CN100406632C - A kind of nanoscale diameter biodegradable fiber non-woven fabric and preparation method - Google Patents

Abstract

A nanoscale fiber non-woven fabric of polyhydroxybutyrate biodegradable polymer and a preparation method thereof. The average diameter of the nano-scale fiber is about 1 nm to 200 nm, and the diameter distribution range is narrow. Dissolve polyhydroxybutyrate polymers and a small amount of additives in organic solvents to obtain a transparent and uniform solution. Electrospinning is carried out with this solution to obtain polyhydroxybutyrate biodegradable fiber non-woven fabric with nanoscale diameter. The method adopted in the present invention is simple and easy to implement, and does not require high equipment. Nano-scale polyhydroxybutyrate biodegradable fiber non-woven products can be widely used in medicine and health, tissue engineering and other fields.

Description

A kind of nanoscale diameter biodegradable fiber non-woven fabric and preparation method

technical field

The invention relates to the field of preparation of organic nanofibers, in particular to the preparation of nanofibers by electrospinning and a preparation method.

Background technique

The diameter of conventional ordinary fiber materials is mostly in the range of 5 to 50 μm. The diameter of the newly developed superfine denier fiber can reach 0.4-4μm. When shrinking in diameter from micrometers to submicrometers or nanometers, polymer fibers exhibit several surprising properties compared to corresponding fiber materials. Its characteristics mainly include: microfiber effect, electrical properties, and mechanical properties such as very large specific surface area (the specific surface area is nearly a hundred times that of micron fibers), flexibility and super mechanical behavior (such as hardness and tensile strength), these Excellent properties make nanofibers suitable for many important applications. The electrospinning technology has the potential to conveniently prepare nano-scale fibers, which has attracted the attention of researchers from all over the world. The fiber diameters obtained by electrospinning range from tens of nanometers to tens of microns. Due to the different properties of various organic substances and the differences in the selected solvents and additives, only a small part of polymers can be spun to a fiber diameter below 100 nanometers.

Polyhydroxybutyrate (PHB) and its copolymers are natural polymer materials with abundant raw materials, good biocompatibility and bioabsorbability. In recent years, the preparation of tissue engineering scaffolds as bioabsorbable materials has attracted increasing attention. Due to the development of extensive research on electrospinning technology and its ability to prepare nanoscale and micron-scale fibers. PHB polymers are also used in electrospinning to prepare fiber non-woven fabrics. In order to obtain better characteristics while obtaining nanometer diameters.

But at present, there is no bibliographical report (Seong OkHan, Won Keun Son, Dongwhan Cho, Polymer Degradation and Stability, 86 (2004) 257-262; Jae Shin Choi, Sung Won Lee) that PHB class polymer is prepared into average diameter less than 200nm , Lim Jeong, Su-Hyun Bae, Bum Chan Min.J ₁ Ho Youk, Won Ho Park, International Journal of Biological Macromolecules 34 (2004) 249-256) and other PHB biodegradable materials reported in some literature by electrospinning The average fiber diameter is above 200nm and the distribution is wide.

Contents of the invention

The object of the present invention is to provide a polyhydroxybutyrate (PHB) biodegradable nanoscale fiber non-woven fabric with an average diameter of 1-200 nanometers (nm).

Another object of the present invention is to provide a method for preparing polyhydroxybutyrate (PHB) biodegradable nanoscale fiber non-woven fabrics with an average diameter of 1-200 nanometers (nm).

The invention is a polyhydroxybutyrate (PHB) biodegradable nano-scale fiber non-woven fabric with an average diameter of 1-200 nanometers (nm). The biodegradable polyester fiber is polyhydroxybutyrate or a copolymer of hydroxybutyric acid and other hydroxy acids. The molecular weight of the biodegradable polyester fiber is 20,000 to 1,500,000, and the hydroxybutyrate in the copolymer accounts for 40% to 100% of the total monomer mole.

Through the selection of the solvent and additives of the electrospinning stock solution, and the precise control of the spinning parameters in the electrospinning process, PHB biodegradable nanoscale fibers with an average diameter of 1-200 nanometers are obtained.

The preparation method of the polyhydroxybutyrate (PHB) biodegradable nano-scale fiber non-woven fabric with an average diameter of 1-200 nanometers (nm) of the present invention comprises the steps:

1. Dissolving the purified PHB polymer and additives in an organic solvent to obtain a transparent and uniform organic solution containing 0.01% to 3% by weight of PHB and 0 to 5% by weight of additives. Prepared as spinning dope.

2. Electrospinning is carried out with the prepared spinning stock solution, the spinning stock solution is added into the container, fixed on the micro-injection pump, the nozzle is connected to the high-voltage positive electrode, and the receiving device is grounded. Controlling various parameters of electrospinning to collect PHB-like biodegradable nanofiber nonwovens

Above-mentioned organic solvent is: N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), alcohol, dichloromethane, trichloromethane, 1,2-dichloroethane, One or more mixed solvents in tetrahydrofuran, diethyl ether, trichloroethylene, cyclohexanol, dimethyl sulfoxide or trifluoroethanol all adopt commercially available products.

The above additives include: triethanolamine, triethanolamine oleic acid soap, fatty amine polyoxyethylene ether, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, dodecane One or more of dimethyl amine oxide or alkylolamide phosphate.

The electrospinning parameters controlled above include: voltage 5kv ~ 20kv, nozzle aperture 1μm ~ 2mm, solution flow rate 1μl/h ~ 10ml/h, ambient temperature 0 ~ 100℃; the recommended distance between the receiving plate and the spinneret is 2 ~ 50cm.

The above-mentioned receiving device can be a collection device of different shapes such as a flat plate, a roller or a metal frame.

The average diameter of the PHB biodegradable fiber non-woven fabric with a nanoscale diameter prepared by the method of the invention is 1 nm to 200 nm.

The raw materials required in the method of the invention are all general chemical reagents, and the whole method is simple. The non-woven fabric product of the present invention can be widely used in the fields of medicine and sanitation, tissue engineering and the like.

Description of drawings

The scanning electron micrograph of the polyhydroxybutyrate biodegradable fiber of Fig. 1 average diameter 146nm;

The diameter distribution of the polyhydroxybutyrate biodegradable fiber of Fig. 2 mean diameter 146nm;

The scanning electron micrograph of the polyhydroxybutyrate biodegradable fiber of Fig. 3 average diameter 80nm;

The diameter distribution of the polyhydroxybutyrate biodegradable fiber of Fig. 4 mean diameter 80nm;

The scanning electron micrograph of the polyhydroxybutyrate biodegradable fiber of Fig. 5 average diameter 190nm;

Fig. 6 Diameter distribution of polyhydroxybutyrate-based biodegradable fibers with an average diameter of 190 nm.

Detailed ways

The following examples will help to understand the present invention, but do not limit the content of the present invention.

Example 1

Solution preparation

PHB Chloroform/alcohol mixed solvent Benzyltriethylammonium chloride Mass (g) 1 88/11 03 source Ningbo Tianan Biomaterials Co., Ltd. Suzhou City Union Innovative Materials Co., Ltd. Shanghai Chemical Reagent Company

Electrospinning parameter control

Voltage Nozzle aperture Solution flow rate Distance between receiving plate and nozzle ambient temperature 10kv 0.4mm 1ml/h 15cm 40℃

The purified PHB polymer and benzyltriethylammonium chloride that are 1% by weight fraction are dissolved in an organic solvent to obtain a transparent and uniform PHB polymer containing 1% by weight and 0.3% by weight of An organic solution of benzyltriethylammonium chloride, namely the electrospinning stock solution.

Electrospinning was carried out with the prepared electrospinning stock solution. The spinning parameters were controlled at a voltage of 10kv, a nozzle aperture of 0.4mm, a solution flow rate of 1ml/h, an ambient temperature of 40°C, and a distance of 15cm between the receiving plate and the nozzle.

Among them, the average diameter of PHB biodegradable fibers is 146nm. Figure 1 is a scanning electron microscope photo, and Figure 2 is the diameter distribution.

Example 2

Solution preparation

PHBV (Hydroxybutyrate Valerate Copolyester) Dichloromethane/ether Triethanolamine mass (g) 0.4 90/10 0.01 source Ningbo Tianan Biomaterials Co., Ltd. Suzhou City Union Innovative Materials Co., Ltd. Xingtai Auxiliary Factory

Electrospinning parameter control

Voltage Nozzle aperture Solution flow rate Distance between receiving plate and nozzle ambient temperature 16kv 0.05mm 007ml/h 8cm 50℃

Dissolve the purified PHB polymer and triethanolamine in an organic solvent to obtain a transparent and uniform organic solution containing 0.4% by weight of the purified PHB polymer and 0.01% by weight of triethanolamine. That is, the electrospinning stock solution.

0.01 wt% triethanolamine was dissolved in the solution.

Electrospinning was carried out with the prepared electrospinning stock solution. The spinning parameters were controlled at a voltage of 16kv, a nozzle aperture of 0.05mm, a solution flow rate of 0.07ml/h, an ambient temperature of 50°C, and a distance between the receiving plate and the nozzle of 8cm.

Among them, the average diameter of PHB biodegradable fibers is 80nm. Figure 3 is a scanning electron micrograph, and Figure 4 is a diameter distribution.

Example 3

Solution preparation

PHBV (Hydroxybutyrate Valerate Copolyester) Chloroform Alkylolamide Phosphates mass (g) 0.3 99 1 source Ningbo Tianan Biomaterials Co., Ltd. Suzhou City Union Innovative Materials Co., Ltd. Shanghai Chemical Reagent Company

Electrospinning parameter control

Voltage Nozzle aperture Solution flow rate Distance between receiving plate and nozzle ambient temperature 20kv 1mm 0.4ml/h 12cm 30℃

Dissolve the purified PHB polymers and alkylolamide phosphates in an organic solvent to obtain a transparent and uniform organic compound containing 03% by weight of the purified PHB polymers and 1% by weight of the alkylolamide phosphates. solution. That is, the electrospinning stock solution.

Electrospinning was carried out with the prepared electrospinning stock solution. The spinning parameters are controlled at a voltage of 20kv, a nozzle aperture of 1mm, a solution flow rate of 04ml/h, an ambient temperature of 30°C, and a distance between the receiving plate and the nozzle of 8cm.

Among them, the average diameter of PHB biodegradable fibers is 190nm. Figure 5 is a scanning electron micrograph, and Figure 6 is a diameter distribution.

Claims (6)

1. the preparation method of the biodegradable polyesters fabric nonwoven cloth of a nanometer grade diameter is characterized in that adopting following steps:

(1), will be dissolved in the electrostatic spinning liquid that makes transparent homogeneous in the organic solvent through the polymer and the additive of purification poly butyric ester or hydroxybutyric acid and other carboxylic acids; The poly butyric ester or the polymer of hydroxybutyric acid and other carboxylic acids and the additive of 0～5% weight that contain 0.01%～3% weight in the described electrostatic spinning liquid; Described additive is one or more in triethanolamine, trihydroxy ethylamine oleate soap, aliphatic amine polyoxyethylene ether, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride, benzyl tributyl ammonium chloride, DDAO or the alkylolamides phosphoric acid fat;

(2), carry out electrostatic spinning with above-mentioned electrostatic spinning liquid, extrude by micro-injection pump, spout connects high-voltage positive electrode, receiving device ground connection, and it is voltage 5kv～20kv that the static of control spins parameter, spout aperture 1 μ m～2mm, solution flow rate 1 μ l/h～10ml/h, 0～100 ℃ of environment temperature is collected nano fiber non-woven fabric;

Described biodegradable polyesters fiber is the copolymer of poly butyric ester or hydroxybutyric acid and other carboxylic acids.

2. method according to claim 1 is characterized in that described biodegradable polyesters fiber molecule amount is 20,000 to 1,500,000, and wherein butyric ester accounts for 40%～100% of total monomer mole in the copolymer.

3. method according to claim 1, the average diameter that it is characterized in that fiber in the described nonwoven fabric is 1nm～200nm.

4. method according to claim 1, it is characterized in that described organic solvent is N, dinethylformamide, N, N-dimethylacetylamide, alcohol, carrene, chloroform, 1, one or more mixed solvents in 2-dichloroethanes, oxolane, ether, trichloro-ethylene, cyclohexanol, methyl-sulfoxide or the trifluoroethanol.

5. method according to claim 1 is characterized in that described receiving device is the gathering-device of flat board, cylinder or metal frame.

6. method according to claim 1 is characterized in that described receiving device and spout spacing 2～50cm.

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