KR20160082485A - Synthesis method of polyetherimides - Google Patents

Abstract

The present invention relates to a method for synthesizing polyetherimide. The method of the present invention includes the following steps: (S1) adding a cryptand-based or a crown ether-based ligand catalyst as a phase-transfer catalyst into a reactor into which a 10-30% concentrated bisimide monomer and a solvent are added therein; and (S2) adding an anionic monomer represented by chemical formula 2 into the reactor, into which the catalyst is added from the previous step (S1), in the same molecular weight (error range within +/- 0.05) of the bisimide monomer, and then carrying out a reaction so as to obtain polyetherimide.

Description

SYNTHESIS METHOD OF POLYETHERIMIDES < RTI ID = 0.0 >

The present invention relates to a method for synthesizing a polyetherimide.

Polyetherimide (PEI), a class of polyimide, has an imide group that imparts heat resistance and strength to a molecular structure and an ether group that can improve processability (moldability) at the same time, It is an amorphous thermoplastic polymer. Since polyetherimide has high heat resistance, excellent dimension and thermal stability, chemical resistance and flame resistance, plastic resin including it is widely used in electric and electronic parts such as DC converter, semiconductor tray and HDD substrate holder, automobile parts, .

Polyetherimides can generally be prepared in two ways. The first method involves reacting a dianhydride monomer having a flexible group by an ether (-O-) bond in a molecule with a diamine monomer in dimethyl acetamide (DMAc), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) to form a polyamic acid (PAA), which is thermally cured or chemically cured to produce PEI. Since this method is difficult to proceed with 100% imidization without additional processing, there is a high possibility that property changes will occur in the process of making a product (extrusion, injection) using PEI.

On the other hand, the second method is a method in which PEI is prepared by introducing a monomer containing hydroxylimide and a halogenated bisimide having imidization of 100% into a solvent and then polymerizing under high temperature in the presence of a catalyst. This method uses a monomer with 100% imidization, so that it can be imidized sufficiently without further processing, and no change in properties occurs in the process of making the product (extrusion, injection). Despite the disadvantage that the molecular weight control of PEI by Side reaction is difficult because of high temperature conditions, the second method is more advantageously applied to the polyetherimide production method than the first method .

With regard to the process for preparing polyetherimides from bisimides, U.S. Pat. No. 5,229,482 discloses a process for the preparation of polyetherimides from bisimides in the presence of a thermally stable phase transfer catalyst such as a hexaalkyl guanidinium halide in a low polarity solvent such as dichlorobenzene ≪ / RTI > for the preparation of polyetherimides. In addition, U.S. Patent No. 5,830,974 discloses a method of using a monoalkoxybenzene such as anisole as a solvent.

Despite the presence of these prior arts, the development of optimal methods for the production of polyetherimides from bisimides remains a challenge. Particularly, it is important to develop a method capable of obtaining a polyetherimide having a high molecular weight in a shorter time in the field of manufacture.

Accordingly, the present invention provides a method for synthesizing PEI having a high molecular weight in a reaction time faster than that using a conventionally used catalyst such as hexaalkyl guanidinium in the process for producing polyetherimide (PEI) .

A preferred embodiment of the present invention for solving the above problems is characterized in that (S1) a solvent and a bismediimide monomer represented by the following general formula (1) are added in a concentration of 10% to 30% to a reaction vessel containing a clogende or crown ether ligand Dropping a catalyst; And (S2) an anionic monomer represented by the following formula (2) is added dropwise into a reaction vessel in which the catalyst is dropped in the step (S1) in the same molar amount (within an error range of 0.05) as the bisimide monomer and reacted to react the polyetherimide ≪ RTI ID = 0.0 > polyetherimide < / RTI >

≪ Formula 1 >

Wherein A is selected from among F, Cl, Br, I and NO ₂ , R ₁ is selected from the group consisting of Cyclohexane, Cyclopentadiene, A bivalent linking group derived from one organic compound selected from biphenyl and diphenyl ether, or phenylene.

(2)

Wherein B is K or Na and R ₂ is selected from alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, phenylene, divalent biphenyl, bivalent diphenyl sulfone, bivalent diphenyl ketone and bivalent diphenyl propane One species.

The reaction vessel according to this embodiment is disposed in an oil bath, and the oil bath may be heated to 130 to 210 ° C in step (S1).

The solvent according to this embodiment may also be selected from the group consisting of toluene, xylene, ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, diphenylsulfone, , Veratrol, and mixtures thereof, wherein the catalyst is at least one of 18-Crown-6 and Cryptand 221 when B is Na in Formula 2, and B is K And may be at least one of 21-Crown-7 and Cryptand 222. [

At this time, the catalyst is preferably added in an amount of 0.01 to 0.1 mol% based on the total moles of the bisimide monomer.

Further, the reaction in (S2) according to the above embodiment may be carried out for 1 to 5 hours, and the weight average molecular weight of the polyetherimide obtained in (S2) may be 10,000 to 70,000.

According to the present invention, unlike the conventional method of dissolving anionic monomers by using a polar catalyst, by using a catalyst in which no ions are present in the molecular structure, even a small amount of catalyst can be used in a short period of time High molecular weight polyetherimides can be synthesized and prepared.

In particular, since the catalyst used in the present invention forms a chelate with Na or K, the present invention can be more easily performed in a method of producing PEI using an anionic monomer containing Na or K ions.

1 shows chemical structures of 18-Crown-6, 21-Crown-7, Cryptand 221 and Cryptand 222, which are one example of a phase transfer catalyst according to the present invention.

The present invention has been proposed as a method for producing a polyetherimide from a bisimide monomer already containing an imide group in a monomer structure, and it has been proposed to use a cryptand or crown ether ligand catalyst instead of hexaalkyl guanidinium, It is possible to provide a method for synthesizing a polyetherimide having a high polymerization degree within a fast reaction time without removing water.

Generally, an anionic salt is used as a reactant with bisimide in the production of a polyetherimide using a bisimide monomer. However, the anionic salt does not dissolve well when it is not a protonic solvent such as water or alcohol. However, since the solvent capable of dissolving the bisimide monomer is not a protonic solvent, it is inevitable to use a catalyst to dissolve the anionic salt in the solvent in the reaction using the bisimide monomer.

As the catalyst, hexaalkyl guanidinium chloride has been used. In this case, since hexaalkyl guanidinium chloride has ions in the molecule, it is difficult to remove the bound moisture in the synthesis process and the moisture in the air and the There is a disadvantage to combine. Accordingly, if the reaction can not be controlled properly, the imide bond group is attacked by moisture and is broken, so that PEI having high polymerization degree can not be obtained. Therefore, in the method using hexaalkylguanidinium as a catalyst, the removal of water generated during the reaction, that is, the purification process is indispensable.

However, in the case of the cryptand or crown ether ligand catalyst used in the present invention, since there is no polarity, it is easy to remove moisture in the synthesis process. In addition, since the water does not easily bind to the water encountered in the course of the experiment, a separate purification process of water is not required, and thus the synthesis can be performed more easily, and since the imide group is not broken by moisture, It is possible to obtain a polymerization degree of PEI.

The specific method of the present invention that enables this can be performed in the following steps.

Step 1 (S1)

First, the process for producing a polyetherimide of the present invention comprises the steps of dropping a criptide or crown ether ligand catalyst as a phase transfer catalyst into a reaction tank in which a solvent and a bisimide monomer represented by the following formula (1) are introduced at a concentration of 10% to 30% Lt; / RTI >

≪ Formula 1 >

, Cyclopentadiene

, Biphenyl

및 diphenyl ether

중 선택된 1종의 유기 화합물로부터 유도된 2가의 결합기이거나, phenylene

이다. In Formula 1, A is selected from among F, Cl, Br, I and NO ₂ , R ₁ is selected from Cyclohexane

, Cyclopentadiene

, Biphenyl

And diphenyl ether

Or a divalent linking group derived from one organic compound selected from phenylene

to be.

At this time, it is preferable that the solvent is selected as a solvent in which the bismediimide monomer can be dissolved, and toluene, xylene, ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4- Chlorobenzene, diphenylsulfone, phenetole, anisole, veratrol, and mixtures thereof.

In the bisimide monomer, the substituent group A is a leaving group. Since the polymerization reaction with the anionic monomer may proceed during the reaction, it may be advantageous to use a halogen atom having high electronegativity or substituted with NO ₂ . If the concentration of the bisimide monomer is less than 10%, the concentration of the bisimide monomer may be lowered to produce only low molecular weight PEI. When the concentration exceeds 30% , The monomer may not be completely dissolved in the solvent, resulting in a low yield due to the monomer not participating in the reaction, or the viscosity of the solvent may become too high and the stirring may not be performed.

In the present invention, the reaction vessel is disposed in an oil bath, and the oil bath is preferably heated to 130 to 210 ° C, more preferably to 150 to 200 ° C in the step (S1). The reason for raising the temperature of the oil bath is to reach a temperature suitable for the polymerization reaction and also to induce the bisimide monomer to be dissolved in the solvent more easily in the reaction tank. If the temperature of the oil bath is 210 캜 or lower, a sufficiently high molecular weight PEI can be obtained. However, if the temperature is lower than 130 캜, sufficient polymerization can not be carried out in subsequent reaction, resulting in a low molecular weight of PEI.

On the other hand, the catalyst is added to enhance the solubility of the anionic monomer to be added in the second step (S2), which will be described later, and is preferably a cryptand or crown ether ligand catalyst. In particular, considering the kind of the anionic monomer to be charged in step (S2), if the anionic monomer contains Na ions, the catalyst is preferably at least one of 18-Crown-6 and Cryptand 221, and the anionic monomer When K ions are included, the catalyst is preferably at least one of 21-Crown-7 and Cryptand 222.

In the present invention, it is preferable that the catalyst is added in an amount of 0.01 to 0.1 mol% based on the total moles of the bisimide monomer. If the addition amount of the catalyst is less than 0.01 mol%, the reaction rate is slow and the desired molecular weight can not be obtained. If the amount is more than 0.1 mol%, the reaction rate is rather slow and the desired molecular weight can not be obtained.

As shown in FIG. 1, the catalyst of the present invention has a feature of forming a chelate complex by trapping alkali metal ions, especially Na or K, in a three-dimensional space as a polydentate ligand which is crosslinked three-dimensionally to form an annular ligand. In the case of hexaethyl guanidium chloride, which is often used in the production of polyetherimides, ionic bonds exist in the molecule and are easily combined with moisture generated in the PEI synthesis process or moisture present in the air. Therefore, However, since the catalyst of the present invention has no ionic bond in the molecule, the activity of the catalyst is excellent even when there is no process for removing moisture in the synthesis process, and thus a high molecular weight PEI can be obtained in a short time .

Step S2 (S2)

Next, in step (S1), the anionic monomer represented by the following formula (2) is added dropwise to the reaction vessel in which the catalyst is dripped in the same molar amount as the above-mentioned bisimide monomer (within an error range of 0.05) Lt; RTI ID = 0.0 > C, < / RTI > the polyetherimide can be finally obtained.

(2)

, 2가의 biphenyl

, 2가의 diphenyl sulfone

, 2가의 diphenyl ketone

및 2가의 diphenyl propane

중 선택된 1종이다. Wherein B is K or Na, R ₂ is alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, phenylene

, Divalent biphenyl

, Divalent diphenyl sulfone

, Divalent diphenyl ketone

And bivalent diphenyl propane

≪ / RTI >

In the present invention, the anionic salt is a diol or phenolic anionic salt having two hydroxyl groups (-OH), such as diol or hydroquinone such as ethylene glycol, 4,4'-hydroxy bisphenol, bis (4- (K, potassium) or sodium (Na, sodium) is substituted for H of the hydroxyl group in a phenol compound such as bisphenol A, bis (4-hydroxyphenyl) sulfone, bis As a result, the anion salt is ionized and the potassium cation (K ⁺ ) or the sodium cation (Na ⁺ ) is collected by the catalyst, and the anion portion is a halogen atom having a high electronegativity at the end of the bisimide or NO ₂ And ether bonds with the terminal of the bisimide to polymerize into the polyetherimide.

At this time, since the anionic salt is substituted with potassium or sodium, the trapping activity by the catalyst becomes more active, so that the reaction rate can be remarkably accelerated even with a small amount of the catalyst. That is, if the process of purifying water under the same amount of catalyst is omitted, when the preparation according to the production method of the present invention is carried out, the weight average molecular weight (Mw) is 10,000 to 70,000, more preferably 20,000 To 70,000, and most preferably from 50,000 to 70,000. In case of using hexaethyl guanidium chloride, a reaction time of 4 hours to 6 hours to obtain an equivalent level of polymerization degree Is more demanding. That is, considering that ultimately a water purification process is unnecessary, the present invention provides an efficient polymerization method for producing PEI having a high degree of polymerization in a short time.

The weight average molecular weight (Mw) described in the present invention may mean that the polystyrene reduced weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) (model name e2695, manufactured by Waters). More specifically, the polymer to be measured was dissolved in dimethylformamide (DMF) to a concentration of 1%, and 20 μl was injected into GPC. The solution was flowed at a flow rate of 1.0 mL / min and analyzed at 30 ° C. . At this time, the column can be used by connecting two Styragel HR3 of Waters Co., Ltd. in series, and the detector is measured at 40 캜 using an RI detector (Waters, 2414).

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.

The reagents used throughout the examples of the present invention are as follows.

Bis-4-chlorophthalimide-4-phthalimidobenzene (B-4-CPI-4-PIB, Mw: 437.535), Bis- (4- chlorophthalimido) (B-4-CPI-4-PPE, Mw: 529.33)

- Bisphenol-A-Dipotassium anion (BPAP-2, Mw: 304.47), Bisphenol-A-Disodium anion (BPAS-2, Mw: 272.25)

- Solvent: O-dichlorobenzene (ODCB, Solvent)

- phase transition catalysts: Cryptand 222 (Mw: 376.488), Cryptand 221 (Mw: 332.44)

Example  One

In a 250 ml three-necked flask placed in an oil bath, 100 ml of ODCB and 9.6 g (22.0 mmol) of B-4-CPI-4-PIB were added and the temperature of the oil bath was raised to 150 캜, CPI-4-PIB was dissolved in the solvent. Further, 0.00082 g of Cryptand 222 relative to B-4-CPI-4-PIB was added to the flask in an amount of 0.01 mol% (0.0022 mmol). Subsequently, 6.7 g (22.0 mmol) of BPAP-2 was added dropwise to the warmed solution using a funnel. When the dropwise addition was completed, the temperature was raised to 150 ° C and the mixture was stirred for 3 hours. After 3 hours, the solution was cooled to room temperature, and the cooled solution was poured into 500 ml of methanol to confirm that a brown precipitate was obtained in the form of synthesized PEI.

Example  2

PEI was synthesized in the same manner as in Example 1 except that 0.05 mol% (0.011 mmol) of the catalyst was added to the monomer (B-4-CPI-4-PIB).

Example  3

PEI was synthesized in the same manner as in Example 1 except that 0.1 mol% (0.022 mmol) of the catalyst was added to the monomer (B-4-CPI-4-PIB).

Example  4

PEI was synthesized in the same manner as in Example 1, except that the final heating temperature was increased from 150 캜 to 180 캜.

Example  5

PEI was synthesized in the same manner as in Example 1, except that the final temperature was raised from 150 캜 to 200 캜.

Example  6

PEI was synthesized in the same manner as in Example 1 except that the reaction time over 3 hours was adjusted to 1 hour.

Example  7

PEI was synthesized in the same manner as in Example 1, except that the reaction time over 3 hours was adjusted to 2 hours.

Example  8

PEI was synthesized in the same manner as in Example 1 except that the reaction time over 3 hours was adjusted to 5 hours.

Example  9

PEI was synthesized in the same manner as in Example 1 except that 11.64 g (22.0 mmol) of B-4-CPI-4-PPE was added instead of B-4-CPI-4-PIB.

Example  10

11.64 g (22.0 mmol) of B-4-CPI-4-PPE instead of B-4-CPI-4-PIB, 0.00073 g (0.0022 mmol) of Cryptand 221 instead of Cryptand 222 and 5.98 g (22.0 mmol) of BPAP- PEI was synthesized in the same manner as in Example 1 except that BPAS-2 was used.

Example  11

PEI was synthesized in the same manner as in Example 1 except that the final temperature-raising temperature was lowered from 150 占 폚 to 100 占 폚.

Example  12

PEI was synthesized in the same manner as in Example 1 except that the final temperature-raising temperature was lowered from 150 占 폚 to 140 占 폚.

Example  13

PEI was synthesized in the same manner as in Example 1 except that the final temperature-raising temperature was set at 210 占 폚.

Example  14

PEI was synthesized in the same manner as in Example 9, except that 0.15 mol% (0.11 mmol) of Cryptand 222 catalyst was used as the bisimide monomer (B-4-CPI-4-PPE).

Example  15

PEI was synthesized in the same manner as in Example 10, except that 0.15 mol% (0.11 mmol) of Cryptand 221 catalyst was used as the bisimide monomer (B-4-CPI-4-PPE).

Comparative Example  One

PEI was synthesized in the same manner as in Example 1 except that the catalyst was not used.

Comparative Example  2

Except that 0.1mol% (0.022 mmol) of hexaethyl guanidium chloride (Angene Chemical, China) catalyst was used in place of the bisimide monomer (B-4-CPI-4-PIB) Were synthesized.

Comparative Example  3

PEI was synthesized in the same manner as in Comparative Example 2, except that the water generated in the synthesis of Comparative Example 2 was removed (purified).

Comparative Example  4

PEI was synthesized in the same manner as in Comparative Example 3, except that the reaction temperature in Comparative Example 3 was increased from 150 ° C to 200 ° C.

Then, the molecular weights (Mw) of the PEI obtained from each of Examples 1 to 10 and Comparative Examples 1 to 9 were measured by gel permeation chromatography (GPC) (satandard: polystyrene) Respectively.

division Bisimide monomer / anionic monomer catalyst Reaction temperature
(° C) Reaction time
(time) Molecular Weight
(Mw) Example 1 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 150 3 35000 Example 2 B-4-CPI-4-PIB / BPAP-2 0.05 mol% Cryptand222 150 3 45000 Example 3 B-4-CPI-4-PIB / BPAP-2 0.1 mol% Cryptand222 150 3 50000 Example 4 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 180 3 53000 Example 5 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 200 3 65000 Example 6 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 200 One 15000 Example 7 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 200 2 55000 Example 8 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 200 5 65000 Example 9 B-4-CPI-4-PPE / BPAP-2 0.01 mol% Cryptand222 150 3 45000 Example 10 B-4-CPI-4-PPE / BPAS-2 0.01 mol% Cryptand221 150 3 40000 Example 11 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 100 3 25000 Example 12 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 140 3 33000 Example 13 B-4-CPI-4-PIB / BPAP-2 0.01 mol% Cryptand222 210 3 47000 Example 14 B-4-CPI-4-PPE
BPAP-2 0.15 mol%
Cryptand  222 150 3 32000 Example 15 B-4-CPI-4-PPE
BPAS-2 0.15 mol%
Cryptand  221 150 3 30000 Comparative Example 1 B-4-CPI-4-PIB / BPAP-2 - 150 3 12000 Comparative Example 2 B-4-CPI-4-PIB / BPAP-2 0.01 mol% HEGCl 150 3 32000 Comparative Example 3 B-4-CPI-4-PIB / BPAP-2 0.01 mol%  Purified HEGCl 150 3 45000 Comparative Example 4 B-4-CPI-4-PIB / BPAP-2 0.01 mol%  Purified HEGCl 200 3 65000

As can be seen from the above Table 1, the polymerization degree of PEI obtained in Comparative Example 1 in which catalyst was not used and Comparative Example 2 in which HEGCI was used as a catalyst, in Example 1 of the present invention using creptand as a phase- . In addition, when the content of the catalyst was further increased as in Example 2 or 3, it was found that the degree of polymerization was equal to or higher than that of Comparative Example 3 in which the reaction was induced while removing moisture. However, when the catalyst content exceeds 0.1 mol% of the monomer content, it is confirmed that the reaction rate is lowered and the desired molecular weight can be lowered as in Examples 14 and 15.

On the other hand, it was confirmed that sufficient polymerization was carried out at 150 to 200 ° C in the same reaction time as in Examples 1, 4 and 5. However, when the temperature was lowered as in Examples 11 and 12, the degree of polymerization could be somewhat lowered, As shown in Fig. 13, the higher the temperature, the higher the degree of polymerization. Also, as in Examples 4 and 5, the polymerization degree can be improved when the reaction temperature is high in the same reaction time. However, as can be seen from Examples 5 and 8, the reaction time is maximally 5 hours, Respectively.

In particular, comparing the results of Example 5 and Comparative Example 4, or comparing the results of Example 9 and Comparative Example 3, it can be seen that when the amount of catalyst and the reaction conditions are the same, Can be obtained. That is, according to the above results, the method of synthesizing polyetherimide according to the present invention can synthesize PEI having a high degree of polymerization without the purification reaction of water, and the reaction is performed by applying a catalyst that has conventionally been used under the same conditions It can be confirmed that it can be performed in a shorter time.

Claims (7)

Dropping a clogende or crown ether ligand catalyst as a phase transfer catalyst in a reaction vessel where the solvent (S1) and the bisimide monomer represented by the following formula (1) are introduced at a concentration of 10% to 30%; And
≪ Formula 1 >

Wherein A is selected from among F, Cl, Br, I and NO ₂ , R ₁ is selected from the group consisting of Cyclohexane, Cyclopentadiene, A bivalent linking group derived from one organic compound selected from biphenyl and diphenyl ether, or phenylene.
(S2) In step (S1), an anionic monomer represented by the following formula (2) is added dropwise to the reaction vessel in which the catalyst is dropped in the same molar amount (within an error range of 0.05) as that of the bisimide monomer and reacted to obtain a polyetherimide ≪ RTI ID = 0.0 > polyetherimide < / RTI >
(2)

Wherein B is K or Na and R ₂ is selected from alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, phenylene, divalent biphenyl, bivalent diphenyl sulfone, bivalent diphenyl ketone and bivalent diphenyl propane One species.
The method according to claim 1, wherein the reaction tank is disposed in an oil bath, and the oil bath is heated to 130 to 210 캜 in step (S1).
The method of claim 1, wherein the solvent is selected from the group consisting of toluene, xylene, ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, diphenylsulfone, , Veratrol, and mixtures thereof. ≪ RTI ID = 0.0 > 8. < / RTI >
The catalyst according to claim 1, wherein the catalyst is at least one of 18-Crown-6 and Cryptand 221 when B is Na in Formula 2, and 21-Crown-7 and Cryptand 222 when B is K in Formula 2 ≪ RTI ID = 0.0 > 1, < / RTI >
The method for synthesizing polyether imide according to claim 1, wherein the catalyst is added in an amount of 0.01 to 0.1 mol% based on the total moles of the bisimide monomer.
The method for synthesizing polyetherimide as claimed in claim 1, wherein the reaction in (S2) is performed for 1 to 5 hours.
The polyetherimide synthesis method according to claim 1, wherein the polyetherimide obtained in the step (S2) has a weight average molecular weight of 10,000 to 70,000.

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