CN103936921B - A kind of method of water-water mode synthetic polymer microballoon - Google Patents
A kind of method of water-water mode synthetic polymer microballoon Download PDFInfo
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- CN103936921B CN103936921B CN201410160246.5A CN201410160246A CN103936921B CN 103936921 B CN103936921 B CN 103936921B CN 201410160246 A CN201410160246 A CN 201410160246A CN 103936921 B CN103936921 B CN 103936921B
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Abstract
A kind of method that the invention discloses water-water mode synthetic polymer microballoon.The method comprises the steps: that (1), by soluble in water to water-soluble monomer, PAA and polymethyl acyloxyethyl trimethyl ammonium chloride, and stirs；(2) in the system of step (1), add oil-soluble initiator and N, N bismethacrylamide, proceed stirring；(3) system of heating steps (2) is to 70～80 DEG C, and aggregated reaction i.e. obtains polymer microballoon.The present invention utilizes oil-soluble initiator, and with polymethyl acyloxyethyl trimethyl ammonium chloride as dispersant, by water-soluble monomer acrylamide AM and PAA and N, N bismethacrylamide, in the way of water-water, ternary random copolymerization forms polymer microballoon.The method preparing polymeric microball material that the present invention provides, simple process, it is easy to operation, production cost is low.
Description
Technical field
A kind of method that the present invention relates to water-water mode synthetic polymer microballoon.
Background technology
Polymer microsphere refers to that diameter, at nanoscale to micron order, is shaped as the spherical or macromolecular material of other solid
Or polymer composite.Research and the application of polymeric microball material developed very fast, due to special in recent years
Pattern and size, polymer microsphere possesses the specific function not available for other material.The application of polymer microsphere is
Through penetrating into each corner of people's life, from bulk products such as coating, paper surface coating, cosmetics, to using
Micro-capsule, the high added value of Separation of Proteins chromatography media in medicament slow release control have been applied to polymer microsphere material
Material.The methods such as emulsion polymerization, micro-emulsion polymerization, conversed phase micro emulsion copolymerization, suspension polymerisation are used to prepare polymer at present
Microballoon, uses oil phase as foreign minister in preparation process, is in use susceptible to safety problem, also results in
Cost is high, and product stability is poor.
Summary of the invention
A kind of method that it is an object of the invention to provide water-water mode synthetic polymer microballoon, the method for the present invention is not required to
Wanting oil phase, use the polymerization methods of water-water, sintetics water is foreign minister, and security is good, and cost is relatively low simultaneously, closes
Become technique simple, it is easy to industrialized production.
The method of a kind of water-water mode synthetic polymer microballoon provided by the present invention, comprises the steps:
(1) by soluble in water to water-soluble monomer, PAA and polymethyl acyloxyethyl trimethyl ammonium chloride,
And stir；
(2) in the system of step (1), add oil-soluble initiator and N, N-bismethacrylamide, continue into
Row stirring；
(3) system of heating steps (2) is to 70～80 DEG C, and aggregated reaction i.e. obtains polymer microballoon.
In the method for above-mentioned water-water mode synthetic polymer microballoon, in step (1), described water-soluble monomer can be
In acrylamide, acrylate and propenyl at least one.
In the method for above-mentioned water-water mode synthetic polymer microballoon, in step (1), described water-soluble monomer, institute
Stating PAA, described polymethyl acyloxyethyl trimethyl ammonium chloride can be 15～20 with the mass ratio of described water:
4～5:0.8～1.2:80～100, concretely 15:4:0.8:80,20:5:1.0:100,18:6:1.2:
90；
Described polymethyl acyloxyethyl trimethyl ammonium chloride is as dispersant.
In the method for above-mentioned water-water mode synthetic polymer microballoon, in step (1), the rotating speed of described stirring can be
10000～15000r/min, the time of described stirring can be 30～60min, and described stirring can be 45～50 DEG C in temperature
Under the conditions of carry out.
In the method for above-mentioned water-water mode synthetic polymer microballoon, in step (2), described oil-soluble initiator selects
From azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO), azo-bis-isobutyrate hydrochloride, (V-50 causes
Agent), dialkyl, peroxidating two acyl, in tertiary amine and naphthenate at least one；
Described oil-soluble initiator, described N, N-bismethacrylamide with the mass ratio of described water-soluble monomer can be
0.015～0.020:0.05～0.1:15～20, concretely 0.015:0.05:20,0.018:0.1:20,0.018:
0.75:18 or 0.02:0.05:15；
Described N, N-bismethacrylamide is as crosslinking agent.
In the method for above-mentioned water-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-water mode synthetic polymer microballoon, in step (2), the time of described polymerisation
It can be 6～8 hours；
Described polymerisation can be carried out under the mixing speed of 10000～15000r/min.
The method of the water-water mode synthetic polymer microballoon that the present invention provides, has the following characteristics that
1) present invention utilizes oil-soluble initiator, with polymethyl acyloxyethyl trimethyl ammonium chloride as dispersant,
By water-soluble monomer acrylamide AM and PAA and N, N-bismethacrylamide, in the way of water-water three
Unit's random copolymerization forms polymer microballoon.
2) method preparing polymeric microball material that the present invention provides, simple process, it is easy to operation, production cost
Low.
3) the polymer microballoon size that prepared by the present invention is distributed at 50nm～500nm.
Accompanying drawing explanation
Fig. 1 is the Size Distribution of polymer microballoon prepared by the embodiment of the present invention 1 water-water method.
Fig. 2 is the stereoscan photograph of polymer microballoon prepared by the embodiment of the present invention 1 water-water method.
Fig. 3 is the Size Distribution of polymer microballoon prepared by the embodiment of the present invention 2 water-water method.
Fig. 4 is the stereoscan photograph of polymer microballoon prepared by the embodiment of the present invention 2 water-water method.
Fig. 5 is the Size Distribution of polymer microballoon prepared by the embodiment of the present invention 3 water-water method.
Fig. 6 is the Size Distribution of polymer microballoon prepared by the embodiment of the present invention 4 water-water method.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
Embodiment 1, water-water method prepare polymer microballoon
1) by 15g acrylamide, 4g PAA and 0.8g dispersant polymethyl acyloxyethyl trimethyl ammonia chloride
Ammonium is dissolved in 80g water, stirs 30min, and temperature is 45 DEG C；
2) in above-mentioned solution, oil-soluble initiator benzoyl peroxide (BPO) 0.020g and N, N-dimethyl is added
Bisacrylamide crosslinker 0.05g, speed of agitator is 10000r/min, and temperature is 50 DEG C.
3) to 70 DEG C and above-mentioned solution liter high-temperature being incubated 8 hours, speed of agitator is 10000r/min, obtains water
The polymer microballoon that bag is hydrated.
Fig. 1 is polymer microballoon Size Distribution prepared by the present embodiment, by this figure it is known that prepared by the present embodiment
The diameter dimension of polymer microballoon is 100～500nm；Its stereoscan photograph is as shown in Figure 2.
Embodiment 2, water-water method prepare polymer microballoon
1) by 20g acrylamide, 5g PAA and 1.0g dispersant polymethyl acyloxyethyl trimethyl ammonia chloride
Ammonium is dissolved in 100g water, stirs 60min, and temperature is 50 DEG C；
2) in above-mentioned solution, oil-soluble initiator azodiisobutyronitrile (AIBN) 0.015g and N, N-dimethyl is added
Bisacrylamide crosslinker 0.05g, speed of agitator is 10000r/min, and reaction temperature is 50 DEG C.
3) to 90 DEG C and above-mentioned solution liter high-temperature being incubated 6 hours, speed of agitator is 15000r/min, is gathered
Compound microballoon.
Fig. 2 is the Size Distribution of polymer microballoon prepared by the present embodiment, by this figure it is known that prepared by the present embodiment
The diameter dimension of polymer microballoon 100～500nm, its stereoscan photograph is as shown in Figure 4.
Embodiment 3, water-water method prepare polymer microballoon
1) by 20g acrylamide, 5g PAA and 1.0g dispersant polymethyl acyloxyethyl trimethyl ammonia chloride
Ammonium is dissolved in 100g water, stirs 60min, and temperature is 50 DEG C；
2) in above-mentioned solution, oil-soluble initiator azo-bis-isobutyrate hydrochloride (V-50 initiator) 0.018g is added
And N, N-bismethacrylamide crosslinking agent 0.1g, speed of agitator is 15000r/min, reaction temperature 50 DEG C.
3) to 85 DEG C and above-mentioned solution liter high-temperature being incubated 7 hours, speed of agitator is 12000r/min, is gathered
Compound microballoon.
Fig. 3 is the Size Distribution of polymer microballoon prepared by the present embodiment, by this figure it is known that prepared by the present embodiment
The diameter dimension of polymer microballoon 50～300nm.
Embodiment 4, water-water method prepare polymer microballoon
1) by 18g acrylamide, 6g PAA and 1.2g dispersant polymethyl acyloxyethyl trimethyl ammonia chloride
Ammonium is dissolved in 90g water, stirs 45min, and temperature is 50 DEG C；
2) in above-mentioned solution, add oil-soluble initiator dialkyl 0.018g and the double acryloyl of N, N-dimethyl
Amine crosslinker 0.75g, speed of agitator is 10000r/min, and reaction temperature is 50 DEG C.
3) to 90 DEG C and above-mentioned solution liter high-temperature being incubated 7 hours, speed of agitator is 15000r/min, is gathered
Compound microballoon.
Fig. 4 is the ball Size Distribution that polymer prepared by the present embodiment is micro-, by this figure it is known that prepared by the present embodiment
The diameter dimension of polymer microballoon 50～200nm.
Claims (7)
1. a method for water-water mode synthetic polymer microballoon, comprises the steps:
(1) water-soluble monomer, PAA and polymethyl acyloxyethyl trimethyl ammonium chloride are dissolved in water
In, and stir；
Described water-soluble monomer, described PAA, described polymethyl acyloxyethyl trimethyl ammonium chloride with
The mass ratio of described water is 15～20:4～5:0.8～1.2:80～100；
(2) in the system of step (1), oil-soluble initiator and N, N-bismethacrylamide are added,
Proceed stirring；
(3) system of heating steps (2) is to 70～80 DEG C, and aggregated reaction i.e. obtains polymer microballoon.
Method the most according to claim 1, it is characterised in that: in step (1), described water-soluble mono
Body is at least one in acrylamide and propenyl.
Method the most according to claim 1 and 2, it is characterised in that: in step (1), described stirring
Rotating speed be 10000～15000r/min, the time of described stirring is 30～60min, and described stirring in temperature is
Carry out under conditions of 45～50 DEG C.
Method the most according to claim 1 and 2, it is characterised in that: in step (2), described oil soluble
Property initiator in azodiisobutyronitrile, dialkyl, peroxidating two acyl, tertiary amine and naphthenate extremely
Few one；
The quality of described oil-soluble initiator, described N, N-bismethacrylamide and described water-soluble monomer
Ratio is 0.015～0.020:0.05～0.1:15～20.
Method the most according to claim 4, it is characterised in that: described peroxidating two acyl is benzoyl peroxide
Formyl.
Method the most according to claim 1 and 2, it is characterised in that: in step (2), described stirring
Rotating speed be 10000～15000r/min；
Described stirring is carried out under conditions of temperature is 50～55 DEG C.
Method the most according to claim 1 and 2, it is characterised in that: in step (2), described polymerization
The time of reaction is 6～8 hours；
Described polymerisation is carried out under the mixing speed of 10000～15000r/min.
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| CN201410160246.5A CN103936921B (en) | 2014-04-21 | 2014-04-21 | A kind of method of water-water mode synthetic polymer microballoon |
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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 copolymerizing synthetic process of semi-intercrossing network reversible pH sensitive aquagel |
-
2014
- 2014-04-21 CN CN201410160246.5A patent/CN103936921B/en active Active
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 copolymerizing synthetic process of semi-intercrossing network reversible pH sensitive aquagel |
Non-Patent Citations (2)
| Title |
|---|
| 两性聚丙烯酰胺水分散体系的制备;刘含雷 等;《青岛科技大学学报(自然科学版)》;20100831;第31卷(第4期);第371-375页 * |
| 分散聚合法制备两性聚丙烯酰胺"水包水"乳液絮凝剂;吉春艳 等;《石油化工》;20140131;第43卷(第1期);第61-67页 * |
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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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