JPS58129017A - Preparation of polyamide having hetero condensed ring of tricyclic type - Google Patents

Abstract

PURPOSE:To obtain the titled by one process without diaminating a heterocyclic compound, by subjecting a specific heterocyclic compound of the tricyclic type and a polyisocyanate compound to addition polymerization in the presence of Fridel-Crafts catalyst. CONSTITUTION:(A) A polyisocyanate compound such as p-phenylene diisocyanate, etc. having two or more isocyanate groups and (B) a heterocyclic compound of the tricyclic type (e.g., dibenzo-p-dioxane, etc.) shown by the formulaIand/or formula II[X1-X3 are -O-, -S-, -SO2-, etc.; R1-R4 are 1-5C alkyl, alkoxy, or tertiary amino group, n1-n4 are integer of 0-30]are subjected to addition polymerization in the presence of (C) Fridel-Crafts catalyst such as aluminum chloride, etc. to give the desired polyamide. EFFECT:The reaction and operation are simple, and a reaction device, etc. are not corroded by by-products since no by-products such as H2O, HCl, etc. are produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a novel method for producing a polyamide having a tricyclic heterofused ring, and more specifically to a method for diaminating a trinomial heterofused ring compound. The present invention relates to a method for producing a polyamide having a tricyclic heterofused ring directly from the compound in a single process without producing any by-products.

[Prior art and its problems]

Conventionally, the basic method for producing aromatic polyamides has utilized a polycondensation reaction between an aromatic cyanide 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, and has a high melting point and high crystallinity, making injection and molding impossible. Met. Therefore, the molding into fibers, films, coatings, etc. is extremely time consuming, which is a significant practical limitation.

For this reason, research into aromatic polyamides that also have excellent moldability has been carried out, for example, in US Patent No. 3.503.9.
Aromatic polyetheramides, as seen in No. 31 of the journal Oppolymer Ichiban Science:
Polymer Chemistry Edition, $18 volume,
2163 pages, 1980 [Journal of Po
polymer 8cimce: Polymer Ch
emlstry TMmut1on.

Mo1.18, 2163 (1980)) '4 has been proposed to have a tricyclic heterofused ring. Among these, the latter polyand has excellent heat resistance and moldability.

This is expressed by the following reaction formula: % Formula % [As expressed by the following reaction formula, diaminated tricyclic fused ring compound (1) is mixed in a solvent such as N-methyl-pyrrolidone,
Polycondensation reaction with an aromatic di-acid chloride [synthesis] is used to obtain boriad m having a tricyclic heterofused ring.

However, this reaction had serious drawbacks.

11E1 requires many steps to diaminate the tricyclic fused heterocyclic compound prior to this reaction,
This means that prices will rise overall.

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, since the reaction reagents diaminated form m and diacid clophyte form (1) are both unstable, it is difficult to store and handle them.

[Purpose of the invention]

The present invention solves the above-mentioned drawbacks in the method for producing polyamides having tricyclic heterofused rings, and as soon as a tricyclic heterofused ring compound is diaminated, the compound can be directly processed in one process. The object of the present invention is to provide a method for producing a polyamide having a tricyclic condensed heterocyclic ring without producing by-products.

[Summary of the invention]

The present invention provides a polyisocyanate compound having two or more incyanate groups;
-S-1-SO, -1-PO, -1-CO-1-NR,
-; R1, R, , R, and R4 are each an alkyl group having 1 to 5 carbon atoms, an alkoxy group represented by -〇R, and R7 and R are each an alkyl group having 1 to 5 carbon atoms. represents: rh, nt, Xl Hatake and R4 each represent an integer of 0 to 3. Also, Xl and X, , R
, and 8-fold, R8 and R6, and R1 and R, may be the same or different, respectively, and town, n snow, n
When @ and R4 are integers of 2 to 3, multiple R11
2, Rs and R6 may be the same or different, respectively. ) with at least one tricyclic heterofused ring compound represented by: 7 in the presence of a Riederukla 7 type catalyst.

Examples of the polyisocyanate compound having two or more inocyanate groups used in the present invention include p-fluorinated diisocyanate, 2,4-tolylene diisocyanate (,2
t 6-1” lylene diisocyanate, 2,6-xylene-1,4-diisocyanate, l-methylbenzene-
7 such as 2,4,6-doliisocyanate), 1,3,5-trimethylbenzene-2,4,6-)diisocyanate, etc.
enylbolyinocyanate and its derivatives; or biphenyl-4,4'-diisocyanate, biphenyl-
2,4,4'-) diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diincyanate, diphenyl Sulfide-4゜4'-diisocyanate, diphenylsulfone-4゜4'-diincyanato, diphenylmethane-2゜4,4'-) diisocyanate, 4,4
'-dimethyldiphenylmethane-2,2',5,5
Diphenyl polyisocyanate and derivatives thereof such as '-tetraisocyanate; Or naphthalene polyisocyanate and derivatives thereof such as naphthalene-1,5-diisocyanate and naphthalene-1,3,7-triisocyanate; Triphenylmethane polyisocyanate and derivatives thereof such as triphenylmethane-4,4'-diisocyanate and triphenylmethane-4,4',4''-triisocyanate; Polymethylene polyphenyl polyisocyanate and derivatives thereof, where 0 represents an integer; or polymethylene polyisocyanate such as hexamethylene diisocyanate and derivatives thereof;

Among these, in the method of the present invention, p-phenylene diyne cyanate), 2,4-)'J diisocyanate, diphenylmethane-4,4'-diisocyanate,
Naphthalene-1,5-diisocyanate is preferred.

The tricyclic heterofused ring compounds used in the present invention include dibenzo-p-dioxin, 2,7-dimethyl-dibenzo-
p-dioxin, phenoxathiin, phenoxathiin-10,10-dioxide, 2,7-simethoxyphenoxathiin-10,10-dioxide, thianthrene, thianthrene-10°lO-dioxide, thianthrene-5,5, 10,10-dioxide, 2,8-dimethylamino-thianthrene, N-methyl-7dinoxazine, N-methyl-phenothiazine, anthraquinone, diphenylene oxide, diphenylene sulfite, diphenylene sulfone, N-methyl-carbasol, etc. is exemplified.

Among these, diphenylene oxide, diphenylene sulfite, dipenzo-p-dioxin, and phenoxathiin are preferred in the method of the present invention.

In addition, in the tricyclic heterofused ring compound, R3 to B.

Specific examples of the alkyl group having 1 to 5 carbon atoms represented by include methyl, ethyl, propyl, 1-propyl, n-butyl, t-butyl, amyl, and the like.

Furthermore, the Friedel-Krach type catalyst used in the present invention includes aluminum chloride, ferric chloride, tin chloride, titanium chloride, zinc chloride, antimony chloride, indium chloride,
Chlorinated steel, boron trisulfide, phosphorus trifluoride, phosphorus pentoxide,
Examples include inorganic acids such as fluoroboric acid, fluoric acid, hydrochloric acid, sulfuric acid, and heteropolyacids, and organic acids such as I)-) luenesulfonic 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.

Among these, in the case of bulk polymerization, it is preferable to heat the reaction reagent and the catalyst while stirring to bring them into a uniform state, and then polymerize. A high molecular weight polyamide can be obtained by reaction at θ°C to 200°C for 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. A high molecular weight polyamide can be obtained by reaction at 0°C to 200°C for 1 to 30 hours.

The above-mentioned solvents include 0-dichlorobenzene, 1.3
．． ! Examples include $bortrifluorobenzene, 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 polymerization methods, the blending ratio of the polyisocyanate compound and tricyclic heterofused ring compound used is as follows:
Equimolar amounts are preferable in order to smoothly proceed with the polyaddition reaction.

The amount of the Friedel-Krach type catalyst to be used varies depending on the reaction reagent and polymerization conditions, but is preferably in the range of 0.3 to 1.5 equivalents based on the incyanato groups of the polyinocyanate compound used.

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 incyanato groups, and after pouring into ice water, the precipitate is separated by F, washed, The desired polyamide can be obtained by subjecting it to the usual drying process.

[Effect of release]

According to the present invention, a polyamide having a trinomial heterofused ring can be produced directly from a core compound in one step without requiring a step of diaminating the trinomial heterofused ring compound. First, 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 corrosion of the reaction equipment etc. due to by-products is unlikely to occur, so it is of great industrial value.

[Implementation example]

Example 1 69.7 F (0.4 mol) of 2.4-tolylene diisocyaner (2.4-tolylene diisocyaner) was added in a nitrogen gas atmosphere to a four-way flask equipped with a nitrogen gas inlet tube, a reflux condenser, a thermometer, and a stirring bar.
and anhydrous aluminum chloride 106.7r (0.8 mol)
and dipenzo-p-dioxy 7 while stirring.
73.7 F (0.4 liters) was added little by little at a temperature of about 30° C., and then heated to 80° C. and reacted for 4 hours.

A dark red solid polymer was obtained. After adding 100 d of methanol to react with the remaining 7-anate groups, the mixture was poured into 3 g of ice water with stirring. Next, the whole is filtered to separate the precipitate, which is washed with methanol and acetone, dried, and then dimethylformamide (DM
F) and the resulting solution was poured into two volumes of water.

Further, the whole is subjected to F treatment to separate the precipitate, and then dried to form a white powder 1.
21.92 (yield: 85 kg) was obtained.

This poly! - It was possible to form a strong film by melting. In addition, in L Spectrum (KBr tablet method),
1655 cst-", 3300 cm-' showed strong absorption of amide groups. Melting point (m-p) was 354°C, intrinsic viscosity [η) 1.os (o, st/xcol
In the heating loss measurement using a differential thermal balance (5° C./min, in air), the weight did not decrease up to 420° C. (Hereinafter, the temperature at which heating weight loss starts is expressed as Td).

Example 2 2.4-) Reranged in Cyanur) 69.7F (0,4
mol) and phenoxathiine 80.1F (0.4 mol) were reacted at 90°C for 10 hours in the presence of anhydrous aluminum chloride 1G6.7F (0.8 mol). Processed to yield 121.3f white powder (yield: 81%)
I got it.

Conopoly i- is m, p: 321°C, w: 1.33
, Td: 382°C.

Example 3 2.4-) lylene diisocyanate 69.7F (0,4
Mol) Horse chestnut 86.5? (0.4 mol) was reacted in the presence of anhydrous aluminum chloride 106.7 F (0.8 mol) at 120°C for 6 hours, and then post-treated in the same manner as in Example 1 to give a white powder of 118. 7F (yield 76-)
Get it.

This poly i- is N,N-dimethylacetamide, N-
It is soluble in methyl-pyrrolidone, Peng-cresol, etc., and it is possible to form a strong film by melting.
m, p: 298°C, ma: 1.51, Td: 350°C
Met.

Back example 4 2.4-tolylene diisocyaner) 69.7F (0,4
mole) and phenoxathiin-10,10-dioxide 9
2.9 t (0.4 mol) in the presence of anhydrous aluminum chloride 106.7 F (0.8 mol) at 150°C, 1
After reacting for 0 hours, the mixture was post-treated in the same manner as in Example 1 to obtain yellow powder 117.1f (yield 72-).

This polymer was ff1Js: 392°C, 9:0.56
, Td: 4B3°C.

Example 5 2.4-Tolylene diisocyaner) 69.7 F(0
, 4 mol) and diphenylene oxide 67.3 t (0.4 mol)
mol), anhydrous aluminum chloride 106.7 F (0,
After reacting for 8 hours at 100°C in the presence of 8 mol), the same post-treatment as in Example 1 was carried out to obtain a white powder of 126. Of(yield 9
2-) was obtained.

A strong film could be formed from this polymer by melting it. m, p: 372°C, w: 1.13, Td: 43
The temperature was 7°C.

Example 6 Siben'/-p'' in 100 m of nitrobenzene
') Oxine 18.4 F (0.1 mol) and diphenylmethane diincyanate 25. Of (0,1 mol)
were reacted at 100°C for 5 hours in the presence of anhydrous a4 chloride 4*26.7F (0.2+L), and then post-treated in the same manner as in Example 1 to obtain white powders 3B and 6F (IL ratio 89 嗟) was obtained.

This polymer was able to be melted into a tough film. IR spectrum: 1650cx-” a33
12ag-”, m-1): 375°C, W: 0.84,
'ra: It was 3so℃.

Claims (1)

[Scope of Claims] A polyisocyanate compound having two or more incyanate groups;
1-so, -1-PO-rich-1-co-1-NR1-; R1, R, , R, and R4B, each an alkyl group having 1 to 5 carbon atoms, -OR; B, , R, and 几 each represent an alkyl group having 1 to 5 carbon atoms; "@, '11% I'm and R4 each represent an integer of O to 3; \ and Xl,
R1 and R, , R, and R4 and R1 and 8 may be the same or different, respectively<, nl, n,
, n, and R4 are integers of 2 to 3, a plurality of R
1, R1, R1 and turtle may be the same or different bottles. ) with at least one trinomial heterofused ring compound represented by: 7) in the presence of a Riedel-Crafts catalyst. .