阅读说明：本技术 一种引发剂及聚合物/金属氧化物复合材料的制备方法 (Initiator and preparation method of polymer/metal oxide composite material ) 是由 王振华 张鹏芳 黄维 范文如 高小宇 王晨 于 2020-12-22 设计创作，主要内容包括：本发明开发了一种引发剂及聚合物/金属氧化物复合材料的制备方法,制备方法,包括以下步骤：将金属氧化物纳米粒子、四氢呋喃混合,超声分散,加入引发剂后继续超声分散,离心-分散,干燥得到修饰后的纳米粒子；将修饰后的纳米粒子、铜催化剂、单体、溶剂混合,超声分散,在无氧条件下加入还原剂搅拌,采用表面引发自由基转移聚合生长聚合物,聚合至一定粘度后终止反应,离心后加入适量沉淀剂离心沉淀,干燥得到聚合物/金属氧化物复合材料。该引发剂普适性好与金属氧化物的结合比较稳定,而且使修饰后的金属氧化物带有荧光,最终得到的聚合物/金属氧化物复合材料可应用于防伪和生物成像等领域,应用广泛。(The invention discloses a preparation method of an initiator and a polymer/metal oxide composite material, which comprises the following steps: mixing metal oxide nanoparticles and tetrahydrofuran, performing ultrasonic dispersion, adding an initiator, continuing to perform ultrasonic dispersion, performing centrifugation-dispersion, and drying to obtain modified nanoparticles; mixing the modified nano particles, a copper catalyst, a monomer and a solvent, carrying out ultrasonic dispersion, adding a reducing agent under an anaerobic condition, stirring, carrying out surface-initiated free radical transfer polymerization to grow a polymer, terminating the reaction after polymerization to a certain viscosity, adding a proper amount of a precipitator after centrifugation, carrying out centrifugal precipitation, and drying to obtain the polymer/metal oxide composite material. The initiator has good universality and is stably combined with metal oxide, the modified metal oxide has fluorescence, and the finally obtained polymer/metal oxide composite material can be applied to the fields of anti-counterfeiting, biological imaging and the like and has wide application.)

1. An initiator for preparing a polymer/metal oxide composite material, characterized in that it has the following structure:

2. initiator according to claim 1, characterized in that it is based on 5 initiator molecules/nm^-2The theoretical graft density of (a).

3. A preparation method of a polymer/metal oxide composite material is characterized by comprising the following steps:

mixing metal oxide nano particles and tetrahydrofuran, performing ultrasonic dispersion, adding an initiator 2-bromo-N- (2- (((((8-hydroxyquinoline-2-yl) methyl) amino) ethyl) -2-methylpropanamide, and continuing to perform ultrasonic dispersion, wherein 5 initiator molecules/nm are added into the initiator^-2The theoretical graft density of (a); centrifuging, dispersing and drying to obtain modified nano particles;

mixing the modified nano particles, a copper catalyst, a monomer and a solvent, carrying out ultrasonic dispersion, adding a reducing agent under an anaerobic condition, stirring, carrying out surface-initiated free radical transfer polymerization to grow a polymer, terminating the reaction after polymerization to a certain viscosity, adding a proper amount of a precipitator after centrifugation, carrying out centrifugal precipitation, and drying to obtain the polymer/metal oxide composite material.

4. The production method according to claim 3, characterized in that: the particle size of the metal oxide nano particles is less than or equal to 100 nm.

5. The production method according to claim 3, characterized in that: the molar ratio of the copper catalyst to the reducing agent is 1: 16.

6. The production method according to claim 3, characterized in that: the metal oxide nanoparticles are nano zinc oxide, nano titanium oxide, nano tin oxide, nano zirconium oxide, nano lanthanum oxide, nano samarium oxide, alpha-phase nano aluminum oxide, nano barium titanate, gamma-phase nano aluminum oxide, nano gadolinium oxide, nano antimony tin oxide, nano yttrium oxide, nano tungsten oxide or nano cerium oxide.

7. The production method according to claim 3, characterized in that: the copper catalyst is copper bromide/tripropylene glycol methyl ether acetate, copper bromide/tris (2-dimethylaminoethyl) amine, copper bromide/pentamethyl diethylenetriamine, N, N, N ', N' -tetra (2-picolyl) ethylenediamine or copper bromide/N, N-di (2-pyridylmethyl) ethylenediamine.

8. The production method according to claim 3, characterized in that: the monomer is methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate, allyl methacrylate, ethyl methacrylate, butyl methacrylate, polyethylene glycol dimethacrylate, N-diethylamino ethyl methacrylate, N-dimethylamino ethyl methacrylate, trifluoroethyl acrylate or trifluoroethyl methacrylate.

9. The production method according to claim 3, characterized in that: the solvent is dimethylformamide, anisole, dimethyl sulfoxide, toluene or dimethylacetamide.

10. The production method according to claim 3, characterized in that: the reducing agent is ascorbic acid/dimethyl sulfoxide, elemental copper, elemental silver, stannous octoate or azodiisobutyronitrile;

the precipitant is methanol, diethyl ether or water.

Technical Field

The invention belongs to the technical field of materials, relates to preparation of a polymer/metal oxide composite material, and particularly relates to an initiator and a preparation method of the polymer/metal oxide composite material.

Background

Hybrid materials formed by combining polymers and metal oxides are widely concerned due to excellent physicochemical properties and processing properties, wherein an initiator capable of being fixed on the surface of metal oxide particles is very critical. Currently, only a few initiators can stably modify the surface of metal oxide particles, and they have poor universality and are only suitable for individual metal oxide particles. In addition, the bonding force between the initiator and the metal oxide is weak, so that the finally obtained polymer hybrid material has poor mechanical property, is unstable and has limited application.

Disclosure of Invention

The invention provides an initiator and a preparation method of a polymer/metal oxide composite material, aiming at solving the problems of poor universality, low bonding strength, poor mechanical property of the prepared polymer/metal oxide composite material, limited application and the like of a common initiator on metal oxide modification. The method can realize the modification of the surfaces of various metal oxides, has good stability and fluorescence effect, and adopts SI-ATRP (surface initiated atom transfer radical polymerization) technology to grow polymer chains with different polymerization degrees, polydispersities and different functions on the surfaces, so that the prepared polymer/metal oxide composite material has good performance and wide application.

The invention is realized by the following technical scheme:

an initiator for preparing a polymer/metal oxide composite material, which has the following structure:

the initiator is prepared according to 5 initiator molecules/nm^-2The theoretical graft density of (a).

A method for preparing a polymer/metal oxide composite material, comprising the steps of:

mixing metal oxide nano particles and tetrahydrofuran, performing ultrasonic dispersion, adding an initiator 2-bromo-N- (2- (((((8-hydroxyquinoline-2-yl) methyl) amino) ethyl) -2-methylpropanamide, and continuing to perform ultrasonic dispersion, wherein 5 initiator molecules/nm are added into the initiator^-2The theoretical graft density of (a); centrifuging, dispersing and drying to obtain modified nano particles;

mixing the modified nano particles, a copper catalyst, a monomer and a solvent, carrying out ultrasonic dispersion, adding a reducing agent under an anaerobic condition, stirring, carrying out surface-initiated free radical transfer polymerization to grow a polymer, terminating the reaction after polymerization to a certain viscosity, adding a proper amount of a precipitator after centrifugation, carrying out centrifugal precipitation, and drying to obtain the polymer/metal oxide composite material.

As a further improvement of the invention, the particle size of the metal oxide nanoparticles is less than or equal to 100 nm.

As a further improvement of the invention, the molar ratio of the copper catalyst to the reducing agent is 1: 16.

As a further improvement of the invention, the metal oxide nanoparticles are nano zinc oxide, nano titanium oxide, nano tin oxide, nano zirconium oxide, nano lanthanum oxide, nano samarium oxide, alpha-phase nano aluminum oxide, nano barium titanate, gamma-phase nano aluminum oxide, nano gadolinium oxide, nano antimony tin oxide, nano yttrium oxide, nano tungsten oxide or nano cerium oxide.

As a further improvement of the invention, the copper catalyst is copper bromide/tripropylene glycol methyl ether acetate, copper bromide/tris (2-dimethylaminoethyl) amine, copper bromide/pentamethyldiethylenetriamine, N, N, N ', N' -tetrakis (2-pyridylmethyl) ethylenediamine or copper bromide/N, N-bis (2-pyridylmethyl) ethylenediamine.

As a further development of the invention, the monomers are methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate, allyl methacrylate, ethyl methacrylate, butyl methacrylate, polyethylene glycol dimethacrylate, N-diethylaminoethyl methacrylate, N-dimethylaminoethyl methacrylate, trifluoroethyl acrylate or trifluoroethyl methacrylate.

As a further improvement of the invention, the solvent is dimethylformamide, anisole, dimethyl sulfoxide, toluene or dimethylacetamide.

As a further improvement of the invention, the reducing agent is ascorbic acid/dimethyl sulfoxide, elemental copper, elemental silver, stannous octoate or azobisisobutyronitrile;

the precipitant is methanol, diethyl ether or water.

Compared with the prior art, the invention has the following advantages:

the initiator is used for initiating the preparation of the polymer/metal oxide composite material, and has the following specific advantages: firstly, the limitation that a common initiator can only modify individual inorganic nanoparticles is broken through, and the method can be applied to surface modification of various metal oxide nanoparticles; secondly, due to the coordination effect between the hydroxyquinoline and the metal oxide in the structure, the hybrid particle has good mechanical property and fluorescence, and can be applied to the fields of anti-counterfeiting and biological imaging; finally, the polymer with specific polymerization degree, polydispersity and specific functionality can be grown on the surfaces of different modified nanoparticles as an initiator in SI-ATRP (surface initiated atom transfer radical polymerization) technology, and the application is wide.

The invention discloses a novel initiator with universal modified metal oxide nanoparticles and a method for grafting a polymer on the surface of modified particles thereof, and aims to provide a method for stably combining the initiator and the metal oxide to prepare a composite material of the metal oxide and the polymer. The novel initiator has good universality, breaks through the limitation that a common initiator can only modify individual inorganic nanoparticles, is stably combined with metal oxide, enables the modified metal oxide to have fluorescence, and can be applied to the fields of anti-counterfeiting, biological imaging and the like, so that the finally obtained polymer/metal oxide composite material is wide in application.

Drawings

In order to illustrate the embodiments of the present invention more clearly, the drawings that are needed to be applied in the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only embodiments of the present invention, and it is obvious to those skilled in the art that other drawings can be obtained based on these drawings without inventive effort.

FIG. 1 is a detailed flow chart of the practice of the present invention.

FIG. 2 is the resulting Y2O3 nanoparticles modified with the novel initiator of example 1-1 of the present invention;

FIG. 3 is a graph showing the dynamic light scattering of the resulting polymethyl acrylate/nano yttrium oxide composite (FIG. a) and polymethyl methacrylate/nano cerium oxide composite (FIG. b) of examples 2-1 and 2-3.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.

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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The invention provides a novel initiator for preparing polymer/metal oxide composite materials, which can be stably fixed on the surfaces of various metal oxide nano particles, so that polymers can be grafted on the surfaces, and the formed polymer hybrid particles can be applied to many fields due to excellent physicochemical properties and processability. The novel initiator 2-bromo-N- (2- ((((((8-hydroxyquinolin-2-yl) methyl) amino) ethyl) -2-methylpropanamide has the following structure:

for example, hydroxyquinoline in the initiator structure can emit fluorescence after being combined with metal oxide, so that the hybrid material of the polymer and the metal oxide nanoparticles can be applied to the fields of anti-counterfeiting and biological imaging.

As shown in fig. 1, the present invention provides a novel initiator for universal modification of metal oxide nanoparticles and a method for grafting a polymer on the surface of modified particles, comprising the following steps:

1. modifying the surfaces of the metal oxide nanoparticles by using a novel initiator: mixing metal oxide nanoparticles (100 nm) and tetrahydrofuran in a glass bottle, placing the glass bottle in a cell disruption ultrasonic instrument for ultrasonic oscillation for 20 minutes, adding a novel initiator to perform ultrasonic dispersion in an ultrasonic bath for 3 hours, performing centrifugation-dispersion circulation for 3 times, and naturally drying to obtain modified nanoparticles.

2. Grafting a polymer on the surface of the metal oxide by using SI-ATRP technology: placing the modified nano particles, the copper catalyst, the monomer, the solvent and the stirrer in a Schlenk bottle, ultrasonically dispersing for 1 hour, introducing nitrogen for 20 minutes, adding a reducing agent under an anaerobic condition, stirring and polymerizing to a certain viscosity, terminating the reaction, transferring to a centrifuge tube, adding a proper amount of a precipitator, centrifugally precipitating for 2 times, and naturally drying to obtain the polymer/metal oxide composite material.

Wherein, the molar ratio of the copper catalyst to the reducing agent is 1:16, and the content of the copper ligand is one millionth.

The method comprises the following concrete implementation steps:

1) modifying the surface of the metal oxide:

taking 0.5g of metal oxide nanoparticles (zinc oxide, titanium oxide, tin oxide, magnesium oxide, zirconium oxide, lanthanum oxide, samarium oxide, barium titanate, gadolinium oxide, antimony tin oxide, yttrium oxide, tungsten oxide and aluminum oxide) with a certain diameter, and adding 5 initiator molecules/nm^-2Taking a certain amount of novel initiator. The nanoparticles are combined with the initiator by ultrasonic dispersion.

2) And (3) growing a polymer on the surface of the modified particle:

0.1g of modified nanoparticles (initiator) and 0.1ml of CuBr were added in sequence to a 10ml Schlenk reaction flask₂TPMA (catalyst), 2ml of DMF (solvent) and 2ml of monomers (methyl methacrylate (MMA), Methyl Acrylate (MA), Ethyl Acrylate (EA), Butyl Acrylate (BA) etc.) were placed in an ultrasonic bath to be uniformly dispersed, and then 0.5ml of AA/DMSO (reducing agent) was added under oxygen-free conditions to be polymerized.

The present invention will be described in further detail with reference to specific examples.

Example 1

The method specifically comprises the following steps:

1. modifying the surface of the metal oxide:

1) taking 0.5g of metal oxide nanoparticles (zinc oxide, titanium oxide, tin oxide, magnesium oxide, zirconium oxide, lanthanum oxide, samarium oxide, barium titanate, gadolinium oxide, antimony tin oxide, yttrium oxide, tungsten oxide, aluminum oxide, etc.) with a certain diameter, and adding 5 initiator molecules/nm^-2Taking a certain amount of novel initiator. Taking zinc oxide as an example, 0.5g of nano zinc oxide and 0.0542g of novel initiator are takenAn agent;

2) putting 0.5g of nano zinc oxide into a 20ml glass bottle, adding THF, and performing ultrasonic dispersion for 20min by using an ultrasonic cell disruptor;

3) 0.0542g of novel initiator is added and the mixture is placed in an ultrasonic bath for dispersion for 3 hours;

4) the mixture was transferred to a 50ml centrifuge tube, THF was added to 25ml, and after 3 cycles of centrifugation-dispersion, the tube was left open overnight to allow the remaining solvent to evaporate.

2. The surface of the modified metal oxide nano particle adopts SI-ATRP technology long polymer (taking zinc oxide and MMA as examples):

1) 0.1g of modified zinc oxide nano particles, 0.1ml of CuBr2/TPMA, 2ml of MMA and 2ml of DMF are put into a Schlenk reaction bottle and dispersed for 1 hour in an ultrasonic bath; (wherein CuBr2/TPMA is 1:4, concentration is 10mg/ml)

2) Introducing nitrogen for 30min, adding 0.48ml AA/DMSO (concentration of 25mg/ml), and placing on a magnetic stirrer to polymerize for 36 h; wherein [ CuBr2/TPMA ]/[ AA/DMSO ] ═ 1/16, CuBr2/TPMA ═ 1/4, and the content of CuBr2 is in ppm level.

3) The polymerized mixture was transferred to a centrifuge tube, added to 40ml of methanol, centrifuged 2 times, left open overnight.

Examples 1 to 1

Will Y₂O₃(0.5g) nanoparticles: (<Mixing 40nm and tetrahydrofuran (8ml) in a glass bottle (20ml), and placing in a cell disruption ultrasonic instrument for ultrasonic oscillation for 20 minutes; adding a novel initiator (0.0455g) to perform ultrasonic dispersion in an ultrasonic bath for 3 hours, performing centrifugal-dispersion circulation for 3 times, and naturally drying to obtain modified nanoparticles.

Examples 1 to 2

Adding CeO₂(0.5g) nanoparticles: (<Mixing 50nm and tetrahydrofuran (8ml) in a glass bottle (20ml), and placing in a cell disruption ultrasonic instrument for ultrasonic oscillation for 20 minutes; adding a novel initiator (0.0256g) to perform ultrasonic dispersion in an ultrasonic bath for 3 hours, performing centrifugal-dispersion circulation for 3 times, and naturally drying to obtain modified nanoparticles.

Example 2-1

Modifying the modified nano-Y₂O₃(0.1g) and methyl methacrylate (2ml), 0.1ml copper catalyst (copper bromide/tripropylene glycol methyl ether acetate: 1/4, concentration 10mg/ml), dimethyl formamide (2ml), a stirrer are placed in a Schlenk bottle, ultrasonic dispersion is carried out for 1 hour, nitrogen is introduced for 20 minutes, ascorbic acid/dimethyl sulfoxide (25mg/ml, 0.5ml) is added under the anaerobic condition, stirring polymerization is carried out until certain viscosity is reached, then the reaction is stopped and transferred to a centrifuge tube, methanol is added until 40ml, centrifugal precipitation is carried out for 2 times, and natural drying is carried out to obtain the polymer/metal oxide composite material.

Examples 2 to 2

Modifying the modified nano-Y₂O₃(0.1g), allyl methacrylate (2ml), 0.1ml copper catalyst (copper bromide/tripropylene glycol methyl ether acetate: 1/4, concentration 10mg/ml), dimethyl formamide (2ml) and a stirrer are placed in a Schlenk bottle, ultrasonic dispersion is carried out for 1 hour, nitrogen is introduced for 20 minutes, ascorbic acid/dimethyl sulfoxide (25mg/ml, 0.5ml) is added under the anaerobic condition, stirring polymerization is carried out until certain viscosity is reached, the reaction is stopped and transferred to a centrifuge tube, methanol and water are added until 40ml, centrifugal precipitation is carried out for 2 times, and natural drying is carried out to obtain the polymer/metal oxide composite material.

Examples 2 to 3

The modified nano CeO₂(0.1g) and methyl methacrylate (2ml), 0.1ml copper catalyst (copper bromide/tripropylene glycol methyl ether acetate: 1/4, concentration 10mg/ml), dimethyl formamide (2ml), a stirrer are placed in a Schlenk bottle, ultrasonic dispersion is carried out for 1 hour, nitrogen is introduced for 20 minutes, ascorbic acid/dimethyl sulfoxide (25mg/ml, 0.5ml) is added under the anaerobic condition, stirring polymerization is carried out until certain viscosity is reached, then the reaction is stopped and transferred to a centrifuge tube, methanol is added until 40ml, centrifugal precipitation is carried out for 2 times, and natural drying is carried out to obtain the polymer/metal oxide composite material.

Examples 2 to 4

The modified nano CeO₂(0.1g) with allyl methacrylate (2ml), 0.1ml copper catalyst (copper bromide/tripropylene glycol methyl ether acetate: 1/4, concentration 10mg/ml), dimethyl formamide (2ml), stirring bar, placing in Schlang bottle, ultrasonic dispersing for 1 hr, introducing nitrogen gas for 20min, adding ascorbic acid under oxygen-free conditionStirring and polymerizing the ascorbic acid/dimethyl sulfoxide (25mg/ml, 0.5ml) to a certain viscosity, terminating the reaction, transferring the mixture into a centrifugal tube, adding methanol and water to 40ml, carrying out centrifugal precipitation for 2 times, and naturally drying to obtain the polymer/metal oxide composite material.

As shown in FIG. 2, Y obtained in example 1-1 of the present invention and modified with a novel initiator 2-bromo-N- (2- ((((((8-hydroxyquinolin-2-yl) methyl) amino) ethyl) -2-methylpropanamide₂O₃The nano particles have obvious fluorescence phenomenon under the irradiation of an ultraviolet lamp, which shows that the initiator is successfully fixed on the surface of the metal oxide.

FIG. 3 is a graph showing the dynamic light scattering patterns of the polymethyl acrylate/nano yttrium oxide composite and the polymethyl methacrylate/nano cerium oxide composite obtained in examples 2-1 and 2-3 of the present invention; as shown in the figure, the average particle size of polymethyl acrylate/nano yttrium oxide is 243.3nm, and the average particle size of polymethyl methacrylate/nano cerium oxide is 149.8nm, which indicates that the modified metal oxide surface is successfully grafted with the polymer.

In summary, the present invention develops a universal novel initiator for modifying metal oxide nanoparticles and a method for grafting a polymer on the modified particle surface, and aims to provide a method for stably combining the initiator and the metal oxide to prepare a composite material of the metal oxide and the polymer, wherein the combination and uniform dispersion of the novel initiator and the metal oxide are mainly realized by ultrasonic oscillation, the polymer is grown on the modified metal oxide surface by adopting SI-ATRP (surface initiated radical transfer polymerization) technology, and the polymer/metal oxide composite material with specific polymerization degree, polydispersity and specific function can be prepared by controlling parameters such as the grafting density of the initiator, the type of the monomer, the ratio of the monomer to the initiator, and the like. The novel initiator has good universality, breaks through the limitation that a common initiator can only modify individual inorganic nanoparticles, is stably combined with metal oxide, enables the modified metal oxide to have fluorescence, and can be applied to the fields of anti-counterfeiting, biological imaging and the like, thereby being wide in application.

All articles and references disclosed above, including patent applications and publications, are hereby incorporated by reference for all purposes. The term "consisting essentially of …" describing a combination shall include the identified element, ingredient, component or step as well as other elements, ingredients, components or steps that do not materially affect the basic novel characteristics of the combination. The use of the terms "comprising" or "including" to describe combinations of elements, components, or steps herein also contemplates embodiments that consist essentially of such elements, components, or steps. By using the term "may" herein, it is intended to indicate that any of the described attributes that "may" include are optional.

A plurality of elements, components, parts or steps can be provided by a single integrated element, component, part or step. Alternatively, a single integrated element, component, part or step may be divided into separate plural elements, components, parts or steps. The disclosure of "a" or "an" to describe an element, ingredient, component or step is not intended to foreclose other elements, ingredients, components or steps.

It is to be understood that the above description is intended to be illustrative, and not restrictive. Many embodiments and many applications other than the examples provided would be apparent to those of skill in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are hereby incorporated by reference for all purposes. The omission in the foregoing claims of any aspect of subject matter that is disclosed herein is not intended to forego such subject matter, nor should the applicant consider that such subject matter is not considered part of the disclosed subject matter.