CN108864699A - The method that silane coupling agent auxiliary prepares magnetic dendrimer nanocomposite - Google Patents

The method that silane coupling agent auxiliary prepares magnetic dendrimer nanocomposite Download PDF

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CN108864699A
CN108864699A CN201810464224.6A CN201810464224A CN108864699A CN 108864699 A CN108864699 A CN 108864699A CN 201810464224 A CN201810464224 A CN 201810464224A CN 108864699 A CN108864699 A CN 108864699A
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magnetic
methanol
daiamid
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coupling agent
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CN108864699B (en
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郭兴忠
孙玉坤
李冬云
杨辉
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Zhejiang University ZJU
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0054Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron
    • C08K2003/2275Ferroso-ferric oxide (Fe3O4)
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

A kind of method for assisting preparing magnetic dendrimer nanocomposite the invention discloses silane coupling agent KH560, includes the following steps:1) it, takes magnetic nano powder to be added in alcohol water mixed solution, concentrated ammonia liquor stirring is then added;2) ethyl orthosilicate, KH560, stirring, is added to resulting suspension;3) step 2), is reacted to obtained product Magneto separate, is cleaned, it is dry, obtain the magnetic nano-particle of KH560 modification activation;4), first by daiamid ultrasonic dissolution in methanol, daiamid methanol solution is obtained;It disperses the magnetic nano-particle of KH560 modification activation in methanol, is then added into above-mentioned daiamid methanol solution, is stirred to react;5) step 4), is reacted to obtained product Magneto separate, is cleaned, it is dry, obtain the magnetic dendrimer nanocomposite of KH560 auxiliary grafting.Preparation process of the present invention is simple, raw material easily obtains, and graft effect is good.

Description

The method that silane coupling agent auxiliary prepares magnetic dendrimer nanocomposite
Technical field
The invention belongs to technical field of function materials, are related to a kind of preparation side of magnetic dendrimer nanocomposite Method.
Background technique
Magnetic dendrimer nanocomposite is using magnetic nanoparticle as core, using molecular link in surface grafting tree Dendritic macromolecules form a kind of composite material of core-shell structure.This material has had both magnetic particle and dendritic macromole two The performance advantage of kind material, has a large amount of active function groups, good bioactivity, the easy functionalization of superparamagnetism and surface etc. special Point.
By taking the magnetic dendrimer of ferroso-ferric oxide/daiamid (PAMAM) as an example.PAMAM is because having molecular structure essence Really, largely surface terminal functionality, relative molecular weight be controllable, molecule has nano-scale and good biocompatibility etc. Characteristic becomes studies a kind of most commonly used dendrimer at present, is each field focus of attention.Ferroso-ferric oxide is One of magnetic material being most widely used at present, nano ferriferrous oxide have high saturation and magnetic intensity, ultralow coercivity, surpass The characteristics such as paramagnetism, good biocompatibility, nanometer size effect and high specific surface area make it have a wide range of applications Prospect.If the two can be combined, a kind of nanocomposite of core-shell structure is formed, it will be in biological medicine, medical diagnosis, drug There is huge application potential in many biomedical and Industrial Engineering fields such as sustained release, sewage treatment, catalyst.
But it can not be directly grafted between dendritic macromole and magnetic core, need to assist using other substances, first by magnetic core Surface introduces active group.
Currently used for auxiliary grafting dendritic macromole and magnetic core have 3- aminopropyl triethoxysilane, polystyrene, The many kinds of substance such as gold chloride, cysteamine, 1,4-Diaminobutane, but more or less all with the method for these substances auxiliary grafting There are preparation processes, and cumbersome, reactant is not easy obtains, reaction condition requirement is high, environmental pollution or poor biocompatibility and magnetic Property particle access active group after the technological deficiencies such as group activity is weaker.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of novel preparation magnetism dendrimer nanocomposites Method.
In order to solve the above technical problem, the present invention provides a kind of silane coupling agent KH560 to assist preparation magnetic tree-shaped big The method of molecule nano composite material, includes the following steps:
1) magnetic nano powder (ferroso-ferric oxide), is taken to be added in alcohol water mixed solution, (jitter time is about ultrasonic disperse 15 ± 5 minutes), then addition concentrated ammonia liquor (ammonium hydroxide that mass concentration is 25%~28%) is 11 ± 0.5 up to pH, continues to stir 04.~0.6 hour (preferably 0.5 hour);It obtains suspension (black suspension);
2), according to the dosage of every 0.2 gram of magnetic nano powder adapted 0.8~1.2ml (preferably 1ml) ethyl orthosilicate Ethyl orthosilicate is added than, the suspension (black suspension) that obtains to step 1) and stirs that (preferably 1 is small 0.8~1.2 hour When), KH560 (γ-glycidyl ether oxygen propyl trimethoxy silicane) then is added, continue to be stirred to react 11~13 hours (compared with Good is 12 hours);The volumetric usage of KH560 and ethyl orthosilicate ratio is 1:0.9~1.1 (preferably 1:1);
3) step 2), is reacted to obtained product (black product) Magneto separate, cleaning obtains after dry (freeze-drying) The magnetic nano-particle of KH560 modification activation;
4), first by daiamid (PAMAM) ultrasonic dissolution in methanol, daiamid (PAMAM) methanol solution is obtained;It will The magnetic nano-particle of KH560 modification activation is scattered in methanol, is then added to above-mentioned daiamid (PAMAM) methanol solution In, it is stirred to react 22~26 hours (preferably 24 hours);
The magnetic nano-particle of KH560 modification activation:The mass ratio of daiamid (PAMAM) is 0.18~0.22:1 (compared with Good is 0.2:1);
Remarks:Daiamid (PAMAM), that is, daiamid dendritic macromole;
5) step 4), is reacted to obtained product (black product) Magneto separate, cleaning obtains after dry (freeze-drying) The magnetic dendrimer nanocomposite of KH560 auxiliary grafting.
The method of magnetic dendrimer nanocomposite is prepared as silane coupling agent KH560 auxiliary of the invention It improves:
In the step 1), magnetic nano powder is the monodisperse ferriferrous oxide nano flower that partial size is 40~60 nanometers.
The method of magnetic dendrimer nanocomposite is prepared as silane coupling agent KH560 auxiliary of the invention It is further improved:
In the step 1), alcohol water mixed solution is 7~8 by volume ratio:1 (preferably 7.5:1) ethyl alcohol and water forms;
The alcohol water mixed solution of 150~200ml of every 0.2 gram of magnetic nano powder adapted (preferably 170ml).
The method of magnetic dendrimer nanocomposite is prepared as silane coupling agent KH560 auxiliary of the invention It is further improved:
According to the amount ratio of every gram of daiamid (PAMAM) adapted 25~35ml (preferably 30ml) methanol, by polyamide Amine (PAMAM) ultrasonic dissolution is in methanol;
According to magnetic nano-particle adapted 80~120ml (preferably 100ml) methanol of every 0.2 gram of KH560 modification activation Amount ratio, by KH560 modification activation magnetic nano-particle be scattered in methanol.
The daiamid (PAMAM) is whole generation daiamid, that is, daiamid macromolecular is whole generation macromolecular.
The method of magnetic dendrimer nanocomposite is prepared as silane coupling agent KH560 auxiliary of the invention It is further improved:The cleaning of the step 3) and step 5) is:It is successively cleaned with second alcohol and water.
The method of magnetic dendrimer nanocomposite is prepared as silane coupling agent KH560 auxiliary of the invention It is further improved:The drying of the step 3) and step 5) is freeze-drying.
The step 3) is:After the corresponding obtained product Magneto separate of every 0.2 gram of magnetic nano powder, cleaning, retain 20 ± 5 Milliliter water, it is 24 ± 2 hours dry in -86 ± 5 DEG C;
The step 5) is:It is the corresponding obtained product Magneto separate of magnetic nano-particle after every 0.2 gram of KH560 activation, clear After washing, retain 20 ± 5 milliliters of water, it is 24 ± 2 hours dry in -86 ± 5 DEG C.
KH560 full name is γ-glycidyl ether oxygen propyl trimethoxy silicane, is a kind of common silane coupling agent, Organic active group is epoxy group and ehter bond.KH560 can be coated on magnetic-particle surface after meeting water and hydrolyzing, and make magnetism Particle surface is rich in epoxy group and ehter bond, and the group of these high activities easily reacts with macromolecular amino end group, after being convenient for Continuous reactive grafting.Due to the above-mentioned characteristic of KH560, become ferriferrous oxide nano magnetic core and daiamid dendroid The good auxiliary material of macromolecular grafting.
The present invention accesses one layer of active group on magnetic nano-particle surface using the hydrolytic polymerization of KH560, with rear addition Amino end group dendritic macromole reactive grafting, magnetic dendrimer nanocomposite is prepared.It is made using the present invention Standby ferroso-ferric oxide/daiamid magnetism dendrimer nanocomposite out has good magnetic and stable and uniform Core-shell structure, will be in ferroso-ferric oxide and daiamid two-phase well reactive grafting.The magnetic tree that the method for the present invention is prepared Shape macromolecular nanocomposite, will be in many biologies such as biological medicine, medical diagnosis, medicament slow release, sewage treatment, catalyst There is huge application potential in medicine and Industrial Engineering field.
The preparation method is that inventor is obtained by conscientiously studying, testing.The beneficial effect that the present invention generates Fruit is:It is compared with other methods, preparation process of the present invention is simple, raw material easily obtains, and graft effect is more preferable;Magnetic tree obtained Shape macromolecular nanocomposite has stable structure and good dispersibility, has both maintained the excellent magnetism of magnetic core particle Can, also maintain the good group activity of macromolecular.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is the transmission electron microscope photo of magnetic dendrimer nanocomposite prepared by embodiment 1.
Fig. 2 is the IR spectrogram of magnetic dendrimer nanocomposite prepared by embodiment 1.
Fig. 3 is the hysteresis loop figure of magnetic dendrimer nanocomposite prepared by embodiment 1.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in This.
Select the SK2200HP type ultrasonic cleaner of Shanghai High Kudos Science Instrument Co., Ltd., working frequency 53kHz function Rate 100w;Speed of agitator is 500~600 rpms;
2.0 generation daiamid dendritic macromoles, can be according to having published《The production work of dendroid daiamid Skill》(publication No. CN103601895B) is prepared.
The method that embodiment 1, a kind of silane coupling agent KH560 auxiliary prepare magnetic dendrimer nanocomposite, Successively follow the steps below:
1) 0.2 gram of ferroso-ferric oxide (the monodisperse ferriferrous oxide nano flower that partial size is 40~60 nanometers), is taken to be added to Ultrasonic disperse 15 minutes in the mixed solution of 20 milliliters of water and 150 milliliters of ethyl alcohol, about 1 milliliter of concentrated ammonia liquor is then added, and (quality is dense The ammonium hydroxide that degree is 25~28%), so that regulation system pH is 11, continue stirring 0.5 hour;It obtains suspension (black suspension);
2) black suspension that, obtains to step (1) is added 1 milliliter of ethyl orthosilicate and is stirred to react 1 hour, then plus Enter 1 milliliter of KH560, continues to be stirred to react 12 hours;
3), the black product Magneto separate for obtaining reaction, is successively cleaned respectively with 50 milliliters of ethyl alcohol and 50 milliliters of water, Freeze-drying obtains the magnetic Nano of KH560 modification activation after (retaining about 20 milliliters of water, 24 hours dry under -86 degrees Celsius) Particle;
4) magnetic nano-particle after, taking 0.2 gram of KH560 activation is scattered in 100 ml methanols, is then added by 1 gram 2.0 generation daiamid macromoleculars are dissolved in the solution that 30 ml methanols obtain, and are stirred to react 24 hours;
5), the black product Magneto separate for obtaining reaction, is successively cleaned respectively with 50 milliliters of ethyl alcohol and 50 milliliters of water, Freeze-drying obtains KH560 auxiliary grafting magnetism after (retaining about 20 milliliters of water, 24 hours dry under -86 degrees Celsius) is tree-shaped Macromolecular nanocomposite.
Experiment one, magnetic dendrimer nanocomposite produced by the present invention have stable structure and good point Property is dissipated, the excellent magnetic property of magnetic core particle had both been maintained, also maintains the good group activity of macromolecular.
Fig. 1 is the images of transmissive electron microscope shot using Japan Electronics JEM-2100 type transmission electron microscope, can be seen that magnetic in figure Core surface cladding thickness is uniform, does not destroy magnetic core structure, and maintain preferable dispersibility.
Fig. 2 is the infrared of the magnetic dendrimer that 5700 type infrared spectrometer of ThermoFisher Nicolet is measured Spectrogram, it can clearly be seen that the infrared signature peak of KH560 and PAMAM, illustrates to successfully pass the auxiliary of KH560 on magnetic core surface in figure Adjuvant grafting branch PAMAM macromolecular, in 3400cm-1Nearby there is the infrared absorption peak of very strong amino end group, illustrates have on the surface of the material A large amount of amino group.
Fig. 3 is the room temperature magnetic that the magnetic dendrimer that magnetometer (VSM) is measured is vibrated using 7410 type of Lakeshore Hysteresis curves, it can be seen that the coercivity of material only has about 12Oe, (low-coercivity facilitates material in water from hysteresis loop Dispersion and recycling), saturation magnetization 44.164emu/g illustrates magnetic core after surface grafting dendritic macromole High magnetic response characteristic is still kept.
Comparative example 1-1,
Step 2) is changed to:2), the black suspension obtained to step 1) is only added 1 milliliter of ethyl orthosilicate and stirs anti- It answers 12 hours;
Remaining is equal to embodiment 1.
Comparative example 1-2,
Step 2) is changed to:2) black suspension, obtained to step 1) is added 1 milliliter of ethyl orthosilicate and is stirred to react 1 hour, 2 milliliters of KH560 are then added, continue to be stirred to react 12 hours;
Remaining is equal to embodiment 1.
Comparative example 2,
1 milliliter of KH560 of addition in step 2) is changed to the Silane coupling agent KH550 that 1 milliliter of amino groups is added,
And 2.0 generation daiamid macromoleculars in step 4) are changed to 2.5 generation daiamid macromoleculars, dosage is constant;
Remaining is equal to embodiment 1.
Comparative example 3-1,
Step 2) is changed to:2), 1 milliliter of KH560 is only added in the black suspension obtained to step 1), and is stirred to react 12 Hour;
Remaining is equal to embodiment 1.
Comparative example 3-2,
Step 2) is changed to:2) black suspension, obtained to step 1) is added 1 milliliter of methyl orthosilicate and is stirred to react 1 hour, 1 milliliter of KH560 is then added, continues to be stirred to react 12 hours;
Remaining is equal to embodiment 1.
Comparative example 4,
Step 1) is changed to:1) 0.2 gram of ferroso-ferric oxide (monodisperse ferroso-ferric oxide that partial size is 40~60 nanometers, is taken Nano flower) it is added in the mixed solution of 20 milliliters of water and 150 milliliters of ethyl alcohol ultrasonic disperse 15 minutes, then stir 0.5 hour;
Remaining is equal to embodiment 1.
Comparative example 5,
The freeze-drying of step 3) is changed to:60 degrees Celsius drying to constant weight;
The freeze-drying of step 5) is changed to:60 degrees Celsius drying to constant weight;
Remaining is equal to embodiment 1.
Comparative experiments, the detection that above-mentioned all comparative examples are carried out to performance according to one the method for experiment, acquired results As shown in table 1 below.
Table 1
And embodiment 1 is:Monodisperse, package are uniformly, good with macromolecular grafting.
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure All deformations for directly exporting or associating, are considered as protection scope of the present invention.

Claims (6)

1. the method that silane coupling agent KH560 auxiliary prepares magnetic dendrimer nanocomposite, it is characterized in that include with Lower step:
1) magnetic nano powder, is taken to be added in alcohol water mixed solution, ultrasonic disperse, then be added concentrated ammonia liquor until pH be 11 ± 0.5, continue stirring 04.~0.6 hour;Obtain suspension;
2) it, according to the amount ratio of every 0.2 gram of magnetic nano powder adapted 0.8~1.2ml ethyl orthosilicate, is obtained to step 1) Suspension is added ethyl orthosilicate and stirs 0.8~1.2 hour, and KH560 is then added, continues to be stirred to react 11~13 hours; The volumetric usage of KH560 and ethyl orthosilicate ratio is 1:0.9~1.1;
3) step 2), is reacted to obtained product Magneto separate, cleaning after dry, obtains the magnetic nano particle of KH560 modification activation Son;
4), first by daiamid ultrasonic dissolution in methanol, daiamid methanol solution is obtained;By the magnetism of KH560 modification activation Nanoparticle is scattered in methanol, is then added into above-mentioned daiamid methanol solution, is stirred to react 22~26 hours;
The magnetic nano-particle of KH560 modification activation:The mass ratio of daiamid is 0.18~0.22:1;
5) step 4), is reacted to obtained product Magneto separate, cleaning, after dry, the magnetism for obtaining KH560 auxiliary grafting is tree-shaped big Molecule nano composite material.
2. silane coupling agent KH560 auxiliary according to claim 1 prepares magnetic dendrimer nanocomposite Method, it is characterized in that:
In the step 1), magnetic nano powder is the monodisperse ferriferrous oxide nano flower that partial size is 40~60 nanometers.
3. silane coupling agent KH560 auxiliary according to claim 2 prepares magnetic dendrimer nanocomposite Method, it is characterized in that:
In the step 1), alcohol water mixed solution is 7~8 by volume ratio:1 ethyl alcohol and water forms;
The alcohol water mixed solution of 150~200ml of every 0.2 gram of magnetic nano powder adapted.
4. it is nano combined to prepare magnetic dendrimer for any silane coupling agent KH560 auxiliary according to claim 1~3 The method of material, it is characterized in that:
According to the amount ratio of every gram of daiamid adapted 25~35ml methanol, by daiamid ultrasonic dissolution in methanol;
According to the amount ratio of magnetic nano-particle adapted 80~120ml methanol of every 0.2 gram of KH560 modification activation, KH560 is repaired The magnetic nano-particle of decorations activation is scattered in methanol.
5. silane coupling agent KH560 auxiliary according to claim 4 prepares magnetic dendrimer nanocomposite Method, it is characterized in that:The cleaning of the step 3) and step 5) is:It is successively cleaned with second alcohol and water.
6. silane coupling agent KH560 auxiliary according to claim 5 prepares magnetic dendrimer nanocomposite Method, it is characterized in that:The drying of the step 3) and step 5) is freeze-drying.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110379577A (en) * 2019-07-09 2019-10-25 中国科学院化学研究所 Switching mode lotion based on magnetic-particle and preparation method thereof
CN115073755A (en) * 2021-03-12 2022-09-20 中国石油化工股份有限公司 Dendritic macromolecule coupling agent and preparation method and application thereof

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CN101864167A (en) * 2007-11-13 2010-10-20 中国科学院金属研究所 Magnetic iron oxide-dendritic polyamide core-shell nano complex and preparation thereof
CN101955231A (en) * 2010-10-20 2011-01-26 华东师范大学 Preparation method of surface dendritic macromolecule modified superparamagnetism ferroferric oxide nano particle
CN103553181A (en) * 2013-10-31 2014-02-05 东南大学 Preparation method of magnetic antiphase demulsifier

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Publication number Priority date Publication date Assignee Title
CN101864167A (en) * 2007-11-13 2010-10-20 中国科学院金属研究所 Magnetic iron oxide-dendritic polyamide core-shell nano complex and preparation thereof
CN101955231A (en) * 2010-10-20 2011-01-26 华东师范大学 Preparation method of surface dendritic macromolecule modified superparamagnetism ferroferric oxide nano particle
CN103553181A (en) * 2013-10-31 2014-02-05 东南大学 Preparation method of magnetic antiphase demulsifier

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110379577A (en) * 2019-07-09 2019-10-25 中国科学院化学研究所 Switching mode lotion based on magnetic-particle and preparation method thereof
CN110379577B (en) * 2019-07-09 2020-07-07 中国科学院化学研究所 Switch type emulsion based on magnetic particles and preparation method thereof
CN115073755A (en) * 2021-03-12 2022-09-20 中国石油化工股份有限公司 Dendritic macromolecule coupling agent and preparation method and application thereof
CN115073755B (en) * 2021-03-12 2024-05-14 中国石油化工股份有限公司 Dendritic macromolecule coupling agent and preparation method and application thereof

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