JPS61251636A - P-phenylenebisglutaric acid, linear polyimide and production thereof - Google Patents

Abstract

NEW MATERIAL:p-Phenylenebisglutaric acid expressed by formula I. USE:A raw material for synthesis of a linear aliphatic polyimide, having superior heat resistance and capable of being pre-molded. PREPARATION:A p-phenylene-bis(alpha-cyanoacrylic acid ester) expressed by formula II (R is 1-4C alkyl) is reacted with a cyclic diester expressed by formula III (R1 and R2 represent 1-4C alkyl) or its salt to obtain the p-phenylenebisglutaric acid expressed by formula I. This compound expressed by formula I and acetic acid are boiled together to produce an acid anhydride expressed by formula IV, and further heated to carry out polycondensation in the presence of an aromatic symmetric diamine in a solvent to obtain the linear polyimide having a recurring structural unit expressed by formula V.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel tetracarboxylic acid useful as a raw material for synthesizing linear polyimide, a method for producing the same, a linear polyimide derived from the tetracarboxylic acid, and a method for producing the same. Regarding the method. Ya・啼÷→te In detail, it has excellent heat resistance,
Preformable aliphatic linear polyimide, tetracarboxylic acid as a raw material for its synthesis, and method for producing the same [Prior art] Formable, heat resistant, insulating, abrasion resistant, and radiation resistant Polyimide has attracted attention as a material with excellent properties, and its use is increasing as it is used for printed circuit boards, laminates, structural members, etc.

Recently, carboxylic acid components that have an aliphatic structure have attracted attention because, if appropriate, it is possible to obtain resins that are cheaper than fully aromatic polyimides and have physical properties similar to those of fully aromatic polyimides. ing.

[Problem that the invention seeks to solve]

The method using the above-mentioned carboxylic acid having an aliphatic structure is as follows:
There is a problem that the synthesis of tetracarboxylic acid is relatively troublesome, and it is difficult to be satisfied in practical terms.

An object of the present invention is to provide a tetracarboxylic acid that can be industrially advantageously synthesized and is useful as a raw material for the synthesis of polyimide having an aliphatic structure that has excellent heat resistance and can be preformed. be.

Furthermore, another object of the present invention is an aliphatic structure having preformability, transparency, toughness, and high heat resistance. To provide a polyimide having a polyimide of 0.0 [Means for solving the morphological point] The inventor focused on p-phenylenebisglutaric acid, a novel tetracarboxylic acid, and as a result of researching its synthesis method, We have discovered an industrially advantageous method using taraldehyde as a starting material. Furthermore, the polyimide obtained by condensing p-phenylene bisglutaric anhydride with an aromatic diamine is preformable, transparent, tough, and heat resistant. Firstly, the present invention is represented by the following structural formula Il+;
Concerning p-phenylenebisglutaric acid.

xt The present invention secondly provides p- represented by the above structural formula (I).
The method for producing 7-enylenebisglutaric acid involves p-7enylenebis(α
- cyanacrylic acid ester) and the following general formula (seal) (R
1 and island are alkyl groups having 1 to 4 carbon atoms. It is characterized by reacting a cyclic diester represented by the following formula or a salt thereof.

The general formula (p-) diel bis(α-cyanoacrylic acid ester) used as a starting material in the above production method is obtained by the condensation of terephthalaldehyde and cyanacetic acid ester.This condensation reaction is
It can be expressed by the following reaction formula.

N However, R is an alkyl group of carbon a1 to 4 ff1
The brazing diester represented by the general formula il+, which is used as another starting material in the process for producing p-7 enylene bisglutaric acid, is synthesized from malonic acid and dialkyl ketone as shown in the following formula.

(!] (In the formula, R8 and 82 are as described above.) Formula t
In the cyclic diester surrounded by i+, R1,R.

Melt diamic acid (formula Vl below) in which is a methyl group can be easily obtained from malonic acid and acetone, and there is an industrially produced NFC commercially available product (Aldrich, USA) (v
ll Melt dimuic acid is made acidic by active methylene and reacts with sodium hydroxide to form a sodium salt.

It was found that the reaction between melted sodium demium acid and p-)nyrelene bis(α-cyanoacrylate esterne) proceeded without any catalyst and produced an adduct.9 This adduct was hydrolyzed with hydrochloric acid and p- -phenylene bisglutarium
(Equation 111) 1 obtained -7<.

This reaction is expressed by the following formula.

The p-phenylenebisglutaric acid obtained as described above is a new tetracarboxylic acid (melting point: 260-261°C
)O p-Phenylenebisglutaric acid is converted to citric anhydride (formula (V) below) by boiling with acetic anhydride.0 (Vl p-)Nyrelenebisglutaric anhydride? By dissolving the aromatic symmetrical diamine in a suitable solvent such as dimethylformamide, dimethylsulfoxide dimethylacetamide, and stirring at room temperature and normal pressure, a polyamic acid soluble in these reaction solvents can be obtained. Reduced viscosity 0.3-1117di
(measured in a dimethylacedeamide solution with a polymer concentration of 0.211/di at 30°C) A corresponding novel polyimide is obtained by casting the polyimide into a film and then heating it under reduced pressure.

Accordingly, the present invention relates, thirdly, to a linear polyimide characterized in that it consists essentially of the following repeating structural unit ([V)].

(In the formula, g is an aromatic symmetrical diamine residue.)Furthermore, the present gA has a fourth structure substantially including the above-mentioned repeating unit [fV
) The manufacturing method involves polycondensation by heating p-phenylenepisglutaric anhydride represented by the above formula [Vl and aromatic symmetric diamine t-solvent. It is characterized by causing

Specific examples of aromatic symmetrical diamines to be reacted with p-phenylene bisglutaric anhydride include the following formula (To, (to),
0) O and (Xl) (wherein) I-C&-1-S -, -0-, -aH, -
.

〔Effect of the invention〕

As a manufacturing method for dicarboxylic acid, is cinnamic acid ester and malonic acid ester? Michael Shrink & i5
A method of preparing phenylglutaric acid is known (Or
g.

5) Fn, 53JiL 193 (I973)).

p-phenylene bis(α-
cyanacrylic acid ester) (Formula 111), p-phenylenebisglutaric acid (Formula 11
1) is fraudulent.

The above method uses an alkali metal alcolade as a catalyst,
For example, sodium ethoxide can be used, but if water is present in the system, the catalyst will be decomposed, so absolute alcohol must be used as the solvent.

On the other hand, the cyclic diester used in the present invention, for example,
Since Meldrum's acid, in the form of an alkali metal salt, is soluble in water and aqueous alcohol, it is possible to carry out carbonylation in a hydroalcoholic t-solvent. This reaction is industrially advantageous because it does not require dehydration of the solvent and can be carried out without using any special catalyst.

p-Phenylenebisglutaric anhydride, which can be obtained relatively inexpensively by the method of the present invention, easily polymerizes with aromatic symmetrical diamines to produce polyamic acid with a high degree of polymerization. Polyimide can be obtained by coating and heating under reduced pressure. The resulting polyimide is insoluble in solvents, pale yellow and transparent, flexible, and tough. Heat resistance varies somewhat depending on the diamine component used, but the temperature at which 10% weight loss occurs in air is about 400°C.

As mentioned above, polyimide obtained from p-phenylene bisglutaric anhydride and aromatic diamine has physical properties comparable to fully aromatic polyimide, such as transparency, toughness, and heat resistance, and can be used as a molding material, film, etc. It has the potential for a wide range of uses, including coach ink, enamel facings, and 7il materials.

〔Example〕

The present invention will be specifically described below with reference to Examples.0 Example 1 Synthesis of p-phenylenebisglutaric acid p-7enylenebis(α-7anoethyl acrylate) 64.8,9 (0.2 mol) t - Grind well, 800
Disperse in wJ ethanol and use Magnetech Star 2
-7 Keep it stirring, friend. On the other hand, dissolve sodium hydroxide 2019 in water 200a and add Meldrum 1 to the solution.
Add k63.4 & (0.44 mol) 1 little at a time to make an aqueous solution of Meldrum's acid sodium salt. An aqueous solution of sodium Meldrum was added dropwise to the ethanol solution of p-7 enylenebis(α-cyano)ethyl acrylate under stirring over 2 hours, and the mixture was further stirred at room temperature for 10 hours. After this, a completely homogeneous reaction solution was obtained.

Concentrated hydrochloric acid was added to the reaction solution to adjust p)l=3, and ethanol and water were completely distilled off using a rotary evaporator. 200ml of concentrated hydrochloric acid was added to the resulting tomo carving, and the mixture was heated under reflux for 12 hours to dissolve it. t-crystals precipitated by cooling while left standing 1! -F separate and dry. Yield 52.1# (Yield 77.
1%) and friend.

The above crystals were recrystallized from a mixed solvent of acetic acid: water = 9 = 1,
Crystals with a melting point of 260-261°C were obtained.

p-7 enylene bisglutaric acid. The elemental analysis values are as follows.

Actual value C: 56.26 excellent, H: 5.50% Calculated value C: 56.80%, H: 5.33% The infrared absorption spectrum of the obtained sample (KBr tablet) is shown in Figure 1. The 2#MR spectrum measured with dimethyl sulfoxide solution is as follows:90 (ppm) 12.06
(s t 4H*carboxyl group), 7.16 (s +
4 H + benzene nucleus), 3-34 to 3-42 (m
*2H, methine group), 2.44-2.65 (m, 8H.

methylene group) O p-7x=V:/-bisglutaric acid 33.8.9 (0
, 1 mol) in 250 d of acetic anhydride, heated under reflux until a homogeneous solution was obtained, and the reaction mixture was left to cool. The precipitated product kF was separated, washed with ether, and dried to give a solution with a melting point of 279 to
Obtained crystals at 280°C. p-7 enylene bisglutaric anhydride. The yield was 19.6II (yield 64.9%). The elemental analysis values were as follows.

Actual value C: 63.28 excellent H: 4.77% Calculated value C: 63.58 poor H: 4.64 The infrared absorption spectrum of the obtained sample (KBr tablet) is shown in FIG.

The 9NMB spectrum measured with dimethyl sulfoxide solution was as follows. (ppm) 7.30 (s, 4H,
benzene nucleus), 3.50-3.61 (m, 2H, methine group), 2.91-3.10 (m, 8H, methylene group) 0 Synthesis of Example 2゜ Diaminodiphenyl ether 0.60 # (0 , 03 mol)'i6.4yd in dimethylacetamide and stirred at room temperature to obtain p-phenylenebisglutaric anhydride.After addition of the acid anhydride, the mixture was further stirred at room temperature for 24 hours to obtain a viscous reaction. After the liquid was cast onto a glass plate, it was heated together with the glass plate at 120°C for 2 hours, then at 200°C for 1 hour to evaporate the solvent, and then heated under reduced pressure at 200°C for 10 hours to make it transparent. A yellowish film was obtained.The next product obtained was polyimide, and the reaction formula is thought to follow the following equation.

The obtained polyimide is insoluble in solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, and formic acid, but the polymer (polyamide I) before heating under reduced pressure
Since it is soluble in these solvents, the reduced viscosity is measured next. Using dimethylacetamide as a solvent, concentration o, 2 #
/dz, the reduced viscosity at 30°C is 0.79. FIG. 3 shows the infrared absorption spectrum (film) 1 of polyimide.

In addition, the heating loss curve of the obtained polyimide in air and nitrogen gas (heating rate 5 ° C / min, solid line in air,
The dotted line corresponds to nitrogen gas. Below, Figure 5~tlE9
The same goes for the diagram. ) is shown in Figure 4. From Figure 4, we determined the temperature at which 10% weight loss was observed.
The temperature was 40°C.

Examples 3 to 7 In place of diaminodiphenyl ether in Example 2, diaminodiphenyl sulfide (Example 3), diaminodiphenylmethane (Example 4), p, p'-dicyanom,
Each was prepared in the same manner as in Example 2, except that equimolar (0.03 mol) amounts of godimethoxydiphenyl (Actual tfA Example 5), o-phenylenediamine (Example 6), and p-phinylenediamine were used. The corresponding polyimide 7 was synthesized.

The heating loss curves of the obtained polyimide are shown in FIGS. 5 to 9. Table 1 summarizes the measurement results of the temperature at which the 10% weight loss of each polyimide is shown and the reduced viscosity of the corresponding polyamic acid.

Below margin

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of p-funyrelene bisglutaric acid according to the present invention. FIG. 2 is an infrared absorption spectrum of p-7 enylene bisglutaric acid s hydrate. FIG. 3 is an infrared first yield spectrum of polyimide 9 obtained from p-7 enylene bisglutaric anhydride and diaminodiphenyl ether. Figure 4 shows the heating loss curve in air (solid line) and the heating loss curve in nitrogen gas (dotted line) of the polyimide. Figures 5, 6, 7, 8 and 9. is the fourth
These are the heating loss curves in air (solid line) and heating loss curves in nitrogen gas (dotted lines) for five types of polyimide different from those shown in the figure. Temperature (°C) Figure 4 Figure 5 Figure 6 Figure 9 Amendment to figure procedure (voluntary) June 1985 / L + Japan Patent Office Commissioner Manabu Shiga 1, Indication of the case Original Patent No. 91232 filed in 1985 Name of the invention P-phenylene bisglutaric acid, linear/liimide , and their manufacturing method 3, relationship with the case of the person making the amendment Patent applicant name Daicel Chemical Industries, Ltd. 4, agent 5o Subject of amendment 1. "Claims" column 2 of the specification, description Column 6 of "Detailed Description of the Invention", Contents of Amendment 1, Attachment] (2) The following is corrected in the first line of page 6 of the specification. (3) The statement is corrected in the second line of the same page. (R1 and . (5) In the seventh line of the same page, insert the following sentence between "ester" and "terephthal." ``It is known that H. Kaufman (H. Kaufman)
fmann ): Berichte (B@'r, )50,
525 (I917), this compound is described in "."
, the other... (formula ■ below) is Ma'' is corrected to ``Meldrum's acid used in is Ma''. (7) In the specification, page 7, line 10 (bottom right of the chemical reaction formula in the middle of page 7), the word "(to)" is corrected to "(to)". (8) On page 10, line 11 of the specification, the statement ``is corrected.'' (9) On page 12 of the specification, lines 4 to 5, the statement ``cyclic diester, for example,'' is deleted. In the top row of Table 1 on page 20 of the αQ specification, in the "/IJ amic acid" column, there is "ηOP/C (d4/) J".
Correct it as 7sP/C (4'Ii) J. The statement in the ``diamine'' column of ``Example 5'' on the same page in the same table has been corrected.'' 7゜Amended list of attached documents Claims 1 copy 2, Claims 1) p-7 enylene bisglutaric acid represented by the following structural formula (I) 2) The following general formula Q[) (R# i is an alkyl group having 1 to 4 carbon atoms. The following structural formula (
A method for producing p-7 enylenepisglutanosic acid represented by I). 3) A linear polyimide characterized by substantially exfoliating the following repeating structural unit (wherein R/ is an aromatic symmetric diamine residue) 4)
Substantially characterized in that p-phenylene bisglutaric anhydride and aromatic symmetric diamine represented by the following formula (to) are coexisted in a solvent and heated to form a polycondensate. A method for producing a linear polyimide consisting of the following repeating structural unit ω. beat

Claims (1)

[Claims] 1) P-phenylenebisglutaric acid represented by the following structural formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) 2) The following general formula (II) ▲ Numerical formulas, chemical formulas, There are tables etc. ▼ (II) (R is an alkyl group having 1 to 4 carbon atoms) p-phenylenebis (α-cyanoacrylic acid ester) and the following general formula (III) ▲ Numerical formula, chemical formula, There are tables etc. ▼(III) (R_1 and R_2 are alkyl groups having 1 to 4 carbon atoms.) The following structural formula (I) characterized by reacting a cyclic diester or its salt ▲Math. , chemical formula, table, etc. ▼(I) Manufacturing method of p-phenylenebisglutaric acid represented by. 3) A linear polyimide characterized by consisting essentially of the following repeating structural unit (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R' is an aromatic symmetric diamine residue.) 4)
The following formula (V) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (V) Polycondensation is carried out by coexisting p-phenylene bisglutaric anhydride and aromatic symmetric diamine in a solvent and heating them. A method for producing a linear polyimide consisting essentially of the following repeating structural unit (IV).