JPH046732B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a diacetylene-containing imide polymer having a terminal ethynyl group, which is easily crosslinked by ethynyl groups and diacetylene groups, and has excellent moldability and heat resistance. [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 moduli using this method. ing. (For example, "Organic Nonlinear Optical Materials", CMC (1985), Macromolecule Chemistry Vol.
Volume 134, page 219 (1970), Journal of Polymer Science Volume B9, page 133 (1971),
Journal of Polymer Science Polymer Physics Edition Volume 12, Page 1511 (1974). ) [Problems to be Solved by the Invention] However, the polymers of diacetylene compounds that have been synthesized so far have been obtained by optically or thermally polymerizing powder or single crystals of raw material monomers, so it is difficult to form them into large pieces. Since many polymers themselves are insoluble in water and organic solvents, their 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 intermolecular interactions between diacetylene compounds and to develop various derivatives, and there are great expectations for the potential of topochemical reactions and their practical application. From this point of view, diacetylene group-containing imide polymers are of great interest, but so far, diacetylene group-containing imide polymers that exhibit such topochemical reactivity are hardly known. [Means for Solving the Problem] The present inventors have conventionally investigated methods of introducing various groups such as an alkyl group next to a diacetylene group and the characteristics of the obtained compounds, but in the process, the terminal We succeeded in synthesizing a diacetylene group-containing imide polymer having an ethynyl group, and as a result of further research, we arrived at the present invention. That is, the present invention provides a diacetylene-containing imide polymer having a terminal ethynyl group represented by the following general formula. (Here, R ₁ , R ₂ , R ₃ are divalent hydrocarbon groups having 1 to 30 carbon atoms, and Z is a divalent hydrocarbon group having 1 to 40 carbon atoms.
is a tetravalent hydrocarbon group, and the degree of polymerization n is 2 to 250.
It is. ) In the present invention, R ₁ , R ₂ , and R ₃ each have 1 to 30 carbon atoms.
are divalent hydrocarbon groups, and each may be the same or different. _Examples include _-CH2- , _-CH2H4 , _{-C3H6- , -C4H3- ,}
−C ₅ H ₁₀ −, −C ₈ H ₁₆ −, −C ₁₀ H ₂₀ −, −C ₁₂ H ₂₄ −,
−C ₁₂ H ₄₀

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Aliphatic groups such as [Formula], and alicyclic groups,

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[Formula] etc. aromatic group, and

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Examples include composite groups of aromatic groups, aliphatic groups, and alicyclic groups such as [Formula], and some of the hydrogen atoms of these R ₁ , R ₂ , and R ₃ are
It may be substituted with a halogen atom, nitro group, hydroxyl group, cyano group, carboxyl group, amino group, amide group, ester group, carbonyl group, alkoxy group, etc., and even if these are repeated or combined. Alternatively, these hydrocarbon groups may be connected by other bonding groups. Examples of bonding groups other than such hydrocarbon groups include -O-, -
S-, -SO ₂ -, -CO-, -NH-, -NCH ₃ -, -
COO−, −CONH−,

[Formula], -NHCO -NH-, -N=N-, -HC=N-, etc., and these may be combined or repeated. From the viewpoint of ease of synthesis and topochemical properties, preferred as R ₁ , R ₂ , and R ₃ are -CH ₂ -,

[Formula], −C ₂ H ₄ −,

[Formula] etc. In the present invention, Z is a tetravalent hydrocarbon group having 1 to 40 carbon atoms, examples of which include C,
CHCH, CHCH ₂ CH, CHCH ₂ CH ₂ CH
,

[Formula], CH(CH ₂ ) ₈ CH, CH(CH ₂ ) ₁₂ CH,

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[Formula] etc. are listed, and The hydrocarbon group may be bonded to a functional group having a heteroatom, such as in the case of the present invention. Further, some or all of the hydrogen atoms of the above divalent hydrocarbon group may be substituted with a halogen atom, nitro group, cyano group, carboxyl group, amide group, ester group, carbonyl group, alkoxy group, etc. . Among these Z, preferable ones are from the viewpoint of ease of synthesis and reactivity.

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[Formula] etc. The terminal ethynyl group of the present invention is necessary in order to act as a crosslinking group and increase the crosslinking density like the diacetylene group, as shown in JP-A-52-259. In the present invention, the degree of polymerization n is 2 to 250, and from the mechanical properties after molding, the degree of polymerization n is preferably 5 or more, particularly preferably 7 or more. The diacetylene-containing imide polymer having a terminal ethynyl group of the present invention can be synthesized by making effective use of known organic synthesis reactions. The first method is to use an amic acid derivative, which is a precursor of an imide polymer. For example, the diaminodiacetylene compound H ₂ N−R ₂ −
C≡C-C≡C-R ₃ -NH ₂ , acenoacetylene compound H ₂ N-R ₁ -C≡CH and

[Formula] or

Reacting an acid anhydride or carboxylic acid represented by the formula in an amide solvent, First, a diacetylene-containing amic acid derivative having a terminal ethynyl group represented by is synthesized. Another method for synthesizing the amic acid derivative is H ₂ N-R-C
≡CH (here R represents R ₁ , R ₂ and R ₃ mentioned above)
and

Amic acid obtained by reacting with [Formula] (Here, R represents R ₁ , R ₂ and R ₃ described above.) A method of oxidative coupling polymerization using a metal catalyst is mentioned. The amide solvent used at this time is not particularly limited, but examples thereof include N,N-dimethylformamide, N-methylpyrrolidone, and the like. Furthermore, the metal catalyst used in the oxidative coupling polymerization is not particularly limited, and examples include copper chloride () and copper acetate (), and the solvent used is also not particularly limited, and examples include pyridine, triethylamine, etc. . Therefore, in order to synthesize the diacetylene-containing imide polymer having terminal ethynyl groups of the present invention, for example, amic acid can be condensed by heating as it is, or condensation can be carried out using a dehydrating agent such as acetic anhydride, polyphosphoric acid, or dicyclohexylcarbodiimide. For example, the method of A method for directly synthesizing the imide polymer of the present invention without going through an amic acid derivative is to synthesize H ₂ N-R-C≡CH (where R represents R ₁ , R ₂ and R ₃ described above).

Imide obtained by heating and dehydrating [Formula] in a solvent (Here, R represents R ₁ , R ₂ and R ₃ described above.) Examples include a method in which oxidative coupling polymerization is carried out using a metal catalyst. [Effects of the Invention] The diacetylene-containing imide polymer having a terminal ethynyl group of the present invention undergoes thermal crosslinking or solid phase polymerization by heat pressure and light using the terminal ethynyl group and diacetylene group to increase the molecular weight in three dimensions. Provide moisturizing material. When thermogravimetric analysis of the crosslinked product was performed in air,
In general, it shows extremely good heat resistance without losing weight even at temperatures above 200°C, especially above 300°C. Further, for example, a molded product of the diacetylene-containing imide polymer having a terminal ethynyl group of the present invention,
Its mechanical properties, such as its elastic modulus, are also good, and while general organic polymers have an elastic modulus of 1 to 3 GP _a , it can easily exhibit an elastic modulus of 5 GP _a or more. In addition, depending on the purpose, it can be used in various forms such as powder, lump, solution, and suspension, and it can also be used in inorganic and organic fibrous, powder, and flaky materials. It can be used in combination with other curable resins, polymeric materials, colorants, stabilizing materials, etc., and can be molded into various shapes. By having the above characteristics, it can be used as coating material, base material of reinforcing material, sealant, etc.
It is extremely useful as a source of a wide variety of high-performance materials such as potting materials, electronic materials, and heat-resistant films. [Example] Example 1 Synthesis of 3,3'-4, in 500ml of N-methylpyrrolidone
4′-Benzophenonetetracarboxylic anhydride
0.2mol (64.4g) and 1,6-diamino-2,4-
0.18 mol (19.44 g) of hexadiine was added and a reaction was carried out for 3 hours. Subsequently, 0.03 mol (1.65 g) of propargylamine was added and the reaction was continued for another 2 hours, and the mixture was poured into methanol to obtain 64 g of white powder (yield: 90% or more). The infrared absorption spectrum showed an ethynyl group absorption at 3260 cm ^-1 , a triple bond absorption at 2190 cm ^-1 and an acid amide absorption at 1675 cm ^-1 , 1550 cm ^{-1 and} 1270 cm ^-1 . Furthermore, the degree of polymerization n was determined to be 134 based on the determination of the terminal ethynyl group by IR spectrum. When this product was heated, it had no melting point up to 300°C, but it turned red, indicating that thermal solid-state polymerization of the diacetylene moiety was occurring. Further, when thermogravimetric analysis was performed in air, although there was some weight loss due to dehydration and cyclization, there was almost no weight loss up to 320°C, and the heat resistance was good. The heat-treated material was imidized according to its infrared absorption spectrum. Example 2 1,6-diamino-2,4 hexadiyne
The synthesis was performed in the same manner as in Example 1, except that the amount was changed to 0.196 mol (21.168 g), and 65 g (yield: 95% or more) of white powder was obtained. From the infrared absorption spectrum, absorption of ethynyl group, triple bond, and acid amide was confirmed as in Example-1. The degree of polymerization n was 246. When this product was heated, it had no melting point up to 300°C, but turned red as in Example-1.
Further, thermogravimetric analysis in air revealed that although there was some weight loss due to dehydration and cyclization, there was almost no weight loss up to 340°C, indicating good heat resistance. The heat-treated material was imidized according to its infrared absorption spectrum. Example 3 Synthesis was carried out in the same manner as in Example 1, except that pyromellitic anhydride was used as the acid anhydride, and 51.3 g (yield: 90%) of white powder was obtained. From the infrared absorption spectrum, absorption of ethynyl group, triple bond, and acid amide was confirmed as in Example-1. The degree of polymerization n was 43. When this product was heated, it had no melting point up to 300°C, but turned red as in Example-1. Thermogravimetric analysis in air revealed that although there was some weight loss due to dehydration and cyclization, there was almost no weight loss up to 350°C, indicating good heat resistance. The heat-treated material was imidized according to its infrared absorption spectrum. Example 4 Pyromellitic anhydride 0.1 mol (21.8 g) in acetic acid
Dissolve 0.2 mol (11 g) of propargylamine and
The reaction was carried out while refluxing acetic acid. After cooling, the mixture was poured into water, and the precipitate was washed with water and filtered repeatedly (Product A). Next, add 0.01 mol (1 mol) of cuprous chloride to pyridine.
g) is dissolved in pyridine while bubbling oxygen into the solution in the flask.
0.05 mol (12.9 g) of A was added dropwise to react. Thereafter, it was dropped into a large amount of water, and the precipitate was washed and filtered repeatedly to obtain 5 g of pale yellow powder. From the infrared absorption spectrum, absorption of ethynyl group, triple bond, and amide was confirmed. Degree of polymerization n
It was 3. When this product was heated, it had no melting point up to 300°C, but it turned red as in Example-1. In addition, when thermogravimetric analysis was performed in air, 350
There was no weight loss up to ℃, and the heat resistance was good.

Claims (1)

[Scope of Claims] 1. A disethylene-containing imide polymer having a terminal ethynyl group represented by the following general formula. (Here, R ₁ , R ₂ , R ₃ are divalent hydrocarbon groups having 1 to 30 carbon atoms, and Z is a divalent hydrocarbon group having 1 to 40 carbon atoms.
is a tetravalent hydrocarbon group, and the degree of polymerization n is 2 to 250.
It is. )