TWI684683B - Manufacturing method of modified polyamide - Google Patents

Abstract

80~95 parts by weight of caprolactam, 0.5~2.5 parts by weight of adipic acid, 4~16 parts by weight of poly(butyl ether) diamine, and 0.3~1.2 parts by weight of diethylenetriamine are copolymerized. The poly(butyl ether) diamine has a structure of formula (II): wherein a+c is 1~20, and b is 4~50

Description

Method for making modified polyamide

The invention relates to a method for preparing modified polyamide. In particular, it relates to a method for preparing modified polyamide using diethyltriamine as a reactant.

Since the advent of Nylon fiber, it has been widely used in various fabrics, clothing, and medical supplies because of its many advantages such as toughness, wear resistance, smoothness, light weight, and low static electricity generation. However, when Nylon fiber is composed of only a single polyamide, it cannot meet the needs of various products. In view of this, there is an urgent need to develop other polyamides to make nylon fibers, so as to change the properties of nylon fibers to meet the needs of various products.

其中a+c為1~20，且b為4~50。 The invention provides a method for preparing modified polyamide, which comprises: copolymerizing caprolactam, adipic acid, polybutyl ether diamine and diethyltriamine (DETA), wherein caprolactam is 80~ 95 parts by weight, adipic acid is 0.5 to 2.5 parts by weight, polybutyl ether diamine is 4 to 16 parts by weight, and diethyl triamine is 0.3 to 1.2 parts by weight, wherein polybutyl ether diamine has the formula (II) The structure:

Where a+c is 1-20, and b is 4-50.

In one embodiment, the average molecular weight of polybutyl ether diamine is 1000.

In one embodiment, caprolactam is 81.9-93.8 parts by weight.

In one embodiment, adipic acid is 0.7 to 2.1 parts by weight.

In one embodiment, polybutyl ether diamine is 5-15 parts by weight.

In one embodiment, diethyltriamine is 0.5 to 1 part by weight.

In one embodiment, the melting point of the modified polyamide is 213.6°C to 221.0°C.

The following disclosure provides many different embodiments or examples to implement different features of the present invention. The composition and layout of specific examples are described below to simplify the present invention. Of course, these are only examples, not for limitation.

The invention provides a method for preparing modified polyamidoamine, which uses internal amide with 6-12 carbons, linear dicarboxylic acid with 4-18 carbons, polybutyl ether diamine and diethyltriamine ( Diethylenetriamine (DETA) is used as a reactant to form modified polyamide by copolymerization. After copolymerization, these reactants will be bonded to each other with amide bonds in a random arrangement. Formation of modified polyamide.

In one embodiment, the copolymerization reaction of internal amide, linear fatty dicarboxylic acid, polybutyl ether diamine and diethyl triamine is carried out at a temperature of 200 to 270°C and an absolute pressure of 0.1 to 3 bar. . In detail, in one embodiment, the internal amide is hydrolyzed at a temperature of 200 to 260°C and an absolute pressure of 1 to 3 bar for 1 to 2.5 hours. Next, adjust the absolute pressure to 1~1.3bar (can be adjusted by introducing or drawing out nitrogen), and increase the temperature to 240~280℃, so that the hydrolyzed internal amide, linear fatty dicarboxylic acid, polybutyl ether di Copolymerization of amine and diethyltriamine. Following that, the pressure is gradually reduced to 0.1 to 0.5 bar.

The properties of the modified polyamide can be adjusted by adjusting the weight ratio between the reactants. In one embodiment, the internal amide is 80 to 95 parts by weight, the linear fatty dicarboxylic acid is 0.5 to 2.5 parts by weight, the polybutyl ether diamine is 4 to 16 parts by weight, and the diethyltriamine is 0.3 to 1.2 parts by weight. In another embodiment, the weight percentage concentration of diethyltriamine in amide, linear fatty dicarboxylic acid, polybutyl ether diamine and diethyltriamine is 0.3wt%~1.2wt %. In another embodiment, the weight percent concentration of polybutyl ether diamine in the amide, linear fatty dicarboxylic acid, polybutyl ether diamine, and diethyl triamine is 4 wt% to 16 wt%.

The properties of the modified polyamide can also be adjusted by selecting different combinations of reactants. In one embodiment, the internal amide is caprolactam (CPL) having 6 carbons, and the linear aliphatic dicarboxylic acid is adipic acid (AA) having 6 carbons.

其中，a+c為1~20，b為4~50，m為5~11，n為2~16，x為100~220，y為1~6。在一實施方式中，改質聚醯胺的分子量為13000~25000。 In one embodiment, the modified polyamide of the present invention has the structure of formula (I):

Among them, a+c is 1-20, b is 4-50, m is 5-11, n is 2-16, x is 100-220, and y is 1-6. In one embodiment, the molecular weight of the modified polyamide is 13000-25000.

As mentioned above, after the copolymerization reaction, modified polyamide is formed. In detail, after the copolymerization reaction, the product should be a mixture, and the mixture includes modified polyamides with different molecular weights. Modified polyamides with different molecular weights may form hydrogen bonds or the Coulomb force makes the above products more flexible overall.

其中a+c為1~20，且b為4~50。在一實施方式中，聚丁醚二胺的分子量為500~1500。此聚丁醚二胺具有柔軟的長鏈而較具彈性，從而改質聚醯胺具有良好的延展性和彈性。然而，本發明並不限於此，其他的聚丁醚二胺亦可用於本發明之製作方法。 The modified polyamide described above is formed by using polybutyl ether diamine having the structure of formula (II) as a reactant. Formula (II) is as follows:

Where a+c is 1-20, and b is 4-50. In one embodiment, the molecular weight of polybutyl ether diamine is 500-1500. This polybutyl ether diamine has a soft long chain and is more elastic, so that the modified polyamide has good ductility and elasticity. However, the present invention is not limited to this, and other polybutyl ether diamines can also be used in the manufacturing method of the present invention.

In addition, the present invention further provides a nylon composite fiber, which includes a first nylon fiber and a second nylon fiber. The first nylon fiber includes the aforementioned modified polyamide and has better elasticity. In one embodiment, the first nylon fiber includes multiple modified polyamides with different molecular weights. The second nylon fiber includes a first polyamide or a second polyamide with poor elasticity. The first polyamide is formed by polymerizing an internal amide having 6 to 12 carbons, and the second polyamide is composed of linear aliphatic diamine having the N ₁ carbon atoms and straight-chain aliphatic dicarboxylic acid having N ₂ carbons polymerization, for example, wherein N ₁ 4 ~ 10, N _2, for example, 6 to 14, and (N ₂ - The value of 2) is an integer multiple of the value of (N ₁ -2), and the first nylon fiber and the second nylon fiber are arranged side by side. Specifically, in some embodiments, the first polyamide may be Nylon 6, Nylon 11, or Nylon 12. In one embodiment, the second polyamide may be Nylon 4.6, Nylon 6.6, Nylon 6.10, Nylon 6.12, Nylon 6.14, or Nylon 10.10.

The properties of the nylon composite fiber can be adjusted by adjusting the weight ratio between the first nylon fiber and the second nylon fiber. In one embodiment, the weight ratio of the first nylon fiber to the second nylon fiber is 40:60 to 60:40.

As mentioned above, since the modified polyamide has better elasticity and has poor dimensional stability, and the first polyamide or the second polyamide has poor elasticity and has better dimensional stability, therefore, when having When the nylon composite fiber of two kinds of stable nylon fibers with different sizes is properly tensioned, the nylon composite fiber will spontaneously produce a spiral curl.

The following embodiments are used to describe specific aspects of the present invention and enable those with ordinary knowledge in the technical field to which the present invention belongs to implement the present invention. However, the following examples should not be used to limit the present invention.

Experimental Example 1: Synthesis and characterization of modified polyamide

In this experimental example, caprolactam (CPL), adipic acid (AA), polybutyl ether diamine having the structure of formula (II) and diethyltriamine (DETA) were copolymerized as reactants, To form a product containing modified polyamide. The average molecular weight of polybutyl ether diamine is 1,000. Please refer to Table 1 for the weight percent concentration of each reactant and the nature of each product.

It can be seen from Table 1 that the melting point of the product is between 213°C and 221°C, and the relative viscosity of the product is between 1.4 and 1.7. This experimental example can prove that the modified polyamide of the present invention can meet the needs of spinning to make fibers.

Experimental Example 2: Rheological experiment

In this experimental example, at temperatures of 260°C, the products of Examples 1 to 3 were analyzed using rheological experiments. Observe the viscosity of each product under different shear rates. Please refer to Table 2 for experimental results.

Table II

It can be seen from Table 2 that when the shear rate is small, the products of Examples 1 to 3 will have a larger viscosity; on the contrary, when the shear rate is large, for example, the shear rate is 6000~10000 (1/s), Examples 1 to Three products still have at least 30Pa. Viscosity above s. Since the shear rate usually reaches 6000 to 10000 (1/s) during the spinning process, the above results show that the modified polyamide of the present invention can meet the general needs of spinning to make fibers and is suitable for further processing into fibers .

Experimental Example 3: Plastic sheet property test

In this experimental example, the products of Examples 1 to 3 were made into plastic tablets. In addition, in Comparative Example 1, after copolymerization of caprolactam, adipic acid and polybutyl ether diamine having the structure of formula (II), the product is made into a plastic tablet, in which caprolactam is 88.6% by weight, adipic acid is 1.4% by weight, and polybutyl ether diamine having the structure of formula (II) is 10% by weight. Next, test the above separately The maximum tensile strength and elongation at break of the plastic sheet. For experimental results, please refer to Table 3 below.

It is worth noting that the main difference between Examples 1 to 3 and Comparative Example 1 is that the reactants of Examples 1 to 3 include diethyltriamine, and the reactants of Comparative Example 1 do not contain diethyltriamine. It can be seen from Table 3 that the maximum tensile strength and elongation at break of the plastic sheets of Examples 1 to 3 are higher than those of Comparative Example 1. The above results show that the present invention uses diethyltriamine as one of the reactants. Can achieve the effect of improving the strength and ductility of the product.

Experimental Example 4: Property Test of Nylon Composite Fiber

In this experimental example, the properties of nylon composite fibers were tested. Nylon composite fibers include first Nylon fibers and second Nylon fibers, and are side-by-side Nylon composite fibers. In Examples 7 to 11, the first nylon fiber includes the product of Example 2, and the second nylon fiber includes nylon 6. In Comparative Example 2, the first nylon fiber includes the product of Comparative Example 1, and the second nylon fiber includes nylon 6. Table 4 lists the strength, elongation and spontaneous crimp (CC) of the nylon composite fibers made with the first nylon fibers and the second nylon fibers with different weight ratios.

Table 4

It can be seen from Table 4 that the nylon composite fiber of the present invention has good strength and elongation, which is equivalent to the level of the commonly used nylon fiber material, and the spontaneous shrinkage rate can reach more than 16%, and is suitable for manufacturing elastic nylon fabric. From Examples 7 to 11 and Comparative Example 2, it can be seen that in the case where the first nylon fiber includes modified polyamide synthesized with diethyltriamine as one of the reactants, the resistance Long composite fiber has better spontaneous crimp rate. The above results show that the nylon composite fiber of the present invention can have good elasticity without the need for false twist processing or the addition of other elastic fibers.

Experimental Example 5: Elongation recovery test of nylon fabric

The nylon composite fiber of Example 9 is made into a nylon fabric, and then the elongation recovery rate test is performed. In addition, in Comparative Example 3, nylon 6 is made into a nylon fabric, and the nylon fabric is also subjected to elongation recovery Rate test. For the experimental results, please refer to Table 5 below.

It can be seen from Table 5 that the elongation recovery rate of the nylon fabric composed of the nylon composite fibers of the present invention after a fixed elongation of 10% and 20% is better than that of the nylon fabric of Comparative Example 3, but after a fixed elongation of 30% The elongation recovery rate is similar to the nylon fabric of Comparative Example 3. The above results show that the nylon composite fiber of the present invention is suitable for making nylon fabric, and the nylon fabric can have a high elongation recovery rate and durable elasticity.

In summary, the modified polyamide of the present invention has good elasticity, strength and extensibility, and is suitable for being made into nylon fiber. In addition, the Nylon composite fiber of the present invention includes the first Nylon fiber containing the modified polyamide and the second Nylon fiber with good dimensional stability, so that the Nylon composite fiber has spontaneously crimping characteristics , And has good strength and elongation. Therefore, this nylon composite fiber can be used to manufacture an elastic nylon fabric with high elongation recovery and durability.

Although the present invention has been disclosed as above, other embodiments are also possible. Therefore, the spirit and scope of the requested items are not limited to the description contained in the embodiments herein.

Anyone who is familiar with this skill can understand that various changes and modifications can be made without departing from the spirit and scope of the present invention, so the scope of protection of the present invention shall be deemed as defined by the scope of the attached patent application.

Claims (7)

A method for preparing modified polyamide includes: copolymerizing caprolactam, adipic acid, polybutyl ether diamine and diethyltriamine, wherein the caprolactam is 80 to 95 parts by weight, The adipic acid is 0.5 to 2.5 parts by weight, the polybutyl ether diamine is 4 to 16 parts by weight, and the diethyl triamine is 0.3 to 1.2 parts by weight, wherein the polybutyl ether diamine has Structure of formula (II):

Where a+c is 1-20, and b is 4-50. The production method according to claim 1, wherein the average molecular weight of the polybutyl ether diamine is 1,000. The production method according to claim 1, wherein the caprolactam is 81.9 to 93.8 parts by weight. The production method according to claim 1, wherein the adipic acid is 0.7 to 2.1 parts by weight. The production method according to claim 1, wherein the polybutyl ether diamine is 5 to 15 parts by weight. The production method according to claim 1, wherein the diethyltriamine is 0.5 to 1 part by weight. The production method according to claim 1, wherein the melting point of the modified polyamide is 213.6°C to 221.0°C.