Multi-component surfacing organic-inorganic composite nanoparticle as well as preparation method and application thereof

Abstract

The invention relates to a multi-component surfacing organic-inorganic composite nanoparticle as well as a preparation method and an application thereof, in the preparation process, a series of poly (tert-butyl methacrylate)-containing block polymers with different compositions and different molecular weights are prepared by using a living polymerization method; trifluoroacetic acid is utilized to selectively hydrolyze tert-butyl groups on two or more block polymers at the same time, and a self-assembly process is induced through hydrolysis to prepare nano self-assembly particles; carboxyl groups in the obtained nano self-assembled particle nucleus are complexed with metal ions, and the organic-inorganic composite nanoparticles are generated in situ through a reduction reaction of a reducing agent. Compared with the prior art, the shell layer of the prepared novel multi-component surface organic-inorganic composite nanoparticles contains two or more polymer components, the core contains metal nanoparticles, and the method has the advantages of adjustable surface functionalization, controllable assembly morphology, simple operation, strong versatility, high solid content and the like.

Description

technical field

[0001] The invention relates to the technical field of polymer materials, in particular to a multi-component surfaced organic-inorganic composite nanoparticle, a preparation method and application thereof. Background technique

[0002] In the field of polymer materials, organic-inorganic composite nanoparticles have become a new generation of advanced materials because they have the stability, dispersibility and biocompatibility of organic parts and the comprehensive properties of mechanical, optical and electrical properties of inorganic nanoparticles. research focus. At present, organic-inorganic composite nanoparticles have been used in many fields, including optoelectronic materials, catalytic sensing, biomedicine, functional coatings, environmental energy, etc.

[0003] Generally, there are three main methods to prepare organic-inorganic composite nanoparticles, including surface functional modification method, self-assembly method and one-pot method (C...

Examples

Embodiment 1

[0050] This example is Fe 3 o 4 @【Polyisoprene-b-polyacrylic acid / polyethylene oxide-b-polyacrylic acid】Preparation of composite nanoparticles

[0051] (1) Preparation of polyisoprene-b-poly-tert-butyl acrylate (PI-b-PtBA) block polymer

[0052] Preparation of hydroxyl-terminated polyisoprene (PI-OH):

[0053] First, inject 122.0mL cyclohexane (95.04g), 1.10mL tetrahydrofuran (0.96g), and 35.0mL isoprene (24.0g) into a dry and clean 250mL ampoule in sequence, place in an ice-water bath and start stirring, and Fill with nitrogen to balance the air pressure. Then, 4.0 mL of n-butyllithium (1.6 mmol / mL) was quickly poured into the ampoule, and reacted for 30 minutes to obtain a polyisoprene homopolymer. Finally, 6.64 g of ethylene oxide was added to terminate the reaction, and the white product was obtained after repeated precipitation with methanol three times, and the purified final product PI-OH was vacuum-dried at 40° C. to constant weight. (M n,SEC =5600g / mol, M w / M ...

Embodiment 2

[0065] This example is the preparation of Co@[polystyrene-b-polyacrylic acid / polydimethylsiloxane-b-polyacrylic acid] composite nanoparticles

[0066] (1) Preparation of polystyrene-b-poly-tert-butyl acrylate (PS-b-PtBA) block polymer

[0067] The preparation of polystyrene macromolecular initiator (PS-CTA): First, 33.1mL toluene (28.95g), 33.1mL styrene (30.0g), 1.05g 2-(dodecyl trithiocarbonate group )-2-Methylpropionic acid (DMP) and 94.60 mg of azobisisobutyronitrile (AIBN) were sequentially added into a 250 mL eggplant-shaped bottle and mixed thoroughly. Then, nitrogen gas was blown for 30 minutes to fully remove oxygen, and polymerization was carried out at 65° C. for 35 hours. Finally, the crude product was added to methanol for precipitation, repeated 3 times, and the purified polymer (PS-CTA) was vacuum-dried at 60° C. for 24 hours. (M n,SEC =5800g / mol, M w / M n = 1.12).

[0068]Preparation of polystyrene-b-poly(tert-butyl acrylate) (PS-b-PtBA) block polymer: Fi...

Embodiment 3

[0076] This example is TiO 2 @【Polyisoprene-b-polyacrylic acid / polyhexafluorobutylmethacrylate-b-polymethacrylic acid】Preparation of composite nanoparticles

[0077] (1) Preparation of polyhexafluorobutyl methacrylate-b-poly-tert-butyl methacrylate (PHFBMA-b-PtBMA) block polymer

[0078] The preparation of polyhexafluorobutyl methacrylate macroinitiator (PHFBMA-Br): with embodiment 1

[0079] PI-Br in (1) is replaced by ethyl bromoisobutyrate, tert-butyl acrylate is replaced by hexafluorobutyl methacrylate, and other steps are the same as in Example 1, the macroinitiator PHFBMA-Br can be prepared. (M n,SEC =7000g / mol, M w / M n = 1.22).

[0080] Preparation of polyhexafluorobutyl methacrylate-b-poly-tert-butyl methacrylate (PHFBMA-b-PtBMA) block polymer: PI-Br in Example 1 (1) is replaced with PHFBMA-Br, other The steps are the same as in Example 1, and the PHFBMA-b-PtBMA block polymer can be prepared. (M n,SEC =17000g / mol, M w / M n =1.30)

[0081] (2) Preparation of...

technical field

[0001] The invention relates to the technical field of polymer materials, in particular to a multi-component surfaced organic-inorganic composite nanoparticle, a preparation method and application thereof. Background technique

[0002] In the field of polymer materials, organic-inorganic composite nanoparticles have become a new generation of advanced materials because they have the stability, dispersibility and biocompatibility of organic parts and the comprehensive properties of mechanical, optical and electrical properties of inorganic nanoparticles. research focus. At present, organic-inorganic composite nanoparticles have been used in many fields, including optoelectronic materials, catalytic sensing, biomedicine, functional coatings, environmental energy, etc.

[0003] Generally, there are three main methods to prepare organic-inorganic composite nanoparticles, including surface functional modification method, self-assembly method and one-pot method (C...

Examples

Embodiment 1

[0050] This example is Fe 3 o 4 @【Polyisoprene-b-polyacrylic acid / polyethylene oxide-b-polyacrylic acid】Preparation of composite nanoparticles

[0051] (1) Preparation of polyisoprene-b-poly-tert-butyl acrylate (PI-b-PtBA) block polymer

[0052] Preparation of hydroxyl-terminated polyisoprene (PI-OH):

[0053] First, inject 122.0mL cyclohexane (95.04g), 1.10mL tetrahydrofuran (0.96g), and 35.0mL isoprene (24.0g) into a dry and clean 250mL ampoule in sequence, place in an ice-water bath and start stirring, and Fill with nitrogen to balance the air pressure. Then, 4.0 mL of n-butyllithium (1.6 mmol / mL) was quickly poured into the ampoule, and reacted for 30 minutes to obtain a polyisoprene homopolymer. Finally, 6.64 g of ethylene oxide was added to terminate the reaction, and the white product was obtained after repeated precipitation with methanol three times, and the purified final product PI-OH was vacuum-dried at 40° C. to constant weight. (M n,SEC =5600g / mol, M w / M ...

Embodiment 2

[0065] This example is the preparation of Co@[polystyrene-b-polyacrylic acid / polydimethylsiloxane-b-polyacrylic acid] composite nanoparticles

[0066] (1) Preparation of polystyrene-b-poly-tert-butyl acrylate (PS-b-PtBA) block polymer

[0067] The preparation of polystyrene macromolecular initiator (PS-CTA): First, 33.1mL toluene (28.95g), 33.1mL styrene (30.0g), 1.05g 2-(dodecyl trithiocarbonate group )-2-Methylpropionic acid (DMP) and 94.60 mg of azobisisobutyronitrile (AIBN) were sequentially added into a 250 mL eggplant-shaped bottle and mixed thoroughly. Then, nitrogen gas was blown for 30 minutes to fully remove oxygen, and polymerization was carried out at 65° C. for 35 hours. Finally, the crude product was added to methanol for precipitation, repeated 3 times, and the purified polymer (PS-CTA) was vacuum-dried at 60° C. for 24 hours. (M n,SEC =5800g / mol, M w / M n = 1.12).

[0068]Preparation of polystyrene-b-poly(tert-butyl acrylate) (PS-b-PtBA) block polymer: Fi...

Embodiment 3

[0076] This example is TiO 2 @【Polyisoprene-b-polyacrylic acid / polyhexafluorobutylmethacrylate-b-polymethacrylic acid】Preparation of composite nanoparticles

[0077] (1) Preparation of polyhexafluorobutyl methacrylate-b-poly-tert-butyl methacrylate (PHFBMA-b-PtBMA) block polymer

[0078] The preparation of polyhexafluorobutyl methacrylate macroinitiator (PHFBMA-Br): with embodiment 1

[0079] PI-Br in (1) is replaced by ethyl bromoisobutyrate, tert-butyl acrylate is replaced by hexafluorobutyl methacrylate, and other steps are the same as in Example 1, the macroinitiator PHFBMA-Br can be prepared. (M n,SEC =7000g / mol, M w / M n = 1.22).

[0080] Preparation of polyhexafluorobutyl methacrylate-b-poly-tert-butyl methacrylate (PHFBMA-b-PtBMA) block polymer: PI-Br in Example 1 (1) is replaced with PHFBMA-Br, other The steps are the same as in Example 1, and the PHFBMA-b-PtBMA block polymer can be prepared. (M n,SEC =17000g / mol, M w / M n =1.30)

[0081] (2) Preparation of...

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