阅读说明：本技术 一种高分子纳米凝胶颗粒/碳酸钙复合材料及其制备方法 (Polymer nano gel particle/calcium carbonate composite material and preparation method thereof ) 是由 宁印 董迎香 宁国宏 李丹 于 2021-07-14 设计创作，主要内容包括：本发明公开了一种高分子纳米凝胶颗粒/碳酸钙复合材料及其制备方法,属于功能纳米复合材料技术领域。本发明的高分子纳米凝胶颗粒/碳酸钙复合材料是以碳酸钙晶体为载体,高分子纳米凝胶均匀地内嵌于所述碳酸钙晶体中。所述高分子纳米凝胶颗粒的粒径为20～500nm,所述碳酸钙的粒径为10～50μm。本发明通过自由基分散聚合法制备的近单分散、稳定性好的高分子纳米凝胶颗粒在碳酸钙晶体生长过程中高效地嵌入其中,克服了结晶的排异性和不同物质界面的不相容性。(The invention discloses a polymer nano gel particle/calcium carbonate composite material and a preparation method thereof, belonging to the technical field of functional nano composite materials. The polymer nano gel particle/calcium carbonate composite material takes calcium carbonate crystals as a carrier, and the polymer nano gel is uniformly embedded in the calcium carbonate crystals. The particle size of the polymer nano gel particles is 20-500 nm, and the particle size of the calcium carbonate is 10-50 mu m. The nearly monodisperse and high-stability polymer nano gel particles prepared by the free radical dispersion polymerization method are efficiently embedded in the calcium carbonate crystal growth process, so that the rejection of crystallization and the incompatibility of different material interfaces are overcome.)

1. The composite material features that calcium carbonate crystal as carrier and nanometer polymer gel particle embedded homogeneously inside the calcium carbonate crystal.

2. The polymer nanogel particle/calcium carbonate composite material as claimed in claim 1, wherein the particle size of the polymer nanogel particle is 20-500 nm, and the particle size of the calcium carbonate is 10-50 μm.

3. The polymer nanogel particle/calcium carbonate composite material as claimed in claim 1, wherein the preparation method of the polymer nanogel particle comprises the following steps: the polymerized monomer is thermally initiated to form high molecular nanometer gel particles under the action of a stabilizer, a cross-linking agent and an initiator, and the high molecular nanometer gel particles are centrifuged for later use.

4. The polymer nanogel particle/calcium carbonate composite material as claimed in claim 3, wherein the polymeric monomer is methacrylic acid or methacrylate, the stabilizer is N-vinylamide polymer, the crosslinking agent is bifunctional ethylene glycol dimethacrylate or divinylbenzene, and the initiator is alcohol-soluble initiator.

5. The polymer nanogel particle/calcium carbonate composite material according to claim 4, wherein the polymerized monomer is 2- (phosphonooxy) ethyl methacrylate, the stabilizer is poly-N-vinyl pyrrolidone, the crosslinking agent is ethylene glycol dimethacrylate, and the initiator is azobisisobutyronitrile.

6. The polymer nanogel particle/calcium carbonate composite material as claimed in claim 3, wherein the mass ratio of the polymerized monomer to the stabilizer to the cross-linking agent to the initiator is 0.8:0.8 (0-0.08): 0.02.

7. The polymer nanogel particle/calcium carbonate composite material as claimed in claim 3, wherein the thermal initiation is to add a polymerization monomer, a stabilizer, a crosslinking agent and an initiator into methanol, the mass volume ratio of the polymerization monomer to the methanol is 0.8g:20mL, nitrogen is introduced into an ice water bath for 10-20 min, and the mixture is placed in an oil bath at 50-70 ℃ for reaction for 12-36 h.

8. The polymer nanogel particle/calcium carbonate composite material as claimed in claim 3, wherein the centrifugation is performed 8 to 10 times by using methanol.

9. The preparation method of the polymer nanogel particle/calcium carbonate composite material as claimed in any one of claims 1 to 8, which is characterized by comprising the following specific steps:

dispersing the polymer nano gel particles in water to obtain nano gel particle dispersion liquid; preparing a calcium chloride solution, adding the nano gel particle dispersion liquid, and performing calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material.

10. The method for preparing polymer nano gel particles/calcium carbonate composite material according to claim 9, wherein the calcium chloride solution is 1.5-30 mM calcium chloride solution, and the nano gel particle dispersion liquid accounts for 0.02-2 wt% of the calcium chloride solution.

Technical Field

The invention relates to the technical field of functional nano composite materials, in particular to a high-molecular nano gel particle/calcium carbonate composite material and a preparation method thereof.

Background

The organic/inorganic nano composite material belongs to a research field with multiple disciplines crossed, and covers the disciplines of inorganic, organic, material, physics and the like. The material has wide application in various fields of mechanics, optics, thermals, electromagnetism and the like because the material integrates the respective advantages of organic matters and inorganic matters. Therefore, how to prepare high-performance nanocomposites has been a research hotspot in the field of material science. Researchers have been working on developing new methods and new processes to prepare new nanocomposites and exploring the interrelations between particle size, interface structure, organic phase content, etc. and their properties in nanocomposites. Common methods for preparing inorganic/organic nanocomposites include in-situ polymerization, in-situ formation, blending, chemical vapor deposition, electrolytic plating, radiation synthesis, sol-gel, intercalation, and self-assembly techniques. So far, no technical report for embedding the high molecular nanogel particles into the calcium carbonate crystals exists. Unlike conventional methods of preparation, the preparation of novel composite materials by efficiently embedding nanoparticles into growing inorganic crystals is very challenging, and the method needs to overcome the rejection of crystallization and incompatibility of different material interfaces.

Disclosure of Invention

The invention aims to provide a high-molecular nano gel particle/calcium carbonate composite material and a preparation method thereof.

In order to achieve the purpose, the invention provides the following scheme:

the invention provides a high-molecular nano gel particle/calcium carbonate composite material, which takes a calcium carbonate crystal as a carrier, and the high-molecular nano gel particles are uniformly embedded in the calcium carbonate crystal.

Furthermore, the particle size of the polymer nano gel particles is 20-500 nm, and the particle size of the calcium carbonate is 10-50 μm.

Further, the preparation method of the polymer nanogel particles comprises the following steps: the polymerized monomer is thermally initiated to form high molecular nanometer gel particles under the action of a stabilizer, a cross-linking agent and an initiator, and the high molecular nanometer gel particles are centrifuged for later use.

Further, the polymerization monomer is methacrylic acid or methacrylate, the stabilizer is N-vinylamide polymer, the crosslinking agent is glycol dimethacrylate or divinylbenzene with bifunctional groups, and the initiator is alcohol-soluble initiator.

Further, the polymerization monomer is 2- (phosphonooxy) ethyl methacrylate, the stabilizer is poly-N-vinyl pyrrolidone, the crosslinking agent is ethylene glycol dimethacrylate, and the initiator is azobisisobutyronitrile.

Furthermore, the mass ratio of the polymerized monomer to the stabilizer to the cross-linking agent to the initiator is 0.8:0.8 (0-0.08): 0.02.

Further, the thermal initiation is to add a polymerization monomer, a stabilizer, a cross-linking agent and an initiator into methanol, wherein the mass volume ratio of the polymerization monomer to the methanol is 0.8g:20mL, introduce nitrogen into an ice water bath for 10-20 min, and place the mixture in an oil bath at 50-70 ℃ for reaction for 12-36 h.

Further, the centrifugation is carried out 8-10 times by using methanol.

The invention also provides a preparation method of the polymer nano gel particle/calcium carbonate composite material, which comprises the following specific steps:

dispersing the polymer nano gel particles in water to obtain nano gel particle dispersion liquid; preparing a calcium chloride solution, adding the nano gel particle dispersion liquid, and performing calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material.

Further, the calcium chloride solution is 1.5-30 mM of calcium chloride solution, and the nano gel particle dispersion liquid accounts for 0.02-2 wt% of the calcium chloride solution.

The invention discloses the following technical effects:

the invention provides a novel method for efficiently embedding polymer nano gel particles into calcium carbonate crystals to obtain a polymer/inorganic nano composite material with a unique structure, and breaks through the technical problems of rejection of crystals and incompatibility of different substance interfaces. The invention prepares the nearly monodisperse and good-stability macromolecule nanogel particles by a free radical dispersion polymerization method, the nanogel has negative charges and can generate electrostatic interaction with the calcium carbonate growth crystal face with positive charges on the surface, so the nanogel particles can be adsorbed on the calcium carbonate growth crystal face and are gradually submerged by a crystal growth step, and the embedding of the nanogel particles in the calcium carbonate crystal is realized. The high molecular nanometer gel particles can be embedded into calcium carbonate single crystals efficiently to obtain high molecular gel particles/inorganic crystal nanometer composite materials with special structures.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a scanning electron microscope photograph of polymer nanogel particles with a crosslinking degree of 5% in example 1;

FIG. 2 is a scanning electron micrograph (lower magnification) of calcium carbonate-embedded polymer nanogel particles having a crosslinking degree of 5% according to example 1;

FIG. 3 is a scanning electron micrograph (high magnification) of calcium carbonate-embedded polymer nanogel particles with a crosslinking degree of 5% according to example 1;

FIG. 4 is a scanning electron micrograph (lower magnification) of calcium carbonate embedded in polymer nanogel particles with a degree of crosslinking of 2.5% of example 4;

FIG. 5 is a scanning electron micrograph (high magnification) of calcium carbonate embedded in polymer nanogel particles with a degree of crosslinking of 2.5% of example 4;

FIG. 6 is a scanning electron microscope photograph of polymer nanogel particles with a crosslinking degree of 10% in example 5;

FIG. 7 is a scanning electron micrograph (low power) of non-crosslinked polymeric nanogel particles embedded in calcium carbonate according to example 6;

FIG. 8 is a scanning electron micrograph (high magnification) of calcium carbonate-embedded polymer nanogel particles without crosslinking according to example 6.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

In the invention, the calcium carbonate crystal growth is carried out by an ammonia diffusion method, which specifically comprises the following steps: ammonium carbonate decomposes to produce ammonia gas and carbon dioxide gas, which enter an aqueous solution of calcium chloride to trigger the growth of calcium carbonate crystals.

Example 1

Adding 0.8g of 2- (phosphonooxy) ethyl methacrylate, 0.8g of poly-N-vinylpyrrolidone (K60, 360000g/mol), 0.02g of azobisisobutyronitrile and 0.04g of ethylene glycol dimethacrylate into a round-bottomed flask filled with 20mL of methanol, introducing nitrogen into an ice-water bath for 15min to remove oxygen, placing the flask in an oil bath at 60 ℃ for reaction for 24h, and centrifuging the flask with methanol for 10 times to obtain a nanogel particle dispersion liquid with the crosslinking degree of 5 wt% (based on the monomers) (the nanogel particle scanning electron microscope picture is shown in figure 1); preparing 10mL of 1.5mM calcium chloride solution, adding the nano gel particle dispersion liquid into the solution to enable the mixed system to contain 0.1 wt% of the nano gel particle dispersion liquid, and performing calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material (the scanning electron microscope photos are shown in figure 2 and figure 3).

Example 2

Adding 0.8g of 2- (phosphonooxy) ethyl methacrylate, 0.8g of poly-N-vinylpyrrolidone (K60, 360000g/mol), 0.02g of azobisisobutyronitrile and 0.04g of ethylene glycol dimethacrylate into a round-bottom flask filled with 20mL of methanol, introducing nitrogen into an ice-water bath for 10min to remove oxygen, placing the flask in an oil bath at 50 ℃ for reaction for 36h, and centrifuging the flask 8 times by using methanol to obtain a nanogel particle dispersion liquid with the crosslinking degree of 5 wt% (based on the monomer); preparing 10mL of 1.5mM calcium chloride solution, adding the nano gel particle dispersion liquid into the solution to enable the mixed system to contain 0.02 wt% of the nano gel particle dispersion liquid, and performing calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material.

Example 3

Adding 0.8g of 2- (phosphonooxy) ethyl methacrylate, 0.8g of poly-N-vinylpyrrolidone (K60, 360000g/mol), 0.02g of azobisisobutyronitrile and 0.04g of ethylene glycol dimethacrylate into a round-bottom flask filled with 20mL of methanol, introducing nitrogen into an ice-water bath for 20min to remove oxygen, placing the flask in an oil bath at 70 ℃ for reaction for 12h, and centrifuging the flask 10 times by using methanol to obtain a nanogel particle dispersion liquid with the crosslinking degree of 5 wt% (based on the monomers); preparing 10mL of 30mM calcium chloride solution, adding the nano gel particle dispersion liquid into the solution to enable the mixed system to contain 2 wt% of the nano gel particle dispersion liquid, and carrying out calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material.

Example 4

Adding 0.8g of 2- (phosphonooxy) ethyl methacrylate, 0.8g of poly-N-vinylpyrrolidone (K60, 360000g/mol), 0.02g of azobisisobutyronitrile and 0.02g of ethylene glycol dimethacrylate into a round-bottom flask filled with 20mL of methanol, introducing nitrogen into an ice-water bath for 15min to remove oxygen, placing the flask in an oil bath at 60 ℃ for reaction for 24h, and centrifuging the flask 10 times by using methanol to obtain a nanogel particle dispersion liquid with the crosslinking degree of 2.5 wt% (based on the monomer); preparing 10mL of 1.5mM calcium chloride solution, adding the nano gel particle dispersion liquid into the solution to enable the mixed system to contain 0.1 wt% of the nano gel particle dispersion liquid, and performing calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material (the scanning electron microscope photos are shown in figure 4 and figure 5).

Example 5

Adding 0.8g of 2- (phosphonooxy) ethyl methacrylate, 0.8g of poly-N-vinylpyrrolidone (K60, 360000g/mol), 0.02g of azobisisobutyronitrile and 0.08g of ethylene glycol dimethacrylate into a round-bottomed flask filled with 20mL of methanol, introducing nitrogen into an ice-water bath for 15min to remove oxygen, placing the flask in an oil bath at 60 ℃ for reaction for 24h, and centrifuging the flask with methanol for 10 times to obtain a nanogel particle dispersion liquid with the crosslinking degree of 10 wt% (based on the monomers) (the nanogel particle scanning electron microscope picture is shown in figure 6); preparing 10mL of 1.5mM calcium chloride solution, adding the nano gel particle dispersion liquid into the solution to enable the mixed system to contain 0.1 wt% of the nano gel particle dispersion liquid, and performing calcium carbonate crystal growth by an ammonia diffusion method to obtain the polymer nano gel particle/calcium carbonate composite material.

Example 6

Adding 0.8g of 2- (phosphonooxy) ethyl methacrylate, 0.8g of poly-N-vinyl pyrrolidone (K60, 360000g/mol) and 0.02g of azobisisobutyronitrile into a round-bottom flask filled with 20mL of methanol, introducing nitrogen into an ice-water bath for 15min to remove oxygen, placing the flask in an oil bath at 60 ℃ for reaction for 24h, and centrifuging the flask for 10 times by using the methanol to obtain a non-crosslinked nano gel particle dispersion liquid; 10mL of 1.5mM calcium chloride solution is prepared, the nanogel particle dispersion liquid is added into the solution, the mixed system contains 0.1 wt% of nanogel particle dispersion liquid, and calcium carbonate crystal growth is carried out by an ammonia diffusion method, so that the high-molecular nanogel particle/calcium carbonate composite material is obtained (the scanning electron microscope photos are shown in figure 7 and figure 8).

Comparative example 1

The same as example 1 except that calcium carbonate crystal growth was performed by adding 10mL of 1.5mM aqueous sodium carbonate solution to obtain a polymer nanogel particle/calcium carbonate composite.

The thermal stability of the polymer nanogel particle/calcium carbonate composite material was tested, and the results are shown in table 1.

TABLE 1 thermal stability of Polymer nanogel particle/calcium carbonate composites

	Thermal stability
		Example 1	700℃
Example 2	702℃
		Example 3	690℃
Example 4	710℃
		Example 5	660℃
Example 6	450℃
		Comparative example 1	360℃

The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.