CN111058120B - Method for preparing intelligent fiber through water-phase interface reaction spinning - Google Patents

Abstract

The invention relates to the technical field of functional fibers, in particular to a method for preparing smart fibers by water-phase interface reaction spinning. The invention proposes to use aqueous solution instead of traditional chain extender diamine or diol as chain extender, and prepare smart fiber material with temperature response, shape memory and temperature regulation functions by reactive spinning method. Compared with the traditional technology, the method has the characteristics of simple operation, energy saving and environmental friendliness.

Description

A method for preparing smart fibers by water-phase interface reaction spinning

technical field

The invention relates to the technical field of functional fibers, in particular to a method for preparing smart fibers by water-phase interface reaction spinning.

Background technique

Polyurethane fiber has excellent characteristics such as excellent resilience, and has the reputation of textile "MSG-like" fiber. As long as a little spandex (mass fraction 2% to 25%) is added to the fabric, the performance of the fabric can be improved, and the grade of the fabric can be improved. With the development of chemical, chemical fiber and textile technology, its application fields are constantly expanding, and it is one of the typical shape memory fibers. Usually, such fibers are prepared by wet spinning or dry spinning, but the preparation process requires a large amount of solvent, and the material transportation consumes a lot of energy; reaction spinning is to prepare polyurethane prepolymer first, and then add solvent to prepare a solution, Then, it is chain-extended and solidified in a coagulation bath through a spinning head. The coagulation bath is composed of diamine or diol and a solvent. The diamine or diol chemically reacts with the silk liquid to accelerate the coagulation speed and form polyurethane elastic fibers with a three-dimensional structure. Due to the strong volatility of diamine or diol, it is easy to cause environmental pollution, and its application is limited.

SUMMARY OF THE INVENTION

In order to solve the above problems, the present invention provides a method for preparing smart fibers by water-phase interface reaction spinning, and the fiber preparation process is as follows:

S1. Preparation of polyurethane prepolymers containing polyether segments

First, diphenylmethane diisocyanate was dissolved in toluene, stirred at 180 r/min, and heated to 80 °C. After mixing uniformly, a small amount of dibutyltin dilaurate was added dropwise, and after mixing, solution A was obtained; The alcohol is dissolved in toluene to obtain solution B, solution B is added dropwise to solution A, and the reaction is continued for 1.5-2 h after the drop is completed; after the reaction is completed, the product is centrifuged to remove impurities to obtain a prepolymer;

S2. Prepare a water-based reaction medium and inject it into a molding tank with a temperature control device

The prepolymer prepared in step S1 is injected into the spinneret, extruded from the spinneret orifice by a metering pump, and the extruded liquid flow enters the forming tank, reacts with the water-based medium and solidifies for 4-5min to form fibers, draws out the fibers, and uses infrared rays to form fibers. After drying, winding is obtained to obtain intelligent responsive fibers.

In described step S1, solution A is made up of diphenylmethane diisocyanate, toluene and dibutyltin dilaurate, and the ratio between each raw material is: the mass ratio of diphenylmethane diisocyanate and toluene is 1:60. -1:90; the mass ratio of dibutyltin dilaurate to diphenylmethane diisocyanate is 1:25-1:20.

In the step S1, the solution B is composed of polyethylene glycol and toluene, and the mass ratio of polyethylene glycol and toluene is 1:7-1:10.

Further, in the step S1, the molar ratio of diphenylmethane diisocyanate in solution A to polyethylene glycol in solution B is 2:1-2.2:1. The dropwise addition time of solution B is 0.5h, and the continuous reaction time is 1.5-2h after the dropwise addition of solution B is completed.

Further, in the step S1, the molecular mass of polyethylene glycol is 1000-4000.

In described step S2, water _- based reaction medium is by dimethylformamide (DMF), NaHCO or ethanol in any one and the mixture that water forms, wherein DMF or NaHCO or ethanol and the mass mixing ratio of water is ₁₀ . :90-15:85.

Therefore, in the step S2, the prepolymer extruded from the spinneret and the water-based medium are reacted and solidified at 10-30°C, and the filaments are dried and wound by infrared rays to obtain intelligent responsive fibers.

The present invention simultaneously claims the phase-change temperature-regulating function and temperature-responsive fibers prepared by the above method.

In the present invention, diphenylmethane diisocyanate is selected as the reaction raw material for polyurethane synthesis, and its main function is to react with polyethylene glycol to form a polyurethane prepolymer, which constitutes the hard segment of the polyurethane macromolecule after chain extension. The functions of toluene in the present invention are: as a solvent and a water-carrying agent in the reaction process. The function of dibutyltin dilaurate in the present invention is as a catalyst for polyurethane synthesis. In the present invention, polyethylene glycol is a phase-change substance, and polyethylene glycol first reacts with diphenylmethane diisocyanate to form a prepolymer, and then extends the chain to form a soft segment. Limiting the molecular weight of polyethylene glycol to 1000-4000 can effectively control the phase change enthalpy and phase change temperature of the phase change polyurethane.

Beneficial effects:

The invention proposes to use aqueous solution instead of traditional chain extender diamine or diol as chain extender, and prepare smart fiber material with temperature response, shape memory and temperature regulation functions by reactive spinning method. Compared with the traditional technology, the method has the characteristics of simple operation, energy saving and environmental friendliness.

Description of drawings

Figure 1 shows the responsive phase change polyurethane fiber;

Figure 2 Infrared spectrum of polyurethane.

Among them, SSPCPU1-4 are respectively used in chain extension: 10wt% NaHCO ₃ , pure water, 10wt% DMF, 10wt% ethanol.

Detailed ways

The present invention is described in detail below through specific embodiments, but the protection scope of the present invention is not limited. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can be obtained from commercial channels.

Example 1

Dissolve 1.93 g of diphenylmethane diisocyanate in 150 g of toluene, stir at 180 r/min, heat the temperature to 80 °C, and after mixing evenly, add 0.08 g of dibutyltin dilaurate dropwise, and mix to obtain solution A; 7 grams of polyethylene glycol 2000 was dissolved in 49 grams of toluene to obtain solution B, and solution B was added dropwise to solution A in 0.5 h, and the reaction was continued for 2 hours after the dripping; after the reaction, the product was centrifugally filtered at 3000 r/min. Impurities are obtained as prepolymers; the prepolymers are extruded from the spinneret holes into the aqueous solution, the reaction solidifies for 5 minutes, the fibers are drawn out, and the polyurethane fibers are obtained after infrared drying. The phase transition enthalpy is 34.58J/g, and the phase transition temperature It is 32.2°C and has a temperature response at 32°C.

Example 2

Dissolve 1.93 g of diphenylmethane diisocyanate in 150 g of toluene, stir at 180 r/min, heat the temperature to 80 °C, and after mixing evenly, add 0.06 g of dibutyltin dilaurate dropwise, and mix to obtain solution A; Dissolve 3.5 grams of polyethylene glycol 1000 in 35 grams of toluene to obtain solution B, add solution B dropwise to solution A for 0.5 h, and continue to react for 1.5 hours after the dripping; after the reaction is completed, the product is centrifugally filtered at 3000 r/min. Impurities are obtained as prepolymers; the prepolymers are extruded from the spinneret holes into a 10wt% sodium carbonate aqueous solution, and the reaction is solidified for 5 minutes, the fibers are drawn out, and the polyurethane fibers are obtained after infrared drying, and the phase change enthalpy is 40.1J/ g, The phase transition temperature is 28.2 °C, with a temperature response at 30 °C.

Example 3

Dissolve 1.76 g of diphenylmethane diisocyanate in 105 g of toluene, stir at 180 r/min, heat the temperature to 80 °C, and after mixing evenly, add 0.08 g of dibutyltin dilaurate dropwise to obtain solution A after mixing; 7 grams of polyethylene glycol 2000 was dissolved in 60 grams of toluene to obtain solution B, and solution B was added dropwise to solution A in 0.5 h, and the reaction was continued for 2 hours after dripping; after the reaction, the product was centrifugally filtered at 3000 r/min. Impurities are obtained as prepolymers; the prepolymers are extruded from the spinneret holes into a 10 wt% dimethylformamide aqueous solution, and the reaction is solidified for 5 minutes, the fibers are drawn out, and the polyurethane fibers are obtained after infrared drying. The phase change enthalpy is 53J/g, the phase transition temperature is 31℃, and it has a temperature response at 30℃.

Example 4

Dissolve 1.93 g of diphenylmethane diisocyanate in 150 g of toluene, stir at 180 r/min, heat the temperature to 80 °C, and after mixing evenly, add 0.06 g of dibutyltin dilaurate dropwise, and mix to obtain solution A; 7 grams of polyethylene glycol 2000 was dissolved in 50 grams of toluene to obtain solution B, and solution B was added dropwise to solution A in 0.5 h, and the reaction was continued for 1.5 hours after dripping; after the reaction, the product was centrifugally filtered at 3000 r/min. Impurities are obtained as prepolymers; the prepolymers are extruded from the spinneret holes into a 10 wt% dimethylformamide aqueous solution, and the reaction is solidified for 5 minutes, the fibers are drawn out, and the polyurethane fibers are obtained after infrared drying. The phase change enthalpy is 53.43J/g, the phase transition temperature is 31.07℃, and it has a temperature response at 31℃.

Example 5

Dissolve 1.93 g of diphenylmethane diisocyanate in 150 g of toluene, stir at 180 r/min, heat the temperature to 80 °C, and after mixing evenly, add 0.06 g of dibutyltin dilaurate dropwise, and mix to obtain solution A; 7 grams of polyethylene glycol 2000 was dissolved in 50 grams of toluene to obtain solution B, and solution B was added dropwise to solution A in 0.5 h, and the reaction was continued for 1.5 hours after dripping; after the reaction, the product was centrifugally filtered at 3000 r/min. Impurities are obtained as prepolymers; the prepolymers are extruded from the spinneret holes into a 10wt% ethanol aqueous solution, the reaction is solidified for 3 minutes, the fibers are drawn out, and the polyurethane fibers are obtained after infrared drying, and the phase change enthalpy is 48.66J/g , the phase transition temperature is 27.6 °C, and it has a temperature response at 29 °C.

The above is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or modification of the created technical solution and its inventive concept shall be included within the protection scope of the present invention.

Claims (3)

1. a method for preparing intelligent fiber by water-phase interface reaction spinning, is characterized in that, this fiber preparation process is specifically as follows: S1. Preparation of polyurethane prepolymers containing polyether segments First, diphenylmethane diisocyanate was dissolved in toluene, stirred at 180 r/min, and heated to 80 °C. After mixing uniformly, a small amount of dibutyltin dilaurate was added dropwise, and after mixing, solution A was obtained; The alcohol is dissolved in toluene to obtain solution B, solution B is added dropwise to solution A, and the reaction is continued after the dripping; after the reaction is completed, the product is centrifuged to remove impurities to obtain a prepolymer; the molecular weight of polyethylene glycol is 1000-4000; The ratio between the raw materials of solution A is: the mass ratio of diphenylmethane diisocyanate and toluene is 1:60-1:90; the mass ratio of dibutyltin dilaurate and diphenylmethane diisocyanate is 1 :25-1:20; The mass ratio of polyethylene glycol and toluene in solution B is 1:7-1:10; the molar ratio of diphenylmethane diisocyanate in solution A and polyethylene glycol in solution B is 2:1-2.2:1 S2. Prepare a water-based reaction medium and inject it into a molding tank with a temperature control device The prepolymer prepared in step S1 is injected into the spinning pot, extruded from the spinneret orifice by the metering pump, and the extruded liquid flow enters the molding tank, reacts with the water-based medium, and reacts at 10-30 ° C and solidifies for 4-5min. The fiber is drawn out, dried with infrared rays and then wound to obtain intelligent responsive fiber; The water-based reaction medium is a mixture composed of any one of DMF, NaHCO ₃ or ethanol and water, wherein the mass mixing ratio of DMF or NaHCO ₃ or ethanol and water is 10:90-15:85. 2 . The method for preparing smart fibers by water-phase interface reaction spinning according to claim 1 , wherein the dropwise addition time of solution B is 0.5h, and the continuous reaction time of solution B after dropwise addition is 1.5-2h. 3 . 3 . The fiber with phase change temperature regulation function and temperature responsiveness, characterized in that it is prepared by the method of claim 1 .

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