CN116836413A - Preparation method of nylon 6 composite microsphere with adjustable size under high filling quantity - Google Patents
Preparation method of nylon 6 composite microsphere with adjustable size under high filling quantity Download PDFInfo
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- CN116836413A CN116836413A CN202310562391.5A CN202310562391A CN116836413A CN 116836413 A CN116836413 A CN 116836413A CN 202310562391 A CN202310562391 A CN 202310562391A CN 116836413 A CN116836413 A CN 116836413A
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 77
- 239000004005 microsphere Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000011049 filling Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 123
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052582 BN Inorganic materials 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 17
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- 229920002223 polystyrene Polymers 0.000 claims description 52
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000005530 etching Methods 0.000 claims description 26
- 239000000956 alloy Substances 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 23
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- 239000000203 mixture Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 2
- 238000006297 dehydration reaction Methods 0.000 claims 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000005191 phase separation Methods 0.000 abstract description 15
- 230000033444 hydroxylation Effects 0.000 abstract description 14
- 238000005805 hydroxylation reaction Methods 0.000 abstract description 14
- 239000000945 filler Substances 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000010146 3D printing Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 150000001450 anions Chemical group 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 caprolactam anions Chemical class 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
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- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of nylon 6 composite microspheres with adjustable size under high filling quantity. The invention coats the hydroxylation boron nitride in an in-situ anion polymerization mode, thereby greatly improving the dispersion effect of the hydroxylation boron nitride; the polarity of boron nitride is increased through hydroxylation modification of the boron nitride, caprolactam is grafted to the surface of the hydroxylated boron nitride during anion ring-opening polymerization, and nylon 6 coated boron nitride is realized through a reaction induced phase separation process; the invention adopts hydroxylation boron nitride to carry out filling modification on nylon 6 microspheres. Compared with the prior art, the hydroxyl content of the hydroxylated boron nitride is regulated, so that the size of the microsphere is regulated under the condition of high filler filling amount, and the finally obtained hydroxylated boron nitride/nylon 6 composite microsphere powder has good processability, excellent electrical insulation and thermal conductivity. Can meet the requirements on the microsphere dimension in the process of manufacturing functional fibers by 3D printing electronic devices and in-situ microfibrillation.
Description
Technical Field
The invention belongs to the field of nylon microspheres, and particularly relates to a preparation method of a nylon 6 composite microsphere with adjustable size under high filling quantity.
Background
The nylon 6 microsphere powder has the advantages of high strength, good wear resistance, light weight, easy processing and transportation, and the like, and is widely applied to the fields of 3D printing and spinning. However, the conventional PA6 microsphere powder has the defects of poor heat resistance, poor impact strength, poor dimensional stability and the like, so that the nylon 6 microsphere powder can be modified by the filler with high heat conductivity, high strength and high modulus, and the problems can be effectively solved.
BN has the characteristics of high thermal conductivity, high strength and high modulus, and has received more and more attention in the field of heat conducting and reinforcing composite materials. Chinese application publication No. CN111393836A, nylon and boron nitride are mixed homogeneously in a low speed mixer, and the mixture is hot pressed in different mold to obtain heat conducting nylon in different shapes. Chinese application publication No. CN110330786A, a plurality of powders such as graphene, boron nitride and the like are added into caprolactam melt, and after anionic polymerization is carried out by adding an initiator and an activator, the mixture is cast into a die to obtain the heat-conducting nylon composite material. Chinese application patent publication No. CN112080137A, hexagonal boron nitride, multiwall carbon nanotube and other materials are added into the PA6 microsphere matrix to obtain the heat conducting, electromagnetic shielding and high strength PA6 composite material. But incompatibility between BN and polymer tends to result in less than desired properties of the resulting composite. Thus, researchers have modified the surface of BN to improve its interface with the polymer matrix and have made some progress.
After ultrasonic stripping of BN, yang Wei et al (ACS appl. Mater. Interfaces 2018,10,40032-40043), the single layer BN was dispersed in NaOH solution with ultrasonic agitation and finally the OH-BN was obtained by hydrothermal reaction. Cui Zhenhua et al (small 2014,10, no.12, 2352-2355) use a high temperature of 1000 ℃ to cause defects on the BN surface, allowing oxygen to intercalate into the BN lattice to obtain OH-BN. Chinese application publication No. CN109852044a, hyperbranched polyester with terminal hydroxyl groups is grafted into boron nitride, and then mixed with nylon 6 and extruded to obtain the oriented heat conductive nylon with boron nitride. The above studies introduce polar groups into the inert boron nitride surface to activate it, helping to improve the dispersion of the boron nitride in the polymer matrix. However, as the amount of the added hydroxylated boron nitride increases, the interaction of B and N atoms between adjacent layers still tends to cause stacking thereof, so that increasing the interlayer spacing is a necessary requirement for preventing severe stacking.
The polymer and the filler particles are compounded in an in-situ polymerization mode, so that the interlayer spacing of the sheet can be increased to prevent the filler from agglomerating. Chinese application publication No. CN110734642a, in which hydroxylated boron nitride is added to caprolactam, and at the same time of hydrolysis ring-opening polymerization of caprolactam, a grafting reaction is performed between hydroxylated boron nitride and caprolactam, nylon 6 is grafted onto hydroxylated boron nitride, and the grafted polymer is used to increase lamellar spacing. Chinese application patent publication No. CN105949760A, the nylon monomer and the oxygen-containing functional group of graphene oxide form a firm chemical bond through in-situ polymerization, so that the problems of poor dispersibility and easy agglomeration of graphene in the nylon monomer are solved. Furthermore, on the basis of in-situ polymerization, the polymer is coated with the filler in the form of microspheres, so that the obtained functional microsphere powder is more convenient to store, transport and use, and is favored in the fields of 3D printing and in-situ microfibrillation. Chinese application publication No. CN105622932a uses polyether polymer and caprolactam to perform anionic polymerization, and the nylon 6 microsphere powder is obtained by reaction-induced phase separation. Chinese application patent publication No. CN111154096A, nylon 6 is grafted onto the functionalized graphene in an in-situ polymerization mode, and the functionalized graphene/PA 6 microsphere powder is obtained by utilizing a reaction-induced phase separation process. The filler is coated by the matrix material in the mode of in-situ polymerization and microsphere coating, so that the filler is uniformly dispersed in the matrix, and finally the functional microsphere powder is obtained, thereby being an effective method for improving the utilization rate of the filler and reducing the processing and using difficulties. However, in the current technical scheme, the addition of a large amount of filler can cause the change of the size and sphericity of the microsphere, which is not beneficial to processing and use.
In conclusion, how to regulate and control the size of the nylon 6 functional microsphere under high filling amount, improve the performance of the microsphere, reduce the processing and use difficulties of the microsphere, and have great significance in the fields of 3D printing and functional fiber manufacturing.
Disclosure of Invention
The invention aims to provide a preparation method of nylon 6 composite microspheres with adjustable size under high filling amount. Finally, high-performance microsphere powder with different sizes is obtained, the production requirements of various fields are met, the preparation process is simpler and more convenient, and the time consumption is shorter.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of nylon 6 composite microspheres with adjustable size under high filling quantity, which comprises the following steps:
mixing boron nitride and hydrogen peroxide to obtain boron nitride/hydrogen peroxide suspension, transferring the suspension into an autoclave, stirring and heating to initiate hydrothermal reaction, cleaning a product after the hydrothermal reaction, and drying to obtain hydroxylated boron nitride;
adding hydroxylated boron nitride, caprolactam and a phase-separated polymer into a three-neck flask, heating and melting to obtain a mixed solution, and then adding an initiator and an activator to initiate anionic polymerization to obtain hydroxylated boron nitride/nylon 6/phase-separated polymer alloy;
and crushing the alloy, and then etching to remove the split-phase polymer to finally obtain the hydroxylated boron nitride/nylon 6 microsphere.
Preferably, the boron nitride/hydrogen peroxide suspension has a boron nitride content of 0.05-0.5g/ml.
Preferably, the boron nitride/hydrogen peroxide suspension is stirred in the autoclave at a rate of 500-1000r/min for a period of 12-36 hours.
Preferably, the hydrothermal reaction is carried out at a temperature of 80-160 ℃ for a period of 12-36 hours.
Preferably, the product after the hydrothermal reaction is rinsed with deionized water for 5-8 times to neutrality, and then dried in vacuum at 40-80 ℃.
Preferably, the loading of the hydroxylated boron nitride is 0.5-10wt% of the caprolactam mass.
Preferably, the phase-separated polymer is one of Polystyrene (PS), polyethylene glycol (PEG) and Polyether Polyol (PPG).
Preferably, in the mixed solution, the phase-separated polymer accounts for 10-30% of the total mass, and the melting temperature is 80-150 ℃.
Adding hydroxylated boron nitride, caprolactam and a phase-separated polymer into a reactor, and heating and melting to obtain a mixed solution, wherein the method specifically comprises the following steps of:
firstly, adding caprolactam into a reactor, heating and melting the caprolactam, then adding hydroxylated boron nitride, performing ultrasonic dispersion in boiling water, adding polystyrene, and dissolving the polystyrene in a nitrogen environment at 110-130 ℃ to obtain a mixed solution.
Preferably, the initiator used is sodium hydroxide.
Preferably, the initiator is added before vacuum dewatering at 120-170 ℃ for 0.5-1h, the amount of the added initiator is 0.2-0.6% of the mass of caprolactam, the initiator is added after vacuum dewatering at 150-170 ℃ for 0.5-1h, and the initiator is stabilized for 0.5-1h after dewatering.
Preferably, the activator is toluene diisocyanate.
Preferably, the amount of the activator is 0.2-0.6% of the mass of caprolactam, and the activator is added and then uniformly shaken at a distance, and then the mixture is kept stand for 0.5-1h at 150-240 ℃.
Preferably, after the obtained alloy is crushed into powder, the dispersed phase polymer is etched by using a Soxhlet extractor, wherein the etching temperature is 80-120 ℃, and the etching time is 12-36 hours.
Preferably, the etched powder is dried in a vacuum oven at 40-80 ℃ for 12-36 hours.
In the present invention, unless otherwise specified, the raw materials used for the preparation are commercially available products known to those skilled in the art
In the present invention, boron nitride is added to a 30% hydrogen peroxide solution and dispersed with stirring in an autoclave, wherein the boron nitride content of the dispersion is 0.05 to 0.5g/ml, more preferably 0.1 to 0.5g/ml. When the boron nitride content is 0.1 to 0.5g/ml, the smaller the boron nitride content, the higher the degree of hydroxylation. The caprolactam and the hydroxylated boron nitride have stronger interaction force, and in the initial stage of polymerization, the caprolactam is rapidly polymerized on the surface of the hydroxylated boron nitride, and the viscosity of the PA6/CL enrichment phase taking the hydroxylated boron nitride as the center is rapidly increased. The viscosity difference of the PA6/CL enrichment phase and the PS enrichment phase is rapidly reduced in a short time, the inversion point of the system is lagged, and finally larger microspheres are formed. When the boron nitride content is less than 0.1g/ml, the boron nitride is hydroxylated to a high degree, and the surface thereof will contain a large number of-OH groups. The OH group can play a certain end-capping role in the caprolactam polymerization process, and the molecular weight of the nylon 6 polymer obtained by final polymerization is reduced, so that the viscosity of the PA6/CL enrichment phase is reduced during phase separation, and the phase separation speed is increased. The large amount of fine PA 6-rich phase undergoes viscoelastic phase separation and is rapidly immobilized due to the rapid rate of anionic polymerization. Meanwhile, collision is easy to occur among the PA6 enrichment phases which are generated in a large amount in a short time, so that the morphology regularity and the size uniformity of the obtained PA6 microsphere are reduced. When the boron nitride content is more than 0.5g/mol, a small amount of hydrogen peroxide is insufficient to support the complete hydroxylation of boron nitride, and the surface of the hydroxylated boron nitride has a small number of hydroxyl groups and has insufficient polarity. Resulting in the difficulty of dispersion of the hydroxylated boron nitride in the caprolactam monomer and easy stacking between sheets, and the difficulty of grafting the hydroxylated boron nitride to nylon 6 during polymerization. The stirring speed in the autoclave is 500-1000r/min, and the stirring time is 12-36h. More preferably, the boron nitride content of the dispersion is 0.3g/ml, the stirring rate is 800r/min, and the stirring time is 24 hours. The hydrothermal reaction is carried out at a temperature of 80-160 ℃, more preferably 120 ℃; the hydrothermal reaction time is 12-36h, more preferably 24h, and then the reaction time is 5-8 times, more preferably 5 times, of washing with deionized water; drying at 40-80 deg.c to obtain hydroxylated boron nitride, and preferably at 60 deg.c.
The split-phase polymer in the invention is one or more of Polystyrene (PS), polyethylene glycol (PEG) and Polyether Polyol (PPG), and more preferably polystyrene. Caprolactam in the reaction system is a strong polar monomer and has certain affinity with hydroxylated boron nitride. Therefore, when less polar polystyrene is selected as the phase-splitting polymer, the hydroxylated boron nitride is selectively distributed in the caprolactam monomer.
The content of the hydroxylated boron nitride added in the present invention is 0.5wt% to 10wt%, more preferably 0.5wt% to 5wt%. When the content of the hydroxylated boron nitride is 0.5-5 wt%, the size of the composite microsphere gradually increases with the increase of the content. This is because the addition of the hydroxylated boron nitride increases the viscosity of the CL-rich phase, resulting in a reduced viscosity difference between the CL-rich phase and the PS-rich phase, and the PA6 droplets formed by the final polymerization are more prone to collision and coalescence, forming larger microspheres. However, when the content of the hydroxylated boron nitride exceeds 5wt%, the hydroxylated boron nitride tends to agglomerate and cause non-uniformity in the viscosity of the CL/PS/hydroxylated boron nitride mixture as the filler content increases. Due to the interaction between CL and hydroxylated boron nitride, the PS molecular chain cannot be broken and isolate the CL/hydroxylated boron nitride enrichment phase with high viscosity at the initial stage of polymerization, the CL/PA6 enrichment phase increases and the viscosity increases as the reaction proceeds, the PS enrichment phase is further inhibited, and finally the PS enrichment phase is broken into smaller PS enrichment phase, so that PA6 is formed as a continuous phase and PS is formed as a dispersed phase, and PA6 microspheres cannot be formed. While microspheres can still be formed in areas where the hydroxylated boron nitride content is low.
In the caprolactam/hydroxylated boron nitride/split-phase polymer mixed solution, the split-phase polymer is polystyrene, and the consumption of the polystyrene is 10-30 wt% of the mixed solution, and more preferably 15-25 wt%. In the reaction-induced phase separation process, when the polystyrene content is less than 15wt%, polystyrene cannot form a continuous phase with sufficient strength in the phase separation process, and PA6 is easy to crush a continuous PS film under the action of surface tension, so that the PA6 dispersed phase cannot be separated into pellets by the polystyrene, and finally the PA6 microspheres cannot be formed through complete phase separation. When the polystyrene content is between 15wt% and 25wt%, the size of the PA6 microsphere is reduced along with the increase of the polystyrene content, and after the polystyrene content exceeds 25wt%, the influence of the polystyrene content on the microsphere size is not great. The temperature at which the caprolactam/polystyrene mixture is melted is 80℃to 150℃and more preferably 120 ℃.
The initiator used in the invention is sodium hydroxide, the amount of the added initiator is 0.2-0.6% of the mass of caprolactam, more preferably 0.4-0.6%, and when the sodium hydroxide is less than 0.4%, the amount of the added initiator is difficult to support the sufficient polymerization of the monomer; when the sodium hydroxide usage amount is higher than 0.6%, the polymerization reaction is accelerated, the molecular weight of PA6 is reduced, the viscosity of the PA6/CL enriched phase is reduced, the phase separation speed is increased, and finally the morphology regularity and the size uniformity of the obtained PA6 microsphere are reduced.
The activator used in the invention is Toluene Diisocyanate (TDI), the amount of the activator added is 0.2% -0.6% of the mass of caprolactam, more preferably 0.4% -0.6%, when the amount of the activator is less than 0.4%, the monomer conversion rate is reduced, and the microsphere morphology is irregular. This is because in the course of conventional alkali metal hydroxide initiated anionic polymerization, caprolactam monomer under the action of an initiator produces caprolactam anions which in turn react with the monomer by addition to produce reactive anionic dimers. Subsequently, the caprolactam monomer in the reaction system rapidly undergoes a chain growth reaction under attack of the reactive anionic dimer. However, the activation energy of this reaction to form reactive anionic dimers is high, resulting in excessively high reaction temperatures. The activating agent TDI can react with caprolactam monomer to produce acylated caprolactam, and the acylated caprolactam and caprolactam anion are added to obtain active acylated dimer. When the amount of the activator is too small, the small amount of amidated dimer formed rapidly initiates the chain growth reaction and induces the occurrence of phase separation. However, the conversion of CL in the PA 6/CL-rich phase is too low, resulting in a low viscosity of the PA 6/CL-rich phase, which does not provide sufficient surface tension to maintain sphericity upon phase separation. The microsphere finally obtained has irregular morphology, low monomer conversion rate and is unfavorable for production. When the usage amount of the activating agent is higher than 0.6%, the ring-opening anionic polymerization speed of caprolactam is increased, a large amount of PA6 molecular chains are rapidly formed and phase separation occurs, the formed PA6 enrichment phase is not enough for nucleation and growth, and finally the formed microspheres are different in size and the sphericity is reduced. In the polymerization, the temperature used is 150-240 ℃, more preferably 170 ℃, and when the temperature is lower than 150 ℃, the PA6 polymerization cannot be carried out, while when the temperature is higher than 200 ℃, the polymerization rate is increased, the system viscosity is reduced, and the phase separation rate is also increased. Too low a viscosity results in a lack of sufficiently stable interruptions between the PA 6-rich phases formed, easy collision agglomeration between the PA6 phases, formation of a larger size PA 6-rich phase, and even loss of the phase inversion process, the PA6 forming a continuous phase.
In the invention, the polystyrene in the microsphere is etched by using a Soxhlet extractor, the etching liquid used is tetrahydrofuran or toluene, and the etching temperature is 80-120 ℃ according to the etching liquid used, more preferably 90 ℃; the etching time is 12h-36h, more preferably 24h, the etched microsphere is put into a vacuum oven with the temperature of 40-80 ℃ to be dried for 12-36h, more preferably at the temperature of 60 ℃ to be dried for 24h, and finally the PA6 functional composite microsphere powder modified by the hydroxylation boron nitride is obtained.
Compared with the prior art, the invention has the beneficial effects that:
the invention coats the hydroxylation boron nitride in an in-situ anion polymerization mode, thereby greatly improving the dispersion effect of the hydroxylation boron nitride; the polarity of boron nitride is increased through hydroxylation modification of the boron nitride, caprolactam is grafted to the surface of the hydroxylated boron nitride during anion ring-opening polymerization, and nylon 6 coated boron nitride is realized through a reaction induced phase separation process; the invention adopts hydroxylation boron nitride to carry out filling modification on nylon 6 microspheres. Compared with the prior art, the hydroxyl content of the hydroxylated boron nitride is regulated, so that the size of the microsphere is regulated under the condition of high filler filling amount, and the finally obtained hydroxylated boron nitride/nylon 6 composite microsphere powder has good processability, excellent electrical insulation and thermal conductivity and is widely applied to the fields of 3D printing, automobiles, electronic devices, fibers and the like.
The invention has no special equipment requirement, does not need to change the raw material proportion of the microsphere synthesis process, has short time consumption and simple operation, and the prepared hydroxylated boron nitride/nylon 6 microsphere has controllable size and good sphericity.
Drawings
FIG. 1 is a graph showing the size distribution of the hydroxylated boron nitride/nylon 6 composite microspheres of examples 1, 6, and 11.
FIG. 2 is a scanning electron microscope image of the hydroxylated boron nitride/nylon 6 composite microsphere of example 11.
FIGS. 3 and 4 are graphs showing the distribution of element B in the case of mapping analysis of the hydroxylated boron nitride/nylon 6 composite microsphere of example 11.
Fig. 5 is a drawing of an electron microscope of the ultra fine fiber obtained after etching in the application example.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Comparative example 1
15g of caprolactam was added to a three-necked flask and the caprolactam was melted by heating at 80 ℃.5g of polystyrene (Mw=20.0×10 was added 4 ，Mn＝9.6×10 4 ) And 0.15g of boron nitride, polystyrene was dissolved at 120℃under nitrogen atmosphere. After the polystyrene is completely dissolved, vacuum is pumped out to remove water and the temperature is gradually increased to 150 ℃. After 0.5h of water removal, 0.06g of NaOH was added, water removal was continued and the temperature was raised to 170 ℃. After 0.5h of water removal, the mixture was kept under nitrogen for 0.5h. Finally, 65. Mu.L of TDI was added, and the mixture was vigorously shaken for 30 seconds, and then allowed to stand for 1 hour to obtain a PA6/PS alloy. Taking out the alloy, crushing the alloy into powder, taking tetrahydrofuran as a solvent, etching PS at 90 ℃ by using a Soxhlet extractor, and vacuum drying at 60 ℃ after etching to obtain PA6 microspheres.
Example 1
1.5g of boron nitride was added to 15ml of 30% strength hydrogen peroxide solution and stirred in an autoclave at 750r/min for 24 hours. And then carrying out hydrothermal reaction for 24 hours at 120 ℃, washing the obtained mixed solution with water for 5 times, and drying the obtained solid for 24 hours in a vacuum oven at 60 ℃ to obtain the hydroxylated boron nitride. 15g of caprolactam was added to a three-necked flask and the caprolactam was melted by heating at 80 ℃. 0.15g of hydroxylated boron nitride is added and dispersed ultrasonically in boiling water for 1h. 5g of polystyrene (Mw=20.0×10 was added 4 ，Mn＝9.6×10 4 ) At 12Polystyrene was dissolved at 0℃under nitrogen. After the polystyrene is completely dissolved, vacuum is pumped out to remove water and the temperature is gradually increased to 150 ℃. After 0.5h of water removal, 0.06g of NaOH was added, water removal was continued and the temperature was raised to 170 ℃. After 0.5h of water removal, the mixture was kept under nitrogen for 0.5h. Finally, 65. Mu.L of TDI (toluene diisocyanate, 0.08 g) was added, and the mixture was vigorously shaken for 30s, and then allowed to stand for 1 hour to obtain a hydroxylated boron nitride/PA 6/PS alloy. Taking out the alloy, crushing the alloy into powder, taking tetrahydrofuran as a solvent, etching PS at 90 ℃ by using a Soxhlet extractor, and vacuum drying at 60 ℃ after etching to obtain the hydroxylated boron nitride/PA 6 microspheres.
Example 2
Other conditions were the same as in example 1 except that the amount of boron nitride added was 3g.
Example 3
Other conditions were the same as in example 1, except that the amount of boron nitride added was 4.5g.
Example 4
The other conditions were the same as in example 1, except that the amount of boron nitride added was 6g.
Example 5
The other conditions were the same as in example 1, except that the amount of boron nitride added was 7.5g.
Table one: average particle diameter of hydroxylated boron nitride/PA 6 composite microspheres in comparative example 1 and examples 1 to 5
List one
As can be seen from Table one and FIG. 1, the size of the microspheres becomes smaller by adding the hydroxylated boron nitride, and the average size of the microspheres can be controlled between 18.8 μm and 33.1 μm as the degree of hydroxylation increases.
Comparative example 2
15g of caprolactam was charged into a three-necked flask and melted by heating at 80 ℃.5g of polystyrene and 0.45g of boron nitride were added, and the polystyrene was dissolved at 120℃under a nitrogen atmosphere. After the polystyrene is completely dissolved, vacuum is pumped out to remove water and the temperature is gradually increased to 150 ℃. After 0.5h of water removal, 0.06g of NaOH was added, water removal was continued and the temperature was raised to 170 ℃. After 0.5h of water removal, the mixture was kept under nitrogen for 0.5h. Finally, 65. Mu.L of TDI was added, and the mixture was vigorously shaken for 30 seconds, and then allowed to stand for 1 hour to obtain a PA6/PS alloy. Taking out the alloy, crushing the alloy into powder, taking tetrahydrofuran as a solvent, etching PS at 90 ℃ by using a Soxhlet extractor, and vacuum drying at 60 ℃ after etching to obtain PA6 microspheres.
Example 6
1.5g of boron nitride was added to 15ml of 30% strength hydrogen peroxide solution and stirred in an autoclave for 24 hours. And then carrying out hydrothermal reaction for 24 hours at 120 ℃, washing the obtained mixed solution with water for 5 times, and drying the obtained solid for 24 hours in a vacuum oven at 60 ℃ to obtain the hydroxylated boron nitride. 15g of caprolactam was added to a three-necked flask and the caprolactam was melted by heating at 80 ℃. 0.45g of hydroxylated boron nitride is added and dispersed ultrasonically in boiling water for 1h. 5g of polystyrene (Mw=20.0×10 was added 4 ，Mn＝9.6×10 4 ) Polystyrene was dissolved at 120℃under nitrogen. After the polystyrene is completely dissolved, vacuum is pumped out to remove water and the temperature is gradually increased to 150 ℃. After 0.5h of water removal, 0.06g of NaOH was added, water removal was continued and the temperature was raised to 170 ℃. After 0.5h of water removal, the mixture was kept under nitrogen for 0.5h. Finally, 65 mu L of TDI is added, and the mixture is vigorously shaken for 30s, and then left for 1h to obtain the hydroxylated boron nitride/PA 6/PS alloy. Taking out the alloy, crushing the alloy into powder, taking tetrahydrofuran as a solvent, etching PS at 90 ℃ by using a Soxhlet extractor, and vacuum drying at 60 ℃ after etching to obtain the hydroxylated boron nitride/PA 6 microspheres.
Example 7
Other conditions were the same as in example 6 except that the amount of boron nitride added was 3g.
Example 8
Other conditions were the same as in example 6 except that the amount of boron nitride added was 4.5g.
Example 9
The other conditions were the same as in example 6 except that the amount of boron nitride added was 6g.
Example 10
Other conditions were the same as in example 6 except that the amount of boron nitride added was 7.5g.
And (II) table: average particle diameter of hydroxylated boron nitride/PA 6 composite microspheres in comparative example 2 and examples 6 to 10
Watch II
As can be seen from Table II and FIG. 1, the size of the microspheres becomes smaller by adding the hydroxylated boron nitride, and the average size of the microspheres can be controlled between 34.6 μm and 51.6 μm as the degree of hydroxylation increases.
Comparative example 3
15g of caprolactam was added to a three-necked flask and the caprolactam was melted by heating at 80 ℃.5g of polystyrene and 0.75g of boron nitride were added, and the polystyrene was dissolved at 120℃under a nitrogen atmosphere. After the polystyrene is completely dissolved, vacuum is pumped out to remove water and the temperature is gradually increased to 150 ℃. After 0.5h of water removal, 0.06g of NaOH was added, water removal was continued and the temperature was raised to 170 ℃. After 0.5h of water removal, the mixture was kept under nitrogen for 0.5h. Finally, 65. Mu.L of TDI was added, and the mixture was vigorously shaken for 30 seconds, and then allowed to stand for 1 hour to obtain a PA6/PS alloy. Taking out the alloy, crushing the alloy into powder, taking tetrahydrofuran as a solvent, etching PS at 90 ℃ by using a Soxhlet extractor, and vacuum drying at 60 ℃ after etching to obtain PA6 microspheres.
Example 11
1.5g of boron nitride was added to 15ml of 30% strength hydrogen peroxide solution and stirred in an autoclave for 24 hours. And then carrying out hydrothermal reaction for 24 hours at 120 ℃, washing the obtained mixed solution with water for 5 times, and drying the obtained solid for 24 hours in a vacuum oven at 60 ℃ to obtain the hydroxylated boron nitride. 15g of caprolactam was added to a three-necked flask and the caprolactam was melted by heating at 80 ℃. 0.75g of hydroxylated boron nitride is added and dispersed ultrasonically in boiling water for 1h. 5g of polystyrene (Mw=20.0×10 was added 4 ，Mn＝9.6×10 4 ) Polystyrene was dissolved at 120℃under nitrogen. After the polystyrene is completely dissolved, vacuum is pumped out to remove water and the temperature is gradually increased to 150 ℃. After 0.5h of water removal, 0.06g of NaOH was added, water removal was continued and the temperature was raised to 170 ℃. After 0.5h of water removal, the mixture was kept under nitrogen for 0.5h. Finally, 65 mu L of TDI is added, and the mixture is vigorously shaken for 30s and then left for 1h to obtain hydroxylated boron nitride/PA 6-PS alloy. Taking out the alloy, crushing the alloy into powder, taking tetrahydrofuran as a solvent, etching PS at 90 ℃ by using a Soxhlet extractor, and vacuum drying at 60 ℃ after etching to obtain the hydroxylated boron nitride/PA 6 microspheres.
Example 12
Other conditions were the same as in example 11 except that the amount of boron nitride added was 3g.
Example 13
Other conditions were the same as in example 11 except that the amount of boron nitride added was 4.5g.
Example 14
Other conditions were the same as in example 11 except that the amount of boron nitride added was 6g.
Example 15
Other conditions were the same as in example 11 except that the amount of boron nitride added was 7.5g.
Table three: the average particle diameters of the hydroxylated boron nitride/PA 6 composite microspheres in comparative example 3 and examples 11 to 15 are shown in Table III
As can be seen from Table III and FIG. 1, the size of the microspheres becomes smaller by adding the hydroxylated boron nitride, and the average size of the microspheres can be regulated and controlled between 46.3 μm and 65.7 μm as the degree of hydroxylation increases.
As can be seen from fig. 2, 3 and 4, the microspheres have good sphericity and uniform size at 5% of the filling amount of the hydroxylated boron nitride, and the hydroxylated boron nitride is successfully coated by the PA6 microspheres and uniformly dispersed.
Application example
40g of polypropylene particles and 10g of microspheres of any of the above sizes were fed into a twin-screw extruder for extrusion, wherein the extrusion temperature was 240℃and the screw speed was 50rpm, and the fiber draw ratio was 5. And then etching the polypropylene of the obtained composite fiber in toluene environment to finally obtain the filling modified superfine fiber formed after micro-fibrillation of the microspheres. According to the microspheres with different sizes, the thickness of the superfine fiber can be regulated and controlled within a certain range.
As shown in FIG. 5, the polypropylene was etched to obtain a uniform size of the filling modified microfibers.
Claims (10)
1. The preparation method of the nylon 6 composite microsphere with adjustable size under high filling amount is characterized by comprising the following steps:
1) Mixing boron nitride and hydrogen peroxide to obtain boron nitride/hydrogen peroxide suspension, transferring the boron nitride/hydrogen peroxide suspension into a reactor, stirring and heating to initiate hydrothermal reaction, cleaning a product after the hydrothermal reaction, and drying to obtain hydroxylated boron nitride;
2) Adding the hydroxylated boron nitride, caprolactam and the phase-separated polymer into a reactor, heating and melting to obtain a mixed solution, and then adding an initiator and an activator to initiate anionic polymerization to obtain the hydroxylated boron nitride/nylon 6/phase-separated polymer alloy;
3) Crushing the hydroxylated boron nitride/nylon 6/phase-separated polymer alloy, and etching to remove the phase-separated polymer, thereby finally obtaining the hydroxylated boron nitride/nylon 6 microsphere.
2. The method of claim 1, wherein in step 1), the boron nitride/hydrogen peroxide suspension has a boron nitride content of 0.05-0.5g/ml.
3. The method according to claim 1, wherein in step 1), the stirring conditions are: the stirring speed is 500r/min-1000r/min, and the stirring time is 12h-36h.
4. The method according to claim 1, wherein in step 1), the hydrothermal reaction conditions are as follows: the temperature of the hydrothermal reaction is 80-160 ℃, and the time of the hydrothermal reaction is 12-36h.
5. The method according to claim 1, wherein in step 2), the hydroxylated boron nitride is used in an amount of 0.5 to 10% by weight of the mass of caprolactam.
6. The method of claim 1, wherein in step 2), the phase-separated polymer is one of polystyrene, polyethylene glycol, and polyether polyol.
7. The method according to claim 1, wherein in the step 2), the phase-separated polymer accounts for 10% -30% of the total mass of the mixed solution, and the melting temperature is 80 ℃ -150 ℃.
8. The preparation method according to claim 1, wherein in the step 2), before the initiator is added, the mixed solution is subjected to vacuum dehydration at 120-170 ℃ for 0.5-1 h;
vacuum dehydration is carried out for 0.5h to 1h at the temperature of 150 ℃ to 170 ℃ after the initiator is added, and the water is stabilized for 0.5h to 1h after the water is removed;
the initiator is sodium hydroxide, and the use amount of the initiator is 0.2-0.6% of the mass of the mixed solution.
9. The preparation method according to claim 1, wherein in the step 2), the activator is added and mixed uniformly, and the mixture is left to stand for 0.5 to 1 hour at 150 to 240 ℃;
the activating agent is toluene diisocyanate, and the amount of the activating agent is 0.2% -0.6% of the mass of the mixed solution.
10. The method according to claim 1, wherein in the step 3), the etching is extraction etching, the etching temperature is 80-120 ℃, and the etching time is 12-36h.
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