JPS59168030A - Production of thermoplastic polyether-imide - Google Patents

Abstract

PURPOSE:To obtain an injection-moldable thermoplastic polyetherimide having good thermal stability and fluidity in a high-temperature range, by polycondensing an aromatic bis(ether-acid anhydride) with an aromatic diamine. CONSTITUTION:A compound of formula I [wherein R is m-phenylene, p-phenylene or one of the groups of formula II-VII (wherein Z is -SO2-, -CO-, formula VIII, formula IX, -O-, or -CH2-; R1 is a 1-4C alkyl; R2 is a 1-4C alkyl, or a halogen, and n is 0 or 1-4)] and, optionally, trimellitic acid chloride are polycondensed with a compound of formula X (wherein X is -SO2-, -CO-, formula VIII, formula IX, -O-, or -CH2-, R3 is a 1-4C alkyl; R4 is a 1-4C alkyl, or a halogen; p is 0, or 1-4, and q is 1-25). Examples of the compounds of formula I include 2,2- include 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel heat-resistant thermoplastic polymer. More specifically, the present invention relates to a method for producing a novel thermoplastic aromatic polyetherimide polymer that has both good thermal stability and fluidity in a high temperature range and is injection moldable.

It is already known from JP-A-50-69196 that aromatic polyetherimide with excellent heat resistance can be obtained by polycondensing aromatic bis(ether acid anhydride) and aromatic diamine. ing. However, when the aromatic polyetherimides that have been proposed so far are intended to be used as melt molding materials, they have poor thermal stability during melt molding, fluidity during melt molding, and physical properties of melt molded products. However, the overall balance was not always satisfactory.

Therefore, the present inventors have developed an aromatic polyether that has good melt moldability by combining good thermal stability and fluidity in the temperature range of 300 to 400°C, and has an excellent balance of physical properties in the molded product. As a result of extensive research aimed at obtaining imides, it was discovered that a new thermoplastic aromatic polyetherimide polymer having the desired properties could be obtained by using a specific aromatic diamine, and the present invention was achieved. Reached.

In other words, the present invention is as follows.

(A+ General formula (I) 0 111 0 81 [However, in formula 1.4, R is a metaphenylene group or a paraphenylene group.

H2OBr　Br　CH3 One (However, Z is SO2, Co'+C.

CH3 F3 ■ -C-, -O- or -CHf, B+1 is a C1-C4 alkyl group, R2 is a C1-4 alkyl group or halogen, n is 0 or a C1-4 alkyl group, is an integer, and each R1, each R2, and each n may be the same or different)]
A compound represented by

CB+ If necessary, trimellitic acid chloride and (C) General formula TIE) CH3 (However, in the 2 formulas, X is -802-, -CO+, -
〇-.

F3 represents -C-, -0- or -CH2-, R3 is an alkyl group having 1 to 4 carbon atoms, R4 is an alkyl group having 1 to 4 carbon atoms or halogen, p is O or an integer of 1 to 4 .

q represents an integer from 1 to 25, and each R1, each R2, each X, each p, and each q may be the same or different.)
The present invention relates to a method for producing a thermoplastic polyetherimide polymer, which is characterized by subjecting a compound represented by the following formula to a polycondensation reaction.

Specific examples of the aromatic bis(ether acid anhydride) represented by the general formula (1) used in the present invention include 9, for example, 2,2-bis(4-L-(2,3-dicarboxyphenoxy)) phenyl]propanihydride, 4゜4'-bis(2,3-dicarboxyphenoxy7)diphenyl ether dimhydrate, i,a-bis(2,3-dicarboxyphenoxy)benzenylideanhydride, 4.4' -Bis(2,
3-dicarboxyphenoxy) diphenylsulfide anhydride, 1,4-bis(2,3-dicarboxyphenoxy)benzene anhydride, 4,4'-bis(3-dicarboxyphenoxy) diphenylsulfone dianhydride , 2.
2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4.4'-bis(3,4
-dicarboxyphenoxy) diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,3-bis(34
4-dicarboxyphenoxy)benzene anhydride, 1,
4-bis(3,4-dicarboxyphenoxy)benzene hydrate, 4.4-bis(3,4-dicarboxyphenoxy)dinenylsulfone dianhydride, 2.5-bis(
4-(3,4-dicarboxyphenoxynoenyl:)
-1,1,1,3,3,3-hexafluoropropanihydride, bis[4-(3-(3,4-dicarboxyphenoxy)phenoxy)quenylsulfone dianhydride, and the like.

Specific examples of the aromatic diamine represented by the general formula (It) include:

Shitl and side chain-containing derivatives thereof.

In producing the polyetherimide polymer of the present invention, an aromatic diamine represented by the general formula (Ill),
It is also possible to copolymerize by adding other aromatic diamines, such as metaphenylene diamine and diaminodiphenyl ether, but the amount of these other aromatic diamines to be used in the copolymerization depends on the amount of the polyetherimide polymer to be produced. It should be limited to an amount that does not significantly reduce melt processability, such as 50 moles of the total diamine component, preferably 30 moles or less.

The compound represented by general formula (1), the aromatic diamine represented by general formula (If), and, if necessary, trimellitic acid chloride can be reacted at 100 to 250°C in an organic solvent. The total composition of the compound represented by the general formula (If) and trimellitic acid chloride is the general formula (II
per mole of the compound represented by I).

0.5-2 mol, preferably 0.69-1.1 mol is used. The reaction is preferably carried out while dehydrating.

After the reaction is completed, one reaction solution is cooled, added to a precipitant such as methanol, and washed through 9 passes to recover a thermoplastic polyetherimide polymer. As the organic solvent, it is preferable to add a polar solvent such as N-methylpyrrolidone, dimethylacetamide, and dimethylacetamide.

In addition, the compound represented by the general formula <1) and trimellitic acid chloride (4-chloroformylphthalic anhydride) are
The former is preferably used in a ratio of 10 to 100 mol and the latter 0 to 90 mol.

If the amount of trimellitic acid chloride is too large, it will be difficult to achieve the effects of the present invention.

The polymer obtained according to the present invention has the general formula (JJI) (I
II) (However, in formula 9, R, R31R4+ In this case, the compound further has a repeating unit represented by the general formula (■) (in formula 9, I R31R4+ X , p and q are the same as in the general formula (If)).

Note that the thermoplastic polyetherimide obtained in the present invention has the above general formula (II) and (in the target).

Among the imidocarbonyl groups, a portion of which corresponds to an amide carbonyl group may be included.

The aromatic polyetherimide polymer of the present invention is.

It can be used for various purposes such as compression molded products, injection molded products, films, and wire-coated enamel. Further, different polymers, additives, fillers, reinforcing agents, etc. can be added as necessary.

Example 1 52 parts by weight of 2.2-bisC4-<3.4-dicarboxyphenoxy)phenyl]furopanni anhydride.

41 parts by weight of 2,2-bis(4-(4-aminophenoxy)phenyl)propane, N-methylpyrrolidone 100
A mixture consisting of 0 parts by weight and 300 parts by weight of toluene was stirred at room temperature for about 1 hour, and then refluxed at 150°C for about 1 hour. At this time, the water produced was azeotropically distilled off. Furthermore, 200 parts by weight of toluene was added, and while the toluene was distilled off, 1
After raising the temperature to 80°C, it was cooled. Pour the reaction solution into methanol.

The polymer was isolated. Infrared spectral analysis of the obtained phosphorus powder confirmed that the heptapolymer was composed of <silica units of the following formula.

The infrared absorption spectrum (KBr method) of the obtained compound is shown in FIG. The results of single element analysis were as follows.

Theoretical value - C near 7.84 inches H: 4.73 inches N: 3.13
%O: 14.30% Flowability with a high-performance flow tester is 2.5 x 1o-3cc/S (260℃, 100~/,
-i) Soybean paste dissolved in dimethylformamide at 30°C
The reduced viscosity measured at was 0.55 dl/f/-.

Example 2 43.2 parts by weight of bisC4-13-aminophenoxy)phenyl]sulfone, 52 parts by weight of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride
A mixture of 1000 parts by weight of N-methylpyro' and 300 parts by weight of toluene was refluxed at 150° C. for about 1 hour. At this time, the water produced was distilled off by azeotropic distillation. After cooling the reaction solution, it was poured into methanol to isolate polymer 9. From the infrared spectrum of the polymer (imidocarbonyl absorption at 1720 cm-'' and 177 Qcm-') and manufacturing method.

It was found that the product consisted of the following <silica unit>.

The results of elemental analysis of the above product are as follows.

Experimental values - C near 1.96 inches H: 3.92 inches N: 3.
10% S: 3.43% O: 17.59% (remainder) Theoretical value - C near 2.04% H: 3.96% N: 3.06
Chi S: 3.50% 0: 17.44% Again. Flowability with Koka type flow tester is 3.1XlO
-3CC/S (260°C, 100Kf/i) was dissolved in dimethylformamide and measured at 30°C, and the reduced viscosity was 0.5F3dllP.

Example 3 2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl'II-1,1,1,,3,3,3-hexafluoropropanihydride 62.8 weight m, 2.2-
Bis(4-(4-aminophenoxy)phenyl)-1゜1,1.3.3.3-hexafluoropropylene51.
A mixture consisting of 8 parts by weight, 1000 parts by weight of m-cresol, and 200 parts by weight toluene was heated and refluxed for about 1 hour. While the mixture was being heated, the water produced in one reaction was continuously distilled off by azeotropic distillation. The reaction solution was poured into methanol to isolate the heptapolymer. Infrared spectrum of the polymer (1720 cm-' and U 1775 cm-' K
It was found from the imidocarbonyl absorption structure and the production method that it consists of the following repeating units.

The results of elemental analysis of this copolymer are as follows.

Experimental value-C: 62.60% H: 2.81% N-4
48% F: 20.33% O: 11.78% (remainder) Theoretical value - C: 62.71 hits H: 2.72 hits N: 2.5
2-F': 20.53chi 0:tl, 52% again. The flowability with Koka type flow tester is 1.7XIOcc/5
(260℃, 100 K'i/cm"
) and got 45. The reduced viscosity measured at 30'C after dissolving in dimethylformamide was 0.53 v/y-.

Example 4 4.1y-starbis(,4-(4-aminophenoxy)phenyl)propane, 1.561-2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl)
Furopane dim water Qkt, 1.47 y-04-chloroformylphthalic anhydride and 30 m1. The vN-methylpyrrolidone was mixed at room temperature and stirred until clear.

During this time, the temperature rose to nearly 40°C due to the heat of one reaction. After cooling, the 9 reaction liquids were applied on glass, and the solvent was removed and the imide ring-closing reaction was performed at a temperature of 150 to 280°C. Infrared absorption spectrum (1720 cm and 1
Absorption of imidocarbonyl group at 770 m and 165
From the absorption ratio of amide carbonyl at 0 cm-' and the production method, it was confirmed that this polymer consisted of repeating units of the following formulas fV) and (Vll) in a ratio of 7 to 30 of the latter.

(Vll The results of elemental analysis of the above polymer are as follows.

Experimental value - C near 6.77 inches H: 4.74 inches N: 4.
11%0: 14.38 inches (remainder) Theoretical value - C near 6.93 inches H: 4.67 inches N: 4.
21CH0: 14.19% In addition, the flowability of the above polymer using a Koka type flow tester was determined to be 2.5×10”3 cc/S (280° C., 100 N/Crr?).

Example 5 4.3f! -bis(4-(3-aminophenoxy)phenyl)sulfone, 1.04F!-2,2-bis[4
-(2,3-dicarboxyphenoxy)pheni-]propanihydride, 1.685' of 4-chloroformylphthalic anhydride was dissolved in 30 yd of N-methylpyrrolidone. When stirred at room temperature, heat was generated and a transparent polymer solution was obtained. Which solution was cast as a film at a temperature of 150 to 280°C to obtain an imidized copolymer film. Infrared absorption spectrum of the film (1720 cm-” and 1770 cm-”
absorption of imidocarbonyl group at cm-” and 1650
cm-” with absorption of amide carbonyl group) and the method for producing the polymer.

It was found that the following formula (support) and the adjacent repeating unit consist of 8 of the former and 2 of the latter.

The results of elemental analysis of the above polymer are as follows.

Experimental value -〇: 68.50% H: 3.44chi N: 4.
33chi S: 4.72% O: 19.01% (remainder) Theoretical value -〇: 68.66%] (: 3.57 俤 N: 4.2
8chi S 24.90% 0:18.59! Also, the flowability of the above polymer using a Koka type flow tester was 1.2X10-''cc/S (280℃, 100℃/S).
Crr? )Met.

Example 6 5,18 F-2,2-bis[:4-(4-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane, 1.887 of 2,2 -Bis [4
-(3゜4-dicarboxyphenoxy)phenyl: ]
-1,1°1,3.3.3-hexafluoropropane dihydrate.

1. Mix 477-4-chloroformylphthalic anhydride and 4Qml of N-methylpyrrolidone at room temperature.

Stir until clear. Since the reaction generates heat, one reaction solution was cast on glass after cooling and imidization reaction was carried out at a temperature of 150 to 280°C to obtain an aromatic polyimide copolymer film. Infrared absorption spectrum of polymer (
The following formula (D(l and (X)
The results of elemental analysis of the above polymer were found to be a polymer consisting of the former 7 and the latter 3.

Experimental value - C: 63.39 cracks H: 2.93% N: 3.
40% F: 18.22% O: 12.05% (remainder) Theoretical value -○: 63.52% H: 2.88 chi N: 3.4
8% F: 18.40% O: 11.72% Example 7 72.7 parts by weight of bis(4-(3-(3,4-dicarboxyphenoxy)phenoxy)phenyl)sulfonic dianhydride and 41 parts by weight 2.2-1111'' after stirring a mixture of (4-(4-aminophenoxy)phenyl)furopane, 1,000 parts by weight N-methylpyrrolidone and 300 parts by weight toluene at room temperature for about 1 hour.

The mixture was refluxed at 150°C for about 1 hour. At this time, the water produced was distilled off azeotropically. Furthermore, add 200 parts of toluene,
The temperature was raised to 180° C. while toluene was distilled off, and then cooled. The reaction solution was poured into methanol to isolate polymer 9.

The obtained powder was subjected to infrared spectrum analysis (1720 cm-
Imidocarbonyl group absorption 6 at ``and 1770 cm-''
D) It was confirmed that the polymer was composed of repeating units of the following formula.

The results of elemental analysis of this polymer are as follows.

Experimental value - C near 3.02% H: 4.09chi N: 2.
49% S: 2.83 inches Q: 17.57 inches (remainder) theoretical value - C near 3.08 inches H: 4.03% N: 2.54
Chi S: 2.91% O: 17.44 Chi also. Dissolving the above polymer in dimethylformamide,
The reduced viscosity measured at 30°C was 0.52 dl/1.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the polymer obtained in Example 1. -21;

Claims (1)

[Claims] 1, (A+ General formula (1) 0 111 111 0 [However, in formula 1, R is a metaphenylene group, panphenylene group. Equal) 3r Br L:N3 (However, Z is -802-, -Co-, -C-, -
C-. 1 H3CFs -〇- or -CH2-, R1 is an alkyl group having 1 to 4 carbon atoms, and 2 is an alkyl group having 1 to 4 carbon atoms or a halogen. n is O or an integer of 1 to 4, and each R1 + each R2 and each n may be the same or different. FB) Trimellitic acid chloride and (iE)b as necessary (However, in formula 1, X is -8O□, -co-, -c-
. represents F3 1 -C-, O- or -CH2-, R13 is an alkyl group having 1 to 4 carbon atoms, R4 is an alkyl group having 1 to 4 carbon atoms or halogen, and p is 0 or 1 to 4 carbon atoms. integer. q represents an integer from 1 to 25, each R3, each R4, and each X. A method for producing a thermoplastic polyetherimide polymer, which comprises polycondensing a compound represented by p and q, each of which may be the same or different.