CN114225496B

CN114225496B - Purification method and purification device for high-performance polymer resin

Info

Publication number: CN114225496B
Application number: CN202111485735.4A
Authority: CN
Inventors: 路延东; 陈兴; 贾斌; 王奇; 豆秀丽; 孙朝景; 左立辉; 李涛
Original assignee: Minseoa Beijing Advanced Materials Development Co Ltd
Current assignee: Minseoa Beijing Advanced Materials Development Co Ltd
Priority date: 2021-12-07
Filing date: 2021-12-07
Publication date: 2023-04-11
Anticipated expiration: 2041-12-07
Also published as: CN114225496A

Abstract

The invention discloses a purification method and a purification device for high-performance polymer resin. The polymer resin purification device comprises a filter, a dispersion pipe and a metal ion purifier; a stirrer is arranged in the filter, and a stirring paddle of the stirrer extends into the filter; a screw rod is inserted into the dispersion pipe from top to bottom and is connected with a motor; the lower end of the screw rod is a dense spiral, the middle end is a thin thread, and the top end is a wolf tooth structure; the first outlet of the filter arranged at the non-filtering end is connected with the first inlet at the bottom of the dispersion pipe; the second outlet of the filter arranged at the filtering end is connected with the inlet of the metal ion purifier; the outlet of the metal ion purifier is connected with the second inlet at the bottom of the dispersion pipe; the middle part of the dispersion pipe is provided with a third inlet for introducing polymer resin solution; the outlet at the top of the dispersion pipe is connected with the inlet of the filter. The device and the method can synchronously carry out the powdering and the purification of the resin solution, improve the production efficiency and improve the purification effect.

Description

Purification method and purification device for high-performance polymer resin

Technical Field

The invention belongs to the field of high molecular materials, and particularly relates to a purification method and a purification device for high-performance polymer resin.

Background

High performance polymers are widely used because of their excellent mechanical properties, heat resistance, and low dielectric properties. In particular, the electronics industry is currently developing rapidly, and therefore new demands and requirements are being placed on electronic grade polymer materials. High performance polymeric materials are typically polymerized by solution polycondensation, limited by the effects of raw materials, additives, and by-products. The products obtained by direct polymerization hardly meet the requirements of the electronic industry, and the requirements of the electronic materials applied in the field of semiconductor chips on the quality and purity of the products are severer. Since the polymer material plays an important role in electronic devices, the quality and reliability of the polymer material directly determine the quality of the final product. A great deal of effort has been made to improve the purity and quality of the product.

Taking polyimide resin, polybenzoxazole polymer resin, phenol polymer resin, epoxy polymer resin, liquid crystal polymer resin, polyamide resin, etc. (hereinafter referred to as resin) as examples, they are widely used in the field of electronic materials, and are used in electronic products such as Liquid Crystal Displays (LCD), integrated circuit manufacturing (IC), flexible Copper Clad Laminate (FCCL), etc., and thus have different requirements for resin in different product applications. In addition to the differences in requirements, it has been found that the same stringent requirements are placed on the ionic content of the resin material, since this factor directly affects the performance of the final product.

At present, the polyimide resin must contain extremely low concentration of metal ions in the application of semiconductor packaging, and the most main functional groups in the composition of the resin are amino, imide, amide or acid groups, so that the resin has chelation force on the metal ions, and the metal ions are difficult to remove by the conventional purification method. Therefore, after the resin is prepared into a formula product at the later stage, the content of metal ions is higher, and the later-stage application performance is influenced. Therefore, the polyimide resin needs to be purified in advance to reduce the gold impurity content to a certain extent.

The existing resin post-treatment methods mainly comprise the following steps:

after the poor solvent is settled, the mixture is crushed into powder by using a ball milling device, and the powder is dried after being washed and filtered. The problems of overlong flow, large occupied area of equipment, easy pollution introduction in the grinding process and difficult continuous production exist.

The superfine powder is obtained by spraying, and then washing, filtering and drying are carried out. The problem that the separation process is difficult and long in time due to the fact that the powder is formed in one step and is too fine, production efficiency and the later purification effect are seriously affected is solved, and the final residual concentration of metal ions and impurities is high.

There are other processing modes, such as a mode of emulsifying a poor solvent into fine particles, a mode of mixing and dispersing, etc., and a spinning flow solidification mode. The method has the problems that the bundle with too large particles is hard to purify and the particles with too small particles are hard to separate.

While richard W mecarol et al also attempted to purify the polymerization by using metal complexing agents, the metal ions of the polymer, nickel and magnesium, were brought to very low levels, less than 1-10ppm, by adding metal complexing agents to the precipitant. The method is not versatile because the metal complexing agent has a high degree of selectivity and therefore the types of metal ions to be treated are limited, and cannot meet the ppb level of metal ions.

The modes are all curing treatment modes of the existing common resin, and meet the requirement of general materials, but the problem of overhigh metal impurities exists in the field of the electronic industry with increasing requirements.

Disclosure of Invention

The invention aims to provide a purification method and a purification device for high-performance polymer resin, which can simultaneously remove metal impurities to complete purification in the process of powdering resin solution.

The invention provides a polymer resin purification device, which comprises a filter, a dispersion pipe and a metal ion purifier, wherein the dispersion pipe is arranged on the filter;

a stirrer is arranged in the filter, and a stirring paddle of the stirrer extends into the filter;

a screw rod is inserted into the dispersion pipe from top to bottom, and the screw rod is connected with a motor; the lower end of the screw is a dense thread, the middle end of the screw is a dilute thread, and the top end of the screw is of a wolf tooth structure;

the first outlet of the filter arranged at the non-filtering end is connected with the first inlet at the bottom of the dispersion pipe; the second outlet of the filter arranged at the filtering end is connected with the inlet of the metal ion purifier; the outlet of the metal ion purifier is connected with the second inlet at the bottom of the dispersion pipe; the middle part of the dispersion pipe is provided with a third inlet for introducing a polymer resin solution; the outlet at the top of the dispersion pipe is connected with the inlet of the filter.

In the above apparatus for purifying polymer resin, the first outlet of the filter at the non-filtration end is connected to the first inlet at the bottom of the dispersion pipe via a flow meter;

the second outlet of the filter arranged at the filtering end is connected with the inlet of the metal ion purifier through a liquid pump;

and a metering pump is arranged at a third inlet of the dispersion pipe.

In the above-mentioned polymer resin purifying apparatus, a filter plate is provided at the bottom of the filter; a stirring paddle of the stirrer extends into the filter from top to bottom;

the inlet of the filter is arranged at the top of the filter; the first outlet of the filter is arranged on the side wall of the upper edge of the filter plate; the second outlet of the filter is arranged at the bottom of the filter plate;

the bottom of the filter plate is also provided with a third outlet for discharging waste liquid; and a diaphragm metering pump is arranged at a third outlet of the filter.

In the above polymer resin purifying apparatus, a pitch ratio of the dense flight at the lower end of the screw to the dilute flight at the middle end of the screw may be 1:2 to 4; the thread height ratio of the thin thread at the middle end of the screw to the dense thread at the lower end of the screw can be 0.5-1: 1;

the thin thread at the middle end of the screw rod can be an irregular thin thread; the irregular thin thread refers to different thread pitches of two adjacent teeth and/or different thread heights; specifically, the pitch ratio of the irregular thin thread to the dense thread is 2-4: 1 are distributed irregularly, the thread height of the irregular thin thread is 0.5-1: 1 are distributed irregularly;

in the wolf tooth structure, a plurality of rows of wolf teeth are distributed along the axial position of the screw rod; in each row of wolf teeth, a plurality of wolf teeth are distributed around the screw along the radial position of the screw;

the distance between two adjacent rows of wolf teeth can be 1-5 cm; in each row of wolf teeth, the included angle of two adjacent wolf teeth at the radial position can be 15-90 degrees; the ratio of the height of the wolf tooth protruding out of the screw to the height of the dense thread at the lower end of the screw is 0.7-1: 1;

the wolf tooth structure can be an irregular wolf tooth structure; the irregular wolf tooth structure refers to that the distances between two adjacent rows of wolf tooth structures on the axial position are different;

the length ratio of the dense thread section, the dilute thread section and the wolf tooth structure section in the dispersion pipe can be 1:0.5 to 1.5:0.5 to 1.

The main body of the shell of the dispersion pipe is made of stainless steel, and the lining of the dispersion pipe is made of polytetrafluoroethylene;

and two ends of the shell of the dispersion pipe are connected with the screw rod through flanges.

The invention provides a method for purifying polymer resin, which is used for purifying the polymer resin by using a purification device and comprises the following steps:

(1) Injecting a reagent consisting of organic acid and a poor solvent of the polymer resin into the filter, controlling the rotation speed of a screw in the dispersion pipe to be a first rotation speed, and circulating the reagent in the dispersion pipe and the filter under the drive of a dense spiral at the lower end of the dispersion pipe;

(2) Diluting a polymer resin solution to be purified to a specified viscosity, injecting the diluted polymer resin solution into the dispersion pipe, mixing the polymer resin solution with the reagent in the step (1) under the drive of irregular thin threads in the middle of the dispersion pipe, and separating out solid polymer resin under the action of a poor solvent in the reagent; the solid polymer resin is beaten and broken by a wolf tooth structure at the top end in the dispersion pipe to form a suspension in the dispersion pipe; the suspension enters the filter, and the rotating speed of a stirrer in the filter is controlled to enable the polymer resin to be in a suspended state all the time; circulating the suspension in the dispersion pipe and the filter until all solid polymer resin is separated out, and controlling the rotation speed of a screw in the dispersion pipe to be a second rotation speed, wherein the second rotation speed is less than the first rotation speed; metal ions chelated in the polymer resin in the suspension enter the solvent under the action of the organic acid in the reagent; after circulation is finished, stopping stirring of the screw in the dispersion pipe and the stirrer in the filter, filtering the suspension by the filter plate, and keeping a filter cake;

(3) Adding a brand-new poor solvent of the polymer resin into the filter for retaining the filter cake in the step (2), and controlling the rotating speed of the stirrer to enable the filter cake and the poor solvent to form a suspension; starting the metal ion purifier, controlling the rotating speed of a screw in the dispersion pipe to be a third rotating speed, filtering turbid liquid in the filter, then feeding the turbid liquid into the metal ion purifier, and then feeding the turbid liquid into the dispersion pipe, wherein a poor solvent circulates in the filter, the metal ion purifier and the dispersion pipe until metal ions are all enriched by the metal ion purifier; the third rotational speed is less than the first rotational speed; and after circulation is finished, stopping stirring of the screw rod in the dispersion pipe and the stirrer in the filter, filtering turbid liquid by the filter plate, collecting filter cakes, and drying to realize purification of the polymer resin.

Further, in the step (1), the mass fraction of the organic acid in the reagent may be 0.1% to 50%, preferably 1% to 10%, such as 5%.

Further, in the step (1), the organic acid may be one or more of saturated or unsaturated organic acids having 2 to 16 carbons, preferably one or more of acetic acid, propionic acid, butyric acid, valeric acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, n-decanoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecenoic acid, p-methoxybenzoic acid, m-methylbenzoic acid, benzoic acid, mandelic acid, trans-2-hexenoic acid, 3,7-dimethyl-6-octanoic acid, sorbic acid, 3,5,5-trimethylhexanoic acid, lauric acid, lactic acid, β -hydroxybutyric acid and glycolic acid.

Further, in the step (1), the poor solvent of the polymer resin may be water or an organic solvent whose mixture with water can be kept uniform without phase separation; the organic solvent capable of keeping the mixed solution with water homogeneous and non-phase separation is preferably one or more of N-methyl pyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, methanol, ethanol, N-propanol, isopropanol, N-butanol, N-pentanol, N-hexanol, heptanol, octanol, decanol, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether.

Further, in the step (1), the first rotating speed is 500-1000rpm, such as 600rpm; the holding time of the first rotational speed may be 10min to 60min, such as 20min.

Further, in the step (2), the polymer resin solution to be purified may be an original polymer solution in which a polymerization reaction is completed or a polymer solution obtained by dissolving a polymer resin to be purified, which has an unqualified ion content, in a benign solvent; the polymer resin to be purified may be polyimide resin, polybenzoxazole polymer resin, phenol polymer resin, epoxy polymer resin, liquid crystal polymer resin, polyamide resin, etc. which may be dissolved in or prepared as a high molecular compound resin in a good solvent.

Further, in step (2), the specified viscosity may be 5 to 500cp, preferably 50 to 200cp, such as 100cp.

Further, in the step (2), the polymer resin solution to be purified is diluted to a specified viscosity by a benign solvent of the polymer resin; the benign solvent of the polymer resin can be one or more of N-methyl pyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, methanol, ethanol, N-propanol, isopropanol, N-butanol, N-pentanol, N-hexanol, heptanol, octanol, decanol, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate.

Further, in the step (2), the volume ratio of the polymer resin solution to the reagent entering the dispersion tube may be 1:2-1, preferably 1:5-1, such as 1; in a specific embodiment of the present invention, the flow rate of the polymer resin solution may be 0.5L/min, and the flow rate of the reagent may be 10L/min;

further, in the step (2), after the circulation at the first rotation speed is finished, the particle size of the solid polymer resin is 0.5 to 1000 μm, preferably 10 to 100 μm.

Further, in the step (2), the second rotation speed may be 100 to 180rpm, such as 180rpm; the holding time of the second rotation speed may be 10 to 60min, such as 60min.

Further, in the step (3), the third rotation speed may be 100 to 180rpm, such as 180rpm; the holding time of the third rotating speed can be 4-12h, such as 4h;

further, in the step (3), the volume ratio of the poor solvent of the completely new polymer resin entering the dispersion pipe to the suspension of the filter cake and the poor solvent can be 1:9-9:1, such as 1:1.

In the invention, the final particle size of the high polymer resin can be adjusted according to the rotating speed of the dispersion pipe and the purification running time, the minimum particle size can reach 50nm, and the preferable total cycle time is 2-20 h.

The invention has the following beneficial effects:

the device and the method can synchronously carry out the powdering and the purification of the resin solution, improve the production efficiency and improve the purification effect. Compared with the traditional treatment method, the method reduces the consumption of solvents in the powdering process, simplifies the purification steps of the high molecular polymer resin, saves a large amount of solvents, and shortens the flow and time required by purification.

Drawings

FIG. 1 is a schematic view of the structure of the purification apparatus of the present invention.

FIG. 2 is a schematic view of the structure of a dispersion pipe in the purification apparatus of the present invention.

In the figure, the respective symbols are as follows:

1-a filter; 2-a dispersion tube; 3-a metal ion purifier; 4-a filter plate; 5-stirring paddle; 6-a stirrer motor; 7-filter inlet; 8-a first outlet of the filter; 9-a second outlet of the filter; 10-a third outlet of the filter; 11-a screw; 12-a high-speed variable frequency motor; 13-the dispersion tube first inlet; 14-a second inlet of the dispersion tube; 15-third inlet of dispersion tube; 16-a metering pump; 17-outlet of the dispersion pipe; 18-a flow meter; 19-liquid pump.

FIG. 3 is a scanning electron micrograph of the surface of the purified polymer resin A1 of example 2 (A), example 5 (B) and comparative example 1 (C).

FIG. 4 is a scanning electron micrograph of the surface of a polymer resin A2 purified in example 3 (A), example 6 (B) and comparative example 2 (C).

FIG. 5 is a scanning electron micrograph of the surface of the polymer resin A3 after purification in example 4 (A), example 7 (B) and comparative example 3 (C).

FIG. 6 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in example 2.

FIG. 7 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in example 3.

FIG. 8 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in example 4.

FIG. 9 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in example 5.

FIG. 10 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in example 6.

FIG. 11 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in example 7.

FIG. 12 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in comparative example 1.

FIG. 13 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in comparative example 2.

FIG. 14 is a scanning electron micrograph of resin particles (A) after 20min of operation and (B) after the end of operation of the apparatus in comparative example 3.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of "first," "second," and similar terms in the present application do not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect.

The term thread refers to a continuous protrusion with a defined profile formed along a spiral on a cylindrical or conical surface, wherein the protrusion refers to the solid portion between two flanks of the thread, also called a tooth (see national technical standard, thread term GB/T14791-93).

The term pitch refers to the axial distance between corresponding points on the pitch diameter of two adjacent teeth on the thread;

the term thread height, i.e. profile height, refers to the distance on the thread profile from the crest to the root in a direction perpendicular to the thread axis.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

Example 1 Polymer resin purification device

As shown in FIG. 1, the polymer resin purification apparatus of the present invention comprises a closed filter 1, a dispersion pipe 2 and a metal ion purifier 3; the filter 1 is cylindrical, and the bottom of the filter is provided with a filter plate 4; a stirrer is arranged in the filter 1 and comprises a stirring paddle 5 and a stirrer motor 6, and the stirring paddle 5 extends into the filter 1 from top to bottom; the sealed lid in top of filter is equipped with entry 7, is equipped with first export 8 on the filter 4 along locating the tank wall, and the bottom of filter passes through three-way valve connection second export 9 and third export 10, and third export 10 is as the waste liquid discharge port, and waste liquid discharge port department is equipped with the diaphragm metering pump, and the waste liquid discharge port passes through the diaphragm metering pump to be connected with effluent treatment plant.

As shown in fig. 2, a screw 11 is inserted into the dispersion pipe 2 from top to bottom, and the screw 11 is connected with a high-speed variable frequency motor 12; the lower end of the screw rod 11 is provided with dense threads, the middle end is provided with irregular thin threads with different thread pitches and/or different thread heights of two adjacent threads, and the top end is provided with an irregular wolf tooth structure; the pitch ratio of the dense threads at the lower end of the screw to the dilute threads at the middle end of the screw is 1:2 to 4; the thread height of the thin thread at the middle end of the screw and the dense thread at the lower end of the screw is 0.5-1: 1; in the wolf tooth structure, a plurality of rows of wolf teeth are distributed along the axial position of the screw rod; in each row of wolf teeth, a plurality of wolf teeth are distributed around the screw along the radial position of the screw; the distance between two adjacent rows of wolf teeth is 1-5 cm; in each row of wolf teeth, the included angle of two adjacent wolf teeth at the radial position is 15-90 degrees; the ratio of the height of the wolf tooth protruding out of the screw to the height of the dense thread at the lower end of the screw is 0.7-1: 1; the length ratio of the dense thread section, the dilute thread section and the wolf tooth structure section in the dispersion pipe is 1:0.5 to 1.5:0.5 to 1; the shell of the dispersion pipe is made of 316L stainless steel, the lining is made of polytetrafluoroethylene PFA, and the upper end and the lower end of the shell are connected with the screw rod 11 through flanges; the bottom of the dispersion pipe is provided with a first inlet 13 and a second inlet 14; a third inlet 15 for introducing the polymer resin solution is formed in the middle of the dispersion pipe, and a metering pump 16 is arranged at the third inlet; the top of the dispersion pipe is provided with an outlet 17;

the first outlet 8 of the filter is connected to the first inlet 13 of the dispersion pipe via a flow meter 18; the second outlet 9 of the filter is connected with the inlet of the metal ion purifier 3 through a liquid pump 19; the outlet of the metal ion purifier 3 is connected with the second inlet 14 of the dispersion pipe; the outlet 17 of the dispersion pipe is connected to the inlet 7 of the filter.

When used, the polymer resin is purified according to the following steps:

(1) Injecting a reagent consisting of organic acid and poor solvent of polymer resin into the filter 1 from a 7-filter inlet by using a liquid inlet pump, controlling the rotating speed of a screw 11 in a dispersion pipe to be 500-1000rpm by a high-speed variable frequency motor 12 of the dispersion pipe 2, sequentially allowing the reagent to enter the filter 1 under the driving of a dense spiral at the lower end of the screw 11 of the dispersion pipe and then to flow out from a first outlet 8 of the filter, and returning the reagent to the dispersion pipe 2 from a first inlet 13 of the dispersion pipe so as to circulate to form high-speed circulating water flow;

(2) Diluting a polymer resin solution to be purified to a specified viscosity, metering the solution by a metering pump 16, injecting the solution into a dispersion pipe 2 from a third inlet 15 in the middle of the dispersion pipe, mixing the solution with a reagent in a dispersion pipe 2 in a step (1) metered by a flowmeter 18 according to a certain proportion, separating out solid polymer resin under the action of a poor solvent in the reagent, striking and crushing the solid polymer resin by a wolf tooth structure at the top end of a screw 11 in the dispersion pipe to form a suspension in the dispersion pipe, allowing the suspension to flow out from an outlet 17 of the dispersion pipe, allowing the suspension to enter a filter 1 from an inlet 7 of the filter, and controlling the rotation speed of a stirrer 6 in the filter to keep the polymer resin in the filter 1 in a suspension state all the time, the suspension flows out from the first outlet 8 of the filter, flows back into the dispersion pipe 2 again from the first inlet 13 of the dispersion pipe, then enters the filter 1, circulates for 10-60min until the solid polymer resin is completely separated out, the high-speed variable frequency motor 12 controls the rotating speed of a screw in the dispersion pipe to be the second rotating speed of 100-180rpm and continuously circulates for 10-60min, in the circulating process, the suspension circulates through the dispersion pipe to enable the high polymer resin solution to be fully contacted with the acid separated liquid, metal ions chelated in the polymer resin in the suspension enter the solvent under the action of organic acid in the reagent, simultaneously the incompletely cured high polymer resin is completely cured, and the resin is continuously crushed to enable the particle size distribution to be more uniform; after circulation is finished, stopping stirring of the screw in the dispersion pipe and the stirrer in the filter, filtering suspension by the filter plate, retaining filter cakes, and discharging waste liquid from a waste liquid outlet;

(3) Adding a brand-new poor solvent of the polymer resin into the filter 1 for retaining the filter cake in the step (2) from a 7-filter inlet by using a liquid inlet pump, and controlling the rotating speed of a stirrer by using a motor 6 to enable the filter cake and the poor solvent to form suspension; starting the metal ion purifier, controlling the rotation speed of a screw in a dispersion pipe to be a third rotation speed of 100-180rpm, starting a liquid pump 19 at the bottom of the device, filtering suspension in a filter 1 through a filter plate 4, then entering the metal ion purifier 3 from a second outlet 9 of the filter through the liquid pump 19, then entering a dispersion pipe 2 from a second inlet 14 of the dispersion pipe, gradually crushing resin, fully diffusing free ions in the suspension into a liquid reagent, allowing a poor solvent to flow out of an outlet 17 of the dispersion pipe, then entering the filter 1 from an inlet 7 of the filter, circulating for 4-12h in the filter 1, the metal ion purifier 3 and the dispersion pipe 2 until all metal ions are enriched by the metal ion purifier 3, and allowing ions in the high polymer resin to be reduced to a very low level; after circulation, stop the stirring of agitator in screw rod and the filter in the dispersion tube, the turbid liquid is filtered by the filter, collects the filter cake, dries, and the waste liquid is discharged by the waste liquid discharge port, so far can realize polymer resin's purification.

The purification device can realize continuous precipitation, pipeline dispersion and circulating cleaning and purification of resin, can synchronously perform resin solution powdering and purification, improves the production efficiency and improves the purification effect.

The efficacy of the present invention is demonstrated by the following experimental examples and comparative examples, which are prepared as a solution of the resin and by directly preparing the polymer original solution.

Example 2 purification of Polymer resin

A polyamic acid solution is prepared. 16890.60g of NMP,2002.40g of 4,4' -diaminodiphenyl ether (ODA) were added in succession to a 50L glass reactor equipped with a mechanical stirrer, thermometer and nitrogen guard and dissolved with stirring at a controlled temperature of 25 ℃ to form a diamine solution. 2072.14g pyromellitic dianhydride (PMDA) and 148.11g Phthalic Anhydride (PA) are added into the diamine solution, and stirring is continued for 4 hours; 7037.75gNMP was then added to adjust the viscosity to 100cp. A polymer solution A1 was obtained.

Treating the obtained polymer solution A1 with equipment, adjusting the rotating speed of a dispersion tube to 600rpm, selecting a 5% lactic acid aqueous solution as a poor solvent, controlling the flow of the 5% lactic acid aqueous solution at 10L/min and the flow of a glue solution metering pump at 0.5L/min, and measuring the particle size distribution of partial solid powder at 10-300 μm by using an electron microscope after running for 20 min; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-20 mu m.

Experimental example 3 purification of Polymer resin

A polyamic acid ester resin solution was prepared. Pyromellitic dianhydride (PMDA), 14.82g of n-butanol, 14.24g of pyridine and 116g N-methyl pyrrolidone (NMP) were sequentially added to a 10L four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature for 6 hours to produce the corresponding dibutyl PMDA-dioate. Then reacted with 23.79g of thionyl chloride (SOCl 2) at 0-10 ℃ for 2h and at room temperature for 4h to give the corresponding PMDA-diacyl-dibutyl ester.

In a 50L glass reaction kettle, 35.66g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 153g of NMP are added in sequence and stirred to dissolve the materials to form a homogeneous transparent diamine solution; cooling the diamine solution to below 10 ℃ by adopting an ice water bath, and dripping the prepared TPDA-diacid dichloride dibutyl ester into the diamine solution for 0.5h; then, reacting for 10 hours at room temperature; then adding 1.48g of phthalic anhydride, and continuing stirring for 1h; the reaction solution was cooled to room temperature and 7037.75g NMP was added to adjust the viscosity to 100cp. A polymer solution A2 was obtained.

Treating the part A2 of the obtained polymer solution by using equipment, adjusting the rotating speed of a dispersion pipe to 600rpm, selecting a 5% lactic acid aqueous solution as a poor solvent, controlling the flow of the 5% lactic acid aqueous solution to be 10L/min, controlling the flow of a glue solution metering pump to be 0.5L/min, operating for 20min, and taking part of solid powder to perform a competitive scanning test to obtain the solid powder with the particle size distribution of 1-220 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total operation time of the equipment is 320min, and the particle size distribution of the final resin particles is 1-20 μm.

Experimental example 4 purification of Polymer resin

A polyimide solution is prepared. In a 50L glass reactor equipped with a mechanical stirrer, thermometer and nitrogen blanket, 25179.00g NMP,3202.35g hexafluoromethyl diphenylenediamine (TFDB), 50g pyridine were sequentially added and dissolved with stirring at a controlled temperature of 25 ℃ to form a diamine solution. 2885.05g of 4,4' -oxydiphthalic anhydride (ODPA) is then added to the diamine solution and stirring is continued for 4h; then, 1000g of toluene was added to the above reaction solution, and heated to reflux temperature (120-200 ℃ C.), and a part of toluene was distilled to take out the produced water. The reaction solution was cooled to room temperature and 7037.75g NMP was added to adjust the viscosity to 100cp. A polymer solution A3 was obtained.

Treating the part A3 of the obtained polymer solution by using equipment, adjusting the rotating speed of a dispersion tube to 600rpm, selecting a 5% lactic acid aqueous solution as a poor solvent, controlling the flow of the 5% lactic acid aqueous solution to be 10L/min, controlling the flow of a glue solution metering pump to be 0.5L/min, operating for 20min, and taking part of solid powder to perform a competitive scanning test to ensure that the particle size is distributed between 1 and 300 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-20 mu m.

Example 5 purification of Polymer resin

Treating the obtained polymer solution A1 by using equipment, adjusting the rotating speed of a dispersion tube to 600rpm, selecting a 5% acetic acid aqueous solution as a poor solvent, 10L/min of the 5% acetic acid aqueous solution, controlling the flow rate by a glue solution metering pump to be 0.5L/min, operating for 20min, and taking part of solid powder to perform a reactive scanning test to obtain a particle size distribution of 1-350 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-50 μm.

EXAMPLE 6 purification of Polymer resin

Treating the part A2 of the obtained polymer solution by using equipment, adjusting the rotating speed of a dispersion tube to 600rpm, selecting a 5% acetic acid aqueous solution as a poor solvent, 10L/min of the 5% acetic acid aqueous solution, controlling the flow rate of a glue solution metering pump to be 0.5L/min, operating for 20min, and taking part of solid powder to perform a reactive scanning test to test the particle size distribution to be 1-200 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-50 μm.

EXAMPLE 7 purification of Polymer resin

Treating the part A3 of the obtained polymer solution by using equipment, adjusting the rotating speed of a dispersion tube to 600rpm, selecting a 5% acetic acid aqueous solution as a poor solvent, controlling the flow of the 5% acetic acid aqueous solution to be 10L/min, controlling the flow of a glue solution metering pump to be 0.5L/min, operating for 20min, and taking part of solid powder to perform a competitive scanning test to ensure that the particle size is distributed between 1 and 300 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-80 μm.

Comparative examples 1,

Treating the obtained polymer solution A1 by using equipment, adjusting the rotating speed of a dispersion tube to 600rpm, selecting pure water as a poor solvent, controlling the flow of the pure water to be 10L/min, controlling the flow of a glue solution metering pump to be 0.5L/min, running for 20min, and taking part of solid powder to perform electric competition scanning test to test the particle size distribution to be 1-400 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-50 μm.

Comparative examples 2,

Treating the part A2 of the obtained polymer solution by using equipment, adjusting the rotating speed of a dispersion pipe to 600rpm, selecting pure water as a poor solvent, controlling the flow rate of the pure water to be 10L/min and controlling the flow rate of a glue solution metering pump to be 0.5L/min; after 20min of operation, taking part of solid powder to perform electric competitive scanning test to test the particle size distribution to be 1-200 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The total equipment running time is 320min, and the particle size distribution of the final resin particles is 1-50 μm.

Comparative examples 3,

Treating the part A3 of the obtained polymer solution by using equipment, adjusting the rotating speed of a dispersion pipe to 600rpm, selecting pure water as a poor solvent, controlling the flow of the pure water to be 10L/min, controlling the flow of a glue solution metering pump to be 0.5L/min, running for 20min, and taking part of solid powder to perform an electric competition scanning test to test the particle size distribution to be 1-200 mu m; the rotating speed of the dispersion pipe is controlled to 180rpm for 60min. Filtering to remove the precipitated liquid, pumping new pure water with the same amount into the mixing pipe, starting a motor of the mixing pipe to adjust the rotating speed to 180rpm, simultaneously starting a purified water equipment pump linked with the bottom of the filter to convey the soaking liquid (water) to the purification equipment, and after the soaking liquid (water) is treated and cleaned, entering the soaking system from the mixing pipe again. And (3) after the equipment circularly runs for 4 hours, filtering to remove all soaking liquid, taking out a filter cake, performing vacuum drying at 80 ℃ for 24 hours to obtain resin, and sampling and testing. The device run time totaled 320min. The final resin particles have a particle size distribution of 1-80 μm.

The test apparatus is shown in table 1.

TABLE 1 detection device

Test items	Device	Type number
			Ion content	ICP-MS/MS	Agilent 8900ICP-MS/MS
Powder particle state	Scanning electron microscope	SEM3000

The morphology of the purified high molecular polymer resin is mostly irregular porous particles, and scanning electron micrographs are shown in figures 3-5. The results of comparison of the contents of metal ions in the final filtered eluate are shown in Table 2. Fig. 6 to 14 are graphs showing comparison of particle diameters before and after example 2, example 3, example 4, example 5, example 6, example 7, comparative example 1, comparative example 2, and comparative example 3, respectively.

TABLE 2 comparison of ion content test results

Through table 2 test result comparison, all kinds of resin powderization degree also can satisfy most scene demands, and the state all relatively with have the hole, easily dissolve and purification treatment. The purified resin reaches the electronic grade standard, the content of metal ions except Na is slightly higher than 10ppb in individual species, and the content of other metal ions is less than 10ppb, so that the purification time can be increased to further reduce the ion content.

The ultrapure reagent washing liquid constantly concentrates ions in the ultrapure reagent purifying equipment to be removed, the reagent is recycled, and no waste liquid is generated, so that the method is more environment-friendly.

In summary, the present invention utilizes the apparatus and method of the present invention to remove metal ion impurities contained in the resin to achieve the purification effect. Meanwhile, the invention can synchronously carry out the powdering and purification of the resin solution, thereby improving the production efficiency and the purification effect. Compared with the traditional treatment method, the method reduces the consumption of solvents in the powdering process, simplifies the purification steps of the high molecular polymer resin, saves a large amount of solvents, and shortens the flow and time required by purification.

Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A polymer resin purification device comprises a filter, a dispersion pipe and a metal ion purifier;

a screw is inserted into the dispersion pipe from top to bottom, and the screw is connected with a motor; the lower end of the screw is a dense thread, the middle end of the screw is a dilute thread, and the top end of the screw is of a wolf tooth structure;

2. The purification apparatus of claim 1, wherein: a first outlet of the filter, which is arranged at the non-filtering end, is connected with a first inlet at the bottom of the dispersion pipe through a flowmeter;

and a metering pump is arranged at a third inlet of the dispersion pipe.

3. The purification apparatus according to claim 1 or 2, wherein: the bottom of the filter is provided with a filter plate; the stirring paddle of the stirrer extends into the filter from top to bottom;

4. The purification device of claim 1 or 2, wherein: the pitch ratio of the dense threads at the lower end of the screw to the dilute threads at the middle end of the screw is 1:2 to 4;

the thread height ratio of the fine threads at the middle end of the screw to the dense threads at the lower end of the threads is 0.5-1: 1;

in the wolf tooth structure, a plurality of rows of wolf teeth are distributed along the axial position of the screw; in each row of wolf teeth, a plurality of wolf teeth are distributed around the screw along the radial position of the screw;

the distance between two adjacent rows of wolf teeth is 1-5 cm; in each row of wolf teeth, the included angle of two adjacent wolf teeth at the radial position is 15-90 degrees; the ratio of the height of the wolf tooth protruding out of the screw to the height of the dense thread at the lower end of the screw is 0.7-1: 1;

the length ratio of the dense thread section, the dilute thread section and the wolf tooth structure section in the dispersion pipe is 1: 0.5-1.5: 0.5 to 1.

5. A method for purifying a polymer resin by using the purification apparatus of claim 3, comprising the steps of:

(1) Injecting a reagent consisting of organic acid and a poor solvent of the polymer resin into the filter, controlling the rotating speed of a screw in the dispersion pipe to be a first rotating speed, and circulating the reagent in the dispersion pipe and the filter under the driving of a dense spiral at the lower end of the dispersion pipe;

(3) Adding a brand-new poor solvent of the polymer resin into the filter for retaining the filter cake in the step (2), and controlling the rotating speed of the stirrer to enable the filter cake and the poor solvent to form a suspension; starting the metal ion purifier, controlling the rotating speed of a screw in the dispersion pipe to be a third rotating speed, filtering suspension in the filter, then entering the metal ion purifier, and then entering the dispersion pipe, wherein a poor solvent circulates in the filter, the metal ion purifier and the dispersion pipe until metal ions are all enriched by the metal ion purifier; the third rotational speed is less than the first rotational speed; and after circulation is finished, stopping stirring of the screw rod in the dispersion pipe and the stirrer in the filter, filtering turbid liquid by the filter plate, collecting filter cakes, and drying to realize purification of the polymer resin.

6. The purification method according to claim 5, characterized in that: in the step (1), the mass fraction of organic acid in the reagent is 0.1-50%;

in the step (1), the organic acid is one or more of saturated or unsaturated organic acids containing 2-16 carbon atoms;

in the step (1), the poor solvent of the polymer resin is water or an organic solvent capable of keeping a uniform and non-phase separation of a mixed solution of water and water.

7. The purification process according to claim 6, characterized in that: the organic acid is one or more of acetic acid, propionic acid, butyric acid, valeric acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethyl butyric acid, heptanoic acid, caprylic acid, n-pelargonic acid, isononanoic acid, n-decanoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecylenic acid, p-methoxybenzoic acid, m-methylbenzoic acid, benzoic acid, mandelic acid, trans-2-hexenoic acid, 3,7-dimethyl-6-octanoic acid, sorbic acid, 3,5,5-trimethylhexanoic acid, lauric acid, lactic acid, beta-hydroxybutyric acid and glycolic acid;

the organic solvent capable of keeping the mixed solution with water uniform and non-phase separation is one or more of N-methyl pyrrolidone, N '-dimethyl acetamide, N' -dimethyl formamide, dimethyl sulfoxide, gamma-butyrolactone, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, methanol, ethanol, N-propanol, isopropanol, N-butanol, N-pentanol, N-hexanol, heptanol, octanol, decanol, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether.

8. Purification process according to any one of claims 5 to 7, characterized in that: in the step (1), the first rotating speed is 500-1000rpm, and the maintaining time of the first rotating speed is 10-60 min.

9. Purification process according to any one of claims 5 to 7, characterized in that: in the step (2), the specified viscosity is 5-500 cp;

in the step (2), the polymer resin solution to be purified is diluted to a specified viscosity by a benign solvent of the polymer resin; the benign solvent of the polymer resin is one or more of N-methyl pyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, methanol, ethanol, N-propanol, isopropanol, N-butanol, N-pentanol, N-hexanol, heptanol, octanol, decanol, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate;

in the step (2), the volume ratio of the polymer resin solution and the reagent entering the dispersion pipe is 1:2-1.

10. Purification process according to any one of claims 5 to 7, characterized in that: in the step (2), after the circulation at the first rotation speed is finished, the particle size of the solid polymer resin is 0.5-1000 μm;

in the step (2), the second rotating speed is 100-180rpm, and the maintaining time of the second rotating speed is 10-60 min.

11. Purification process according to any one of claims 5 to 7, characterized in that: in the step (3), the third rotating speed is 100-180rpm, and the maintaining time of the third rotating speed is 4-12 h;

in the step (3), the volume ratio of the poor solvent of the brand-new polymer resin entering the dispersion pipe to the suspension formed by the filter cake and the poor solvent is 1:9 to 9:1.