CN101530771A - Method for preparing polymer microspheres - Google Patents
Method for preparing polymer microspheres Download PDFInfo
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- CN101530771A CN101530771A CN200910096583A CN200910096583A CN101530771A CN 101530771 A CN101530771 A CN 101530771A CN 200910096583 A CN200910096583 A CN 200910096583A CN 200910096583 A CN200910096583 A CN 200910096583A CN 101530771 A CN101530771 A CN 101530771A
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Abstract
The invention relates to a method for preparing polymer microspheres. The method comprises: mixing composite emulsion polymerization inhibitor, stabilizing agent and de-ionized water in a reaction kettle, then introducing nitrogen into the mixture, adding a polymer monomer into the mixture, stirring the mixture, raising temperature to a reaction temperature between 70 and 90 DEG C, adding an initiating agent into the mixture, and thermostatically stirring the mixture to react for 3 to 6 hours under the reaction temperature; and after the reaction is finished, filtering, drying and crushing the reactants to form the polymer microspheres, wherein the composite emulsion polymerization inhibitor comprises the following components in percentage by weight: 40 to 90 percent of 3, 4, 5-trihydroxybenzoic acid, 5 to 50 percent of hexamethylene tetramine, and 5 to 15 percent of sodium chloride. The composite emulsion polymerization inhibitor is added during suspension polymerization, and can effectively inhibit the occurrence of emulsion polymerization during suspension polymerization for preparing polystyrene microspheres and polyacrylic acid microspheres; and the prepared microspheres have good size evenness.
Description
Technical field
The invention belongs to the material technology field, relate to a kind of preparation method of polymer microballoon, be specifically related to a kind of styrene monomer or acrylic monomer obtain dimensional homogeneity by suspension polymerisation in the presence of the emulsion polymerisation inhibitor polymer microballoon technology.
Background technology
Polymer microballoon has played special and crucial effect because of its special size and structure at many key areas.The microballoon of different-grain diameter and pattern is being undertaken different functions, is widely used in coating, paper surface processing, plastic additive, and many fields such as construction material.For example the poly (methyl methacrylate) micro-sphere opening agent that can be made into the anti-stick company of polyolefin film (in vistanex, behind the blending poly (methyl methacrylate) micro-sphere particle, is configured as film.At this moment can form very small bulbous protrusion at film surface, these ultra micro projections can prevent the inter-adhesive phenomenon between the film just, increase " opening " effect.Because compare with inorganic powder " opening agent ", the refractive index of this functional particle and vistanex are very close, so under the situation that obtains same anti-stick even effect, can make the higher film of the transparency).Therefore, polymer microballoon is applied in the traditional product, can promote the added value of traditional product greatly.Especially over past ten years, along with going deep into of polymer microsphere research, the application of polymer microballoon from the past general industry application development to high sophisticated technology field, for example chromatograph packing material and chromatographic column microballoon, clinical diagnosis microballoon (immune carrier microballoon, magnetic microsphere, fluorescent microsphere), opto-electronics microballoon (LCD is microballoon, scatter plate microballoon, conductive micro-balloons at interval), solid phase is synthesized microballoon, ion-exchange microballoon, standard metering microballoon and other functional microspheres etc.
Polystyrene type microballoon and polyacrylic microballoon are typical two kinds of polymer microballoons, and the dimensional homogeneity of microballoon (the single dispersion) has significant effects to the application of microballoon.There is several different methods to prepare polystyrene type microballoon and polyacrylic microballoon microballoon, as mechanical milling method, emulsion polymerization, dispersion copolymerization method, suspension polymerization etc.In these methods, mechanical milling method time consumption and energy consumption, uneconomical also is difficult to obtain the size uniform microsphere.Though the mono-dispersion microballoon of emulsion polymerisation process energy production single-size, the particle diameter of microballoon is restricted to about 0.1 μ m, is very limited in the application.The polyalcohol microspherulite diameter that dispersion copolymerization method obtains is big slightly than emulsion polymerization, about about 1 μ m, but will consume a large amount of organic substances as solvent, both uneconomically also environment is polluted.Suspension polymerization can produce large-sized microballoon, and the while as reaction dissolvent, prepares a kind of method for optimizing of large scale, monodisperse polystyrene class microballoon and polyacrylic microballoon microballoon with water beyond doubt.Yet, in the suspension polymerisation process, usually be accompanied by the generation of emulsion polymerisation, it will reduce the productive rate and the polymerization stability of suspension polymerisation, further, emulsion polymerisation will reduce the product quality of suspension polymerisation, especially when microspherulite diameter needed at 0.1～500 μ m, because the stabilizing agent addition is bigger, the solubility of polymerization single polymerization monomer in water increased, the emulsion polymerisation odds is bigger, and accessory substance is more thereby the size thus obtained microsphere particle diameter is inhomogeneous.
For monodisperse polystyrene class microballoon and the polyacrylic microballoon that obtains single-size, in the suspension polymerisation process, add the generation that the water-soluble inorganic inhibitor suppresses emulsion polymerisation usually in early days.For example Japan Patent JP-A-55-82125 adds 0.01～10% thiocyanic acid amine or stannous chloride as emulsion polymerisation inhibitor, Japan Patent JP-A-60-8 in the suspension polymerisation process, 302 usefulness vanadic anhydrides or with the combination formulations of stannous chloride as emulsion polymerisation inhibitor, Japan Patent JP-A-62-205,108 usefulness sodium nitrate (potassium) are as the emulsion polymerisation inhibitor.Yet in the suspension polymerisation process of polymer microballoon, the effect of water-soluble inorganic inhibitor a little less than, the addition of inhibitor is bigger, especially the diameter along with the suspension polymerisation thus obtained microsphere is more little, the inhibition effect of water-soluble inorganic inhibitor is weak more.Patent JP-A-61-255,355 use water-soluble sulfhydryl compound to suppress emulsion polymerisation has obtained effect preferably, but since its smell is awful, this bad smell also easy cleaning not in product, thereby be restricted on using.
Analyze theoretically, emulsion polymerisation is mainly carried out on the border of suspension liquid phase, so inhibitor only is distributed in the border of hanging drop phase, could suppress the generation of emulsion polymerisation effectively.If inhibitor is water-soluble too high, it is relatively poor then to suppress effect, and conversely, if the dissolubility of inhibitor in organic monomer is too high, then it will guide chain to shift in hanging drop, thereby suppress the carrying out of suspension polymerisation.Therefore, in theory can be from the appropriate emulsion polymerisation inhibitor of the angle Selection of water/oil-soluble balance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method for preparing polymer microballoon is provided.
The inventive method is that composite emulsion polymerization inhibitor and stabilizing agent are mixed with deionized water in reactor, charge into nitrogen then, add polymer monomer again, stir, temperature rises to 70～90 ° of reaction temperatures, adds initator, and isothermal reaction is 3～6 hours under reaction temperature, stir simultaneously, mixing speed is 1000-5000 rev/min.After reaction finished, filtration, dry, pulverizing promptly got polymer microballoon.Mixing speed is influential to the diameter of thus obtained microsphere, and mixing speed increases, and the diameter of thus obtained microsphere then reduces; Mixing speed reduces, and the diameter of thus obtained microsphere then increases.
The composite emulsion polymerization inhibitor that adds and the weight ratio of polymer monomer are 1:10～100, the weight ratio of stabilizing agent and polymer monomer is 1:10～100, the weight ratio of initator and polymer monomer is 1:10～100, and the weight ratio of deionized water and polymer monomer is 5～10:1.
Described polymer monomer is styrene monomer or acrylic monomer.
Described styrene monomer is styrene, p-methylstyrene, divinylbenzene, in the methoxy styrene one or more, described acrylic monomer is one or more in methyl methacrylate, methyl acrylate, trimethylolpropane triacrylate, ethylacrylic acid, the acrylic acid.
The component of described composite emulsion polymerization inhibitor is: 40～90% 3,4,5-trihydroxybenzoic acid, 5～50% hexamethylenetetramine, 5～15% sodium chloride, percentage is weight percentage.
Described stabilizing agent is a kind of in polyvinyl alcohol, Sodium Polyacrylate, polyvinylpyrrolidone, the carboxymethyl cellulose.
Described initator is a kind of in fine of benzoyl peroxide, methyl ethyl ketone peroxide, azo two isobutyls.
The present invention adds 3,4 in the suspension polymerisation process, 5-trihydroxybenzoic acid, hexamethylenetetramine, sodium chloride ternary complex be as the emulsion polymerisation inhibitor.This composite emulsion polymerization inhibitor can suppress the generation of emulsion polymerisation effectively in suspension polymerization polystyrene type microballoon and polyacrylic microballoon process, make the microballoon of preparation obtain good dimensional homogeneity.
The specific embodiment
Embodiment 1.
Agitator, condensing reflux pipe, thermometer, inert gas N are being housed
2Charge in the reactor of mouth, add the deionized water of 800g, 8g polyvinyl alcohol and 8g composite emulsion polymerization inhibitor (comprising 3.2g3,4,5-trihydroxybenzoic acid, 3.6g hexamethylenetetramine, 1.2g sodium chloride) are mixed at deionized water, charge into nitrogen.Add 79.5g styrene and 0.5g divinylbenzene then, stir, temperature rises to 70 °, adds the 8g benzoyl peroxide, 70 ° of constant temperature, and stirring reaction 6 hours, mixing speed is 5000 rev/mins.After reaction finishes, adopt centrifugal filtration process to carry out liquid-solid phase and separate,, promptly get the microballoon that average grain diameter is 50 μ m through super-dry, pulverizing.
Embodiment 2.
Agitator, condensing reflux pipe, thermometer, inert gas N are being housed
2Charge in the reactor of mouth, the deionized water that adds 400g, 4g polyvinylpyrrolidone and 0.8g composite emulsion polymerization inhibitor (comprising 0.72g3,4,5-trihydroxybenzoic acid, 0.04g hexamethylenetetramine, 0.04g sodium chloride) mix at deionized water, charge into nitrogen.Add the 79g methyl methacrylate then, the 1g trimethylolpropane triacrylate stirs, and temperature rises to 90 °, adds the 0.8g methyl ethyl ketone peroxide, 90 ° of constant temperature, and stirring reaction 3 hours, mixing speed is 2500 rev/mins.After reaction finishes, adopt centrifugal filtration process to carry out liquid-solid phase and separate,, promptly get the microballoon that average grain diameter is 100 μ m through super-dry, pulverizing.
Embodiment 3.
In the reactor that agitator, condensing reflux pipe, thermometer, inert gas N2 charge into mouthful is housed, the deionized water that adds 800g, 0.8g carboxymethyl cellulose and 4g composite emulsion polymerization inhibitor (comprising 1.6g3,4,5-trihydroxybenzoic acid, 2g hexamethylenetetramine, 0.4g sodium chloride).Add 55g styrene, 20g methyl acrylate, 5g divinylbenzene then, stir, temperature rises to 90 °, and adding 4g azo two isobutyls are fine, 80 ° of constant temperature, and stirring reaction 4.5 hours, mixing speed is 2000 rev/mins.After reaction finishes, adopt centrifugal filtration process to carry out liquid-solid phase and separate,, promptly get the microballoon that average grain diameter is 150 μ m through super-dry, pulverizing.
Embodiment 4.
Agitator, condensing reflux pipe, thermometer, inert gas N are being housed
2Charge in the reactor of mouth, add the deionized water of 600g, 3.3g Sodium Polyacrylate and 4.5g composite emulsion polymerization inhibitor (comprising 2.8g3,4,5-trihydroxybenzoic acid, 1.2g hexamethylenetetramine, 0.5g sodium chloride).Add 85g methyl methacrylate, 5g trimethylolpropane triacrylate then, stir, temperature rises to 80 °, adds the 5g benzoyl peroxide, 80 ° of constant temperature, and stirring reaction 4.5 hours, mixing speed is 1500 rev/mins.After reaction finishes, adopt centrifugal filtration process to carry out liquid-solid phase and separate,, promptly get the microballoon that average grain diameter is 320 μ m through super-dry, pulverizing.
Embodiment 5.
In the reactor that agitator, condensing reflux pipe, thermometer, inert gas N2 charge into mouthful is housed, the deionized water that adds 1000g, 2g carboxymethyl cellulose and 7.5g composite emulsion polymerization inhibitor (comprising 6.75g3,4,5-trihydroxybenzoic acid, 0.375g hexamethylenetetramine, 0.375g sodium chloride).Add 85g methyl styrene, 30g then to methoxy styrene, 30g methyl acrylate, 5g ethylacrylic acid, stir, temperature rises to 80 °, and adding 4g azo two isobutyls are fine, 80 ° of constant temperature, and stirring reaction 4.5 hours, mixing speed is 1000 rev/mins.After reaction finishes, adopt centrifugal filtration process to carry out liquid-solid phase and separate,, promptly get the microballoon that average grain diameter is 480 μ m through super-dry, pulverizing.
Claims (6)
1, a kind of preparation method of polymer microballoon, it is characterized in that this method is that composite emulsion polymerization inhibitor and stabilizing agent are mixed with deionized water in reactor, charge into nitrogen then, add polymer monomer again, stir, temperature rises to 70～90 ° of reaction temperatures, add initator, isothermal reaction is 3～6 hours under reaction temperature, stirs simultaneously, and mixing speed is 1000-5000 rev/min; After reaction finishes, after filtration, dry, pulverize after, promptly get polymer microballoon;
The composite emulsion polymerization inhibitor that adds and the weight ratio of polymer monomer are that the weight ratio of 1:10～100, stabilizing agent and polymer monomer is that the weight ratio of 1:10～100, initator and polymer monomer is that the weight ratio of 1:10～100, deionized water and polymer monomer is 5～10:1.
2, the preparation method of a kind of polymer microballoon as claimed in claim 1 is characterized in that described polymer monomer is styrene monomer or acrylic monomer.
3, the preparation method of a kind of polymer microballoon as claimed in claim 1, the component that it is characterized in that described composite emulsion polymerization inhibitor is: 40～90% 3,4,5-trihydroxybenzoic acid, 5～50% hexamethylenetetramine, 5～15% sodium chloride, percentage is weight percentage.
4, the preparation method of a kind of polymer microballoon as claimed in claim 1 is characterized in that described stabilizing agent is a kind of in polyvinyl alcohol, Sodium Polyacrylate, polyvinylpyrrolidone, the carboxymethyl cellulose.
5, the preparation method of a kind of polymer microballoon as claimed in claim 1 is characterized in that described initator is a kind of in fine of benzoyl peroxide, methyl ethyl ketone peroxide, azo two isobutyls.
6, the preparation method of a kind of polymer microballoon as claimed in claim 2, it is characterized in that described styrene monomer be styrene, p-methylstyrene, divinylbenzene, in the methoxy styrene one or more; Described acrylic monomer is one or more in methyl methacrylate, methyl acrylate, trimethylolpropane triacrylate, ethylacrylic acid, the acrylic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100965831A CN101530771B (en) | 2009-03-09 | 2009-03-09 | Method for preparing polymer microspheres |
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| CN2009100965831A CN101530771B (en) | 2009-03-09 | 2009-03-09 | Method for preparing polymer microspheres |
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| CN101530771B CN101530771B (en) | 2011-04-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665398A (en) * | 2013-12-15 | 2014-03-26 | 桂林理工大学 | Preparation method for completely biodegradable and biocompatible composite microspheres |
| CN105504566A (en) * | 2016-01-26 | 2016-04-20 | 西南科技大学 | Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier |
-
2009
- 2009-03-09 CN CN2009100965831A patent/CN101530771B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665398A (en) * | 2013-12-15 | 2014-03-26 | 桂林理工大学 | Preparation method for completely biodegradable and biocompatible composite microspheres |
| CN103665398B (en) * | 2013-12-15 | 2015-12-09 | 桂林理工大学 | The preparation method of fully biodegradable and biocompatible complex microsphere |
| CN105504566A (en) * | 2016-01-26 | 2016-04-20 | 西南科技大学 | Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier |
| CN105504566B (en) * | 2016-01-26 | 2018-01-16 | 西南科技大学 | A kind of preparation method of column styrene divinylbenzene copolymer hydrophobic catalyst carrier |
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Effective date of registration: 20131023 Address after: 226600 No. 106 middle Yangtze Road, Haian County, Nantong, Jiangsu Patentee after: Haian Service Center for Transformation of Scientific Achievements Address before: Hangzhou City, Zhejiang province 310018 Jianggan District Xiasha Higher Education Park No. 2 street Patentee before: Hangzhou Electronic Science and Technology Univ |
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