JPS6366226A - Diacetylene-containing polyamic acid derivative and polyimide having terminal ethynyl group - Google Patents

Abstract

PURPOSE:To obtain the titled derivative and polyimide, having ethynyl groups at the terminals and containing diacetylene groups, capable of providing a material readily polymerizable in the solid phase by thermal crosslinking or heat, pressure or light to provide a high molecular weight in the three- dimensional direction and having improved heat resistance as well as moldability. CONSTITUTION:A polyamic acid derivative and polyimide, containing at least one kind of repeating unit expressed by formula I or II (R1, R2 and R3 are bivalent hydrocarbon; Z1 and Z2 are tetravalent hydrocarbon group; X is halogen, hydroxyl, alkoxy or amino) and having >=1 diacetylene groups based on 1 ethynyl group. In formula I or II, -CH2-, -C2H4-, etc., are preferred as R1-R3 and -Cl, etc., are preferred as X. The ratio of the terminal ethynyl group to the diacetylene group is preferably 1:>=3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] Attempts have been made to develop various highly crystalline polymers having high elastic modulus using the techniques described in [Industrial Field of Application].

(For example, "Organic nonlinear optical materials", CMC (1
985), Macromolecule Chemistry Vol. 134, p. 219 (1970), Journal of Polymer Science Vol. 39, p. 133 (1971), Journal of Polymer Science Polymer Physics Edition Vol. 12, p. 1511 ( 1974
). ) [Problem that the invention seeks to solve] However,
Polymers of diacetylene compounds that have been synthesized so far have been obtained by photochemically or thermally polymerizing raw material monomer powders or single crystals, so they cannot be obtained as large molded bodies, and the broken polymer itself cannot be obtained. Since many of them are insoluble in water and organic solvents, the processability of polymerization is extremely poor.

It was limited to compounds and their derivatives, which hindered the progress of research. In contrast, in materials with nitrogen atoms introduced, the electronegativity and cohesive force of nitrogen atoms can be utilized, and if the nitrogen atoms have -Nl (- bonds, intermolecular forces due to hydrogen bonds and reactions of nitrogen atoms) It is possible to strengthen the intermolecular interaction between diacetylene compounds, such as by utilizing their properties, 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 polyamic acid derivatives and polyimir H11 are of great interest, but diacetylene group-containing polyamic acid derivatives and polyimir H11 that exhibit topochemical reactivity like conventional ones are , is almost unknown.

The present inventors have conventionally investigated the method of introducing various groups such as an alkyl group next to a diacetylene group and the properties of the obtained compounds. We succeeded in synthesizing polyamic acid derivatives and polyimide, and as a result of further research, we arrived at the present invention.

To polyamic acid derivatives and polyimides having terminal ethynyl groups as shown above (wherein R1+R,, R3 are divalent hydrocarbon groups, Zl
t z= is a tetravalent hydrocarbon group. X is a nitrogen atom, a hydroxyl group, an alkoxy group or an amine group. ).

In the present invention, R1+ R2+ R3 has 1 to 3 carbon atoms.
They may be connected by OH, -OH. Examples of bonding groups other than such hydrocarbon groups include -〇- and -S-.

-SO鵞-, -00+, -book one, -No) (, -, -
000-.

100NH-, -0ON-, -NHOO-NH-t -
N=N-.

2H5 -HO=N-, etc., and these may be combined or repeated nine times. Rt+ R1+ lLL+
Preferably, the hydrocarbon group may be bonded to a functional group having a hetero atom such as 8- for ease of synthesis and topochemical properties. In addition, some or all of the hydrogen atoms of the above divalent hydrocarbon group are halogen atoms,
Even if it is substituted with a nitro group, a cyano group, a carp-xyl group, an ami-p group, an ester group, a carzenyl group, an ether bond, etc.

Among these Z1 + Z2, in view of ease of synthesis and reactivity, in the present invention, X is a non-logne atom, a hydroxyl group, an alkoxy group, or an amino group, examples of which include F, On,
Br, I@OH,0OH3,002H5
゜-0OIIH,,-004H4,-QC! 5H...
-006) (13, -007H1,.

00@Hty + 009H19+ 0O10H2
1+ NH2+ -NH-OH3.

It also includes copolymers. In this case, there are no particular restrictions on the <silicone unit> other than the general structural formula (1) or (2), but <silica units such as amide P1 imide, amide imide P1 ester, and ether are preferably used. In such a copolymer, the general structural formula (1) of the present invention
and/or ij: The amount of repeating units in (2) is not particularly limited, but is preferably 1 mol% or more, particularly preferably 5 mol% or more.

In the present invention, the general structural formula (1) is an amic acid derivative, and the general structural formula (2) is an imide, but the amic acid derivative has better solubility in solvents, and depending on the application [;)7 may be preferably an amic acid derivative.

The terminal ethynyl group of the present invention is described in JP-A-52-259, etc.; j
, ≦ As shown, it acts as a crosslinking group like the diacetylene group and is necessary to increase the crosslinking density.

In the present invention, a polyamic acid derivative containing a terminal ethynyl group and diacetylene can be synthesized by making effective use of known organic synthesis reactions. For example, the diaminodiacetylene compound H, N -R, -030-0=0-
几3-NFh, aminoacetylene compound HxNRs
O4:OH and the aforementioned zl and z2 are shown. A diacetylene-containing polyamic acid having a terminal ethynyl group represented by an acid anhydride represented by ) is synthesized. Or H,N
-⇠-o=oH (here, ⇠ represents the above-mentioned R1+ 'R'2 and ⇠3) and OO) are reacted, and the resulting amic acid R1+ R,
and R3, and Z represents the aforementioned Z and Zl. ) is subjected to oxidative coupling polymerization using a metal catalyst. There are no particular restrictions on the ami-P solvent used at this time, but examples include N,N-dimethylformamide, N
- A method of condensing a polyamic acid having a diacetylene group such as methyl pyrrolyne by heating it directly, or when X (herein, X represents the aforementioned X) is -OH, acetic anhydride, polyphosphoric acid, Ha Jiimi P
Examples include a method of condensation using a dehydrating agent such as.

Or, H, N-R-OEIEOI ((Here, R is the above-mentioned R1, R.

-[-Effects of the Invention] The diacetylene-containing polyamic acid derivative and polyimide P having a terminal ethynyl group of the present invention are thermally crosslinked by the terminal ethynyl group and diacetylene group, or solid phase polymerized by thermal pressure or light, Provides a material whose molecular weight can be increased in three dimensions.

When thermogravimetric analysis of the crosslinked product is performed in air, it is generally found that 2
It exhibits extremely good heat resistance without losing weight even at temperatures above 00°C, especially above 300°C.

In addition, for example, the di) "j) having a terminal ethynyl group of the present invention can be used in various forms such as liquid and suspension, and can also be mixed with inorganic or organic fibrous materials, powders, and flakes. It can also be used in combination with other curable resins, polymeric materials, colorants, stabilizing materials, etc., and can be molded into various shapes.

Due to the above characteristics, it is extremely useful as a source of a wide variety of high-performance materials, such as coating materials, base materials for reinforcing materials, sealants, potting materials, electronic materials, and heat-resistant films.

〔Example〕

Example-1 N-methylpyrrolid y500m/3, a'-4,
4'-benzophenone tetracarponic acid anhydride 0.2m
oλ (64,4F) and 1,6-diami2,4-hexadiyne 0.18 mof), (19,44t)
Although there was no reaction for 3 hours, the color 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.

=17- The infrared absorption spectrum of the heat-treated material is
It had been made into

Example-2 0.196 1,6-diami2,4-hexadiyne
White powder 652 (yield 95%) was synthesized in the same manner as in Example-1 except that mol (21, 1689) was used.
came.

When this product was heated, its melting point reached 300°C, and the infrared absorption spectrum of the heat-treated product showed that it had been imidized.

Example-3 A white powder 51.3 (
A yield of 90% was obtained.

In the infrared absorption spectrum, absorption of ethynyl group, triple bond, and acid amide was confirmed as in Example-1.

When this product was heated, it had no melting point up to 3001: but turned red as in Example-1. Further, 0.2 mon (11y) of propargylamine was dissolved and reacted while refluxing acetic acid. After cooling, the mixture was poured into water, and the precipitate was washed with water and filtered again (Product A). Next, add 0.05moff (12,9y) of product A dissolved in pyridine without bubbling oxygen into the solution in the flask containing 0.01moff (1y) of cuprous chloride in pyridine.
was added dropwise to react. Thereafter, the precipitate was poured into a large amount of water, washed with water, filtered, and repeated to obtain 5 pieces of pale yellow powder.

In the infrared absorption spectrum, absorption of ethynyl group, triple bond, and imide was confirmed.

When this product was heated, there was no melting point up to 300°C, but it turned red as in Example-1.

Furthermore, when thermogravimetric analysis was performed in air, there was no weight loss up to 350°C, and the heat resistance was excellent.

Example-5 Example-1 was repeated except that 0.04 moJ2 of 1,6-diami-2,4-hexadione was added.

IR3259cm, 2190Q11, 167
6 cm, 15480111350 (to)-1 Example-7 0.16 moj! And then 0.04 moj of diaminodiphenylmethane! Example 3 was recombined except for the addition.

Claims (1)

[Scope of Claims] A polyamide containing at least one type of repeating unit represented by the following general structural formula (1) or (2), and having a terminal ethynyl group in which the number of diacetylene groups is one or more per one ethynyl group. Acid derivatives and polyimides. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) (In the formula, R_1, R_2, R_3 are divalent hydrocarbon group,
Z_1 and Z_2 are tetravalent hydrocarbon groups. X is a halogen atom, a hydroxyl group, an alkoxy group, or an amino group. )