阅读说明：本技术 一种温感聚乳酸纤维的制备方法 (Preparation method of temperature-sensitive polylactic acid fiber ) 是由 郭松华 于 2021-08-04 设计创作，主要内容包括：本发明公开了一种温感聚乳酸纤维的制备方法,包括三种液体分别静电纺丝,得到的纤维碰撞、连接在一起的步骤,其中一种液体为聚乳酸液体。本发明制备方法实现了以聚乳酸为原料,制备温感聚乳酸纤维。本发明制备方法,得到的温感聚乳酸纤维,具有优异的温感性能。三种液体分别静电纺丝,得到的纤维碰撞、连接在一起的工艺,相对于两种液体工艺,具有更好的温感性能。(The invention discloses a preparation method of temperature-sensitive polylactic acid fiber, which comprises the steps of respectively carrying out electrostatic spinning on three liquids, and colliding and connecting the obtained fibers together, wherein one liquid is polylactic acid liquid. The preparation method of the invention realizes the preparation of the temperature-sensitive polylactic acid fiber by using the polylactic acid as the raw material. The temperature-sensitive polylactic acid fiber prepared by the preparation method has excellent temperature-sensitive performance. The three liquids are respectively subjected to electrostatic spinning, and the obtained fiber collision and connection process has better temperature-sensing performance compared with the two liquid processes.)

1. A preparation method of temperature-sensitive polylactic acid fiber is characterized by comprising the steps of respectively carrying out electrostatic spinning on three liquids, and colliding and connecting obtained fibers together, wherein one liquid is polylactic acid liquid.

2. The method of claim 1, comprising the steps of:

s01, adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into the sodium alginate gel, and stirring to obtain a first liquid;

s02, adding dehydrated poly (hexanediol adipate) diol, polycaprolactone and stannous octoate into triethyl phosphate, and stirring to obtain a second liquid;

s03, adding the polylactic acid master batch into triethyl phosphate, and stirring to obtain a third liquid;

and S04, performing electrostatic spinning on the first liquid, the second liquid and the third liquid, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

3. The method according to claim 1 or 2, wherein the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine in S01 is 50 (40-50) to (5-10);

and/or in S01, the weight ratio of the sodium alginate to the water in the sodium alginate gel is (4-5) to (95-96);

and/or in S01, the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to sodium alginate gel is (4-5) to (95-96).

4. The process according to any one of claims 1 to 3, wherein in S01, stirring is carried out at 20 to 30 ℃ for 3 to 5 hours.

5. The method according to any one of claims 1 to 4, wherein the dehydration in S02 is performed at 130-150 ℃ for 0.5-1.5 h.

6. The method according to any one of claims 1 to 5, wherein in S02, the weight ratio of the polyhexamethylene adipate diol, the polycaprolactone and the stannous octoate is (40-50): (40-50): (5-10);

and/or in S02, the weight ratio of the poly (hexanediol adipate) glycol, the polycaprolactone and the stannous octoate to the triethyl phosphate is 5: 95.

7. The method according to any one of claims 1 to 6, wherein the weight ratio of the polylactic acid masterbatch to the triethyl phosphate in S03 is (5-20) to (80-95).

8. The process according to any one of claims 1 to 7, wherein in S03, stirring is carried out at 20 to 30 ℃ for 20 to 50 min.

9. The method according to any one of claims 1 to 8, wherein the weight-to-volume ratio of the first liquid, the second liquid and the third liquid in S04 is (1-1.2): (1-1.2): (1-1.2).

10. The preparation method according to any one of claims 1 to 9, wherein the electrostatic spinning process power supply voltage is 40 to 60V, the spinning environment conditions are that the temperature is 20 to 30 ℃, the relative humidity is 60 to 80 percent, the number of the needle heads of the spinning unit is 80 to 100, and the distance between the three needle heads is 8 to 12 cm;

preferably, the electrostatic spinning process power supply voltage is 50KV, the spinning environmental condition is 25 ℃, the relative humidity is 70%, the number of the spinning unit needles is 90, and the distance between the three needles is 10 cm.

Technical Field

The invention belongs to the technical field of spinning, and particularly relates to a preparation method of temperature-sensitive polylactic acid fibers.

Background

Textile materials are the most traditional materials for human body apparel, and serve to provide health and comfort to the wearer. New requirements are put on the clothes, and the clothes are expected to adapt to the physiological requirement change after activities and environment change. Apparel manufacture began using intelligent temperature-adjustable fabrics with excellent thermal comfort and serviceability.

Polylactic acid, also known as polylactide, is a polyester polymer obtained by polymerizing lactic acid as a main raw material, and is a novel biodegradable material. The polylactic acid has excellent biocompatibility, skin-friendly property and softness, and the processed fabric is mild, smooth and good in drapability.

Most of the existing temperature-sensitive fibers take chemically synthesized fibers as main raw materials, and the temperature-sensitive fibers taking polylactic acid as a raw material are not available.

Disclosure of Invention

The present invention has been made in view of the preparation of a temperature-sensitive fiber using polylactic acid as a raw material.

The invention discloses a preparation method of temperature-sensitive polylactic acid fiber, which comprises the steps of respectively carrying out electrostatic spinning on three liquids, and colliding and connecting the obtained fibers together, wherein one liquid is polylactic acid liquid.

In some preferred embodiments of the present invention, the following steps are included:

s01, adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into the sodium alginate gel, and stirring to obtain a first liquid;

s02, adding dehydrated poly (hexanediol adipate) diol, polycaprolactone and stannous octoate into triethyl phosphate, and stirring to obtain a second liquid;

s03, adding the polylactic acid master batch into triethyl phosphate, and stirring to obtain a third liquid;

and S04, performing electrostatic spinning on the first liquid, the second liquid and the third liquid, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

In some preferred embodiments of the present invention, the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine in S01 is 50 (40-50) to 5-10.

In some preferred embodiments of the present invention, in S01, the weight ratio of sodium alginate to water in the sodium alginate gel is (4-5): (95-96).

In some preferred embodiments of the present invention, the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to sodium alginate gel in S01 is (4-5): 95-96).

In some preferred embodiments of the invention, in S01, stirring is carried out at 20-30 ℃ for 3-5 h.

In some preferred embodiments of the present invention, the dehydration in S02 is performed at 130-150 ℃ for 0.5-1.5 h.

In some embodiments of the invention, the weight ratio of the polyhexamethylene adipate diol, the polycaprolactone and the stannous octoate in S02 is (40-50): (40-50): (5-10).

In some preferred embodiments of the invention, in S02, the weight ratio of polyhexamethylene adipate diol, polycaprolactone and stannous octoate to triethyl phosphate is 5: 95.

In some preferred embodiments of the present invention, in S03, the weight ratio of the polylactic acid masterbatch to the triethyl phosphate is (5-20): 80-95).

In some preferred embodiments of the invention, in S03, stirring is carried out at 20-30 ℃ for 20-50 min.

In some preferred embodiments of the present invention, in S04, the weight-to-volume ratio of the first liquid, the second liquid, and the third liquid is (1-1.2): (1-1.2): (1-1.2).

In some preferred embodiments of the invention, the voltage of the electrostatic spinning process power supply is 40-60V, the spinning environmental conditions are that the temperature is 20-30 ℃, the relative humidity is 60-80%, the number of the spinning unit needles is 80-100, and the distance between the three needles is 8-12 cm;

preferably, the electrostatic spinning process power supply voltage is 50KV, the spinning environmental condition is 25 ℃, the relative humidity is 70%, the number of the spinning unit needles is 90, and the distance between the three needles is 10 cm.

In some preferred embodiments of the invention, the heating is performed in a water bath with stirring at a temperature controlled by the following PID algorithm:

wherein, Δ u (c) is the variation of the temperature in the time interval corresponding to the two testing temperatures; kc is a constant, 5-6; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; TS is sampling period, 0.8-1.5; TI is integration time, 1.0-1.5 min; TD is differential time, 1.5-2.0 min.

In some preferred embodiments of the present invention, the method further comprises the step of evaluating the stirring:

s11, determining the conventional temperature, stirring speed and stirring time, mixing, taking 5 samples, measuring the viscosity, and recording as vector X1;

s12, taking the mixed sample of S11, increasing the stirring speed by 10 percent, prolonging the stirring time by 20 percent, mixing, taking 5 samples, measuring the viscosity, and recording the viscosity as a vector X2;

s13, calculating the homogeneity of X1 and X2 by:

if both t1 and t2 are greater than-1.40, mixing is carried out at the temperature, stirring speed and stirring time of S11, otherwise mixing is carried out at the temperature, stirring speed and stirring time of S12.

The invention has the beneficial effects that:

(1) the preparation method of the invention realizes the preparation of the temperature-sensitive polylactic acid fiber by using the polylactic acid as the raw material.

(2) The temperature-sensitive polylactic acid fiber prepared by the preparation method has excellent temperature-sensitive performance. The three liquids are respectively subjected to electrostatic spinning, and the obtained fiber collision and connection process has better temperature-sensing performance compared with the two liquid processes. Furthermore, the obtained temperature-sensitive polylactic acid fiber has unexpected temperature-sensitive performance under the condition of specific parameters.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

The electrostatic spinning process has the power supply voltage of 50KV, the spinning environmental conditions are that the temperature is 25 ℃, the relative humidity is 70%, the number of the needle heads of the spinning unit is 90, and the distance between the three needle heads is 10 cm.

Unless otherwise specified, the examples and comparative examples are parallel tests with the same components, component contents, preparation steps, preparation parameters.

Example 1

A preparation method of temperature-sensitive polylactic acid fiber comprises the following steps:

(1) adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into sodium alginate gel, and stirring at room temperature (25 ℃) for 4 hours to obtain a first liquid; the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine is 50:50:10, the weight ratio of sodium alginate to water in the sodium alginate gel is 5:95, and the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to the sodium alginate gel is 5: 95;

(2) adding the polyhexamethylene glycol adipate diol dehydrated for 1h at the temperature of 140 ℃, polycaprolactone and stannous octoate into triethyl phosphate, and stirring for 30min at the temperature of 80 ℃ to obtain a second liquid; the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate is 50:50:10, and the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate to the triethyl phosphate is 5: 95;

(3) adding the polylactic acid master batch into triethyl phosphate, and stirring for 30min at room temperature (25 ℃) to obtain a third liquid; the weight ratio of the polylactic acid master batch to the triethyl phosphate is 5: 95;

(4) and (3) carrying out electrostatic spinning on the first liquid, the second liquid and the third liquid according to the weight-volume ratio of 1:1:1, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

Example 2

A preparation method of temperature-sensitive polylactic acid fiber comprises the following steps:

(1) adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into sodium alginate gel, and stirring at room temperature (25 ℃) for 4 hours to obtain a first liquid; the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine is 50:50:10, the weight ratio of sodium alginate to water in the sodium alginate gel is 4:96, and the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to the sodium alginate gel is 4: 96;

(2) adding the polyhexamethylene glycol adipate diol dehydrated for 1h at the temperature of 140 ℃, polycaprolactone and stannous octoate into triethyl phosphate, and stirring for 30min at the temperature of 80 ℃ to obtain a second liquid; the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate is 40:50:10, and the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate to the triethyl phosphate is 5: 95;

(3) adding the polylactic acid master batch into triethyl phosphate, and stirring for 30min at room temperature (25 ℃) to obtain a third liquid; the weight ratio of the polylactic acid master batch to the triethyl phosphate is 10: 90;

(4) and (3) carrying out electrostatic spinning on the first liquid, the second liquid and the third liquid according to the weight-volume ratio of 1.2:1.2:1, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

Example 3

A preparation method of temperature-sensitive polylactic acid fiber comprises the following steps:

(1) adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into sodium alginate gel, and stirring at room temperature (25 ℃) for 4 hours to obtain a first liquid; the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine is 50:50:10, the weight ratio of sodium alginate to water in the sodium alginate gel is 10:90, and the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to the sodium alginate gel is 5: 95;

(2) adding the polyhexamethylene glycol adipate diol dehydrated for 1h at the temperature of 140 ℃, polycaprolactone and stannous octoate into triethyl phosphate, and stirring for 30min at the temperature of 80 ℃ to obtain a second liquid; the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate is 50:40:10, and the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate to the triethyl phosphate is 5: 95;

(3) adding the polylactic acid master batch into triethyl phosphate, and stirring for 30min at room temperature (25 ℃) to obtain a third liquid; the weight ratio of the polylactic acid master batch to the triethyl phosphate is 5: 95;

(4) and (3) carrying out electrostatic spinning on the first liquid, the second liquid and the third liquid according to the weight-volume ratio of 1:1:1.2, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

Example 4

A preparation method of temperature-sensitive polylactic acid fiber comprises the following steps:

(1) adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into sodium alginate gel, and stirring at room temperature (25 ℃) for 4 hours to obtain a first liquid; the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine is 50:50:5, the weight ratio of sodium alginate to water in the sodium alginate gel is 5:95, and the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to the sodium alginate gel is 5: 95;

(2) adding the polyhexamethylene glycol adipate diol dehydrated for 1h at the temperature of 140 ℃, polycaprolactone and stannous octoate into triethyl phosphate, and stirring for 30min at the temperature of 80 ℃ to obtain a second liquid; the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate is 50:50:5, and the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate to the triethyl phosphate is 5: 95;

(3) adding the polylactic acid master batch into triethyl phosphate, and stirring for 30min at room temperature (25 ℃) to obtain a third liquid; the weight ratio of the polylactic acid master batch to the triethyl phosphate is 5: 95;

(4) and (3) carrying out electrostatic spinning on the first liquid, the second liquid and the third liquid according to the weight-volume ratio of 1:1:1, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

Example 5

A preparation method of temperature-sensitive polylactic acid fiber comprises the following steps:

(1) adding trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine into sodium alginate gel, and stirring at room temperature (25 ℃) for 4 hours to obtain a first liquid; the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine is 50:50:10, the weight ratio of sodium alginate to water in the sodium alginate gel is 5:95, and the weight ratio of trans-polyisoprene, polycaprolactone and tri-tert-butylphosphine to the sodium alginate gel is 5: 95;

(2) adding the polyhexamethylene glycol adipate diol dehydrated for 1h at the temperature of 140 ℃, polycaprolactone and stannous octoate into triethyl phosphate, and stirring for 30min at the temperature of 80 ℃ to obtain a second liquid; the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate is 50:50:10, and the weight ratio of the poly (hexanediol adipate) diol, the polycaprolactone and the stannous octoate to the triethyl phosphate is 5: 95;

(3) adding the polylactic acid master batch into triethyl phosphate, and stirring for 30min at room temperature (25 ℃) to obtain a third liquid; the weight ratio of the polylactic acid master batch to the triethyl phosphate is 20: 80;

(4) and (3) carrying out electrostatic spinning on the first liquid, the second liquid and the third liquid according to the weight-volume ratio of 1:1.2:1.2, and colliding and connecting the obtained fibers together to obtain the temperature-sensitive polylactic acid fiber.

Example 6

A method for preparing a temperature-sensitive polylactic acid fiber, which is different from example 1 in that the polylactic acid fiber is heated in a water bath while being stirred at a certain temperature, and the temperature is controlled by the following PID algorithm:

wherein, Δ u (c) is the variation of the temperature in the time interval corresponding to the two testing temperatures; kc is a constant, 5-6; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; TS is sampling period, 0.8-1.5; TI is integration time, 1.0-1.5 min; TD is differential time, 1.5-2.0 min.

The temperature control method in this embodiment 1 can reduce fluctuation in the temperature rise process, and can control the temperature of the system more accurately.

Example 7

A method for producing a temperature-sensitive polylactic acid fiber, which is different from example 1 in that the method further comprises the step of stirring evaluation:

s11, determining the conventional temperature, stirring speed and stirring time, mixing, taking 5 samples, measuring the viscosity, and recording as vector X1;

s12, taking the mixed sample of S11, increasing the stirring speed by 10 percent, prolonging the stirring time by 20 percent, mixing, taking 5 samples, measuring the viscosity, and recording the viscosity as a vector X2;

s13, calculating the homogeneity of X1 and X2 by:

if both t1 and t2 are greater than-1.40, mixing is carried out at the temperature, stirring speed and stirring time of S11, otherwise mixing is carried out at the temperature, stirring speed and stirring time of S12.

In the embodiment, the viscosity is taken as an index, the stirring effect is considered, the full stirring condition and parameter can be rapidly determined, and the trial and groping time is reduced.

Comparative example 1

The difference between the preparation method of the temperature-sensitive polylactic acid fiber and the embodiment 1 is that the polylactic acid master batch is added into triethyl phosphate and then added into a first liquid, and only two liquids are subjected to electrostatic spinning.

Comparative example 2

The difference between the preparation method of the temperature-sensitive polylactic acid fiber and the embodiment 1 is that the polylactic acid master batch is added into triethyl phosphate and then added into a second liquid, and only two liquids are subjected to electrostatic spinning.

Investigation of temperature sensing Performance

The materials of the examples and comparative examples were woven into fabrics according to the same parameters and formula, and the air permeability at 35 ℃ and room temperature (25 ℃) was measured according to the Frazier method, and the results are shown in Table 1.

TABLE 1 air permeability of woven cloth of temperature-sensitive polylactic acid fiber

The results show that at 25 ℃, there is no significant difference in air permeability between examples 1-5 and comparative examples 1, 2, and at 35 ℃, the air permeability of examples 1-5 is significantly better than comparative examples 1, 2, with example 4 being significantly better than examples 1-3 and example 5, with unexpected temperature-sensitive properties.

While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.