JPH0366335B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of Application of the Invention] The present invention relates to a method for producing a diacetylene group-containing polyamic acid, and more specifically, it relates to a method for producing a diacetylene group-containing polyamic acid, and more specifically, a diacetylene group-containing polyamic acid that has extremely excellent moldability and can be easily crosslinked with diacetylene groups. The present invention relates to a method for producing polyamic acid, which is a precursor of polyimide. [Prior art] In recent years, the synthesis of single-crystalline polymers using topochemical reactions through solid-state polymerization has attracted attention, and attempts have been made to develop various highly crystalline polymers with high elastic modulus using this method. It is being (For example, "Organic Nonlinear Optical Materials", CMC (1985), Macromolecule Chemistry Vol. 134, p. 219 (1970), Journal of Polymer Science Vol. B9, p. 133 (1971), Journal of Polymer Science (Idix Edition Vol. 12, p. 1511 (1974).) However, the polymers of diacetylene compounds that have been synthesized so far have been obtained by photochemically or thermally polymerizing powders or single crystals of raw material monomers. Therefore, it is not possible to obtain a large molded product, and since the polymer itself is often insoluble in water and organic solvents, the processability after polymerization is extremely poor. In addition, diacetylene compounds with topochemical polymerizability that have been synthesized and studied so far are
The research has been limited to compounds having a hydroxyl group such as HOCH ₂ C≡C-C≡CCH ₂ OH and derivatives thereof, which has hindered the progress of research. On the other hand, in materials with nitrogen atoms introduced, the electronegativity and cohesive force of the nitrogen atoms can be utilized, and if the nitrogen atoms have -NH- bonds, the intermolecular force due to hydrogen bonds and the reactivity of the nitrogen atoms can be utilized. This method can be used to strengthen the intermolecular interactions between diacetylene compounds and to develop various derivatives, and there are great expectations for the practical application of the potential of topochemical reactions. From this point of view, diacetylene group-containing polyamic acids and polyimides are of great interest, but so far, diacetylene group-containing polyamic acids and polyimides that exhibit such topochemical reactivity are hardly known. The present inventors have been studying the methods of introducing various groups such as alkyl groups next to diacetylene groups and the properties of the resulting compounds. The synthesis was successful. [Problems to be solved by the present invention] However, these diacetylene group-containing polyamic acid derivatives and polyimides that have been developed so far do not have a sufficiently high degree of polymerization, and therefore cannot be formed into films or fibers. It was difficult to mold, and even if it could be molded, it was brittle and impractical, so there were limits to its industrial use. [Means for Solving the Problems] In order to solve the above problems, the present inventors have
The type of raw material monomer, its synthesis process, purity,
After intensive research on the method for polymerizing this, the polymerization conditions, and the synthesis process, we found that, in particular,
It was found that the selection and degree of purification of the raw material monomer species, and the selection and conditions of the polymerization means were extremely important, and it was discovered that the degree of polymerization of the obtained diacetylene group-containing polyamic acid derivatives was dramatically improved. As a result, we have arrived at the present invention. That is, in the present invention, a salt of a diaminodiacetylene compound H ₂ N-R-C≡CC≡C-R'-NH ₂ is converted into a free diaminodiacetylene compound H ₂ N-R- using a base in a reaction system. After converting to C≡CC≡C-R'- _NH2 , acid anhydride

The present invention provides a method for producing a diacetylene group-containing polyamic acid, which is characterized by polyaddition with [Formula]. (Here, R and R' represent a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a tetravalent hydrocarbon group having 1 to 20 carbon atoms.However, R ，
When either R' is an aliphatic group, the acid component of the salt is an acid selected from organic carboxylic acids, sulfonic acids, sulfuric acids, phosphoric acids, and perchloric acids. ) In the present invention, R and R' have carbon numbers from 1 to
Up to 20 divalent hydrocarbon groups, examples _of which are _-CH2- , _{-C2H4- , -C3H6- , -C4H8-} , -
C ₅ H ₁₀ −, −C ₈ H ₁₆ −, −C ₁₀ H ₂₀ −, −C ₁₂ H ₂₄ −, −
C ₂₀ H ₄₀ −,

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[Formula] etc. aliphatic groups and alicyclic groups,

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Aromatic groups such as [Formula], and

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Examples include complex groups of an aromatic group, an aliphatic group, and/or an alicyclic group such as [Formula]. Further, the hydrocarbon group may be connected with an ether bond, a sulfonyl group, a carbonyl group, etc. Specific examples include -CH ₂ OCH ₂ -,

【formula】

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[Formula] etc. In addition, some or all of the hydrogen atoms of the divalent hydrocarbon groups of R and R' are halogen atoms, nitro groups, cyano groups, carboxyl groups, carbonyl groups,
It may be substituted with an ether bond or the like. Particularly preferred R and R' are -CH2-, _-CH2- ,

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[Formula] etc., most preferably -CH ₂ -,

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[Formula]. In the present invention, Z is a tetravalent hydrocarbon group having 1 to 20 carbon atoms, and particularly preferred is an aromatic hydrocarbon group.

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[Formula] etc. Among these Z, the most preferable one is the one based on ease of synthesis and reactivity.

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[Formula] etc. In the present invention, various combinations of R, R', and Z are possible, but some preferred examples from the viewpoint of synthesis, heat resistance, reactivity, etc. are as follows:
(R, R′, Z) is (−CH ₂ −, −CH ₂ −,

[Formula]), (−CH ₂ −, −CH ₂ −,

[Formula]), (−CH ₂ −, −CH ₂ −,

[Formula]), (−CH ₂ −, −CH ₂ −,

[Formula]), (−CH ₂ −,

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[Formula]), (−CH ₂ −,

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[Formula] (−CH ₂ −,

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[Formula]), (− CH ₂ −,

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[Formula]) etc. Among these combinations, particularly the ability to improve the degree of polymerization,
The most preferable combination in terms of moldability and reactivity is (-CH ₂ -, -CH ₂ -,

[Formula]), (−CH ₂ −, −CH ₂ −,

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[Formula]. The manufacturing method of the present invention will be described below. Conventionally, polyamic acids are synthesized by polyaddition of diamines and acid anhydrides. However, when a diaminodiacetylene compound is used as the diamine, it is difficult to obtain a high polymer using existing methods. This is because the diaminodiacetylene compound is
This is because it is extremely susceptible to the effects of temperature, the presence of air, and light, and is chemically unstable, making it difficult to achieve a high purity state no matter how many times it is purified. Therefore, the inventors have discovered that by converting a diaminodiacetylene compound into a salt with a certain type of acid, purifying the salt, and then subjecting it to polymerization, a diacetylene group-containing polyamic acid with a high degree of polymerization can be obtained. The greatest feature of the present invention lies in the fact that the diaminodiacetylene compound is used in the form of a salt. Diaminodiacetylene compound H ₂ N-R-C≡
The salt of CC≡C-R'-NH ₂ can be obtained by reacting the diaminodiacetylene with an acid according to a conventional method. When both R and R' are aromatic, the acid used is not particularly limited, but hydrogen halide is preferred. On the other hand, when either R or R' is an aliphatic group, the acid is selected from organic carboxylic acids, sulfonic acids, sulfuric acids, phosphoric acids, and perchloric acids. It is preferable that the salts of these diaminodiacetylene compounds be sufficiently purified before use. As for its purification method, it is preferable to purify the solvent to be used by repeated distillation or other methods, and then repeat recrystallization several times in an inert gas in a dark place. must be carefully selected depending on the type of diaminodiacetylene compound. Generally, it is necessary to avoid excessive heating or to set the temperature at the time of crystal precipitation to be low. Regarding the synthesis method for salts of diaminodiacetylene compounds, a method is used in which the diaminodiacetylene compound is first synthesized, sufficiently purified at this stage, and then hydrolyzed. It is extremely important to consider factors such as temperature, light, etc. Further, high purity is also required for the tetracarboxylic acid component constituting the repeating unit of the present invention. Thus, it is extremely important that raw materials have a high degree of purity;
% or more, especially 99.5% or more purity is preferable. General purification methods such as distillation, recrystallization, and sublimation can be used to obtain such raw materials, but it is important to repeat these purification methods to obtain the required purity. For this purity determination,
Infrared spectroscopy, the magnetic resonance method, X-ray method, and chromatography can be used. Next, regarding the polymerization method, a method in which a diaminodiacetylene salt is reacted with an acid anhydride in, for example, an amide solvent is preferred, and at this time, diaminodiacetylene must be converted back to a free amine. In this case, it is preferable to add 2 mol or more of a base per 1 mol of the diaminodiacetylene salt to the reaction system in advance. In this case, the base used is not particularly limited as long as it does not inhibit the polymerization reaction, but it is best to use a strong base such as NaOH, NaHCO ₃ , NaCO ₃ , KOH,
Examples include inorganic bases such as K ₂ CO ₃ and Ca(OH) ₂ , and organic bases such as pyridine, trimethylamine, and triethylamine. In the polymerization of the above polyamic acid, a salt of a diaminodiacetylene compound and an acid anhydride are used.

〔Effect of the invention〕

The diacetylene group-containing high molecular weight polyamic acid obtained by the present invention has an intrinsic viscosity at 30°C.
Since it has a high value of 0.7 or more, it is extremely effective as a new crosslinkable material with excellent moldability. This polyamic acid has good properties for producing membrane-like and fibrous molded products, and is extremely effective in causing solid-state reactions between polymer chains through diacetylene groups due to the cohesive force of heteroatoms. It is easily oriented and crosslinked, and therefore exhibits excellent heat resistance and high elastic modulus. In particular, regarding the polyimide obtained by ring-condensing the polyamic acid,
Extremely good heat resistance. As described above, the diacetylene group-containing high molecular weight polyamic acid obtained by the present invention and the further derived polyimide are new materials that have good moldability, high elastic modulus, and excellent heat resistance.
It is extremely useful in fields where these characteristics are required, such as the electronics field and the precision industry field.
(In particular, when implementing the present invention as a material, moldability is the most important factor, and a high molecular weight is essential.) [Examples] Examples will be given below to further clarify the present invention. However, it goes without saying that the scope of the present invention is not limited to these examples. Example 1 Synthesis of (C ₂ H ₅ CONH-CH ₂ -C≡C-) ₂ was hydrolyzed with dilute sulfuric acid to precipitate (H ₂ NCH ₂ -C≡C)- ₂ .
H ₂ SO ₄ was recrystallized three times at −50° C. using methanol. This H ₂ NCH ₂ C≡CC≡CCH ₂ NH ₂・
1 mole of H ₂ SO ₄ and 1 mole of pyromellitic anhydride
2 moles of NaOH, 4 moles of triethylamine,
Dissolve in N-methylpyrrolidone and heat at 0 to 40℃ for 2 hours.
The reaction was carried out in high purity helium for an hour. After the reaction, the reaction product was poured into water, and the precipitated polymer was isolated by suction filtration. The polymer yield obtained was quantitative. IR (film); 3276cm ^-1 , 1648cm ^-1 , 1600cm ^-1 Intrinsic viscosity of the polymer (hereinafter referred to as [η])
was 0.86. Reference example 1 Synthesis The polyamic acid of Example 1 was dissolved in N-methylpyrrolidone, a large excess of acetic anhydride was added under a nitrogen stream, and the mixture was reacted at 120°C for 5 hours. The yield of the obtained polymer was quantitative. IR; 3000 cm ^-1 , 1740 cm ^-1 , 1600 cm ^-1 [Comparative example] H ₂ NCH ₂ -C≡C-C≡C- in Example 1
CH ₃ CONH−CH ₂ instead of CH ₂ NH ₂・H ₂ SO ₄
H ₂ NCH ₂ -C≡C-C≡ obtained by hydrolyzing -C≡C-C≡C-CH ₂ -NH-CO-CH ₃ with hydrochloric acid
Example 1 _was repeated except using C- _CH2NH2.2HCl . [η] of the obtained polyamic acid is
It was 0.61. Example 2 In place of pyromellitic anhydride in Example 1, 3,
Example 1 was repeated except that 3'-4,4'-benzophenonetetracarboxylic anhydride was used. [η] of the obtained polyamic acid was 0.91. Polyimide was synthesized from this polyamic acid by the same method as in Example 2. The yield of the obtained polymer was quantitative. Example 3 When the polymerization time was changed to 5 hours in Example 1, the obtained polyamic acid reached [η] 0.91. Example 4 In Example 1, C ₂ H ₅ CONHCH ₂ −C≡C−
C≡C-CH ₂ NH-COC ₂ H ₅ was hydrolyzed with a dilute solution of perchloric acid, the obtained perchlorate was recrystallized, and the same operation as in Example 3 was repeated. The obtained polyamic acid had a [η] of 0.85. Example 5 In Example 1, C ₂ H ₅ CONHCH ₂ −C≡C
−C≡C−CH ₂ NH−COC ₂ H ₅ instead Example 1 was repeated, except using 10% and an excess of triethylamine instead of NaOH. The yield of the obtained polymer was quantitative, and the [η] of the polyamic acid was 0.83. IR (film); 3276cm ^-1 , 1648cm ^-1 , 1600cm ^-1 Example 6 Synthesis of H ₂ NCH ₂ C≡CC≡ in Example 1
Instead of CCH ₂ NH ₂・H ₂ SO ₄ , obtained by hydrolyzing with hydrochloric acid Example 1 was repeated except using: The yield of the obtained polymer was 99%, and the [η] of the polymer was 1.12. IR (film); 3300cm ^-1 , 3000cm ^-1 , 1648cm ^-1 , 1600
cm ^-1 reference example 2 Synthesis of Example 2 The method of Example 2 was repeated except that the polyamic acid of Example 6 was used. The yield of polymer obtained was quantitative. IR (Nujol); 3000cm ^-1 , 1728cm ^-1 , 1600cm ^-1 Example 7 Synthesis of Example 6 instead of obtained by hydrolyzing with hydrochloric acid Example 6 was repeated except that . The yield of the obtained polymer was quantitative, and the [η] of the polymer was 1.38. IR (film); 3300cm ^-1 , 3000cm ^-1 , 1648cm ^-1 , 1600
cm ^-1 reference example 3 Synthesis Using the polyamic acid of Example 7, the method of Reference Example 1 was repeated. The yield of polymer obtained was quantitative. IR (Nujoi); 3000cm ^-1 , 1728cm ^-1 , 1600cm ^-1 Comparative example 2 Example 7 instead of

Example 7 was repeated using the formula and also without NaOH and triethylamine. [η] of the obtained polyamic acid was 0.59. Example 8 Synthesis of copolymer of Example 1 _H2N - _CH2C≡C -C≡C- _CH2-
0.8 mol of NH ₂ H ₂ SO ₄ and

Example 1 was repeated by adding 0.2 mol of [Formula]. The yield of the obtained polymer was quantitative, and the [η] of the polymer was 0.88. IR (film); 3275cm ^-1 , 1650cm ^-1 , 1600cm ^-1 Reference example 4 and Synthesis of copolymer of Example 8 The polyamic acid of Example 8 was imidized by the method of Reference Example 1. The yield of polymer obtained was quantitative. IR (Nujol); 3000cm ^-1 , 1740cm ^-1 , 1600cm ^-1 Example 9 and Synthesis of copolymer of Example 7 in Example 6. using 0.3 mol and as an acid anhydride.

The method of Example 1 was repeated except that the formula was used. The yield of the obtained polymer was quantitative, and the [η] of the polyamic acid was 0.81. IR (film); 3300cm ^-1 , 3000cm ^-1 , 1645cm ^-1 , 1603
cm ^-1 reference example 5 and Synthesis of copolymer of Example 9 The polyamic acid of Example 9 was imidized by the method of Reference Example 1. The yield of polymer obtained was quantitative. IR (Nujol); 3000cm ^-1 , 1743cm ^-1 , 1600cm ^-1

Claims (1)

[Claims] 1. Diaminodiacetylene compound H ₂ N-R-C
A salt of ≡CC≡C-R′-NH ₂ is converted into a free diaminodiacetylene compound H ₂ N- using a base in a reaction system.
A method for producing a diacetylene group-containing polyamic acid, which comprises converting it into R-C≡CC≡C-R'-NH ₂ and then polyadding it with an acid anhydride. (Here, R,
R' represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a tetravalent hydrocarbon group having 1 to 20 carbon atoms. However, when either R or R' is an aliphatic group, the acid component of the salt is an acid selected from organic carboxylic acids, sulfonic acids, sulfuric acids, phosphoric acids, and perchloric acids. )