KR20200072087A - A process for producing an improved polyether ketone ketone and polyether ketone ketone thereof - Google Patents

Abstract

The present invention relates to a method for preparing improved polyetherketoneketone and polyetherketoneketone prepared thereby and, more particularly, to a method for preparing improved polyetherketoneketone which has an enhanced injection molding processability by using 1,4-diphenyl benzene as a monomer of reaction or using a mixture of 1,4-diphenyl benzene and diphenyl oxide to increase a crystallization rate of polymerization, while enhancing resin flowability by adding a capping agent to the monomer later, as well as polyetherketoneketone prepared thereby. The present invention provides a method for preparing polyetherketoneketone, comprising the steps of: preparing a reaction solution by adding at least one selected from 1,4-diphenoxy benzene and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) into terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), and a liquid reaction medium in a reactor, and dissolving the resulting solution at the same time; (b) lowering a temperature of the reaction solution to input a catalyst; (c) directly infusing an inactive gas into the reaction solution and stirring the resulting solution after the inputting of the catalyst; and (d) adding a first capping agent after the inputting of the inactive gas. Accordingly, the present invention provides an effect of increasing a crystallization rate of polymerization to enhance injection molding processibility and improve resin flowability.

Description

Improved polyether ketone ketone manufacturing method and polyether ketone ketone produced thereby {A process for producing an improved polyether ketone ketone and polyether ketone ketone thereof}

The present invention relates to an improved polyether ketone ketone (hereinafter also referred to as PEKK) manufacturing method and a polyether ketone ketone produced thereby. More specifically, 1,4-diphenyl benzene is used as a reaction monomer, or 1,4-diphenyl benzene and diphenyl oxide are mixed to increase the crystallization rate of the polymerization reaction and improve injection molding processability. In addition, during the polymerization reaction, a capping agent is added to the monomer to improve the flowability of the resin, thereby providing an improved method for producing polyether ketone ketone and a polyether ketone ketone prepared thereby.

Polyether ketone is a generic term for a known industrial resin, and includes polyether ketone, polyether ether ketone, polyether ketone ketone, and a copolymer in which a part of polyether ketone and polyether ketone ketone are mixed.

Polyether ketone ketone (PEKK) represented by the following formula is widely used as an engineering plastic because of its high heat resistance and excellent strength. Engineering plastics are used in fields such as automobiles, aircraft, electrical and electronic equipment, and machinery, and their application areas are gradually expanding.

[Formula]

As the application area of engineering plastics expands, there is a need for a polyether ketone compound that exhibits improved properties as its use environment becomes more severe. In addition, there is a need for a manufacturing process with a high yield in order to reduce costs during polymerization.

In addition, the balance of melting temperature and crystallization in the polymerization process was limited in the properties and proportions of the monomers.

Therefore, while maintaining the melting temperature of the polyether ketone ketone resin at an appropriate level, it is difficult to improve the injection process and improve the flowability of the resin by improving the crystallization rate.

In addition, the monomers input to the polyether ketone ketone polymerization reaction are polymerized through a Friedel-Crafts Acylation chain reaction. In order to improve the efficiency of the chain reaction, it is possible to increase the content of the reactants, increase the reaction temperature and time, or increase the amount of the catalyst, but it is possible to have a cost problem.

In fact, during the polymerization reaction, hydrochloric acid (HCl) is generated as a by-product, and there is a problem in that the reaction efficiency is reduced due to aggregation between resin particles. Accordingly, various techniques have been studied to increase the reaction efficiency by removing hydrochloric acid and increasing the dispersion power of the reactants.

U.S. Patent No. 3,767,620 provides a polyketone based on diphenyl ether and terephthaloyl and isophthaloyl halide, characterized by having greater thermal stability than known polymers, but is limited to diphenyl ether. However, there is no disclosure about 1,4-diphenoxy benzene with more ether groups.

In addition, U.S. Patent No. 4,816,556 discloses a copolymer having a specific T/I ratio by adjusting the ratios for terephthaloyl and isophthaloyl halide, lowering the melting point, and further improving processability. Also, the composition and effect of 1,4-diphenoxy benzene have not been disclosed.

U.S. Patent No. 4,918,237 relates to a polymerization process of 1,4-bis(4-phenoxybenzoyl)benzene, which is an intermediate of polyether ketone polymerization, for the purpose of solving the defects of aluminum chloride used in the polymerization process, It is difficult to say that the problem is fundamentally solved.

Finally, U.S. Patent No. 9,023,468 relates to a method of preparing a polyetherketone ketone by constructing a repeating unit, in particular, referring to the ratio of isophthaloyl halide and terephthaloyl, bis1,4(4-phenoxy benzoyl )Benzene is disclosed, but there is no mention of diphenyl oxide and mixtures thereof. In addition, although AlCl ₃ is used as a catalyst, a process for removing by-products generated during the reaction and suppressing scale formation is not suggested.

Accordingly, in the PEKK polymerization reaction, it is necessary to improve the crystallization rate of the polymerization resin while controlling the content ratio of the reactants and thereby improve the molding processability. In addition, a process in which resin flowability is improved by controlling molecular weight is also required.

At the same time, there is a need for a process capable of rapidly inhibiting the formation of resin particles by simultaneously removing hydrochloric acid, a by-product generated during polymerization, and minimizing the amount of oligomers generated, while simultaneously preventing resin particle aggregation.

Therefore, there is a need to develop a PEKK manufacturing method to overcome the above problems and efficiently obtain a high molecular weight resin.

U.S. Patent No. 3,767,620 U.S. Patent No. 4,816,556 U.S. Patent No. 4,918,237 U.S. Patent No. 9,023,468

The present invention aims to solve all of the above-mentioned problems.

The object of the present invention is to provide an improvement in the crystallization rate of the polymer resin through an increase in the phenyl ether (Phenyl ether) ratio in the polyether ketone ketone (PEKK) repeat unit structure. Accordingly, there is an object to provide an improvement in injection molding processability.

An object of the present invention is to improve the flowability of the resin by adding a capping agent in the polyether ketone ketone (PEKK) polymerization process.

Another object of the present invention is to efficiently remove the by-product hydrochloric acid and obtain a high molecular weight resin by blowing nitrogen gas inside the liquid reaction medium and stirring at the same time.

In order to achieve the object of the present invention as described above and to realize the characteristic effects of the present invention described later, the characteristic configuration of the present invention is as follows.

(a) At least one selected from 1,4-diphenoxy benzene and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) in the reactor is terephthaloyl chloride (TPC), isophthaloyl chloride Preparing a reaction solution by dissolving (IPC) in a liquid phase and simultaneously dissolving; (b) lowering the temperature of the reaction solution and then adding a catalyst; (c) after the catalyst is introduced, directly blowing and stirring an inert gas into the reaction solution; And (d) adding the first capping agent (capping agent) after the inert gas input; provides a method for producing a polyether ketone ketone comprising a.

The 1,4-diphenoxy benzene is characterized in that it further comprises diphenyl oxide (DPO).

The 1,4-diphenoxy benzene and diphenyl oxide (DPO) are characterized in that the weight ratio is 10 to 50:90 to 50.

According to an embodiment of the present invention, in step (a), a second capping agent is added to the reaction solution, and the molar ratio of the second capping agent to the first capping agent is 1 to It includes 3:1. In detail, the second capping agent and the first capping agent are characterized in that they contain at least one or more of a compound in which an aliphatic or aromatic hydrocarbon is bonded to a benzoyl chloride and benzoyl chloride benzene ring.

The compound is at least one selected from benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone and biphenyl 4-benzenesulfonylphenyl phenyl ether. It may include.

According to an embodiment of the present invention, the weight ratio of the terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) is 7 to 10: 3 to 0.

The inert gas includes at least one selected from nitrogen, helium, neon, argon, and krypton, and a nozzle for blowing the inert gas directly into the reaction solution is formed at the top or bottom of the reactor and injected in multiple directions. It is characterized by.

In addition, the reaction medium of the liquid phase is characterized in that it is at least one or more solvents selected from ortho-dichlorobenzene (oDCB) and dichloromethane,

The catalyst includes at least one selected from aluminum chloride (AlCl 3 ), potassium carbonate (K 2 CO 3) and iron chloride (FeCl 3 ).

The agitating step disperses the inert gas input by rotating a stirrer having a plurality of stirring blades, and the stirrer is provided in at least two or more in the reactor, and rotates in at least two directions to generate a vortex phenomenon. .

According to an embodiment of the present invention, the temperature of the reaction solution in step (b) is -10 to -5°C.

In addition, while stirring in step (c), the reactor was heated to 80°C to 100°C to produce polymerized polyether ketone ketone.

The first capping agent added in step (d) includes adding in the range of 70°C to 110°C.

And washing the polymerized polyether ketone ketone with a solution of methanol (CH ₃ OH), hydrochloric acid and sodium hydroxide (NaOH), and washing three times with deionized water (DI water).

It characterized in that it further comprises the step of obtaining a polyether ketone ketone polymerized resin powder by vacuum drying at 170 to 190 ℃ after the washing step.

According to an embodiment of the present invention, a polyether ketone ketone prepared by the manufacturing method according to the above is provided, and a component material manufactured including the polyether ketone ketone is provided.

According to the present invention, the effect of improving the crystallization rate of the resin in the mold during injection processing of polyether ketone ketone resin by increasing the proportion of ether and terephthaloyl chloride in the repeating unit of the polymer chain of polyether ketone ketone (PEKK) Provides

Accordingly, a polyether ketone ketone (PEKK) resin injection molding process provides an effect of improving the moldability.

According to the present invention, in particular, by adding or post-adding a capping agent, benzoyl groups, which are difficult to form radicals at high temperature processing, are formed at the ends of the polyether ketone ketone (PEKK) polymer chain, and polyether ketone is activated through the binding activation of the capping agent. A benzoyl group is formed at most of the ketone polymer chain ends, and by controlling the molecular weight of polyether ketone ketone (PEKK), there is an effect of improving resin flowability.

In addition, according to the present invention, by blowing nitrogen gas into the reaction medium in the liquid phase of the polymerization reaction and simultaneously stirring, it is possible to efficiently remove by-product hydrochloric acid and obtain a high molecular weight resin.

Figure 1 shows the analysis results of the crystallization rate of the polyether ketone ketone prepared according to the present invention.
2 is an H-NMR graph of the benzoyl group at the end of the polyether ketone ketone chain of the present invention.
3 is an H-NMR graph of a benzoyl group at the end of a PEKK chain polymerized without post-adding a capping agent.
4 is a view showing a process of adding (post-adding) a first capping agent during polymerization of the polyether ketone ketone.
5 and 6 are views showing a device capable of simultaneously stirring and flowing nitrogen gas in the reaction solution according to the method for producing a polyether ketone ketone of the present invention.

For a detailed description of the present invention, which will be described later, reference is made to the accompanying drawings that illustrate, by way of example, specific embodiments in which the invention may be practiced. These examples are described in detail enough to enable those skilled in the art to practice the present invention. It should be understood that the various embodiments of the invention are different, but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the invention in relation to one embodiment. In addition, it should be understood that the location or placement of individual components within each disclosed embodiment can be changed without departing from the spirit and scope of the invention. Therefore, the following detailed description is not intended to be taken in a limiting sense, and the scope of the present invention, if appropriately described, is limited only by the appended claims, along with all ranges equivalent to those claimed. In the drawings, similar reference numerals refer to the same or similar functions across various aspects.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to enable those skilled in the art to easily implement the present invention.

In the present invention, polyether ketone ketone (Poly Ether Ketone Ketone, PEKK) promotes the Friedel-Crafts Acylation chain reaction of monomers to be added to polymerization, minimizes oligomer content and scale production, and improves crystallization rate in the polymerization process. Provided is a method for producing a polyether ketone ketone with improved moldability and a polyether ketone ketone produced thereby.

More specifically, the present invention uses 1,4-diphenoxy benzene as the monomer used in the reaction, or diphenyl oxide (DPO) and 1,4-diphenoxy benzene. (1,4-diphenoxy benzene) is used by mixing. Therefore, it provides an effect of increasing the crystallization rate while maintaining the melting temperature of a conventional polyether ketone ketone. It provides a polyether ketone ketone (PEKK) polymerization technology that improves injection molding processability while promoting crystallization speed.

In addition, conventionally, radicals are generated locally in some polyether ketone ketone (PEKK) polymer chains or at the ends of the chains due to high temperature during processing, so that the radical electrons can bond with adjacent polyether ketone ketone (PEKK) polymer chains. there was. When a network or branch is formed in the polymer by the interchain linkages generated through this mechanism, an increase in the melt viscosity is caused by an increase in the storage modulus. This deteriorates the workability by applying a load to the equipment, which has been the cause of deterioration of the work piece density and apparent quality.

To solve the above problems and to add a capping agent to adjust the molecular weight of the resin, the capping agent that should prevent the formation of radicals at the PEKK polymer chain end during high temperature processing of resins is a competitor with TPC and IPC monomers, which are reactants when polymerizing in the existing polymerization method There was a problem that could not play my role. That is, when the polyether ketone ketone (PEKK) polymerization monomers TPC, IPC, and DPO are simultaneously mixed with a capping agent, the polymerization initial capping agent is a carbonyl carbocation produced by Al-Cl coordination of the catalyst AlCl3, such as TPC and IPC. Will change to In addition, while heating the polymerization solution, the carbocation of TPC and IPC and the carbocation of the capping agent competed with each other during the electrophile reaction to DPO, and there was a problem that it did not function as a capping agent.

Accordingly, in the present invention, a portion of the capping agent input is post-added during the polymerization reaction so that the chain ends of the polyether ketone ketone (PEKK) are capped with a benzoyl group resistant to high temperatures, thereby inhibiting crosslinking of the chain to improve resin flow and thermal stability. Provides an improving effect.

In other words, in the present invention, when a capping agent that must prevent local radicals from being generated at the end of the polyether ketone ketone (PEKK) chain during high temperature polymerization is introduced, it is impossible to perform its original role by reaction with a catalyst. To prevent this, it is provided to cap the PEKK polymer chain ends with a benzoyl group by post-adding a capping agent. The benzoyl group is difficult to form radicals at high temperature processing. Accordingly, the molecular weight of the polyether ketone ketone (PEKK) capped with a benzoyl group at the PEKK polymer chain end is controlled, thereby improving resin flowability and thermal stability. That is, by post-adding the capping agent, most of the PEKK polymer chain ends are formed with benzoyl groups through binding activation, thereby providing resin flow and thermal stability improvement through PEKK molecular weight control.

In addition, conventionally, due to the process of simply purging and applying N ₂ nitrogen gas inside the reactor, hydrochloric acid (HCl) is easily generated as a by-product of the polymerization reaction, and there is a problem that scale is generated due to the low dispersion force of the reactant particles. . Therefore, in the present invention, the inert gas is directly blown into the reaction medium in the liquid phase to rapidly remove by-product hydrochloric acid (HCl) generated during the reaction and at the same time prevent the aggregation of resin particles to suppress scale generation. Provide a manufacturing method.

According to an embodiment of the present invention (a) at least one or more selected from 1,4-diphenoxy benzene and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) in the reactor terephthaloyl chloride ( Terephthaloyl chloride (TPC), isophthaloyl chloride (IPC) and a liquid phase of the reaction medium and dissolved simultaneously to prepare a reaction solution; (b) lowering the temperature of the reaction solution and then adding a catalyst; It includes; (c) a step of blowing and stirring an inert gas directly into the reaction solution after the catalyst is added, and (d) adding a first capping agent after the inert gas is added.

The 1,4-diphenoxy benzene may further include diphenyl oxide (DPO). In this case, the 1,4-diphenoxy benzene and diphenyl oxide (DPO) are characterized in that the weight ratio is 10 to 50:90 to 50.

Polyether ketone ketone is a polymer produced by chain polymerization of terephthaloyl represented by the following chemical structure 1 and isophthaloyl represented by the following chemical structure 2, and its properties are determined according to the ratio. do. The terephthaloyl moiety has a rigid rigidity in a straight line, and the isophthaloyl moiety gives structural diversity due to its curved structure. Isophthaloyl affects the flexibility, fluidity and crystallization properties of the polymer chain.

[Chemical structure 1]

[Chemical structure 2]

In addition, diphenyl oxide (Diphenyl oxide, DPO) corresponding to the monomer of the polyether ketone ketone is as shown in Chemical Structure 3. It has a structure with one ether group and affects the crystallization rate properties.

[Chemical structure 3]

According to an embodiment of the present invention, the polyether ketone ketone uses diphenyl oxide (DPO) 1,4-diphenoxy benzene having two ether groups alone, or die By using a mixture of phenyl oxide (Diphenyl oxide, DPO), it is provided to improve the crystallization rate.

[Chemical structure 4]

The 1,4-diphenoxy benzene and diphenyl oxide (DPO) are characterized in that the weight ratio is 10 to 50:90 to 50.

Preferably a range from 30 to 50:70 to 50 is provided. When 1,4-diphenoxy benzene is 10 or less, there is a problem that the effect of increasing the crystallization rate is not clear. Conversely, in the case of 50 or more, there is a problem of a decrease in tensile strength, so the above range is preferable.

According to an embodiment of the present invention, in the step (a), a second capping agent is added to the reaction solution. Specifically, when dissolving the monomer in a liquid reaction medium, a second capping agent may be simultaneously added to dissolve the monomer. That is, when the three monomers (1,4-Diphenoxy benzene,TPC,IPC) or four (1,4-Diphenoxy benzene, DPO, TPC,IPC) are put into a liquid reaction medium and dissolved, the capping agent is simultaneously capped. agent) to dissolve together, and in this case, benzoyl chloride may be preferably used as a capping agent.

The capping agent is added to the polymerization medium to serve to cap the polymer at at least one end of the polyether ketone ketone polymer chain. This terminates the continuous extension of the polyether ketone ketone polymer chain and controls the molecular weight of the polymerized polymer.

The molar ratio of the second capping agent and the first capping agent is 1 to 3:1. Preferably a range of 3:1 is provided. For example, when the second capping agent is included at 1.5 mol%, the first capping agent may be included at 0.5 mol%. However, it is not limited thereto.

According to one embodiment of the present invention, when in the above 3:1 range, the present invention can maximize the role as a desired capping agent, thereby controlling the molecular weight to improve the effect of resin flowability. to provide. Also, in this case, the second and first capping agents may or may not be the same type.

According to one embodiment of the present invention, the second capping agent and the first capping agent include at least one or more of a compound in which an aliphatic or aromatic hydrocarbon is attached to a benzoyl chloride and benzoyl chloride benzene ring. The compound is at least one selected from benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone and biphenyl 4-benzenesulfonylphenyl phenyl ether. It may include, and preferably may include benzoyl chloride. However, it is not limited thereto.

According to an embodiment of the present invention, upon polymerization of a polyether ketone ketone, terephthaloyl chloride, terephthaloyl chloride (TPC) and isophthaloyl chloride, and isophthaloyl chloride (IPC) are simultaneously applied as ketone group monomers. The rate of crystallization and the melting temperature of the polyether ketone ketone are determined by the input ratio.

In general, the higher the Terephthaloyl chloride (TPC) ratio of the polyether ketone ketone, the faster the crystallization rate, but the higher the Terephthaloyl chloride (TPC) ratio compared to Isophthaloyl chloride (IPC), the more difficult to melt. For example, if the ratio of terephthaloyl chloride:isophthaloyl chloride is 10:0, the melting temperature rises to about 400°C, which is difficult to melt, which is disadvantageous in terms of injection processability.

In addition, in the present invention, a part of the PEKK polymerization monomer (Diphenyl oxide, DPO) is used for the purpose of increasing the crystallization rate while maintaining the melting temperature of the polyether ketone ketone at about 350° C., which is the melting temperature of the conventional polyether ketone ketone. It is used by mixing with 1,4-diphenoxy benzene with 2 ether groups. Through this, the melting temperature of the resin can be lowered, and the application rate of terephthaloyl chloride can be maximized during PEKK polymerization, the crystallization rate of the PEKK polymerization resin can be increased, and injection processability is improved.

In detail, the content ratio of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) is 7 to 10: 3 to 0. Preferably a 9:1 range is provided. When terephthaloyl chloride (TPC) is 7 or less, there is a problem that the crystallization rate decreases. When isophthaloyl chloride (IPC) exceeds 3, there is a problem that the crystallization rate decreases as well, so the above range is preferable.

According to one embodiment of the invention, the inert gas is characterized in that at least one or more selected from nitrogen, helium, neon, argon and krypton. The inert gas may be used alone or in combination during the polymerization reaction.

According to the method for preparing a polyether ketone ketone of the present invention, a device capable of simultaneously flowing and stirring nitrogen gas in a reaction solution is shown in FIGS. 5 and 6. 5 and 6, according to an embodiment of the present invention, in the PEKK manufacturing method, a nozzle for blowing the inert gas directly into the reaction solution may be formed at the top or bottom of the reactor and injected in multiple directions. This can make the removal of hydrochloric acid by an inert gas more quickly and efficiently.

In addition, the reaction medium of the liquid phase may be at least one or more solvents selected from ortho-dichlorobenzene (oDCB) and dichloromethane, but is not limited thereto, and is generally used as a solvent for the Friedel-Crafts Acylation polymerization reaction. If it is used, it is possible.

According to an embodiment of the present invention, when the catalyst is added in the manufacturing method, the temperature of the reaction solution is lowered before being input. At this time, the temperature may vary depending on the catalyst, but is preferably -10 to -5°C.

The catalyst may be at least one selected from aluminum chloride (AlCl 3 ), potassium carbonate (K 2 CO 3 ), and iron chloride (FeCl 3 ), but is not limited thereto, and may be any commonly used catalyst for the Friedel-Crafts Acylation polymerization reaction.

According to an embodiment of the present invention, the agitating step is characterized in that a plurality of agitator blades formed with a stirrer is rotated to disperse the inert gas, and at least two agitators are provided in the reactor. It can be rotated in two or more directions to generate a vortex phenomenon. The rotating shaft of the stirrer may be provided to rotate at a predetermined angle alternately in the forward and reverse directions. In addition, the stirring blade is formed to form a predetermined angle with the rotating shaft can increase the dispersion force of the composition in the reactor.

According to an embodiment of the present invention, the cooling temperature of step (b) may include -10 to -5°C. That is, when the catalyst is added in the manufacturing method according to the present invention, the temperature of the reaction solution is lowered before being input. At this time, the temperature may vary depending on the catalyst, but is preferably -10 to -5°C.

After the inert gas was added, the reactor was heated to 80°C to 100°C while stirring to polymerize the polyether ketone ketone. According to an embodiment of the present invention, the polymerization reaction may be performed in various reactors, but may preferably be performed in a continuous stirring reactor (CSTR) or loop reactor.

The temperature of step (d) may be 70 to 110°C, preferably 80 to 100°C, and more preferably 90°C. Specifically, it may be provided that the first capping agent, benzoyl chloride, is additionally added to the polyether ketone ketone while the temperature of step (d) is maintained at 90°C.

According to an embodiment of the present invention, after the step (d), washing with at least one of methanol (CH 3 OH), hydrochloric acid and NaOH solution, and washing with deionized water (DI water) may further include. After the step of performing a vacuum drying at 170 to 190 ℃ may further include the step of obtaining a PEKK polymer resin powder.

Accordingly, the present invention provides a polyether ketone ketone prepared according to the above production method.

In addition, it provides a component material manufactured by including the polyether ketone ketone. One example of a component material is a vehicle material, an electronic device material, an industrial pipe material, a construction engineering material, a 3D printer material, a textile material, a coating material, a machine tool material, a medical material, an aviation material, a solar material It provides parts materials selected from the group consisting of, battery materials, sports materials, household materials, household materials, and cosmetic materials. However, it is not limited to this.

The polyether ketone ketone produced by the above manufacturing method shows improved physical properties compared to the polyether ketone ketone produced through the prior art.

In particular, by increasing the proportion of ether and terephthaloyl chloride in the repeating unit of the polymer chain of polyether ketone ketone, the rate of crystallization of the resin in the mold during PEKK resin injection processing is improved, and molding during the injection process of polyether ketone ketone resin It provides the effect of improving the processability.

In addition, in the case of the polymerized polyether ketone ketone, benzoyl groups, which are difficult to form radicals at high temperature processing, are formed at the ends of the polymer chain of the polyether ketone ketone (PEKK). Particularly, by adding the capping agent, benzoyl groups are formed on most of the polymer chain ends of the polyether ketone ketone through the binding activation of the capping agent, so that the molecular weight of the polyether ketone ketone can be controlled, thereby improving resin flow and thermal stability. Provides the effect.

In addition, during the polymerization reaction, by blowing nitrogen gas inside the reaction medium and stirring at the same time, the reaction by-product hydrochloric acid is rapidly removed, and the formation of resin particles is prevented to prevent the formation of scale, thereby suppressing the formation of a high-scale polyether ketone ketone. It is characterized in that can be obtained at a high yield.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be interpreted as limiting the present invention by any means.

The contents not described herein will be sufficiently technically inferred by those skilled in the art, and thus the description thereof will be omitted.

<Example>

Example 1

The reaction solvent is 1,4-diphenoxy benzene, a monomer, diphenyl oxide (DPO), terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) and 1.5 mol% of benzoyl chloride, a capping agent, in the reactor. Phosphorus is added to ortho-dichlorobenzene (oDCB) and dissolved at the same time, and then the reactor temperature is lowered to -10 to -5 °C. In this case, the ratio of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) is 9:1.

AlCl ₃ as a catalyst is added while maintaining the solution temperature constant at -10 to -5°C. After the catalyst is added, N ₂ is blown into the solution and the solution is stirred and the reactor is heated to 100° C. to polymerize polyether ketone ketone (PEKK). Thereafter, 0.5 mol% of benzoyl chloride is added to PEKK while maintaining at 90°C. The final polymerized resin was washed with methanol 3 times, 1M hydrochloric acid and 0.5M NaOH solution, washed with DI water 3 times and vacuum dried to obtain PEKK polymerized resin.

Comparative Example 1

The monomers Diphenyl oxide (DPO), Terephthaloyl chloride (TPC) and Isophthaloyl chloride (IPC) were added to the reaction agent ortho-dichlorobenzene (oDCB), a Benzoyl chloride 2.0 mol% reaction solvent, as a capping agent. The reactor temperature is lowered to -10 to -5 °C.

AlCl ₃ as a catalyst is added while maintaining the solution temperature constant at -10 to -5°C. After the catalyst is added, N ₂ is blown into the solution, and at the same time, the solution is stirred and the reactor is heated to 100° C. to polymerize PEKK. The polymerized resin was washed with methanol 3 times, 1M hydrochloric acid and 0.5M NaOH solution, washed with DI water 3 times and vacuum dried to obtain PEKK polymerized resin.

Experimental Example 1

Measurement of half-crystallization rate using D SC

The PEKK polymerization resin according to Example 1 and Comparative Example 1 was measured using DSC to measure the time required for half-crystallization. It is shown in [Table 1]. The measurement method is an isothermal method, and the heating rate is fixed constant (10℃/min) and quenched to the crystallization temperature in the state where the polymer is melted (quenching, temperature reduction rate -500℃/min). The rate of crystallization is measured by calculating the time required to reach a certain degree of crystallization through the change. The measuring equipment is DSC 8000 from Perkin Elmer.

Experimental Example 2

H-NMR analysis (benzoyl group analysis)

The increase of benzoyl groups at the ends of the polyether ketone ketone (PEKK) chains of Example 1 and Comparative Example 1 was confirmed by H-NMR, and the results are shown in the graphs of FIGS. 2 and 3. In addition, the area of H-NMR of hydrogen atoms A and B excluding hydrogen atom C among the three bonded to the benzoyl group is shown in Table 1 below. At this time, the hydrogen atom C has a peak with another hydrogen atom bound to the PEKK back bone, resulting in a difficult to read result.

Experimental Example 3

Measurement of Inherent Viscosity and Melt Index

Inherent Viscosity and Melt Index of Example 1 and Comparative Example 1 were measured, respectively, and the results are shown in Table 3 below. Inherent Viscosity is the value obtained by dividing the viscosity of a thin polymer solution by the viscosity of a pure solvent. The Melt Index is a measure of the outflow of molten resin according to a certain pressure and temperature using an extruded plasticity meter, and is expressed in units of g/10min.

Example Comparative example Melt temperature 355 340 Half-crystallization
(Based on 210℃, second) 49 520

H-NMR analysis peak area Hydrogen atom A (7.80 ppm) Hydrogen atom B (7.65 ppm) Example 0.470 0.050 Comparative example 0.344 0.028

Inherent Viscosity (dL/g) Melt Index(g/10min) Example 1.14 28 Comparative example 1.26 5

As described in Table 1, PEKK of Example 1 prepared with 4 monomers (TPC, IPC, DPO, 1,4-diphenoxy benzene) according to the present invention has 3 monomers (TPC, IPC, DPO) Using, it was confirmed that the time required for half-crystallization was reduced to about 1/10 compared to the prepared comparative example 1.

Referring to Table 2 and Figures 2 and 3, it can be seen that there are more benzoyl groups at the chain ends of the PEKK of the Examples than the benzoyl groups at the PEKK chain ends of the comparative example polymerized without post-addition of benzoyl chloride. That is, it can be seen from the H-NMR graph that the chain end of the PEKK polymerized by the polymerization production method of PEKK of the present invention is capped with a strong benzoyl group. In addition, as shown in Table 1, it can be seen that the area of the hydrogen atoms in the example is smaller than that of the comparative example. According to the polymerization method of the existing PEKK, it can be seen that the radicals were generated locally at the ends of some polymer chains because the capping agent did not function due to the reaction between the catalyst and the capping agent. On the other hand, PEKK polymerized by the manufacturing method including the step of post-adding the capping agent according to the present invention, the chain end is capped with a stable benzoyl group at high temperature, so that the resin flowability is improved by not forming radicals at high temperature of the resin. Can be.

As in Table 3, the Inherent Viscosity of the embodiment of the present invention was 1.14, and the Melt Index was measured to be 28 (g/10min). On the other hand, the Inherent Viscosity of the comparative example was 1.26 (dL/g), and the Melt Index was measured to be 5 (g/10min), showing a difference of almost 5 times in the case of the Melt Index.

Therefore, in the case of the Examples, it can be seen that the capping agent is capped with a benzoyl group that inhibits the Fridel-Crafts Acylation reaction at the end of the PEKK polymer chain to adjust the molecular weight.

On the other hand, as shown in the result of the comparative example, the step of post-adding the capping agent is not included, so that the initial polymerization capping agent is changed to a carbonyl carbocation produced by Al-Cl coordination of the catalyst AlCl3, like TPC and IPC. In addition, it can be seen that while heating the polymerization solution, the carbocation of TPC and IPC and the carbocation of the capping agent competed in the electrophile reaction to DPO, so that the problem of not functioning as a capping agent was not solved. have.

According to an embodiment of the present invention, by increasing the proportion of ether and terephthaloyl chloride in the repeating unit of the polymer chain of polyether ketone ketone, the effect of improving the crystallization rate of resin in the mold during PEKK resin injection processing is provided. . Therefore, the polyether ketone resin provides an effect of improving molding processability during the injection process.

According to an embodiment of the present invention, in particular, a benzoyl group, which is difficult to form radicals at high temperature processing by adding or post-adding a capping agent, is formed at the ends of a polymer chain of polyether ketone ketone (PEKK), and activates the binding activity of the capping agent. Through the polyether ketone ketone polymer chain, a benzoyl group is formed at most of the ends, thereby controlling the PEKK molecular weight, thereby improving resin flowability and thermal stability.

In addition, according to an embodiment of the present invention, the polyether ketone ketone production method has an effect of minimizing oligomers in the resin particles and preventing aggregation of the resin particles to suppress scale generation.

In the above, the present invention has been described by specific matters such as specific components and limited embodiments and drawings, but this is provided only to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments , Those skilled in the art to which the present invention pertains can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention is not limited to the above-described embodiment, and should not be determined, and all claims that are equally or equivalently modified as well as the claims below will fall within the scope of the spirit of the present invention. Would say

Claims (21)

(a) At least one selected from 1,4-diphenoxy benzene and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) in the reactor is terephthaloyl chloride (TPC), isophthaloyl chloride (IPC) and the step of preparing a reaction solution by dissolving at the same time in the reaction medium of the liquid phase;
(b) lowering the temperature of the reaction solution and then adding a catalyst;
(c) after the catalyst is introduced, directly blowing and stirring an inert gas into the reaction solution; And
(d) adding the first capping agent after the inert gas is introduced; a method for producing a polyether ketone ketone comprising a.
According to claim 1,
The 1,4-diphenoxy benzene further comprises diphenyl oxide (DPO)
A method for producing polyether ketone ketone.
According to claim 2,
The 1,4-diphenoxy benzene and diphenyl oxide (DPO) is a method for producing a polyether ketone ketone, characterized in that the weight ratio is 10 to 50:90 to 50.
According to claim 1,
A method for producing a polyether ketone ketone, characterized in that a second capping agent is added to the reaction solution in step (a).
The method of claim 4,
A method for producing a polyether ketone ketone, wherein the molar ratio of the second capping agent and the first capping agent is 1 to 3:1.
The method of claim 4,
The second capping agent and the first capping agent is a benzoyl chloride (benzoyl chloride) and benzoyl chloride method of producing a polyether ketone ketone, characterized in that it contains at least one of a combination of aliphatic or aromatic hydrocarbon benzene ring .
The method of claim 6,
The compound is at least one selected from benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone and biphenyl 4-benzenesulfonylphenyl phenyl ether. Method for producing a polyether ketone ketone comprising a.
According to claim 1,
Method for producing polyether ketone ketone, characterized in that the weight ratio of the terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) is 7 to 10:3 to 0.
According to claim 1,
The inert gas is a method for producing polyether ketone ketone, characterized in that at least one selected from nitrogen, helium, neon, argon and krypton.
According to claim 1,
A method for producing a polyether ketone ketone, characterized in that a nozzle for blowing the inert gas directly into the reaction solution is formed at the top or bottom of the reactor and injected in multiple directions.
According to claim 1,
The liquid reaction medium is ortho-dichlorobenzene (oDCB) and a method for producing polyether ketone ketone, characterized in that at least one solvent selected from dichloromethane.
According to claim 1,
The catalyst is a method of producing polyether ketone ketone, characterized in that at least one selected from aluminum chloride (AlCl 3 ), potassium carbonate (K 2 CO 3) and iron chloride (FeCl 3 ).
According to claim 1,
The stirring step is a method of manufacturing a polyether ketone ketone, characterized in that a stirrer having a plurality of stirring blades is rotated to disperse the inert gas.
According to claim 1,
The stirrer is provided in at least two or more in the reactor, the method of producing a polyether ketone ketone, characterized in that to rotate in at least two directions to generate a vortex phenomenon.
According to claim 1,
Method of producing a polyether ketone ketone, characterized in that the temperature of the reaction solution in the step (b) is -10 to -5 ℃.
According to claim 1,
A method for producing a polyether ketone ketone, characterized in that, while stirring in step (c), the reactor is heated to 80°C to 100°C to produce polymerized polyether ketone ketone.
According to claim 1,
The method for producing a polyether ketone ketone, wherein the first capping agent added in step (d) is added in a range of 70°C to 110°C.
The method of claim 16,
The polymerized polyether ketone ketone is washed with methanol (CH ₃ OH), hydrochloric acid and sodium hydroxide (NaOH) solution, and washed three times with deionized water (DI water) of the polyether ketone ketone. Manufacturing method.
The method of claim 18,
A method of producing a polyether ketone ketone further comprising the step of vacuum drying at 170 to 190° C. after the washing step to obtain a polyether ketone polymer resin powder.
A polyether ketone ketone prepared by the method according to any one of claims 1 to 19.
Part material manufactured including the polyether ketone ketone according to claim 20.

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