JPS642130B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyamide resin. Conventional aromatic polyamide as polyamide resin,
Aliphatic polyamides are known. Although these polyamide resins generally have good heat resistance, they have poor transparency, moldability, and water resistance, which limits their range of use. The object of the present invention is to add tricyclo[5.2.1.0 ^2.6 ]decane structure or pentacyclo[6.5.1.1 ^3.6 . 0 ^2.7 ． 0 ^9.13 ] The object of the present invention is to provide a polyamide resin having a pentadecane structure and having good transparency, moldability, and heat resistance. The polyamide resin according to the present invention has the general formula ₍ In _{the formula ,} It is an alkyl group, m represents 1 or 2), and has a reduced viscosity (concentration 0.5 g/dl, 30°C, in o-chlorophenol) of 0.3 to 3 g/dl. Features. Examples of the polyamide resin of the present invention include dicarboxytricyclo[5.2.1.0 ^2.6 ]decane, dicarboxypentacyclo[6.5.1.1 ^3.6 . 0 ^2.7 ． 0 ^9.13 ] Obtained by a polycondensation reaction between pentadecane, a dicarboxylic acid ester thereof, or a dicarboxylic acid halide thereof and a diamine selected from aliphatic diamines, alicyclic diamines, and aromatic diamines. The aliphatic diamine has the general formula NH ₂ −(CH ₂ )
It is represented by n- _NH2 (in the formula, n is an integer of 1 to 12), and preferred examples are hexamethylene diamine, tetramethylene diamine, pentamethylene diamine, octamethylene diamine, and decamethylene diamine. Examples of alicyclic diamines include:

【formula】

【formula】

(In the formula, R′ ₁ to R′ ₄ are each hydrogen or carbon number 1 to
4 alkyl group, p and q are integers of 0 to 2), (In the formula, R″ ₁ to R″ ₆ are each hydrogen or carbon number 1
-4 alkyl group, p and q are as described above),

【formula】

【formula】

【formula】

Examples include [Formula]. As aromatic diamines, e.g.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[In the formula, Q is -CO-, -SO ₂ -, -S-, -O-,

[Formula] -CONH-, -NHCONH-, etc., and Q' and Q'' are -(CH ₂ ) _l - (l is an integer from 0 to 4)
] is used. The hydrogen atoms of these aromatic rings may be replaced by substituents that do not react with carboxyl groups, acid halide groups, and amino groups. The above diamines may be used alone or in combination of two or more. Preferred diamine components in terms of the properties of the obtained polymer are _NH2- ( _CH2 ) ₆ - _NH2 ,

【formula】

【formula】

【formula】

It is. The polymer of the present invention has a molecular weight of 0.3 to 3, preferably 0.5 to 3.
It has a reduced viscosity of 2 (measured at 30°C with 0.5 g of polymer dissolved in 100 ml of o-chlorophenol). The polymer of the present invention can be obtained using commonly used polymerization methods such as hot-melt polymerization, low-temperature solution polymerization, interfacial polymerization, oligomer method, and high-temperature solution polymerization. As the polymerization solvent used in the above polymerization method, all commonly used polymerization solvents can be used, such as dimethylacetamide, N-methylpyrrolidone, N-methylpyrrolidone,
- Methylcaprolactam, tetramethylurea, polyphosphoric acid, dimethylformamide, hexamethylenephosphoramide, dimethyl sulfoxide, chlorobenzene, chlornaphthalene, nitrobenzene, dichloroethane, chloroform, methylene chloride, diphenyl sulfone, trichlorobiphenine, benzophenone, meth- It is appropriately selected from phenyl, chlorinated biphenyl, dichlorobenzene, etc. and used alone or in combination of two or more. If necessary, a solvent inert to the polymerization reaction, such as methyl ethyl ketone, cyclohexanone, tetrahydrofuran, benzene, heptane, toluene, xylene, etc., may be present as a diluent. In order to increase the solubility of the polymer in the polymerization solvent, LiCl, CaCl ₂ , MgCl ₂ , ZnCl _{2 ,} etc. may be dissolved in the polymerization solvent and used. In the polycondensation reaction of diamine and acid chloride, tertiary amines and quaternary ammonium salts are used as polymerization catalysts, preferably triethylamine and pyridine. As the polymerization solvent, N-methylpyrrolidone/hexamethylene phosphoramide system is also preferably used, but in this case, it is not necessary to use a polymerization catalyst. In the direct condensation polymerization reaction of diamine and dicarboxylic acid, a triphenyl phosphite/imidazole system can be used as a polymerization catalyst. Here, phosphorus trichloride, condensed phosphoric acid ester, etc. can be used instead of triphenyl phosphite. Pyridine can also be used instead of imidazole. Because the thermoplastic resins produced according to the present invention have excellent physical, mechanical, chemical, electrical, and thermal properties, their uses are many and varied. For example, they can be used alone or in combination with various known fillers, additives, colorants, and antioxidants. The polyamide resin of the present invention can also be used with other known polymers such as styrene-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene copolymer, vinyl chloride polymer, ABS resin, polyphenylene oxide. ，
Epoxy resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate,
It can also be used in combination with polyacetal, polyamide, polyvinylidene fluoride, chlorinated butyl rubber, AES resin, polysulfone, acrylic polymer, polyarylate, polyether ether ketone, PPS, etc. The resins of the present invention can be molded according to known methods to produce molded parts such as gears, ratchet cams, impact parts, gaskets, valves, seats and the like. Also, their molding,
It can be used to produce cast, calendered, extruded products such as films, sheets, bars, coatings, filaments, tapes, etc. Furthermore, foamed sheets and foamed molded products can be obtained using known foaming agents. Next, the present invention will be explained in more detail with reference to Examples. Example 1 The inside of a glass reaction vessel equipped with a stirrer was sufficiently purged with nitrogen, cooled to 10°C, and p-phenylenediamine 10.81
g (0.1mol), N-methylpyrrolidone 466ml;
Completely dissolve 20g of LiCl and add triethylamine.
27.90ml, after adding 26.20g (0.1mol) of dichloroformyltricyclo[5.2.1.0 ^2,6 ]decane 10
Polymerization was carried out for 3 hours at °C. The polymer solution was precipitated in methanol, washed thoroughly with water, and thoroughly dried in a vacuum dryer to obtain a polymer. The yield was 95%. The obtained polymer is
IR analysis, melting temperature measurements, and reduced viscosity measurements were performed. The reduced viscosity was measured in a thermostat at 30° C. after dissolving 0.5 g of the polymer in 100 ml of o-chlorophenol. Figure 1 shows the IR analysis results. 1680cm ^-1

[Formula] 3350cm ^-1 −NH−, 1620cm ^-2

[Formula] Stretching vibration of tricyclo[5.2.1.0 ^2,6 ]decane hydrocarbon is observed between 2900 and 3000 cm ^-1 . A polymer having the structure was obtained. Melting temperature: 386°C, reduced viscosity: 0.98.
After dissolving this polymer in o-chlorophenol, a sheet was prepared by the casting method and then boiled in water.
No weight change was observed after soaking for 300 hours. Example 2 Polymerization was carried out under the same conditions as in Example 1 except that m-phenylenediamine was used instead of p-phenylenediamine. The yield of the obtained polymer was 95%. The resulting polymer had a melting temperature of 282°C and a reduced viscosity of 0.98. Also, the IR analysis results are shown in Example 1.
It was the same as the polymer of Example 3 Hexamethylene diamine 11.60 was used instead of p-phenylene diamine under the polymerization conditions of Example 1.
Polymerization was carried out under the same polymerization conditions as in Example 1, except that g (0.1 mol) was used. The yield of the obtained polymer was 95%. The results of IR analysis of the polymer are shown in Figure 2. 1650cm ^-1

[Formula] 3320cm ^-1 −NH− is observed, A polymer having the structure was obtained. The resulting polymer had a melting temperature of 196°C and a reduced viscosity of 0.47. Example 4 The inside of a stainless steel reaction vessel equipped with a stirrer was sufficiently purged with nitrogen, and 11.62 g of hexamethylene diamine was added.
(0.1mol), dicarboxytricyclo[5.2.1.0 ^2,6 ]
22.40 g (0.1 mol) of decane was added and heating started. Water began to distill out at an internal temperature of 183°C. Stirring was started at this point. 2 hours after water started to distill out, slowly increasing the vacuum level to 0.1mm in 1 hour.
It was up to Hg. During this time, the temperature inside the polymerization tank was set to 240°C. Thereafter, the polymerization temperature was maintained at 240 to 250°C and polymerization was carried out for 4 hours. The yield of the obtained polymer was 98%
It was hot. The melting temperature is 210℃, and the reduced viscosity is
It was 1.01. Moreover, the IR analysis results were the same as in Example 3. Example 5 25.25 g of bis(methoxycarbonyl)tricyclo[5.2.1.0 ^2,6 ]decane instead of dicarboxytricyclo[5.2.1.0 ^2,6 ]decane in Example 4
A polycondensation reaction was carried out using (0.1 mol). Internal temperature
Methanol began to distill out at 190°C. The reaction was carried out under the polycondensation conditions of Example 4, except that the degree of vacuum and internal temperature were raised 2 hours after methanol began to distill out. The yield of the obtained polymer was 98%. The melting temperature was 204°C and the reduced viscosity was 0.82.
Moreover, the IR analysis results were the same as in Example 3. ^{Example 6 In Example 1, dichloroformylpentacyclo[6.5.1.1 3.6 .} 0 ^2.7 ． 0 ^9.13 ] Example 1 except that 32.73 g (0.1 mol) of pentadecane was used.
The reaction was carried out under the following polymerization conditions. The yield of the obtained polymer was 95%. The resulting polymer had a melting temperature of 450°C and a reduced viscosity of 0.92. After dissolving this polymer in o-chlorophenol,
A sheet was prepared by the casting method and immersed in boiling water for 300 hours, but no weight change was observed. Example 7 In Example 5, 11.60 g (0.1 mol) of hexamethylene diamine was used instead of p-phenylene diamine.
The reaction was carried out under the polymerization conditions of Example 5 except that . The yield of the obtained polymer was 95%. The resulting polymer had a melting temperature of 263°C and a reduced viscosity of 0.51. Example 8 In Example 4, dicarboxytricyclo[5.2.1.0 ^2,6 ]decane was replaced with dicarboxypentacyclo[6.5.1.1 ^3.6 . 0 ^2.7 ． 0 ^9.13 〕Pentadecane
The reaction was carried out under the polymerization conditions of Example 4, except that 29.04 g (0.1 mol) was used and the polymerization temperature was 295°C.
The yield of the obtained polymer was 98%. The melting temperature was 280°C and the reduced viscosity was 0.96. Comparative Example 1 20.30 g of terephthalic acid chloride was used in place of 26.20 g (0.1 mol) of dichloroformyltricyclo[5,2,1,0 ^2,6 ]decane used in Example 1.
Polymerization was carried out in the same manner as in Example 1 except that triethylamine (0.1 mol) was used and triethylamine was not used, and the yield was 98.
%, a polymer with a reduced viscosity of 3.24 dl/g (in 98% concentrated sulfuric acid) was obtained. The melting temperature of the obtained polymer was higher than the thermal decomposition temperature, and it was also insoluble in organic solvents, resulting in poor processability.

[Brief explanation of the drawing]

Figures 1 and 2 show infrared absorption spectra of the polymer of the present invention.

Claims (1)

[Claims] 1. General formula (In the formula, X represents _a residue from an aliphatic diamine, an _alicyclic diamine, or _an aromatic diamine from which an amino group has been _removed ; is an alkyl group, m is 1 or 2
A polyamide-based thermoplastic resin having a repeating unit represented by (representing the following) and having a reduced viscosity (concentration 0.5 g/dl, 30°C, in o-chlorophenol) of 0.3 to 3 g/dl.