CN101768282B - Method for preparing nylon random copolymer micro-sphere with controllable melting point and grain diameter - Google Patents
Method for preparing nylon random copolymer micro-sphere with controllable melting point and grain diameter Download PDFInfo
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- CN101768282B CN101768282B CN2008102081031A CN200810208103A CN101768282B CN 101768282 B CN101768282 B CN 101768282B CN 2008102081031 A CN2008102081031 A CN 2008102081031A CN 200810208103 A CN200810208103 A CN 200810208103A CN 101768282 B CN101768282 B CN 101768282B
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Abstract
The invention relates to a method for preparing a nylon random copolymer micro-sphere with controllable melting point and grain diameter. The method comprises the processing steps of dissolution, anionic polymerization, nylon random copolymer micro-sphere extraction and the like. The grain diameter of the micro-sphere prepared in the invention can be controlled at 1-200mum, the melting point of the nylon copolymer micro-sphere can be controlled at 50-250 DEG C, and even the nylon copolymer micro-sphere with no melting point can be obtained. The invention has the advantages of simple production process, low energy consumption and environmental protection, and the used solvent can be basically recycled.
Description
Technical field
The present invention relates to a kind of method for preparing the nylon random copolymer micro-sphere that fusing point is controlled, particle diameter is controlled, the nylon random copolymer micro-sphere for preparing can be used as protein carrier, powder coating, rotation molding raw material etc.
Background technology
In recent years; Microballoon with uniform-dimension and regular shape has obtained everybody increasing concern; Especially the polymer microballoon that contains functional groups such as hydroxyl, amino, carboxyl, aldehyde radical; Be widely used especially and make the carrier of protein (enzyme, antibody etc.) Covalent Immobilization, great application prospect is also arranged at aspects such as biosensor, biocatalysis, bioseparation.And nylon micro-sphere itself contains-NH
2With-OH base, so that it comprises that at makeup and bioengineering field the above-mentioned protein of mentioning such as fixes at the application prospect of aspect is quite wide.Add that nylon material itself has that intensity height, wear resistance are good, the advantage of resistance to chemical attack and resistance to deterioration, nylon micro-sphere also has purposes widely at aspects such as coating, rotation molding raw materials.
The nylon micro-sphere of before mentioning in the patent report (powder) traditional preparation process method mainly comprises: solution deposit, emulsion method, direct polymerization method and mechanical crushing method etc.But all above-mentioned these preparing methods' operational path is too complicated, and productive rate is low, is difficult to realize industriallization, and the nylon particle out-of-shape that obtains, and distribution of sizes is very wide, brings a lot of difficulties for the application in later stage.
EP1636292 utilizes emulsion polymerization like patent, and patent WO 2003/097228 AL prepares polyamide particles through interface polycondensation.These two method complex process, and need a large amount of solvent and dispersion agent, be not suitable for industriallization.Patent CN1624025 then is with as the Silon of disperse phase with as the water-soluble polymers blend of external phase, obtains polyamide particles thereby remove water-soluble polymers then.This method power consumption is excessive.Patent CN101077910A has proposed to utilize the method for anionoid polymerization, prepares regular shape, the controlled nylon micro-sphere of granularity, technology simple possible through phase reversion.But its shortcoming is exactly the melting range for preparing the gained nylon micro-sphere to be changed too narrow.
Summary of the invention
The object of the invention is exactly the preparation method that the controlled nylon random copolymer micro-sphere of a kind of fusing point and particle diameter is provided for the deficiency that overcomes above-mentioned prior art existence.
The object of the invention can be realized through following technical scheme: the preparation method of the nylon random copolymer micro-sphere that a kind of fusing point and particle diameter are controlled is characterized in that this method comprises following process step:
(1) dissolving
Will be with the polymkeric substance C of polymeric amide consistency difference, a kind ofly in addition can cause lactam monomers polymeric polymer monomer B and lactam monomers A heating for dissolving, stir into homogeneous solution; Solution temperature remains on 100-200 ℃ and stirred 3～5 hours, treats to vacuumize after it fully dissolves dewatering, and obtains mixed solution;
(2) anionoid polymerization
Keep constant temperature, then catalyzer is added in the gained solution, mix, cause the lactan anionic ring-opening polymerization, obtain the in-situ alloy of nylon random copolymer/polymkeric substance C;
(3) nylon random copolymer micro-sphere extracts
The alloy that (2) obtain is pulverized, selected a kind of dissolution with solvents to fall polymkeric substance C, obtain the controlled nylon random copolymer micro-sphere of fusing point and particle diameter after the drying.
Can regulate the melting range of nylon copolymer microballoon through the ratio of adjustment lactam monomers A and comonomer B component, through adjusting the content of polymkeric substance C in the alloy, the particle size range that can regulate the nylon copolymer microballoon.
The part by weight of described lactam monomers A and comonomer B component is 10: 90-95: 5, and the add-on of polymkeric substance C is the 5-50wt% of the total amount of lactam monomers A, comonomer B and polymkeric substance C
Described polymkeric substance C is and the organic polymer of nylon compatibility difference, comprises: PS and verivate thereof, ppe and verivate thereof, gather (methyl) propenoate and verivate thereof; Polymkeric substance C can be one or both or a two or more mixture wherein, also their monomeric multipolymers.
Described lactam monomers A can be a kind of, two or more the mixture of lactam monomers such as hexanolactam, laurolactam.
Described polymer monomer B itself carries the functional group that can cause implementing anionic lactam polymerisation, like ester group etc.; Like caprolactone, phenyl ester, CBT etc., also can be their polymkeric substance such as PCL, PBT, PTT, PC etc.
Described catalyzer comprises various lactan metallic compounds such as sodium caprolactam(ate); Various basic metal such as potassium, sodium, lithium, their hydrogenate such as NaH, LiH; Alkali metal hydroxide such as NaOH, KOH; Various alkali metal alcoholates or the like; The add-on of catalyzer is 0.2%-5.0wt%.
Described solvent is that the good solvent of polymkeric substance C is the poor solvent of nylon random copolymer simultaneously.
Key point of the present invention is the polymkeric substance C with polymeric amide consistency difference to be dissolved in obtain two successive phase structures altogether mutually in the solution of lactan A and comonomer B, carries out anionoid polymerization fast then.Because the existence of factors such as IT, viscosity difference between inconsistent two phases is so when polymkeric substance C content was low, polymkeric substance C was a disperse phase in the alloy of formation; And when polymkeric substance C content increased to certain value, the alloy pattern promptly began to take place phase reversion, and this moment, polymkeric substance C was an external phase, and the multipolymer of lactam monomers A, polymer monomer B then is present in the external phase of polymkeric substance C with the form of microballoon.
Characteristic of the present invention at first is need not any anionic polymerization initiator of extra interpolation, and the copolymerization monomer B that directly introduces itself carries the functional group that can cause anionic polymerization of lactam.Secondly, because the fusing point of the comonomer of introducing and the fusing point of polymeric amide differ greatly the broadness more so the adjustable scope of the fusing point of the nylon copolymerization microsphere that obtains just becomes.Once more, can obtain the nylon copolymer microballoon of different-grain diameter size through the ratio of component in the adjustment alloy.Principle is: because the polymkeric substance viscosity differs greatly in the system, the existence of anionoid polymerization rapid speed characteristic makes that phase reversion promptly appears in system when polymkeric substance C content is low, and along with the increase of polymkeric substance C content, the nylon copolymer microballoon obviously diminishes.
The present invention prepares thus obtained microsphere size particle diameter and can be controlled between the 1-200 μ m, and gained nylon copolymer microballoon fusing point can be controlled between 50-250 ℃, even can not had the nylon copolymer microballoon of fusing point fully.It is simple that the present invention has production technique concurrently, and energy consumption is low, the advantage of environmental protection, and all spent solvents basically can recycling.
Embodiment
Embodiment 1
Ppe (PPO) (10wt%) mixes with hexanolactam, CBT (weight ratio 90: 10) heating and melting, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 3 hours; Add NaOH 0.4wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PPO/PA6-CBT (90: 10) the alloy fragmentation, with the toluene dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 2
Ppe (PPO) (10wt%) mixes with hexanolactam, CBT (weight ratio 70: 30) heating and melting, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 4 hours; Add NaOH 0.2wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PPO/PA6-CBT (70: 30) the alloy fragmentation, with the toluene dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 3
Ppe (PPO) (10wt%) mixes with hexanolactam, CBT (weight ratio 50: 50) heating and melting, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 5 hours; Add sodium caprolactam(ate) 1.2wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PPO/PA6-CBT (50: 50) the alloy fragmentation, with the toluene dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 4
PS (PS) (10wt%) and hexanolactam-laurolactam (mass ratio 1: 1), CBT (weight ratio 70: 30) heating and melting mix; 130 ℃ of constant temperature stirred 3.5 hours; Vaccum dewatering 15min adds sodium caprolactam(ate) 2.4wt% then, after mixing; Carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/ (PA6-PA12)-CBT (70: 30) alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 5
PS (PS) (10wt%) and hexanolactam-laurolactam (mass ratio 2: 1), CBT (weight ratio 50: 50) heating and melting mix; 130 ℃ of constant temperature stirred 4.5 hours; Vaccum dewatering 15min adds potassium 0.8wt% then, after mixing; Carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/ (PA6-PA12)-CBT (50: 50) alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 6
PS (PS) (10wt%) mixes with laurolactam, phenyl ester (weight ratio 30: 70) heating and melting, and 100 ℃ of constant temperature stirred vaccum dewatering 15min 5 hours; Add KOH 0.4wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA12-phenyl ester (30: 70) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 7
PS (PS) (10wt%) mixes with hexanolactam, caprolactone (weight ratio 95: 5) heating and melting, and 180 ℃ of constant temperature stirred vaccum dewatering 15min 3 hours; Add sodium caprolactam(ate) 4.2wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PCL (95: 5) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 8
PS (PS) (10wt%) mixes with hexanolactam, PCL (weight ratio 90: 10) heating and melting, and 165 ℃ of constant temperature stirred vaccum dewatering 15min 5 hours; Add sodium caprolactam(ate) 5.0wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PCL (90: 10) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 9
PS (PS) (50wt%) mixes with hexanolactam, caprolactone (weight ratio 80: 20) heating and melting, and 200 ℃ of constant temperature stirred vaccum dewatering 15min 4 hours; Add sodium caprolactam(ate) 3.5wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PCL (80: 20) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 10
PS (PS) (5wt%) mixes with hexanolactam, PBT (weight ratio 90: 10) heating and melting, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 5 hours; Add LiH 0.4wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PBT (90: 10) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 11
PS (PS) (15wt%) mixes with hexanolactam, PTT (weight ratio 90: 10) heating and melting, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 3 hours; Add NaOH 0.4wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PTT (90: 10) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 12
PS (PS) (30wt%) mixes with hexanolactam, caprolactone (weight ratio 90: 10) heating and melting, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 5 hours; Add NaOH 0.4wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PCL (90: 10) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Embodiment 13
Rohm tech inc (40wt%) and hexanolactam, caprolactone (weight ratio 10: 90) heating and melting mix, and 130 ℃ of constant temperature stirred vaccum dewatering 15min 5 hours; Add NaOH 0.4wt% then; After mixing, carry out static casting, die temperature is controlled at 150～180 ℃.
After gained PS/PA6-PCL (10: 90) the alloy fragmentation, with the THF dissolving, and dry, the nylon copolymer microsphere volume median size (laser diffractometry), the fusing point (DSC) that obtain are seen table 1.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Particle diameter (μ m) | 116 | 103 | 102 | 55 | 53 | 54 | 52 | 53 | 51 | 120 | 25 | 20 | 5 |
| Fusing point (℃) | 201 | 186 | 152 | 143 | Do not have | 189 | 190 | 134 | 103 | 134 | 133 | 133 | 133 |
Claims (4)
1. the preparation method of the controlled nylon random copolymer micro-sphere of fusing point and particle diameter is characterized in that this method comprises following process step:
(1) dissolving
Will be with the polymkeric substance C of polymeric amide consistency difference, a kind ofly in addition can cause lactam monomers polymeric polymer monomer B and lactam monomers A heating for dissolving, stir into homogeneous solution; Solution temperature remains on 100-200 ℃ and stirred 3～5 hours, treats to vacuumize after it fully dissolves dewatering, and obtains mixed solution;
(2) anionoid polymerization
Keep constant temperature, then catalyzer is added in the gained solution, mix, cause the lactan anionic ring-opening polymerization, obtain the in-situ alloy of nylon random copolymer/polymkeric substance C;
(3) nylon random copolymer micro-sphere extracts
The alloy that (2) obtain is pulverized, selected a kind of dissolution with solvents to fall polymkeric substance C, obtain the controlled nylon random copolymer micro-sphere of fusing point and particle diameter after the drying;
The part by weight of described lactam monomers A and polymer monomer B component is 10: 90-95: 5, and the add-on of polymkeric substance C is the 5-50wt% of the total amount of lactam monomers A, polymer monomer B and polymkeric substance C;
Described polymer monomer B itself carries the functional group that can cause implementing anionic lactam polymerisation, and said functional group comprises caprolactone, phenyl ester, CBT or their polymer PC L, PBT, PTT, PC;
Described catalyzer comprises sodium caprolactam(ate), potassium, sodium, lithium, NaH, LiH, NaOH, KOH or various alkali metal alcoholates; The add-on of catalyzer is 0.2%-5.0wt%;
Described solvent is that the good solvent of polymkeric substance C is the poor solvent of nylon random copolymer simultaneously.
2. the preparation method of the nylon random copolymer micro-sphere that a kind of fusing point according to claim 1 and particle diameter are controlled; It is characterized in that; Regulate the melting range of nylon copolymer microballoon through the ratio of adjustment lactam monomers A and polymer monomer B component, the particle size range of the content adjusting nylon copolymer microballoon through polymkeric substance C in the adjustment alloy.
3. the preparation method of the nylon random copolymer micro-sphere that a kind of fusing point according to claim 1 and particle diameter are controlled; It is characterized in that; Described polymkeric substance C is and the organic polymer of nylon compatibility difference, comprises: PS and verivate thereof, ppe and verivate thereof, gather (methyl) propenoate and verivate thereof; Polymkeric substance C is one or more a mixture wherein, or their monomeric multipolymer.
4. the preparation method of the nylon random copolymer micro-sphere that a kind of fusing point according to claim 1 and particle diameter are controlled is characterized in that, described lactam monomers A is one or both the mixture in hexanolactam, the laurolactam.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665839B (en) * | 2012-09-14 | 2017-02-08 | 合肥杰事杰新材料股份有限公司 | Polyamide microspheres and preparation method thereof |
| CN104045826B (en) * | 2014-06-25 | 2016-03-30 | 江苏科技大学 | A kind of environment-friendly type preparation method of polymeric amide microballoon |
| CN104830053A (en) * | 2015-01-08 | 2015-08-12 | 杭州师范大学 | Caprolactam-laurolactam co-polymer modified by glass fiber and preparation method of powder thereof |
| CN107434891B (en) * | 2016-05-27 | 2019-10-22 | 中国科学院理化技术研究所 | A kind of nylon/polystyrene alloy microballoon and the preparation method and application thereof |
| CN113651950B (en) * | 2021-08-23 | 2023-12-22 | 陈强 | Biodegradable polymer microsphere and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434069A (en) * | 2001-04-27 | 2003-08-06 | 中国科学院化学研究所 | Thermoplastic high polymer micro balloons and method for preparing same |
| CN1786049A (en) * | 2005-12-06 | 2006-06-14 | 河北工业大学 | Nylon 6/ poly methylene imine molecular composite material and its preparation method |
| CN101077910A (en) * | 2006-05-23 | 2007-11-28 | 上海杰事杰新材料股份有限公司 | Method for preparing particle diameter controllable high molecular weight nylon micro-sphere |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434069A (en) * | 2001-04-27 | 2003-08-06 | 中国科学院化学研究所 | Thermoplastic high polymer micro balloons and method for preparing same |
| CN1786049A (en) * | 2005-12-06 | 2006-06-14 | 河北工业大学 | Nylon 6/ poly methylene imine molecular composite material and its preparation method |
| CN101077910A (en) * | 2006-05-23 | 2007-11-28 | 上海杰事杰新材料股份有限公司 | Method for preparing particle diameter controllable high molecular weight nylon micro-sphere |
Non-Patent Citations (1)
| Title |
|---|
| 刘彤莹等."己内酰胺-己内酯共聚物的合成与表征".《北京服装学院学报》.2005,第25卷(第2期),第8-12页. |
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Effective date of registration: 20220812 Address after: 241200 Chungu 3D Printing Industrial Park, Fanchang Economic Development Zone, Wuhu City, Anhui Province Patentee after: Wuhu Weiqiu New Material Technology Co., Ltd. Address before: 230601 No. 2388 Lianhua Road, Hefei economic and Technological Development Zone, Anhui, China Patentee before: HEFEI GENIUS NEW MATERIALS Co.,Ltd. |