阅读说明：本技术 一种采用皮克林乳液制备的可降解高分子复合纸及方法 (Degradable high-molecular composite paper prepared from pickering emulsion and preparation method thereof ) 是由 刘汉斌 杨晓晗 李志健 于 2021-09-06 设计创作，主要内容包括：本发明一种采用皮克林乳液制备的可降解高分子复合纸及方法,所述方法包括以下步骤：将可降解的高分子材料溶解在油相中,之后依次加入去离子水和纳米颗粒进行剪切,纳米颗粒为纳米蒙脱土、纳米二氧化硅或纳米二氧化钛,纳米颗粒占高分子材料质量的0.03～0.8％,制得高分子皮克林乳液；将高分子皮克林乳液涂布在纸上进行热压,得到可降解高分子复合纸,强度高、可降解,扩大纸张的使用范围,使其在印刷、包装等诸多领域都有广泛应用前景。(The invention relates to degradable high-molecular composite paper prepared by pickering emulsion and a method, wherein the method comprises the following steps: dissolving a degradable high polymer material in an oil phase, and then sequentially adding deionized water and nano particles for shearing, wherein the nano particles are nano montmorillonite, nano silicon dioxide or nano titanium dioxide, and account for 0.03-0.8% of the mass of the high polymer material to prepare high polymer pickering emulsion; the high-molecular Pickering emulsion is coated on paper to be hot-pressed to obtain the degradable high-molecular composite paper, which has high strength and degradability, enlarges the application range of the paper and has wide application prospect in various fields such as printing, packaging and the like.)

1. A method for preparing degradable high-molecular composite paper by adopting Pickering emulsion is characterized by comprising the following steps:

dissolving a degradable high polymer material in an oil phase, and then sequentially adding deionized water and nano particles for shearing, wherein the nano particles are nano montmorillonite, nano silicon dioxide or nano titanium dioxide, and account for 0.03-0.8% of the mass of the high polymer material to prepare high polymer pickering emulsion;

and coating the high-molecular Pickering emulsion on paper for hot pressing to obtain the degradable high-molecular composite paper.

2. The method for preparing degradable polymer composite paper by using Pickering emulsion according to claim 1, wherein the degradable polymer material is polylactic acid, poly (butylene adipate/terephthalate) or polybutylene succinate.

3. The method for preparing degradable polymer composite paper by adopting Pickering emulsion according to claim 1, wherein the ratio of the polymer material to the oil phase is (1-1.5) g: (10-30) mL.

4. The method for preparing degradable polymer composite paper by using Pickering emulsion according to claim 1, wherein the average particle size of the nanoparticles is 5-20 nm.

5. The method for preparing degradable polymer composite paper by using Pickering emulsion as claimed in claim 1, wherein the oil phase is dichloromethane or chloroform.

6. The method for preparing degradable polymer composite paper by using Pickering emulsion according to claim 1, wherein the volume ratio of the oil phase to the deionized water is (1-2): (1-2).

7. The method for preparing degradable polymer composite paper by using Pickering emulsion according to claim 1, wherein the shearing is carried out at 3000-9000 r/min for 5-120 min.

8. The method for preparing degradable polymer composite paper by using pickering emulsion as claimed in claim 1, wherein the paper is qualitative filter paper.

9. The method for preparing degradable polymer composite paper by using pickering emulsion according to claim 1, wherein the hot pressing is performed at 120-180 ℃ for 10-15 min.

10. A degradable polymer composite paper obtained by the method for preparing the degradable polymer composite paper by using the Pickering emulsion as claimed in any one of claims 1 to 9.

Technical Field

The invention belongs to the field of special functional paper materials, and particularly relates to degradable high-molecular composite paper prepared from Pickering emulsion and a preparation method thereof.

Background

Since the first generation of plastic phenolic resins developed in 1907, plastic manufacturing technology has continued to evolve, producing large quantities of lightweight, durable, inert, and corrosion resistant plastics in bulk, but these materials have been an increasing environmental problem. The durability of plastics makes them so attractive materials for use as well as high resistance to degradation, and therefore disposal of waste plastics has been problematic and the progress of replacing plastics with paper is imperative.

The first paper was originally produced to simplify the complicated writing process, and paper has evolved to date to a variety of uses, such as low basis weight coated paper, often used for printing various art pictures, pictorial newspapers, labels, and the like. The structure and properties of paper have limited the use of paper. With the development of modern science and technology, people find that paper can also be used as a functional material in various frontier fields. But the paper has poor strength, is not water-resistant and is easy to damage. Most of synthetic polymer plastics with better strength have better corrosion resistance, but are difficult to decompose in natural environment, thereby causing serious pollution. Therefore, it is necessary to develop a composite paper having good strength and being degradable.

Disclosure of Invention

Aiming at the defects and shortcomings of paper, the invention provides the degradable high-molecular composite paper prepared by adopting the Pickering emulsion and the preparation method thereof, the strength is high, the paper is degradable, the use range of the paper is expanded, and the paper has wide application prospects in various fields such as printing, packaging and the like.

The invention is realized by the following technical scheme:

a method for preparing degradable high-molecular composite paper by adopting Pickering emulsion comprises the following steps:

dissolving a degradable high polymer material in an oil phase, and then sequentially adding deionized water and nano particles for shearing, wherein the nano particles are nano montmorillonite, nano silicon dioxide or nano titanium dioxide, and account for 0.03-0.8% of the mass of the high polymer material to prepare high polymer pickering emulsion;

and coating the high-molecular Pickering emulsion on paper for hot pressing to obtain the degradable high-molecular composite paper.

Preferably, the degradable high polymer material is polylactic acid, poly (butylene adipate/terephthalate) or polybutylene succinate.

Preferably, the ratio of the polymer material to the oil phase is (1-1.5) g: (10-30) mL.

Preferably, the average particle size of the nanoparticles is 5-20 nm.

Preferably, the oil phase is dichloromethane or chloroform.

Preferably, the volume ratio of the oil phase to the deionized water is (1-2): (1-2).

Preferably, the shearing is carried out for 5-120 min at 3000-9000 r/min.

Preferably, the paper is qualitative filter paper.

Preferably, the hot pressing is carried out at 120-180 ℃ for 10-15 min.

The degradable polymer composite paper is prepared by the method for preparing the degradable polymer composite paper by adopting the Pickering emulsion.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention relates to a method for preparing degradable high-molecular composite paper by pickering emulsion, which comprises the steps of dissolving a degradable high-molecular material in an oil phase, sequentially adding deionized water and nano particles for shearing, thus preparing the degradable high-molecular pickering emulsion, wherein the emulsion has the functions of environmental protection, degradability and good biocompatibility, and has degradable high-molecular polymers with strong mechanical properties.

Drawings

FIG. 1 is a graph showing the change of mechanical properties of polymer-based composite paper prepared by PLA in example 1 of the present invention compared with plain paper used in this example.

FIG. 2 is a graph showing the change in mechanical properties of polymer-based composite paper prepared using PBAT according to example 3 of the present invention compared with ordinary paper used in this example.

Detailed Description

The invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention, and the scope of the invention as claimed is not limited to the examples.

The invention discloses a method for preparing degradable high-molecular composite paper by pickering emulsion, which comprises the following steps:

step 1, dissolving degradable natural polymer material in an oil phase, adding deionized water, adding nanoparticles, and performing high-speed shearing to prepare a polymer Pickering emulsion, wherein the oil phase is an organic solvent such as dichloromethane or chloroform, and the volume ratio of the oil phase to the deionized water is (1-2): (1-2), wherein the shearing rate is 3000-9000 r/min, and the shearing time is 5-120 min;

the nano particles account for 0.03-0.8% of the mass of the high polymer material, and the ratio of the high polymer material to the oil phase is (1-1.5) g: (10-30) mL, the degradable high polymer material is polylactic acid (PLA), poly (butylene adipate/terephthalate) (PBAT), polybutylene succinate (PBS) or the like, and the nano particles are nano montmorillonite, nano silicon dioxide or nano titanium dioxide with the average particle size of 5-20 nm;

and 2, coating 10mL of high-molecular Pickering emulsion on qualitative filter paper, and carrying out hot pressing at 120-180 ℃ for 10-15 min to obtain the high-performance degradable high-molecular composite paper.

Example 1:

taking dichloromethane as an oil phase and deionized water as a water phase, completely dissolving 1.2g of degradable high polymer material PLA in 20mL of dichloromethane, and then, according to the weight percentage of the oil: water 2: 1, adding 0.05 percent of nano-silica particles, shearing for 5min by a high-speed shearing machine at 5000rmp to prepare degradable high-molecular Pickering emulsion, taking 10mL of the prepared high-molecular emulsion, uniformly coating the emulsion on qualitative filter paper by a glass rod, and carrying out hot pressing at 180 ℃ for 10min to prepare the degradable high-molecular composite paper.

The tensile strength of the common filter paper and the composite paper is measured by using a servo type tensile testing machine, as shown in figure 1, compared with the tensile strength of the common filter paper, the tensile strength of the PLA composite paper is increased to 35MPa, and the mechanical property is obviously enhanced.

Example 2:

taking dichloromethane as an oil phase and deionized water as a water phase, completely dissolving 1.2g of degradable high polymer material PLA in 20mL of dichloromethane, and then, according to the weight percentage of the oil: water 2: 1, adding 0.05 percent of nano montmorillonite, shearing for 5min by a high-speed shearing machine at 5000rmp to prepare degradable high-molecular Pickering emulsion, taking 10mL of the prepared high-molecular emulsion, uniformly coating the emulsion on qualitative filter paper by a glass rod, and carrying out hot pressing at 180 ℃ for 10min to prepare the degradable high-molecular-based composite paper.

Example 3:

taking dichloromethane as an oil phase and deionized water as a water phase, completely dissolving 1.2g of degradable high molecular material PBAT in 20mL of dichloromethane, and then, according to the weight percentage of the oil: water 1: 2, adding 0.05 percent of nano-montmorillonite, shearing for 5min by a high-speed shearing machine at 5000rmp to prepare degradable high-molecular Pickering emulsion, taking 10mL of the prepared high-molecular emulsion, uniformly coating the emulsion on qualitative filter paper by a glass rod, and hot-pressing for 10min at 150 ℃ to prepare the degradable high-molecular-based composite paper.

As shown in FIG. 2, compared with the tensile strength of the common filter paper, the tensile strength of the PBAT composite paper is increased to 34.7MPa, and the mechanical property is obviously enhanced.

Example 4:

taking dichloromethane as an oil phase and deionized water as a water phase, completely dissolving 1.2g of degradable high molecular material PBAT in 20mL of dichloromethane, and then, according to the weight percentage of the oil: water 1: 2, adding 0.05 percent of nano-silica, shearing for 5min by a high-speed shearing machine at 5000rmp to prepare degradable high-molecular Pickering emulsion, taking 10mL of the prepared high-molecular emulsion, uniformly coating the emulsion on qualitative filter paper by a glass rod, and hot-pressing for 10min at 150 ℃ to prepare the degradable high-molecular-based composite paper.

Example 5:

chloroform is used as an oil phase, deionized water is used as a water phase, 1.2g of degradable high polymer material PBS is completely dissolved in 20mL of chloroform, and then the weight percent of the degradable high polymer material PBS is calculated according to the following steps: water 1: 1, adding 0.05 percent of nano montmorillonite, shearing for 120min by a high-speed shearing machine at 3000rmp to prepare degradable high-molecular Pickering emulsion, taking 10mL of the prepared high-molecular emulsion, uniformly coating the emulsion on qualitative filter paper by a glass rod, and hot-pressing for 10min at 120 ℃ to prepare the degradable high-molecular-based composite paper.

Example 6:

chloroform is used as an oil phase, deionized water is used as a water phase, 1.2g of degradable high polymer material PBS is completely dissolved in 20mL of chloroform, and then the weight percent of the degradable high polymer material PBS is calculated according to the following steps: water 1: 1, adding 0.05 percent of nano-silica, shearing for 120min by a high-speed shearing machine at 3000rmp to prepare degradable high-molecular Pickering emulsion, taking 10mL of the prepared high-molecular emulsion, uniformly coating the emulsion on qualitative filter paper by a glass rod, and hot-pressing for 10min at 120 ℃ to prepare the degradable high-molecular-based composite paper.