CN112876674A - Method for preparing polyamide microspheres through in-situ hydrolytic ring opening - Google Patents
Method for preparing polyamide microspheres through in-situ hydrolytic ring opening Download PDFInfo
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- CN112876674A CN112876674A CN202110288645.XA CN202110288645A CN112876674A CN 112876674 A CN112876674 A CN 112876674A CN 202110288645 A CN202110288645 A CN 202110288645A CN 112876674 A CN112876674 A CN 112876674A
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- microspheres
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- caprolactam
- polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
Abstract
A method for preparing polyamide microspheres (PA6 microspheres) by in-situ hydrolytic ring opening, which comprises the following steps: (1) adding a surfactant and an auxiliary agent A into caprolactam, uniformly mixing and melting to obtain a mixed solution; (2) heating the mixed solution obtained in the step (1) to 240-260 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 2-5 h; (3) and (3) adding the auxiliary agent B into the product obtained in the step (2) at normal temperature and normal pressure, and reacting for 1-3h to obtain the polyamide microspheres. The method has the advantages of simple process, convenient operation, high efficiency and low cost, adopts in-situ polymerization for reaction, is suitable for industrial production, and has the advantages of regular microspherical shape of the obtained PA6 and higher industrial application value.
Description
Technical Field
The invention belongs to the field of chemical engineering, and particularly relates to a method for preparing polyamide microspheres by in-situ hydrolytic ring opening.
Background
Polyamide microspheres (PA6 microspheres) are of great interest for their potential applications in the fields of drug carriers, substance absorption and desorption, biotechnology, etc. Due to the unique surface characteristics, the polyamide microspheres can be widely applied to the industrial fields of rotary forming, powder coating, pressing and sintering, 3D printing and the like.
At present, the preparation methods of polyamide microspheres include two major types, namely physical methods (mechanical grinding method, solvent precipitation method and melt blending method) and chemical methods (precipitation polymerization, emulsion polymerization, suspension polymerization and reaction induced phase separation method). But the physical method has large energy consumption, irregular microspherical shape and poor fluidity; although the sphericity of the microspheres is greatly improved by a chemical method (particularly a reaction-induced phase separation method), the solvent consumption is large in the reaction process, the post-treatment process is complicated, and the industrialization degree is influenced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the method for preparing the polyamide microspheres by in-situ hydrolytic ring opening, which has the advantages of low energy consumption, simple method and regular shape of the obtained microspheres.
The specific technical scheme is as follows:
a method for preparing polyamide microspheres (PA6 microspheres) by in-situ hydrolytic ring opening, which comprises the following steps:
(1) adding a surfactant and an auxiliary agent A into caprolactam, uniformly mixing and melting to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 240-260 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 2-5 h;
(3) and (3) adding the auxiliary agent B into the product obtained in the step (2) at normal temperature and normal pressure, and reacting for 1-3h to obtain the polyamide microspheres. The normal pressure is one atmosphere, and the normal temperature is 15-25 ℃.
Further, in the step (1), the surfactant is a perfluoro polyoxypropylene-polyethylene glycol-perfluoro polyoxypropylene triblock copolymer (PFPE-PEG-PFPE, ABA for short).
Furthermore, the addition amount of the perfluoro polyoxypropylene-polyethylene glycol-perfluoro polyoxypropylene triblock copolymer is 10-30 wt% of the mass of caprolactam.
Further, in the step (1), the assistant A is sodium bicarbonate.
Still further, the addition amount of the sodium bicarbonate is 1 wt% -10 wt% of the mass of the caprolactam.
Further, in the step (2), the assistant B is citric acid (or called citric acid).
Still further, the addition amount of the citric acid is 1 to 10 weight percent of the mass of the caprolactam.
Further, in the step (2), the pressure is maintained at 0.8 to 1.2MPa by distillation under reduced pressure.
Further, the obtained polyamide microspheres are washed with water, preferably three times.
The invention also provides the polyamide microsphere prepared by the method.
The invention has the following beneficial effects:
the method has the advantages of simple process, convenient operation, high efficiency and low cost, adopts in-situ polymerization for reaction, is suitable for industrial production, and has the advantages of regular microspherical shape of the obtained PA6 and higher industrial application value.
Drawings
FIG. 1 is a scanning electron micrograph of polyamide microspheres obtained in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The perfluoropolyoxypropylene-polyethylene glycol-perfluoropolyoxypropylene triblock copolymer (PFPE-PEG-PFPE) in the specific embodiment is purchased from new materials ltd of anseridae.
Example 1
A method for preparing polyamide microspheres by in-situ hydrolytic ring opening comprises the following steps:
(1) to 100g of caprolactam were added 10g of PFPE-PEG-PFPE, 1g of NaHCO3Stirring uniformly under the protection of nitrogen, and keeping the temperature at 100 ℃ for 1 hour until the mixture becomes transparent liquid to obtain mixed liquid;
(2) gradually heating the mixed solution obtained in the step (1) to 240 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 2 hours; distilling under reduced pressure to maintain pressure of 0.8 Mpa;
(3) and (3) decompressing the product obtained in the step (2) to normal pressure, adding 1g of citric acid at normal temperature and normal pressure, reacting for 1h, discharging to obtain a composite microsphere material, putting the composite microsphere material into water, washing for three times, and filtering to obtain the polyamide microsphere.
The scanning electron micrograph of the obtained polyamide microspheres is shown in fig. 1.
Example 2
A method for preparing polyamide microspheres by in-situ hydrolytic ring opening comprises the following steps:
(1) to 100g of caprolactam were added 15g of PFPE-PEG-PFPE, 4g of NaHCO3Stirring uniformly under the protection of nitrogen, and keeping the temperature at 100 ℃ for 1 hour until the mixture becomes transparent liquid to obtain mixed liquid;
(2) gradually heating the mixed solution obtained in the step (1) to 250 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 3 hours; the pressure is maintained at 0.9MPa by reduced pressure distillation;
(3) and (3) decompressing the product obtained in the step (2) to normal pressure, adding 4g of citric acid at normal temperature and normal pressure, reacting for 2 hours, discharging to obtain a composite microsphere material, putting the composite microsphere material into water, washing for three times, and filtering to obtain the polyamide microsphere.
Example 3
A method for preparing polyamide microspheres by in-situ hydrolytic ring opening comprises the following steps:
(1) to 100g of caprolactam were added 20g of PFPE-PEG-PFPE, 6g of NaHCO3Stirring uniformly under the protection of nitrogen, and keeping the temperature at 100 ℃ for 1 hour until the mixture becomes transparent liquid to obtain mixed liquid;
(2) gradually heating the mixed solution obtained in the step (1) to 260 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 4 hours; the pressure is maintained at 1.2MPa by reduced pressure distillation;
(3) and (3) decompressing the product obtained in the step (2) to normal pressure, adding 6g of citric acid at normal temperature and normal pressure, reacting for 2 hours, discharging to obtain a composite microsphere material, putting the composite microsphere material into water, washing for three times, and filtering to obtain the polyamide microsphere.
Example 4
A method for preparing polyamide microspheres by in-situ hydrolytic ring opening comprises the following steps:
(1) to 100g of caprolactam were added 25g of PFPE-PEG-PFPE, 8g of NaHCO3Stirring uniformly under the protection of nitrogen, and keeping the temperature at 100 ℃ for 1 hour until the mixture becomes transparent liquid to obtain mixed liquid;
(2) gradually heating the mixed solution obtained in the step (1) to 250 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 5 hours; the pressure is maintained at 1.0MPa by reduced pressure distillation;
(3) and (3) decompressing the product obtained in the step (2) to normal pressure, adding 8g of citric acid at normal temperature and normal pressure, reacting for 3h, discharging to obtain a composite microsphere material, putting the composite microsphere material into water, washing for three times, and filtering to obtain the polyamide microsphere.
Example 5
A method for preparing polyamide microspheres by in-situ hydrolytic ring opening comprises the following steps:
(1) to 100g of caprolactam were added 30g of PFPE-PEG-PFPE, 10g of NaHCO3Stirring uniformly under the protection of nitrogen, and keeping the temperature at 100 ℃ for 1 hour until the mixture becomes transparent liquid to obtain mixed liquid;
(2) gradually heating the mixed solution obtained in the step (1) to 260 ℃ in the process of reduced pressure distillation, and carrying out in-situ hydrolysis bulk polymerization reaction for 5 hours; the pressure is maintained at 1.1MPa by reduced pressure distillation;
(3) and (3) decompressing the product obtained in the step (2) to normal pressure, adding 10g of citric acid at normal temperature and normal pressure, reacting for 3h, discharging to obtain a composite microsphere material, putting the composite microsphere material into water, washing for three times, and filtering to obtain the polyamide microsphere.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The method for preparing the polyamide microspheres through in-situ hydrolytic ring opening is characterized by comprising the following steps of:
(1) adding a surfactant and an auxiliary agent A into caprolactam, uniformly mixing and melting to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 240 ℃ and 260 ℃ in the process of reduced pressure distillation, and reacting for 2-5 h;
(3) and (3) adding the auxiliary agent B into the product obtained in the step (2) at normal temperature and normal pressure, and reacting for 1-3h to obtain the polyamide microspheres.
2. The method according to claim 1, wherein in step (1), the surfactant is a perfluoropolyether-polyethylene glycol-perfluoropolyether triblock copolymer.
3. The method according to claim 2, wherein the amount of the perfluoropolyether-polyethylene glycol-perfluoropolyether triblock copolymer is 10 wt% to 30 wt% based on the mass of caprolactam.
4. The method according to claim 1, wherein in step (1), the auxiliary agent A is sodium bicarbonate.
5. The method of claim 4, wherein the sodium bicarbonate is added in an amount of 1 wt% to 10 wt% based on the mass of caprolactam.
6. The method according to claim 1, wherein in the step (2), the auxiliary agent B is citric acid.
7. The method according to claim 6, wherein the citric acid is added in an amount of 1-10 wt% based on the mass of caprolactam.
8. The method according to claim 1, wherein in the step (2), the pressure is maintained at 0.8 to 1.2MPa by distillation under reduced pressure.
9. The process according to claim 1, characterized in that the polyamide microspheres obtained are subjected to a water wash.
10. Polyamide microspheres obtained using the method according to any one of claims 1-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127513A (en) * | 1997-03-18 | 2000-10-03 | Ube Industries, Ltd. | Spherical polyamide and process for preparing the same |
| CN102532523A (en) * | 2010-12-30 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN106543433A (en) * | 2015-09-21 | 2017-03-29 | 上海杰事杰新材料(集团)股份有限公司 | A kind of nylon powder and its preparation method and application |
| CN110612320A (en) * | 2017-05-12 | 2019-12-24 | 东丽株式会社 | Method for producing polyamide microparticles and polyamide microparticles |
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- 2021-03-17 CN CN202110288645.XA patent/CN112876674A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127513A (en) * | 1997-03-18 | 2000-10-03 | Ube Industries, Ltd. | Spherical polyamide and process for preparing the same |
| CN102532523A (en) * | 2010-12-30 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN106543433A (en) * | 2015-09-21 | 2017-03-29 | 上海杰事杰新材料(集团)股份有限公司 | A kind of nylon powder and its preparation method and application |
| CN110612320A (en) * | 2017-05-12 | 2019-12-24 | 东丽株式会社 | Method for producing polyamide microparticles and polyamide microparticles |
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