JPH0331730B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention is a novel high copolyamide (hereinafter referred to as copolyamide), which has heat resistance and solubility, and which can be used as a material for fibers, films, and molded products. Regarding polyamide. Conventional technology Generally, when aliphatic polyamide is made into fiber,
As an excellent fiber, it is widely used in clothing. However, although aliphatic polyamide fibers have a high elongation, their uses are limited because they have lower strength, lower elastic modulus, and poorer heat resistance than aromatic polyamide fibers. On the other hand, wholly aromatic polyamides have high softening and melting points, and have extremely good mechanical properties such as heat resistance such as strength retention at high temperatures and strength-elasticity modulus. However, when made into fibers, not only is the elongation low at less than 5%, but the fibers themselves are fibrillated.
There is a risk of it breaking into several pieces. The reason for this is thought to be that the fibers are manufactured from aromatic polyamide by liquid crystal spinning. In addition, Korsiatsk et al. Journal of Macromol.
Sci., Rev. Macromol.Chem., Cll, 45, 1974)
reported on soluble polyamides, but this report does not show any examples that have both the properties of solubility and moldability. Problems to be Solved by the Invention Although aromatic polyamides, which generally have great rigidity and high symmetry, have excellent mechanical properties, they have a high melting point and are close to the decomposition point, so they are difficult to melt and mold. be. Furthermore, it has the disadvantage of poor solubility, making it difficult to use as an industrial material. Poly(P-phenylene terephthalamide), a typical aromatic polyamide, is soluble in concentrated sulfuric acid or hexamethylphosphorylamide or N-methylpyrrolidone in which lithium chloride, calcium chloride, etc. are dissolved, but it is still soluble. It has the disadvantage that it is difficult to use as a solution because of its low value. Furthermore, aliphatic polyamides have poor heat resistance, and even partially aromatic poterphthalic acid amide does not have sufficient heat resistance. For example, when hexamethylene diamine or propylene diamine is used as the amine component, there are problems not only in heat resistance but also in solubility. In addition, improved solubility makes it easier to process into films and fibers, but it is not suitable for processing molded products for use in machinery, electrical parts, etc.
Here, as a condition to be able to use the composite processing method using heat, it is required to have a glass transition temperature (Tg) that is not too high, that is, a Tg of 400°C or less. The present invention provides a copolyamide that compensates for the drawbacks of aromatic polyamides and aliphatic polyamides, and has the solubility and high heat resistance of polyamides, as well as moldability using heat. Means/effect for solving the problem That is, the present invention solves the problem by formula (-X-NH-Y-NH)-
It has a structural formula represented by, in which X is the formula (A)

【formula】 , and Y is the formula (B)

[Formula] (However, in the formula, R is one selected from the group consisting of H, CH ₃ and C ₂ H _5. ) and the formula (C) −C _o H _2o −
(However, in the formula, n is a positive number from 2 to 8.) It is a copolyamide consisting of chain members of the formula (B) of Y and the formula
The molar ratio of (C) is 60:40 to 99:1, and the intrinsic viscosity (ηinh) is measured at 30°C of a solution in which 0.5 g of the copolyamide is dissolved in 100 ml of dimethylacetamide.
is 0.25 dl/g or more. The raw materials of formula (A) constituting X in the formula include terephthalic acid chloride, isophthalic acid chloride, etc., and the raw materials of formula (B) constituting Y in the formula include 9,9
-bis(4-aminophenyl)fluorene b, 9,
9-bis(3-methyl-4-aminophenyl)fluorene, 9,9-bis(3-ethyl-4-aminophenyl)fluorene, etc., and raw materials for formula (C) include methylenediamine and 1,2-ethylenediamine. , 1,3-propylenediamine, 1,4-
Examples include butylene diamine, 1,5-pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and the like. When n in formula (C) is a positive number of 2 to 8, solubility and moldability can be improved while maintaining heat resistance. Among these raw materials, the preferred one is the formula (A)
In formula (C), it is terephthalic acid chloride, and in formula (C), it is industrially produced and cheaper 1,3-propylene diamine or hexamethylene diamine, and most preferably 1,3-propylene diamine. Formula Y consists of a chain member formula (B) component and a formula (C) component, but since the ratio of both is related to the solubility of the copolyamide produced, the molar ratio of (B) and (C) is is 60:
It is necessary to set the ratio to 40 to 99:1. That is, when the molar ratio of the chain member formula (C) of the copolyamide of the present invention exceeds 40, the solubility decreases. For example, terephthalic acid chloride and 9,9-
Dimethylacetamide or N
- When polymerizing in methylpyrrolidone, copolyamide precipitates during the process, making it difficult to obtain a copolyamide with a high degree of polymerization. Further, the copolyamide terminals may be left untreated, but preferably the amino groups are acylated to make them less susceptible to oxidation. This acyl group is suitably an acetyl group or a benzoyl group. The method for producing the copolyamide of the present invention includes 9,
It is obtained by dissolving 9-bis(4-aminophenyl)fluorene, diamine, triethylamine, etc. in a solvent such as dimethylacetamide, and gradually adding terephthalic acid chloride while cooling to a low temperature of about 5° C., and reacting for about 2 hours. Synthesis can be carried out using various diamines and dicarboxylic acids under similar reaction conditions. In addition, the copolyamide of the present invention has an intrinsic viscosity (ηinh) of 0.25 dl/g based on the mechanical strength of the copolyamide, which is based on the value measured at 30°C of a solution of 0.5 g of this copolyamide dissolved in 100 ml of dimethylacetamide. It is necessary that it is above 0.30 dl/g, and particularly preferably 0.30 dl/g or above. Further, the glass transition temperature (Tg) is 400° C. or less, preferably 200 to 400, because of the heat resistance of the copolyamide and the ease of thermal molding. Furthermore, this copolyamide is soluble in at least pyridine, m-cresol, o-chlorophenol, N-methylpyrrolidone, and dimethylacetamide. When the copolyamide is dissolved in the above-mentioned solvent and made into fibers or films, uncolored and transparent products can be obtained. The copolyamide provided by the present invention is uncolored, has improved solubility and heat resistance compared to conventional products, and also has good mechanical properties and electrical properties. In addition, the glass transition temperature can be adjusted and thermal molding is easy. A more detailed explanation will be given below based on examples. Examples Example 1 4.18 g of 9,9-bis(4-aminophenyl)fluorene (AF), 0.59 g of 1,3-propylene diamine (PDA) and 4.04 g of triethylamine were dissolved in 100 ml of dimethylacetamide and cooled to 5°C. While stirring, 4.06 g of terephthalic acid chloride (powder) was gradually added. After stirring for 3 hours, triethylamine hydrochloride produced by the reaction was filtered off, and the filtrate was poured into methanol to reprecipitate the polymer. Furthermore, the copolyamide obtained by filtration was heated and dried to obtain the desired product. The yield was 100%. The infrared absorption spectrum of the obtained copolyamide shows that NH absorption is 3250 cm ^-1 , amide carbonyl group absorption is 1660 cm ^-1 , and aliphatic absorption is 3000 to 2850 cm ^-1
, and the aromatic absorption is 3200 to 3000 cm ^-1 ,
It was between 1620 cm ^-1 and 1510 cm ^-1 and showed the characteristic absorption of polyamide. Also, 5.57 g of 9,9-bis(4-aminophenyl)fluorene, 1,3-propylene diamine
Polymerization was carried out in exactly the same manner as in Example 1, except that the amount charged was changed to 0.30 g. The properties of the obtained copolyamide are shown in Table 1. For comparison, Table 1 shows the properties of a polyamide obtained from 4.18 g of 9,9-bis(4-aminophenyl)fluorene and terephthalic acid chloride as a comparative example. Example 2 4.18 g of 9,9-bis(4-aminophenyl)fluorene, 0.59 g of 1,3-propylene diamine and 4.04 g of triethylamine were added to 100 g of dimethylacetamide.
ml, and 4.06 g of terephthalic acid chloride was gradually added as a powder while cooling to 5° C. and stirring.
After 2 hours, 0.5 ml of benzoyl chloride was added, and the mixture was stirred at room temperature for 2 hours. After the by-produced triethylamine hydrochloride was filtered off, the filtrate was poured into methanol, and the precipitated polymer was filtered, washed, and further heated and dried to obtain the desired copolyamide. The yield was 99%. The infrared absorption spectrum of the obtained copolyamide shows NH absorption at 3240 cm ^-1 , aromatic absorption at 3200 to 3000 cm ^-1 , aromatic absorption at 3000 to 2900 cm ^-1 , and 1660 cm ^-1
showed aromatic absorption at 1610 and 1530 cm ^-1 . Also 9,9-bis(4-aminophenyl)fluorene 5.57g, 1,3-propylenediamine 0.30g
Polymerization was carried out in the same manner as in Example 2 except that. The properties of the obtained copolyamide are shown in Table 1. Example 3 6.26 g of 9,9-bis(4-aminophenyl)fluorene (AF), 0.12 g of hexamethylene diamine (HMDA) and 4.04 g of triethylamine were dissolved in 100 ml of dimethylacetamide, and while cooling to 5°C, 4.06 g of terephthalic acid chloride was dissolved. g was gradually added.
After 2 hours of reaction, triethylamine hydrochloride produced as a by-product was filtered off, and the reaction solution was poured into methanol. The released copolyamide was filtered, heated and dried. The properties of the obtained copolyamide are shown in Table 2. For comparison, Table 2 shows the properties of polyamide obtained from hexamethylene diamine and terephthalic acid chloride. Example 4 6.26 g of 9,9-bis(4-aminophenyl)fluorene, 0.12 g of hexamethylenediamine and 4.04 g of triethylamine were added to 100 ml of dimethylacetamide.
After reacting at 5℃ for 2 hours, benzoyl chloride
0.5 ml was added and stirred at room temperature for 2 hours. After filtering off the triethylamine hydrochloride produced as a by-product, the filtrate was poured into methanol, and the precipitated copolyamide was filtered and dried by heating. Further, the same reaction was carried out by changing the amounts of 9,9-bis(4-aminophenyl)fluorene and hexamethylenediamine as shown in Table 3 No. below. The numbers below are comparative examples outside the scope of the present invention. These results are summarized in Table 2, including solubility and heat resistance. The infrared absorption spectra of the copolyamides obtained in Examples 3 and 4 are NH at 3300 cm ^-1 and 3200 to 3000 cm
^-1 is aromatic, 3000~2800cm ^-1 is aliphatic, 1680~
Amide carbonyl absorption was observed at 1670 cm ^-1 , and aromatic absorption was observed at 1610 and 1500 cm ^-1 . The intrinsic viscosity shown in the table of Examples of the present invention is as follows: 0.5 g of the obtained copolyamide was mixed with 100
ml and measured at 30°C to determine the intrinsic viscosity (ηinh). Further, the glass transition temperature and infrared absorption spectrum shown in the examples of the present invention were measured as a film. In the film formation, a thin film prepared by dissolving in dimethylacetamide or the like was used. Thin film creation was easy.

【table】

【table】

[Table] Effects of the Invention The copolyamide of the present invention has improved heat resistance and solubility compared to conventional terephthalic acid-hexamethylene diamine-based or terephthalic acid-propylene diamine-based polyamides. The law has expanded and can be used more widely. That is, by lowering the glass transition temperature,
Thermal compression molding becomes possible, opening the way to processing into molded products, and expanding the range of use by making films rather than melting. It holds great promise especially as an electrical and electronic material.

Claims (1)

[Claims] 1 It has a structural formula represented by the formula (-X-NH-Y-NH)-, in which X represents the formula (A)
[Formula], and Y is the formula (B) [Formula] (wherein R is one selected from the group consisting of H, CH ₃ and C ₂ H ₅ ) and the formula (C) - C _o H _2o −
(However, in the formula, n is a positive number from 2 to 8.) It is a copolyamide consisting of chain members of the formula (B) of Y and the formula
The molar ratio of (C) is 60:40 to 99:1, and the intrinsic viscosity (ηinh) is measured at 30°C of a solution in which 0.5 g of the copolyamide is dissolved in 100 ml of dimethylacetamide.
0.25 dl/g or more. 2 Intrinsic viscosity (ηinh) measured by the above measurement method is 0.30
The soluble heat-resistant copolyamide according to claim 1, which has a dl/g or more. 3 At least pyridine, m-cresol, o-
The soluble copolyamide according to claim 1, which is soluble in chlorphenol, N-methylpyrrolidone, and dimethylacetamide.