CN1341667A - Method for initiating polymerization of microemulsion by means of ultrasonic wave - Google Patents
Method for initiating polymerization of microemulsion by means of ultrasonic wave Download PDFInfo
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- CN1341667A CN1341667A CN 00113154 CN00113154A CN1341667A CN 1341667 A CN1341667 A CN 1341667A CN 00113154 CN00113154 CN 00113154 CN 00113154 A CN00113154 A CN 00113154A CN 1341667 A CN1341667 A CN 1341667A
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- China
- Prior art keywords
- ultrasonic wave
- ultrasonic
- sodium
- microemulsion polymerization
- microemulsion
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- 230000000977 initiatory effect Effects 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 11
- 238000006116 polymerization reaction Methods 0.000 title claims description 8
- 239000004530 micro-emulsion Substances 0.000 title abstract description 7
- 238000012703 microemulsion polymerization Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- -1 1-40 parts Substances 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical group FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 2
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000004147 Sorbitan trioleate Substances 0.000 claims 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 229940080236 sodium cetyl sulfate Drugs 0.000 claims 1
- KNOGXLBAOQDKTG-UHFFFAOYSA-M sodium;2-ethylhexane-1-sulfonate Chemical compound [Na+].CCCCC(CC)CS([O-])(=O)=O KNOGXLBAOQDKTG-UHFFFAOYSA-M 0.000 claims 1
- 235000019337 sorbitan trioleate Nutrition 0.000 claims 1
- 229960000391 sorbitan trioleate Drugs 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 239000004816 latex Substances 0.000 abstract description 4
- 229920000126 latex Polymers 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 2
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000036031 hyperthermia Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Polymerisation Methods In General (AREA)
Abstract
超声波引发微乳液聚合的方法,其特点是利用超声波的分散、乳化、引发等作用,在较低温度和无需引发剂的情况下实现微乳液聚合,制备粒径分布均匀,尺寸在30nm－100nm的乳胶粒。Ultrasonic-induced microemulsion polymerization, which is characterized by the use of ultrasonic dispersion, emulsification, initiation, etc., to achieve microemulsion polymerization at a lower temperature and without the need for an initiator, and to prepare microemulsions with uniform particle size distribution and a size of 30nm-100nm. Latex particles.
Description
The present invention relates to a kind of method of initiating polymerization of microemulsion by means of ultrasonic wave.
Polymer nano material has extremely important application at aspects such as stealth material, information material, high-performance coating and bio-medical materials.Micro-emulsion polymerization is one of important method of preparation polymer nano-particle, existing more research (1.Larpent C., Bernard E, Richard J., Vaslin S., Macromolecules, 1997,30:354.2 Gan L.M., Chew C.H., Lee K.C., Ng S.C..Polymer, 1993,34:3064.3.Gan L.M., Lee K.C., Chew C.H., NgS.C., Gan L.H..Macromolecules, 1994,27:6335).But there are some limitation in conventional micro-emulsion polymerization, and is big as the emulsifying agent consumption, and emulsifying agent/monomer ratio is greater than 1; Need assistant for emulsifying agent, polymkeric substance purification difficult etc.
Cavitation effect takes place when ultrasonic wave is propagated in liquid medium, promptly in extremely short time and minimum space, produce localized hyperthermia (～5000K), high pressure (～10
8Pa), rate of temperature change reaches 10
9K/s, and be attended by the jet that intensive shockwave and speed per hour reach 400 km.This provides a kind of very special physicochemical environment for chemical reaction.Localized hyperthermia's high pressure that the ultrasonic cavitation effect produces and a series of physics, chemical action are enough to make enter in the cavitation bubble or be positioned near its small molecules cracking produce free radical, thereby cause various chemical reactions.This provides condition for initiating polymerization of microemulsion by means of ultrasonic wave.
The objective of the invention is provides a kind of initiating polymerization of microemulsion by means of ultrasonic wave method at the deficiencies in the prior art, be characterized in utilizing effects such as hyperacoustic dispersion, emulsification, initiation, at lesser temps with need not to realize micro-emulsion polymerization under the situation of initiator, the preparation size distribution is even, and size is at nano level emulsion particle.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The method of initiating polymerization of microemulsion by means of ultrasonic wave:
(1) 1～40 part of monomer, emulsifying agent 1-10 part, 60～99 parts in dispersion medium and auxiliary agent thereof add in the ultrasound wave irradiation reactor, again with in the ultrasonic wave horn,amplitude transformer insertion reaction device for 0.2～5 part.
(2) fed nitrogen about 2～10 minutes, logical nitrogen speed is 0.1～50 ml/min, and logical circulator bath temperature is 0-50 ℃.
(3) start ultrasonoscope, carry out polyreaction, the ultrasonic power regulation range is at 50-1500w, frequency 2 * 10
4～10
9Hz, 10 minutes～5 hours reaction times.
Monomer is that methyl methacrylate, ethyl propenoate, butyl acrylate, vinylbenzene, vinyl cyanide, acrylamide and/or the vinyl monomer that has surface-active sulfonic acid group, hydroxy-acid group, quaternary ammonium group are at least a.
Emulsifying agent is that sorbitan monooleate, polyoxyethylene (20) Witconol AL 69-66, succsinic acid two-2-ethylhexyl sodium sulfonate, cetyl trimethylammonium bromide, sodium lauryl sulphate, Sodium palmityl sulfate and Sodium dodecylbenzene sulfonate are at least a.
Auxiliary agent is that Polyvinylpyrolidone (PVP), sodium polyacrylate, polyoxyethylene glycol, n-hexyl alcohol, Pentyl alcohol and propyl carbinol are at least a.
Dispersion medium be water and/or with other solvents of water arbitrary proportion blended as alcohol, ketone etc., for the consideration of economy and environment aspect, the most preferred with water.
The emulsion particle median size of the present invention's preparation is 30-100nm, narrow diameter distribution; Polymericular weight is 10
6The order of magnitude.
The present invention has following advantage:
(1) polymerization does not need initiator;
(2) temperature of reaction is lower;
(3) required emulsifier concentration is lower than conventional micro-emulsion polymerization;
(4) particle diameter is little, is nano level and is evenly distributed;
(5) molecular weight of product is higher;
Embodiment:
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
1. with methyl methacrylate 10g, sodium lauryl sulphate 5g, Pentyl alcohol 1g, water 84g joins in the reactor, feeds about 5 minutes of nitrogen with the oxygen in the eliminating system, and 30 ℃ of control bath temperatures.Open VC-1500 ultrasonic instrument (Sonic﹠amp then; Materials Inc.) beginning polyreaction.Ultrasonic power is 600w in the reaction process, and frequency is 20kHz, and it is constant that nitrogen speed 10 ml/min keep.React and finished in 30 minutes.The polymethylmethacrylate latex particle size of preparation is 36.5nm, and molecular weight is 5.0 * 10
6
2. with butyl acrylate 8g, cetyl trimethylammonium bromide 3g, n-hexyl alcohol 0.5g, water 88.5g joins in the reactor, feeds about 5 minutes of nitrogen with the oxygen in the eliminating system, and 40 ℃ of control bath temperatures.Open VC-1500 ultrasonic instrument (Sonic﹠amp then; Materials Inc.) beginning polyreaction.Ultrasonic power is 200w in the reaction process, and frequency is 40kHz, and it is constant that nitrogen speed 20 ml/min keep.React and finished in 2 hours.The butyl polyacrylate latex particle size of preparation is about 50nm, and molecular weight is 5.5 * 10
6
3. with vinylbenzene 20g, succsinic acid two-2-ethylhexyl sodium sulfonate 4g, Polyvinylpyrolidone (PVP) 0.5g, n-hexyl alcohol 1g, water 74.5g joins in the reactor, feeds about 5 minutes of nitrogen with the oxygen in the eliminating system, and 20 ℃ of control bath temperatures.Open VC-1500 ultrasonic instrument (Sonic﹠amp then; Materials Inc.) beginning polyreaction.Ultrasonic power is 100w in the reaction process, and frequency is 35kHz, and it is constant that nitrogen speed 15 ml/min keep.React and finished in 1 hour.The polystyrene latex grain particle diameter of preparation is about 30nm, and molecular weight is 4.5 * 10
6
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113154 CN1118478C (en) | 2000-09-04 | 2000-09-04 | Method for initiating polymerization of microemulsion by means of ultrasonic wave |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113154 CN1118478C (en) | 2000-09-04 | 2000-09-04 | Method for initiating polymerization of microemulsion by means of ultrasonic wave |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1341667A true CN1341667A (en) | 2002-03-27 |
| CN1118478C CN1118478C (en) | 2003-08-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00113154 Expired - Lifetime CN1118478C (en) | 2000-09-04 | 2000-09-04 | Method for initiating polymerization of microemulsion by means of ultrasonic wave |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1118478C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558322A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Method for polymerizing acrylamide by ultrasonic technology |
| CN106478883A (en) * | 2016-11-30 | 2017-03-08 | 黄河三角洲京博化工研究院有限公司 | A kind of styrene-butadiene latex and preparation method thereof |
-
2000
- 2000-09-04 CN CN 00113154 patent/CN1118478C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558322A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Method for polymerizing acrylamide by ultrasonic technology |
| CN106478883A (en) * | 2016-11-30 | 2017-03-08 | 黄河三角洲京博化工研究院有限公司 | A kind of styrene-butadiene latex and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1118478C (en) | 2003-08-20 |
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Granted publication date: 20030820 |
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