TWI488885B - Polyamide-6 copolymer and method of manufacturing the same - Google Patents

Description

Polyamine-6 copolymer and preparation method thereof

The invention relates to a polyamido-6 copolymer and a preparation method thereof, in particular to a polyamido-6 copolymer which can be dyed at low temperature to form a dyeable fiber and a preparation method thereof.

Polyamide-6 (also known as nylon-6) is easy to be made into textile fiber, and the textile fiber made of polyamide-6 has high strength, good rebound and wear resistance. High in properties, good in moisture absorption, and dyeable, it is widely used in the textile industry. It can be used to make socks, underwear, shirts, sports firs, raincoats, etc., and can also be blended with other fibers to make nylon. Buckle belts, carpets and decorative fabrics are of great economic value.

Polyamido-6 is usually formed into a rubber particle by ring-opening polymerization of caprolactam, and the rubber particles are processed into fibers by a spinning process, and finally subjected to dyeing and finishing. Generally, the dyeing temperature of polyamido-6 fiber is 98 ° C. With the soaring energy prices of petroleum and natural gas, how to reduce the dyeing temperature of polyamido-6 fiber to reduce production cost is the focus of the industry.

An object of the present invention is to provide a polyamido-6 copolymer and a preparation method thereof, whereby a fiber made of a polyamide-6 copolymer has a lower dyeing temperature and can save energy for dyeing and finishing. The cost can also shorten the time of dyeing and finishing, so the production cost can be effectively reduced.

One embodiment in accordance with an aspect of the present invention is to provide a polyamido-6 copolymer.

According to another embodiment of the present invention, there is provided a process for the preparation of a polyamido-6 copolymer comprising providing a polymerization reactant and performing a hydrolysis polymerization step to form a polyamido-6 copolymer.

The aforementioned polymerization reactant contains a mesalamine, a bisamine oligomer, and a carboxyl group-containing compound.

The bisamine oligopolymer has a structure as shown in formula (i): Wherein a is an integer from 12 to 24, b is an integer from 12 to 24, and c is an integer from 12 to 24.

The carboxyl group-containing compound has a structure represented by the formula (iii): HOOC-R ² -COOH (iii), wherein R ² is a saturated aliphatic branch having 6 to 18 carbon atoms, an unsaturated aliphatic branch or an aromatic aliphatic group Group.

In the polymerization reaction, wherein the total content of the decylamine, the bisamine oligopolymer, and the carboxyl group-containing compound is 100% by weight, the content of the bisamine oligopolymer is from 3 to 20% by weight, and the content of the carboxyl group-containing compound It is from 0.2% by weight to 5% by weight, and the total of the indoleamine, the bisamine oligopolymer, and the carboxyl group-containing compound is 100% by weight.

According to the aforementioned preparation method of the polyamido-6 copolymer, the hydrolysis polymerization step can be carried out at 230 ° C to 270 ° C. Before the hydrolysis polymerization step, the stirring and melting step may be first performed to uniformly melt the polymerization product by heating and stirring. After the hydrolysis polymerization step, the extraction and drying steps can be carried out so that the concentration of the secondary amine group of the polyamide-6 copolymer is 35 milli equivalents per kilogram (milliequivalent/kg; meq/kg) to 55 meq/kg. The relative viscosity of the indoleamine-6 copolymer is from 1.6 to 2.4, and the glass transition temperature of the polyamide-6 complex is from 45 °C to 53 °C.

According to the aforementioned preparation method of the polyamido-6 copolymer, the carboxyl group-containing compound may be terephthalic acid.

According to the aforementioned preparation method of the polyamido-6 copolymer, wherein the polymerization reactant may further comprise a monoamine compound having a structure represented by the formula (iv): R ³ -NH ₂ (iv), wherein R ³ is a saturated aliphatic branched, unsaturated aliphatic branched or aromatic aliphatic group having 6 to 18 carbon atoms. The monoamine compound can be aniline.

When the polymerization reactant contains a monoamine compound, which is based on The total content of the amine, the bisamine oligopolymer, the carboxyl group-containing compound, and the monoamine compound is 100% by weight, the content of the bisamine oligopolymer is from 3 to 20% by weight, and the content of the carboxyl group-containing compound is from 0.2% by weight to 5. The percentage by weight and the content of the monoamine compound is from 0.5% by weight to 2% by weight.

100‧‧‧ method

110‧‧‧Provide steps for the polymerization of reactants

120‧‧‧Slurry stirring step

130‧‧‧Hydration polymerization step

140‧‧‧Steps for extraction and drying

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Step flow chart of the method.

Fig. 2 is a scanning diagram of a dynamic viscoelastic mechanical analyzer (DMA) of Example 1.

Fig. 3 is a DMA scan of the second embodiment.

Fig. 4 is a DMA scan of the third embodiment.

Fig. 5A is a ¹ H-NMR spectrum chart of Example 1.

5B graph of Example ¹ a partially enlarged view of the H-NMR spectrum of FIG. 1.

Fig. 6A is a ¹ H-NMR spectrum chart of Example 2.

Fig. 6B is a partial enlarged view of the ¹ H-NMR spectrum chart of Example 2.

Fig. 7A is a ¹ H-NMR spectrum chart of Example 3.

Fig. 7B is a partially enlarged view of the ¹ H-NMR spectrum chart of Example 3.

Fig. 8A is a ¹ H-NMR spectrum chart of Comparative Example 1.

Fig. 8B is a partially enlarged view of the ¹ H-NMR spectrum chart of Comparative Example 1.

Fig. 9 is a graph showing the results of gel permeation chromatography (GPC) inspection of Example 1.

Fig. 10 is a graph showing the results of GPC inspection of Example 2.

Fig. 11 is a graph showing the results of GPC test of Comparative Example 1.

<Polyamine-6 copolymer and its preparation method>

The present invention provides a polyamido-6 copolymer.

With regard to the preparation method of the above polyamine-6 copolymer, please refer to FIG. 1 , which is a flow chart of the steps of the method 100 for preparing the polyamide-6 copolymer according to an embodiment of the present invention, wherein the step 110 is to provide polymerization. The reactant, step 130, is subjected to a hydrolysis polymerization step.

Specifically, step 110 is to provide a polymerization reactant, wherein the polymerization reactant comprises a decylamine, a bisamine oligopolymer, and a carboxyl group-containing compound.

The bisamine oligopolymer has a structure as shown in formula (i): Wherein a is an integer from 12 to 24, b is an integer from 12 to 24, and c is an integer from 12 to 24.

The carboxyl group-containing compound has a structure represented by the formula (iii): HOOC-R ² -COOH (iii), wherein R ² is a saturated aliphatic branched, unsaturated aliphatic branched or aromatic aliphatic group having a carbon number of 6 to 18. group. According to an embodiment of the invention, the carboxyl group-containing compound may be terephthalic acid.

In the polymerization reaction, the total content of the decylamine, the bisamine oligopolymer, and the carboxyl group-containing compound is 100% by weight, the content of the bisamine oligopolymer is from 3 to 20% by weight, and the content of the carboxyl group-containing compound It is from 0.2% by weight to 5% by weight.

The polymerization reactant may optionally comprise a monoamine compound having a structure as shown in formula (iv): R ³ -NH ₂ (iv), wherein the R ³ is a saturated aliphatic branch having a carbon number of 6 to 18. A chain, an unsaturated aliphatic branch or an aromatic aliphatic group. According to an embodiment of the invention, the monoamine compound is aniline.

When the polymerization reactant contains a monoamine compound, the total content of the decylamine, the bisamine oligopolymer, the carboxyl group-containing compound, and the monoamine compound is 100% by weight, and the content of the bisamine oligopolymer is 3 weight percent to 20 The content of the carboxyl group-containing compound is from 0.2% by weight to 5% by weight, and the content of the monoamine compound is from 0.5% by weight to 2% by weight. If the types of the components of the polymerization reactant or the content thereof fall outside the above range, the obtained polyamine-6 copolymer has disadvantages such as difficulty in improving the degree of polymerization and inability to concentrate the molecular weight distribution.

Step 130 is a hydrolysis polymerization step of placing a molten and uniformly stirred polymerization reactant into a prepolymerization column, and performing an endothermic open loop under conditions of, for example, a pressure of 1.2 bar to 2.0 bar and a temperature of 230 ° C to 270 ° C. reaction. After the reaction is completed, it is sent to a polymerization tower having a pressure of 0.4 to 0.8 bar and a temperature of 230 ° C to 260 ° C to carry out an exothermic polycondensation and a polyaddition reaction (which is a continuous process). The same feed rate and liquid level are maintained in the polymerization tower, and the heating temperature is stabilized, and the operation time is 10 hours or more to ensure the stability of the polymerization degree. After the completion of the polymerization, the polyamide-6 copolymer was made into a micelle.

A melt agitation step may be optionally performed prior to performing the above hydrolysis polymerization step, as shown in step 120. In the above-mentioned melt stirring step, the polymerization reactant is placed in a stirring and melting tank to be melted and stirred and dispersed uniformly. In order to prevent the polymerization reactant from being oxidized during the synthesis, the step 120 can be carried out under a nitrogen atmosphere.

Step 140 is to perform an extraction and drying step, the rubber particles prepared in step 130 are placed in an extraction tower to recover the hot water circulation method for extraction, and then the rubber particles are placed in a drying tower to be divided into hot and cold nitrogen gas. The two-stage drying is carried out, and the circulated nitrogen is cooled by ice water below 10 ° C to remove the water, and then reheated and reused. After the extraction and drying steps, the concentration of the secondary amine group of the finally formed polyamido-6 copolymer is 35 meq/kg to 55 meq/kg per kg, and the relative viscosity of the polyamide-6 copolymer is 1.6 to 2.4. And the glass transition temperature of the polyamide-6 copolymer is from 45 ° C to 53 ° C. The foregoing extraction and drying steps can be carried out at a temperature lower than 85 ° C. Further, any conventional means can be used for the extraction and drying steps, and will not be described herein.

Preparation of polyamido-6 copolymer Example 1

First, a polymerization reaction product containing 96.69 wt% of caprolactam, 3 wt% of a bisamine oligopolymer, 0.3 wt% of a carboxyl group-containing compound, and 0.01 wt% of a monoamine compound is melt-stirred, hydrolyzed, and extracted. The steps of drying and the like were carried out to obtain the polyamine-6 copolymer of Example 1. The obtained polyamine-6 copolymer was evaluated in the manner described later, and the results are shown in Table 1.

Examples 2 to 3 and Comparative Example 1

In Examples 2 to 3 and Comparative Example 1, the same production method as in Example 1 was used, except that Examples 2 to 3 changed the amount of the raw materials used in the polymerization reaction, and Comparative Example 1 changed the raw materials in the polymerization reaction. The types and usage of the formulas and evaluation results are shown in Table 1, and are not described here.

Preparation of polyamide-6 fibers and evaluation methods

The polyamido-6 copolymers of Examples 1 to 3 and the polyamide-6 of Comparative Example 1 were made into fibers by a known spinning process, and the dye fastness and dye absorbance of the obtained fibers were evaluated, and the results were as follows. As shown in Table 1.

The aforementioned dye fastness is carried out according to the CNS 1495 L3028 detection process, and will not be further described herein. The above-mentioned detection procedure of dye absorbance is briefly described as follows: (1) The test range is set to 40 ° C to 100 ° C; (2) 7 sets of dye samples are prepared for each test sample, respectively placed in a dyed steel cup, which is contained in the steel cup A dyeing solution with the same dye component; (3) The first group of dye samples were taken out when the 7-group steel cup was heated up to 40 ° C, and a set of dye samples were taken at 10 ° C for each temperature increase. (4) The dyeing intensity and color residue of each dye sample were tested to compare the dyeing rates at each temperature.

Referring to Table 1, the formulations of Examples 1 to 3 and Comparative Example 1 were subjected to dye fastness and dye absorbance.

It can be seen from the results of Table 1 that the fibers of Examples 1 to 3 have better dye absorbance and 90% dye absorbance than those of Comparative Example 1, and the higher the content of the bisamine oligopolymer and the carboxyl group-containing compound, the dye The better the absorption. In other words, when the fibers of Examples 1 to 3 and the fibers of Comparative Example 1 were equal in mass, the fibers of Examples 1 to 3 required a lower dyeing temperature and maintained the dyeing fastness, thereby saving dyeing. The energy consumption of the whole processing and the time of dyeing and finishing are shortened, and the production cost can be effectively reduced.

Please refer to FIGS. 2 to 4, which show DMA of the polyamine-6 copolymer of Example 1 (Fig. 2), Example 2 (Fig. 3) and Example 3 (Fig. 4), respectively. Scanning chart, wherein the glass transition temperature of the polyamido-6 copolymer of Example 1 was 52.7 ° C, and the glass transition temperature of the polyamido-6 copolymer of Example 2 was 50.6 ° C. The polyamine of Example 3 - The copolymer had a glass transition temperature of 47.8 °C. From the above results, it is understood that when the content of the bisamine oligopolymer and the carboxyl group-containing compound is increased, the glass transition temperature of the obtained polyamido-6 copolymer is decreased, in other words, the bisamine oligopolymer is introduced into the polyamine. The structure of 6 allows the resulting polyamide-6 copolymer to have a low crystallinity. Compared with the polyamido-6 of Comparative Example 1, the polyamido-6 copolymers of Examples 1 to 3 have more amorphous regions, which contribute to the entry of the dye into the polyamide-6 copolymer at low temperatures. The dyeing effect is achieved in the molecular structure, so that the polyamido-6 copolymer of the present invention can be dyed at a lower temperature.

5A to 8B, FIG. 5A is a ¹ H-NMR spectrum of Example 1, 5B is a partial enlarged view of the ¹ H-NMR spectrum of Example 1, and FIG. 6A is an example. ¹ H-NMR spectrum of 2, FIG. 6B is a partial enlarged view of the ¹ H-NMR spectrum of Example 2, FIG. 7A is a ¹ H-NMR spectrum of Example 3, and FIG. 7B is a Example 3 A partial enlarged view of the ¹ H-NMR spectrum, 8A is a ¹ H-NMR spectrum of Comparative Example 1, and 8B is a partially enlarged view of a ¹ H-NMR spectrum of a comparative example. 5A to 8B, the peak intensity of the examples 1 to 3 is lower than that of the comparative example 1, and the peak intensity decreases as the content of the bisamine oligopolymer and the carboxyl group-containing compound increases, and FIG. 5A shows The results disclosed in Figure 8B are consistent with the results of the glass transition temperature test.

Please refer to FIG. 9 to FIG. 11 , which show the GPC of the polyamine-6 copolymer of Example 1 (Fig. 9), Example 3 (Fig. 10), and Comparative Example 1 (Fig. 11), respectively. Test result chart. In Figs. 9 to 11, Mn is a number average molecular weight, and PDI is a ratio of a weight average molecular weight to a number average molecular weight. In Fig. 9, the Mn of Example 1 was 21,828 and the PDI was 1.95. In Fig. 10, the Mn of Example 3 was 21,203, the PDI was 2.09, the Mn of Comparative Example 1 was 22,948, and the PDI was 1.89. Although the Mn of the polyamide-6 copolymer of Example 1 and Example 3 was lower than the Mn of Polyamine-6 of Comparative Example 1, resulting in the polyamine-6 copolymer of Example 1 and Example 3. The PDI is higher than the PDI of the polyamido-6 of Comparative Example 1, but still falls within the spinnable range, that is, the polyamido-6 copolymer of the present invention can be produced into a fiber through a spinning process, and is applied to the textile industry. .

It can be seen from the above examples of the present invention that the PDI of the polyamido-6 copolymer of the present invention conforms to the spinnable range, and the fiber made of the polyamide-6 copolymer has a higher ratio than that of the polyamide-6. The low dyeing temperature and the fastness of dyeing can be saved, which is beneficial to save the energy consumption of dyeing and finishing, and shorten the time of dyeing and finishing, so the production cost can be effectively reduced.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

100‧‧‧ method

110‧‧‧Provide steps for the polymerization of reactants

120‧‧‧Slurry stirring step

130‧‧‧Hydration polymerization step

140‧‧‧Steps for extraction and drying

Claims (8)

A method for preparing a polyamido-6 copolymer, comprising: providing a polymerization reactant, the polymerization reaction comprising: a decylamine; a bisamine oligopolymer having a formula (i) One structure: Wherein a is an integer of 12 to 24, the b is an integer of 12 to 24, the c is an integer of 12 to 24; and a carboxyl group-containing compound having a structure represented by the formula (iii): HOOC-R ² -COOH (iii), wherein the R ² is a saturated aliphatic branched, unsaturated aliphatic branched or aromatic aliphatic group having 6 to 18 carbon atoms, based on the decylamine, the bisamine The total content of the oligopolymer and the carboxyl group-containing compound is 100% by weight, the content of the bisamine oligopolymer is from 3 to 20% by weight, and the content of the carboxyl group-containing compound is from 0.2% by weight to 5% by weight; A hydrolysis polymerization step is carried out to form a polyamido-6 copolymer. The process for producing a polyamido-6 copolymer according to claim 1, wherein the hydrolysis polymerization step is carried out at 230 ° C to 270 ° C. The preparation method of the polyamido-6 copolymer of claim 1, before the step of performing the hydrolysis polymerization, further comprises: performing a melt stirring step to heat and melt and stir the polymerization reactant uniformly. The method for preparing a polyamido-6 copolymer according to claim 1, after the step of hydrolyzing, further comprising: performing an extraction and drying step to obtain a concentration of the secondary amine group of the polyamido-6 copolymer For 35 milliequivalents per kilogram (milliequivalent/kg; meq/kg) to 55 meq/kg, one of the polyamido-6 copolymers has a relative viscosity of 1.6 to 2.4, and one of the polyamido-6 copolymers is transferred to glass. The temperature is from 45 ° C to 53 ° C. A process for producing a polyamide-6 copolymer according to claim 1, wherein the carboxyl group-containing compound is terephthalic acid. The method for producing a polyamido-6 copolymer according to claim 1, wherein the polymerization reactant further comprises: a monoamine compound having a structure represented by the formula (iv): R ³ -NH ₂ ( Iv) wherein the R ³ is a saturated aliphatic branched, unsaturated aliphatic branched or aromatic aliphatic group having from 6 to 18 carbon atoms. A process for producing a polyamide-6 copolymer according to claim 6, wherein the monoamine compound is aniline. A polyamido-6 copolymer prepared by the method for producing a polyamido-6 copolymer according to claim 1.