JPS6310724B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the invention] (Field of industrial application) The present invention relates to a novel method for producing a polyamide having a tricyclic heterofused ring, and more specifically, a method for producing a polyamide having a tricyclic heterofused ring without diaminating the tricyclic heterofused ring compound. , relates to a method for producing polyamides having tricyclic heterofused rings directly from said compounds in one step and without producing by-products. (Conventional technology) Conventionally, the basic manufacturing method for aromatic polyamide is as follows:
It utilized a polycondensation reaction between an aromatic diamine compound and an aromatic dicarboxylic acid compound or its acid halide. The obtained aromatic polyamide has excellent heat resistance and mechanical strength properties, but on the other hand, it has poor solubility in organic solvents.
Furthermore, it had a high melting point and high crystallinity, making injection and molding impossible. Therefore, it is extremely difficult to form into fibers, films, coatings, etc., which is a significant practical limitation. For this reason, research into aromatic polyamides, which also have excellent moldability, has been progressing, and for example, US Patent No.
3503931, Journal of Polymer Science: Polymer Chemistry Editions, Volume 18, Page 2163, 1980 [Journal of Polymer Science: Polymer Chemistry Editions]
Polymer Science: Polymer Chemistry
Edition, Vol. 18, 2163 (1980)], polyamides having tricyclic heterofused rings have been proposed. Among these, the latter polyamide has excellent heat resistance and moldability. This is the following reaction equation: As expressed by A polyamide [] having a ring is obtained. However, this reaction had serious drawbacks as described below. First, prior to this reaction, many steps are required to diaminate the tricyclic condensed heterocyclic compound, resulting in an overall high cost. Second, since this reaction is a polycondensation reaction, hydrogen chloride is produced as a by-product. This hydrogen chloride inhibits the polycondensation reaction and corrodes the reaction equipment, which is industrially disadvantageous. Thirdly, both the diaminated form [] and the diacid chloride form [] of the reaction reagent are unstable, making it difficult to store and handle them. (Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks in the method for producing a polyamide having a tricyclic condensed heterocyclic ring. The object of the present invention is to provide a method for producing a polyamide having a tricyclic condensed heterocyclic ring from the compound in a straight line in one step without producing by-products. [Structure of the invention] (Means and effects for solving the problems) The present invention provides a diisocyanate compound and the following formula:

[Formula] or (In the formula, X ₁ , X ₂ and X ₃ are respectively -O-,
-S-,

[Formula]; R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group having 1 to 5 carbon atoms, -
an alkoxy group represented by OR ₆ ,

[Formula] represents a tertiary amino group; R ₅ , R ₆ , R ₇ and R ₈
each represents an alkyl group having 1 to 5 carbon atoms; n ₁ , n ₂ , n ₃ and n ₄ each represent an integer of 0 to 3. Also, X ₁ and X ₂ , R ₁ and R ₂ , R ₃ and
R ₄ and R ₇ and R ₈ may be the same or different, and n ₁ , n ₂ , n ₃ and n ₄ are 2 to 3.
is an integer of R ₁ , R ₂ , R ₃ and R ₄
may be the same or different). It is characterized by carrying out a polyaddition reaction with at least one of the tricyclic heterofused ring compounds represented by: in the presence of a Friedel-Crafts type catalyst. The diisocyanate compounds used in the present invention include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,6-xylene -1,4-diisocyanate and other phenyl diisocyanates and their derivatives; biphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate,
2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-
Diisocyanate, diphenyl sulfide-4,
4'-diisocyanate, diphenyl sulfone-
Diphenyl diisocyanate and its derivatives such as 4,4'-diisocyanate; naphthalene-1,5
-Naphthalene diisocyanate and its derivatives such as diisocyanate; triphenylmethane-4,
Examples include triphenylmethane diisocyanate and its derivatives such as 4'-diisocyanate; or polymethylene diisocyanate and its derivatives such as hexamethylene diisocyanate. Among these, in the method of the present invention, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4' -diisocyanate and naphthalene-1,5-diisocyanate are preferred. The tricyclic heterofused ring compounds used in the present invention include dibenzo-p-dioxin, 2,7-dimethyl-dibenzo-p-dioxin, phenoxathiin, 2,7-dimethylphenoxathiin, thianthrene, 2,8- Dimethylamino-thianthrene, N-methyl-phenoxazine, N-methyl-
Examples include phenothiazine, diphenylene oxide, diphenylene sulfide, and N-methyl-carbazole. Among these, diphenylene oxide, diphenylene sulfide, dibenzo-p-dioxin, thianthrene, and phenoxathiin are preferred in the method of the present invention. In addition, in the tricyclic heterofused ring compound, R ₁ ~
Specific examples of the alkyl group having 1 to 5 carbon atoms represented by R ₈ include methyl, ethyl, propyl, i-
Examples include propyl, n-butyl, t-butyl, amyl, and the like. In addition, the Friedel-Crafts type catalyst used in the present invention includes aluminum chloride, ferric chloride,
Tin chloride, titanium chloride, zinc chloride, antimony chloride, indium chloride, copper chloride, boron trifluoride,
Examples include inorganic acids such as phosphorus trifluoride, phosphorus pentoxide, fluoroboric acid, fluorophosphoric acid, hydrochloric acid, sulfuric acid, and heteropolyacid, and organic acids such as p-toluenesulfonic acid. As the production method of the present invention, any commonly used polyaddition reaction method can be applied. Preferably, bulk polymerization or solution polymerization is used. The polyaddition reaction is expressed as follows. Or [In the above reaction formula, _R9 is an alkylene group substituted or unsubstituted with an alkyl group, an arylene group (-( _CH2 ) _-o ,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula]) (n is an integer) Among these, in the case of bulk polymerization, it is preferable to heat the reaction reagent and catalyst while stirring to make a homogeneous state, and then polymerize. 0℃～200℃,
A high molecular weight polyamide can be obtained in a reaction time of 1 to 20 hours. In the case of solution polymerization, it is preferable to use a solvent that dissolves the reaction reagent and the reaction intermediate and does not cause side reactions with the reaction reagent. -40℃～200℃, 1
A high molecular weight polyamide is obtained in ~30 hours of reaction. Examples of the above-mentioned solvents include o-dichlorobenzene, 1,3,5-trichlorobenzene, nitrobenzene, nitromethane, and carbon tetrachloride. The amount of solvent used is preferably 2 to 40 times the weight of the reaction reagent. In any of the above-mentioned polymerization methods, it is preferable that the diisocyanate compound and tricyclic fused ring compound used be in equimolar amounts in order to smoothly proceed with the polyaddition reaction. The amount of Friedel-Crafts type catalyst used varies depending on the reaction reagent and polymerization conditions, but it is based on the isocyanate group of the diisocyanate compound used.
It is preferably in the range of 0.3 to 1.5 equivalents. In the method of the present invention, an example of a treatment method after the completion of the polyaddition reaction described above is as follows: first, methanol is added to decompose the remaining isocyanate groups;
After pouring into ice water, the desired polyamide can be obtained by separating the precipitate and performing conventional treatments such as washing and drying. (Example) Example 1 69.7 g of 2,4-tolylene diisocyanate was placed in a four-necked flask equipped with a nitrogen gas inlet tube, a reflux condenser, a thermometer, and a stirring bar in a nitrogen gas atmosphere.
(0.4 mol) and anhydrous aluminum chloride 106.7 g
(0.8 mol) and dibenzo-p-
73.7 g (0.4 mol) of dioxin was added little by little over about 30 minutes, and then the mixture was heated to 80°C and reacted for 4 hours. A dark red solid polymer was obtained. After adding 100 ml of methanol to react with the remaining isocyanate groups, the mixture was poured into the ice water in step 3 with stirring. Next, the whole was filtered to separate the precipitate, and this precipitate was washed with methanol and acetone, dried, and then dissolved in dimethylformamide (DMF).
The resulting solution was poured into 2 water. After further filtering the whole to separate the precipitate, dry it to obtain a white powder of 121.9
g (yield 85%) was obtained. A strong film could be formed from this polymer by melting it. In addition, the IR spectrum (KBr tablet method) showed strong absorption of amide groups at 1655 cm ^-1 and 3300 cm ^-1 . The melting point (mp) is 354℃, the intrinsic viscosity [η] 1.05 (0.5g/100ml DMF, 30℃), and the weight loss measurement using a differential thermal balance (5℃/min, in air) shows that there is no weight loss up to 420℃. (Hereafter,
The temperature at which heating weight starts to decrease is expressed as Td). Example 2 2,4-tolylene diisocyanate 69.7g
(0.4 mol) and phenoxathiin 80.1g (0.4 mol)
was reacted at 90° C. for 10 hours in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride, and then post-treated in the same manner as in Example 1 to obtain 121.3 g (yield: 81%) of white powder. This polymer has mp: 321℃, η: 1.33,
Td: It was 382℃. Example 3 2,4-tolylene diisocyanate 69.7g
(0.4 mol) and thianthrene 86.5g (0.4 mol),
After reacting at 120° C. for 6 hours in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride, the mixture was post-treated in the same manner as in Example 1 to obtain 118.7 g (yield: 76%) of white powder. This polymer was soluble in N,N-dimethylacetamide, N-methyl-pyrrolidone, m-cresol, etc., and could be molded into a strong film by melting. mp: 298℃, η: 1.51,
Td: It was 350℃. Example 4 In nitrobenzene 1, 69.7 g (0.4 mol) of 2,4-tolylene diisocyanate and 72.5 g (0.4 mol) of N-methylcarbazole were added at 100°C in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride.
After reacting for 10 hours, the mixture was post-treated in the same manner as in Example 1 to obtain 118.0 g of yellow powder (yield: 83%). This polymer had η: 0.61 and Td: 475°C. Example 5 2,4-tolylene diisocyanate 69.7g
(0.4 mol) and 67.3 g (0.4 mol) of diphenylene oxide were reacted at 100°C for 8 hours in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride, and then post-treated in the same manner as in Example 1 to give a white color. Powder 126.0g (yield
92%). A strong film could be formed from this polymer by melting it. mp: 372℃, η: 1.13, Td:
It was 437℃. Example 6 In 100 ml of nitrobenzene, 18.4 g (0.1 mol) of dibenzo-p-dioxin and 25.0 g (0.1 mol) of diphenylmethane diisocyanate were added in the presence of 26.7 g (0.2 mol) of anhydrous aluminum chloride.
After reacting at ℃ for 5 hours, the mixture was post-treated in the same manner as in Example 1 to obtain 38.6 g of white powder (yield: 89%). A strong film could be formed from this polymer by melting it. IR spectrum: 1650cm ^-1 ,
The temperature was 3312 cm ^-1 , mp: 375°C, η: 0.84, and Td: 380°C. Example 7 Diphenylsulfone-4,4'-diisocyanate instead of 2,4-tolylene diisocyanate
200.4 g (yield: 97%) of white powder was obtained by the same treatment as in Example 3 except that 120.1 g (0.4 mol) was used. This polymer had η: 1.26 and Td: 462°C. Example 8 138.6 g of white powder (yield 92%) was prepared in the same manner as in Example 3 except that 64.1 g (0.4 mol) of m-phenylene diisocyanate was used instead of 2,4-tolylene diisocyanate. ) was obtained. This polymer had η: 1.21 and Td: 438°C. Example 9 1,5-naphthalene diisocyanate 84.1g instead of 2,4-tolylene diisocyanate
(0.4 mol) was used in the same manner as in Example 3 to obtain 145.0 g of white powder (yield: 85%). This polymer had η: 0.87 and Td: 445°C. [Effects of the Invention] According to the present invention, a polyamide having a tricyclic heterofused ring can be produced directly from the tricyclic heterofused ring compound in one step without requiring a step of diaminating the tricyclic heterofused ring compound. Furthermore, since the present invention is a polyaddition reaction, by-products such as water and hydrogen chloride are not produced. Therefore, the reaction operation is simple and the reaction apparatus is not corroded by by-products, so it is of great industrial value.

Claims (1)

[Claims] 1. A diisocyanate compound; and the following formula: [Formula] or (In the formula, X ₁ , X ₂ and X ₃ are respectively -O-,
-S-, represents [Formula]; R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group having 1 to 5 carbon atoms, -
OR represents an alkoxy group represented by ₆ , a tertiary amino group represented by [Formula]; R ₅ , R ₆ , R ₇ and R ₈
each represents an alkyl group having 1 to 5 carbon atoms; n ₁ , n ₂ , n ₃ and n ₄ each represent an integer of 0 to 3. Also, X ₁ and X ₂ , R ₁ and R ₂ , R ₃ and
R ₄ and R ₇ and R ₈ may be the same or different, and n ₁ , n ₂ , n ₃ and n ₄ are 2 to 3.
is an integer of R ₁ , R ₂ , R ₃ and R ₄
may be the same or different. ) with at least one type of tricyclic heterofused ring compound represented by; A method for producing a polyamide having a tricyclic heterofused ring, which is characterized by carrying out a polyaddition reaction in the presence of a Friedel-Crafts type catalyst. .