阅读说明：本技术 一种高效节能合成亚微米级pmma微球的方法 (A kind of method of energy-efficient synthesizing submicron PMMA microsphere ) 是由 于青 解传宝 王忠卫 生杰 王雪梅 沈洪宁 顾亚楠 刘宗茹 于 2019-07-17 设计创作，主要内容包括：本发明公开一种高效节能合成亚微米级PMMA微球的方法,包括以下步骤：(1)选取甲基丙烯酸甲酯、酰基氧化膦类光引发剂、分散剂和溶剂为反应原料,先将酰基氧化膦类光引发剂和分散剂依次加入到反应容器中,然后加入溶剂,搅拌均匀；(2)再将甲基丙烯酸甲酯加入到反应容器中,搅拌3-10分钟,然后用LED灯照射,进行反应；(3)反应完成后,分离、洗涤固体物质,干燥后得到亚微米级PMMA微球。本发明以节能的LED灯为光源,将其与酰基氧化膦类光引发剂配合用于亚微米级PMMA微球的光聚合制备中,相比于其他的制备方法,大大降低了能耗。该方法还具有工艺简单,易于操作,成本低,反应迅速等优点,可以满足当前日益增长的市场需求。(A kind of method that the present invention discloses energy-efficient synthesizing submicron PMMA microsphere; the following steps are included: it is reaction raw materials that (1), which chooses methyl methacrylate, acylphosphine oxide photoinitiator, dispersing agent and solvent; first acylphosphine oxide photoinitiator and dispersing agent are added sequentially in reaction vessel; then solvent is added, stirs evenly；(2) methyl methacrylate is added in reaction vessel again, stirs 3-10 minutes, is then irradiated, reacted with LED light；(3) after the reaction was completed, separation, washed solid obtain submicron order PMMA microsphere after dry.The present invention is used in the photopolymerization preparation of submicron order PMMA microsphere using energy-efficient LED light as light source, by it with the cooperation of acylphosphine oxide photoinitiator, compared to other preparation methods, greatly reduces energy consumption.The advantages that this method also has simple process, easily operated, at low cost, is swift in response can satisfy current ever-increasing market demand.)

1. a kind of method of energy-efficient synthesizing submicron PMMA microsphere, it is characterised in that: select energy-efficient LED light as light It is micro- to synthesize PMMA under the collective effect of efficient photoinitiator and dispersing agent in room temperature, solution system for the light source for causing synthesis Ball；Specific synthesis step is as follows:

(1) choosing methyl methacrylate, acylphosphine oxide photoinitiator, dispersing agent and solvent is reaction raw materials, first by acyl Base phosphinoxides photoinitiator and dispersing agent are added sequentially in reaction vessel, and solvent is then added, and are stirred evenly；

(2) methyl methacrylate is added in reaction vessel again, stirs 3-10 minutes, is then irradiated with LED light, carried out anti- It answers；

(3) after the reaction was completed, separation, washed solid obtain submicron order PMMA microsphere after dry.

2. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute It states acylphosphine oxide photoinitiator and selects 2,4,6- trimethylbenzoy-dipheny phosphine oxide or bis- (2,4,6- trimethyls Benzoyl) phenyl phosphine oxide.

3. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute The mass ratio for stating methyl methacrylate and acylphosphine oxide photoinitiator is 50-200: 1.

4. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute It states dispersing agent and selects polyvinylpyrrolidone.

5. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute The mass ratio for stating dispersing agent and methyl methacrylate is 1-6: 10.

6. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute Solvent is stated as the mixed solvent of alcohols and water composition, the mass ratio of mixed solvent and methyl methacrylate is 5-20: 1.

7. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 6, it is characterised in that: institute It states alcohols and is selected from methanol, ethyl alcohol or butanol, the mass ratio of in the mixed solvent alcohols and water is 2: 3.

8. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute The temperature for stating stirring and reaction process is 15-30 DEG C.

9. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: institute The wavelength for stating LED light is 360-450nm；The irradiation time of LED light is 30-60 minutes.

10. a kind of method of energy-efficient synthesizing submicron PMMA microsphere according to claim 1, it is characterised in that: The separation method is centrifugation or filters；Washing methods is washed 1~3 time for washing 1~3 time, alcohol；Drying means is that room temperature is dried in the air naturally It is dry.

Technical field

The present invention relates to photocuring technology fields, and in particular to a kind of side of energy-efficient synthesizing submicron PMMA microsphere Method.

Background technique

Polymer microballoon is a kind of new material grown rapidly in recent years, because of its special structure and performance, is answered extensively For being catalyzed, biological medicine, chromatographic column filling etc..The preparation method of polymer microballoon is always popular research in recent years One of direction.Polymer microballoon mostly uses thermal polymerization method or light polymerization process to be prepared at present.Wherein, thermal polymerization method is more Select initiator, stabilizer and ultrasonic wave collective effect condition, but this method need at relatively high temperatures (general 70 DEG C with On) reaction, and the reaction time is longer.Compared with thermal polymerization method, photopolymerization (photocuring) consume energy less, pollution it is small and to reaction item Part requirement is low, therefore is a kind of more preferably method for preparing polymer micro.Currently, most of photopolymerization prepares the side of microballoon The problems such as there are still reaction process complexity, pollutions for method greatly, energy consumption is high, the use of RAFT reagent.In addition, gathering obtained by existing method Closing object microballoon is mostly micron order, and it is micro- to the polymer of different-grain diameter that this is also less able to satisfy the fields such as biomedicine, chromatographic isolation The demand of ball.

Summary of the invention

Based on above-mentioned technical problem, a kind of method that the present invention proposes energy-efficient synthesizing submicron PMMA microsphere should Method, which is irradiated using LED light source and acylphosphine oxide class initiator is cooperated to cause photopolymerization, prepares microballoon, and operating procedure is simple, instead Mild condition, environmental protection and energy saving, and the present invention is answered to synthesize the PMMA microsphere of submicron order.

The adopted technical solution is that:

A kind of method of energy-efficient synthesizing submicron PMMA microsphere selects energy-efficient LED light as light-initiated conjunction At light source synthesize PMMA microsphere in room temperature, solution system under the collective effect of efficient photoinitiator and dispersing agent；Tool Body synthesis step is as follows:

(1) choosing methyl methacrylate, acylphosphine oxide photoinitiator, dispersing agent and solvent is reaction raw materials, first Acylphosphine oxide photoinitiator and dispersing agent are added sequentially in reaction vessel (such as there-necked flask, single port bottle, quartz ampoule), Then solvent is added, stirs evenly；

(2) methyl methacrylate is added in reaction vessel again, stirs 3-10 minutes, is then irradiated with LED light, into Row reaction；

(3) after the reaction was completed, separation, washed solid obtain submicron order PMMA microsphere after dry.

Preferably, the acylphosphine oxide photoinitiator selects 2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) or bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides (819).

Preferably, the mass ratio of the methyl methacrylate and acylphosphine oxide photoinitiator is 50-200: 1.

Preferably, the dispersing agent selects polyvinylpyrrolidone (PVP).

Preferably, the mass ratio of the dispersing agent and methyl methacrylate is 1-6: 10.

Preferably, the solvent is the mixed solvent of alcohols and water composition, the matter of mixed solvent and methyl methacrylate Amount is than being 5-20: 1.

Preferably, the alcohols is selected from methanol, ethyl alcohol or butanol, and the mass ratio of in the mixed solvent alcohols and water is 2: 3.

Preferably, the temperature of the stirring and reaction process is 15-30 DEG C.

Preferably, the wavelength of the LED light is 360-450nm；The irradiation time of LED light is 30-60 minutes.

Preferably, the separation method is centrifugation or filters；Washing methods is washed 1~3 time for washing 1~3 time, alcohol；It is dry Method is room temperature naturally dry.

The method have the benefit that:

The present invention is used for PMMA microsphere with the cooperation of acylphosphine oxide photoinitiator using energy-efficient LED light as light source, by it Photopolymerization preparation in, compared to other preparation methods, greatly reduce energy consumption.This method also has simple process, is easy to Operation, it is at low cost, it is low to reaction condition requirement, the advantages that being swift in response, it can satisfy current ever-increasing market demand.

Between 0.4 μm -1.0 μm, favorable dispersibility, microballoon yield reaches object PMMA microsphere particle size of the present invention 90% or more.The submicron order PMMA microsphere of preparation can be used as the carrier of catalyst, the filler of chromatographic column and medical drugs The carrier etc. of object is a kind of polymer material of function admirable.The present invention also extends application range (the different grains of PMMA microsphere Diameter, unlike material microballoon have different performance and application).

Photopolymerization is caused using LED light cooperation acylphosphine oxide class initiator in the application and prepares microballoon, compared to general For needing Macro RAFT agent and PVP cooperation to make the finely dispersed method of PMMA microsphere as dispersing agent, the application is only Needing PVP to do dispersing agent can be obtained evenly dispersed PMMA microsphere, and which reduce the dosages of organic reagent.In addition, the application By stirring disperse monomer in a solvent more uniform in advance, and then make the PMMA microsphere uniform particle diameter of preparation；Pass through conjunction The dosage of suitable dispersing agent PVP and photoinitiator TPO make whole system form the suitable uniform system of a proportion, improve PMMA Microballoon yield；In addition, the particle size of microballoon is controlled by the amount ratio of alcohols and water in cooperation control solvent, it is final to prepare Obtain submicron order PMMA microsphere.

Detailed description of the invention

Fig. 1 is scanning electron microscope (SEM) photo of PMMA microsphere obtained by embodiment 1.

Specific embodiment

It is complicated for reaction process present in traditional ultraviolet curing process, pollution is big, energy consumption is high, RAFT reagent using etc. ask Topic, the present invention provides a kind of methods for preparing PMMA microsphere at room temperature, without RAFT reagent photopolymerization.The present invention uses LED Lamp is used in the photopolymerization preparation of PMMA microsphere as light source, by it with the cooperation of acylphosphine oxide photoinitiator, one side LED The use of lamp reduces pollution and energy consumption, and another aspect operation of the present invention step is simple, and reaction condition is mild, and environmental protection and energy saving are right The industrialized production of PMMA microsphere has positive effect.Moreover, submicron order PMMA microsphere can be made in the present invention, PMMA is extended The application range of microballoon.

The present invention is further explained in the light of specific embodiments.