CN103936921A - Method for synthesizing polymeric microspheres by water-in-water way - Google Patents
Method for synthesizing polymeric microspheres by water-in-water way Download PDFInfo
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Abstract
The invention discloses a method for synthesizing polymeric microspheres by the water-in-water way. The method comprises the following steps: (1) dissolving water-soluble monomers, sodium acrylate and polymethacryloyloxyethyltrimenylammonium chloride in water and stirring the materials uniformly; (2) adding oil-soluble initiators and N,N-dimethylbisacrylamide to a system in the step (1) and further stirring the materials; (3) heating a system in the step (2) to 70-80 DEG C, thereby obtaining the polymeric microspheres through polymerization reaction. The method has the characteristics that ternary random copolymerization is carried out on the water-soluble monomer acrylamide (AM), sodium acrylate and N,N-dimethylbisacrylamide by the water-in-water way by utilizing the oil-soluble initiators and using polymethacryloyloxyethyltrimenylammonium chloride as a dispersing agent to form the polymeric microspheres. The method for preparing the polymer microsphere materials, which is provided by the invention, is simple and convenient in process, is easy to operate and is low in production cost.
Description
Technical field
The present invention relates to a kind of method of water bag water mode synthetic polymer microballoon.
Background technology
Polymer microsphere refer to diameter at nano level to micron order, be shaped as macromolecular material or the polymer composite of spherical or other solid.The research of polymeric microball material and application developed very fast in recent years, and due to special pattern and size, polymer microsphere possesses the not available specific function of other material.The application of polymer microsphere has been penetrated into each corner of people's life, from bulk products such as coating, paper surface coating, makeup, be all applied to polymeric microball material to the micro-capsule for medicament slow release control, protein separation by the high added value of chromatography media.Adopt at present the methods such as letex polymerization, micro-emulsion polymerization, conversed phase micro emulsion copolymerization, suspension polymerization to prepare polymer microballoon, in preparation process, use oil phase as foreign minister, safety problem in use easily occurs, cause cost high simultaneously, product stability is poor.
Summary of the invention
A kind of method that the object of this invention is to provide water bag water mode synthetic polymer microballoon, method of the present invention does not need oil phase, adopts the polymerization methods of water Bao Shui, sintetics water is foreign minister, and security is good, and cost is lower simultaneously, synthesis technique is simple, is easy to suitability for industrialized production.
The method of a kind of water bag water mode synthetic polymer microballoon provided by the present invention, comprises the steps:
(1) by soluble in water to water-soluble monomer, sodium acrylate and polymethyl acyl-oxygen ethyl-trimethyl salmiac, and stir;
(2) in the system of step (1), add oil-soluble initiator and N, N-dimethyl bisacrylamide, proceeds to stir;
(3) system to 70～80 DEG C of heating steps (2), obtain polymer microballoon through polyreaction.
In the method for above-mentioned water bag water mode synthetic polymer microballoon, in step (1), described water-soluble monomer can be at least one in acrylamide, acrylate and vinylcarbinol.
In the method for above-mentioned water bag water mode synthetic polymer microballoon, in step (1), the mass ratio of described water-soluble monomer, described sodium acrylate, described polymethyl acyl-oxygen ethyl-trimethyl salmiac and described water can be 15～20:4～5:0.8～1.2:80～100, specifically can be 15:4:0.8:80,20:5:1.0:100,18:6:1.2:90;
Described polymethyl acyl-oxygen ethyl-trimethyl salmiac is as dispersion agent.
In the method for above-mentioned water bag water mode synthetic polymer microballoon, in step (1), the rotating speed of described stirring can be 10000～15000r/min, and the time of described stirring can be 30～60min, and described stirring can be carried out under temperature is the condition of 45～50 DEG C.
In the method for above-mentioned water bag water mode synthetic polymer microballoon, in step (2), described oil-soluble initiator is selected from least one in Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO), azo-bis-isobutyrate hydrochloride (V-50 initiator), dialkyl, peroxidation two acyls, tertiary amine and naphthenate;
Described oil-soluble initiator, described N, the mass ratio of N-dimethyl bisacrylamide and described water-soluble monomer can be 0.015～0.020:0.05～0.1:15～20, specifically can be 0.015:0.05:20,0.018:0.1:20,0.018:0.75:18 or 0.02:0.05:15;
Described N, N-dimethyl bisacrylamide is as linking agent.
In the method for above-mentioned water bag water mode synthetic polymer microballoon, in step (2), the rotating speed of described stirring is 10000～15000r/min.
In the method for above-mentioned water bag water mode synthetic polymer microballoon, in step (2), the time of described polyreaction can be 6～8 hours;
Described polyreaction can be carried out under the stirring velocity of 10000～15000r/min.
The method of water bag water mode synthetic polymer microballoon provided by the invention, has following characteristics:
1) the present invention utilizes oil-soluble initiator, taking polymethyl acyl-oxygen ethyl-trimethyl salmiac as dispersion agent, by water-soluble monomer acrylamide AM and sodium acrylate and N, N-dimethyl bisacrylamide, forms polymer microballoon with the mode ternary random copolymerization of water Bao Shui.
2) method of preparing polymeric microball material provided by the invention, simple process, easy handling, production cost is low.
3) the polymer microballoon size that prepared by the present invention distributes at 50nm～500nm.
Brief description of the drawings
Fig. 1 is the distribution of sizes of the polymer microballoon prepared of the embodiment of the present invention 1 water bag water method.
Fig. 2 is the stereoscan photograph of the polymer microballoon prepared of the embodiment of the present invention 1 water bag water method.
Fig. 3 is the distribution of sizes of the polymer microballoon prepared of the embodiment of the present invention 2 water bag water methods.
Fig. 4 is the stereoscan photograph of the polymer microballoon prepared of the embodiment of the present invention 2 water bag water methods.
Fig. 5 is the distribution of sizes of the polymer microballoon prepared of the embodiment of the present invention 3 water bag water methods.
Fig. 6 is the distribution of sizes of the polymer microballoon prepared of the embodiment of the present invention 4 water bag water methods.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Embodiment 1, water bag water method are prepared polymer microballoon
1) 15g acrylamide, 4g sodium acrylate and 0.8g dispersion agent polymethyl acyl-oxygen ethyl-trimethyl salmiac are dissolved in to 80g water, stir 30min, temperature is 45 DEG C;
2) in above-mentioned solution, add oil-soluble initiator benzoyl peroxide (BPO) 0.020g and N, N-dimethyl bisacrylamide crosslinker 0.05g, mixing speed is 10000r/min, temperature is 50 DEG C.
3), by above-mentioned solution rising temperature to 70 DEG C and be incubated 8 hours, mixing speed is 10000r/min, obtains the polymer microballoon that the hydration of water bag becomes.
Fig. 1 is polymer microballoon distribution of sizes prepared by the present embodiment, can be learnt by this figure, and the diameter dimension of polymer microballoon prepared by the present embodiment is 100～500nm; Its stereoscan photograph as shown in Figure 2.
Embodiment 2, water bag water method are prepared polymer microballoon
1) 20g acrylamide, 5g sodium acrylate and 1.0g dispersion agent polymethyl acyl-oxygen ethyl-trimethyl salmiac are dissolved in to 100g water, stir 60min, temperature is 50 DEG C;
2) in above-mentioned solution, add oil-soluble initiator Diisopropyl azodicarboxylate (AIBN) 0.015g and N, N-dimethyl bisacrylamide crosslinker 0.05g, mixing speed is 10000r/min, temperature of reaction is 50 DEG C.
3), by above-mentioned solution rising temperature to 90 DEG C and be incubated 6 hours, mixing speed is 15000r/min, obtains polymer microballoon.
Fig. 2 is the distribution of sizes of the polymer microballoon prepared of the present embodiment, can be learnt by this figure, and the diameter dimension of polymer microballoon prepared by the present embodiment is at 100～500nm, and its stereoscan photograph as shown in Figure 4.
Embodiment 3, water bag water method are prepared polymer microballoon
1) 20g acrylamide, 5g sodium acrylate and 1.0g dispersion agent polymethyl acyl-oxygen ethyl-trimethyl salmiac are dissolved in to 100g water, stir 60min, temperature is 50 DEG C;
2) in above-mentioned solution, add oil-soluble initiator azo-bis-isobutyrate hydrochloride (V-50 initiator) 0.018g and N, N-dimethyl bisacrylamide crosslinker 0.1g, mixing speed is 15000r/min, 50 DEG C of temperature of reaction.
3), by above-mentioned solution rising temperature to 85 DEG C and be incubated 7 hours, mixing speed is 12000r/min, obtains polymer microballoon.
Fig. 3 is the distribution of sizes of the polymer microballoon prepared of the present embodiment, can be learnt by this figure, and the diameter dimension of polymer microballoon prepared by the present embodiment is at 50～300nm.
Embodiment 4, water bag water method are prepared polymer microballoon
1) 18g acrylamide, 6g sodium acrylate and 1.2g dispersion agent polymethyl acyl-oxygen ethyl-trimethyl salmiac are dissolved in to 90g water, stir 45min, temperature is 50 DEG C;
2) in above-mentioned solution, add oil-soluble initiator dialkyl 0.018g and N, N-dimethyl bisacrylamide crosslinker 0.75g, mixing speed is 10000r/min, temperature of reaction is 50 DEG C.
3), by above-mentioned solution rising temperature to 90 DEG C and be incubated 7 hours, mixing speed is 15000r/min, obtains polymer microballoon.
Fig. 4 is the ball distribution of sizes of the micro polymer prepared of the present embodiment, can be learnt by this figure, and the diameter dimension of polymer microballoon prepared by the present embodiment is at 50～200nm.
Claims (7)
1. a method for water bag water mode synthetic polymer microballoon, comprises the steps:
(1) by soluble in water to water-soluble monomer, sodium acrylate and polymethyl acyl-oxygen ethyl-trimethyl salmiac, and stir;
(2) in the system of step (1), add oil-soluble initiator and N, N-dimethyl bisacrylamide, proceeds to stir;
(3) system to 70～80 DEG C of heating steps (2), obtain polymer microballoon through polyreaction.
2. method according to claim 1, is characterized in that: in step (1), described water-soluble monomer is at least one in acrylamide, acrylate and vinylcarbinol.
3. method according to claim 1 and 2, it is characterized in that: in step (1), the mass ratio of described water-soluble monomer, described sodium acrylate, described polymethyl acyl-oxygen ethyl-trimethyl salmiac and described water is 15～20:4～5:0.8～1.2:80～100.
4. according to the method described in any one in claim 1-3, it is characterized in that: in step (1), the rotating speed of described stirring is 10000～15000r/min, and the time of described stirring is 30～60min, described in to be stirred in temperature be to carry out under the condition of 45～50 DEG C.
5. according to the method described in any one in claim 1-4, it is characterized in that: in step (2), described oil-soluble initiator is selected from least one in Diisopropyl azodicarboxylate, benzoyl peroxide, azo-bis-isobutyrate hydrochloride, dialkyl, peroxidation two acyls, tertiary amine and naphthenate;
Described oil-soluble initiator, described N, the mass ratio of N-dimethyl bisacrylamide and described water-soluble monomer is 0.015～0.020:0.05～0.1:15～20.
6. according to the method described in any one in claim 1-5, it is characterized in that: in step (2), the rotating speed of described stirring is 10000～15000r/min;
The described temperature that is stirred in is to carry out under the condition of 50～55 DEG C.
7. according to the method described in any one in claim 1-6, it is characterized in that: in step (2), the time of described polyreaction is 6～8 hours;
Described polyreaction is carried out under the stirring velocity of 10000～15000r/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684421A (en) * | 2019-07-18 | 2020-01-14 | 浙江省海洋开发研究院 | Surface microstructure self-polishing antifouling coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362827A (en) * | 1986-09-08 | 1994-11-08 | Exxon Research & Engineering Co. | Solution process for preparation hydrophobically functionalized cationic polymers (C-2691) |
| CN1834125A (en) * | 2005-03-18 | 2006-09-20 | 中国科学院理化技术研究所 | Template copolymerization synthesis method of semi-interpenetrating network reversible pH sensitive hydrogel |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362827A (en) * | 1986-09-08 | 1994-11-08 | Exxon Research & Engineering Co. | Solution process for preparation hydrophobically functionalized cationic polymers (C-2691) |
| CN1834125A (en) * | 2005-03-18 | 2006-09-20 | 中国科学院理化技术研究所 | Template copolymerization synthesis method of semi-interpenetrating network reversible pH sensitive hydrogel |
Non-Patent Citations (2)
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| 刘含雷 等: "两性聚丙烯酰胺水分散体系的制备", 《青岛科技大学学报(自然科学版)》, vol. 31, no. 4, 31 August 2010 (2010-08-31), pages 371 - 375 * |
| 吉春艳 等: "分散聚合法制备两性聚丙烯酰胺"水包水"乳液絮凝剂", 《石油化工》, vol. 43, no. 1, 31 January 2014 (2014-01-31), pages 61 - 67 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684421A (en) * | 2019-07-18 | 2020-01-14 | 浙江省海洋开发研究院 | Surface microstructure self-polishing antifouling coating and preparation method thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation |
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