CN112898495A - Reactive core-shell particle and preparation method thereof - Google Patents
Reactive core-shell particle and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
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- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 22
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- 239000003999 initiator Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
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- 238000001914 filtration Methods 0.000 claims description 15
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- 238000005406 washing Methods 0.000 claims description 7
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- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229920006778 PC/PBT Polymers 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 229920000578 graft copolymer Polymers 0.000 abstract description 5
- 229920002857 polybutadiene Polymers 0.000 abstract description 4
- 239000012745 toughening agent Substances 0.000 abstract description 4
- NCEQVKDLNDLGNP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;oxiran-2-ylmethyl 2-methylprop-2-enoate;styrene Chemical group COC(=O)C(C)=C.C=CC1=CC=CC=C1.CC(=C)C(=O)OCC1CO1 NCEQVKDLNDLGNP-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 13
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
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- 229910045601 alloy Inorganic materials 0.000 description 3
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- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNRDADQWVXLHCQ-UHFFFAOYSA-N pentane-2,2,4,4-tetrol Chemical compound CC(O)(O)CC(C)(O)O VNRDADQWVXLHCQ-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
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- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses reactive core-shell particles and a preparation method thereof, and relates to the technical field of high polymer materials. The method provided by the invention comprises the steps of uniformly mixing deionized water, an emulsifier, an initiator, a cross-linking agent, a reaction monomer and styrene to obtain a first reaction mixture, and reacting for 3-4 hours under the condition of nitrogen to obtain a first reaction product; stirring deionized water, an emulsifier and glycidyl methacrylate at room temperature to obtain a second reaction mixture, and dropwise adding the second reaction mixture to the first reaction product under the condition of nitrogen to react to obtain a second reaction product; and demulsifying and drying the second reaction product to obtain reactive core-shell particles, so that the core phase of the reactive core-shell particles has a polybutadiene rubber phase or a PBA flexible chain segment, and the shell phase polymer is a methyl methacrylate-styrene-glycidyl methacrylate graft copolymer, and can be used as a toughening agent of different PC/PBT blending systems, improve the compatibility among blending components and improve the mechanical properties of different PC/PBT materials.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to reactive core-shell particles and a preparation method thereof.
Background
With the rapid development of the automobile industry and the actual demand of replacing steel with plastic, automobile parts such as automobile body panels, automobile bumpers, automobile bases and seats, anti-collision steel beams, electrical appliances, electronics and sports equipment and the like are all applied to Polycarbonate (PC)/polybutylene terephthalate (PBT) alloy materials.
Polybutylene terephthalate (PBT) is a semi-crystalline thermoplastic engineering plastic, is suitable for onyx molding, and has excellent chemical resistance, melt flowability and electric insulation of wires. However, the glass transition temperature of PBT is low, about 45 ℃, the rigidity at high temperature is insufficient, the notch impact strength is low, and the thermal deformation temperature under high load is low, which limits the practical application of PBT materials. Polycarbonate (PC) is amorphous thermoplastic engineering plastic, and has good toughness, high glass transition temperature, good creep resistance, good electrical insulation and dimensional stability. However, PC has high melt viscosity, poor fluidity and solvent resistance, and obvious defects are easily formed in the process of processing and molding. The PC/PBT alloy shows excellent comprehensive performance, can overcome the problems of poor heat resistance, notch impact sensitivity and the like of PBT on one hand, can improve the chemical solvent resistance and the forming processability of PC on the other hand, and is one of the mainstream products in the aspect of modified engineering plastics. However, if PC and PBT are directly blended, the crystallinity of PBT can cause obvious phase separation between blending components, the cohesiveness of two-phase interfaces is weak, the mechanical property of the alloy material is reduced, and the toughness of the material is also greatly reduced.
In order to solve the problem of poor mechanical property of PC/PBT alloy, the prior art melts, blends and post-processes the mixture of polycarbonate and butylene terephthalate and core-shell particles according to the required proportion, the addition of polycarbonate enables the notch sensitivity of the polybutylene terephthalate to be obviously reduced, and the addition of modifier core-shell particles enables the compatibility of the polycarbonate and the polybutylene terephthalate to be well improved, and the tensile strength, the impact strength and the toughness of the material to be maintained, wherein, the preparation method of the core-shell particles can be shown as the technical content disclosed in application No. CN 201410747406.6: synthesizing core-shell particles MBS-g-GMA by adopting an emulsion polymerization method, carrying out the reaction in a water bath at 70 ℃, and respectively adding deionized water, sodium pyrophosphate, glucose, ferrous sulfate, PBL latex, potassium hydroxide and CHP into a three-neck flask; introducing nitrogen, continuously dropwise adding the prepared monomers of St, MMA and CHP into the reaction kettle, and finishing dropwise adding about 3 hours at the rotating speed of 300 r/min; dropwise adding GMA and CHP monomers, adding a small amount of CHP, adding 60mL of antioxidant after 1h, taking out after 0.5h, inverting the magnesium sulfate solution (at the temperature of 65 ℃) to perform demulsification, and filtering to obtain MBS-g-GMA graft copolymer; and finally, drying the mixture in a 60 ℃ forced air drying oven to obtain graft copolymer powder, wherein the monomer ratio in the shell-core particles is as follows: st content 73.1wt%, MMA content 24.4wt%, and GMA content 2.5 wt%.
In the process of implementing the invention, the inventor finds that the following problems exist in the related art:
the preparation method of the core-shell particles provided by the prior art has the advantages that the preparation process is complex, more reaction raw materials are adopted, and a large amount of side reaction products are easily generated in the preparation process, so that the toughening performance of the core-shell particles is influenced; in addition, the existing preparation method of the core-shell particles has higher limitation, can only have toughening effect on specific alloy materials, and cannot be applied to preparation processes of other alloy materials.
Disclosure of Invention
In view of the above problems in the related art, the present invention provides a reactive core-shell particle and a method for preparing the same. The technical scheme of the invention is as follows:
according to a first aspect of embodiments of the present invention, there is provided a method for preparing reactive core-shell particles, the method comprising:
uniformly mixing deionized water, an emulsifier, an initiator, a cross-linking agent, a reaction monomer and styrene to obtain a first reaction mixture, and uniformly stirring and reacting at a reaction temperature of 60-70 ℃ and a stirring speed of 200-300 revolutions per minute for 3-4 hours under the reaction condition of continuously introducing nitrogen to obtain a first reaction product; the reaction monomer is a mixed monomer formed by n-butyl acrylate and styrene in any proportion, butadiene or methyl acrylate; the volume ratio of the deionized water to the reaction monomer in the first reaction mixture is 60-95: 5-40; the mass ratio of the reaction monomer to the styrene in the first reaction mixture is 80-99.9: 0.1-20; the mass ratio of the reaction monomers to the initiator in the first reaction mixture is 90-99.9: 0.1-10; the weight of the emulsifier in the first reaction mixture is 0.5-10% of the weight of the first reaction mixture;
uniformly stirring deionized water, the emulsifier and glycidyl methacrylate at room temperature for 20-30 minutes to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the reaction condition of continuously introducing nitrogen, and uniformly stirring and reacting at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 revolutions per minute for 2-3 hours to obtain a second reaction product; the volume ratio of the deionized water to the glycidyl methacrylate in the second reaction mixture is 60-95: 5-40; the weight of the emulsifier in the second reaction mixture is 0.5-10% of the weight of the second reaction mixture;
and adding the second reaction product into the demulsifier solution, stirring for 5-10min, and filtering, washing, filtering again and drying after layering to obtain the reactive core-shell particles.
In a preferred embodiment, the reactive monomer is a mixed monomer of n-butyl acrylate and styrene, and the mass ratio of the n-butyl acrylate to the styrene in the reactive monomer is 20-80: 20-80.
In a preferred embodiment, the volume ratio of deionized water to the reactive monomers in the first reaction mixture is 70-90: 10-30.
In a preferred embodiment, the mass ratio of the reactive monomers to the styrene in the first reaction mixture is 10-90.9: 1-10.
In a preferred embodiment, the mass ratio of the reactive monomers to the initiator in the first reaction mixture is 95-99: 1-5.
In a preferred embodiment, the emulsifier in the second reaction mixture is at least one of sodium dodecylbenzenesulfonate, Span-80, Span-60, tween 80 or tween 60.
In a preferred embodiment, the volume ratio of the deionized water to the glycidyl methacrylate is 70-90: 10-30.
In a preferred embodiment, the demulsifier used in the demulsifier solution comprises at least one of mineral acid, ferric sulfate, and magnesium sulfate.
In a preferred embodiment, the volume of the breaker solution is 2-3 times the volume of the second reaction product.
According to a second aspect of embodiments of the present invention, there is provided reactive core-shell particles, wherein the reactive core-shell particles are prepared by any of the above-described methods for preparing reactive core-shell particles.
Compared with the prior art, the reactive core-shell particles and the preparation method thereof provided by the invention have the following advantages:
the preparation method of the reactive core-shell particles provided by the invention comprises the steps of uniformly mixing deionized water, an emulsifier, an initiator, a cross-linking agent, a reaction monomer and styrene to obtain a first reaction mixture, and reacting for 3-4 hours at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 r/min to obtain a first reaction product; uniformly stirring deionized water, an emulsifier and glycidyl methacrylate at room temperature for 20-30 minutes to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the condition of nitrogen, and stirring and reacting at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 r/min for 2-3 hours to obtain a second reaction product; and adding the second reaction product into the demulsifier solution, stirring for 5-10min, layering, filtering, washing, filtering again and drying to obtain reactive core-shell particles, wherein the core phase of the prepared reactive core-shell particles has a polybutadiene rubber phase or a PBA flexible chain segment, and the shell phase polymer is a methyl methacrylate-styrene-glycidyl methacrylate graft copolymer which can be used as a toughening agent of different PC/PBT blending systems, so that the compatibility among blending components is improved, and the mechanical properties of different PC/PBT materials are improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a process flow diagram illustrating a method of making reactive core-shell particles according to an exemplary embodiment.
Fig. 2 is a schematic diagram illustrating the synthesis of a reactive core-shell particle, according to an exemplary embodiment.
Fig. 3 is a schematic diagram illustrating the synthesis of another reactive core-shell particle according to an exemplary embodiment.
Detailed Description
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a process flow diagram illustrating a method of preparing reactive core-shell particles according to an exemplary embodiment, in fig. 1, the method of preparing reactive core-shell particles comprising:
step 100: uniformly mixing deionized water, an emulsifier, an initiator, a cross-linking agent, a reaction monomer and styrene to obtain a first reaction mixture, and uniformly stirring and reacting for 3-4 hours at a reaction temperature of 60-70 ℃ and a stirring speed of 200-300 r/min under the reaction condition of continuously introducing nitrogen to obtain a first reaction product.
The reaction monomer is a mixed monomer formed by n-butyl acrylate and styrene in any proportion, butadiene or methyl acrylate; the volume ratio of the deionized water to the reaction monomer in the first reaction mixture is 60-95: 5-40; the mass ratio of the reaction monomer to the styrene in the first reaction mixture is 80-99.9: 0.1-20; the mass ratio of the reaction monomers to the initiator in the first reaction mixture is 90-99.9: 0.1-10; the weight of the emulsifier in the first reaction mixture is 0.5-10% of the weight of the first reaction mixture.
The first reaction mixture and the first reaction product are in the form of an emulsion.
Step 200: uniformly stirring deionized water, the emulsifier and glycidyl methacrylate at room temperature for 20-30 minutes to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the reaction condition of continuously introducing nitrogen, and uniformly stirring and reacting at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 revolutions per minute for 2-3 hours to obtain a second reaction product.
The volume ratio of the deionized water to the glycidyl methacrylate in the second reaction mixture is 60-95: 5-40; the weight of the emulsifier in the second reaction mixture is 0.5-10% of the weight of the second reaction mixture.
The second reaction mixture and the second reaction product are in the form of an emulsion.
Step 300: and adding the second reaction product into the demulsifier solution, stirring for 5-10min, and filtering, washing, filtering again and drying after layering to obtain the reactive core-shell particles.
The reactive core-shell particles provided by the invention are obtained by emulsion polymerization, the method is simple and efficient, and the reactive core-shell particles are suitable for large-scale industrial production, contain epoxy functional groups, can perform ring-opening condensation reaction with matrix macromolecules, improve the compatibility of alloy materials, and improve the notch impact resistance.
The reactive core-shell particle is suitable for toughening modifiers of PC/PBT and other alloys, a shell PMMA copolymerization component of the core-shell particle has good compatibility with PC, an epoxy functional group of a GMA copolymerization component and a terminal carboxyl group of PBT can perform a compatibilization reaction, and the MBS-g-GMA (or MS-g-GMA) reactive core-shell structure toughening agent combines the advantages that the core-shell structure modifier has a controllable structure and is beneficial to improving the interface characteristics of a matrix and a disperse phase through reaction blending, so that the dispersion form of the reactive MBS-g-GMA (or MS-g-GMA) core-shell particle in a PC/PBT blending system is not influenced by the change of the blending composition of the two components, and can be uniformly and stably dispersed all the time, thereby preparing a high-performance product of PC/PBT/MBS-g-GMA (MS-g-GMA).
In addition, the core part in the core-shell particle contains a polybutadiene rubber phase (or the core part contains a PBA flexible chain segment), so that a blending system can be effectively compatibilized; in addition, in the melt blending process, epoxy functional groups on the surfaces of the core-shell particles can perform ring-opening condensation reaction with terminal carboxyl groups of PC and PBT, so that the interface condition is improved, and the interface bonding strength is improved; the nuclear shell particles after ring opening condensation can be used as a compatibilizer of a PC/PBT blending system, the compatibility among blending components is improved, and the mechanical property of the material is fully improved.
For convenience of explaining the preparation method of the reactive core-shell particles provided by the invention, a synthesis schematic diagram of one reactive core-shell particle shown in fig. 2 and 3 is shown. Wherein, the reactive core-shell particles shown in FIG. 2 are MBS-g-GMA, and the reactive core-shell particles shown in FIG. 3 are MS-g-GMA.
In a preferred embodiment, the reactive monomer is a mixed monomer of n-butyl acrylate and styrene, and the mass ratio of the n-butyl acrylate to the styrene in the reactive monomer is 20-80: 20-80.
In a preferred embodiment, the volume ratio of deionized water to the reactive monomers in the first reaction mixture is 70-90: 10-30.
In a preferred embodiment, the mass ratio of the reactive monomers to the styrene in the first reaction mixture is 10-90.9: 1-10.
In a preferred embodiment, the mass ratio of the reactive monomers to the initiator in the first reaction mixture is 95-99: 1-5.
In a preferred embodiment, the emulsifier in the second reaction mixture is at least one of sodium dodecylbenzenesulfonate, Span-80, Span-60, tween 80 or tween 60.
In a preferred embodiment, the volume ratio of the deionized water to the glycidyl methacrylate is 70-90: 10-30.
In a preferred embodiment, the demulsifier used in the demulsifier solution comprises at least one of mineral acid, ferric sulfate, and magnesium sulfate.
In a preferred embodiment, the volume of the breaker solution is 2-3 times the volume of the second reaction product.
In order to better illustrate the beneficial effects of the method for preparing the reactive core-shell particles provided by the present invention, the following examples 1-2 are also shown for illustration:
example 1
Step 100: the method comprises the steps of uniformly mixing deionized water, an emulsifier, an initiator, n-butyl acrylate BA, a cross-linking agent divinylbenzene DVB and styrene St to obtain a first reaction mixture, and uniformly stirring and reacting for 4 hours at a reaction temperature of 70 ℃ and a stirring speed of 300r/min under the reaction condition of continuously introducing nitrogen to obtain a first reaction product.
In the step of this embodiment, the content ratio of each component is shown in table one:
| raw materials | Content (wt%) |
| Deionized water | 75.0 |
| Emulsifier | 3.5 |
| Initiator | 0.5 |
| BA | 12.0 |
| St | 5.0 |
| Cross-linking agent DVB | 4.0 |
Watch 1
Step 2: uniformly stirring deionized water, the emulsifier and glycidyl methacrylate GMA for 30 minutes at room temperature to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the reaction condition of continuously introducing nitrogen, and uniformly stirring and reacting at the reaction temperature of 70 ℃ and the stirring speed of 300r/min for 3 hours to obtain a second reaction product.
In the step of this example, the content ratio of each component is shown in table two:
| raw materials | Content (wt%) |
| Deionized water | 75.0 |
| Emulsifier | 2.0 |
| GMA | 23.0 |
Watch two
Step 300: and adding the second reaction product into the demulsifier solution, stirring for 10min, layering, and filtering, washing, filtering again and drying to obtain the reactive core-shell particles.
Example 2
Step 100: the method comprises the steps of uniformly mixing deionized water, an emulsifier, an initiator, n-butyl acrylate BA, a cross-linking agent divinylbenzene DVB and styrene St to obtain a first reaction mixture, and uniformly stirring and reacting for 3 hours at a reaction temperature of 60 ℃ and a stirring speed of 200 r/min under the reaction condition of continuously introducing nitrogen to obtain a first reaction product.
In the step of this embodiment, the content ratio of each component is shown in table one:
| raw materials | Content (wt%) |
| Deionized water | 80.0 |
| Emulsifier | 3.5 |
| Initiator | 0.5 |
| BA | 8.0 |
| St | 4.0 |
| Cross-linkingAgent DVB | 4.0 |
Watch 1
Step 2: uniformly stirring deionized water, the emulsifier and glycidyl methacrylate GMA for 30 minutes at room temperature to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the reaction condition of continuously introducing nitrogen, and uniformly stirring and reacting at the reaction temperature of 60 ℃ and the stirring speed of 200 r/min for 3 hours to obtain a second reaction product.
In the step of this example, the content ratio of each component is shown in table two:
| raw materials | Content (wt%) |
| Deionized water | 80.0 |
| Emulsifier | 2.0 |
| GMA | 18.0 |
Watch two
Step 300: and adding the second reaction product into the demulsifier solution, stirring for 5min, layering, and filtering, washing, filtering again and drying to obtain the reactive core-shell particles.
In summary, the reactive core-shell particle and the preparation method thereof provided by the invention have the following advantages:
the preparation method of the reactive core-shell particles provided by the invention comprises the steps of uniformly mixing deionized water, an emulsifier, an initiator, a cross-linking agent, a reaction monomer and styrene to obtain a first reaction mixture, and reacting for 3-4 hours at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 r/min to obtain a first reaction product; uniformly stirring deionized water, an emulsifier and glycidyl methacrylate at room temperature for 20-30 minutes to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the condition of nitrogen, and stirring and reacting at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 r/min for 2-3 hours to obtain a second reaction product; and adding the second reaction product into the demulsifier solution, stirring for 5-10min, layering, filtering, washing, filtering again and drying to obtain reactive core-shell particles, wherein the core phase of the prepared reactive core-shell particles has a polybutadiene rubber phase or a PBA flexible chain segment, and the shell phase polymer is a methyl methacrylate-styrene-glycidyl methacrylate graft copolymer which can be used as a toughening agent of different PC/PBT blending systems, so that the compatibility among blending components is improved, and the mechanical properties of different PC/PBT materials are improved.
While the invention has been described in detail in the foregoing by way of general description, and specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof.
Claims (10)
1. A method of preparing reactive core-shell particles, the method comprising:
uniformly mixing deionized water, an emulsifier, an initiator, a cross-linking agent, a reaction monomer and styrene to obtain a first reaction mixture, and uniformly stirring and reacting at a reaction temperature of 60-70 ℃ and a stirring speed of 200-300 revolutions per minute for 3-4 hours under the reaction condition of continuously introducing nitrogen to obtain a first reaction product; the reaction monomer is a mixed monomer formed by n-butyl acrylate and styrene in any proportion, butadiene or methyl acrylate; the volume ratio of the deionized water to the reaction monomer in the first reaction mixture is 60-95: 5-40; the mass ratio of the reaction monomer to the styrene in the first reaction mixture is 80-99.9: 0.1-20; the mass ratio of the reaction monomers to the initiator in the first reaction mixture is 90-99.9: 0.1-10; the weight of the emulsifier in the first reaction mixture is 0.5-10% of the weight of the first reaction mixture;
uniformly stirring deionized water, the emulsifier and glycidyl methacrylate at room temperature for 20-30 minutes to obtain a second reaction mixture, dropwise adding the second reaction mixture to the first reaction product under the reaction condition of continuously introducing nitrogen, and uniformly stirring and reacting at the reaction temperature of 60-70 ℃ and the stirring speed of 200-300 revolutions per minute for 2-3 hours to obtain a second reaction product; the volume ratio of the deionized water to the glycidyl methacrylate in the second reaction mixture is 60-95: 5-40; the weight of the emulsifier in the second reaction mixture is 0.5-10% of the weight of the second reaction mixture;
and adding the second reaction product into the demulsifier solution, stirring for 5-10min, and filtering, washing, filtering again and drying after layering to obtain the reactive core-shell particles.
2. The preparation method according to claim 1, wherein the reaction monomer is a mixed monomer of n-butyl acrylate and styrene, and the mass ratio of n-butyl acrylate to styrene in the reaction monomer is 20-80: 20-80.
3. The method of claim 1, wherein the volume ratio of deionized water to the reactive monomer in the first reaction mixture is 70-90: 10-30.
4. The method according to claim 1, wherein the mass ratio of the reactive monomer to the styrene in the first reaction mixture is 10 to 90.9:1 to 10.
5. The method of claim 1, wherein the mass ratio of the reactive monomer to the initiator in the first reaction mixture is 95-99: 1-5.
6. The method of claim 1, wherein the emulsifier in the second reaction mixture is at least one of sodium dodecylbenzenesulfonate, Span-80, Span-60, tween 80 or tween 60.
7. The method according to claim 1, wherein the volume ratio of the deionized water to the glycidyl methacrylate is 70-90: 10-30.
8. The preparation method of claim 1, wherein the demulsifier used in the demulsifier solution comprises at least one of mineral acid, ferric sulfate and magnesium sulfate.
9. The method of claim 1, wherein the emulsion breaker solution volume is 2-3 times the volume of the second reaction product.
10. A reactive core-shell particle, characterized in that it is prepared by the method of any of claims 1 to 9.
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| CN114015172A (en) * | 2021-10-28 | 2022-02-08 | 滁州杰事杰新材料有限公司 | High-performance PS composite material and preparation method thereof |
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