CN101143926B - Polyamide micro-particle and preparation method thereof - Google Patents
Polyamide micro-particle and preparation method thereof Download PDFInfo
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- CN101143926B CN101143926B CN2006100415240A CN200610041524A CN101143926B CN 101143926 B CN101143926 B CN 101143926B CN 2006100415240 A CN2006100415240 A CN 2006100415240A CN 200610041524 A CN200610041524 A CN 200610041524A CN 101143926 B CN101143926 B CN 101143926B
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Abstract
The invention discloses a polyamide microparticle and a preparation method, wherein, the range of particle size of the polyamide microparticle is between 1 Mu m and 100 Mu m, and the range of thermal decomposition is between 300 DEG C and 420 DEG C. The preparation method includes four steps; firstly, acyl chloride is resolved in organic solution, which is then added with emulsifier while being stired under the temperature between 0 DEG C and 100 DEG C; secondly, after the addition of the emulsifier, deionized water is added until phase inversion occurs, and the emulsion is converted from W/O type to O/W type; thirdly, buffer solution and amine are added and reacted with the acyl chloride resolved in organic phase, so that polyamide is generated; fourthly, after the reaction is finished, the polyamide microparticle is obtained by separation, washing and drying. The polyamide microparticle prepared by the method is a faultless spheral particle, and the range of thermal decomposition is between 300 DEG C and 420 DEG C. The process route of the invention is simple, the requirement on equipment is low, and practicability is strong.
Description
Technical field
The present invention relates to a kind of high molecular polymer micropartical and preparation method thereof, relate to a kind of polyamide micro-particle and preparation method thereof specifically.
Background technology
Poly-and thing micropartical is widely used in medicine, biochemistry, coating, tackiness agent, paper surface processing, fields such as makeup.As aspect the biological medicine, polymeric microsphere is used to toxicity and the easily embedding of inactivation medicine, the embedding of cell, protein and DNA, separation and purifying, and enzyme is fixed, the renaturation of denatured protein etc.Being applied in maximum on the tackiness agent technology of preparing is nuclear-shell mould micropartical, and for example nuclear is urethane resin, and shell is the tackiness agent of polyacrylic ester, and nuclear portion material is used to increase the tackiness agent film strength, and shell portion is used to show viscosity.
General vinyl monomer can prepare as letex polymerization, dispersion polymerization, seeding polymerization, precipitation polymerization with various radical polymerization modes, and suspension polymerization etc. are prepared into micropartical; What the monomer of some condensation polymer types can adopt that precipitation polymerization such as KATSUYA etc. report in patent JP2005097370 prepares polyimide microparticle with dicarboxylic anhydride and diamines by precipitation polymerization.Also can earlier a kind of monomer be emulsified into and disperse to add mutually second kind of monomer reaction again, curing obtains polymeric microsphere; Some natural polymers or synthetic polymer can be by removal of solvents method preparations, and general method is, preparation w/o type, O/W type or W/O/W type emulsion earlier spends then and desolventize or method such as crosslinked is solidified disperse phase, and obtains micropartical.
The preparation method of polyamide micro-particle had report in the past, common preparation method such as Chu etc. are at Journal of Membrane Science, 2001, what report in the 192:27 is the organic solvent and the water that will be dissolved with acyl chlorides, tensio-active agent is directly mixed, machinery emulsification, formation O/W emulsion adds buffered soln again and amine carries out the interfacial polycondensation reaction.Chu etc. are at Langmuir, and 2002, studied the application of polyamide micro-particle aspect medicament slow release among the 18:1856.Alexandridou etc. are at Surface and CoatingsTechnology, polyamide micro-particle and metal codeposition are studied in 1995,71,267, comprise the crocking resistance that organic liquid can improve metallic coating by micropartical.
Phase reversion phenomenon in the emulsion has caused people's interest very early, Brooks, Vaessen, Richmond etc. are at ChemicalEngineering Science, 2002,57:663 and Langmuir, 1996,12:875 and Chemical Engineering Science, 1994,49:1065 studies it.Its mechanism is generally: system is emulsifying agent and oil phase during beginning, along with the progressively adding of water, when water-content hour system form a w/o type emulsion, phase reversion takes place when water-content reaches certain value, changes O/W type emulsion into.Watson etc. are at Colloids and Surface A:Physicochemicaland Engineering Aspects, 2002, prepared alkide resin emulsion with direct emulsion process and phase reversion emulsion process respectively among the 196:121, the result shows that the Synolac dispersed phase size that obtains with the phase reversion method is less than the dispersed phase size that obtains with direct emulsion process.Yang Zhenzhong etc. have reported in patent CN1321697A and have utilized the method for phase reversion to prepare epoxy resin micro-particle.Do not appear in the newspapers as yet about the method for utilizing phase reversion to prepare polyamide micro-particle.
Summary of the invention
The objective of the invention is in conjunction with the phase reversion method, provides a kind of polyamide micro-particle and preparation method thereof on the basis of prior preparation method.
Purpose of the present invention can reach by following measure:
A kind of polyamide micro-particle, it has following molecular structure:
This kind micropartical particle size range is that 1～100 μ m and pyrolysis temperature range are 300～420 ℃.Heat decomposition temperature is tested with thermogravimetric analyzer (TAQ600), 10 ℃/min of temperature rise rate, nitrogen atmosphere.
A kind of method for preparing polyamide micro-particle is dissolved in acyl chlorides in the organic solvent earlier, adds emulsifying agent 0～100 ℃ temperature with under stirring; Progressively add deionized water behind the adding emulsifying agent and take place up to phase reversion, emulsion changes O/W type (wherein W represents water, and O represents organic phase) into by w/o type; Add buffered soln and amine again, with the generation polymeric amide that reacts of dissolved acyl chlorides in the organic phase; After finishing, reaction, promptly obtains polyamide micro-particle through separation, washing, drying.
Purpose of the present invention specifically can reach by following measure:
Utilize acyl chlorides and amine to be raw material, through phase reversion emulsification and interfacial polycondensation is prepared more complete spheroidal particle and it has following molecular structure:
This kind micropartical particle size range is that 1～100 μ m and pyrolysis temperature range are 300～420 ℃.
The add-on of each raw material is by weight in this atomic preparation method:
0.1～10 part of acyl chlorides;
1～50 part of organic solvent;
0.01～20 part of emulsifying agent;
10～100 parts of deionized waters;
0.1～10 part of damping fluid;
0.1～30 part of amine.
Described acyl chlorides is selected from oxalyl chloride, p-phthaloyl chloride, one or more in isophthaloyl first chlorine, certain herbaceous plants with big flowers diacid chloride, hexanedioyl chlorine or the 2-chlorine terephthalyl chloride.
Described organic solvent is selected from one or more in benzene,toluene,xylene, normal hexane, hexanaphthene, sherwood oil, ethyl acetate, methyl acetate or the chloroform.
Described emulsifying agent is selected from C
3～10The alkylaryl Soxylat A 25-7 is as Igepal CA-630, C
2～18Fatty alcohol-polyoxyethylene ether, as Ukanil36, Ukanil43, polyoxyethylene sorbitol is single
C11～18Fatty acid ester, as polysorbate60, tween 80, polysorbate40, or polyoxyethylene sorbitol three C
11～18Fatty acid ester is as in polysorbate65, the polysorbate85 one or more; The ethylene oxide number of repeat unit of described Soxylat A 25-7 is 4～50.
Described buffered soln is selected from one or more in sodium carbonate solution, sodium hydrogen carbonate solution, calcium carbonate soln, solution of potassium carbonate, potassium bicarbonate solution, sodium hydroxide solution or the potassium hydroxide solution.
Described amine is selected from one or more in quadrol, hexanediamine, certain herbaceous plants with big flowers diamines, Ursol D, diethylenetriamine or the triethylene tetramine.
Temperature during described the reaction is 0～100 ℃, preferred 0～60 ℃, and most preferably 0～30 ℃.
The described reaction times is 5min～48h, preferred 10min～24h, most preferably 20min～8h
The rotating speed that stirs is 50～5000 rev/mins, preferred 200～3000 rev/mins, and most preferably 500～2000 rev/mins.
The present invention at first adopts the phase reversion emulsion process to prepare O/W type emulsion, adds in buffered soln and amine and the organic phase dissolved acyl chlorides again and carries out interfacial polycondensation and make polyamide micro-particle.The polyamide particles minor structure that the present invention makes is more complete sphere, and particle size range is that 1～100 μ m and pyrolysis temperature range are 300～420 ℃, and operational path of the present invention is simpler, and is lower to the requirement of equipment, and very strong practicality is arranged.
Description of drawings
The stereoscan photograph of the polyamide micro-particle that Fig. 1, Fig. 2 obtain for the embodiment of the invention 2.
The stereoscan photograph of the polyamide micro-particle that Fig. 3 obtains for Comparative Examples 1.
The infrared spectrogram of the polyamide micro-particle that Fig. 4 obtains for the embodiment of the invention 2.
At 3304cm
-1The absorption peak at place is the stretching vibration of N-H, 1635cm
-1The place is the stretching vibration of C=O in the amide group, 1550cm
-1The absorption at place is the flexural vibration of N-H, this shows that sample is a polymeric amide.
The thermogravimetric curve of polyamide micro-particle in nitrogen that Fig. 5 obtains for the embodiment of the invention 2.
As seen heat decomposition temperature is approximately 400 ℃ in nitrogen atmosphere, the carbon of rest parts for generating.
Embodiment
Embodiment 1:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 800rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 2:
The 3g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, and low whipping speed is 800rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 3:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 3.87g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 800rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 4:
4.5g p-phthaloyl chloride is dissolved in the 10ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbyl alcohol tri-fatty acid ester Tween85 again, low whipping speed is 800rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g sodium hydroxide and 20ml deionized water, the 70ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 5:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifying agent alkylaryl Soxylat A 25-7 Igepal CA-630 again, low whipping speed is 800rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g sodium bicarbonate and 20ml deionized water, the 100ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 6:
The 45g p-phthaloyl chloride is dissolved in the 195ml dimethylbenzene, adds 9g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, and low whipping speed is 800rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 45g yellow soda ash and 300ml deionized water, the 121ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 7:
4.5g p-phthaloyl chloride is dissolved in the 39ml dimethylbenzene, adds 0.45g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 1200rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 4.5g yellow soda ash and 30ml deionized water, the 4ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 8:
6.3g hexanedioyl chlorine is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 2000rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 50rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 24h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 9:
The 21g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, and low whipping speed is 3000rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 200rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml hexanediamine.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 10:
4.5g the certain herbaceous plants with big flowers diacid chloride is dissolved in the 15ml toluene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 5000rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml Ursol D.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 11:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbyl alcohol single-hard ester acid ester Tween60 again, low whipping speed is 5000rpm, 15 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 50rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml triethylene tetramine.React 3h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 12:
4.5g p-phthaloyl chloride is dissolved in the 15ml ethyl acetate, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 800rpm, 60 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g salt of wormwood and 20ml deionized water, the 70ml quadrol.React 48h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 13:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifying agent fatty alcohol-polyoxyethylene ether Ukanil43 again, low whipping speed is 800rpm, 100 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 5min after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 14:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 800rpm, 5 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 10h after separate, the deionization washing obtains polyamide micro-particle.
Embodiment 15:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 2.85g emulsifier polyoxyethylene sorbitol monooleate Tween80 again, low whipping speed is 800rpm, 0 ℃ of down mixed 5min.Progressively add deionized water and O/W emulsion, then emulsification 5min take place to form up to phase reversion.After stirring velocity reduced to 300rpm, add the damping fluid that contains 3.75g yellow soda ash and 20ml deionized water, the 70ml quadrol.React 24h after separate, the deionization washing obtains polyamide micro-particle.
Comparative Examples 1:
4.5g p-phthaloyl chloride is dissolved in the 15ml dimethylbenzene, adds 3g emulsifying agent Tween80 and 135ml deionized water again, low whipping speed is 800rpm15 ℃ of following emulsification 20min.After stirring velocity reduced to 300rpm, add damping fluid (containing 3.75g yellow soda ash, the 20ml deionized water), the 70ml quadrol.React 5h after separate, the deionization washing obtains polyamide micro-particle.
Claims (7)
1. polyamide micro-particle is characterized in that having following molecular structure:
This kind micropartical particle size range is that 1～100 μ m and pyrolysis temperature range are 300～420 ℃;
This atomic preparation method is: earlier acyl chlorides is dissolved in the organic solvent, adds emulsifying agent 0～100 ℃ temperature with under stirring; Progressively add deionized water behind the adding emulsifying agent and take place up to phase reversion, emulsion changes the O/W type into by w/o type; Add buffered soln and amine again, with the generation polymeric amide that reacts of dissolved acyl chlorides in the organic phase; After finishing, reaction, promptly obtains polyamide micro-particle through separation, washing, drying;
Wherein the add-on of each raw material is by weight:
0.1～10 part of acyl chlorides;
1～50 part of organic solvent;
0.01～20 part of emulsifying agent;
10～100 parts of deionized waters;
0.1～10 part of damping fluid;
0.1～30 part of amine;
Described acyl chlorides is selected from one or more in oxalyl chloride, p-phthaloyl chloride, sebacoyl chloride, hexanedioyl chlorine or the 2-chlorine terephthalyl chloride; Described amine is selected from one or more in quadrol, hexanediamine, decamethylene diamine, Ursol D, diethylenetriamine or the triethylene tetramine; Described buffered soln is selected from one or more in sodium carbonate solution, sodium hydrogen carbonate solution, solution of potassium carbonate, saleratus, sodium hydroxide solution or the potassium hydroxide solution.
2. a method for preparing polyamide micro-particle in the claim 1 is characterized in that earlier acyl chlorides being dissolved in the organic solvent, adds emulsifying agent 0～100 ℃ temperature with under stirring; Progressively add deionized water behind the adding emulsifying agent and take place up to phase reversion, emulsion changes the O/W type into by w/o type; Add buffered soln and amine again, with the generation polymeric amide that reacts of dissolved acyl chlorides in the organic phase; After finishing, reaction, promptly obtains polyamide micro-particle through separation, washing, drying; Wherein the add-on of each raw material is by weight:
0.1～10 part of acyl chlorides;
1～50 part of organic solvent;
0.01～20 part of emulsifying agent;
10～100 parts of deionized waters;
0.1～10 part of damping fluid;
0.1～30 part of amine.
3. the preparation method of polyamide micro-particle according to claim 2 is characterized in that described organic solvent is selected from one or more in benzene,toluene,xylene, normal hexane, hexanaphthene, sherwood oil, ethyl acetate, methyl acetate or the chloroform.
4. the preparation method of polyamide micro-particle according to claim 2 is characterized in that described emulsifying agent is selected from C
3～10Alkylaryl Soxylat A 25-7, C
2～18Fatty alcohol-polyoxyethylene ether, the single C of polyoxyethylene sorbitol
11～18Fatty acid ester or polyoxyethylene sorbitol three C
11～18In the fatty acid ester one or more; The ethylene oxide number of repeat unit of described Soxylat A 25-7 is 4～50.
5. the preparation method of polyamide micro-particle according to claim 2, the temperature when it is characterized in that described reaction is 0～60 ℃, the reaction times is 5min～48h.
6. the preparation method of polyamide micro-particle according to claim 2, the temperature when it is characterized in that described reaction is 0～30 ℃, the reaction times is 10min～24h.
7. the preparation method of polyamide micro-particle according to claim 2 is characterized in that the rotating speed that stirs is 50～5000 rev/mins.
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| CN105949494B (en) * | 2016-05-11 | 2019-01-18 | 合肥工业大学 | A kind of microspheres and its preparation method and application |
| CN108395530B (en) * | 2017-02-06 | 2021-12-31 | 中国石油化工股份有限公司 | Method for preparing nylon powder for selective laser sintering based on reversed phase suspension polymerization method |
| CN109456202A (en) * | 2018-11-05 | 2019-03-12 | 昆山博科化学有限公司 | High-carbon alkane diamines and its preparation method and application |
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| Title |
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| JP特开2002-293928A 2002.10.09 |
| JP特开2006-199904A 2006.08.03 |
| 王凤平，张河哲.聚酰胺微胶囊制备工艺的研究.松辽学刊（自然科学版）.1992,(2),18-20. * |
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