CN101357989A - Polyamide microparticle and preparation method thereof - Google Patents
Polyamide microparticle and preparation method thereof Download PDFInfo
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- CN101357989A CN101357989A CNA2007100255354A CN200710025535A CN101357989A CN 101357989 A CN101357989 A CN 101357989A CN A2007100255354 A CNA2007100255354 A CN A2007100255354A CN 200710025535 A CN200710025535 A CN 200710025535A CN 101357989 A CN101357989 A CN 101357989A
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Abstract
The invention discloses polyamide fine particles and a preparation method thereof. The polyamide fine particles are integrated spherical particles with the size ranging from 0.1 to 1 Mu M; the coefficient of standard deviation of the size distribution of the particles ranges from 0.01 to 0.2; the thermal decomposition temperature of the particles ranges from 420 DEG C to 450 DEG C. The preparation method comprises the following steps: a dispersant is added to a solvent; the dispersant is beaten and dissolved; diamine and acyl chloride are added in turn; on completion of reaction, the reactant product is separated, washed and dried to get the polyamide fine particles. The process route of the preparation method is simple; the equipment involved in the preparation method is not highly required; the polyamide fine particles are very practical.
Description
Technical field
The present invention relates to the high molecular polymerization field, be specifically related to a kind of polyamide particles and preparation method thereof.
Background technology
Polymeric amide not only has good mechanical property, and has other satisfactory performance, as thermotolerance, and chemical proofing and insulativity; Therefore, it is widely used as electric, electronic material, materials used in auto manufacturing, the surrogate of metal and pottery, and other application.
The synthetic method of polymeric amide generally adopts precipitation polymerization, and in two steps: the first step system is dissolved in acyl chlorides and diamines in methyl alcohol, ethanol, the Virahol isopolarity solvent; Second step under 0 ℃, reacted these two kinds of solution under hyperacoustic environment, finally obtain polyamide particles.A lot of patents have all been reported the preparation method of polyamide micro-particle: the polyamide particles for preparing narrow size distribution, low porosity as patent CN98107389 by the method for cryoprecipitation in the Fatty Alcohol(C12-C14 and C12-C18) that polymeric amide is dissolved in, size distribution is in 32 μ m-100 μ m, wider distribution; Patent JP2006257345 prepares polyamide micro-particle by precipitation polymerization in two steps: the first step system is dissolved in acyl chlorides and diamines in the organic solvent; Second step under 0 ℃, reacted these two kinds of solution under hyperacoustic environment, finally obtain polyamide particles, size distribution 0.01 μ m-5 μ m, but disperse bad between the particle.
Dispersion copolymerization method is often used preparing the polymeric microsphere from vinyl monomer.Its polymerization system is homogeneous phase solution at first, that is to say monomer, and initiator and stablizer all are dissolved in solvent, but the polymkeric substance after the polymerization must be not dissolved in solvent.Stablizer and solvent, polymkeric substance must all have affinity interaction.After the beginning polymerization, decomposition of initiator and in solvent with monomer reaction, after the polymkeric substance chain length surpassed critical length, just precipitating came out to form nuclear from solvent.Then, a plurality of nuclears are agglomerated into stable growth microballoon mutually, and the absorption stablizer makes polymeric microspheres stabilize in microsphere surface.Then, the growth microballoon absorbs monomer and initiator and polymerization in microballoon from external phase, and promptly the polymerization place moves in the microballoon from external phase.Do not appear in the newspapers as yet about the method for utilizing dispersion copolymerization method to prepare polyamide micro-particle, compare with the preparation method of traditional polyamide micro-particle, the polyamide micro-particle sphere that the present invention obtains is more complete, and deployment conditions is better, and the size distribution Z-factor is littler.
Summary of the invention
The objective of the invention is on the basis of prior preparation method,, provide a kind of polyamide micro-particle in conjunction with dispersion polymerization processes.
The preparation method who the purpose of this invention is to provide a kind of above-mentioned polyamide micro-particle.
Purpose of the present invention can reach by following measure:
A kind of polyamide micro-particle, this micropartical are complete sphere, and its particle size range is that 0.1～1 μ m and pyrolysis temperature range are 420～450 ℃; This micropartical is made by the raw material of following weight part:
0.01～10 part of acyl chlorides,
0.01～10 part of diamines,
0.01～10 part of dispersion agent,
20～100 parts of solvents;
A kind of method for preparing above-mentioned polyamide micro-particle, acyl chlorides by weight: diamines: dispersion agent: solvent=0.01～10: 0.01～10: 0.01～10: 20～100 ratio is got raw material, earlier dispersion agent is added in the solvent, stirring and dissolving adds diamines successively and acyl chlorides reacts; After finishing, reaction, is drying to obtain polyamide micro-particle through separating, washing.
Temperature of reaction is 0～130 ℃, preferred 0～40 ℃, and most preferably 0～20 ℃; Reaction times is 1min～48h, preferred 10min～24h; Stirring velocity is 50～5000 rev/mins, preferred 200～2000 rev/mins.
Purpose of the present invention specifically can reach by following measure:
A kind of polyamide micro-particle is characterized in that particle size range is that 0.1～1 μ m and heat decomposition temperature are greater than 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 characterized in that earlier dispersion agent being added in the solvent, and stirring and dissolving adds diamines and acyl chlorides successively; After finishing, reaction, is drying to obtain polyamide micro-particle through separating, washing.
The present invention utilizes acyl chlorides and diamine compound to be raw material, prepare the narrower spherical polyamide micro-particle of particle size dispersion through dispersion polymerization. this kind micropartical particle size range is 0.1～1 μ m, the standard deviation factor of size distribution be 0.01～0.2 and heat decomposition temperature greater than 420 ℃.
The add-on of each raw material is by weight in this atomic preparation method:
0.01～10 part of acyl chlorides
0.01～10 part of diamines
0.01～10 part of dispersion agent
20～100 parts of solvents
Described acyl chlorides includes but not limited to those used in traditional synthesizing polyamides compounds, preferably one or more in oxalyl chloride, p-phthaloyl chloride, isophthaloyl first chlorine, certain herbaceous plants with big flowers diacid chloride, hexanedioyl chlorine or 2-chlorine terephthalyl chloride.These compounds can be separately or two or more be used in combination.For the present invention, preferred especially p-phthaloyl chloride and m-phthaloyl chloride.
Described diamines includes but not limited to those used in traditional synthesizing polyamides diamine compounds, preferably one or more in quadrol, hexanediamine, certain herbaceous plants with big flowers diamines, Ursol D, diamines yl diphenyl ether, diethylenetriamine or triethylene tetramine.These diamine compounds can use separately, and perhaps two or more materials are used in combination.The preferred especially diamines yl diphenyl ether of the present invention.
In described polyethylene of dispersing agent pyrrolidone (PVP), polyvinyl alcohol (PVA), derivatived cellulose, polyacrylate or the poly-methyl acrylate one or more.Wherein derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, hydroxypropylcellulose, Vltra tears etc.Wherein polyacrylate or poly-methyl acrylate are their sodium salt or sylvite etc.
Described solvent is selected from methyl alcohol, ethanol, Virahol, cyclohexane, ethyl acetate, tetrahydrofuran (THF), chloroform, pentanone, acetone, toluene, dimethylbenzene, dioxane, N, in dinethylformamide, N,N-dimethylacetamide or the N-N-methyl-2-2-pyrrolidone N-one or more.
Among the described preparation method, the temperature during reaction is 0～130 ℃, preferred 0～40 ℃, and further preferred 0～20 ℃, most preferably 0～10 ℃.The described reaction times is 1min～48h, preferred 10min～24h, most preferably 0.5h～5h.Described mixing speed is 50～5000 rev/mins, preferred 100～3000 rev/mins, and most preferably 200～2000 rev/mins.
Contain following structural unit in the polyimide microparticle molecular chain of gained of the present invention:
Wherein, R
1Be the pairing group of acyl chlorides, R
2Be the pairing group of diamines, the standard deviation factor of size distribution is 0.01～0.2.Because polyamide particles is a crosslinking structure, have no idea to be dissolved in the organic solvent, so its polymerization degree cannot be measured.
The reaction equation of acyl chlorides and diamines is as follows:
The present invention adopts diffuse-aggregate method to prepare polyimide microparticle.The polyamide particles minor structure that the present invention makes is complete sphere, particle size range is 0.1～1 μ m, the standard deviation factor of size distribution be 0.01～0.2 and heat decomposition temperature greater than 420 ℃, and operational path of the present invention is simpler, requirement to equipment is lower, and very strong practicality is arranged.The resulting polyimide microparticle of the present invention has thermotolerance, insulativity and other performances of polyimide resin inherent, therefore can be widely used (comprising traditional purposes), coated material in particular as electric insulation part, die material, electric, electronic material, and other matrix materials etc.
Description of drawings
The stereoscan photograph of the polyamide micro-particle that Fig. 1 obtains for the embodiment of the invention 1.
The stereoscan photograph of the polyamide micro-particle that Fig. 2 obtains for Comparative Examples 1.
The thermogravimetric curve of polyamide micro-particle in nitrogen that Fig. 3 obtains for the embodiment of the invention 1.
Heat decomposition temperature is tested with thermogravimetric analyzer (TAQ600), 10 ℃/min of temperature rise rate, nitrogen atmosphere.
Embodiment
The present invention intends by following embodiment and Comparative Examples simple declaration merits and demerits of the present invention, but can not think that the present invention only limits to the content of embodiment.
Embodiment 1:
0 ℃, 200rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving, add methyl alcohol (50mL) solution of diamines yl diphenyl ether (0.1g) successively, methyl alcohol (50ml) solution of p-phthaloyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtains the complete spheric polyamide micro-particle that particle size range is 0.1～1 μ m.
Embodiment 2:
0 ℃, 1000rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds diamines yl diphenyl ether (0.1g) successively, methyl alcohol (50mL) solution of oxalyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 430 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 3:
0 ℃, 2000rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds Ursol D (0.1g) successively, methyl alcohol (50ml) solution of p-phthaloyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 440 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 4:
0 ℃, 200rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent alcohol (PVA) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds Ursol D (0.1g) successively, methyl alcohol (50ml) solution of p-phthaloyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 420 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 5:
0 ℃, 1000rpm stirs down, and 50ml acetone and toluene (volume ratio 1: 1) are joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds diamines yl diphenyl ether (0.1g) successively, the acetone of oxalyl chloride (0.1g) and toluene 50mL) solution, reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 420 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 6:
0 ℃, 200rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent alcohol (PVA) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds diamines yl diphenyl ether (0.1g) successively, methyl alcohol (50ml) solution of p-phthaloyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 450 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 7:
0 ℃, 200rpm stirs down, and 500ml methyl alcohol is joined in the there-necked flask, adds 5g dispersion agent polyacrylic acid potassium again.After treating the dispersion agent dissolving, add methyl alcohol (50mL) solution of hexanediamine (0.1g) successively, methyl alcohol (50ml) solution of second dimethyl chloride (0.1g), reaction 2h, after filtration, washing, drying obtains the complete spheric polyamide micro-particle that particle size range is 430 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 8:
0 ℃, 200rpm stirs down, and 500ml N-N-methyl-2-2-pyrrolidone N-is joined in the there-necked flask, adds 5g dispersion agent polyacrylic acid potassium again.After treating the dispersion agent dissolving, add methyl alcohol (50mL) solution of diamines (0.1g) successively, N-N-methyl-2-2-pyrrolidone N-(50ml) solution of second dimethyl chloride (0.1g), reaction 2h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 420 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 9:
0 ℃, 200rpm stirs down, 25ml dioxane and 25mL chloroform are joined in the there-necked flask, add 0.1g polyethylene of dispersing agent pyrrolidone (PVP) again. after treating the dispersion agent dissolving, add chloroform (100mL) solution of diamines yl diphenyl ether (1g) successively, chloroform (100ml) solution of p-phthaloyl chloride (1g), reaction 0.5h, after filtration, washing, drying obtains the complete spheric polyamide micro-particle that particle size range is 430 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 10:
10 ℃, 200rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent alcohol again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds diamines yl diphenyl ether (0.1g) successively, methyl alcohol (50ml) solution of p-phthaloyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 450 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 11:
0 ℃, 200rpm stirs down, and the 50ml cyclohexane is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds diamines yl diphenyl ether (2g) successively, cyclohexane (50ml) solution of p-phthaloyl chloride (2g), reaction 5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 440 ℃ of 0.1～1 μ m and heat decomposition temperatures
Embodiment 12:
0 ℃, 200rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent alcohol (PVA) again.After treating the dispersion agent dissolving, methyl alcohol (50mL) solution that adds diamines yl diphenyl ether (0.1g) successively, methyl alcohol (50ml) solution of p-phthaloyl chloride (0.1g), reaction 0.5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 430 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Embodiment 13:
1 ℃, 200rpm stirs down, and the 50ml tetrahydrofuran (THF) is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving, tetrahydrofuran (THF) (50mL) solution that adds diamines yl diphenyl ether (2g) successively, methyl alcohol (50ml) solution of m-phthaloyl chloride (2g), reaction 5h, after filtration, washing, drying obtain the complete spheric polyamide micro-particle that particle size range is 420 ℃ of 0.1～1 μ m and heat decomposition temperatures.
Comparative Examples 1:
0 ℃, 0.1g diamines yl diphenyl ether is dissolved in the acetone of 100mL, add the deionized water of 25mL then, 200rpm stirs down, adds the p-phthaloyl chloride of 0.1g, reaction 90min, through centrifugation, washing, drying obtains polyamide particles.
Claims (9)
1, a kind of polyamide micro-particle is characterized in that this micropartical is complete sphere, and its particle size range is that 0.1～1 μ m and pyrolysis temperature range are 420～450 ℃; This micropartical is made by the raw material of following weight part:
0.01～10 part of acyl chlorides,
0.01～10 part of diamines,
0.01～10 part of dispersion agent,
20～100 parts of solvents;
Above-mentioned solvent is selected from methyl alcohol, ethanol, Virahol, hexanaphthene, ethyl acetate, tetrahydrofuran (THF), chloroform, pentanone, acetone, toluene, dimethylbenzene, dioxane, N, in dinethylformamide, N,N-dimethylacetamide or the N-N-methyl-2-2-pyrrolidone N-one or more.
2, polyamide micro-particle according to claim 1 is characterized in that described acyl chlorides is selected from one or more in oxalyl chloride, p-phthaloyl chloride, isophthaloyl first chlorine, certain herbaceous plants with big flowers diacid chloride, hexanedioyl chlorine, second dimethyl chloride or the 2-chlorine terephthalyl chloride.
3, polyamide micro-particle according to claim 1 is characterized in that described diamines is selected from one or more in quadrol, hexanediamine, certain herbaceous plants with big flowers diamines, Ursol D, diamines yl diphenyl ether, diethylenetriamine or the triethylene tetramine.
4, polyamide micro-particle according to claim 1 is characterized in that described dispersion agent is selected from one or more in polyvinylpyrrolidone, polyvinyl alcohol, derivatived cellulose, polyacrylate or the poly-methyl acrylate.
5, a kind of method for preparing each described polyamide micro-particle in the claim 1～4, it is characterized in that acyl chlorides by weight: diamines: dispersion agent: solvent=0.01～10: 0.01～10: 0.01～10: 20～100 ratio is got raw material, earlier dispersion agent is added in the solvent, stirring and dissolving adds diamines successively and acyl chlorides reacts; After finishing, reaction, is drying to obtain polyamide micro-particle through separating, washing.
6, method according to claim 5 is characterized in that temperature of reaction is 0～130 ℃, and the reaction times is 1min～48h.
7, method according to claim 6 is characterized in that temperature of reaction is 0～40 ℃, and the reaction times is 10min～24h.
8, method according to claim 5 is characterized in that stirring velocity is 50～5000 rev/mins.
9, method according to claim 8 is characterized in that stirring velocity is 200～2000 rev/mins.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102796376A (en) * | 2012-08-31 | 2012-11-28 | 江苏亚宝绝缘材料股份有限公司 | Corona-resistant composition and preparation method thereof |
| CN102869706A (en) * | 2010-04-20 | 2013-01-09 | 宇部兴产株式会社 | Polyamide microparticles, manufacturing method therefor, optical film using said polyamide microparticles, and liquid-crystal display device |
| CN103932989A (en) * | 2014-02-24 | 2014-07-23 | 北京化工大学常州先进材料研究院 | Method used for preparing pharmaceutic adjuvant Eudragit RL100 polymer particulates |
| CN105949494A (en) * | 2016-05-11 | 2016-09-21 | 合肥工业大学 | Thermal-expanding microspheres as well as preparation method and application thereof |
| CN109440216A (en) * | 2018-09-28 | 2019-03-08 | 浙江大学 | A kind of functionalization aramid fiber superfine fibre and its preparation method and application |
| CN112996844A (en) * | 2018-11-09 | 2021-06-18 | 东丽株式会社 | Method for producing polyamide microparticles and polyamide microparticles |
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2007
- 2007-08-03 CN CN2007100255354A patent/CN101357989B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102869706A (en) * | 2010-04-20 | 2013-01-09 | 宇部兴产株式会社 | Polyamide microparticles, manufacturing method therefor, optical film using said polyamide microparticles, and liquid-crystal display device |
| CN102796376A (en) * | 2012-08-31 | 2012-11-28 | 江苏亚宝绝缘材料股份有限公司 | Corona-resistant composition and preparation method thereof |
| CN103932989A (en) * | 2014-02-24 | 2014-07-23 | 北京化工大学常州先进材料研究院 | Method used for preparing pharmaceutic adjuvant Eudragit RL100 polymer particulates |
| CN103932989B (en) * | 2014-02-24 | 2016-08-17 | 北京化工大学常州先进材料研究院 | A kind of method preparing pharmaceutic adjuvant Eudragit RL100 polymer particles |
| CN105949494A (en) * | 2016-05-11 | 2016-09-21 | 合肥工业大学 | Thermal-expanding microspheres as well as preparation method and application thereof |
| CN105949494B (en) * | 2016-05-11 | 2019-01-18 | 合肥工业大学 | A kind of microspheres and its preparation method and application |
| CN109440216A (en) * | 2018-09-28 | 2019-03-08 | 浙江大学 | A kind of functionalization aramid fiber superfine fibre and its preparation method and application |
| CN109440216B (en) * | 2018-09-28 | 2020-08-11 | 浙江大学 | Functionalized aramid superfine fiber and preparation method and application thereof |
| CN112996844A (en) * | 2018-11-09 | 2021-06-18 | 东丽株式会社 | Method for producing polyamide microparticles and polyamide microparticles |
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