阅读说明：本技术 一种超疏水粉体材料及其制备方法 (Super-hydrophobic powder material and preparation method thereof ) 是由 王敦 刘群 林立权 于 2020-07-10 设计创作，主要内容包括：本发明涉及一种超疏水粉体材料及其制备方法,包括如下步骤：首先,反应器中充入惰性气体,依次将反应物异氰酸酯和羟基硅油加入四氢呋喃中,在一定温度下搅拌,惰性气体气氛中冷凝回流；停止加热,待体系温度冷却后,缓慢加入含扩链剂与催化剂混合的四氢呋喃溶液,持续在惰性气体气氛中搅拌反应；反应结束后,将反应产物倒入析出相中,抽滤分离,将分离物干燥后研磨、过筛,获得超疏水粉体材料。本发明方法合成步骤简单、安全、高效、易分离、制得的超疏水材料具有结构稳定、性能稳定的特点。且本发明方法对合成设备要求低、成本低、对环境友好、低能耗,有利于大规模工业化生产。(The invention relates to a super-hydrophobic powder material and a preparation method thereof, comprising the following steps: firstly, filling inert gas into a reactor, sequentially adding reactants of isocyanate and hydroxyl silicone oil into tetrahydrofuran, stirring at a certain temperature, and condensing and refluxing in an inert gas atmosphere; stopping heating, slowly adding a tetrahydrofuran solution containing a chain extender and a catalyst mixed after the temperature of the system is cooled, and continuously stirring and reacting in an inert gas atmosphere; and after the reaction is finished, pouring the reaction product into a precipitated phase, performing suction filtration separation, drying the separated substance, grinding and sieving to obtain the super-hydrophobic powder material. The method has the characteristics of simple synthesis steps, safety, high efficiency and easy separation, and the prepared super-hydrophobic material has the characteristics of stable structure and stable performance. The method has low requirements on synthesis equipment, low cost, environmental friendliness and low energy consumption, and is favorable for large-scale industrial production.)

1. The preparation method of the super-hydrophobic powder material is characterized by comprising the following steps: firstly, adding reactants of isocyanate and hydroxyl silicone oil into a tetrahydrofuran solvent, heating and stirring, simultaneously adding into a reactor with inert gas atmosphere, and condensing and refluxing; stopping heating after fully mixing, slowly adding a tetrahydrofuran solution mixed by a chain extender and a catalyst after the temperature of the system is cooled, and continuously stirring and reacting in an inert gas atmosphere; and after the reaction is finished, pouring the reaction product into a precipitated phase, performing suction filtration separation, drying the separated substance, and grinding to obtain the super-hydrophobic powder material.

2. The method for preparing the superhydrophobic powder material of claim 1, comprising the steps of:

s1, adding 1-10g of isocyanate, 1-10g of hydroxyl silicone oil and 1-50mL of tetrahydrofuran into a reactor protected by inert gas atmosphere, stirring, condensing, refluxing and reacting for 0.5-5 h;

s2, stopping heating after the solution system in the step S1 fully reacts, slowly adding 1-50mL of tetrahydrofuran solution dissolved with 0.5-5g of chain extender and 0.1-1g of catalyst after the system is cooled to 5-20 ℃, and continuing to react for 4 hours;

s3, after the reaction in the step S2 is finished, pouring the reaction product into a precipitated phase, carrying out suction filtration and separation, drying the separated substance at 40-100 ℃, grinding and sieving to obtain the super-hydrophobic powder material.

3. The method for preparing the superhydrophobic powder material according to claim 1 or2, wherein: the reaction temperature is 30-90 ℃.

4. The method for preparing the superhydrophobic powder material according to claim 1 or2, wherein: the isocyanate is one or a mixture of more than two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate.

5. The method for preparing the superhydrophobic powder material according to claim 1 or2, wherein: the chain extender is polyamine or polyalcohol.

6. The method for preparing the superhydrophobic powder material of claim 5, wherein: the chain extender is one or a mixture of more than two of ethylenediamine, 1, 5-diaminopentane, 1, 2-propanediamine, diethanolamine, ethylene glycol, glycerol or butanediol.

7. The method for preparing the superhydrophobic powder material according to claim 1 or2, wherein: the catalyst is an amine catalyst or an organic metal catalyst.

8. The method for preparing the superhydrophobic powder material of claim 7, wherein: the catalyst is one or a mixture of more than two of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate or triazine trimerization catalysts.

9. The method for preparing the superhydrophobic powder material according to claim 1 or2, wherein: the precipitated phase is one or more of water, methanol, ethanol, petroleum ether, ethyl acetate, dichloromethane, n-hexane, cyclohexane, etc.

10. A superhydrophobic powder material prepared by the method of any one of claims 1-9.

Technical Field

The invention relates to a super-hydrophobic powder material and a preparation method thereof, belonging to the technical field of chemical and functional materials.

Background

A lot of organisms in the nature have antifouling capacity, and researches find that the surfaces of terrestrial plants and animals have special surface structures, for example, the shark skin has micron-sized grooves to keep the surface of the shark clean; the shell surface has a micro-nano structure, the micro-nano structure on the surfaces of lotus leaves, rice leaves and the like, and special chemical substances secreted by organisms, such as waxy sticky substances, reduce the surface free energy of the shell, and realize self-cleaning. This provides the researcher with inspiration and thinking, i.e. self-cleaning materials mainly relate to two aspects: the surface of the material has a special micro-nano structure; the second is a special chemical substance with low surface area and low surface energy. The super-hydrophobic material has wide application in the fields of self-cleaning, water prevention, pollution prevention and oil-water separation. In recent years, researchers develop technologies such as etching rollover/self-assembly and the like to construct a surface micro-nano structure to realize a super-hydrophobic surface, but the technologies need special equipment and are difficult to apply in a large scale. Therefore, the method for preparing the super-hydrophobic powder with the micro-nano structure directly by a synthesis mode or performing hydrophobic modification with low surface energy on the micro-nano structure or the surface of the powder becomes a necessary choice.

For example, patent CN104672962A discloses a method for producing superhydrophobic powder, which comprises using polymer nanoparticles such as polystyrene/polymethyl acrylate as a template, using hydrosol obtained by hydrolysis of tetraethoxysilane hydrochloric acid as a mother solution, injecting the mother solution into the template to form a gel, then removing polymer microspheres by calcination, grinding the obtained powder, and reacting the ground powder with a silane coupling agent containing hydrophobic groups to obtain superhydrophobic powder with a micro-nano structure and low surface energy group modification. Patent CN108384284A discloses a method for preparing nano-particle hydrogel, heating to dry the nano-particle hydrogel, grinding to obtain dry powder of the rubber powder, reacting the dry powder of the rubber powder with a liquid-phase hydrophobic coupling agent in the presence of a catalyst, and filtering to obtain super-hydrophobic inorganic material powder. If the nano particle hydrogel needs to be cured at 85 ℃ for 24 hours to form the nano particle hydrogel, the drying needs to be carried out at 220 ℃ for 4 hours, and the dry rubber powder dispersoid needs to react with the hydrophobic coupling agent for 18-30 hours.

Therefore, a preparation method which has the characteristics of simple steps, safety, high efficiency, easy separation, low equipment requirement, environmental friendliness, micro-nano structure, hydrophobic group, stable structure, good solvent dispersibility and the like, is carried out at normal temperature and normal pressure and is easy to realize large-scale production is very needed in the technical field of super-hydrophobic materials.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides the preparation method which has the advantages of simple steps, safety, high efficiency, easy separation, low equipment requirement and environmental friendliness, and the prepared super-hydrophobic material has the characteristics of surface micro-nano structure, hydrophobic groups, stable structure, easy dispersion and the like, is carried out at normal temperature and normal pressure, and is easy to realize large-scale production. In addition, the method introduces the micro-nano structure and the hydrophobic group into the super-hydrophobic property of the powder through chemical reaction, so that the powder has stable hydrophobic property, and the super-hydrophobic material prepared by the method can be applied to various fields with hydrophobic requirements.

The technical scheme of the invention is as follows:

a preparation method of a super-hydrophobic powder material is prepared by the following steps: firstly, adding reactants of isocyanate, hydroxyl silicone oil and tetrahydrofuran solvent into a reactor with inert gas atmosphere at the same time, and condensing and refluxing; stopping heating after full reaction, slowly adding a tetrahydrofuran solution in which a chain extender and a catalyst are dissolved after the temperature of the system is cooled, and continuously stirring and reacting in an inert gas atmosphere; and after the reaction is finished, pouring the reaction product into a precipitated phase, performing suction filtration separation, drying the separated substance, and grinding to obtain the super-hydrophobic powder material.

Further, the method comprises the following steps:

s1, adding 1-10g of isocyanate, 1-10g of hydroxyl silicone oil and 1-50mL of tetrahydrofuran into a reactor in an inert gas atmosphere, and stirring, condensing and refluxing for reaction for 0.5-5 h;

s2, stopping heating after the solution system in the step S1 is fully mixed, slowly adding a tetrahydrofuran solution in which 0.5-5g of chain extender and 0.1-1g of catalyst are dissolved after the system is cooled to 5-20 ℃, and continuously reacting for 4 hours;

s3, after the reaction in the step S2 is finished, pouring the reaction product into a precipitated phase, carrying out suction filtration and separation, drying the separated substance at 40-100 ℃, grinding and sieving to obtain the super-hydrophobic powder material.

Further, the reaction temperature is 30-90 ℃.

Further, the isocyanate is one or a mixture of more than two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate.

Further, the chain extender is polyamine or polyalcohol.

Further, the chain extender is one or a mixture of more than two of ethylenediamine, 1, 5-diaminopentane, 1, 2-propanediamine, diethanolamine, ethylene glycol, glycerol or butanediol.

Further, the catalyst is an amine catalyst or an organic metal catalyst.

Further, the catalyst is one or a mixture of more than two of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate or triazine trimerization catalysts.

Further, the precipitated phase is one or more of water, methanol, ethanol, petroleum ether, ethyl acetate, dichloromethane, n-hexane, cyclohexane, etc

The invention also comprises the super-hydrophobic powder material prepared by the steps.

The invention has the following beneficial effects:

1. the preparation method of the super-hydrophobic powder material provided by the invention has the following characteristics: the preparation method is simple, the reaction conditions are mild, the reaction steps are simple, the energy consumption is low, and the prepared super-hydrophobic powder has stable performance.

2. The invention provides a super-hydrophobic powder material which comprises the following components in parts by weight: the hydrophobic powder is prepared by chemically reacting isocyanate, hydroxyl silicone oil containing hydroxyl and amino and having a surface area functional group and a chain extender, introducing a functional group with hydrophobic property, and meanwhile, because the functional group with hydrophobic property is introduced, the synthesized super-hydrophobic material is self-assembled under the action of a solvent to form a micro-nano structure. The existing super-hydrophobic material is generally subjected to hydrophobic modification on the surface of the material by a surface modification method, or a micro-nano structure is constructed on the surface of the material by a template method or a metal deposition or etching method, the steps are relatively complicated, and the hydrophobic properties are inconsistent.

Drawings

FIG. 1 is a sample diagram of the superhydrophobic powder materials of examples 1-4;

FIG. 2 is a scanning electron microscope image of a super-hydrophobic powder material with different enlarged sizes in example 1;

FIG. 3 is a scanning electron microscope image of a super-hydrophobic powder material of example 2 with different enlarged sizes;

FIG. 4 is a scanning electron microscope image of a super-hydrophobic powder material of example 3 with different enlarged sizes;

FIG. 5 is a scanning electron microscope image of a super-hydrophobic powder material of example 4 with different enlarged sizes;

FIG. 6 is an IR spectrum of the superhydrophobic powder materials of examples 1-4;

FIG. 7 is a contact angle test chart of the superhydrophobic powder materials of examples 1-4.

Detailed Description

The invention is described in detail below with reference to the figures and the specific embodiments.

Dicyclohexylmethane 4, 4' -diisocyanate (HMDI) >90.0%, Shanghai Aladdin Biotechnology Ltd; hydroxy silicone oil, ethylenediamine, AR, guangzhou chemical reagent factory; 1' 4-butanediol, 99%, Shanghai Allantin Biotechnology Ltd; di-n-butyl tin dilaurate, 95%, Shanghai Allantin Biotechnology Co., Ltd.; tetrahydrofuran, AR, Szegaku corporation; petroleum ether (60-90), AR, Szegaku corporation;

a heat collection type constant temperature heating magnetic stirrer, DF-101S, Chengxihua Instrument, Inc. in Hill; vacuum drying cabinet, DZF-6050, Shanghai Lindun instruments, Inc.; electronic balance, JJ500, double jie test instruments factory, ever-mature city; optical contact angle/surface interfacial tension measuring instrument, DropMeter (TM) Experience A-300, Ningbo Haiemei Technology, Inc.