WO2016058110A1

WO2016058110A1 - Preparation method for porous collagen modified superfine acrylic fibres

Info

Publication number: WO2016058110A1
Application number: PCT/CN2014/000902
Authority: WO
Inventors: 袁振其
Original assignee: 太仓苏纶纺织化纤有限公司
Priority date: 2014-10-13
Filing date: 2014-10-13
Publication date: 2016-04-21

Abstract

A preparation method for porous collagen modified superfine acrylic fibres, the method comprising: dissolving polyacrylonitrile in a solvent, adding polyvinylpyrrolidone, and stirring evenly to prepare a fibre polymer solution; in a 40^oC environment, adding a collagen solution to the fibre polymer solution, magnetically stirring until even, standing, and producing a collagen modified fibre polymer solution; adding SiO₂ nanoparticles to the collagen modified fibre polymer solution, and magnetically stirring until even, the resulting solution acting as a spinning solution; pouring the spinning solution into a jetting device, spinning under the effect of an additional electric field, depositing into a collecting device by controlling the spinning time and moving a receiving screen, and baking; soaking acrylic fibres containing the SiO₂ nanoparticles with an HF solution and stirring slowly, washing and drying, and obtaining a porous collagen modified superfine acrylic fibre fabric. The preparation method not only improves the dyeing properties of the fabric, but also enables the acrylic fibres to have a soft, smooth feel and the effect of imitating silk.

Description

Preparation method of porous collagen modified superfine acrylic fiber

Technical field

The invention relates to a preparation method of ultrafine acrylic fiber, in particular to a preparation method of porous collagen modified ultrafine acrylic fiber.

Background technique

At present, with the increasing living standards of people and the constant renewal of consumer concepts, consumers are increasingly demanding the quality, variety and color of acrylic textiles. The commonly used acrylic fiber is a kind of synthetic fiber. Because of its soft, fluffy and warmth, it is always favored by the market. However, due to the relatively regular molecular structure of the acrylic fiber and the synthetic fiber, it is a hydrophobic fiber, lacking a hydrophilic group in the macromolecule, having a tight molecular chain structure, high crystallinity and orientation, and poor hydrophilicity. Traditional chemical modification consumes a lot of water and chemicals, which is not only complicated to operate but also pollutes the environment.

The electrospinning method is a device for producing polymer filaments by using electrostatic force. The prepared inorganic fiber structure can be controlled by solution properties, spinning parameters and post-treatment to achieve morphology and structure, and exhibits excellent properties in the field of textile materials. characteristic. Since the molecular structure of the ultrafine acrylic fiber is relatively regular, its hydrophilicity and dyeability are poor, and the fuel easily forms dyed spots such as color flowers and stains on the dye.

In summary, there is an urgent need for a method for preparing a collagen-modified ultrafine acrylic fiber, which can improve the structural controllability of the fabric, improve the dyeability and color fixing property, and make the modified acrylic fiber soft to the touch. , slippery, with the effect of silk-like silk.

Summary of the invention

Collagen is the most abundant protein in mammals. It has good hygroscopicity and skin-friendly properties. Combined with the chemical structure of acrylic fiber, it can effectively improve the hydrophilicity and fill the grooves and cracks on the surface of the fiber. The ultra-fine acrylic fiber has a soft, smooth feel and a silk-like effect. Hydrofluoric acid (HF) is a weak acid that can be specifically reacted with silica (SiO ₂ ) with a chemical reaction equation of SiO ₂ +6HF=H ₂ SIF ₆ +2H ₂ O. The SiO ₂ sacrificial layer is etched by HF. Since the acrylic fiber is expected to react differently with HF ₂ to HF, the effect of pore-forming on the surface of the acrylic fiber can be achieved by means of particle doping and removal, thereby providing a comparative area of the fabric and improving the dyeability. the goal of.

In order to achieve the above object, the technical solution provided by the present invention is:

A method for preparing porous collagen-modified ultrafine acrylic fiber, comprising:

1) dissolving polyacrylonitrile in a solvent, adding polyvinylpyrrolidone, and uniformly preparing a fiber polymer solution;

2) adding a collagen solution to the fiber polymer solution under the environment of 40 ° C, magnetically stirring until uniform, and standing to prepare a protein collagen modified fiber polymer solution;

3) adding SiO ₂ nanoparticles to the protein collagen modified fiber polymer solution, magnetically stirring until uniform, as a spinning solution;

4) pouring the spinning solution into the ejector, spinning under the action of an additional electric field, depositing in the collecting device by controlling the spinning time and moving the receiving screen, and baking;

5) Acrylic fiber containing SiO ₂ nanoparticles is soaked in HF solution and slowly stirred, washed and dried to obtain a porous protein collagen-modified ultrafine acrylic fabric.

Further, the solvent is one of dimethylformamide or dimethylacetamide.

Further, the mass fraction of collagen in the collagen solution is 3% to 7%.

Further, in the step 1), the mass ratio of the polyphenylene nitrile to the solvent is 1:9 to 1:5, and the mass fraction of the polyvinylpyrrolidone is 10%; in the step 2), the fiber polymer solution and the collagen The mass ratio of the solution is 5:1-3:1, and the standing time is 1-2 h; in step 3), the mass fraction of the SiO ₂ nanoparticles is 5-13%, and in step 4), the additional electric field The field strength is 0.2 kv/cm-2 kv/cm, the receiving screen is 10-45 cm from the spinneret, the baking temperature is 400-650 ° C, and in step 5), the mass fraction of the HF solution is 25-55%, Soak and slowly stir for 8-16h.

Further, in the step 1), the mass ratio of the polyphenylene nitrile to the solvent is 1:7, the mass fraction of the polyvinylpyrrolidone is 10%; and in the step 2), the mass ratio of the fiber polymer solution to the collagen solution 4:1, the rest time is 1 h; in step 3), the mass fraction of SiO ₂ nanoparticles is 8%, and in step 4), the additional electric field strength is 1 kv/cm, and the screen distance is required to be spun. The mouth is 25 cm, the calcination temperature is 550 ° C, in step 5), the mass fraction of the HF solution is 45%, and the time of the soaking and slow stirring is 10 h.

Further, the porous ultrafine acrylic fiber has a diameter of 100 to 300 nm.

With the above technical solutions, the beneficial effects of the present invention are as follows:

In the present invention, the collagen-modified ultrafine acrylic fiber is used, and since the collagen has good hygroscopicity, skin-friendly property and the like, combined with the chemical structural characteristics of the acrylic fiber, the hydrophilicity can be effectively improved, and the grooves and cracks on the surface of the fiber are filled. The modified ultra-fine acrylic fiber has a soft touch and a smooth feel, and has the effect of silk-like silk.

In the present invention, the SiO2 sacrificial layer is etched by HF. Since the reaction of the ultrafine acrylic fiber and the SiO ₂ to HF is different, the effect of the pores of the ultrafine acrylic fiber can be achieved by the method of particle doping and removal, mesoporous and microporous structure. Coexistence, can improve the specific surface area of the fabric, controllability of the structure, enhance the surface roughness, and achieve the hole making of the nano material, thereby improving the dyeability.

detailed description

Example 1

The polyacrylonitrile was dissolved in a solvent at a mass ratio of 1:9, 10% polyvinylpyrrolidone was added, and the fiber polymer solution was prepared by stirring uniformly; the solvent was dimethylacetamide.

Adding 3% collagen solution to the fiber polymer solution at a temperature of 40 ° C, the mass ratio of the fiber polymer solution to the collagen solution is 5:1, magnetically stirred until uniform, and after standing for 1 h, it is made into protein collagen. Modified fiber polymer solution.

5% of the SiO ₂ nanoparticles were added to the protein collagen-modified fiber polymer solution, and magnetically stirred until uniform as a spin solution.

The spinning solution was added to an electrospinning machine for electrospinning, the additional electric field strength was 0.2 kV/cm, the screen was received at a distance of 10 cm from the spinneret, and the firing temperature was 400 °C.

The ultrafine acrylic fiber containing SiO ₂ nanoparticles was immersed in a 25% HF solution and slowly stirred for 8 hours, and washed and dried to obtain a porous collagen-modified ultrafine fiber.

Example 2

The polyacrylonitrile was dissolved in a solvent at a mass ratio of 1:5, 10% polyvinylpyrrolidone was added, and the fiber polymer solution was prepared by stirring uniformly; the solvent was dimethylformamide.

In a 40 ° C environment, a 7% collagen solution was added to the fiber polymer solution, and the mass ratio of the fiber polymer solution to the collagen solution was 3:1, magnetically stirred until homogeneous, and allowed to stand for 2 h.

13% of SiO ₂ nanoparticles were added to the protein collagen-modified fiber polymer solution, and magnetically stirred until uniform as a spin solution.

The spinning solution was added to an electrospinning machine to perform electrospinning with an additional electric field strength of 2 kV/cm, a screen distance of 45 cm from the spinneret, and a calcination temperature of 650 °C.

The acrylic fiber containing SiO ₂ nanoparticles was soaked in a 55% HF solution and slowly stirred for 16 hours, and washed and dried to obtain a porous ultrafine acrylic fiber fabric to obtain a collagen-modified ultrafine fiber containing SiO ₂ nanoparticles.

Example 3

The polyacrylonitrile was dissolved in a solvent at a mass ratio of 1:6, 10% polyvinylpyrrolidone was added, and the fiber polymer solution was prepared by stirring uniformly; the solvent was dimethylformamide.

In a 40 ° C environment, a 5% collagen solution was added to the fiber polymer solution, and the mass ratio of the fiber polymer solution to the collagen solution was 4:1, magnetically stirred until homogeneous, and allowed to stand for 1 h.

8% of the SiO ₂ nanoparticles were added to the acrylic fiber polymer solution, and magnetically stirred until uniform as a spin solution.

The spinning solution was added to an electrospinning machine to perform electrospinning, the additional electric field strength was 1 kV/cm, the screen was 25 cm from the spinneret, and the baking temperature was 550 °C.

The ultrafine acrylic fiber containing SiO ₂ nanoparticles was immersed in a 45% HF solution and slowly stirred for 10 hours, and washed and dried to obtain a porous collagen-modified ultrafine acrylic fiber.

The above-mentioned embodiments are merely illustrative of the embodiments of the present invention, and the description thereof is not to be construed as limiting the scope of the invention. It should be noted that A person skilled in the art can make several modifications and improvements without departing from the spirit and scope of the invention.

Claims

A method for preparing porous collagen-modified ultrafine acrylic fiber, characterized in that it comprises:

1) dissolving polyacrylonitrile in a solvent, adding polyvinylpyrrolidone, and uniformly preparing a fiber polymer solution;

2) adding a collagen solution to the fiber polymer solution under the environment of 40 ° C, magnetically stirring until uniform, and standing to prepare a protein collagen modified fiber polymer solution;

3) adding SiO 2 nanoparticles to the protein collagen modified fiber polymer solution, magnetically stirring until uniform, as a spinning solution;

4) pouring the spinning solution into the ejector, spinning under the action of an additional electric field, depositing in the collecting device by controlling the spinning time and moving the receiving screen, and baking;

5) Acrylic fiber containing SiO 2 nanoparticles is soaked in HF solution and slowly stirred, washed and dried to obtain a porous protein collagen-modified ultrafine acrylic fabric.
The method for producing a porous collagen-modified ultrafine acrylic fiber according to claim 1, wherein the solvent is one of dimethylformamide or dimethylacetamide.
The method for preparing a porous collagen-modified ultrafine acrylic fiber according to claim 1, wherein the collagen solution has a mass fraction of collagen of 3% to 7%.
The method for preparing a porous collagen-modified ultrafine acrylic fiber according to claim 1, wherein in the step 1), the mass ratio of the polyphenylene nitrile to the solvent is 1:9 to 1:5, and the polyethylene The mass fraction of pyrrolidone is 10%; in step 2), the mass ratio of the fiber polymer solution to the collagen solution is 5:1-3:1, and the rest time is 1-2 h; in step 3), SiO 2 The mass fraction of the nanoparticles is 5-13%. In the step 4), the additional electric field strength is 0.2 kv/cm-2 kv/cm, the receiving screen is 10-45 cm from the spinneret, and the baking temperature is 400-650 °C. In step 5), the HF solution has a mass fraction of 25-55%, and the soaking and slow stirring time is 8-16 h.
The method for preparing a porous collagen-modified ultrafine acrylic fiber according to claim 4, wherein in the step 1), the mass ratio of the polyphenylene nitrile to the solvent is 1:7, and the mass fraction of the polyvinylpyrrolidone 10%; in step 2), the mass ratio of the fiber polymer solution to the collagen solution is 4:1, and the rest time is 1 h; in step 3), the mass fraction of the SiO 2 nanoparticles is 8%. In step 4), the additional electric field strength is 1 kv/cm, the receiving screen is 25 cm from the spinneret, the baking temperature is 550 ° C, and in step 5), the mass fraction of the HF solution is 45%, and the soaking is performed. The time of slow stirring was 10 h.
The method for producing a porous collagen-modified ultrafine acrylic fiber according to any one of claims 1 to 5, wherein the porous ultrafine acrylic fiber has a diameter of 100 to 300 nm.