Abstract:
A process for preparing a polyimine comprising reacting at least one dialdehyde with at least one diamine in a reaction medium of 100 to about 40 percent by volume of a phenolic compound of the formula, ##STR1## wherein X represents a hydrogen atom or a methyl group, and 0 to about 60 percent by volume of a liquid which is miscible with the phenolic compound.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to a process for preparing polyimines. More particularly, it relates to a process for preparing polyimines having a high molecular weight using a phenolic compound as a reaction medium. 
     2. Description of the Prior Art 
     Since 1950 many researches have been done on polyimines having a plurality of the imine group (--CH═N--) in their main chain of the molecule from the viewpoint of its high bond energy and its possibility of ekaconjugation of double bond chemically formed with an appropriate atomic group. Especially, the characteristics of the imine group such as the resistance to heat, the semiconduction, the photoconduction, the photodielectric character and the insulation have been noted and studied. Also, various methods of preparing polyimines have been proposed. For example, Polymer Letters, 2, 943 (1964) describes a preparation of the polyimine having azulene groups in its main chain of the molecule using dimethylformamide as a solvent at the reaction temperature of 100° C., but the polyimine is only an oligomer. According to Journal of Polymer Science, (Part A-1), 5, 1659 (1967) various polyimines are prepared by using, as a solvent, dimethyl sulfoxide, N-methylpyrrolidone or acetic acid, but the molecular weight of these polyimines are low and at most 3,000. Journal of Macromolecular Science (Reviews of Macromolecular Chemistry), C(3)1, 105 (1969) describes a preparation of various polyimines by a solution polymerization method using, as a solvent, an alcohol and acetic acid, a melting method and an azeotropic method using, as a solvent, benzene. Japanese Patent Application (OPI) No. 138800/1976 describes a method of preparing fibers and films from polyimines having a low melting point in the liquid crystal state and Belgian Patent No. 622,556 describes a preparation of polyimines having aliphatic chains in the molecule using, as a solvent, benzene. 
     However, according to these methods it is hardly possible to produce high molecular weight polyimines, and even if high molecular weight polyimines are obtained, their processability or moldability are low. 
     SUMMARY OF THE INVENTION 
     According to the present invention there is provided a process for preparing a polyimine having repeating units of the formula, 
     
         ═CH--R.sup.1 --CH═N--R.sup.2 --N═ 
    
     wherein 
     R 1  represents a straight chain alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 12 carbon atoms, and, as a branched chain, at least one alkyl group having 1 to 4 carbon atoms, ##STR2## 
     R 2  represents a straight chain alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 12 carbon atoms and, as a branched chain, at least one alkyl group having 1 to 4 carbon atoms, an ether alkylene group having 2 to 6 carbon atoms and 1 to 3 oxygen atoms, ##STR3## 
     wherein R 3  represents a methoxy group or a chlorine atom; R 4  represents --O--, --S--, --SO 2  --, --CH 2  --, --C(CH 3 ) 2  --, --CO 2  --, --NH--, --CONH--, --HNOC--R 6  --CONH-- or --CONH--R 6  --HNOC--, wherein R 6  represents --(CH 2 ) n , n being zero or an integer of 1 to 12, ##STR4## 
     and R 5  represents a methyl group, methoxy group or a chlorine atom, 
     which comprises reacting at least one dialdehyde of the formula 
     
         OCH--R.sup.1 --CHO 
    
     wherein R 1  is the same as defined above, with at least one diamine of the formula 
     
         H.sub.2 N--R.sup.2 --NH.sub.2 
    
     wherein R 2  is the same as defined above, 
     in a reaction medium of 100 to about 40 percent by volume of a phenolic compound of the formula, ##STR5## 
     wherein X represents a hydrogen atom or a methyl group; and Y represents a hydrogen atom, a chlorine atom or a methyl group, 
     and 0 to about 60 percent by volume of a liquid which is miscible with the phenolic compound. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Suitable dialdehydes which may be employed in this invention include ethanedialdehyde, propane-1,3-dialdehyde, butane-1,4-dialdehyde, pentane-1,5-dialdehyde, hexane-1,6-dialdehyde, heptane-1,7-dialdehyde, octane-1,8-dialdehyde, cyclohexane-1,4-dimethyldialdehyde, cyclohexane-1,3-dimethyldialdehyde, terephthalaldehyde, isophthalaldehyde, toluene-2,4-dialdehyde, toluene-2,5-dialdehyde, toluene-2,6-dialdehyde, chlorobenzene-2,4-dialdehyde, chlorobenzene-2,5-dialdehyde, chlorobenzene-2,6-dialdehyde, naphthalene-1,5-dialdehyde, naphthalene-1,8-dialdehyde, naphthalene-2,6-dialdehyde, pyridine-2,4-dialdehyde, pyridine-2,5-dialdehyde and pyridine-2,6-dialdehyde and any mixtures thereof. 
     Suitable diamines which can be employed in this invention include ethylenediamine, diaminobutane, hexamethylenediamine, bis(aminoethyl)propane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, p-phenylenediamine, m-phenylenediamine 2,4-diaminochlorobenzene, 2,5-diaminochlorobenzene, 2,6-diaminochlorobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,4-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyrazine, 3,3&#39;-diaminobiphenyl, 4,4&#39;-diaminobiphenyl, 3,4&#39;-diaminobiphenyl, 3,3&#39;-dimethoxy-4,4&#39;-diaminobiphenyl, 3,3&#39;-dichloro-4,4&#39;-diaminobiphenyl, 3,3&#39;-diaminodiphenylmethane, 4,4&#39;-diaminodiphenylmethane, 4,4&#39;-diaminodiphenylsulfide, 4,4&#39;-diaminodiphenylether, 3,3&#39;-diaminodiphenylsulfone, 4,4&#39;-diaminodiphenylsulfone, 4,4&#39;-diaminodiphenylpropane, 3,3&#39;-diaminodiphenylester, 3,3&#39;-diaminodiphenylamide, 3,3&#39;-dichloro-4,4&#39;-diaminodiphenylmethane, 3,3&#39;-dichloro-4,4&#39;-diaminodiphenylpropane, ##STR6## and any mixtures thereof. 
     Any combinations of the dialdehydes and the diamines of this invention can be employed in the present invention. 
     The total amount of the dialdehydes and the diamines used in this invention is not particularly limited, but generally at least about 1 g per deciliter of the reaction medium. A preferred amount ranges from about 5 g/dl to about 100 g/dl, a more preferred amount ranges from about 10 g/dl to about 50 g/dl. 
     Examples of suitable phenolic compounds of the formula ##STR7## wherein 
     X represents a hydrogen atom or methyl group; and 
     Y represents a hydrogen atom, chlorine atom or methyl group, 
     which can be employed in this invention include phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol and 3,5-xylenol and any mixtures thereof. Of these phenolic compounds, m-cresol is preferred from the viewpoint of its good solubility and its commercial availability 
     Appropriate liquids which are miscible with the phenolic compound and which can be employed in this invention are hydrocarbons and halogenated hydrocarbons. Exemplary hydrocarbons include toluene, xylenes, diphenyl, diphenylmethane and diphenylether. Exemplary halogenated hydrocarbons include methylene chloride, chloroform, tetrachloroethane, chlorobenzene and hexafluoroisopropanol. 
     The amount of the liquids which can be used is at most 60 percent by volume based on the total volume of the reaction medium. A preferred amount of the liquids is at most 40 percent by volume. When the amount of the liquid is more than 60 percent by volume, the rate of polymerization is decreased and the solubility of the polyimines produced in the reaction medium is reduced. 
     The reaction of this invention can be conventionally carried out by mixing the dialdehydes and the diamines in the reaction medium. 
     The reaction temperature which can be employed in this invention is typically from about -10° C. to about 200° C., a preferred range is from about 0° C. to about 120° C., and a more preferred range is from about 5° C. to about 30° C. 
     The reaction time may be varied within wide limits depending upon factors such as the dialdehyde and the diamines selected, the reaction medium chosen, the reaction temperature employed and other factors. Generally, the reaction time is from about 1 minute to about 48 hours. 
     The reaction of this invention may be carried out either at atmospheric pressure, under a pressure above atmospheric or under a reduced pressure. But it is preferred, from an economical standpoint, to carry out the reaction at atmospheric pressure. 
     The reaction of this invention may also be carried out in an atmosphere of air or an inert gas such as nitrogen and argon. 
     The reaction of this invention is postulated to proceed as follows; ##STR8## The reaction is reversible, but the equilibrium is inclined to the direction of the product. When the product is formed and the concentration of the terminal groups becomes dilute, the equilibrium is achieved and the reaction apparently stops. In case the reaction medium, the dialdehyde and the diamine are sufficiently dried before use, the polyimine as the product becomes a high molecular weight polymer for practical uses at the equilibrium achieved. However, the molecular weight of the polyimines of this invention can be further increased by removal of the by-produced water from the reaction system using appropriate methods. Examples of suitable methods which can be employed in this invention include the addition of a dehydrating agent in the reaction medium before the reaction and the removal of part of the reaction medium from the reaction system by distillation during or after the reaction. 
     Exemplary dehydrating agents which can be employed in this invention include calcium chloride, lithium chloride, potassium carbonate and phosphorus pentoxide. The amount of the dehydrating agents used is typically at most 10 percent by weight based on the total weight of the dialdehyde and the diamine. 
     Furthermore, the process of this invention can be advantageously combined with conventional methods of polyimines using a reaction medium. More specifically, the dialdehydes and the diamines are dissolved in a reaction medium such as N,N-diamethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetic acid, benzene and ethanol at the reaction temperature of this invention with stirring and left to stand to precipitate the polyimines. Then, the polyimines precipitated are filtered off and dried. The polyimines thus obtained are low molecular weight polymers and their number average molecular weights are generally at most about 3,000. These low molecular weight polyimines are dissolved in the reaction medium of this invention at the reaction temperature of this invention to further advance the reaction. The resulting polymers solutions contains higher molecular weight polyimines. 
     The polyimines which are prepared by the process of this invention can be advantageously formed into shaped articles such as films, fibers and molded articles in the presence of the reaction medium using conventional methods. More specifically, the polymer solutions as such are charged into molds of shaped articles and then the reaction medium is removed by evaporation. Furthermore, the polyimines containing a small amount of the reaction medium can be subjected to conventional melt moldings. 
     Also the polyimines can be separated from the polymer solutions by precipitation in a non-solvent such as methanol for the polyimines prepared and then subjected to conventional melt moldings. 
     According to the process of this invention the polyimines having a number average molecular weight of from about 2,000 to about 200,000 can be prepared, and the polyimines have various advantageous such as low hygroscopicity, good wet, dry or high temperature dimension stability, high glass transition temperature, good resistance to chemicals and small change in electrical properties under wet and dry conditions and have a wide range of use such as heat resistant insulators, heat resistant coating materials, printed circuit plates, very low temperature materials, photoconductive materials, pyroelectric materials and piezoelectric materials. 
    
    
     The present invention will now be illustrated in more detail by the following examples. In these examples the number average molecular weight of a polymer was calculated from a relative optical density of the terminal --CHO group infrared absorption at 1700 cm -1  to the --CH═N-- group infrared absorption at 1620 cm -1 . The mechanical properties of a polymer was measured by a tension tester of giving tension in a constant rate at 20° C. in a tension rate of 40 percent per minute. The glass transition temperature was measured by a dynamic visco-elastometer at a frequency of 110 Hz in an elevating temperature rate of 4° C. per minute. The crystallinity was measured by wide angle X-ray diffractiometry. The thermogravimetric analysis was carried out in air under a condition of 10° C. per minute. 
     EXAMPLE 1 
     In 200 ml of freshly distilled m-cresol were dissolved 23.3 g of hexamethylenediamine and 26.8 g of terephthalaldehyde at 20° C. with stirring, and the viscosity of the solution rapidly increased to give a viscous polymer solution. After stirring at 20° C. for 2 hours, the polymer solution was poured into methanol to precipitate a fibrillar polymer and the polymer was filtered off and dried with hot air at 80° C. for 2 hours, resulting in 33 g of a white fibrillar polymer having a low crystallinity, a glass transition temperature of 80° C. and a melting point of 170° C. The polymer had the --CH═N-- group infrared absorption at 1650 cm -1  but did not have the terminal --CHO group infrared absorption, and thus the polymer had a high molecular weight. 
     The polymer was extruded from an extruder maintained at 190° C. from a spinneret having a diameter of 0.2 mm to continuously obtain a colorless transparent filament. 
     Also the polymer solution as described above was uniformly cast on a glass plate with a doctor knife, and in order to remove the reaction medium the whole was dried under a reduced pressure of 0.1 mm Hg at 80° C. for 4 hours, at 120° C. for 2 hours and at 160° C. for 2 hours. The film thus obtained had a thickness of 26 microns and the following mechanical properties; 
     Tensile Strength: 389 Kg/cm 2   
     Tensile Elongation: 11.5% 
     Young&#39;s Modulus: 11,585 Kg/cm 2   
     EXAMPLE 2 
     In a mixture of 150 ml of freshly distilled m-cresol and 50 ml of freshly distilled chlorobenzene were dissolved 23.2 g of hexamethylenediamine and 26.8 g of terephthalaldehyde at 20° C. with stirring and the solution was stirred at 20° C. for about 30 minutes, resulting in a highly viscous polymer solution. The polymer solution thus obtained was poured into methanol to precipitate a fibrillar polymer and the polymer was filtered off and dried with hot air at 80° C. for 2 hours. The polymer thus obtained had the --CH═N-- group infrared absorption at 1650 cm -1  and a number average molecular weight of about 56,000. 
     Also the polymer solution as described above was shaped into a film in the same manner as in Example 1 and was obtained a colorless transparent film having a thickness of 30 microns. The mechanical properties of the film were as follows; 
     Tensile Strength: 550 Kg/cm 2   
     Tensile Elongation: 18% 
     Young&#39;s Modulus: 1.1×10 4  Kg/cm 2   
     EXAMPLE 3 
     In 500 ml of freshly distilled m-cresol were dissolved 29 g of hexamethylenediamine, 49.5 g of 4,4&#39;-diaminophenylmethane and 67 g of terephthalaldehyde at 20° C. with stirring. The viscosity of the solution rapidly increased and a pale green polymer solution was obtained. After stirring at 20° C. for 24 hours, the polymer solution was poured into methanol to precipitate a polymer. The polymer was filtered off and dried with hot air at 80° C. for 2 hours and 115 g of a pale yellow polymer were obtained. The polymer had a low crystallinity and the --CH═N-- group infrared absorption at 1625 cm -1  but did not have the terminal --CHO group infrared absorption, and thus the polymer had a very hight molecular weight and was a random copolymer having repeating units of the formulae ##STR9## in a ratio of 1 to 1. 
     Also the polymer solution as described was shaped into a film in the same manner as in Example 1, resulting in a pale yellow film having a thickness of 26 microns, a high tensile elongation and a high Young&#39;s modulus. The film did not have a melting point and began to decrease in its weight at 300° C. 
     EXAMPLE 4 
     In 700 ml of freshly distilled m-cresol were dissolved 18.9 g of terephthalaldehyde and 50 g of an aromatic diamine of the formula, ##STR10## at 20° C. and the solution was stirred at 20° C. for 10 minutes and then at 90° C. for 5 hours under a nitrogen atmosphere and cooled to 20° C. The polymer solution was poured into methanol to precipitate a polymer and the polymer was filtered off and dried at 80° C. for 2 hours, resulting in a pale yellow fine powder polymer having the --CH═N-- group infrared absorption at 1630 cm -1  and the --CONH-- group infrared absorption at 1600 cm -1 , a number average molecular weight of about 7,000 and repeating units of the formula, 
     The polymer did not have a melting point and decomposed above 350° C. 
     EXAMPLE 5 
     In 100 ml of freshly distilled m-cresol was dissolved 6.7 g of terephthalaldehyde and 19.1 g of an aromatic amine of the formula, ##STR11## at 20° C. with vigorous stirring and the solution was stirred at 20° C. for about 40 hours. The polymer solution thus obtained was poured into methanol to precipitate a polymer and the polymer was filtered off and dried at 80° C. for 2 hours, resulting in 14 g of a brown power polymer having the --CH═N-- group infrared absorption at 1660 cm -1 , the --CONH-- group infrared absorption at 1600 cm -1 , a number average molecular weight of about 6500 and repeating units of the formula, 
     The polymer began to decompose at 300° C. 
     Also the polymer solution as described above was shaped into a film in the same manner as in Example 1 and was obtained a pale yellow film having a thickness of 30 microns. 
     EXAMPLE 6 
     In 200 ml of freshly distilled m-cresol were homogeneously dissolved 13.4 g of isophthalaldehyde and 19.8 g of 4,4&#39;-diaminodiphenylmethane at 20° C. with stirring and the solution was stirred at 20° C. for 30 minutes. The polymer solution thus obtained was poured into methanol to precipitate a polymer and the polymer was filtered off and dried with hot air at 80° C. for 2 hours, resulting in 25 g of a pale yellow fibrillar polymer having the --CH═N-- group infrared absorption at 1630 cm -1 , the --CH 2  -- group infrared absorption at 2900 cm -1 , the ##STR12## group infrared absorptions at 1500 cm -1  and 1600 cm -1 , a number average molecular weight of about 18,000, a glass transition temperature of 260° C. and repeating units of the formula, ##STR13## 
     Also the polymer solution as described above was uniformly cast on a glass plate with a doctor knife, and in order to remove the reaction medium the whole was dried under a reduced pressure of 0.1 mm Hg at 80° C. for 3 hours, at 120° C. for 2 hours and at 200° C. for 2 hours to give a colorless transparent film having high tensile elongation. 
     EXAMPLE 7 
     In 280 ml of freshly distilled m-cresol were homogeneously dissolved 8 g of isophthalaldehyde and 5.4 g of terephthalaldehyde at 20° C. with stirring. To the solution was added 19.8 g of 4,4&#39;-diaminodiphenylmethane and the resulting solution was stirred at 20° C. for about 10 minutes to give a homogeneous polymer solution having an increased viscosity. After 100 ml of the m-cresol was distilled off from the polymer solution at 80° C. under a reduced pressure of 1 mm Hg, the polymer solution was cooled to 20° C. to give a highly viscous polymer solution. Part of the polymer solution was uniformly cast on a glass plate with a doctor knife, and in order to remove the reaction medium the whole was dried under a reduced pressure of 0.1 mm Hg at 80° C. for 2 hours and at 160° C. for 2 hours, resulting in a yellow transparent film having a thickness of 30 microns, a number average molecular weight of about 5,900, a glass transition temperature of 150° C., and repeating units of the formula, ##STR14## 
     The mechanical properties and the resistance to chemicals of the film thus obtained were as follows; 
     
         ______________________________________Mechanical Properties______________________________________Tensile Strength:  650 Kg/cm.sup.2Tensile Elongation 20%Young&#39;s Modulus:   8 × 10.sup.3 Kg/cm.sup.2Resistance to Chemicals______________________________________Chemical               Performance______________________________________m-Xylene*             ShrinkedTrichloroethylene*    ShrinkedAcetone*              Not changedAcetic acid**         Not changed10% by weight sodiumhydroxide***          Not changedDimethyl sulfoxide*   Not changedBoiling water****     Decomposed______________________________________ *Immersed in 3 days at 20° C. **Immersed in 7 hours at 20° C. ***Immersed in 5 days at 20° C. ****Immersed in 3 hours 
    
     EXAMPLE 8 
     In 280 ml of freshly distilled o-cresol were added 8 g of isophthalaldehyde, 5.4 g of terephthalaldehyde and 5 g of thoroughly dried calcium chloride at 20° C. with stirring to form a solution. To the solution was added 19.8 g of 4,4&#39;-diaminodiphenylmethane and the resulting solution was stirred at 20° C. for 5 hours. After 100 ml of the m-cresol was distilled off at 80° C. under a reduced pressure of 1 mm Hg, the polymer solution was cooled to 20° C. to give a highly viscous polymer solution. Then, the polymer solution was poured into anhydrous methanol to precipitate a polymer and the polymer was filtered off and dried at 80° C. for 2 hours, resulting in a polymer having a number average molecular weight of about 50,000. The polymer was subjected to an extrusion molding using an extruder maintained at 280° C. at a pressure of 250 Kg/cm 2  to give a stiff stick having a length of 3 cm and a diameter of 1 cm. 
     EXAMPLE 9 
     In 280 ml of a mixed reaction medium consisting of p-cresol and tetrachloroethane in a volume ratio of 8 to 2 were homogeneously dissolved 8 g of isophthalaldehyde and 5.4 g of terephthalaldehyde at 20° C. with stirring. To the solution was added 19.8 g of 4,4&#39;-diaminodiphenylmethane at 20° C. with stirring and the resulting solution was stirred at 20° C. for one hour. After 100 ml of the m-cresol at 80° C. under a reduced pressure of 1 mm Hg, the polymer solution was cooled to 20° C. and poured into methanol to precipitate a yellowish orange polymer. The polymer was filtered off and dried at 80° C. for 2 hours, resulting a polymer having a number average molecular weight of about 18,000. 
     EXAMPLE 10 
     In 400 ml of a mixed reaction medium consisting of phenol and m-cresol in a volume ratio of 7 to 3 were uniformly dissolved 1.34 g of terephthalaldehyde and 12.06 g of of isophthalaldehyde at 20° C. with stirring and in the solution was dissolved 21.6 g of 4,4&#39;-diaminodiphenylsulfide at 20° C. with stirring and the resulting solution was stirred at 20° C. for 10 minutes. Then, the polymer solution thus obtained was shaped into a film in the same manner as in Example 1 and was obtained a pale yellow transparent film having a thickness of 30 microns, a number average molecular weight of about 112,700 and repeating units of the formula, ##STR15## 
     EXAMPLE 11 
     In 200 ml of ethanol were homogeneously dissolved 2.68 g of terephthalaldehyde and 10.72 g of isophthalaldehyde at 20° C. with stirring and to the solution was added 100 ml of an ethanol solution containing 19.8 g of 4,4&#39;-diaminodiphenylethane at 20° C. with stirring to instantly precipitate a yellow polymer. The polymer precipitated was filtered off and dried at 100° C. for 2 hours. The polymer thus obtained had a degree of polymerization of 2 to 3. 
     In 100 ml of freshly distilled m-cresol was homogeneously dissolved 10 g of the polymer at 20° C. with stirring. After 20 ml of the m-cresol was distilled off at 80° C. under a reduced pressure of 1 mm Hg, the polymer solution was cooled to 20° C. and a high viscous polymer solution was obtained. The polymer solution was shaped into a film in the same manner as in Example 1 and was obtained a yellow film having a thickness of 30 microns, a number average molecular weight of about 5,000, a glass transition temperature of 250° C. and repeating units of the formula, ##STR16## 
     EXAMPLE 12 
     In 300 ml of freshly distilled m-cresol were dissolved 10.72 g of isophthalaldehyde and 2.68 g of terephthalaldehyde at 20° C. with stirring and to the solution was added 20.0 g of 4,4&#39;-diaminodiphenylether with stirring and the resulting solution was stirred at 20° C. until the 4,4&#39;-diphenylether was dissolved therein. Then, 100 ml of the m-cresol was distilled off at 100° C. under a reduced pressure of 1 mm Hg and the polymer solution was cooled to 20° C. to give a viscous solution of a polymer having repeating units of the formula, ##STR17## 
     Part of the polymer solution was shaped into a film in the same manner as in Example 1 and was obtained a yellow film having a thickness of 30 microns, a number average molecular weight of about 7,600 and a glass transition temperature of 140° C. 
     EXAMPLE 13 
     In 200 ml of freshly distilled m-cresol were dissolved 21.6 g of 4,4&#39;-diaminodiphenylsulfide and 13.4 g of isophthalaldehyde at 20° C. with stirring and the solution was stirred at 20° C. for about 30 minutes, resulting in a viscous polymer solution. After the polymer solution was left to stand at 20° C. for 2 weeks, the polymer solution was poured into methanol to precipitate a polymer and the polymer was filtered off and dried with hot air at 80° C. for 2 hours to give 29 g of a yellow polymer. The polymer had the --CH═N-- group infrared absorption at 1630 cm -1  and the ##STR18## group infrared absoprtions at 1480 cm -1  and 1580 cm -1 , a number average molecular weight of about 37,000 and repeating units of the formula ##STR19## 
     The polymer did not have a melting point and began to decompose at 400° C. 
     Also the polymer solution as described above was shaped into a film in the same manner as in Example 1 and was obtained a colorless yellow film having a thickness of 26 microns and a high tensile elongation and a high Young&#39;s modulus. 
     EXAMPLE 14 
     In 200 ml of freshly distilled m-cresol were dissolved 5.4 g of m-phenyldiamine, 9.9 g of 4,4&#39;-diaminodiphenylmethane and 13.4 g of isopthalaldehyde at 20° C. with stirring and the solution was stirred at 20° C. for about 30 minutes, resulting in a viscous polymer solution. After 2 hours the polymer solution was poured into methanol to precipitate a polymer and the polymer was filtered off and dried with hot air at 80° C. for 2 hours. The polymer thus obtained had the --CH═N-- group infrared absorption at 1630 cm -1 , the ##STR20## group infrared absorptions at 1500 cm -1  and 1580 cm -1 , a number average molecular weight of about 49,000 and was a random copolymer having repeating units of the formulae ##STR21## in a ratio of 1:1. The polymer did not have a melting point and began to decrease in its weight at 410° C. 
     EXAMPLE 15 
     In 200 ml of freshly distilled m-cresol were dissolved 5.4 g of m-phenylenediamine and 10.0 g of 4,4&#39;-diaminodiphenylether at 70° C. and the solution was cooled to 20° C. and added with 13.4 g of isophthalaldehyde at 20° C. with stirring and the solution was stirred at 20° C. for about 30 minutes, resulting in a yellowish green viscous polymer solution. The polymer solution thus obtained was poured into methanol to precipitate a polymer and the polymer was filtered off and dried with hot air at 80° C. for 2 hours. The polymer had the --CH═N-- group infrared absorption at 1620 cm -1 , the --O-- group infrared absorption at 1230 cm -1  and a molecular weight of about 7,000. The polymer was a random copolymer having repeating units of the formulae, ##STR22## in a ratio of 1 to 1. The polymer did not have a melting point and began to decrease in its weight at 300° C. 
     Also the polymer solution as described above was shaped into a film in the same manner as in Example 1 and was obtained a yellowish green film having a thickness of 26 microns and a high tensile elongation and a high Young&#39;s modulus. 
     Furthermore, the film thus obtained was immersed in each of the chemicals set forth below at 20° C. for 3 days and the results are as follows; 
     
         ______________________________________ Chemical              Performance______________________________________10% by weightsulfuric acid         Decomposed10% by weightsodium hydroxide      Not changedAcetic acid           Not changedTetrachloroethane     Not changedTetrahydrofuran       Not changedDimethylacetamide     Not changedHexamethylphosphorictriamide              Not changedm-Xylene              Not changed______________________________________ 
    
     Also the film was subjected to a heat treatment at 180° C. for 6 hours to obtain a film having a high tensile elongation without any change in its appearance. 
     EXAMPLE 16 
     In 200 ml of freshly distilled m-cresol were dissolved 13.4 g of isophthalaldehyde and 10.8 g of m-phenylenediamine at 20° C. with stirring and the solution was stirred at 20° C. for about one hour, resulting in a yellowish green viscous polymer solution. The polymer solution was shaped into a film in the same manner as in Example 1 and was obtained a yellow film having a thickness of 30 microns. The film had the --CH═N-- group infrared absorption at 1630 cm -1  and the ##STR23## group infrared absorptions at 1480 cm -1  and 1580 cm -1 , a number average molecular weight of about 14,000, a glass transition temperature of above 330° C., a high tensile elongation, a high tensile strength and repeating units of the formula, ##STR24## 
     Furthermore, the film was immersed in each of the chemicals set forth below and the results are as follows; 
     
         ______________________________________ Chemical             Performance______________________________________Acetic acid          Partially corroded10% Sulfuric acid    DecomposedTetrahydrofuran      Not changedTetrachloroethane    Not changedN,N-Dimethylacetamide                Not changedm-Xylene             Not changed10% by weight sodium Not changed*hydroxide______________________________________ *Even when the film was heated in 10% sodium hydroxide, any change was no observed. 
    
     EXAMPLE 17 
     In 400 ml of freshly distilled m-cresol were homogeneously dissolved 13.4 g of terephthalaldehyde and 12.2 g of m-tolylenediamine at 20° C. with stirring and then 100 ml of the m-cresol was distilled off at 80° C. under a reduced pressure of 1 mm Hg and the solution was cooled to 20° C. The polymer solution thus obtained was poured into methanol to precipitate a yellowish orange polymer and the polymer was filtered off, treated with methanol, again filtered off and dried at 80° C. for 2 hours under a reduced pressure of 1 mm Hg, resulting in 20 g of a powder polymer containing 8.6 percent by weight of m-cresol and having a number average molecular weight of about 10,000, a glass transition temperature of 260° C. and repeating units of the formula, ##STR25## 
     The polymer was subjected to a compression molding for 5 minutes using a molder maintained at 260° C. under a load of 250 Kg/cm 2  to a black, stiff stick having a length of 3 cm and a diameter of 5 mm. 
     EXAMPLE 18 
     In 200 ml of freshly distilled o-cresol were homogeneously dissolved 13.4 g of terephthalaldehyde and 14.2 g of 1,4-cyclohexanedimethylamine at 20° C. with stirring and the solution was stirred at 20° C. for 12 hours to give a viscous polymer solution. The polymer solution was poured into methanol to precipitate a polymer and the polymer was filtered off and dried at 80° C. for 2 hours and a white fibrillar polymer was obtained. 
     Also the polymer solution as described above was shaped into a film in the same manner as in Example 1 and was obtained a colorless film having a high tensile elongation, a high Young&#39;s modulus, a number average molecular weight of about 7,800 and repeating units of the formula, ##STR26## 
     EXAMPLE 19 
     In 300 ml of freshly distilled m-cresol was homogeneously dissolved 13.4 g of isophthalaldehyde at 10° C. and then to the solution was added 10.9 g of 2,6-diaminopyridine at 10° C. with stirring. After stirring at 10° C. for 30 minutes, a viscous polymer solution was obtained. 
     The polymer solution was shaped into a film in the same manner as in Example 1, resulting in a yellow transparent film having a thickness of 30 microns, a number average molecular weight of about 24,000 and repeating units of the formula, ##STR27## 
     EXAMPLE 20 
     In 280 ml of freshly distilled m-cresol were homogeneously dissolved 8 g of isophthalaldehyde and 5.4 g of terephthalaldehyde at 20° C., and then to the solution was added 26.7 g of 3,3&#39;-dichloro-4,4&#39;-diaminodiphenylmethane at 20° C. with stirring. After stirring at 20° C. for 30 minutes, a viscous polymer solution was obtained, and then 80 ml of the m-cresol was distilled off therefrom at 80° C. under reduced pressure of 1 mm Hg. The yellow polymer solution thus obtained was cooled to 20° C. and poured into methanol to precipitate a yellow polymer. The polymer was filtered off and dried at 80° C. for 2 hours, resulting in 32 g of a yellow polymer having a number average molecular weight of about 12,000, a glass transition temperature of 300° C. and repeating units of the formula, ##STR28## 
     While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.