Method and device for continuously purifying polyamide acid or polyimide resin

Abstract

The invention relates to the technical field of resin purification, and particularly discloses a continuous purification method and device for polyamide acid or polyimide resin.The continuous purification device comprises a first solution tank, a deionization mechanism, a first collecting tank and a second collecting tank, and the first solution tank is used for containing a resin solution; the deionization mechanism comprises a deionization assembly I, a deionization assembly II and an activation assembly, the first solution tank, the deionization assembly I and the first collection tank are communicated, the first solution tank, the deionization assembly II and the second collection tank are communicated, the deionization assembly I and the deionization assembly II are connected in parallel, and the deionization assembly I and the activation assembly are connected in series; the deionization assembly II is connected with the activation assembly in series; the activation assembly comprises a plurality of solvent tanks, the solvent tanks are mutually independent, the solvent tanks are connected in parallel, and the solvent tanks are used for conveying an activation solvent to the deionization assembly I or the deionization assembly II. According to the invention, activation and purification can be carried out simultaneously, and the working efficiency can be improved.

Description

Technical Field

[0001] The present application relates to the technical field of resin purification, and particularly relates to a continuous purification method and device for polyamic acid or polyimide resin. Background Art

[0002] With the advent of the post-Moore's Law era, traditional chip packaging technologies are difficult to meet the rapidly developing technical requirements. Especially for electronic products such as camera modules, optical communications, and flat panel displays, which are becoming increasingly integrated, multifunctional, and lightweight, the internal packaged chip structures are becoming more compact, the functions are becoming more powerful, the circuit designs are more complex, and the energy consumption management is more severe. Corresponding packaging materials have also been presented with new requirements and challenges. In the synthesis of electronic materials to meet the needs of end products, most are formulated by polymerizing multiple raw materials or adding different materials. Therefore, if the purity can be controlled from the most upstream raw materials, the variation in the quality of electronic materials can be reduced.

[0003] For polyimide (PI) and polyamic acid (PAA), they are widely used in electronic materials. For example, there are instances of using PI in electronic products such as LCD, IC, and flexible copper clad laminate (FCCL). Therefore, under different product applications, there are also different requirements for polyimide resin and polyamic acid resin. In addition to the different requirements, it can be found that polyimide and polyamic acid materials have the same requirements for ion content. Therefore, the ion content will directly affect the performance of the final product.

[0004] Regarding the current purification methods for polyimide or polyamic acid, precipitation or membrane filtration is mostly used as the main method, and the purpose of these methods is only to remove impurities such as unreacted monomers, oligomers, and catalysts in polyimide or polyamic acid. The efficiency of the rare ion exchange resin column method for removing metal ions is also not high. Summary of the Invention

[0005] In order to solve the problem that the existing purification methods for polyimide or polyamic acid have low efficiency in removing metal ions, the present application provides a continuous purification method for polyamic acid or polyimide resin.

[0006] A continuous purification method for polyamic acid or polyimide resin provided by the present application adopts the following technical solution:

[0007] A continuous purification method for polyamic acid or polyimide resin includes the following steps:

[0008] S10: Provide a solution of polyamic acid or polyimide resin containing metal ions;

[0009] S20: Feed the solution into Deionization Component 1 for purification;

[0010] S30: Detect the metal ion concentration in the solution that has passed through Deionization Component 1. If the detection result is greater than 50 PPB, it means that Deionization Component 1 has reached its service limit and needs to be activated; at this time, stop feeding the solution into Deionization Component 1;

[0011] S40: Feed the solution into Deionization Component 2 to continue purification, and at the same time activate Deionization Component 1;

[0012] S50: Detect the metal ion concentration in the solution that has passed through Deionization Component 2. If the detection result is greater than 50 PPB, it means that Deionization Component 2 has reached its service limit and needs to be activated; at this time, stop feeding the solution into Deionization Component 2;

[0013] S60: Feed the solution into Deionization Component 1 to continue purification, and at the same time activate Deionization Component 2;

[0014] S70: Repeat steps S10 - S60.

[0015] By adopting the above technical solution, the deionization device can effectively remove metal ions in the solution, thereby obtaining electronic-grade pure polyamic acid or polyimide resin. By setting Deionization Component 1 and Deionization Component 2, when one of the deionization devices, such as Deionization Component 1, reaches its service limit, Deionization Component 2 is used for purification, and at the same time Deionization Component 1 is activated. When Deionization Component 2 reaches its service limit, Deionization Component 1 is continued to be used for purification, and at the same time Deionization Component 2 is activated, so that purification and activation work can be carried out simultaneously, which helps to improve work efficiency.

[0016] Optionally, the activation in steps S40 and S60 includes the following steps:

[0017] S100: Deliver electronic-grade good solvent to Deionization Component 1 or Deionization Component 2;

[0018] S200: Stop delivering the electronic-grade good solvent, deliver hydrophilic organic solvent to Deionization Component 1 or Deionization Component 2, and replace the electronic-grade good solvent with hydrophilic organic solvent;

[0019] S300: Stop delivering the hydrophilic organic solvent, deliver ultrapure water to Deionization Component 1 or Deionization Component 2, and replace the hydrophilic organic solvent with ultrapure water;

[0020] S400: Stop delivering the ultrapure water, deliver hydrochloric acid aqueous solution to Deionization Component 1 or Deionization Component 2 for activation;

[0021] S500: Repeat steps S100 - S300 in reverse order to complete solvent replacement.

[0022] By adopting the above technical solution, the deionization device can be washed with electronic grade good solvent, hydrophilic organic solvent, ultrapure water and hydrochloric acid aqueous solution, so that the metal ions on the resin in the deionization device can be replaced, thereby restoring the adsorption capacity of the resin to ensure the reuse effect of the deionization device.

[0023] Optionally, in step S20, the flow rate of the solution is between 1 mL / min and 5 mL / min.

[0024] By adopting the above technical solution, too fast flow rate may lead to insufficient contact time of the solution in deionization component one or deionization component two, reducing the effectiveness of ion exchange. If the flow rate is too high, it may damage the structure of deionization component one. Appropriate flow rate helps to improve the ion exchange efficiency during deionization and achieve better purification effect.

[0025] Optionally, in steps S20 and S40, the operating temperatures of deionization component one and deionization component two are both 0 - 75 °C.

[0026] By adopting the above technical solution, too high temperature will cause side reactions or yellowing of polyamic acid. At too low temperature, the solution viscosity increases, resulting in increased system pressure, poor fluidity, and also poor filtration effect. Appropriate ambient temperature can accelerate the rate of ion exchange reaction, promote ion migration, and achieve better purification effect.

[0027] Optionally, the concentration of the hydrochloric acid aqueous solution in step S400 is 5 wt% - 10 wt%.

[0028] By adopting the above technical solution, hydrochloric acid aqueous solution with appropriate concentration can effectively remove impurities and old ions in deionization component one and deionization component two to activate the exchange capacity of the exchange resin in deionization component one and deionization component two and ensure good purification effect.

[0029] Optionally, in step S200, the electronic grade good solvent includes one or more of phenolic reagents.

[0030] Optionally, in step S200, the hydrophilic organic solvent includes one or more of alcohol solvents, ketone solvents, ether solvents, and amide solvents.

[0031] Optionally, there are a first solution tank, a deionization mechanism, a first collection tank, and a second collection tank. The first solution tank is used to hold a solution of a polyamic acid or polyimide resin containing metal ions. The deionization mechanism includes a first deionization component, a second deionization component, and an activation component. There is a connection between the first solution tank, the first deionization component, and the first collection tank. There is also a connection between the first solution tank, the second deionization component, and the second collection tank. The first deionization component and the second deionization component are in parallel, and the first deionization component is in series with the activation component; the second deionization component is in series with the activation component;

[0032] The activation component includes multiple solvent tanks. Each solvent tank is independent of each other, and each solvent tank is in parallel. The solvent tank is used to transport the activation solvent to the first deionization component or the second deionization component.

[0033] By adopting the above technical solution, the continuous purification device provided by the present application can perform activation and purification simultaneously. When one set of deionization components reaches the usage limit, activation is carried out, while the other set of deionization components can continue to perform purification, which helps to improve work efficiency and ensure a good purification effect.

[0034] Optionally, both the first deionization component and the second deionization component include a housing and a fiber membrane. The fiber membrane is provided with multiple layers and is spaced in the housing. The multiple layers of fiber membranes divide the first deionization component and the second deionization component into multiple deionization chambers, and each deionization chamber is filled with an ion exchange resin.

[0035] By adopting the above technical solution, by setting multiple fiber membranes, multi-layer filtration of the solution in the deionization chamber can be achieved, which helps to achieve a better deionization effect.

[0036] Optionally, both the first deionization component and the second deionization component are provided with at least one inlet and at least one outlet. The inlet is connected to the first solution tank, the solution enters the housing from the inlet, flows through the deionization chamber, and then flows out from the outlet. Along the flow direction of the solution, the pH values of the ion exchange resins in each deionization chamber are in turn: strong acid, weak acid, strong base, weak base.

[0037] Optionally, the weakly basic ion exchange resin is one or more of macroporous acrylic weakly basic anion exchange resin, weakly basic anion resin D301-F, MonoPlusMP 64 weakly basic macroporous anion exchange resin, macroporous weakly basic styrene-based anion exchange resin; the strongly basic ion exchange resin is strongly basic anion resin D201MBP, strongly basic DOWEX MSA-1 anion exchange resin, TulsimerA-62MP strongly basic anion exchange resin, One or more of IRA402 strong-base anion exchange resin and D201 macroporous strong-base anion resin; the strong-acid ion exchange resin is one or more of strong-acid macroporous C150H cation exchange resin, strong-acid cation resin D001MBP, Amberlyst 35 strong-acid cation exchange resin, Amberlyst15 strong-acid cation exchange resin, NKC-9 strong-acid cation exchange resin, and D001 macroporous strong-acid cation resin; the weak-acid ion exchange resin is one or more of macroporous acrylic weak-acid anion exchange resin, weak-acid C-115E cation exchange resin, DuPont IRC76CRF H weak-acid cation resin, macroporous weak-acid styrene-acrylonitrile cation exchange resin, and chelating resin D402, which are not limited herein.

[0038] By adopting the above technical solution and the above pH combination method, a better deionization effect can be achieved, and the purity of the obtained resin solution is higher, which can be applied to the electronic chip industry.

[0039] Compared with the prior art, the present application includes at least one of the following beneficial technical effects:

[0040] 1. By providing two sets of deionization devices in the present application, when one of the deionization components, such as deionization component one, reaches the usage limit, deionization component two can be used for purification, and at the same time, deionization component one can be activated; when deionization component two reaches the usage limit, deionization component one continues to be used for purification, and at the same time, deionization component two is activated, so that purification and activation work can be carried out simultaneously, which helps to improve work efficiency;

[0041] 2. By setting appropriate temperature and flow rate, it helps to improve the ion exchange efficiency during the purification process and achieve a better purification effect;

[0042] 3. By setting the pH of the exchange resin in the order of strong acid, weak acid, strong base, and weak base along the flow direction of the solution, the deionization effect is better, the purity of the obtained resin solution is higher, and it can be applied to the electronic chip industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is the overall process schematic diagram of the embodiment of the present application.

[0044] Figure 2 is the structural schematic diagram of deionization component one or deionization component two in the embodiment of the present application.

[0045] Figure 3 is the overall process schematic diagram of the embodiment of the present application.

[0046] In the figure:

[0047] 1. First solution tank; 2. Deionization mechanism; 21. First deionization component; 211. Outer shell; 212. Fiber membrane; 213. Deionization chamber; 214. Exchange resin; 215. Inlet; 216. First outlet; 217. Second outlet; 22. Second deionization component; 23. Activation component; 231. Solvent tank; 31. First collection tank; 32. Second collection tank; 4. Main pipe; 41. First branch pipe; 42. Second branch pipe; 43. Activation pipe; 44. Connecting pipe; 45. Valve 1; 46. Pump 1; 47. Valve 2; 48. Valve 3; 49. Valve 4; 50. Valve 5; 51. Valve 6; 52. Valve 7; 53. Pump 2; 55. Sub - pipe; 56. Valve 9; 57. Control valve 1; 58. Control valve 2; 59. Control valve 3; 60. Control valve 4; 61. Valve 11; 62. Valve 12; 63. Valve 13; 64. Valve 10; 65. Storage tank; 66. First liquid outlet pipe; 68. First collection pipe; 69. Second liquid outlet pipe; 71. Second collection pipe. Detailed implementation mode

[0048] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application.

[0049] In the description of the present application, it should be noted that unless otherwise clearly specified and limited, the term "and / or" in this article is only a description of the association relationship of associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this article generally represents an "or" relationship between the associated objects before and after without special explanation.

[0050] Refer to Figures 1 to 3 , the present application provides a continuous purification method for polyamic acid or polyimide resin, including the following steps:

[0051] S10: Provide a solution of polyamic acid or polyimide resin containing metal ions;

[0052] S20: Pass the solution into the first deionization component 21 for purification;

[0053] S21: After 80% of the solution enters, transport the electronic - grade good solvent to the first deionization component 21 through pump 46 to promote the diffusion of the solution;

[0054] S30: Every 20 minutes, sample the solution that has passed through the first deionization component 21 and detect the ion concentration in the solution. If the detection result is greater than 50 PPB, it means that the first deionization component 21 has reached its service limit and needs to be activated. At this time, stop passing the solution through the first deionization component 21;

[0055] S40: Pass the solution through the second deionization component 22 to continue purification, and at the same time activate the first deionization component 21;

[0056] S50: Detect the ion concentration in the solution that has passed through the second deionization component 22. If the detection result is greater than 50 PPB, it means that the second deionization component 22 has reached its service limit and needs to be activated. At this time, stop passing the solution through the second deionization component 22;

[0057] S60: Pass the solution through the first deionization component 21 to continue purification, and at the same time activate the second deionization component 22;

[0058] S70: Repeat steps S10 - S60.

[0059] The continuous purification method of polyamic acid or polyimide resin provided by this application can efficiently remove metal ions in the solution of polyamic acid or polyimide resin by providing a deionization device, thereby obtaining electronic-grade polyamic acid or polyimide resin. By providing two sets of deionization devices, when one of the deionization devices, such as the first deionization component 21, reaches its service limit, the second deionization component 22 can be used for purification while activating the first deionization component 21; when the second deionization component 22 reaches its service limit, continue to use the first deionization component 21 for purification while activating the second deionization component 22, so that purification and activation work can be carried out simultaneously, which helps to improve work efficiency.

[0060] Further, the activation in steps S40 and S60 includes the following steps:

[0061] S100: Deliver the electronic-grade good solvent to the first deionization component 21 or the second deionization component 22;

[0062] S200: Stop delivering the electronic-grade good solvent, deliver the hydrophilic organic solvent to the first deionization component 21 or the second deionization component 22, and replace the electronic-grade good solvent with the hydrophilic organic solvent;

[0063] S300: Stop delivering the hydrophilic organic solvent, deliver ultrapure water to the first deionization component 21 or the second deionization component 22, and replace the hydrophilic organic solvent with ultrapure water;

[0064] S400: Stop delivering ultrapure water, deliver the hydrochloric acid aqueous solution to the first deionization component 21 or the second deionization component 22 for activation;

[0065] S500: Repeat steps S100 - S300 in reverse order, that is, sequentially introduce ultrapure water, hydrophilic organic solvent, and electronic - grade good solvent into deionization component 1 or deionization component 2 to complete solvent replacement.

[0066] Washing the deionization device with electronic - grade good solvent, hydrophilic organic solvent, ultrapure water, and hydrochloric acid aqueous solution can replace the metal ions on the resin in the deionization device, thereby restoring the adsorption capacity of the resin to ensure the reuse effect of the deionization device.

[0067] It can be understood that in step S20, the flow rate of the solution is between 1 mL / min and 5 mL / min. In this embodiment, the flow rate of the solution is preferably 3 mL / min. Too fast a flow rate may cause insufficient contact time of the solution in deionization component 1 or deionization component 2, reducing the effectiveness of ion exchange. If the flow rate is too high, it may damage the structure of deionization component 1. An appropriate flow rate helps to improve the ion - exchange efficiency during deionization and achieve a better purification effect.

[0068] In steps S20 and S40, the working temperatures of deionization component 1 and deionization component 2 are both 0 - 75 °C. An appropriate ambient temperature can accelerate the rate of ion - exchange reaction and promote the migration of ions.

[0069] In step S400, the concentration of the hydrochloric acid aqueous solution is 5 wt% - 10 wt%. In this embodiment, it is preferably 8 wt%. An appropriately concentrated hydrochloric acid aqueous solution can effectively remove impurities and old ions in deionization component 1 and deionization component 2 to activate the exchange capacity of the exchange resin 214 in deionization component 1 and deionization component 2 and ensure a good purification effect.

[0070] In steps S21 and S200, the electronic - grade good solvent includes one or more of phenolic reagents, specifically, it can be one or more of cresol, m - cresol, and o - cresol, which is not limited here.

[0071] In step S200, the hydrophilic organic solvent includes one or more of alcohol solvents, ketone solvents, ether solvents, and amide solvents. Specifically, the alcohol solvent can be methanol, ethanol, propanol, n - butanol, etc., the ketone solvent can be acetone, butanone, etc., the ether solvent can be diethyl ether, etc., and the amide solvent can be N,N - dimethylformamide, N,N - dimethylacetamide, N - methyl - 2 - pyrrolidone, etc., which is not limited here.

[0072] In addition, refer to Figure 1, the present application also provides a continuous purification device for polyamic acid or polyimide resin, including a first solution tank 1, a deionization mechanism 2, a first collection tank 31 and a second collection tank 32. The first solution tank 1 is connected in series with the deionization mechanism 2. The first solution tank 1 is used to hold a solution of polyamic acid or polyimide resin containing metal ions. The deionization mechanism 2 includes a first deionization component 21, a second deionization component 22 and an activation component 23. Among them, the first deionization component 21 and the second deionization component 22 are connected in parallel. One end of the first deionization component 21 is connected to the first solution tank 1, and the other end is connected to the first collection tank 31. The first deionization component 21 is connected in series with the activation component 23. One end of the second deionization component 22 is connected to the first solution tank 1, and the other end is connected to the second collection tank 32. The second deionization component 22 is connected in series with the activation component 23. The activation component 23 includes a plurality of solvent tanks 231. Each solvent tank 231 is independent of each other and connected in parallel. The solvent tank 231 is used to transport the activation solvent to the first deionization component 21 or the second deionization component 22.

[0073] In this way, the solution containing metal ions is transported from the first solution tank 1 to the first deionization component 21. The solution is deionized in the first deionization component 21. The solution passing through the first deionization component 21 is sampled, and the metal ion concentration in the solution is detected. If the detection result is greater than 50 PPB, it means that the first deionization component 21 has reached the service limit. Stop transporting the resin solution to the first deionization component 21, activate the activation component 23, and sequentially introduce the solutions in the plurality of solvent tanks 231 into the first deionization component 21 to activate the first deionization component 21. At the same time, introduce the solution into the second deionization component 22 to purify the solution in the second deionization component 22. Thus, the continuous purification device provided by the present application can perform activation and purification simultaneously. When one set of deionization components reaches the service limit, activation is carried out, and at the same time, the other set of deionization components can continue to carry out purification, which helps to improve work efficiency and ensure good purification effect.

[0074] Further, referring to Figure 2, in this embodiment, the deionization component 1 (21) and the deionization component 2 (22) have the same structure. Taking the deionization component 1 (21) as an example, the deionization component 1 (21) includes a housing (211) and a fiber membrane (212). A plurality of layers of fiber membranes (212) are arranged inside the housing (211). The plurality of layers of fiber membranes (212) divide the deionization component 1 (21) into multiple deionization chambers (213). Ion exchange resins (214) are filled in each deionization chamber (213). Specifically, in this embodiment, there are six layers of fiber membranes (212), and adjacent layers of fiber membranes (212) are arranged at intervals. The six layers of fiber membranes (212) divide the deionization component 1 (21) into seven deionization chambers (213). The deionization component 1 (21) has at least one inlet (215) and at least one outlet. The solution enters the inside of the housing (211) from the inlet (215), flows through each deionization chamber (213) in sequence, and then flows out from the outlet. Along the flow direction of the solution, the pH values of the exchange resins (214) are in sequence: strong acid, weak acid, strong base, weak base. Specifically, in this embodiment, there are two outlets, namely the first outlet (216) and the second outlet (217). The inlet (215) is arranged in the middle of the deionization component 1 (21), and the first outlet (216) and the second outlet (217) are respectively arranged at both ends of the deionization component 1 (21), that is, the inlet (215) is arranged between the first outlet (216) and the second outlet (217). After the solution enters the deionization chamber (213) from the inlet (215), it is split in the deionization chamber (213), and is respectively discharged from the first outlet (216) and the second outlet (217) on both sides of the deionization component 1 (21). That is to say, a part of the solution entering the deionization component 1 (21) is discharged from the first outlet (216), and another part of the solution entering the deionization component 1 (21) is discharged from the second outlet (217). The structure of the deionization component 2 (22) is the same as that of the deionization component 1 (21), and will not be elaborated here.

[0075] Further, in this embodiment, the pH values of the ion exchange resins (214) in the deionization component 1 (21) and the deionization component 2 (22) are in sequence: weak base, strong base, weak acid, strong acid, weak acid, strong base, weak base from the first outlet (216) to the second outlet (217). That is to say, the resin solution enters the deionization component 1 (21) or the deionization component 2 (22) from the inlet (215), and is divided into two streams in the deionization component 22. One stream passes through the ion exchange resins (214) with pH values of strong acid, weak acid, strong base, weak base in sequence and is discharged from the first outlet (216), and the other stream passes through the ion exchange resins (214) with pH values of strong acid, weak acid, strong base, weak base in sequence and is discharged from the second outlet (216). In this way, a better deionization effect can be achieved, and the purity of the obtained solution is higher.

[0076] Next, the technical solution provided by the present application will be evaluated for performance in combination with specific embodiments.

[0077] Example 1

[0078] At 25°C, a solution of a polyamic acid or polyimide resin containing metal ions is pumped to deionization component 1 (21) at a flow rate of 3 ml / min. When the ion exchange resin (214) in deionization component 1 (21) reaches its usage limit, the solution is pumped to deionization component 2 (22), and at the same time, deionization component 1 (21) is activated. The ion exchange resins (214) in deionization component 1 (21) and deionization component 2 (22) are, in sequence from the first outlet (216) to the second outlet (217), weakly basic anion resin D301-F, Tulsimer A-62MP strongly basic anion exchange resin, DuPont IRC76CRF H weakly acidic cation resin, Amberlyst 35 strongly acidic cation exchange resin, weakly acidic C-115E cation resin, IRA402 strongly basic anion exchange resin, MonoPlus MP 64 weakly basic macroporous anion exchange resin.

[0079] Example 2

[0080] The difference between Example 2 and Example 1 is that in Example 2, the ion exchange resins (214) in deionization component 1 (21) and deionization component 2 (22) are, in sequence from the first outlet (216) to the second outlet (217), macroporous weakly basic styrene-based anion exchange resin, D201 macroporous strongly basic anion resin, macroporous weakly acidic phenylpropene-based cation exchange resin, strongly acidic macroporous C150H cation exchange resin, macroporous acrylic acid-based weak acid anion exchange resin, strongly basic DOWEX MSA-1 anion exchange resin, macroporous acrylic acid-based weak base anion exchange resin.

[0081] Example 3

[0082] The difference between Example 3 and Example 1 is that in Example 3, the ion exchange resins (214) in deionization component 1 (21) and deionization component 2 (22) are, in sequence from the first outlet (216) to the second outlet (217), macroporous weakly basic styrene-based anion exchange resin, D201 macroporous strongly basic anion resin, strongly basic DOWEX MSA-1 anion exchange resin, macroporous acrylic acid-based weak base anion exchange resin, weakly basic anion resin D301-F, Tulsimer A-62MP strongly basic anion exchange resin, IRA402 strongly basic anion exchange resin.

[0083] Example 4

[0084] Example 4 is different from Example 1 in that the ion exchange resins 214 in the deionization component 1 21 and the deionization component 2 22 are, in sequence from the first outlet 216 to the second outlet 217, IRC76CRF H weakly acidic cation resin, Amberlyst35 strongly acidic cation exchange resin, weakly acidic C-115E cation exchange resin, macroporous weakly acidic styrene-based cation exchange resin, strongly acidic macroporous C150H cation exchange resin, macroporous acrylic acid-based weak acid anion exchange resin, and NKC-9 strongly acidic cation exchange resin.

[0085] It can be seen that in Examples 1 and 2, the acidity and alkalinity of the ion exchange resin 214 are in the order of weak base, strong base, weak acid, strong acid, weak acid, strong base, and weak base from left to right; Examples 3 and 4 do not satisfy the order of weak base, strong base, weak acid, strong acid, weak acid, strong base, and weak base for the acidity and alkalinity of the ion exchange resin 214 from left to right. The total amount of anions, total amount of cations, total amount of calcium ions, and total amount of chloride ions in the solution before and after purification were detected, and the specific parameters and test results are shown in Table 1.

[0086]

[0087] Table 1

[0088] Thus, it can be seen that in the above Examples 1 and 2, the total amount of anions, total amount of cations, total amount of calcium ions, and total amount of chloride ions after purification are lower, while in Examples 3 and 4, the total amount of anions, total amount of cations, total amount of calcium ions, and total amount of chloride ions in the purified solution are higher. It can be seen that using a combination of weak base, strong base, weak acid, strong acid, weak acid, strong base, and weak base in sequence from left to right for the ion exchange resin 214 filled in the ion exchange cavity has a better deionization effect and a higher purity of the obtained resin solution, and can be applied to the electronic chip industry.

[0089] In addition, referring to Figure 3, in this embodiment, a main pipe 4 is connected to the first solution tank 1. A first branch pipe 41 and a second branch pipe 42 are connected to the main pipe 4. The first branch pipe 41 is connected to the deionization component one 21, and the second branch pipe 42 is connected to the deionization component two 22. An activation pipe 43 is connected between the first branch pipe 41 and the second branch pipe 42. A plurality of connecting pipes 44 are connected to the activation pipe 43. Each connecting pipe 44 is respectively connected to a solvent tank 231. A control valve is provided on each connecting pipe 44. In this embodiment, there are specifically four connecting pipes 44 and four solvent tanks 231. Each solvent tank 231 is respectively used to accommodate an electronic-grade good solvent, a hydrophilic organic solvent, ultrapure water, and an aqueous hydrochloric acid solution. There are also four control valves, namely control valve one 57, control valve two 58, control valve three 59, and control valve four 60. Among them, control valve one 57 is used to control the electronic-grade good solvent, control valve two 58 is used to control the hydrophilic organic solvent, control valve three 59 is used to control ultrapure water, and control valve four 60 is used to control the aqueous hydrochloric acid solution.

[0090] A valve one 45 and a pump one 46 are connected to the main pipe 4. A valve two 47 and a valve three 48 are connected to the first branch pipe 41. A valve four 49 and a valve five 50 are connected to the second branch pipe 42. A valve six 51 and a valve seven 52 are connected to the activation pipe 43. A pump two 53 is connected to the activation pipe 43 between the valve six 51 and the valve seven 52. Each connecting pipe 44 is connected to the pump two 53. A branch pipe 55 is also connected to the main pipe 4. The branch pipe 55 is connected to a storage tank 65. The storage tank 65 is used to store the electronic-grade good solvent. A valve nine 56 is connected to the branch pipe 55. One end of the deionization component one 21 away from the first solution tank 1 is connected to a first liquid outlet pipe 66. A valve ten 64 is provided on the first liquid outlet pipe 66. A first collection tank 31 is connected to the first liquid outlet pipe 66. The first collection tank 31 and the first liquid outlet pipe 66 are connected through a first collection pipe 68. A valve twelve 62 is provided on the first collection pipe 68; One end of the deionization component two 22 away from the first solution tank 1 is connected to a second liquid outlet pipe 69. A valve eleven 61 is provided on the second liquid outlet pipe 69. A second collection tank 32 is connected to the second liquid outlet pipe 69. The second collection tank 32 and the second liquid outlet pipe 69 are connected through a second collection pipe 71. A valve thirteen 63 is provided on the second collection pipe 71.

[0091] By setting multiple valves, it is convenient to control the flow direction of the resin solution and the solvent, so as to achieve a better purification and activation effect, effectively remove metal ions in the resin solution, and ensure work efficiency.

[0092] The implementation principle of the continuous purification device for polyamic acid or polyimide resin provided by this application is as follows:

[0093] Step 1: At 25 °C, open the valve one 45, valve two 47, valve three 48, and valve twelve 62, close other valves, and transport the solution containing metal ions to the deionization component one 21 through the pump one 46;

[0094] Step 2: After the solution enters 80%, open valve nine 56, and send the electronic grade good solvent to deionization component one 21 through pump one 46 to promote the diffusion of the solution in deionization component one 21.

[0095] Step 3: Every 20 minutes, open valve ten 64 for sampling and detecting the ion content. If the detection result is greater than 50 PPB, it means that deionization component one 21 has reached the service limit and needs to be activated. At this time, close valve one 45, valve two 47, valve three 48, and valve twelve 62, open valve four 49, valve five 50, and valve thirteen 63, and transport the solution containing metal ions to deionization component two 22 through pump one 46. After the solution enters 80%, open valve nine 56, and send the electronic grade good solvent to deionization component two 22 through pump one 46 to promote the diffusion of the solution in deionization component two 22 and continue to purify the solution. At the same time, activate the exchange resin 214 in deionization component one 21. Specifically, the activation process is as follows:

[0096] First, open control valve one 57, valve six 51, and valve three 48, and send the electronic grade good solvent to deionization component one 21 through pump two 53. After 20 - 30 minutes, close control valve one 57, open control valve two 58, and send the hydrophilic organic solvent to deionization component one 21 through pump two 53 to replace the electronic grade good solvent with the hydrophilic organic solvent. After 20 - 30 minutes, close control valve two 58, open control valve three 59, and send ultrapure water to deionization component one 21 through pump two 53 to replace the hydrophilic organic solvent with ultrapure water. After 20 - 30 minutes, close control valve three 59, open control valve four 60, and send 8% wt hydrochloric acid aqueous solution to deionization component one 21 to activate the exchange resin 214. Then repeat the above steps in reverse order to complete the activation and solvent replacement of the exchange resin 214.

[0097] Step 4: Every 20 minutes, open valve eleven 61 to sample the solution in deionization component two 22 and detect its concentration. If the concentration is greater than 50 PPB, close valve four 49, valve five 50, valve eleven 61, and valve thirteen 63, open valve three 48, valve four 49, and valve twelve 62, and let the solution enter deionization component one 21 for purification. At the same time, activate deionization component two 22, and cycle to purify all solutions to obtain a high - purity solution.

[0098] The above are all preferred embodiments of this application, and do not limit the protection scope of this application accordingly. Therefore, all equivalent changes made according to the structure, shape, and principle of this application should be covered within the protection scope of this application.

Claims

1. A continuous purification method for polyamic acid or polyimide resin, characterized in that: The steps include: S10: providing a solution of polyamic acid or polyimide resin containing metal ions; S20: passing the solution into a deionization component (21) for purification; S30: Detecting the metal ion concentration in the solution passing through the deionization component 1 (21). If the detection result is greater than 50 PPB, it means that the deionization component 1 (21) has reached its usage limit and needs to be activated; At this time, stop passing the solution into the deionization component 1 (21); S40: passing the solution into the second deionization component (22) to continue purification, while activating the first deionization component (21); S50: Detecting the metal ion concentration in the solution passing through the second deionization component (22). If the detection result is greater than 50 PPB, it means that the second deionization component (22) has reached its usage limit and needs to be activated; At this time, stop passing the solution into the deionization component 2 (22); S60: passing the solution into the deionization component one (21) to continue purification, and activating the deionization component two (22) at the same time; S70: Repeat steps S10-S60.

2. The continuous purification method of a polyamic acid or polyimide resin according to claim 1, characterized in that: The activation described in step S40 and step S60 includes the following steps: S100: transporting the electronic grade good solvent to the deionization component 1 (21) or the deionization component 2 (22); S200: Stop delivering the electronic-grade good solvent, deliver the hydrophilic organic solvent to the deionization component 1 (21) or the deionization component 2 (22), and replace the electronic-grade good solvent with the hydrophilic organic solvent; S300: Stop delivering the hydrophilic organic solvent, deliver ultrapure water to the deionization component 1 (21) or the deionization component 2 (22), and replace the hydrophilic organic solvent with ultrapure water; S400: Stop delivering ultrapure water, and deliver the hydrochloric acid aqueous solution to the deionization component 1 (21) or the deionization component 2 (22) for activation; S500: Repeat steps S100-S300 in reverse order to complete solvent replacement.

3. The continuous purification method of a polyamic acid or polyimide resin according to claim 1, characterized in that: In step S20, the flow rate of the solution is between 1 mL / min and 5 mL / min.

4. The continuous purification method of a polyamic acid or polyimide resin according to claim 1, characterized in that: In the steps S20 and S40, the operating temperatures of the deionization component 1 (21) and the deionization component 2 (22) are both 0 to 75°C.

5. The continuous purification method of a polyamic acid or polyimide resin according to claim 2, characterized in that: The concentration of the hydrochloric acid aqueous solution in step S400 is 5 wt % to 10 wt %.

6. The continuous purification method of a polyamic acid or polyimide resin according to claim 2, characterized in that: In the step S200, the electronic grade good solvent includes one or more phenolic reagents.

7. The continuous purification method of a polyamic acid or polyimide resin according to claim 2, characterized in that: In the step S200, the hydrophilic organic solvent includes one or more of an alcohol solvent, a ketone solvent, an ether solvent, and an amide solvent.

8. A continuous purification device for polyamic acid or polyimide resin, characterized in that: include: A first solution tank (1), a deionization mechanism (2), a first collecting tank (31) and a second collecting tank (32), wherein the first solution tank (1) is used to contain a solution of polyamic acid or polyimide resin containing metal ions, the deionization mechanism (2) comprises a first deionization component (21), a second deionization component (22) and an activation component (23), the first solution tank (1), the first deionization component (21) and the first collecting tank (31) are connected, the first solution tank (1), the second deionization component (22) and the second collecting tank (32) are connected, the first deionization component (21) and the second deionization component (22) are connected in parallel, the first deionization component (21) and the activation component (23) are connected in series, and the second deionization component (22) and the activation component (23) are connected in series; The activation component (23) comprises a plurality of solvent tanks (231), each of the solvent tanks (231) is independent of each other, and each of the solvent tanks (231) is connected in parallel, and the solvent tanks (231) are used to transport the activation solvent to the deionization component one (21) or the deionization component two (22).

9. The continuous purification device for polyamic acid or polyimide resin according to claim 8, characterized in that: The deionization component one (21) and the deionization component two (22) both include a housing (211) and a fiber membrane (212); the fiber membrane (212) is provided with multiple layers and is arranged at intervals in the housing (211); the multiple layers of the fiber membrane (212) divide the deionization component one (21) and the deionization component two (22) into multiple deionization chambers (213); each of the deionization chambers (213) is filled with an exchange resin (214).

10. The continuous purification device for polyamic acid or polyimide resin according to claim 9, characterized in that: The deionization component 1 (21) and the deionization component 2 (22) are both provided with at least one inlet (215) and at least one outlet, wherein the inlet (215) is connected to the first solution tank (1), and the solution enters the housing (211) from the inlet (215), flows through the deionization chamber (213), and then flows out from the outlet, and along the flow direction of the solution, the pH of the exchange resin (214) in each deionization chamber (213) is: strong acid, weak acid, strong base, weak base.

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