TW201943902A - 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

   Preparation method of modified polyamide   

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

Since the emergence of nylon fiber, it has been widely used in various fabrics, clothing and medical supplies due to its many advantages such as toughness, abrasion resistance, smoothness, light weight and resistance to static electricity. However, when the nylon fiber is only composed of 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, thereby changing 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 polyammoniumamine, comprising: copolymerizing caprolactam, adipic acid, polybutyl ether diamine, and diethyltriamine (DETA), wherein caprolactam is 80 ~ 95 parts by weight, 0.5 to 2.5 parts by weight of adipic acid, 4 to 16 parts by weight of polybutyl ether diamine, and 0.3 to 1.2 parts by weight of diethyl triamine, wherein polybutyl ether diamine has formula (II) The structure:

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

In one embodiment, the polybutylene ether diamine has an average molecular weight of 1,000.

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

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

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

In one embodiment, the 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 invention. The composition and layout of specific examples are described below to simplify the present invention. These are, of course, examples only and are not intended to be limiting.

The present invention provides a method for preparing modified polyammonium amine, which uses lactamamine having 6 to 12 carbons, linear fatty dicarboxylic acid having 4 to 18 carbons, polybutyl ether diamine, and diethyl triamine ( diethylenetriamine (DETA) as a reactant, copolymerization to form modified polyfluorene. After copolymerization, these reactants will be bonded to each other in a random arrangement to form modified polyamides.

In one embodiment, the copolymerization reaction of lactam, linear aliphatic dicarboxylic acid, polybutyl ether diamine, and diethyl triamine is performed at a temperature of 200 to 270 ° C and an absolute pressure of 0.1 to 3 bar. . Specifically, in one embodiment, the lactam 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, the absolute pressure is adjusted to 1 to 1.3 bar (can be adjusted by introducing or extracting nitrogen), and the temperature is raised to 240 to 280 ° C, so that the hydrolyzed linamine, linear fatty dicarboxylic acid, and polybutyl ether Amine and diethyltriamine are copolymerized. Then, 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 lactam 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 diethyltriamine has a weight percentage concentration of 0.3% by weight to 1.2% by weight of the linamine, linear fatty dicarboxylic acid, polybutyl ether diamine, and diethyl triamine. %. In another embodiment, the polybutyl ether diamine has a weight percentage concentration of 4% to 16% by weight of the linoleamide, the linear fatty dicarboxylic acid, the polybutyl ether diamine, and the diethyl triamine.

The properties of the modified polyamide can also be adjusted by selecting different combinations of reactants. In one embodiment, the lactam is caprolactam (CPL) having 6 carbons, and the linear fatty 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 a 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 13,000 to 25,000.

As before, after the copolymerization reaction, modified polyamines are formed. In detail, after the copolymerization reaction, the product should be a mixture, and the mixture includes modified polyamides of different molecular weights. The modified polyamidoamines of different molecular weights may form hydrogen bonds or make the above products more elastic as a whole by the Coulomb force.

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 polyamine is formed by using polybutyl ether diamine having a structure of formula (II) as a reactant. The formula (II) is as follows:

Where a + c is 1-20, and b is 4-50. In one embodiment, the molecular weight of the polybutylene diamine is 500-1500. The polybutylene ether diamine has a soft long chain and is more elastic, so the modified polyamine 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 resistant composite fiber, which includes a first nylon resistant fiber and a second nylon resistant fiber. The first nylon fiber includes the aforementioned modified polyamide and has better elasticity. In one embodiment, the first nylon fiber includes a plurality of modified polyamides having different molecular weights. The second nylon fiber comprises a first polyamide or a second polyamide having poor elasticity. The first polyamide is polymerized from 6 to 12 carbons of lactam, 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 and second nylon fibers are arranged side by side. Specifically, in some embodiments, the first polyamide may be Nailon 6, Nailon 11, or Nailon 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, because the modified polyamide has better elasticity and has poor dimensional stability, while the first or second polyamide has poor elasticity and has better dimensional stability, therefore, when it has After two kinds of stable nylon fiber with different sizes are resistant to proper tension, the nylon composite fiber will spontaneously generate spiral curls.

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

Experimental Example 1: Synthesis of modified polyfluorene and performance test

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

As can be seen from Table 1, 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 requirements of spinning fibers.

Experimental Example 2: Rheological Experiment

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

Table II

As can be seen from Table 2, when the shear rate is small, the products of Examples 1 to 3 will have a larger viscosity; conversely, when the shear rate is large, for example, the shear rate is 6000 to 10000 (1 / s), Examples 1 to The product of three still has at least 30Pa. viscosity above s. Because the shear rate usually reaches 6000 ~ 10000 (1 / s) during the spinning process, the above results show that the modified polyamide of the present invention can meet the requirements of spinning fibers, and is suitable for further processing into fibers. .

Experimental example 3: Plastic film property test

In this experimental example, the products of Examples 1 to 3 are made into plastic tablets, respectively. In addition, in Comparative Example 1, caprolactam, adipic acid, and polybutyl ether diamine having the structure of formula (II) were copolymerized, and then the product was made into a plastic tablet, wherein caprolactam was 88.6 wt%, adipic acid was 1.4 wt%, and polybutyl ether diamine having a structure of formula (II) was 10 wt%. Next, the maximum tensile strength and elongation at break of the plastic sheet were tested separately. The experimental results are shown in 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 known from Table 3 that the maximum tensile strength and elongation at break point 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. It 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 the nylon composite fiber were tested. The nylon composite fiber includes a first nylon composite fiber and a second nylon composite fiber, and is a side-by-side nylon composite fiber. In Examples 7 to 11, the first nylon fiber includes the product of Example 2, and the second nylon fiber includes the nylon 6. In Comparative Example 2, the first nylon fiber includes the product of Comparative Example 1, and the second nylon fiber includes the nylon 6. Table 4 lists the strength, elongation, and spontaneous crimp contraction (CC) of the nylon composite fiber made of the first nylon fiber and the second nylon fiber with different weight ratios.

Table four

As can be seen from Table 4, the strength and elongation of the nylon composite fiber of the present invention are good, comparable to that of commonly used nylon fiber materials, and the spontaneous shrinkage rate can reach more than 16%, which 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 polyfluorene synthesized by using diethyltriamine as one of the reactants, Long fiber has better spontaneous shrinkage. The above results show that the nylon composite fiber of the present invention can have good elasticity without being subjected to false twist processing or adding other elastic fibers.

Experimental example 5: Test of elongation recovery rate of nylon fabric

The Nylon composite fiber of Example 9 was made into a Nylon fabric, and then the elongation recovery rate test was performed. In addition, in Comparative Example 3, Nylon 6 was made into a Nylon fabric, and the elongation recovery was also performed on this Nylon fabric. Rate test. Please refer to Table 5 below for the experimental results.

It can be seen from Table 5 that the elongation recovery rate of the nylon fabric composed of the nylon composite fiber of the present invention after the fixed elongation of 10% and 20% is better than that of the nylon fabric of the comparative example 3, and after the fixed elongation of 30%, The elongation recovery rate is similar to the resistant 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 this nylon fabric can have high elongation recovery rate and durable elasticity.

In summary, the modified polyamide of the present invention has good elasticity, strength, and stretchability, and is suitable for being made into durable fibers. In addition, the nylon-resistant composite fiber of the present invention includes a first nylon-resistant fiber containing the modified polyamide and a second nylon-resistant fiber having good dimensional stability, so that the nylon-resistant composite fiber has the characteristic of spontaneous crimping. , And has good strength and elongation. Therefore, this nylon composite fiber can be used for manufacturing elastic nylon fabric with high elongation recovery rate and durability.

Although the present invention has been disclosed in the above embodiments, 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 skilled in this art will understand that, without departing from the spirit and scope of the present invention, various modifications and retouching can be made. Therefore, the scope of protection of the present invention shall be determined by the scope of the attached patent application.

Claims (7)

A method for preparing modified polyammoniumamine, comprising: 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 polybutylene ether diamine has an average molecular weight of 1,000.         The manufacturing method according to claim 1, wherein the caprolactam is 81.9 to 93.8 parts by weight.         The manufacturing method according to claim 1, wherein the adipic acid is 0.7 to 2.1 parts by weight.         The manufacturing 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 manufacturing method according to claim 1, wherein the melting point of the modified polyamide is 213.6 ° C to 221.0 ° C.