阅读说明：本技术 一种水性聚合物无机复合纳米颗粒及应用 (Water-based polymer inorganic composite nano-particles and application thereof ) 是由 刘倩 童飞 岳昌智 于 2021-08-20 设计创作，主要内容包括：本发明公开了一种水性聚合物无机复合纳米颗粒及应用,具体操作步骤包括：取3～5份的聚四氢呋喃醚二醇、2,2-二羟甲基丙酸和含双聚硅氧烷支链的二醇置于三口烧瓶中搅拌后,在120℃下,减压脱水2h,冷却至室温；按顺序向步骤一中制得的混合溶液中加入1～2份的4,4-二环己基甲烷二异氰酸酯后,再加入二月桂酸二丁基锡在85～90℃下反应,与现有技术相比,本发明的有益效果是：该水性的聚合物/无机纳米粒子复合纳米颗粒及应用,通过对纳米颗粒表面进行包覆,从而使得纳米颗粒之间建立起一道“屏障”,进而降低其化学活性的同时,提高了分散性,保证了纳米颗粒之间不会发生聚合,使得纳米颗粒可以保持稳定性进而保证其使用效果。(The invention discloses an inorganic composite nano-particle of a water-based polymer and application thereof, and the specific operation steps comprise: placing 3-5 parts of polytetrahydrofuran ether glycol, 2-dimethylolpropionic acid and diol containing a dimeric siloxane branched chain into a three-neck flask, stirring, dehydrating under reduced pressure for 2 hours at 120 ℃, and cooling to room temperature; adding 1-2 parts of 4, 4-dicyclohexylmethane diisocyanate into the mixed solution prepared in the first step in sequence, and then adding dibutyltin dilaurate to react at 85-90 ℃, wherein compared with the prior art, the method has the beneficial effects that: according to the water-based polymer/inorganic nanoparticle composite nanoparticles and the application, the surfaces of the nanoparticles are coated, so that a 'barrier' is established between the nanoparticles, the chemical activity of the nanoparticles is reduced, the dispersibility is improved, the nanoparticles are prevented from polymerizing, and the nanoparticles can keep stability and further ensure the using effect.)

1. The water-based polymer inorganic composite nano-particles and the application thereof are characterized in that the specific operation steps comprise:

1) 3-5 parts of polytetrahydrofuran ether glycol, 2-dimethylolpropionic acid and diol containing a dimeric siloxane branched chain are placed in a three-neck flask, stirred, dehydrated under reduced pressure for 2 hours at the temperature of 120 ℃, and cooled to room temperature.

2) And (3) adding 1-2 parts of 4, 4-dicyclohexylmethane diisocyanate into the mixed solution prepared in the first step in sequence, and then adding dibutyltin dilaurate to react at 85-90 ℃.

3) And (3) adding acetone into the mixed solution prepared in the second step, and then adding 1-2 parts of triethylamine for reaction.

4) And (3) adding distilled water into the third step, then dispersing at a high speed, and then adding 1-2 parts of isophorone diamine for reaction for 15 min.

5) Removing acetone under reduced pressure at 60 deg.C to obtain polyurethane containing polysiloxane side chain.

6) Mixing the nano titanium dioxide powder with distilled water, introducing the mixed solution and the solution prepared in the step five into a differential speed reactor, starting the reactor, mixing the nano titanium dioxide powder and the solution under the action of centrifugal force, and enabling the finished product nano crystal particles to leave from an outlet of the reactor.

2. The waterborne polymer-inorganic composite nanoparticle and the application thereof according to claim 1, wherein the water-based polymer-inorganic composite nanoparticle comprises: the relative molecular mass of the polytetrahydrofuran ether glycol in the first step is 2000, the mass fraction of-COOH in the 2, 2-dimethylolpropionic acid is 1%, and the relative molecular masses are 396, 1156, 1773 and 2215.

3. The waterborne polymer-inorganic composite nanoparticle and the application thereof according to claim 1, wherein the water-based polymer-inorganic composite nanoparticle comprises: the reaction time in the second step is 2.5-3 hours, and the reaction time in the third step is 0.5 hour.

4. The waterborne polymer-inorganic composite nanoparticle and the application thereof according to claim 1, wherein the water-based polymer-inorganic composite nanoparticle comprises: the content of the polysiloxane side chain-containing polyurethane obtained in the step five is 35%, and the n (-NCO): n (-OH) ═ 1.3: 1.

5. The aqueous polymer/inorganic nanoparticle composite nanoparticle and the use thereof according to claim 1, wherein: and water distillation in the sixth step: and (3) titanium dioxide is 4-6: 1.

6. The aqueous polymer/inorganic nanoparticle composite nanoparticle and the use thereof according to claim 1, wherein: the centrifugation time in the sixth step is 3 hours, and the centrifugation temperature is 80-110 ℃.

Technical Field

The invention relates to the technical field of nano particles, in particular to an inorganic composite nano particle of a water-based polymer and application thereof.

Background

The aqueous polymer/inorganic nano particle composite nano particle is a new material developed in the last 80 th century, and refers to a composite material with at least one phase of dispersed phase size and one dimension less than 10nm, and because of the small volume of the nano particle, the surface can generate a series of effects to enable the nano particle to have the characteristics of strengthening and toughening, so the nano material is also called as the most promising material in the 21 st century.

However, the existing aqueous polymer/inorganic nanoparticle composite nanoparticles have extremely large surface activity because the particle size of the nanoparticles is extremely small, so that the nanoparticles are polymerized to increase the volume, and the original effect is lost. In order to solve the problems, innovative design based on the original aqueous polymer/inorganic nanoparticle composite nanoparticles is urgently needed.

Disclosure of Invention

The present invention is directed to a waterborne polymer/inorganic nanoparticle composite nanoparticle and an application thereof, and aims to solve the problems of the background art that the surface of the existing waterborne polymer/inorganic nanoparticle composite nanoparticle has a very large activity due to a very small particle size, such that each nanoparticle is polymerized, the volume is increased, and the original effect is lost.

In order to achieve the purpose, the invention provides the following technical scheme: the water-based polymer inorganic composite nano-particles and the application thereof comprise the following concrete operation steps:

1) 3-5 parts of polytetrahydrofuran ether glycol, 2-dimethylolpropionic acid and diol containing a dimeric siloxane branched chain are placed in a three-neck flask, stirred, dehydrated under reduced pressure for 2 hours at the temperature of 120 ℃, and cooled to room temperature.

2) And (3) adding 1-2 parts of 4, 4-dicyclohexylmethane diisocyanate into the mixed solution prepared in the first step in sequence, and then adding dibutyltin dilaurate to react at 85-90 ℃.

3) And (3) adding acetone into the mixed solution prepared in the second step, and then adding 1-2 parts of triethylamine for reaction.

4) And (3) adding distilled water into the third step, then dispersing at a high speed, and then adding 1-2 parts of isophorone diamine for reaction for 15 min.

5) Removing acetone under reduced pressure at 60 deg.C to obtain polyurethane containing polysiloxane side chain.

6) Mixing the nano titanium dioxide powder with distilled water, introducing the mixed solution and the solution prepared in the step five into a differential speed reactor, starting the reactor, mixing the nano titanium dioxide powder and the solution under the action of centrifugal force, and enabling the finished product nano crystal particles to leave from an outlet of the reactor.

Preferably, the relative molecular mass of the polytetrahydrofuran ether glycol in the first step is 2000, the mass fraction of — COOH in the 2, 2-dimethylolpropionic acid is 1%, and the relative molecular masses are 396, 1156, 1773 and 2215.

Preferably, the reaction time in the second step is 2.5-3 h, and the reaction time in the third step is 0.5 h.

Preferably, the polysiloxane side chain-containing polyurethane prepared in the fifth step has an inverse solid content of 35%, and the n (-NCO): n (-OH) ═ 1.3: 1.

Preferably, the distilled water in the sixth step: and (3) titanium dioxide is 4-6: 1.

Preferably, the centrifugation time in the sixth step is 3 hours, and the centrifugation temperature is 80-110 ℃.

Compared with the prior art, the invention has the beneficial effects that: according to the water-based polymer inorganic composite nano-particles and the application thereof, the surfaces of the nano-particles are coated, so that a 'barrier' is established between the nano-particles, the chemical activity of the nano-particles is reduced, the dispersity is improved, the nano-particles are prevented from polymerizing, and the nano-particles can keep the stability and further ensure the using effect of the nano-particles.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Implementing one step:

1) 3-5 parts of polytetrahydrofuran ether glycol, 2-dimethylolpropionic acid and diol containing a dimeric siloxane branched chain are placed in a three-neck flask, stirred, dehydrated under reduced pressure for 2 hours at the temperature of 120 ℃, and cooled to room temperature.

2) And (3) adding 1-2 parts of 4, 4-dicyclohexylmethane diisocyanate into the mixed solution prepared in the first step in sequence, and then adding dibutyltin dilaurate to react at 85-90 ℃.

3) And (3) adding acetone into the mixed solution prepared in the second step, and then adding 1-2 parts of triethylamine for reaction.

4) And (3) adding distilled water into the third step, then dispersing at a high speed, and then adding 1-2 parts of isophorone diamine for reaction for 15 min.

5) Removing acetone under reduced pressure at 60 deg.C to obtain polyurethane containing polysiloxane side chain.

6) Mixing the nano titanium dioxide powder with distilled water, introducing the mixed solution and the solution prepared in the step five into a differential speed reactor, starting the reactor, mixing the nano titanium dioxide powder and the solution under the action of centrifugal force, and enabling the finished product nano crystal particles to leave from an outlet of the reactor.

The second implementation:

1) 3-5 parts of polytetrahydrofuran ether glycol, 2-dimethylolpropionic acid and diol containing a dimeric siloxane branched chain are placed in a three-neck flask, stirred, dehydrated under reduced pressure for 2 hours at the temperature of 120 ℃, and cooled to room temperature.

2) And (3) adding 6-8 parts of 4, 4-dicyclohexylmethane diisocyanate into the mixed solution prepared in the first step in sequence, and then adding dibutyltin dilaurate to react at 85-90 ℃.

3) And (3) adding acetone into the mixed solution prepared in the second step, and then adding 1-2 parts of triethylamine for reaction.

4) And (3) adding distilled water into the third step, then dispersing at a high speed, and then adding 1-2 parts of isophorone diamine for reaction for 15 min.

5) Removing acetone under reduced pressure at 60 deg.C to obtain polyurethane containing polysiloxane side chain.

6) Mixing the nano titanium dioxide powder with distilled water, introducing the mixed solution and the solution prepared in the step five into a differential speed reactor, starting the reactor, mixing the nano titanium dioxide powder and the solution under the action of centrifugal force, and enabling the finished product nano crystal particles to leave from an outlet of the reactor.

And (3) implementation:

1) 3-5 parts of polytetrahydrofuran ether glycol, 2-dimethylolpropionic acid and diol containing a dimeric siloxane branched chain are placed in a three-neck flask, stirred, dehydrated under reduced pressure for 2 hours at the temperature of 120 ℃, and cooled to room temperature.

2) And (3) adding 1-2 parts of 4, 4-dicyclohexylmethane diisocyanate into the mixed solution prepared in the first step in sequence, and then adding dibutyltin dilaurate to react at 85-90 ℃.

3) And D, adding acetone into the mixed solution prepared in the step two, and then adding 5-7 parts of triethylamine for reaction.

4) And (3) adding distilled water into the third step, then dispersing at a high speed, and then adding 1-2 parts of isophorone diamine for reaction for 15 min.

5) Removing acetone under reduced pressure at 60 deg.C to obtain polyurethane containing polysiloxane side chain.

6) Mixing the nano titanium dioxide powder with distilled water, introducing the mixed solution and the solution prepared in the step five into a differential speed reactor, starting the reactor, mixing the nano titanium dioxide powder and the solution under the action of centrifugal force, and enabling the finished product nano crystal particles to leave from an outlet of the reactor.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.