CN115418072B - Method for toughening ABS (Acrylonitrile butadiene styrene) by aerogel micro powder and toughened ABS plastic - Google Patents
Method for toughening ABS (Acrylonitrile butadiene styrene) by aerogel micro powder and toughened ABS plastic Download PDFInfo
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- CN115418072B CN115418072B CN202211223368.5A CN202211223368A CN115418072B CN 115418072 B CN115418072 B CN 115418072B CN 202211223368 A CN202211223368 A CN 202211223368A CN 115418072 B CN115418072 B CN 115418072B
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 115
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000004964 aerogel Substances 0.000 title claims abstract description 24
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title abstract description 86
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 36
- 229920001971 elastomer Polymers 0.000 claims abstract description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011324 bead Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- 229920003023 plastic Polymers 0.000 abstract description 10
- 239000004033 plastic Substances 0.000 abstract description 10
- 229920006351 engineering plastic Polymers 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000010954 inorganic particle Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005543 nano-size silicon particle Substances 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010146 3D printing Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WPUHLWYDTKIMGG-UHFFFAOYSA-L magnesium;2-hydroxyoctadecanoate Chemical class [Mg+2].CCCCCCCCCCCCCCCCC(O)C([O-])=O.CCCCCCCCCCCCCCCCC(O)C([O-])=O WPUHLWYDTKIMGG-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention belongs to the technical field of engineering plastics, and particularly provides a method for toughening ABS (Acrylonitrile butadiene styrene) by utilizing aerogel micro powder and toughened ABS plastic. The toughened ABS plastic is toughened by utilizing micron-sized silica aerogel particles, the silica aerogel particles belong to micron-sized silica aerogel particles, are easy to disperse and have rich nanopores, the ABS high rubber powder is dissolved into liquid infiltration nanopores, so that the ABS high rubber powder is adsorbed in the penetrated nanopores to obtain modified silica aerogel, the modified silica aerogel and the ABS are further melt extruded in a screw extruder, the penetrated nanopores and an ABS network are interpenetrating, the specific surface area of the nanopores is large, the interfacial area with the ABS is increased, more microcracks and plastic deformation can be generated when the material is impacted, and therefore, more impact energy is absorbed, and the toughening effect is improved. The preparation method is simple and easy to control, and is suitable for batch production.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a method for toughening ABS by utilizing aerogel micro powder and toughened ABS plastic.
Background
The performance of the polymer material product is continuously improved, and the application range of engineering plastics is wider and wider. The current application of engineering plastics relates to the industrial manufacturing fields of household appliances, electric appliances, automobiles, airplanes, machinery and the like, and the performance requirements on the engineering plastics are also higher and higher. Such as tensile strength, rigidity, toughness, flexural modulus, high temperature resistance, corrosion resistance, abrasion resistance, etc., of materials are becoming increasingly demanding.
ABS (acrylonitrile-butadiene-styrene copolymer) is a widely used engineering plastic with toughness, hardness and rigidity. At present, ABS is well-developed in housings and parts of household appliances such as televisions, washing machines, refrigerators, air conditioners, dust collectors, fans, printers and the like. The ABS is further reinforced and toughened, so that the ABS can be applied to various industrial products, and the ABS is used for automobile bumpers, pump impellers and bearings.
In the ABS modification treatment, it is difficult to improve both rigidity and toughness. Generally, the addition of rigid inorganic particles to ABS increases rigidity and dimensional stability, but it is very likely to cause the toughness of ABS to decrease and the product to become brittle. The use of toughening agents such as elastomers can increase the toughness and impact resistance of ABS, but the stiffness and strength of the article can be reduced.
At present, in order to simultaneously improve the rigidity and the toughness of ABS during modification, a mature technology is adopted to modify by utilizing glass fibers. The glass fiber modified ABS has the rigidity of inorganic materials, and meanwhile, the fiber can greatly improve the flexural modulus and the shock resistance of the materials. However, when the glass fiber is used for modifying ABS, the glass fiber is continuously sheared due to shearing of repeated processing of screw extrusion, so that the impact resistance effect of the fiber is lost. Meanwhile, aiming at the development of the prior ABS to spraying-free plastics, the glass fiber toughened ABS is difficult to color; in addition, ABS is prepared into 3D printing consumables, so that the ABS can be widely applied to rapid printing industrial accessories, becomes a main stream material for high polymer 3D printing, and glass fiber toughened ABS is difficult to adapt to the tight control of 3D printing, and printing consumables are rough in silk.
For ABS to be used in a wider range of applications, it is urgent to find new, more efficient and more suitable toughening techniques. The nano inorganic particles are a material with the granularity at the nano level, and have higher specific surface area, so that if the nano particles are uniformly dispersed in the ABS, when the ABS product is impacted by external force, microcracks and micro plastic deformation can be generated on the ABS product, so that the impact force is absorbed and dispersed, and the product maintains good impact toughness.
The nano inorganic particles such as nano calcium carbonate, nano barium sulfate, nano silicon dioxide and other materials are commonly used toughening agents at present, but the nano inorganic particles have extremely strong agglomeration force due to the existence of nano particles, so that the nano inorganic particles need to be treated by a coupling agent, an interface modifier, a dispersing agent and the like, so that the dispersion and the compatibility of the nano inorganic particles in ABS are improved.
According to the technical scheme disclosed in the Chinese patent publication No. CN102464839B, the composite toughening modifier for plastics and the preparation method thereof are disclosed, and nano calcium carbonate and polyacrylate elastomer coated outside the nano calcium carbonate are adopted as toughening materials, so that the nano calcium carbonate is uniformly dispersed in a matrix, and the compatibility of the nano calcium carbonate and the matrix can be improved.
Chinese patent publication No. CN103897434B discloses a method for preparing nano calcium carbonate for plastic master batch by controlling nano CaCO 3 Is simultaneously activated by wet method to avoid the crystal form and the particle sizeNo nano CaCO caused by dry method activation modification 3 Particle agglomeration and secondary surface coating, and the primary conventional coating improves nano CaCO 3 The dispersibility of the nano CaCO is reduced, the oil absorption value is reduced, and the nano CaCO is improved by secondary coupling coating 3 Compatibility with polyolefin plastic, effectively improves nano CaCO 3 The processability and compatibility in the use of the master batch lead the prepared nano master batch to have the characteristics of reinforcement, toughening, high dispersion and high extrusion.
The Chinese patent publication No. CN114539651A discloses a nano silicon dioxide reinforced and toughened master batch and a preparation method thereof, wherein a coupling agent and nano silicon dioxide are added into a high-speed mixer to be stirred, so that the coupling agent is fully coated on the surface of the nano silicon dioxide, then a lubricant, a dispersing agent and polyethylene are added into the high-speed mixer in proportion to be stirred at high speed until materials are fully and uniformly mixed, and then extrusion granulation is carried out by a homodromous parallel double-screw extruder, wherein the silane coupling agent contains an inophilic group and an organophilic group, plays a role of a ligament, increases the compatibility of the nano silicon dioxide and the polyethylene, and the modified magnesium hydroxystearate and reasonable screw combination can effectively open the nano silicon dioxide aggregate, so that the nano silicon dioxide can be well dispersed in the polyethylene, and the modification effect of the nano silicon dioxide is effectively improved.
Clearly, the nano-interface effect is effective in improving the toughness of plastics. However, according to the prior art, the dispersion treatment process of the nano inorganic particles is complex and unstable, and the dispersion of the nano particles in the modified material can migrate and agglomerate due to long-time storage, which is also a barrier for restricting the large-area use of the reinforcing and toughening of the nano particles in the polymer material.
Disclosure of Invention
The invention aims to more conveniently apply the toughening effect of the nano interface to the toughening of ABS. Therefore, a method for toughening ABS by utilizing aerogel micro powder and toughened ABS plastic are provided.
Unlike traditional nanometer inorganic particles dispersed directly in ABS for toughening, the present invention toughens nanometer pore size of micron aerogel. Compared with nano particles, the excellent aerogel particles which are shown in the micron level are easier to disperse, and the micron level aerogel particles have abundant through nano holes, are interpenetrating with an ABS network, have large specific surface area and increase the interfacial area with the ABS, thereby realizing better enhancement of toughness.
In order to achieve the above purpose, the present invention is implemented by adopting the following specific technical scheme:
a method for toughening ABS by utilizing aerogel micro powder is characterized in that: the specific method comprises the following steps:
(1) ABS high rubber powder and N, N-dimethylformamide are mixed according to the mass ratio of 1:30-40, stirring in a sealed stirring kettle until the modified liquid is completely dissolved, then adding the silica aerogel into the modified liquid in the sealed stirring kettle, continuously stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, and continuously removing residual N, N-dimethylformamide by a vacuum evaporator at the temperature of 150-155 ℃ to obtain the modified silica aerogel;
(2) 90-95 parts of ABS, 2-4 parts of modified silica aerogel, 1-2 parts of glass beads, 1-2 parts of calcium sulfate whisker, 0.2-0.5 part of silane coupling agent and 0.1-0.2 part of antioxidant are added into a high-speed mixer according to parts by weight, and dispersed for 15-20min at the rotating speed of 200-500rpm to obtain premix;
(3) And (3) feeding the premix obtained in the step (2) into a double-screw extruder for melt extrusion, and granulating the braces to obtain the toughened ABS plastic.
Preferably, the silica aerogel in the step (1) has a particle size of 20-50 μm, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600m 2 Particles per gram.
Preferably, the ABS high rubber powder in the step (1) is high rubber powder with the butadiene content of 68-70%, and has good toughness.
Preferably, in the step (1), the mixing mass ratio of the silica aerogel to the modifying liquid in the sealed stirring kettle is 1:15-20. The micron-sized silica aerogel particles have abundant nanopores, and the ABS high-rubber powder is dissolved into liquid to infiltrate the nanopores, so that the through nanopores are adsorbed with the ABS high-rubber powder to obtain the modified silica aerogel, the modified silica aerogel has good compatibility with ABS when the ABS is melt extruded in a screw extruder, the through nanopores and the ABS are easy to interpenetrate with a network, the specific surface area of the nanopores is large, the interfacial area with the ABS is increased, and when the material is impacted, more microcracks and plastic deformation can be generated, so that more impact energy is absorbed, and the toughening effect is improved.
The purpose of using N, N-dimethylformamide in the step (1) is to serve as a solvent, and the ABS high-gel powder is easily adsorbed by the nano holes of the silica aerogel after being dissolved. After the carrying function is completed, the N, N-dimethylformamide needs to be removed, redundant modified liquid is filtered out through natural filtration, and then the residual N, N-dimethylformamide is removed in a vacuum evaporator. Preferably, the residual N, N-dimethylformamide is removed under the vacuum degree of-0.085 MPa, and the vacuum evaporator can not only reduce the boiling point of the solution, but also facilitate the quick removal of volatile matters.
Preferably, in the step (2), the glass beads with the particle size less than or equal to 20nm are selected. The glass beads are dispersed in ABS, are spherical particles, have good dispersibility and fluidity, and are beneficial to improving the appearance of plastic products; meanwhile, when the spherical particles are impacted by external force, the impact force can be dispersed, so that the impact resistance of the ABS product is improved.
Preferably, in the step (2), the calcium sulfate whisker is calcium sulfate whisker with the whisker length of 20-100um and the diameter of 1-3 um. Unlike short glass fiber, the calcium sulfate whisker has short length and small diameter and can not be excessively sheared in repeated extrusion processing of the screw.
Preferably, the silane coupling agent in the step (2) is at least one of 3-aminopropyl triethoxysilane (KH-550) and gamma- (2, 3-glycidoxy) propyl trimethoxysilane (KH-560).
Preferably, the antioxidant in the step (2) is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant DNP.
Preferably, the twin-screw extruder in the step (3) is a co-rotating twin-screw extruder, and the temperature process of melt extrusion of the twin-screw extruder is controlled as follows: a first-stage temperature: 160-170 ℃; two-stage temperature: 175-180 ℃; three-stage temperature: 185-195 ℃; four-stage temperature: 200-205 ℃; five-stage temperature: 210-215 ℃; six-stage temperature: 200-205 ℃; seven-stage temperature: 185-195 ℃; eight-stage temperature: 175-180 ℃; nine-stage temperature: 175-180 ℃; ten-stage temperature: 175-180 ℃.
The invention further provides the toughened ABS plastic prepared by the method. The specific surface area of the nano inorganic particles is increased, the contact interface between the particle interface and the resin matrix is large, and when the material is impacted, microcracks and plastic deformation can be generated, so that more impact energy is absorbed, and the toughening effect is improved. However, the nano particles are difficult to disperse and are easy to agglomerate, and the interfacial toughening effect of the nano particles is difficult to fully exert. In view of this, the toughened ABS plastic of the present invention toughens ABS using micron sized silica aerogel particles. The micron-sized silica aerogel particles belong to micron-sized silica aerogel particles, are easy to disperse and have rich nanopores, the ABS high rubber powder is dissolved into liquid to infiltrate the nanopores, so that the ABS high rubber powder is adsorbed in the penetrated nanopores to obtain modified silica aerogel, the modified silica aerogel and ABS are further melt extruded in a screw extruder, the penetrated nanopores and an ABS network are interpenetrating, the specific surface area of the nanopores is large, the phase interface area with the ABS is increased, more microcracks and plastic deformation are generated when the material is impacted, and therefore, more impact energy is absorbed, and the toughening effect is improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention is different from the traditional toughening of dispersing nano inorganic particles in ABS, but realizes the toughening by utilizing the principle that the contact interface between the nano pores in the micron-sized silica aerogel and the ABS is increased. The problem that the nano inorganic particles are difficult to disperse is solved.
(2) The glass beads are dispersed in the ABS in an auxiliary mode, and when the spherical particles are impacted by external force, impact force can be dispersed, so that the impact resistance of the ABS product is improved.
(3) The invention is assisted in using calcium sulfate whisker to strengthen and toughen ABS, the calcium sulfate whisker has short length and small diameter, and can not be excessively shortened in repeated extrusion processing of the screw rod.
(4) The preparation method is simple and easy to control, and is suitable for batch production.
Detailed Description
For a further clear and complete description of the technical solution of the invention. Practical operation tests were carried out with the following examples, it being evident that the examples described are some, but not all, of the examples of the invention.
Example 1
(1) ABS high rubber powder with 70% butadiene content and N, N-dimethylformamide are mixed according to the mass ratio of 1:30 stirring in a sealed stirring kettle until the silica aerogel is completely dissolved to form a modified liquid, and then adding the silica aerogel (the silica aerogel has a particle size of 20-50 mu m, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600m 2 Particles per g) are added into the modified liquid of the sealed stirred tank, and the mixing mass ratio of the silicon dioxide aerogel to the modified liquid is 1:15, continuing stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, removing residual N, N-dimethylformamide in a vacuum evaporator at 155 ℃ and a vacuum degree of-0.085 MPa, and enabling the ABS high rubber powder to adhere to the through nano hole interfaces of the silica aerogel to obtain the modified silica aerogel;
(2) Adding 95 parts of ABS (Qimei ABS-PA 777B), 2 parts of modified silica aerogel, 2 parts of glass beads with the particle size less than or equal to 20nm, 2 parts of calcium sulfate whisker with the length of 20-100um and the diameter of 1-3um, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 into a high-speed mixer according to parts by weight, and dispersing for 15 minutes at the rotating speed of 200rpm to obtain premix;
(3) Feeding the premix obtained in the step (2) into a co-rotating twin-screw extruder for melt extrusion, wherein the temperature process of melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
Example 2
(1) ABS high rubber powder with 70% butadiene content and N, N-dimethylformamide are mixed according to the mass ratio of 1:30 stirring in a sealed stirring kettle until the mixture is completely dissolvedDecomposing to form modified liquid, and then adding silica aerogel (the silica aerogel has a particle diameter of 20-50 μm, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600 m) 2 Particles per g) are added into the modified liquid of the sealed stirred tank, and the mixing mass ratio of the silicon dioxide aerogel to the modified liquid is 1:15, continuing stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, removing residual N, N-dimethylformamide in a vacuum evaporator at 155 ℃ and a vacuum degree of-0.085 MPa, and enabling the ABS high rubber powder to adhere to the through nano hole interfaces of the silica aerogel to obtain the modified silica aerogel;
(2) Adding 95 parts of ABS (Qimei ABS-PA 777B), 3 parts of modified silica aerogel, 1 part of glass beads with the particle size less than or equal to 20nm, 2 parts of calcium sulfate whiskers with the length of 20-100um and the diameter of 1-3um, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 into a high-speed mixer according to parts by weight, and dispersing for 15 minutes at the rotating speed of 200rpm to obtain premix;
(3) Feeding the premix obtained in the step (2) into a co-rotating twin-screw extruder for melt extrusion, wherein the temperature process of melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
Example 3
(1) ABS high rubber powder with 70% butadiene content and N, N-dimethylformamide are mixed according to the mass ratio of 1:30 stirring in a sealed stirring kettle until the silica aerogel is completely dissolved to form a modified liquid, and then adding the silica aerogel (the silica aerogel has a particle size of 20-50 mu m, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600m 2 Particles per g) are added into the modified liquid of the sealed stirred tank, and the mixing mass ratio of the silicon dioxide aerogel to the modified liquid is 1:15, continuously stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, removing residual N, N-dimethylformamide in a vacuum evaporator under the conditions of 155 ℃ and vacuum degree of-0.085 MPa, and attaching ABS high rubber powder to the interfaces of the through nano holes of the silica aerogelThen, obtaining modified silica aerogel;
(2) Adding 95 parts of ABS (Qimei ABS-PA 777B), 3 parts of modified silica aerogel, 2 parts of glass beads with the particle size less than or equal to 20nm, 1 part of calcium sulfate whisker with the length of 20-100um and the diameter of 1-3um, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 into a high-speed mixer according to parts by weight, and dispersing for 15 minutes at the rotating speed of 200rpm to obtain premix;
(3) Feeding the premix obtained in the step (2) into a co-rotating twin-screw extruder for melt extrusion, wherein the temperature process of melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
Comparative example 1
(1) 95 parts of ABS (Qimei ABS-PA 777B) and 2 parts of silica aerogel (the silica aerogel is selected from 20-50 mu m in particle size, less than or equal to 20nm in pore size and more than 600m in specific surface area) are mixed according to parts by weight 2 Particles per gram), 2 parts of glass beads with the particle size less than or equal to 20nm, 2 parts of calcium sulfate whiskers with the length of 20-100um and the diameter of 1-3um, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 are added into a high-speed mixer, and dispersed for 15min at the rotating speed of 200rpm to obtain premix;
(2) Feeding the premix into a co-rotating double screw extruder for melt extrusion, wherein the temperature process of the melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
According to the scheme of the comparative example, silica aerogel is directly used in a test, modification is not carried out, so that molten ABS can not be effectively filled in the nano holes of the aerogel when the silica aerogel is extruded in a screw machine, network mutual transmission is poor, and the toughening effect of a nano interface is weakened.
Comparative example 2
(1) Adding 95 parts of ABS (Qimei ABS-PA 777B), 2 parts of ABS high rubber powder with 70% butadiene content, 2 parts of glass beads with the particle size less than or equal to 20nm, 2 parts of calcium sulfate whisker with the length of 20-100um and the diameter of 1-3um, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 into a high-speed mixer according to parts by weight, and dispersing for 15min at the rotating speed of 200rpm to obtain premix;
(2) Feeding the premix into a co-rotating double screw extruder for melt extrusion, wherein the temperature process of the melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
In the scheme of the comparative example, modified silica aerogel is not used in the test, but ABS high rubber powder is directly used, and the ABS high rubber powder has certain toughness, but has limited toughening effect compared with the modified silica aerogel.
Comparative example 3
(1) ABS high rubber powder with 70% butadiene content and N, N-dimethylformamide are mixed according to the mass ratio of 1:30 stirring in a sealed stirring kettle until the silica aerogel is completely dissolved to form a modified liquid, and then adding the silica aerogel (the silica aerogel has a particle size of 20-50 mu m, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600m 2 Particles per g) are added into the modified liquid of the sealed stirred tank, and the mixing mass ratio of the silicon dioxide aerogel to the modified liquid is 1:15, continuing stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, removing residual N, N-dimethylformamide in a vacuum evaporator at 155 ℃ and a vacuum degree of-0.085 MPa, and enabling the ABS high rubber powder to adhere to the through nano hole interfaces of the silica aerogel to obtain the modified silica aerogel;
(2) Adding 95 parts of ABS (Qimei ABS-PA 777B), 2 parts of modified silica aerogel, 2 parts of calcium sulfate whisker with the length of 20-100um and the diameter of 1-3um, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 into a high-speed mixer according to parts by weight, and dispersing for 15min at the rotating speed of 200rpm to obtain premix;
(3) Feeding the premix obtained in the step (2) into a co-rotating twin-screw extruder for melt extrusion, wherein the temperature process of melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
The glass beads are not used in the test of the comparative example scheme, and the toughening effect is affected to a certain extent.
Comparative example 4
(1) ABS high rubber powder with 70% butadiene content and N, N-dimethylformamide are mixed according to the mass ratio of 1:30 stirring in a sealed stirring kettle until the silica aerogel is completely dissolved to form a modified liquid, and then adding the silica aerogel (the silica aerogel has a particle size of 20-50 mu m, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600m 2 Particles per g) are added into the modified liquid of the sealed stirred tank, and the mixing mass ratio of the silicon dioxide aerogel to the modified liquid is 1:15, continuing stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, removing residual N, N-dimethylformamide in a vacuum evaporator at 155 ℃ and a vacuum degree of-0.085 MPa, and enabling the ABS high rubber powder to adhere to the through nano hole interfaces of the silica aerogel to obtain the modified silica aerogel;
(2) Adding 95 parts of ABS (Qimei ABS-PA 777B), 2 parts of modified silica aerogel, 2 parts of glass beads with the particle size less than or equal to 20nm, 0.5 part of silane coupling agent KH-560 and 0.2 part of antioxidant 1010 into a high-speed mixer according to parts by weight, and dispersing for 15min at the rotating speed of 200rpm to obtain premix;
(3) Feeding the premix obtained in the step (2) into a co-rotating twin-screw extruder for melt extrusion, wherein the temperature process of melt extrusion is controlled as follows: a first-stage temperature: 160 ℃; two-stage temperature: 175 ℃; three-stage temperature: 185 ℃; four-stage temperature: 200 ℃; five-stage temperature: 210 ℃; six-stage temperature: 200 ℃; seven-stage temperature: 195 deg.c; eight-stage temperature: 180 ℃; nine-stage temperature: 175 ℃; ten-stage temperature: 175 ℃; and (5) granulating the braces to obtain the toughened ABS plastic.
In the scheme of the comparative example, no calcium sulfate whisker is used in the test, the toughening effect is affected to a certain extent, and the tensile strength is not improved basically.
The unmodified Qimei ABS-PA777B, examples 1-3 and comparative examples 1-4 were tested for tensile strength and elongation at break by proofing, reference to GB/T1040, test conditions of 50 mm/min; with reference to GB/T1843, a nominal energy of 2.75J is tested, and the notched Izod impact strength at 23℃and-30℃respectively. The toughening effect of the toughened ABS is evaluated by notch impact strength by taking unmodified Qimei ABS-PA777B as a reference sample. The test results are shown in Table 1.
Table 1:
the foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A method for toughening ABS by utilizing aerogel micro powder is characterized in that: the specific method comprises the following steps:
(1) ABS high rubber powder and N, N-dimethylformamide are mixed according to the mass ratio of 1:30-40, stirring in a sealed stirring kettle until the modified liquid is completely dissolved, then adding the silica aerogel into the modified liquid in the sealed stirring kettle, continuously stirring to enable the modified liquid to infiltrate the nano holes of the silica aerogel, naturally filtering to remove the modified liquid, and continuously removing residual N, N-dimethylformamide by a vacuum evaporator at the temperature of 150-155 ℃ to obtain the modified silica aerogel; the silica aerogel has a particle diameter of 20-50 μm, a pore diameter of less than or equal to 20nm and a specific surface area of more than 600m 2 Particles per gram;
(2) 90-95 parts of ABS, 2-4 parts of modified silica aerogel, 1-2 parts of glass beads, 1-2 parts of calcium sulfate whisker, 0.2-0.5 part of silane coupling agent and 0.1-0.2 part of antioxidant are added into a high-speed mixer according to parts by weight, and dispersed for 15-20min at the rotating speed of 200-500rpm to obtain premix;
(3) And (3) feeding the premix obtained in the step (2) into a double-screw extruder for melt extrusion, and granulating the braces to obtain the toughened ABS plastic.
2. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: the ABS high rubber powder in the step (1) is high rubber powder with the butadiene content of 68-70%.
3. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: in the step (1), the mixing mass ratio of the silica aerogel to the modifying liquid in the sealed stirring kettle is 1:15-20.
4. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: the vacuum degree using the vacuum evaporator in the step (1) was-0.085 MPa.
5. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: and (3) selecting glass beads with the particle size less than or equal to 20nm in the step (2).
6. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: in the step (2), the calcium sulfate whisker is selected from calcium sulfate whiskers with the whisker length of 20-100um and the diameter of 1-3 um.
7. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: the silane coupling agent in the step (2) is at least one of 3-aminopropyl triethoxysilane and gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
8. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: the antioxidant in the step (2) is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant DNP.
9. The method for toughening ABS with aerogel micro powder according to claim 1, wherein: the double-screw extruder in the step (3) is a homodromous double-screw extruder.
10. A toughened ABS plastic prepared by the process of any of claims 1-9.
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