JPH0565530B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a diacetylene group-containing polyimide. More specifically, the present invention relates to a diacetylene group-containing polyimide that is easily crosslinked by diacetylene groups contained in the polymer main chain to give a highly rigid molded article. [Prior Art] It is well known that certain diacetylene compounds can be polymerized in a crystalline state by heat and high-energy rays such as gamma rays or ultraviolet rays (topochemical polymerization). Most of the research has focused on diacetylene compounds, and although there have been some reports on polymers containing diacetylene groups, there are only a few research examples. (Macromonochemical Chemistry (Makromol.Chem.,) 134 , 219
(1970), Journal of Polymer Science Polymer Chemistry Editions (J.
Polym.Sci.Polym.Chem.Ed.) 19 , 1154 (1981)). In addition, the present inventors focused on the characteristics of diacetylene groups, and by molding polyurethane or polyester containing a diacetylene structure under high pressure conditions in a solid state below their decomposition temperature or below their melting temperature. It has been found that a highly rigid molded body can be obtained. [Problems to be Solved by the Invention] Although diacetylene group-containing polyurethanes and polyesters can yield highly rigid molded products, there are problems with their moldability, heat resistance, and the like. The inventors of the present invention thought that in order to produce a highly rigid molded product with excellent moldability, thermal properties, etc., it would be best to introduce a polar group and increase the rigidity of the polymer main chain. , discovered a diacetylene group-containing polyimide and arrived at the present invention. [Means for Solving the Problems] The present invention provides a diacetylene group-containing polyimide having a number average molecular weight of 5000 or more and consisting of repeating units represented by the following general formula (). (In the formula, R ¹ and R ² are aliphatic hydrocarbons, aromatic hydrocarbons, or a divalent hydrocarbon group having 1 to 20 carbon atoms combined with these, and Z is an alkylene chain, ether bond, thioether A tetravalent aromatic hydrocarbon group having 1 to 30 carbon atoms, which may be a group connected by a bond, a carbonyl group, or a sulfone group. n represents an integer of 2 or more.) The present invention In, R ¹ and R ² are divalent hydrocarbon groups each having 1 to 20 carbon atoms, for example, as an aliphatic hydrocarbon group, -CH ₂ -,

【formula】 【formula】

【formula】

【formula】 【formula】

[Formula] −C ₂ H ₄ −, −C ₃ H ₆ −, −C ₄ H ₈ −,

[Formula] etc. As an aromatic hydrocarbon group,

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. As a complex hydrocarbon group, etc. As a preferable divalent hydrocarbon group, from the viewpoint of easy availability of raw materials for production, price, and rigidity of the produced polyimide,

【formula】 【formula】

−CH ₂ −, −C ₂ H ₄ −,

[Formula] etc. In the present invention, Z is 4 having a carbon number of 1 to 30.
It is a valent aromatic hydrocarbon group, and may be a group connected by an alkylene chain, an ether bond, a thioether bond, a carbonyl group, or a sulfone group. For example, as an aromatic hydrocarbon group,

【formula】

【formula】

【formula】 【formula】

etc. As a linked aromatic hydrocarbon group, (X is O, S,

[Formula] CH ₂

[Formula]) etc. Preferred tetravalent aromatic hydrocarbon groups include, from the viewpoint of ease of obtaining raw materials for production, price, etc.

【formula】

【formula】 〔Effect of the invention〕

The diacetylene group-containing polyimide of the present invention is molded using a normal polymer molding method, and then the diacetylene groups are crosslinked to form a densely crosslinked, excellent thermal property and highly rigid molded product. can. Depending on the use, it can be used in powder form, sheet form, film form, tube form, maintenance form, textile form, cotton form, etc.
It can be used in various shapes such as plates, rods, flakes, lumps, solutions, and suspensions, as well as inorganic and organic fibrous materials, powders, flakes, sheets, and films. It can be mixed with objects, tubular objects, woven objects, plate-like objects, rod-like objects, cotton-like objects, or mixed with other curable resins, polymeric materials, colorants, stabilizing materials, etc. is also possible. Since diacetylene group-containing polyamic acids and their derivatives are soluble in organic solvents, they can be easily formed into films by solvent casting. Therefore, uniaxial or biaxial orientation is also possible. Thereafter, the desired polyimide can be obtained by dehydrating and cyclizing using heat or a chemical cyclizing agent. Furthermore, since the molded product of the diacetylene group-containing polyimide of the present invention is crosslinked by π-electron conjugation, it can also be applied as a conductive material or a highly functional material such as a nonlinear optical material by doping. . [Example] Next, the present invention will be described in more detail with reference to Examples. In the example, the intrinsic viscosity (ηinh) was measured at 30° C. after diluting the polymer solution with N-methylpyrrolidone to a ratio of 0.5 g of polymer/100 ml of solvent. In the text, all parts are expressed in parts by weight. Note that the examples do not limit the scope of the present invention. Reference example (synthesis of bisacetylene monomer) 2,2-bis{4-(3,4-dicarboxylphate) was added to a 4-necked flask with a capacity of 1 equipped with a stirring device, a dropping device, a nitrogen inlet tube, and a thermometer under a nitrogen stream. 52 parts of enoxy)phenyl}propane dianhydride were dissolved in 100 ml of dry dimethylformamide. Next, 11.5 parts of propargylamine was added dropwise into the flask with stirring. Thereafter, the reaction was carried out at 60°C to 80°C for 2 hours. Furthermore, 102 parts of acetic anhydride and 10 parts of toluethylamine were added and reacted for 3 hours. After the reaction is completed, the reaction solution is cooled and poured into 10 times the amount of water to precipitate the reaction product, filtered and washed.
It was dried for one day and night at 60°C under reduced pressure. The yield of product was 61 parts. It was further purified using a silica gel column. When this product was analyzed by IR spectrum and NMR spectrum, it was found that 2,2
-Bis{4-(N-propargyl phthalimide-)
It was confirmed to be 4-oxy)-phenyl}propane. Similarly, propargylamine was changed to aminophenylacetylene, and 2,2-bis{4-(N-(3
-Ethynylphenyl)phthalimido-4-oxy}-phenyl]propane was synthesized. Example 1 Synthesis of 500 equipped with a stirring device, oxygen inlet tube, and thermometer
1.98 parts (0.02 mol) of cuprous chloride in a 4-neck flask,
Dissolve 2.32 parts (0.02 mol) of tetramethylethylenediamine in 200 ml of orthodichlorobenzene.
The mixture was stirred for 20 minutes under an oxygen stream. Next, 2,2-bis{4-
(N-propargyl phthalimido-4-oxy)-
59.5 parts of phenyl}propane were added, and polymerization was carried out at room temperature for 60 minutes and at 60° C. for 120 minutes under an oxygen stream. After the polymerization was completed, the reaction solution was poured into methanol (2) with vigorous stirring to separate the polymer. The resulting polymer was washed three times with methanol and dried under reduced pressure at room temperature for about 100 hours. The yield of product was 55.2 parts, giving a yield of 92.8%. When this product was analyzed by IR spectrum, it was confirmed that it was the desired diacetylene group-containing polyimide. Further, as a result of molecular weight measurement by GPC (gel permeation chromatography), the number average molecular weight was 10,700 (in terms of polystyrene). The IR spectrum of this polyimide is shown in Figure 1. Thermogravimetric analysis of this polyimide in air showed that there was no weight loss up to 355°C, and the heat resistance was good. Example 2 Synthesis of 2,2-bis[4-{N-(3-
ethynyl phenyl) phthalimido-4-oxy)
Example 1 was repeated except that 71.8 parts of -phenyl}propane were used. The yield of product was 66.7 parts. The IR spectrum confirmed that it was the desired diacetylene group-containing polyimide. The yield was 93.2%. The IR spectrum is shown in Figure 2. When this polyimide was subjected to thermogravimetric analysis in air, there was no significant weight loss up to 410°C, and it was found to have good heat resistance. Example 3 Synthesis 1 equipped with a stirrer, nitrogen inlet tube, and thermometer
Dissolve 23.2 parts (0.1 mol) of 3,3'-diaminodiphenylbutadiyne in 450 ml of dry N-methylpyrrolidone in a 4-necked flask, cool in a 20°C water bath,
Under a nitrogen stream, 21.8 parts of pyromellitic anhydride was added with vigorous stirring. Subsequently, polymerization was continued at room temperature. After the reaction was completed, the reaction solution was poured into water to separate the polymer. After filtering and washing the precipitated polymer, it was dried under reduced pressure at room temperature for about 100 hours. Product yield was quantitative. The resulting diacetylene group-containing polyamic acid had a viscous conductivity (ηinh) of 0.59. It was confirmed by IR spectrum that it was a diacetylene group-containing polyamic acid represented by the following formula. IR (film) 3400cm ^-1 , 1730cm ^-1 , 1640cm ^-1 Add N-methylpyrrolidone to the above polyamic acid solution
300 ml, 31 parts of acetic anhydride, and 22 parts of pyridine were added and reacted for one day and night at room temperature. The reaction was further carried out at 60°C for 2 hours to complete the cyclization reaction. The obtained polymer dispersion solution was poured into methanol 3 with vigorous stirring to separate the polymer. After washing the obtained polymer three times with methanol,
It was dried under reduced pressure at room temperature for about 100 hours. The yield of product was 42.2 parts. Analysis by IR spectrum confirmed that it was the desired diacetylene group-containing polyimide. Yield is 94%
It was hot. The IR spectrum is shown in Figure 3. When this polyimide was subjected to thermogravimetric analysis in air, there was no weight loss up to 420°C, and the heat resistance was good. Example 4 Synthesis of Example 3 Polymerization was carried out in the same manner as in Example 3, using benzophenonetetracarboxylic dianhydride instead of pyromellitic anhydride. Product yield was quantitative. The viscosity (ηinh) of polyamic acid was 0.27. It was confirmed by IR spectrum that it was a diacetylene group-containing polyamic acid represented by the following formula. IR (film) 3400cm ^-1 , 1730cm ^-1 , 1665cm ^-1 , 1640
cm ⁻¹ , followed by dehydration and ring closure in the same manner as in Example 3. The yield of the product was 54.1 parts, which was 98%. The IR spectrum is shown in Figure 4. Thermogravimetric analysis of this polyimide in air resulted in a temperature of 430°C.
There was no weight loss and the heat resistance was good. Example 5 Synthesis of H ₂ NCH ₂ -C≡C-C≡C-CH ₂ NH ₂・
1 mol of 2HCl, 1 mol of pyromellitic anhydride and 2 mol of sodium hydroxide were mixed with 500 mol of N-methylpyrrolidone.
ml and reacted at 30°C for 2 hours under nitrogen. After the reaction, the reaction product was poured into water, and the precipitated polymer was isolated by suction filtration. The yield was quantitative. IR (film) 3276cm ^-1 , 1648cm ^-1 , 1600cm ^-1 This polyamic acid was heated at 300℃ under a nitrogen stream.
A polyimide was obtained by heat treatment for 30 minutes. The yield was quantitative. IR (Nujol) 3000 cm ^-1 , 1740 cm ^-1 , 1600 ^-1 The thermogravimetric analysis of this product in air showed no weight loss up to 350°C, indicating good heat resistance. Example 6 In Example 5, N ₂ NCH ₂ C≡CC≡CCH ₂
Instead of _NH2.2HCl , Example 5 was repeated except using . The yield was 93%. IR (film) 3300cm ^-1 , 3000cm ^-1 , 1648cm ^-1 , 1600
cm ^-1Using this polyamic acid, in acetic anhydride,
It was heated at 120°C for 1 hour. The yield was 96%. IR (Nujol) 3000cm ^-1 , 1728cm ^-1 , 1600cm ^-1 This product was subjected to thermogravimetric analysis in air and showed no weight loss up to 400°C, indicating good heat resistance. Example 7 Synthesis Example 5 was repeated except that 3,3'-4,4'-benzophenonetetracarboxylic anhydride was used in place of pyromellitic anhydride. The yield was 92%. IR (film) 3270 cm ^-1 , 1648 cm ^-1 , 1600 cm ^-1 The heat treatment of Example 5 was repeated using this polyamic acid. The yield was quantitative. IR (Nujol) 3000cm ^-1 , 1728cm ^-1 , 1600cm ^-1 This product was subjected to thermogravimetric analysis in air and showed no weight loss up to 400°C, indicating good heat resistance. Example 8 Synthesis of 0.1 mol of 3,3'-4,4'-benzophenonetetracarboxylic acid anhydride and 0.2 ml of propargylamine were subjected to a cyclodehydration reaction in acetic acid to obtain a white reaction product. (Product A) Next, 0.05 mole of product A dissolved in pyridine was added dropwise to a flask containing 0.01 mole of cuprous chloride dissolved in pyridine while bubbling oxygen to cause a reaction. Thereafter, the reaction product was poured into water, and the precipitated polymer was isolated by suction filtration. The yield was 34%. IR (Nujol) 3260cm ^-1 , 2195cm ^-1 , 1780cm ^-1 , 1710
cm ^-1 Thermogravimetric analysis of this product in air showed no weight loss up to 340°C, indicating good heat resistance.

[Brief explanation of the drawing]

1 to 4 are diagrams showing IR spectra of diacetylene group-containing polyimides obtained in Examples 1 to 4, respectively.

Claims (1)

[Claims] 1. The following general formula () (In the formula, R ¹ and R ² are aliphatic hydrocarbons, aromatic hydrocarbons, or a divalent hydrocarbon group having 1 to 20 carbon atoms combined with these, and Z is an alkylene chain, ether bond, thioether A tetravalent aromatic hydrocarbon having 1 to 30 carbon atoms, which may be a group connected by a bond, a carbonyl group, or a sulfone group, and n represents an integer of 2 or more.) Number average molecular weight consisting of units 5000
The above diacetylene group-containing polyimide.