JPH03181519A - Polyether-based block copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, excellent in crystallinity and heat resistance and useful in automotive fields, etc., by reacting a dihalogenobenzonitrile with hydroquinone under specific conditions and then reacting the reaction system with the hydroquinone and a dihalogenobenzophenone. CONSTITUTION:The objective copolymer, obtained by reacting (A) a dihalogenobenzonitrile with (B) hydroquinone in the presence of an alkali metal compound in a neutral polar solvent and then reacting the resultant reaction system with the component (B) and a 4,4'-dihalogenobenzophenone and having 0.15-0.35 molar composition ratio [formula I/(formula I + formula II)] of recurring units expressed by formula I (m is as follows: 10<=m<=100) and recurring units expressed by formula II and >=500P melt viscosity at 400 deg.C temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyether block copolymer and a method for producing the same, and more specifically.

It has crystallinity and exhibits sufficient heat resistance, as well as excellent solvent resistance and mechanical strength.
This invention relates to a polyether-based polycopolymer useful as a material in the mechanical field, etc., and a manufacturing method that can efficiently obtain it through simple steps.

[Prior art and problems to be solved by the invention] In recent years,
Plastics having various structures have been developed as engineering resins and are used in a wide range of fields, such as the automobile field, electrical/electronic field, TRI-secure machinery field, OA equipment field, and optical communication equipment field.

However, its performance has not yet reached full satisfaction in all aspects, and furthermore, the required performance has become stricter, so the development of new materials is desired.

On the other hand, a polyether copolymer, which is one of these engineering resins, is a resin particularly excellent in heat resistance, and various proposals have been made regarding this resin as well.

For example, in Japanese Patent Application Laid-open No. 47-14270,
A method for producing an aromatic polyether copolymer has been proposed in which dinitrobenzonitrile, dihalogenobenzophenone, and dihydric phenol are reacted in the presence of an alkali metal compound.

However, according to this method, only a low molecular weight copolymer with a melt viscosity of less than 200 voids at 400°C can be obtained, and the resulting copolymer cannot be said to have sufficient heat resistance or mechanical strength. hard.

Furthermore, in JP-A No. 60-235835, by simultaneously reacting dihalogenobenzonitrile, 4,4'-dihalogenobenzophenone, and an alkali metal salt of a dihydric phenol, a compound represented by the following formula (a): and a repeating unit represented by the linear formula (b) (however, Ar in the above formula is a divalent aromatic group), and the composition of the repeating unit represented by the above formula (a). A method for producing a polyether copolymer having a ratio of 0.5 or more has been proposed.

However, since this polyether copolymer is amorphous, it cannot maintain mechanical strength in a temperature range exceeding the glass transition temperature, and cannot be said to have sufficient heat resistance.

The present invention has been made to improve the above situation.

The object of the present invention is to create a novel polyether block copolymer that is crystalline and exhibits extremely excellent heat resistance, has a sufficiently high molecular weight, has excellent mechanical strength, etc., and is useful as a new material. The object of the present invention is to provide a manufacturing method that can efficiently obtain this polyether block copolymer.

[Means for solving the problem The invention of claim 1, which is a distant relative of the above object, is based on the following formula (
I); (I) (1m is an integer satisfying 10≦m≦100)
A repeating unit represented by the following formula (■); 4 consisting of a repeating unit represented by
+(II))] is from 0.15 to 0.35, and has a melt viscosity of 500 voids or more at a temperature of 400°C.

Further, the invention according to claim 2 provides a method of reacting dihalogenobenzonitrile and hydroquinone in a neutral polar solvent in the presence of an alkali metal compound, and then adding hydroquinone and 4.4'-dihalogenobenzophenone to the reaction system. This is a method for producing a claimed polyether block copolymer, which comprises adding and reacting the above polyether block copolymers sequentially or simultaneously.

The present invention will be explained in detail below.

- Polyether block copolymer - The important point in the polyether block copolymer according to claim 1 is that the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) are and the composition ratio of the repeating unit represented by the formula (I) is a molar ratio [(1)/I(I)+(II))]
is in the range of 0.15 to 0.35, and m is 10<
m < 100.

If the composition ratio of the repeating unit block represented by the formula (1) is less than 0.15, the glass transition temperature of the polyether block copolymer will be low, resulting in a decrease in heat resistance or a high melting point. This may lead to a decrease in moldability. On the other hand, when it exceeds 0.35, the crystallinity of the polyether block copolymer is lost, and heat resistance, solvent resistance, and chemical resistance are reduced.

Moreover, if m is less than 10, no blocking effect will occur, and if m exceeds 100, a homopolymer will be produced, which is not preferable.

Furthermore, it is important that the polyether block copolymer of the present invention has a melt viscosity of 500 voids or more at a temperature of 400'C.

This is because a low molecular weight polyether block copolymer having a melt viscosity of less than 500 voids cannot maintain sufficient heat resistance and mechanical strength.

The polyether block copolymer of the present invention has a crystal melting point of about 330 to 400°C, has crystallinity, has a sufficiently high molecular weight, exhibits sufficient heat resistance, and has excellent solvent resistance. It has excellent mechanical strength and can be suitably used as a new material in, for example, electrical/electronic equipment fields, mechanical fields, etc.

1. Method for producing a polyether block copolymer - The polyether block copolymer according to claim 1 is prepared by adding dihalogenobenzonitrile and hydroquinone to an alkali metal compound according to the method according to claim 2. After reacting in the presence of a neutral polar solvent (first step), hydroquinone and 4,4'-dihalogenobenzophenone are reacted sequentially or in addition to the same (second step). , can be manufactured.

In this method, specific examples of the dihalogenobenzonitrile used include 2,6 dihalogenobenzonitrile represented by the following formula: (However, in the formula, X has the same meaning as above.) 2,4-dihalogenobenzonitrile and the like can be mentioned.

Among these, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2.4
-dichlorobenzonitrile, 2,4-difluorobenzonitrile, and particularly preferred is 2,6-dichlorobenzonitrile.

In the method of the present invention, as a first step, the dihalogenobenzonitrile and hydroquinone represented by the following formula are reacted in a neutral polar solvent in the presence of an alkali metal compound.

The alkali metal compound is not particularly limited as long as it can convert the hydroquinone into an alkali metal salt, and preferred are alkali metal carbonates and alkali metal hydrogen carbonates.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal carbonated water; J salt include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.

Among these, preferred are sodium bicarbonate, '
rRW potassium hydrogen.

In the method of the present invention, among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzizoic acid amide, N-methyl-2-pyrrolidone, N
-ethyl-2-pyrrolidone, N-inpropyl-2-
Pyrrolidone, N-isobutyl-2-pyrrolidone, N-n
-Propyl-2-pyrrolidone, Nn-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-
Methyl-2-pyrrolidone, N-methyl-3,4,5-)
Riftyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2
-piperitone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ditylbiperitone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxinsulfolane, 1-ethyl-1-oxinsulfolane,
Examples include 1-phenyl-1oxosulfolane, N,N-dimethylimidazolidinone, and diphenylsulfone.

The proportion of the dihalogenobenzonitrile used is a molar ratio to the total amount of dihalogenobenzonitrile and 4,4°-dihalogenobenzophenone, and is usually 0.15 to 0.3.
5. Preferably the ratio is 0.2 to 0.3.

If the molar ratio is less than 0.15, the glass transition temperature of the resulting copolymer will be lowered, resulting in insufficient heat resistance, and the melting point will be higher, leading to a decrease in moldability. If the ratio is greater than 0.35, the resulting copolymer will be amorphous, resulting in a decrease in not only heat resistance but also solvent resistance and chemical resistance.

Further, the proportion of the hydroquinone used is 0.90 to 0.99 or 1.01 to 10 in molar ratio to the dihalogenobenzonitrile.

In the present invention, by adjusting the molar ratio within the above range so that the amount of hydroquinone used is slightly insufficient or excessive relative to dihalogenobenzonitrile, the uninvented method can be obtained. Block copolymers can be produced.

When this molar ratio is less than 0.90 or more than 1.10, it is not possible to obtain a block copolymer, and when the molar ratio is more than 0.99 or less than 0.01, +ii
This is not preferable because it produces a homopolymer consisting of units of formula (1).

The ratio of the alkali metal compound used is usually 1.01 to 2.5 per hydroxyl group of the hydroquinone.
The proportion is 0 equivalents, preferably 1.02 to 1,20 equivalents.

There is no particular restriction on the amount of the neutral polar solvent used, but it is usually the sum of the dihalogenohenzonitrile, the hydroquinone, and the alkali metal compound +oo
z3. Per part, 200-2,000j%E part is selected.

The reaction temperature in the first step is usually 150 to 250°C,
The temperature is preferably 180 to 210°C, and the reaction time is usually 30 minutes to 3 hours, preferably 40 minutes to 2 hours.

In the production method of the present invention, in the second step, the reaction product (oligomer) obtained in the first step, hydroquinone, and 4,4°-dihalogenobenzophenone are reacted.

The above-mentioned 4,4'-dihalogenobenzophenone used is a compound represented by the following formula: (wherein, X has the same meaning as above), and in the method of the present invention, 114,4'-difluoro Benzophenone and 4.4"-dichlorobenzophenone can be particularly preferably used.

In the second step, the amount of hydroquinone used is substantially 1 mol 51.5% based on the total amount of the dihalogenobenzonitrile and 4,4'-dihalogenobenphenone. This is the counterfeit obtained by subtracting the moles of l\hydroquinone consumed in the first step.

In the second step, hydroquinone is charged first and 4,4'-dihalogenobenzophenone is charged later, or hydroquinone and 44°-dihalogenobenzophenone are charged simultaneously.

In the case of +iil Pt, the reaction temperature between the reaction product obtained in the first step and hydroquinone is usually 150 to 3
The temperature is 50°C, preferably 180 to 320°C, and the reaction time is usually 30 minutes to 3 hours, preferably 30 minutes to 1 hour. The reaction temperature when 4.4'-dihalogenobenzophenone is added later may be the same as above, but the reaction time is usually 30 minutes to 5 hours, preferably 30 minutes to 2 hours.

In the latter case, that is, when hydroquinone is charged simultaneously with 4,4°-dihalogenobenzophenone, the reaction temperature with the reaction product obtained in the first step may be the same as above, but
The reaction time is usually 10 minutes to 5 [1 yen], preferably 30 minutes to 2 hours.

In either case, if the reaction temperature is less than 150°C, the reaction will be
! ! ! The temperature is too slow to be practical, 350'C
Exceeding this may lead to side reactions.

After completion of the reaction at about 2° C., the desired polyether block copolymer can be separated from the neutral polar solvent solution and produced according to a known method.

In this way, according to the present invention, the polyether block copolymer described in claim sn 1 can be easily prepared. It can be efficiently manufactured with nL.

[Examples] Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples.

(Example 1) First process: 16.85 g of hydroquinone (0,153
mole), 2. S-dichlorohenodinitrile 25.8
0 g (0.15 mol),) potassium pyrochloride 82.9
g (0.6 mol) and N-methyl-2-pyrrolidone 0.
After argon gas was introduced, the temperature was raised from room temperature to 195°C over 1 hour.

After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy. Thereafter, the reaction was carried out at 195°C for 1 hour.

When the molecular weight of the product (oligomer) obtained here was measured by foul pressure osmosis method (VPO method), the V average molecular weight was 5.
It was 800.

2nd step: Add hydroquinone 3 to the solution of the product obtained in the 1st step.
A solution of 7.65 g (0,315 mol) of N-methyl-2-pyrrolidone dissolved in 0.7 mol of N-methyl-2-pyrrolidone was added and reacted at 195°C for 30 minutes. A solution of 0.15 mol) dissolved in 0.71 mol of N-methyl-2-pyrrolidone was added, and the mixture was reacted at 195°C for 1 hour.

In this second step as well, toluene was added to the produced water to remove water by azeotropy.

Recovery of co-π polymer: After the reaction path T of the second step, the product was pulverized using Brengu, washed with methanol, water, and methanol in this order, and dried to obtain 126.5 g of copolymer (yield 96%). I got it.

Identification of the J1 coalescence obtained in this way: Infrared absorption spectrum analysis of the J1 coalescence obtained in this way revealed that there was an absorption by the nitrile group at the 222°ClIn river position and an absorption by the carbonyl group at the 1650 cm-1 position. Absorption due to an ether bond was confirmed at the 1240 cm I position.

From these results, the results of elemental analysis, and the results of molecular oxygen measurement using the VPO method described above, this co-π polymer was recognized to be a polyether-based block copolymer having the following chemical structure.

(I) (n) Molar composition ratio [(1) / (CI) + (n) l E = o,
3° However, m is 28.

Measurement of physical properties: 400 for the above polyether blow 2 copolymer
The melt viscosity (zero shear viscosity) at °C, glass transition temperature, crystal melting point, and thermal decomposition onset temperature were measured.

The results are shown in Table 1.

Next, the degree of crystallinity was measured based on the scattering intensity by wide-angle X-rays, and it was found to be 38%. Regarding solvent resistance, it was insoluble in acetone, chloroform, carbon tetrachloride, methylene chloride, ethanol, toluene, and xylene, and was not attacked by hydrochloric acid or nitric acid. Further, a test piece was injection molded from this polyether-based blown copolymer, and its tensile strength, bowing elastic modulus, and elongation were measured in accordance with ASTM D-638.

The results are shown in Table 2.

(Example 2) Hydroquinone and 2.6- in the first step of Example 1
The same procedure as in Example 1 was carried out, except that the molar ratio of the molar ratio of dichlorobenzonitrile to dichlorobenzonitrile was 1.03, and the molar ratio of 2,6-dichlorobenzonitrile to 4.4'-difluorobenzophenone was 0.2. A polyether block copolymer having the following chemical structure was produced.

Example 1 shows the physical properties of this polyether block copolymer.
It was measured in the same manner.

The results are shown in Tables 1 and 2.

Note that the solvent resistance and acid resistance of this polyether block copolymer were the same as in Example 1.

(I) (II) Molar composition ratio [(I) / (CI) + (II) l ] =0.
30 However, m is 18.

(Example 3) fjIJl process: Same as the first step of Example 1.

2nd step: 37.65 g (0,315 mol) of /hydrone and 76.37 g (0,35 mol) of 4,4-difluorobenzophenone were added to the oligomer solution obtained in the 1st step. A solution dissolved in 1.4 grams of N-methyl-2-pyrrolidone was added and reacted at 195°C for 1 hour.

Note that the produced water was removed by azeotropic distillation with the addition of toluene.

Recovery of copolymer: After the completion of the reaction in the second step, the product is pulverized with a blender,
Wash with methanol, water, methanol in this order, dry,
129.1 g (yield 98%) of copolymer was obtained.

Identification of copolymer: Infrared absorption spectrum analysis of the above copolymer revealed that there was an absorption by a nitrile group at a position of 2.220 cm and an absorption by a carbonyl group at a position of 1,650 cm. However, absorption due to an ether bond was confirmed at a position of 1,240 cm l.

From these results, the results of elemental analysis, and the results of molecular weight measurement by VPO method, this copolymer was recognized to be a polyether block copolymer having the following chemical structure.

(I) (TI) Molar composition E (I) / ((:I) + (IT) l ]
=0.30 However, 1m is 28.

Measurement of physical properties: The physical properties of the polyether block co-hair polymer were measured in the same manner as in Example 1.

The results are shown in Tables 1 and 2.

The solvent resistance and acid resistance of the polyether block copolymer described in Section 4 were the same as in Example 1.

Table 1 [Effects of the Invention] (1) The polyether-based block copolymer of the invention of Claimeda 1 exhibits a specific melt viscosity at a specific repeating medium with a composition ratio within a specific range. Therefore, it has a sufficiently high molecular weight, exhibits sufficient heat resistance due to its crystallinity, and is also excellent in mechanical strength, solvent resistance, etc.

Therefore, it is useful as a new material in the fields of electricity, electronic equipment, machinery, etc.

(2) According to the invention of claim 2, the novel polyether block copolymer having the above-mentioned excellent properties is
It is possible to provide an industrially useful manufacturing method that can be efficiently obtained through simple steps.

Claims (2)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, m is an integer satisfying 10≦m≦100)
A repeating unit represented by the following formula (II); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) Consisting of a block of repeating units represented by the following formula (II), the molar composition ratio of the repeating unit represented by the formula (I) [ (I
)/{(I)+(II)}] is from 0.15 to 0.35, and has a melt viscosity of 500 poise or more at a temperature of 400°C. (2) Dihalogenobenzonitrile and hydroquinone are reacted in a neutral polar solvent in the presence of an alkali metal compound, and then hydroquinone and 4,4'-dihalogenobenzophenone are added sequentially or simultaneously to the reaction system. 2. The method for producing a polyether block copolymer according to claim 1, which comprises: