JPS6366228A - Polyamic acid derivative and amide-imide derivative thereof having diacetylene group - Google Patents

Abstract

PURPOSE:To obtain the titled compound, containing repeating units having a specific diacetylene-containing group linked to a specific carbonyl-containing group, and capable of providing a material, readily reactive in the solid phase to assume effective orientation and having extremely high heat resistance as well as elastic modulus. CONSTITUTION:A polyamide derivative and amide-imide derivative thereof, containing repeating units having at least one selected from diacetylene group- containing groups expressed by formula I, II or III (R<1> and R<2> are bivalent hydrocarbon) linked to at least one selected from carbonyl group-containing groups expressed by formula IV or V (Z is trivalent hydrocarbon; X is halogen, hydroxyl group, alkoxy or amino). In formula I, II or III, -CH2-, CH2H4-, etc., are preferred as R<1> and R<2> and -Cl, etc., are preferred as X.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamic acid derivative having a diacetylene group and having excellent moldability and heat resistance, and an amide-imidized product thereof.

[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 use this technique to develop various highly crystalline polymers having high elastic moduli.

(For example, “Organic Nonlinear Optical Materials J, CMC (/
9♂Yu), Macromolecule Chemistry Vol. 73, No. 7/9 (I970), Journal of Polymer Science No. B? Volume, page 733 (/97/
), Journal of Polymer Science Polymer Physics Edition Vol. 7.2, p. 7577 (/97g). ) [Problems to be solved by the invention] However, polymers of diacetylene compounds that have been synthesized so far have been synthesized by photochemically or thermally polymerizing powders or single crystals of raw material monomers. (Diacetylene compounds with topochemical polymerizability that have been investigated include HOCi(, CiC・-C≡CCH, O
This research has been limited to compounds with hydroxyl groups such as H and their derivatives, which has hindered the progress of research. On the other hand, in materials into which nitrogen atoms have been introduced, the electronegativity and cohesive force of the nitrogen atoms can be utilized in -1-, but when the nitrogen atoms have -NH- bonds, the intermolecular force due to hydrogen bonds and the nitrogen IG1 bond can be utilized. The reactivity of diacetylene compounds can be utilized to strengthen the intermolecular interactions between diacetylene compounds, and the development of various derivatives can be considered, and there are great expectations for the potential of topochemical reactions and their practical application.

From this point of view, diacetylene group-containing polyamic acid derivatives and polyamideimides are of great interest; , is hardly known.

The present inventors have conventionally examined the method of introducing various groups such as an alkyl group next to a diacetylene group and the characteristics of the obtained compoundsff-1', and in the process, they After successfully synthesizing an acid derivative and its amide imidide, and as a result of intensive research, the present invention was arrived at. The object of the present invention is to provide a polyamic acid derivative containing a repeating unit formed by bonding at least seven selected groups and at least one type selected from carbonyl-containing groups represented by (1) or V, and an amide-imidized product thereof. .

-HN-R1-C≡C-CE:C-R2-NH-...
1\N-R'-C≡C-C≡C-R2-NH-・-1\
N-R1-c=e-C≡C-R2-N'
...lOX (in the formula, R1 and R2 are divalent secondary hydrogen groups, 2 is trivalent -
It is a divalent hydrocarbon group, and R1 and R'' may be holes. Examples include CI2-1-C21!,
-1-C3H6-5-C4H,--1-C,I16--
--CsH+5-1-C,. Examples include complex groups of Il, -1- and alicyclic groups, and these R,
Some of the hydrogen atoms of H are halogen atoms, nitro groups,
It may have a hydroxyl group, a cyano group, or a carboxyl group.

Examples of bonding groups other than such hydrocarbon groups include -〇-1-s-1-80. -1-CO-1-NH-1-
NCH3-1-COO-1-C0NH-1zhs
7-, and these may be combined or repeated.

Preferred as R, , R, in terms of ease of synthesis and in the present invention, 2 is a trivalent hydrocarbon group with carbon number/~g θ; examples thereof include 1. The hydrocarbon group may be connected by a functional group having a tooth hetero atom such as: CHCH, -1-♂ -. Further, some or all of the hydrogen atoms of the above covalent hydrocarbon group may be substituted with a halogen atom, nitro group, cyano group, carboxyl group, amide group, ester group, carbonyl group, ether bond, etc. .

Among these trivalent hydrocarbon water-carrying groups, preferred are 91 In the present invention, X is a halogen atom, a hydroxyl group, an alkoxy group, or an amino group, examples of which are -F, -C
6, -Br, -I, -011, -0CH3, -QC,
H,, -QC3H,, -004H,, -0C5Hn, -
QC,H13,-QC,H,,,-008H1,,-Q
CgHz, -0C1o)1st, -N)(,, -NH
-CHm, preferably -Ct, -Br,
-〇11, -0CH3, -QC,H,, -NH2, -N
H-CH,, N(CHi)x, etc.

The present invention provides at least one diacetylene-containing group represented by the general structural formula I of the present invention,
Also included are so-called -/θ- copolymers with repeating units other than repeating units formed by combining at least seven carbonyl-containing groups represented by (1) or V. In this case, there are no particular limitations on the repeating unit other than the general structural formula 1 or A, but repeating units such as amide, imide, amide-imide, ester, and ether are preferably used. In such a copolymer, the cyanoacrylic acid represented by the general structural formula 1 of the present invention, (1), or the diacetylene group of the present invention has a diacetylene group.

Minodiacetylene compound H2N-R1-C-1=c-C
A method of oxidative coupling polymerization using C-R2-NH2 is proposed.

The amide solvent used at this time is not particularly limited, but examples thereof include N,N-dimethylformamide, N-methylpyrrolidone, and the like. In addition, there are no particular restrictions on the phosphorus group catalyst used in oxidative coupling polymerization, such as copper chloride (+) and copper acetate (1), and there are no particular restrictions on the bath medium used. Examples include pyridine and l-ethylamine.

In order to synthesize the polyamideimide having diacetylene groups of the present invention, for example, the polyamide acid having diacetylene groups of the present invention is heated as it is, and a dehydrating agent such as phosphoric acid or dicyclohexylcarbodiimide is used. Examples include a method of condensation.

Examples include a method in which a heated dehydration reaction is carried out, and the resulting imide is subjected to oxidative coupling polymerization.

〔Effect of the invention〕

The diacetylene group-containing polyamic acid derivative and polyamide-imide of the present invention have a cohesive force due to heteroatoms (secondarily, polymer chains have an orientation that is extremely effective for causing a solid-phase reaction due to diacetylene groups, and are easily crosslinked). ,
Therefore, it has a high elastic modulus, and in general organic polymers /
The elastic modulus is ~j GPa (2), but an elastic modulus of 30 Pa or more can be easily achieved.

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 or organic fibrous, powder, or flaky materials. It is extremely good.

As described above (2), the polyamic acid derivative and polyamide imide containing the diacetylene paper of the present invention are new materials that have good moldability, heat resistance, and high elastic modulus, and are suitable for fields that require these characteristics. Extremely useful.

[Example J Example-/11/G-H,NCH,-C≡C-C≡C-CH2NH20.2 mol and 0.7 mol of G-chloroformyl-phthalic anhydride were mixed with N-methylpyrrolidone copolymer. The mixture was dissolved in θθ− and reacted at θ°C for 1 hour in nitrogen atmosphere. After the reaction, the reaction product was poured into water, and the precipitated polymer was isolated by suction filtration. The yield of polymer obtained was quantitative.

I R (film) 3270cm-”, / Otog θc
The polyamic acid of rn-', /OtθOtyn-1 Example-CoExample-/ was heated at 30θ℃ under a nitrogen stream.
, heat treatment was performed for 30 minutes. The yield of polymer obtained was quantitative.

I R (Nujol) 3 da θgcm-', /73♂
crn-1, /O θOcm-” When this product was subjected to thermogravimetric analysis in air, there was no weight loss up to 2♂0°C and the heat resistance was good.

Example-3 Synthesis of −/j − In Example-7, H,N-CH,-, C≡C-C≡C
-CH2NHtIR (film) 3300cm-
”, 3θθθcIn-1, /1.￥♂α-1, /≦θθ
crn"" Example-I R (Nujol) 3θ0θα-1, /72♂
cm-'', /l θθ Sub-1 Knee 1 product was subjected to thermogravimetric analysis in air, and there was no weight loss up to 3 days θ°C, indicating that it had good heat resistance.

Example 3 was repeated except that Example 3 was used. The yield of polymer obtained was quantitative.

IR (fth m) 33θθcn1-', 3θθθcI
n-", /l'l (5'cm-"Example-Y7tJ was synthesized.

Example 2 The method of Example 7 was repeated using the polyamic acid of Example 7.

IR (Nujol) 3θθθcfn-', /7daθ(m-', /Otsuθ3ttn-'Example-D-/♂-0.02 mol was added, and Example-3 was repeated.

IR (film) 330θCrn-1, 3θ00
tyn-", /Otsujθgo1/6θOcm-' Example-/θ

Claims (1)

[Scope of Claims] At least one type selected from diacetylene-containing groups represented by the following general structural formulas I, II, or III and at least one type selected from carbonyl-containing groups represented by IV or V. A polyamic acid derivative containing a repeating unit formed by bonding and its amide imide compound -HN-R^1-C≡C-C≡C-R^2-NH-...
・ I > N-R^1-C≡C-C≡C-R^2-NH-
...II>N-R^1-C≡C-C≡C-R^2-N<
...III▲There are mathematical formulas, chemical formulas, tables, etc.▼...IV ▲There are mathematical formulas, chemical formulas, tables, etc.▼...V (In the formula, R^1 and R^2 are divalent hydrocarbon groups , Z is 3
It is a valent hydrocarbon group, and X is a halogen atom, a hydroxyl group, an alkoxy group, or an amino group. )