CN103694483A - Preparation method of submicron PET (polyethylene terephthalate) microspheres - Google Patents
Preparation method of submicron PET (polyethylene terephthalate) microspheres Download PDFInfo
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- CN103694483A CN103694483A CN201410008526.4A CN201410008526A CN103694483A CN 103694483 A CN103694483 A CN 103694483A CN 201410008526 A CN201410008526 A CN 201410008526A CN 103694483 A CN103694483 A CN 103694483A
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Abstract
The invention discloses a preparation method of submicron PET microspheres. The preparation method is characterized by being carried out according to the following steps: preparing PET solution by using mixed solution of phenol and tetrachloroethane as a solvent, and using PET resin particles as solute; adding the PET solution into water solution of lauryl sodium sulfate, emulsifying to obtain PET emulsion; mixing PET emulsion with demulsifying agent to obtain white precipitate, and washing the white precipitate to obtain the submicron PET microspheres. According to the invention, the submicron PET microspheres are prepared by an emulsifying-demulsifying method; the preparation method is simple, and solves the problems that boiling point of the PET solvent is high, the PET microspheres cannot be obtained by solvent evaporation, moreover, each PET solvent with single component is a polar solvent and the PET solution formed by the polar solvent cannot prepare steady emulsion.
Description
Technical field
The present invention relates to a kind of preparation method of submicron level PET microballoon, it is that to take recycled PET (polyethylene terephthalate) resin particle be raw material, by techniques such as dissolving, emulsification, breakdowns of emulsion, is prepared from, and belongs to engineering plastics field.
Technical background
Because PET has higher hardness, good dimensional stability, chemical stability, thermostability and physiology inertia and low production cost, and be widely used in the numerous areas such as textile process, food product pack, mechanical means, biomedicine, optical material, information industry, be a kind of thermoplastics being widely used.But, because PET is a kind of polymkeric substance of highly crystalline, and in molecular chain without hydrophilic radical, cause its surface can be higher, poor with the consistency of other materials, some relate to the application in the technique of Surface Physical Chemistry process in absorption, bonding, dyeing, printing and plating etc. to have limited to a great extent PET.As a rule, need to carry out surface modification to PET.Because PET adopts melt polycondensation reaction synthetic, be difficult to be prepared into the product that specific surface area is larger, thereby much modification is all to carry out on PET film, this also makes micron and the nanometer of PET goods be restricted.If obtain specific surface area than the larger micron of film or the PET microballoon of nano-scale, and carry out modification or functionalization at microsphere surface, will greatly expand the application of PET in microcosmic research field.
The polymkeric substance of directly take is prepared microballoon as raw material and is conventionally comprised two steps: the one, polymkeric substance is become to fluid (dissolving, emulsification, thawing etc.), and the 2nd, solidify plastotype (precipitation, breakdown of emulsion, solidify etc.), obtain target product.Wherein the simplest, be also that the most original method is dissolving-direct precipitation method, be about to polymer dissolution in its good solvent, be made into low concentration solution, then solution is poured in the poor solvent of number of polymers, polymer particle is precipitated out.But this method is difficult to control sedimentation speed, easily flocculate into block polymkeric substance precipitation, but not polymer microballoon.Spray-drying process and solvent evaporated method are also the modal methods (International Journal of Pharmaceutics2004,282:1-18) of directly preparing polymer microballoon.By after polymer dissolution/emulsification, use spray-drying process, or stirring/ultrasonic dispersion-solvent evaporation method is except desolventizing, also can obtain polymer microballoon.But all must use volatile solvent in these two kinds of methods.For PET, because the rigidity of its molecular chain structure and highly crystalline, its solvent is high boiling polar solvent, as oil of mirbane, three cresols etc., or use mixed solvent, as tetrachloroethane-cresols (or phenol), phenol-tetracol phenixin etc., thereby can not adopt above-mentioned two kinds of methods to prepare PET microballoon.Within 1999, there is software engineering researchers invent for the melting emulsion process (Polymer1999 of polycaprolactone, 40:1731-1735), they are by polyoxyethylene glycol heating and melting together with emulsifying agent, and use it for external phase, to gather (6-caprolactone) adds this external phase to be made into emulsion, be cooled to-20 ℃, polycaprolactone disperse phase is solidified, obtain polycaprolactone microballoon sphere.Can be by thawing, emulsification, cooling curing legal system for microballoon for low melting point polymer.But the solvent of PET is intensive polar solvent, the PET that the method by direct dissolving-precipitation will obtain bulk precipitates, and polar solvent and shipwreck are to form heterogeneous emulsion.The fusing point of PET is 260 ℃ of left and right, makes to prepare in this way PET microballoon also very difficult.
Summary of the invention
The object of the invention is to utilize emulsion system to form and destroy principle, from waste PET resin particle raw material, first prepare the stabilized emulsion system that disperse phase is PET solution, re-use suitable precipitation agent (ethanol), under specific deposition condition, prepare submicron level PET microballoon, for micron and the nanometer of PET goods are opened up new way.
Technical solution problem of the present invention adopts following technical scheme:
The preparation method of submicron level PET microballoon of the present invention, its feature is to carry out as follows:
A, take the mixing solutions of phenol and tetrachloroethane as solvent, take PET resin particle as solute, preparation PET solution;
B, the PET solution that step a is obtained join in the aqueous solution of sodium lauryl sulphate, and emulsification obtains PET emulsion;
C, the PET emulsion that step b is obtained are mixed acquisition white depositions with emulsion splitter, clean described white depositions, obtain PET microballoon.
Preparation method of the present invention, its feature is also:
Step a carries out as follows: by the phenol of heating and melting and tetrachloroethane 1:2 mixing in mass ratio, be cooled to room temperature, obtain solvent; In described solvent, add PET resin particle, be then heated to 95 ℃, be stirred to PET resin particle and dissolve completely, be cooled to room temperature, obtain PET solution; The mass ratio of described solvent and described PET resin particle is 49:1;
Step b carries out as follows: the aqueous solution of the sodium lauryl sulphate that preparation quality concentration is 2%, the PET solution that then adds therein step a to obtain, is used high speed dispersion clarifixator with 1 * 10
4the rotating speed emulsification 3min of r/min, obtains PET emulsion; The mass ratio of the aqueous solution of described sodium lauryl sulphate and described PET solution is 1:9.
Described in step c, emulsion splitter is dehydrated alcohol.
Step c be as follows one or mode two carry out:
Mode one: dehydrated alcohol is placed in to ultrasonic cleaning instrument, and dropwise to add wherein PET emulsion to solution be oyster white, obtain oyster white suspension liquid; Described oyster white suspension liquid is standing, centrifugal acquisition lower sediment thing then; Described lower sediment thing is dispersed in ethanol, and after supersound washing, recentrifuge is collected, and obtains PET microballoon;
Mode two: described PET emulsion is placed in to ultrasonic cleaning instrument, under ultrasonication, splashes into dehydrated alcohol and make emulsion breaking, centrifugation after the product precipitation obtaining, by throw out ultrasonic cleaning in ethanol, obtains PET microballoon.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention by emulsification-breakdown of emulsion legal system for submicron level PET microballoon, to take the mixing solutions of phenol and tetrachloroethane to be solvent preparation PET solution, further make PET emulsion, finally by breakdown of emulsion, obtain PET microballoon, method is simple, has solved PET solvent boiling point high, cannot obtain PET microballoon by solvent flashing, and the PET solvent of one-component is polar solvent, the PET solution of its formation cannot be prepared the problem of stable emulsion;
2, the present invention prepares PET microballoon can to adopt waste PET resin particle is raw material, and the cost that economizes on resources is low;
3, the PET microballoon size that prepared by the present invention (200nm～1 μ m) in sub-micrometer range, this is achieved micron and the nanometer of PET goods, if carry out modification or functionalization at microsphere surface, will greatly expand the application of PET in microcosmic research field.
Accompanying drawing explanation
Fig. 1 is that the SEM of the submicron level PET microballoon of the embodiment of the present invention 1 preparation characterizes photo;
Fig. 2 is that the SEM of the submicron level PET microballoon of the embodiment of the present invention 2 preparations characterizes photo.
Specific embodiment
The invention will be further described for following examples, and its object is only to understand better object of the present invention, rather than limits the scope of the invention.
Embodiment 1
Under room temperature, the phenol of 50g heating and melting is joined in 100g tetrachloroethane, stir and obtain clear solvent; In 98g solvent, add 2g waste PET resin particle, be then heated to 95 ℃, be stirred to PET resin particle and dissolve completely, be cooled to room temperature, obtain PET solution, sealing is preserved;
1.8g sodium lauryl sulphate (SDS) is dissolved in 88.2g water, the SDS aqueous solution that preparation quality concentration is 2%, the PET solution that then adds therein 10g step a to obtain, is used high speed dispersion clarifixator with 1 * 10
4the rotating speed emulsification 3min of r/min, obtains stable white PET emulsion;
Dehydrated alcohol is placed in to ultrasonic cleaning instrument, and dropwise adds PET emulsion wherein, along with adding of PET emulsion, ethanol starts to gradually become light blue from clear, until while just bleaching, stop dripping PET emulsion, obtains oyster white suspension liquid; By after oyster white suspension liquid standing over night, through centrifugation, obtain lower sediment thing (centrifugal force be 2400 * g, 10min); Lower sediment thing is dispersed in ethanol, and after supersound washing, recentrifuge is collected, and this washing process repeats 3 times, obtains submicron level PET microballoon.
As shown in Figure 1, the median size that measures PET microballoon is 373nm to the pattern of the present embodiment gained sample, and polydispersity index (PDI) is 1.52.
Embodiment 2
The phenol of 50g heating and melting and 100g tetrachloroethane are mixed, be cooled to room temperature, obtain clear solution.In 98g solvent, add 2g waste PET resin particle, be then heated to 95 ℃, be stirred to PET resin particle and dissolve completely, be cooled to room temperature, obtain PET solution, sealing is preserved;
Under room temperature, 1.8g sodium lauryl sulphate (SDS) is dissolved in 88.2g water, the SDS aqueous solution that preparation quality concentration is 2%, the PET solution that then adds therein 10g step a to obtain, is used high speed dispersion clarifixator with 1 * 10
4the rotating speed emulsification 3min of r/min, obtains stable white PET emulsion;
This PET emulsion is placed in to ultrasonic cleaning instrument, under ultrasonication, splashes into dehydrated alcohol (rate of addition is about 0.25mL/s) and make emulsion breaking.The product obtaining is through precipitation, centrifugation, then ultrasonic cleaning in ethanol, obtains submicron level PET microballoon.
As shown in Figure 2, the median size that measures PET microballoon is 497nm to the pattern of the present embodiment gained sample, and PDI is 2.17.
Claims (5)
1. a preparation method for submicron level PET microballoon, is characterized in that carrying out as follows:
A, take the mixing solutions of phenol and tetrachloroethane as solvent, take PET resin particle as solute, preparation PET solution;
B, the PET solution that step a is obtained join in the aqueous solution of sodium lauryl sulphate, and emulsification obtains PET emulsion;
C, the PET emulsion that step b is obtained are mixed acquisition white depositions with emulsion splitter, clean described white depositions, obtain PET microballoon.
2. preparation method according to claim 1, is characterized in that: step a carries out as follows: by the phenol of heating and melting and tetrachloroethane 1:2 mixing in mass ratio, be cooled to room temperature, obtain solvent; In described solvent, add PET resin particle, be then heated to 95 ℃, be stirred to PET resin particle and dissolve completely, be cooled to room temperature, obtain PET solution; The mass ratio of described solvent and described PET resin particle is 49:1.
3. preparation method according to claim 1, it is characterized in that: step b carries out as follows: the aqueous solution of the sodium lauryl sulphate that preparation quality concentration is 2%, then the PET solution that adds therein step a to obtain, is used high speed dispersion clarifixator with 1 * 10
4the rotating speed emulsification 3min of r/min, obtains PET emulsion; The mass ratio of the aqueous solution of described sodium lauryl sulphate and described PET solution is 1:9.
4. preparation method according to claim 1, is characterized in that: described in step c, emulsion splitter is dehydrated alcohol.
5. preparation method according to claim 4, is characterized in that: step c be as follows one or mode two carry out:
Mode one: dehydrated alcohol is placed in to ultrasonic cleaning instrument, and dropwise to add wherein PET emulsion to solution be oyster white, obtain oyster white suspension liquid; Described oyster white suspension liquid is standing, centrifugal acquisition lower sediment thing then; Described lower sediment thing is dispersed in ethanol, and after supersound washing, recentrifuge is collected, and obtains PET microballoon;
Mode two: described PET emulsion is placed in to ultrasonic cleaning instrument, under ultrasonication, splashes into dehydrated alcohol and make emulsion breaking, centrifugation after the product precipitation obtaining, by throw out ultrasonic cleaning in ethanol, obtains PET microballoon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410008526.4A CN103694483A (en) | 2014-01-08 | 2014-01-08 | Preparation method of submicron PET (polyethylene terephthalate) microspheres |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109866355A (en) * | 2017-12-04 | 2019-06-11 | 株式会社富研 | The method for manufacturing optics microballon, the optics microballon being produced from it and reflectance coating and light source assembly comprising it |
| CN112284851A (en) * | 2020-10-26 | 2021-01-29 | 南开大学 | Preparation method of nontoxic nano-scale plastic microparticles |
-
2014
- 2014-01-08 CN CN201410008526.4A patent/CN103694483A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 徐永飞: ""PET表面功能化和共混改性的辐射化学研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109866355A (en) * | 2017-12-04 | 2019-06-11 | 株式会社富研 | The method for manufacturing optics microballon, the optics microballon being produced from it and reflectance coating and light source assembly comprising it |
| CN112284851A (en) * | 2020-10-26 | 2021-01-29 | 南开大学 | Preparation method of nontoxic nano-scale plastic microparticles |
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Application publication date: 20140402 |