyarylene ethers includes organic acid and toluene. The organic acid accounts for 1-2% of the total mass of the washing wastewater from the production of thermosetting end-capped polyarylene ethers, and the toluene accounts for less than 1% of the total mass of the washing wastewater from the production of thermosetting end-capped polyarylene ethers by weight.
4. The preparation method according to any one of claims 1-3, characterized in that, The COD value of the washing wastewater from the production of thermosetting end-capped polyarylene ethers is 5000~500000ppm, preferably 50000~100000ppm.
5. The preparation method according to any one of claims 1-4, characterized in that, The temperature at which the double-hydroxyl-terminated polyarylene ether solution is washed with the washing wastewater from the production of thermosetting end-capped polyarylene ethers is 40-70℃, preferably 50-60℃.
6. The preparation method according to any one of claims 1-5, characterized in that, The solution of the double-hydroxyl-terminated polyarylene ether is washed with the washing wastewater from the production of thermosetting end-capped polyarylene ethers. The stirring speed is 70-90 rpm and the stirring time is 5-60 min, preferably 10-15 min.
7. The preparation method according to claim 1, characterized in that, The settling time is 5-60 minutes, preferably 20-30 minutes.
8. The preparation method according to claim 1, characterized in that, The separation process includes one or more of the following: anti-solvent method, volatile matter extrusion, thin film evaporation, or flash evaporation for volatile matter removal.
9. The preparation method according to claim 1, characterized in that, In the monomer solution, the molar ratio of 2,6-dimethylphenol to tetramethylbisphenol is 1:1 to 20:1; And / or, the catalyst is a copper-amine catalyst; And / or, the organic solution is toluene; And / or, the oxidant is oxygen; And / or, the amount of catalyst used is 1 to 10% of the weight of the 2,6-dimethylphenol; And / or, the chelating agent aqueous solution is an aqueous solution of the sodium salt of ethylenediaminetetraacetic acid; And / or, the polymerization reaction is carried out at a temperature of 35-45°C; the polymerization reaction is carried out under inert gas conditions.
10. A hydroxyl-terminated polyarylene ether, characterized in that, It is prepared by the preparation method according to any one of claims 1-9; the glass transition temperature of the double-hydroxyl-terminated polyarylene ether is 155-158℃.