CN101357989B - Polyamide microparticle and preparation method thereof - Google Patents
Polyamide microparticle and preparation method thereof Download PDFInfo
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- CN101357989B CN101357989B CN2007100255354A CN200710025535A CN101357989B CN 101357989 B CN101357989 B CN 101357989B CN 2007100255354 A CN2007100255354 A CN 2007100255354A CN 200710025535 A CN200710025535 A CN 200710025535A CN 101357989 B CN101357989 B CN 101357989B
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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, like 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 compound 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 like patent CN98107389 through 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 through 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.Method about utilizing dispersion copolymerization method to prepare polyamide micro-particle is not appeared in the newspapers as yet, compares with the preparation method of traditional polyamide micro-particle, and 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,, a kind of polyamide micro-particle is provided 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.
The object of the invention can reach through 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 processed 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: the ratio of solvent=0.01～10:0.01～10:0.01～10:20～100 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.
The object of the invention specifically can reach through 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 with thermogravimetric analyzer (TAQ600) test, 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
Said 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.
Said 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 said polyethylene of dispersing agent pyrrolidone (PVP), Z 150PH (PVA), derivatived cellulose, polyacrylate or the poly-methyl acrylate one or more.Wherein derivatived cellulose such as methylcellulose gum, CMC 99.5, 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, ETHYLE ACETATE, THF, chloroform, pentanone, acetone, toluene, YLENE, dioxane, N; In dinethylformamide, DMAC N,N 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 following:
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; Therefore insulativity and other performances of polyimide resin inherent can be widely used (comprising traditional use), in particular as the coated material of 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 with thermogravimetric analyzer (TAQ600) test, 10 ℃/min of temperature rise rate, nitrogen atmosphere.
Embodiment
The present invention intends through 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; Through filtering, to wash, 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 is through filtering; 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 is through filtering; 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 is through filtering; 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 is through filtering; 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 is through filtering; 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 diamines (0.1g) successively, methyl alcohol (50ml) solution of second dimethyl chloride (0.1g); Reaction 2h; Through filtering, 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 is through filtering; 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, and 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; Through filtering, 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 is through filtering; 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, add methyl alcohol (50mL) solution of diamines yl diphenyl ether (2g) successively, cyclohexane (50ml) solution of p-phthaloyl chloride (2g); Reaction 5h; Through filtering, washing, drying obtains 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 is through filtering; 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 THF is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.After treating the dispersion agent dissolving; THF (50mL) solution that adds diamines yl diphenyl ether (2g) successively; Methyl alcohol (50ml) solution of m-phthaloyl chloride (2g), reaction 5h is through filtering; 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 spinning, washing, drying obtains polyamide particles.
Claims (7)
1. a 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 processed 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, ETHYLE ACETATE, THF, chloroform, pentanone, acetone, toluene, YLENE, dioxane, N; In dinethylformamide, DMAC N,N or the N-N-methyl-2-2-pyrrolidone N-one or more;
Above-mentioned dispersion agent is selected from one or more in Vinylpyrrolidone polymer, Z 150PH, polyacrylate or the poly-methyl acrylate;
Described acyl chlorides is selected from one or more in oxalyl chloride, p-phthaloyl chloride, isophthaloyl first chlorine, sebacoyl chloride, hexanedioyl chlorine or the 2-chlorine terephthalyl chloride.
2. polyamide micro-particle according to claim 1 is characterized in that described diamines is selected from one or more in quadrol, hexanediamine, decamethylene diamine, Ursol D, the diamines yl diphenyl ether.
3. method for preparing claim 1 or 2 described polyamide micro-particles; 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; Described dispersion agent is selected from one or more in Vinylpyrrolidone polymer, Z 150PH, polyacrylate or the poly-methyl acrylate;
Described acyl chlorides is selected from one or more in oxalyl chloride, p-phthaloyl chloride, isophthaloyl first chlorine, sebacoyl chloride, hexanedioyl chlorine or the 2-chlorine terephthalyl chloride.
4. method according to claim 3 is characterized in that temperature of reaction is 0～130 ℃, and the reaction times is 1min～48h.
5. method according to claim 4 is characterized in that temperature of reaction is 0～40 ℃, and the reaction times is 10min～24h.
6. method according to claim 3 is characterized in that stirring velocity is 50～5000 rev/mins.
7. method according to claim 6 is characterized in that stirring velocity is 200～2000 rev/mins.
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| 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 |
| 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 |
| CN105949494B (en) * | 2016-05-11 | 2019-01-18 | 合肥工业大学 | A kind of microspheres 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 |
| JP6702516B1 (en) * | 2018-11-09 | 2020-06-03 | 東レ株式会社 | Method for producing fine polyamide particles, and fine polyamide particles |
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| JP特开2005-97370A 2005.04.14 |
| JP特开2006-257345A 2006.09.28 |
| JP特开2007-106895A 2007.04.26 |
| 孟祥增等.聚酰胺微粒的制造与应用.《精细石油化工》.中国知网,1993,(第2期),第48-52页. * |
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