WO2016108668A1 - Method for synthesis of polyetherimide - Google Patents

Abstract

The present invention relates to a method for synthesis of a polyetherimide, comprising the steps of: (S1) dripping, as a phase transfer catalyst, a cryptand or a crown ether-based ligand catalyst into a reactor into which a solvent and a bisimide monomer have been added in a concentration between 10% and 30%; and (S2) dripping an anionic monomer represented by formula 2 below, with the same molar amount (error range: within ±0.05) as the bisimide monomer, into the reactor dripped with the catalyst in step (S1) and reacting the same to thereby obtain polyetherimide.

Description

Polyetherimide Synthesis Method

The present invention relates to a method for synthesizing polyetherimide.

Polyetherimide (PEI), a kind of polyimide, has an imide group that imparts heat resistance and strength in the molecular structure and an ether group that can improve processability (formability), thereby improving processability compared to general polyimide. Amorphous thermoplastic polymer. Since polyetherimide has high heat resistance, excellent dimensional and thermal stability, chemical resistance and flame resistance, plastic resins including these are widely used in electric and electronic parts such as DC converters, semiconductor trays, HDD board holders, automotive parts, aircraft sheet fibers, and eyeglasses. It is used.

Polyetherimides can generally be prepared in two ways. In the first method, dianhydride monomers and diamine monomers having a soft group by intramolecular ether (ether, -O-) bonds are converted into dimethylacetamide (DMAc), dimethylformamide (DMF), and N-methyl-2-pyrrolidone. It is a method of preparing PEI by polymerizing in a solvent such as (NMP) to make polyamic acid (PAA) and thermally or chemically curing it. Since this method is difficult to proceed with 100% imidization without an additional process, there is a high possibility that physical property changes occur in the process of making a product (extrusion, injection) using PEI.

On the other hand, the second method is a method of preparing PEI by adding a monomer containing a halogenated bisimide and hydroxide ion 100% imidization in a solvent, followed by high-temperature polymerization under a catalyst. Since this method uses 100% imidized monomer, sufficient imidization is possible without additional process, and there is no change in physical properties in the process of making a product (extrusion, injection). In spite of the disadvantage that there is a limitation that it is difficult to control the molecular weight of PEI by side reaction because high temperature conditions are required, the second method is more usefully applied to the polyetherimide manufacturing method than the first method. .

Regarding the process for preparing polyetherimides from bisimides, US Pat. No. 5,229,482 discloses a low polar solvent such as dichlorobenzene in the presence of a thermally stable phase transfer catalyst such as hexaalkylguanidinium halide. A method for the production of polyetherimides using is disclosed. U. S. Patent No. 5,830, 974 also discloses the use of monoalkoxybenzenes such as anisol as solvents.

Despite these prior arts, the development of optimal methods for the production of polyetherimides from bisimides still remains a challenge. In particular, in the manufacturing field, it is important to develop a method for obtaining a high molecular weight polyetherimide in a short time.

Accordingly, the present invention is to provide a method for synthesizing a high molecular weight PEI in a reaction time faster than using a conventionally used catalyst such as hexaalkylguanidinium in the polyetherimide (PEI) manufacturing method .

Preferred embodiments of the present invention for solving the above problems is (S1) krypton or crown ether ligand as a phase transfer catalyst to the reaction tank in which the solvent and the bisimide monomer represented by the formula (1) at a concentration of 10% to 30% Dropping the catalyst; And (S2) anionic monomer represented by the following Chemical Formula 2 is added dropwise to the reaction tank in which the catalyst is dropped in the step (S1) in the same molar amount (within an error range of ± 0.05) and reacted with the polyetherimide. Polyetherimide synthesis method comprising the step of obtaining.

<Formula 1>

In Formula 1, A is one selected from F, Cl, Br, I, and NO ₂ , and R ₁ is Cyclohexane, Cyclopentadiene, Or a divalent bonding group derived from one organic compound selected from biphenyl and diphenyl ether, or phenylene.

<Formula 2>

In Formula 2, B is K or Na, R ₂ is selected from alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, Phenylene, divalent biphenyl, divalent diphenyl sulfone, divalent diphenyl ketone, and divalent diphenyl propane. It is one kind.

Reactor according to the embodiment is disposed in an oil bath (oil bath), the oil bath may be to be heated to 130 to 210 ℃ in step (S1).

In addition, the solvent according to the embodiment is toluene, xylene, ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, phentol, anisole , Beratrol and a mixture thereof may be one or more selected, and the catalyst is at least one of 18-Crown-6 and Cryptand 221 when B is Na in Formula 2, and B is K in Formula 2 In this case, it may be at least one of 21-Crown-7 and Cryptand 222.

In this case, the catalyst is preferably added 0.01 to 0.1 mol% based on the total moles of bisimide monomer.

Furthermore, the reaction in (S2) according to the above embodiment may be performed 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 monomer using a polar catalyst, by using a catalyst in which no ions are present in the molecular structure, a small amount of catalyst can be synthesized in a shorter time without additional water purification process. 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 may be easier for a method for preparing PEI using an anionic monomer comprising Na or K ions.

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

The present invention has been proposed as a method for preparing polyetherimide from bisimide monomers which already contain imide groups in the monomer structure, and has a kryptan or crown ether ligand catalyst instead of hexaalkylguanidinium which has been used as a phase transfer catalyst. By using it can provide a method for synthesizing a polyetherimide having a high degree of polymerization within a fast reaction time without removing the water.

In general, in the preparation of polyetherimide using bisimide monomers, anionic salts are used as reactants with bisimides. However, the anionic salts do not dissolve well when they are not protic solvents such as water or alcohol. However, since the solvent capable of dissolving the bisimide monomer is not a protic solvent, a catalyst may be used to dissolve the anionic salt in the solvent in the reaction using the bisimide monomer.

In the past, hexaalkylguanidinium chloride was used as the catalyst. However, in this case, hexaalkylguanidinium chloride is difficult to remove water bound during synthesis due to the presence of ions in the molecule, and easily with water in the air encountered during the experiment. There is a drawback to combining. Accordingly, when the reaction is not properly controlled, the imide bond group is attacked and broken by water, and thus, PEI of high degree of polymerization cannot 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 not essential.

However, in the case of the krypton or crown ether ligand catalyst used in the present invention, since there is no polarity, it is easy to remove moisture even during the synthesis process. In addition, since it does not bind easily with the water encountered during the process of the experiment, a separate process of refining the water is unnecessary, and thus, the synthesis can be made more easily, and since the imide group is not broken by water, PEI of degree of polymerization can be obtained.

The specific method of the present invention which enables this can be carried out in the following steps.

Step 1 (S1)

First, the polyetherimide production method of the present invention is a step of dropping a krypton or crown ether ligand catalyst as a phase transfer catalyst to the reaction tank in which the solvent and the bisimide monomer represented by the following formula (1) at a concentration of 10% to 30% Starts from.

<Formula 1>

In Formula 1, A is one selected from F, Cl, Br, I, and NO ₂ , and R ₁ is cycloclohexane

Cyclopentadiene

, Biphenyl

And diphenyl ether

A divalent bonding group derived from one organic compound selected from among

to be.

At this time, the solvent is preferably selected as a solvent in which the bisimide monomer can be dissolved, toluene, xylene, ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4-tri It may be one or more selected from chlorobenzene, diphenyl sulfone, phentol, anisole, beratrol and mixtures thereof.

In the bisimide monomer, the substituent A may be advantageous to use a halogen atom group having a high electronegativity or NO ₂ , because the polymerization reaction with the anionic monomer may proceed only when leaving as a leaving group. In addition, the bisimide monomer is preferably added to the solvent in a concentration of 10% to 30%, when the concentration is less than 10% is low concentration can produce only low molecular weight PEI, when the concentration is greater than 30% As a result, the monomer may not be dissolved in the solvent, and thus the monomer may not participate in the reaction, resulting in low yield or high viscosity in the solvent.

In the present invention, the reaction tank is disposed in an oil bath, and the oil bath is preferably heated to 130 to 210 ° C, more preferably 150 to 200 ° C in 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 better dissolved in the solvent in the reactor. When the temperature of the oil bath is 210 ° C. or less, a sufficiently high molecular weight PEI may be obtained. However, when the temperature of the oil bath is less than 130 ° C., since the polymerization may not be sufficiently performed in the reaction, the molecular weight of the final obtained PEI may be low.

On the other hand, the catalyst is added to improve the solubility in the solvent of the anionic monomer to be introduced in step 2 (S2) to be described later, it is preferable that it is a krypton or crown ether ligand catalyst. In particular, in consideration of the type of anionic monomer to be added in step (S2), when Na ion is included in the anionic monomer, 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 may be preferred that the catalyst is added in an amount of 0.01 to 0.1 mol% based on the total moles of bisimide monomer. When the addition amount of the catalyst is less than 0.01 mol%, it is not preferable because the reaction rate is slow and the desired molecular weight can be obtained. If the amount is more than 0.1 mol%, the reaction rate is rather slow and the problem that the desired molecular weight cannot be obtained may occur.

As shown in FIG. 1, the catalyst of the present invention is a multidentate ligand which is cross-linked in three dimensions to form a ring shape, and has the characteristic of trapping alkali metal ions, particularly Na or K, in a three-dimensional space to form a chelate complex. In the case of hexaalkyl guanidium chloride, which is commonly used in the production of polyetherimide, since ionic bonds exist in the molecule, it is easily combined with moisture generated in the PEI synthesis process or moisture present in the air. Although a purification process is required, the catalyst of the present invention is excellent in the activity of the catalyst even without the process of removing water in the synthesis process because there is no ionic bond in the molecule, it is possible to obtain a high molecular weight PEI in a short time .

Step 2 (S2)

Subsequently, the present invention is added dropwise anionic monomer represented by the following formula (2) to the reaction tank in which the catalyst is dropped in the step (S1) in the same molar amount (within the error range ± 0.05) and the temperature increase in the step (S1) By reacting at this temperature, polyetherimide can finally be obtained.

<Formula 2>

In Formula 2, B is K or Na, R ₂ is alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, and phenylene.

, Divalent biphenyl

Divalent diphenyl sulfone

Divalent diphenyl ketone

And divalent diphenyl propane

It is one selected.

In the present invention, the anionic salt is a diol or phenolic anionic salt having two hydroxyl groups (-OH), diol or hydroquinone such as ethylene glycol, 4,4'-hydroxy bisphenol, bis (4- In phenolic compounds such as hydroxidephenyl) sulfone, bis (4-hydrophenyl) ketone, bisphenol A and the like, it is preferable that H of the hydroxyl group is substituted with potassium (K, potassium) or sodium (Na, sodium). Accordingly, as the anionic salt is ionized, potassium cation (K ⁺ ) or sodium cation (Na ⁺ ) is collected by the catalyst, and the portion showing the anion is a halogen atom having a high electronegativity at the end of bisimide or NO _2. Instead of giving electrons to the polyetherimide, it forms an ether bond with the bisimide terminal instead.

In this case, as the anionic salt is substituted with potassium or sodium, the capture activity by the catalyst becomes more active, and thus the reaction rate can be significantly increased even with a small amount of the catalyst. That is, if the purification process of water is omitted under the same amount of catalyst, when prepared according to the production method of the present invention, the weight average molecular weight (Mw) is 10,000 to 70,000, more preferably 20,000 even after 1 to 5 hours of reaction Polyetherimide of from 70,000 to 70,000, most preferably 50,000 to 70,000 can be obtained, but when using hexaalkyl guanidium chloride (Hexaethyl guanidium Chloride) reaction time of 4 hours to 6 hours to obtain an equivalent degree of polymerization This is more demanding. That is, considering that ultimately the process of purifying water is an unnecessary method, the present invention is to provide an efficient polymerization method for producing a high polymerization degree PEI in a short time.

The weight average molecular weight (Mw) described in the present invention may mean that polystyrene reduced weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC) (manufactured by Waters, model name e2695). More specifically, the polymer to be measured is dissolved in dimethylformamide (DMF) so as to have a concentration of 1%, 20 μl of GPC is injected, and flows at a flow rate of 1.0 mL / min, and the analysis is performed at 30 ° C. To perform. At this time, the column can be used by connecting two Styragel HR3 in Waters in series, the detector is measured at 40 ℃ using RI detector (Waters, 2414) as a detector.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for 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.

Bisimide monomer: Bis-4-Chlorophthalimide-4-phthalimidobenzene (B-4-CPI-4-PIB, Mw: 437.535), Bis- (4-chlorophthalimido)) phenyl-4 '-(N-phthalimido) phenyl ether (B-4-CPI-4-PPE, Mw: 529.33)

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

Solvent: O-dichlorobenzene (ODCB, Solvent)

Phase transfer catalysts: Cryptand 222 (Mw: 376.488), Cryptand 221 (Mw: 332.44)

Example 1

100 ml ODCB and 9.6 g (22.0 mmol) of B-4-CPI-4-PIB were added to a 250 ml three-necked flask placed in an oil bath, and the temperature was increased until the temperature of the oil bath reached 150 ° C. CPI-4-PIB was dissolved in the solvent. In addition, 0.00082g, that is, 0.01 mol% (0.0022 mmol) of Cryptand 222 was added dropwise to the flask. Subsequently, 6.7 g (22.0 mmol) of BPAP-2 was added dropwise to the heated solution using a funnel, and when the dropping was completed, the mixture was stirred for 3 hours while maintaining a temperature rising temperature of 150 ° C. 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 as a synthesized PEI form.

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 relative 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 elevated temperature was increased from 150 ° C to 180 ° C.

Example 5

PEI was synthesized in the same manner as in Example 1 except that the final elevated temperature was increased from 150 ° C. to 200 ° C.

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) instead of BPAP-2 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 elevated temperature was lowered from 150 ° C. to 100 ° C.

Example 12

PEI was synthesized in the same manner as in Example 1 except that the final elevated temperature was lowered from 150 ° C. to 140 ° C.

Example 13

PEI was synthesized in the same manner as in Example 1, except that the final elevated temperature was set to 210 ° C.

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 relative to the bis imide 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 relative to the bis imide monomer (B-4-CPI-4-PPE).

Comparative Example 1

PEI was synthesized in the same manner as in Example 1, except that no catalyst was used.

Comparative Example 2

PEI was prepared in the same manner as in Example 1, except that 0.1 mol% (0.022 mmol) of Hexaethyl Guanidium chloride (Angene Chemical, China) catalyst was used relative to the bisimide monomer (B-4-CPI-4-PIB). Synthesized.

Comparative Example 3

PEI was synthesized in the same manner as in Comparative Example 2, except that moisture generated in the synthesis process 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 raised to 200 at 150 ° C.

Subsequently, the molecular weight (Mw) of PEI obtained from Examples 1 to 10 and Comparative Examples 1 to 9, respectively, was measured using poly permeation chromatography (GPC), and the results are reflected in Table 1 below. It was.

Table 1

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

As can be seen from Table 1, in the case of Example 1 of the present invention using the krypton as the phase transfer catalyst, the degree of polymerization of PEI obtained compared to Comparative Example 1 without using a catalyst, or Comparative Example 2 using HEGCI as a catalyst Was confirmed to be high. In addition, as in Example 2 or 3, when the content of the catalyst is further increased, it was found that the degree of polymerization was equal to or higher than that of Comparative Example 3, which induced a positive reaction while removing water. However, when the catalyst content exceeds 0.1 mol% of the monomer content, as in Examples 14 and 15, rather the reaction rate was confirmed that the desired molecular weight may be lowered.

On the other hand, in the same reaction time as in Examples 1, 4 and 5, it was confirmed that sufficient polymerization is performed at 150 to 200 ° C. However, when the temperature is lowered as in Examples 11 and 12, the degree of polymerization may be somewhat decreased, but As shown in Fig. 13, higher temperature does not indicate higher degree of polymerization. In addition, in the same reaction time as in Examples 4 to 5, the polymerization degree may be improved when the reaction temperature is high, but as can be seen from Examples 5 and 8, even if the reaction time is up to 5 hours, the degree of polymerization is not greatly improved. Seemed to

In particular, by comparing the results of Example 5 and Comparative Example 4 or comparing the results of Example 9 and Comparative Example 3, when the amount of the catalyst and the reaction conditions are the same, the present invention can be reacted with the same degree of polymerization (PEI) even without purification. It could be confirmed that can be obtained. That is, according to this result, the polyether imide synthesis method according to the present invention can synthesize PEI of a high degree of polymerization without purifying water, and the reaction is to apply a catalyst that has been used conventionally under the same conditions. It could be confirmed that it can be made in a shorter time.

Claims (7)

1. (S1) dropping a krypton or crown ether ligand catalyst as a phase transfer catalyst into a reaction tank in which a solvent and a bisimide monomer represented by Formula 1 are added at a concentration of 10% to 30%; And

   <Formula 1>

   

   In Formula 1, A is one selected from F, Cl, Br, I, and NO ₂ , and R ₁ is Cyclohexane, Cyclopentadiene, Or a divalent bonding group derived from one organic compound selected from biphenyl and diphenyl ether, or phenylene.

   (S2) Anionic monomer represented by the following Chemical Formula 2 is added dropwise to the reaction tank in which the catalyst is dropped in the step (S1) in the same molar amount (within the error range ± 0.05) and reacted to obtain a polyetherimide. Polyetherimide synthesis method comprising the step of.

   <Formula 2>

   

   In Formula 2, B is K or Na, R ₂ is selected from alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, Phenylene, divalent biphenyl, divalent diphenyl sulfone, divalent diphenyl ketone, and divalent diphenyl propane. It is one kind.
2. 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 ° C in step (S1).
3. The method of claim 1, wherein the solvent is toluene, xylene, ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, phentol, anisole , Beratrol and a mixture thereof, at least one selected from polyetherimide synthesis method.
4. The method according to claim 1, wherein the catalyst is at least one of 18-Crown-6 and Cryptand 221 when B in the formula (2), Na, 21-Crown-7 and Cryptand 222 when B is K in the formula (2) Polyether imide synthesis method, characterized in that at least one of.
5. The polyether imide synthesis method 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.
6. The polyetherimide synthesis method according to claim 1, wherein the reaction in (S2) is performed for 1 to 5 hours.
7. The polyetherimide synthesis method according to claim 1, wherein the polyetherimide obtained in (S2) has a weight average molecular weight of 10,000 to 70,000.

Images