JPS60252627A - Novel polyether imide and its preparation - Google Patents

Abstract

PURPOSE:A polyether imide having improved heat resistance, flame retardance, and solvent resistance, wherein raw materials are easily obtainable, prepared by reacting a dihydric phenol with a dihalide and an aminophenol in an alkali, reacting the reaction product with an acid anhydride, treating the resultant compound with water. CONSTITUTION:A dihydric phenol shown by the formula HO-Ar-OH (Ar is group shown by the formula I -formula III, etc.; R' is 1-13C bifunctional hydrocarbon) is reacted with a dihalide shown by the formula IV (R is -SO2-, or -CO-; X is halogen) and p-, or m-aminophenol in the presence of an alkali and a solvent to give an oligomer shown by the formula V (n is 1-50), which is reacted with an acid anhydride shown by the formula VI (Ar' is group shown by the formula VII, formula VIII, etc.) in a solvent, and treated with water or an alcohol, to give a polyether imide having a repeating unit shown by the formula IX, terminal groups of -NH2, group shown by the formula X, etc., and >=0.2dl/g reduced viscosity in 0.2g/dl concentration N-methylpyrrolidone solution at 30 deg.C.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a novel polyetherimide and a method for producing the same. This invention relates to easily available polyetherimide and its manufacturing method.

[Technical background of the invention and its problems]

Polyetherimide is known as an engineering glass tinx with excellent heat resistance.
No. 9-103997 discloses a method for obtaining polyetherimide by reacting an aromatic bis(ether acid anhydride) with an organic diamide.

However, in the case of the above method, there are problems in that it is not easy to produce the aromatic bis(ether acid anhydride) used as a raw material, and the heat resistance of the obtained polyetherimide is not necessarily sufficient.

(Object of the present invention) The present invention solves the above-mentioned problems and provides a polyetherimide whose raw materials are easily available, has good heat resistance, and also has excellent flame retardancy and solvent resistance. The purpose is to provide a manufacturing method.

[Summary of the invention]

The novel polyetherimide of the present invention (is (wherein R is -
802-or-C〇-gold representation.

shaO@-, (瀘S(warm, +So, @-1→gD←Rζg
← (wherein, R' represents a divalent hydrocarbon group having 1 to 13 carbon atoms, and Ar/ represents an integer of 1 to 50), and has a repeating unit with a constant terminal group. 2° (same meaning as above), and the reduced viscosity at 30°C of a solution with a concentration of 0.2 dA/dl using N-methylpyrrolidone as a solvent is 0.2 dA/ta or more. , its manufacturing method is as follows: HO-Ar-OH... Beating + SO□+ +
A dihydric phenol represented by R (where R' represents a divalent hydrocarbon group having 1 to 13 carbon atoms).

The following formula: A dihalide and p- or m-aminophenol are reacted in the presence of an alkali and a solvent.

'@-@-Peng...■ (In the formula, R and Ar each have the same meaning as above, and n represents an integer from 1 to 50.) Then, the oligomer is reacted with an acid anhydride represented by the following formula (wherein Ar', 71 σ- represents 〉r〉r〉r℃) in the presence of a solvent.

It is characterized in that the resulting reaction product is then treated with water or alcohol.

The novel polyetherimide of the present invention has a skeleton in which a plurality of repeating units of the formula (CI) formed by polycondensation of the oligomer (2) and the acid anhydride of the formula (9) are connected in a linear chain. ,
The whole terminal is plotted with -NH2,%ol,
.

The polyetherimide of the present invention is dissolved in this polyetherimide kN-menalpyrrolid to a concentration of 0.2f.
/dl, the solution has a molecular weight such that the reduced viscosity (ηsp/c) at 30°C is 0.2 dllIP or more. This ηsp/c is 0.2dllIP
If the degree of polymerization is less than that, the heat resistance will decrease because the monopolymer has a low molecular weight.

The polymerization process of the present invention is produced as follows: a dihydric phenol represented by formula (1), a dihalide represented by formula (g)), and p- or m-aminophenol are mixed in the presence of an alkali. An oligomer production reaction in which an oligomer represented by formula (IV) is obtained by reacting with a solvent and conditions described below.

It is produced by a polycondensation reaction in which this oligomer and the acid anhydride represented by the formula (9) are reacted in a solvent and a columnar atmosphere described below to obtain the desired product. This acid anhydride represented by Formula 1 (b) functions as a condensing agent.

In the compound of formula (II), Ar may be any of those listed above, but in particular <◇(Saka).

In the compound of formula (IIl), R is -502- or -CO
-, and halogen/X is preferably F or C6. Further, in the compound of formula 1, Ar' may be any of those listed above, but especially 1, r
K, p, etc. are preferred.

In the oligomer production reaction, formula (n) and formula (1
The amount of the compound of formula 1) to be used is determined from the relationship with the degree of polymerization of the target polyetherimide, but if the amount of the compound of 20) is 1 a mole and the amount of the compound of formula 1 is b mole. It is preferable that the following relationships are established: 0.6≦Yb≦0.9.

The reaction takes place in an electric medium. There are various solvents that can be used. Solvent 1 For example, dimethylformamide, dimethylacetamide, N-methylpyrolide, dimethylformhokind, sulfolaf, etc. can be mentioned, and the amount used is determined according to each compound of formula 0)1 formula (1) and formula (X'). It is sufficient that the amount is sufficient for dissolution. Furthermore, the alkali used to be added to these solvents is not particularly limited, but includes, for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, or potassium carbonate and sodium carbonate. Alkali metal carbonates and the like are preferred.

Reaction m degree u 140-280℃, preferably 160-2
50°C, reaction time is 0.5 to 8.0 hours, preferably 1
．． It is 0 to 5.0 hours.

Next, in the polycondensation reaction, the oligomer produced by the above reaction and an acid anhydride serving as a condensing agent are reacted in the presence of a solvent. The amount of acid anhydride to be used is the amount of the compound of formula (Il''l used is a mole, and the amount of the compound of formula (,I) is b
It is preferable that it is selected to be (ba) moles when expressed as moles.

The solvent to be used may be the same as that used in the oligomer production reaction described above, and it is actually advantageous to continue using the solvent used in the oligomer production reaction.

The reaction temperature is 0 to 50°C, preferably 20 to 30°C, and the reaction time is 0.1 to 2.0 hours, preferably 0.5 to 1.0 hours.
It's time.

Then, the reaction product obtained through the above process is treated with water or alcohol to precipitate the target product.

As the alcohol, methanol and ethanol are preferred1, and as a treatment method, it is sufficient to simply throw the above reaction product into water or alcohol.

Furthermore, after isolating the target product, a drying treatment may be performed at 180 to 300°C for 1 to 30 hours.

[Embodiments of the invention]

Example 1 Equipped with an argon gas blowing pipe, a stirrer, and a rectification device.
fc, 3oo separable flasks, 4, 4'
-difluorodiphenylsulfone 12.713 F(0
,05 mol) and biphenol 7.44 F (0,0
4 mol), p-aminephenol 2.182 y (o
, 02 mol), potassium carbonate 6.91 F (0,05
Mol), N-methylpyrrolidone IQQm/ and toluene 140 mol were charged, stirred while blowing argon gas, and reacted at 150'C for 2 hours, and then the produced water was distilled off together with toluene. Next.

The temperature was raised to 190°C to remove residual toluene. Subsequently, the reaction was carried out at 190° C. for 3 hours to obtain an oligomer with a polymerization degree of 4. next.

Add 2.1 pyromellitic anhydride to the oligomer at room temperature.
81 (0.01 mol) and N-methylpyrrolidone 20-
was added, and a polycondensation reaction was carried out at 20° C. for 1 hour while stirring. The resulting polymer was poured into methanol to precipitate, pulverized with a blender manufactured by Warning, and heated with hot water IA.
and methanol 11, respectively, and dried under reduced pressure at 120° C. for 8 hours and at 200° C. for 24 hours.

As a result, 1 polymer is 22. IP was obtained (yield 100
%). The reduced viscosity (ηap/c) at 30°C of a solution of the obtained polymer in N-methylpyrrolidone at a concentration of 0.21/dl was 0.46 dl/y-1°. Infrared absorption spectrum analysis (IR analysis) of
%3030ctfl, absorption of benzene/monkey C-H bond at 830m"1, 1590Cl+2
-” Absorption of c-c bonds in Nibe/Ze/Yang, 1240CR
-” absorption of aromatic ether bond, 1780Cfi
, 1730Cfi'', imide bond absorption was observed.

In addition, as a result of thermal analysis of this polymer, the glass transition temperature (T
)) is 241°C, and the thermal decomposition onset temperature (Td) is 49
The temperature was 0°C (same in air and below). Furthermore, this polymerization K
When the solvent resistance was tested using a film press-formed at 350°C, it was found that methanol, acetone, notele chloride/
, showed no solubility in chloroform. In addition, when a flame retardancy test was conducted in which the flame of a lighter was applied to this film piece for 0 seconds and then the flame was moved away, the flame was extinguished immediately and no melt dripping was observed.

Example 2 Polymer was prepared in the same manner as in Example 1, except that 4,4'-dichlorodiphenylsulfone was used instead of 4,4'-difluorodiphenylsulfone as the dihalide. Combined product 22.11 was obtained (100% yield). Reduced viscosity (ηsp/c) is 0.40 d
i/fl (measurement was the same as in Example 1, the same applies hereinafter). Also, the T of this polymer was 234°C, and the Td was 53.
The temperature was 4°C, and the IR analysis, #f solvent properties, and flame retardancy were all similar to Example 1 and Time 1.

Example 3 The amount of biphenol used was 5.58 F (0.03 mol), and the amount of p-aminephenol used was 4.3651 (0.03 mol).
04 mol), use of pyromellitic anhydride ii4.362
Polymer 24.31 was obtained in the same manner as in Example 1 except that F (0.02 mol) was used (yield: 100%). Reduced viscosity (ηsp/c) is 0.54 dl171! , and Td was 270° C. and Td was 484° C., and the IR analysis, solvent resistance, and flame retardance were all the same as in Example 1.

Example 4 Instead of biphenol as the dihydric phenol, 2.2-bis(4-hydroxyphenyl)propane 6.84F (
In the same manner as in Example 3 except that 0.03 mol) was used, 25.59 k of a polymer 7' ((yield Zoo%)) was obtained.

Reduced viscosity (ηsp/c) is 0.41 dllIP,
The tTP was 239°C, and the Td was 480°C. As a result of IR analysis, in addition to each absorption in Example 1, 2970 m
Absorption due to isopropyl group was observed in -1. The test results for solvent resistance and flame retardancy were the same as in Example 1.

Example 5 In place of pyromellitic anhydride as an acid anhydride.

Benzophenone tetracarboxylic dianhydride 3.222y
Polymer 23. IP was obtained (100% yield, reduced viscosity (ηap/c) was 0.35 dllIP, and T
P was 240'C and Td was 499°C. As a result of IR analysis, in addition to each absorption in Example 1, 1670C11
Absorption due to the carbonyl group of hensifenone was observed in No. 1. The test results for solvent resistance and flame retardancy were the same as in Example 1.

Example 6 10.912 (0.05 mol) of 4,4'-difluorobenzophenone was used as a dihalide instead of 4,4'-difluorodiphenylsulfone.

And, instead of biphenol as a dihydric phenol, 2
, 2-bis(4-hydroxyphenyl)furobuff10.
83 (0,0475 mol), the amount of p-amine phenol used was 0.545 f (0,005 mol), and the amount of pyromellitic anhydride was 0.545 P.
Polymer #1 with 0,0025 mol of C) was prepared in the same manner as in the case of Meijo, and the polymer was 22.61!・(Yield Zoo%
). The reduced viscosity (ηsp/c) was 0.63 dlIP. Further, T was 173°C and Td was 473°C. As a result of IR analysis, the test results of solvent resistance and flame retardancy were the same as in Example 5.

Example 7 4,4'-difluorobenzophenone 10.91 P (0.05 mol) was used in place of 4,4'-difluorodiphenylsulfone as the dihalide, and biphenol was used as the dihydric phenol.

2.2-bis(4-hydroxyphenyl)propane 94
Polymer 22. Of was obtained (yield 100%)
. The reduced viscosity (ηap/c) was 0.57 dllIP. Further, TP was heated at 193°C, and Td was heated at 411°C. The IR analysis results, solvent resistance, and flame retardant test results were the same as in Example 1.

Example 8 4,4'-difluorobenzophenone IO,91P (0.05 mol) was substituted with 4,4'-difluorodiphenylsulfone as the dihalide, and 2,2-bis(2,4'-difluorobenzophenone IO,91P (0.05 mol) was substituted for biphenol as the dihydric phenol. 6.84 P (0,03 mol) of 4-hydroxyphenyl)propane was used, and the amount of p-aminophenol used was 4.3
65 F (0.04 mol) and the amount of pyromellitic anhydride used was 4.362 F (0.02 mol), but in the same manner as in Example 1 to obtain 1 polymer 23.79' (
Yield: 100 cm). Reduced viscosity (ηap/c) is 0.58d
11, TP was 205°C, and Td was 439°C. The IR analysis results, solvent resistance, and flame retardant test results were the same as in Example 1.

Example 9 Benzophenonetetracarboxylic dianhydride 3.222 F (0,0
Polymer 23.0 P (yield: 100%) was obtained in the same manner as in Example 7, except that 1 mol) was used.

The reduced viscosity (ηsp/c) was 0.77 dlIP.

Further, TF was 173°C and Td was 411°C. The IR analysis results, solvent resistance, and flame retardant test results were the same as in Example 1.

〔Effect of the invention〕

As is clear from the above description, the polyetherimide of the present invention has superior heat resistance as well as flame retardancy and solvent resistance compared to conventional polyetherimides. Therefore, heat resistance,
It is useful as a material for mechanical parts for electrical and secondary equipment of various companies that require solvent resistance and flame retardancy.

Claims (1)

[Claims] 1. The following formula: (In the formula, R represents -502- or -CO-gold. +R+ (However, R' represents a divalent hydrocarbon group having 1 to 13 carbon atoms) (wherein Ar′n represents an integer from 1 to 50), the terminal group is R, Ar and n each have the same meaning as above), and
N-methylpyrrolidone is used as a solvent. ,2y/dll
Reduced viscosity at 30℃ of 8℃ solution is 0.2d//1
The above novel polyetherimide. z: s, (XOo-, -o-o- 1@-8O2-@--@-R'-@- (where R' represents a divalent hydrocarbon group having 1 to 13 carbon atoms) ) and a dihydric phenol represented by A dihalide represented by the following formula: x+R-/@-x (1) (in the formula, R ore -8O□- or -〇〇-; X represents a halogen atom) and p- or m-aminone enol in the presence of an alkali and a solvent, (wherein R and Ar each have the same meaning as above,
(n represents an integer of 1 to 50) is produced, and then the oligomer is reacted with an acid anhydride represented by (representing) in the presence of a solvent, and the resulting reaction product is then reacted with the acid anhydride represented by Characterized by treatment with water or alcohol. It has a repeating unit of the following formula: (wherein R, Ar, Ar' and n have the same meanings as above), and the terminal group is -NH2゜has the same meanings as above), and A method for producing a novel polyetherimide in which the reduced viscosity at 30° C. of a solution of 0,2 Pldl 111° C. using N-methylpyrolide/ as a solvent is 0.2 dA/ta or more.