CN113234319A - Copolymerized nylon/graphene composite microsphere for selective laser sintering and preparation method thereof - Google Patents
Copolymerized nylon/graphene composite microsphere for selective laser sintering and preparation method thereof Download PDFInfo
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- CN113234319A CN113234319A CN202110739337.4A CN202110739337A CN113234319A CN 113234319 A CN113234319 A CN 113234319A CN 202110739337 A CN202110739337 A CN 202110739337A CN 113234319 A CN113234319 A CN 113234319A
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
The invention belongs to the technical field of material chemistry, and particularly relates to a copolymerized nylon/graphene composite microsphere capable of being used for selective laser sintering and a preparation method thereof, wherein the particle size of the composite microsphere is 5-100 mu m, and the content of graphene is 0.05-1 wt%. The microsphere preparation system disclosed by the invention consists of a polymer, lactam A, lactam B, graphene, a catalyst and an activating agent. The composite microsphere can be used as a consumable material of an SLS selective laser sintering technology, and the application of the SLS technology in the field of high-performance new materials (such as aviation, automobiles, electronic instruments and the like) is widened.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and relates to a copolymerized nylon/graphene composite microsphere for selective laser sintering and a preparation method thereof.
Background
As an Additive Manufacturing (AM, commonly known as 3D printing) technology, Selective Laser Sintering (SLS) has the advantages of no waste of Sintering materials, low cost of manufactured parts, and capability of Manufacturing complex manufactured parts, and becomes one of the most active branches in the field of 3D printing technology.
Among the few polymer-based SLS molding materials known to have practical value, nylon 12(PA12) is considered to be the most desirable polymer-based SLS molding material due to its low melt viscosity, wide molding temperature range, and small water absorption and molding shrinkage, but its price is high. Compared with PA12 and its polymeric monomer laurolactam (LL), nylon 6(PA6) and its polymeric monomer Caprolactam (CL) have great advantages in price (the price of PA6 is only 1/3-1/5 of PA12, and the price of CL is only about 1/200 of LL), so that PA6 still actively plays a role in the research field of SLS technology, and is widely applied.
The SLS forming technology requires that the powder has better sphericity, and a single polymer-based SLS formed part cannot meet the use requirement of high performance. Nylon 6(PA6), the most widely used engineering plastic in nylon series, has the advantages of high strength, good abrasion resistance, etc., but has a large water absorption rate, poor dimensional stability and a high melting point, which limits its wide application in SLS technology. The Wangger of the research institute of physicochemical and technology of Chinese academy of sciences, and the like invented a nylon/silicon dioxide composite microsphere, its preparation method and application (ZL 2016101780847), said composite microsphere is obtained by making silicon dioxide in-situ hydrolysis in the dispersion liquid of porous nylon microsphere. The addition of the silicon dioxide can effectively reduce the water absorption of the porous nylon composite microspheres and improve the thermal stability, crystallization property and mechanical strength.
However, no reports of copolymerized nylon-graphene composite microspheres are found at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a copolymerized nylon/graphene composite microsphere for selective laser sintering and a preparation method thereof.
The technical scheme of the invention is as follows:
a copolymerized nylon/graphene composite microsphere for selective laser sintering is prepared from the following raw material components in parts by weight:
further, the polymer is polystyrene.
Further, the lactam A is caprolactam.
Further, the lactam B is selected from one of enantholactam, capryllactam, laurolactam and 3-amino-enantholactam.
Further, the graphene is selected from one of carboxylated graphene powder, aminated graphene powder or graphene suspension.
Further, the catalyst is selected from one of alkali metal, alkali metal hydride or alkali metal hydroxide.
Further, the activating agent is selected from toluene-2, 4-diisocyanate (TDI) or N, N' -Dicyclohexylcarbodiimide (DCC).
The method for preparing the copolymerized nylon/graphene composite microsphere for selective laser sintering comprises the following steps:
(1) weighing a polymer, a lactam A, a lactam B, graphene and a catalyst in parts by weight, adding the weighed polymer, the lactam A, the lactam B, the graphene and the catalyst into a container, stirring for 0.5-2.5 hours at the temperature of 70-150 ℃ under the protection of nitrogen, and then carrying out reduced pressure distillation to remove trace water remained in a system to obtain a mixed solution;
(2) adding the activating agent into the mixed solution prepared in the step (1), shaking up, immediately pouring into a mold at 110-170 ℃, reacting, and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), dissolving and removing a polymer phase added in a system during preparation by using a solvent, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere for selective laser sintering.
Preferably, in step (3), the solvent is tetrahydrofuran.
The invention has the advantages that:
compared with the nylon composite microspheres of the prior invention, on one hand, the invention reduces the melting point of nylon 6 to a certain extent through copolymerization, thereby being more beneficial to the application of the nylon composite microspheres in selective laser sintering and expanding the types of polymer raw materials which can be used for selective laser sintering; on the other hand, the method utilizes the characteristic of a reaction-induced phase separation method in situ to selectively disperse the graphene into the copolymerized nylon microsphere, thereby obtaining the copolymerized nylon/graphene composite microsphere and solving the common key problem that the molded piece is difficult to sinter by high-performance polymer-based selective laser to a certain extent.
Detailed Description
The invention will now be further illustrated by reference to the following examples.
Example 1:
(1) weighing 40 parts of polystyrene, 36 parts of caprolactam, 24 parts of enantholactam, 0.03 part of aminated graphene and 0.018 part of catalyst sodium hydroxide, adding into a three-necked flask, and dissolving for 0.5-2.5 hours under the protection of nitrogen at 70-150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.018 part of activating agent toluene-2, 4-diisocyanate into the mixed solution prepared in the step (1), shaking up, immediately pouring into a mold preheated to 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 0.05%.
Example 2:
(1) weighing 25 parts of polystyrene, 65 parts of caprolactam, 10 parts of caprylolactam, 0.3 part of carboxylated graphene and 0.5 part of catalyst sodium hydroxide, adding into a three-necked flask, and dissolving for 0.5-2.5 hours under the protection of nitrogen at 70-150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.5 part of activating agent toluene-2, 4-diisocyanate into the mixed solution prepared in the step (1), shaking up, immediately pouring into a preheated mold at 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 0.4%.
Example 3:
(1) weighing 15 parts of polystyrene, 80.75 parts of caprolactam, 4.25 parts of laurolactam, 0.85 part of aminated graphene and 0.85 part of catalyst sodium hydroxide, adding into a three-neck flask, and dissolving for 0.5-2.5 hours under the protection of nitrogen at 70-150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.85 part of activating agent toluene-2, 4-diisocyanate into the mixed solution prepared in the step (1), shaking up, immediately pouring into a preheated mold at 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 1%.
Example 4:
(1) weighing 15 parts of polystyrene, 80.75 parts of caprolactam, 4.25 parts of laurolactam, 0.85 part of carboxylated graphene and 0.85 part of potassium hydroxide serving as a catalyst, adding the materials into a three-neck flask, and dissolving the materials for 0.5 to 2.5 hours under the protection of nitrogen at the temperature of between 70 and 150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.85 part of activating agent N, N' -dicyclohexylcarbodiimide into the mixed solution prepared in the step (1), shaking up, immediately pouring into a preheated mold at 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 0.1%.
Example 5:
(1) weighing 15 parts of polystyrene, 80.75 parts of caprolactam, 4.25 parts of 3-amino-caprolactam, 0.425 parts of aminated graphene and 0.85 part of catalyst metal sodium, adding into a three-neck flask, and dissolving for 0.5-2.5 hours under the protection of nitrogen at 70-150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.85 part of activating agent N, N' -dicyclohexylcarbodiimide into the mixed solution prepared in the step (1), shaking up, immediately pouring into a preheated mold at 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 0.5%.
In order to illustrate the technical effects of the present invention, the applicant further provided the following comparative examples:
comparative example 1
Comparative example 1 differs from example 1 in that the composition of comparative example 1 does not contain lactam a. The method specifically comprises the following steps:
(1) weighing 40 parts of polystyrene, 24 parts of enantholactam, 0.03 part of aminated graphene and 0.018 part of catalyst sodium hydroxide, adding into a three-neck flask, and dissolving for 0.5-2.5 hours under the protection of nitrogen at 70-150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.018 part of activating agent toluene-2, 4-diisocyanate into the mixed solution prepared in the step (1), shaking up, immediately pouring into a mold preheated to 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 0.05%.
Comparative example 2
Comparative example 2 differs from example 1 in that the composition of comparative example 2 does not contain lactam B. The method specifically comprises the following steps:
(1) weighing 40 parts of polystyrene, 36 parts of caprolactam, 0.03 part of aminated graphene and 0.018 part of catalyst sodium hydroxide, adding into a three-neck flask, and dissolving for 0.5-2.5 hours under the protection of nitrogen at 70-150 ℃ and electric stirring so as to completely dissolve the polystyrene; then, carrying out reduced pressure distillation to remove trace water remained in the system to obtain a mixed solution;
(2) adding 0.018 part of activating agent toluene-2, 4-diisocyanate into the mixed solution prepared in the step (1), shaking up, immediately pouring into a mold preheated to 110-170 ℃, reacting and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), extracting and dissolving polystyrene by using tetrahydrofuran, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere with the graphene content of about 0.05%.
Table 1 is a comparison table of the melting point of the nylon-graphene composite microsphere prepared in each example and comparative example and the strength of the selectively laser sintered part thereof.
TABLE 1 comparison of the melt crystallization behavior of the composite microspheres obtained in the examples with the strength of selectively laser sintered parts
Remarking:
sintering technological parameters: the laser type is CO2Laser; laser power 28W; the diameter of the light spot is 200 mu m; the preheating temperature is 185 ℃; the scanning speed is 7.6 m/s; the scanning layer is 0.1mm thick.
And secondly, testing the tensile strength and the bending strength of the sample on an electronic universal testing machine according to GB/T1040-.
And (4) conclusion: it can be seen from examples 1, comparative examples 1 and 2 that the melting point of nylon 6 is reduced to a certain extent by using the components of the present invention, which is more beneficial to the application of the nylon 6 in selective laser sintering, and it can be seen from examples 1 to 5 that the copolymerized nylon-graphene composite microsphere prepared by the present invention has good mechanical properties, and the composite microsphere can be used as a consumable material of SLS selective laser sintering technology, thereby widening the application of the SLS technology in the field of high-performance new materials (such as aviation, automobiles, electronic instruments, etc.).
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The copolymerized nylon/graphene composite microsphere for selective laser sintering is characterized by being prepared from the following raw materials in parts by weight:
2. the copolymerized nylon/graphene composite microsphere for selective laser sintering according to claim 1, wherein: the polymer is polystyrene.
3. The copolymerized nylon/graphene composite microsphere for selective laser sintering according to claim 1, wherein: the lactam A is caprolactam.
4. The copolymerized nylon/graphene composite microsphere for selective laser sintering according to claim 1, wherein: the lactam B is selected from one of enantholactam, capryllactam, lauryl lactam or 3-amino-enantholactam.
5. The copolymerized nylon/graphene composite microsphere for selective laser sintering according to claim 1, wherein: the graphene is selected from one of carboxylated graphene powder, aminated graphene powder or graphene suspension.
6. The copolymerized nylon/graphene composite microsphere for selective laser sintering according to claim 1, wherein: the catalyst is selected from one of alkali metal, alkali metal hydride or alkali metal hydroxide.
7. The copolymerized nylon/graphene composite microsphere for selective laser sintering according to claim 1, wherein: the activating agent is selected from toluene-2, 4-diisocyanate (TDI) or N, N' -Dicyclohexylcarbodiimide (DCC).
8. A method for preparing the copolymerized nylon/graphene composite microspheres for selective laser sintering according to any one of claims 1 to 7, comprising the following steps:
(1) weighing a polymer, a lactam A, a lactam B, graphene and a catalyst in parts by weight, adding the weighed polymer, the lactam A, the lactam B, the graphene and the catalyst into a container, stirring for 0.5-2.5 hours at the temperature of 70-150 ℃ under the protection of nitrogen, and then carrying out reduced pressure distillation to remove trace water remained in a system to obtain a mixed solution;
(2) adding the activating agent into the mixed solution prepared in the step (1), shaking up, immediately pouring into a mold at 110-170 ℃, reacting, and curing to obtain a composite material;
(3) and (3) breaking the composite material obtained in the step (2), dissolving and removing a polymer phase added in a system during preparation by using a solvent, and filtering to obtain black powder, namely the copolymerized nylon/graphene composite microsphere for selective laser sintering.
9. The preparation method of the copolymerized nylon/graphene composite microsphere capable of being used for selective laser sintering according to claim 8, wherein the method comprises the following steps: in the step (3), the solvent is tetrahydrofuran.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337793A (en) * | 2017-07-28 | 2017-11-10 | 湖南华曙高科技有限责任公司 | Copolymer nylon dusty material for selective laser sintering and preparation method thereof |
| CN110551279A (en) * | 2018-05-30 | 2019-12-10 | 上海杰事杰新材料(集团)股份有限公司 | nano carbon material/polyamide microsphere composite material and preparation method thereof |
| CN111154096A (en) * | 2020-01-16 | 2020-05-15 | 浙江工业大学 | Preparation method of submicron nylon 6/graphene functional microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337793A (en) * | 2017-07-28 | 2017-11-10 | 湖南华曙高科技有限责任公司 | Copolymer nylon dusty material for selective laser sintering and preparation method thereof |
| CN110551279A (en) * | 2018-05-30 | 2019-12-10 | 上海杰事杰新材料(集团)股份有限公司 | nano carbon material/polyamide microsphere composite material and preparation method thereof |
| CN111154096A (en) * | 2020-01-16 | 2020-05-15 | 浙江工业大学 | Preparation method of submicron nylon 6/graphene functional microspheres |
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Application publication date: 20210810 |