CN116903990A - Modified ABS composite plastic particle and preparation method thereof - Google Patents
Modified ABS composite plastic particle and preparation method thereof Download PDFInfo
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- CN116903990A CN116903990A CN202311114062.0A CN202311114062A CN116903990A CN 116903990 A CN116903990 A CN 116903990A CN 202311114062 A CN202311114062 A CN 202311114062A CN 116903990 A CN116903990 A CN 116903990A
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- 239000002245 particle Substances 0.000 title claims abstract description 70
- 229920003023 plastic Polymers 0.000 title claims abstract description 38
- 239000004033 plastic Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 40
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims description 60
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- JEUVAEBWTRCMTB-UHFFFAOYSA-N boron;tantalum Chemical compound B#[Ta]#B JEUVAEBWTRCMTB-UHFFFAOYSA-N 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- CDRNYKLYADJTMN-UHFFFAOYSA-N pyridine-3-sulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CN=C1 CDRNYKLYADJTMN-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000033444 hydroxylation Effects 0.000 claims description 9
- 238000005805 hydroxylation reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 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 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 13
- 230000003712 anti-aging effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- 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 relates to modified ABS composite plastic particles and a preparation method thereof, which are characterized by comprising the following components in parts by weight: 72-96 parts of ABS resin, 17-34 parts of organic silicon rubber, 11-22 parts of modified additive, 5-10 parts of plasticizer, 1.3-2.6 parts of lubricant and 0.5-1 part of antioxidant. The ABS resin and the organic silicon rubber are compounded and prepared, the ABS resin has the advantages of good rigidity, high impact strength and excellent electrical performance, the organic silicon rubber has good high temperature resistance and weather resistance, but under general conditions, the compatibility of the ABS resin and the organic silicon rubber is not good, the modified additive added in the ABS resin and the organic silicon rubber can be matched with a lubricant, so that a good effect is achieved on improving the compatibility of the ABS resin and the organic silicon rubber, meanwhile, the modified additive is used as a flame retardant, a plasticizer is used for improving the flexibility, and an antioxidant is used for improving the ageing resistance.
Description
Technical Field
The invention relates to the field of plastic materials, in particular to modified ABS composite plastic particles and a preparation method thereof.
Background
The ABS resin is a terpolymer polymerized by three monomers of acrylonitrile (A), butadiene (B) and styrene (S), has the excellent performances of the three polymer monomers, has excellent chemical resistance, heat resistance, rigidity and tensile resistance of the polyacrylonitrile, has excellent impact resistance of the polybutadiene, has the advantages of excellent processing fluidity, glossiness and the like of the polystyrene, is a thermoplastic engineering plastic with excellent performances, has excellent chemical corrosion resistance, excellent processing performance and excellent physical and mechanical properties, and is widely applied to various industries.
However, ABS resins have the disadvantages of poor flame retardant properties and easy aging, which seriously affects and hinders the development thereof, and in practical applications, a large amount of flame retardant and a certain amount of anti-aging agent are usually added, so that the flame retardant properties and the anti-aging properties of ABS can meet the requirements of practical applications. However, the addition of a large amount of flame retardant tends to reduce the performance of ABS itself, and the existing anti-aging agent is easy to precipitate, which can affect the long-term aging resistance of ABS.
Therefore, the search for a suitable additive that can improve the flame retardant and anti-aging properties of ABS resins without degrading its own excellent properties has become a hot spot of current research.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide modified ABS composite plastic particles and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides modified ABS composite plastic particles, which comprise the following components in parts by weight:
72-96 parts of ABS resin, 17-34 parts of organic silicon rubber, 11-22 parts of modified additive, 5-10 parts of plasticizer, 1.3-2.6 parts of lubricant and 0.5-1 part of antioxidant.
Preferably, the ABS resin has a brand of POLYLAC (Taiwan Qimei) ABS PA-756 and a density of 1.05g/cm 3 A melt volume flow of 45cm 3 /10min(200℃，10kg)。
Preferably, the silicone rubber is identified as TPSIV 3451-80A-TF or XIAMETERTM RBB-2881-80.
Preferably, the plasticizer is at least one of dioctyl phthalate, diethyl phthalate, and dihexyl phthalate.
Preferably, the lubricant is any one of ethylene bis stearamide, pentaerythritol stearate, butyl stearate and polyethylene wax.
Preferably, the antioxidant is any one of a basf antioxidant 1010, a basf antioxidant 168, a basf antioxidant 1330 and a basf antioxidant 1076.
Preferably, the preparation method of the modified additive comprises the following steps:
(1) Dispersing 3-pyridine sulfonic acid in thionyl chloride, introducing inert gas as shielding gas, dropwise adding a plurality of drops of DMF (N, N-dimethylformamide), fully stirring, condensing and refluxing at 65-75 ℃ for 4-6h, and removing the solvent by rotary evaporation after the reaction is finished to obtain 3-pyridine sulfonyl chloride;
wherein the mass ratio of 3-pyridine sulfonic acid to DMF to thionyl chloride is 1.23-2.46:0.05-0.1:6-10;
(2) Fully dispersing aminosilane activated tantalum diboride in chloroform, wherein the mass ratio of the aminosilane activated tantalum diboride to the chloroform is 1:8-12, so as to form a first solution; dispersing 3-pyridine sulfonyl chloride in chloroform sufficiently to form a second solution, wherein the mass ratio of 3-pyridine sulfonyl chloride to chloroform is 1.37-2.74:8-12;
(3) Adding a small amount of triethylamine into the first solution at room temperature, then adding the second solution dropwise while stirring the reaction solution, continuing stirring for 8-12h after the dripping is completed, and removing the solvent and impurities after the reaction is completed to obtain a modified additive;
wherein the mass ratio of the triethylamine to the first solution to the second solution is 0.02-0.06:1:1.3-1.9.
Preferably, the preparation method of the aminosilane activated tantalum diboride comprises the following steps:
s1, dispersing tantalum diboride nano particles in hydrogen peroxide, stirring for 30min at room temperature, then dropwise adding concentrated sulfuric acid, continuously stirring for 30min, removing liquid by suction filtration, washing solid particles to be neutral, and drying in vacuum to obtain tantalum diboride hydroxide particles;
wherein, the grain diameter of the tantalum diboride nano-particles is 200-300nm, and the mass concentration of the concentrated sulfuric acid is 98%; the mass ratio of the tantalum diboride nano particles to the concentrated sulfuric acid to the hydrogen peroxide is 1:0.1-0.3:6-10;
s2, dispersing the tantalum diboride hydroxylate particles in deionized water, adding a silane coupling agent KH-550, heating to 70-80 ℃, preserving heat, stirring for 2-6 hours, removing liquid by suction filtration, washing the solid particles for three times, and vacuum drying to obtain the aminosilane activated tantalum diboride;
wherein the mass ratio of the tantalum diboride hydroxylation particles to the silane coupling agent KH-550 to the deionized water is 1:0.2-0.6:10-20.
In a second aspect, the invention provides a preparation method of modified ABS composite plastic particles, comprising the following steps:
step 1, mixing ABS resin, organic silicon rubber and a modified additive in a high-speed stirrer, wherein the stirring speed is 800-1000rpm, the stirring time is 5-10min, and fully stirring and mixing to obtain a first mixture;
step 2, adding a plasticizer, a lubricant and an antioxidant into the first mixture, fully stirring and mixing again, wherein the stirring speed is 600-800rpm, and the stirring time is 10-20min, so as to obtain a second mixture;
and step 3, placing the second mixture into a double-screw extruder, extruding and granulating, wherein the working temperature is 200-240 ℃, the length-diameter ratio of the screw is 20-30:1, and the rotating speed is 300-500rpm, so as to obtain the modified ABS composite plastic particles.
The beneficial effects of the invention are as follows:
1. the modified ABS composite plastic particles are prepared by compounding the ABS resin and the organic silicon rubber, the ABS resin has the advantages of good rigidity, high impact strength and excellent electrical performance, the organic silicon rubber has good high temperature resistance and weather resistance, but under general conditions, the compatibility of the ABS resin and the organic silicon rubber is not good, the modified additive added in the modified ABS composite plastic particles can be matched with a lubricant, so that a better effect is achieved on the compatibility improvement of the modified additive, meanwhile, the modified additive is also used as a flame retardant, the plasticizer is used for improving the flexibility, and the antioxidant is used for improving the ageing resistance effect.
2. The invention prepares a modified additive, which is mainly used as a flame retardant additive in ABS composite plastics to improve the flame retardant property of ABS, but the subsequent detection shows that the modified additive not only ensures that ABS has better flame retardant effect, but also ensures that the compatibility of ABS and other materials is increased, and simultaneously the mechanical property and the anti-aging effect are improved to a certain extent.
3. The modified additive prepared by the invention is based on inorganic tantalum diboride nano particles with high strength and high thermal stability, and the additive containing pyridyl and sulfonamide simultaneously is obtained after the surface modification treatment. When the modified additive is applied to an ABS material, the crosslinking property of the modified additive with the ABS resin material is relatively good, so that the performance of the ABS material is improved in many aspects, and the modified additive has not only flame retardance, but also good performances in mechanical aspects and anti-aging aspects.
4. In the invention, the modified additive is a pyridine sulfonamide silane coated tantalum diboride material prepared by using aminosilane activated tantalum diboride and 3-pyridine sulfonyl chloride as reactants and carrying out mutual combination reaction on sulfonyl chloride groups and amino groups. The aminosilane activated tantalum diboride is obtained by hydroxylating the surface of the aminosilane activated tantalum diboride and performing aminosilane activation treatment on the surface of the aminosilane activated tantalum diboride. The hydroxylation is to treat tantalum diboride in a strong acid environment and hydrogen peroxide as a solvent, and the aminosilane activation is to treat tantalum diboride and aminosilane coupling agent KH-550 at high temperature in an aqueous solution. Wherein, 3-pyridine sulfonyl chloride is prepared by using 3-pyridine sulfonic acid as a reactant, using DMF (N, N-dimethylformamide) as a catalyst in thionyl chloride solution, and carrying out reflux acyl chlorination treatment.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In order to better understand the above technical solution, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the invention are shown, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention is further described with reference to the following examples.
Example 1
The modified ABS composite plastic particles comprise the following components in parts by weight:
84 parts of ABS resin, 26 parts of organic silicon rubber, 17 parts of modifying additive, 8 parts of plasticizer, 1.9 parts of lubricant and 0.6 part of antioxidant.
Wherein the ABS resin has a brand of POLYLAC (Taiwan Qimei) ABS PA-756 and a density of 1.05g/cm 3 A melt volume flow of 45cm 3 10min (200 ℃,10 kg), the brand of the organic silicon rubber is TPSIV 3451-80A-TF, the plasticizer is dioctyl phthalate, the lubricant is ethylene bis stearamide, and the antioxidant is Basoff antioxidant 1010.
The preparation method of the modified additive comprises the following steps:
(1) Dispersing 3-pyridine sulfonic acid in thionyl chloride, introducing inert gas as shielding gas, dropwise adding a plurality of drops of DMF (N, N-dimethylformamide), fully stirring, condensing and refluxing at 70 ℃ for 5 hours, and removing the solvent by rotary evaporation after the reaction is finished to obtain 3-pyridine sulfonyl chloride; the mass ratio of the 3-pyridine sulfonic acid to the DMF to the thionyl chloride is 1.85:0.06:8;
(2) Fully dispersing aminosilane activated tantalum diboride in chloroform, wherein the mass ratio of the aminosilane activated tantalum diboride to the chloroform is 1:10, so as to form a first solution; taking 3-pyridine sulfonyl chloride and fully dispersing the 3-pyridine sulfonyl chloride in chloroform, wherein the mass ratio of the 3-pyridine sulfonyl chloride to the chloroform is 2.05:10, so as to form a second solution;
(3) Adding a small amount of triethylamine into the first solution at room temperature, then adding the second solution dropwise while stirring the reaction solution, continuing stirring for 10 hours after the dripping is completed, and removing the solvent and impurities after the reaction is completed to obtain a modified additive; the mass ratio of triethylamine, the first solution and the second solution was 0.04:1:1.6.
The preparation method of the aminosilane activated tantalum diboride comprises the following steps:
s1, dispersing tantalum diboride nano particles in hydrogen peroxide, stirring for 30min at room temperature, then dropwise adding concentrated sulfuric acid, continuously stirring for 30min, removing liquid by suction filtration, washing solid particles to be neutral, and drying in vacuum to obtain tantalum diboride hydroxide particles; the particle size of the tantalum diboride nano particles is 200-300nm, and the mass concentration of the concentrated sulfuric acid is 98%; the mass ratio of the tantalum diboride nano particles to the concentrated sulfuric acid to the hydrogen peroxide is 1:0.2:8;
s2, dispersing the tantalum diboride hydroxylation particles in deionized water, adding a silane coupling agent KH-550, heating to 75 ℃, preserving heat and stirring for 4 hours, removing liquid by suction filtration, washing the solid particles for three times, and drying in vacuum to obtain the aminosilane activated tantalum diboride; the mass ratio of the tantalum diboride hydroxylation particles, the silane coupling agent KH-550 and the deionized water is 1:0.4:15.
The preparation method of the modified ABS composite plastic particles comprises the following steps:
step 1, mixing ABS resin, organic silicon rubber and a modified additive in a high-speed stirrer, wherein the stirring speed is 1000rpm, the stirring time is 6min, and fully stirring and mixing to obtain a first mixture;
step 2, adding a plasticizer, a lubricant and an antioxidant into the first mixture, fully stirring and mixing again, wherein the stirring speed is 600rpm, and the stirring time is 15min, so as to obtain a second mixture;
and step 3, placing the second mixture into a double-screw extruder, extruding and granulating, wherein the working temperature is 220 ℃, the length-diameter ratio of the screw is 25:1, and the rotating speed is 400rpm, so as to obtain the modified ABS composite plastic particles.
Example 2
The modified ABS composite plastic particles comprise the following components in parts by weight:
72 parts of ABS resin, 17 parts of organic silicon rubber, 11 parts of modifying additive, 5 parts of plasticizer, 1.3 parts of lubricant and 0.5 part of antioxidant.
Wherein the ABS resin has a brand of POLYLAC (Taiwan Qimei) ABS PA-756 and a density of 1.05g/cm 3 A melt volume flow of 45cm 3 10min (200 ℃,10 kg), the brand of the organic silicon rubber is XIAMETERTM RBB-2881-80, the plasticizer is diethyl phthalate, the lubricant is pentaerythritol stearate, and the antioxidant is Basoff antioxidant 168.
The preparation method of the modified additive comprises the following steps:
(1) Dispersing 3-pyridine sulfonic acid in thionyl chloride, introducing inert gas as shielding gas, dropwise adding a plurality of drops of DMF (N, N-dimethylformamide), fully stirring, condensing and refluxing for 4 hours at 65 ℃, and removing the solvent by rotary evaporation after the reaction is finished to obtain 3-pyridine sulfonyl chloride; the mass ratio of the 3-pyridine sulfonic acid to the DMF to the thionyl chloride is 1.23:0.05:6;
(2) Fully dispersing aminosilane activated tantalum diboride in chloroform, wherein the mass ratio of the aminosilane activated tantalum diboride to the chloroform is 1:8, so as to form a first solution; taking 3-pyridine sulfonyl chloride and fully dispersing the 3-pyridine sulfonyl chloride in chloroform, wherein the mass ratio of the 3-pyridine sulfonyl chloride to the chloroform is 1.37:8, so as to form a second solution;
(3) Adding a small amount of triethylamine into the first solution at room temperature, then adding the second solution dropwise while stirring the reaction solution, continuing stirring for 8 hours after the dripping is completed, and removing the solvent and impurities after the reaction is completed to obtain a modified additive; the mass ratio of triethylamine, the first solution and the second solution was 0.02:1:1.3.
The preparation method of the aminosilane activated tantalum diboride comprises the following steps:
s1, dispersing tantalum diboride nano particles in hydrogen peroxide, stirring for 30min at room temperature, then dropwise adding concentrated sulfuric acid, continuously stirring for 30min, removing liquid by suction filtration, washing solid particles to be neutral, and drying in vacuum to obtain tantalum diboride hydroxide particles; the particle size of the tantalum diboride nano particles is 200-300nm, and the mass concentration of the concentrated sulfuric acid is 98%; the mass ratio of the tantalum diboride nano particles to the concentrated sulfuric acid to the hydrogen peroxide is 1:0.1:6;
s2, dispersing the tantalum diboride hydroxylation particles in deionized water, adding a silane coupling agent KH-550, heating to 70 ℃, preserving heat and stirring for 2 hours, removing liquid by suction filtration, washing the solid particles for three times, and drying in vacuum to obtain the aminosilane activated tantalum diboride; the mass ratio of the tantalum diboride hydroxylation particles, the silane coupling agent KH-550 and the deionized water is 1:0.2:10.
The preparation method of the modified ABS composite plastic particles comprises the following steps:
step 1, mixing ABS resin, organic silicon rubber and a modified additive in a high-speed stirrer, wherein the stirring speed is 800rpm, the stirring time is 5min, and fully stirring and mixing to obtain a first mixture;
step 2, adding a plasticizer, a lubricant and an antioxidant into the first mixture, fully stirring and mixing again, wherein the stirring speed is 600rpm, and the stirring time is 10min to obtain a second mixture;
and step 3, placing the second mixture into a double-screw extruder, extruding and granulating, wherein the working temperature is 200 ℃, the length-diameter ratio of the screw is 20:1, and the rotating speed is 300rpm, so as to obtain the modified ABS composite plastic particles.
Example 3
The modified ABS composite plastic particles comprise the following components in parts by weight:
96 parts of ABS resin, 34 parts of organic silicon rubber, 22 parts of modifying additive, 10 parts of plasticizer, 2.6 parts of lubricant and 1 part of antioxidant.
Wherein the ABS resin has a brand of POLYLAC (Taiwan Qimei) ABS PA-756 and a density of 1.05g/cm 3 A melt volume flow of 45cm 3 10min (200 ℃,10 kg), the brand of the organic silicon rubber is TPSIV 3451-80A-TF, the plasticizer is dihexyl phthalate, the lubricant is polyethylene wax, and the antioxidant is Basoff antioxidant 1076.
The preparation method of the modified additive comprises the following steps:
(1) Dispersing 3-pyridine sulfonic acid in thionyl chloride, introducing inert gas as shielding gas, dropwise adding a plurality of drops of DMF (N, N-dimethylformamide), fully stirring, condensing and refluxing for reaction for 6 hours at 75 ℃, and removing the solvent by rotary evaporation after the reaction is finished to obtain 3-pyridine sulfonyl chloride; the mass ratio of the 3-pyridine sulfonic acid to the DMF to the thionyl chloride is 2.46:0.1:10;
(2) Fully dispersing aminosilane activated tantalum diboride in chloroform, wherein the mass ratio of the aminosilane activated tantalum diboride to the chloroform is 1:12, so as to form a first solution; taking 3-pyridine sulfonyl chloride and fully dispersing the 3-pyridine sulfonyl chloride in chloroform, wherein the mass ratio of the 3-pyridine sulfonyl chloride to the chloroform is 2.74:12, so as to form a second solution;
(3) Adding a small amount of triethylamine into the first solution at room temperature, then adding the second solution dropwise while stirring the reaction solution, continuing stirring for 12 hours after the dripping is completed, and removing the solvent and impurities after the reaction is completed to obtain a modified additive; the mass ratio of triethylamine, the first solution and the second solution was 0.06:1:1.9.
The preparation method of the aminosilane activated tantalum diboride comprises the following steps:
s1, dispersing tantalum diboride nano particles in hydrogen peroxide, stirring for 30min at room temperature, then dropwise adding concentrated sulfuric acid, continuously stirring for 30min, removing liquid by suction filtration, washing solid particles to be neutral, and drying in vacuum to obtain tantalum diboride hydroxide particles; the particle size of the tantalum diboride nano particles is 200-300nm, and the mass concentration of the concentrated sulfuric acid is 98%; the mass ratio of the tantalum diboride nano particles to the concentrated sulfuric acid to the hydrogen peroxide is 1:0.3:10;
s2, dispersing the tantalum diboride hydroxylation particles in deionized water, adding a silane coupling agent KH-550, heating to 80 ℃, preserving heat and stirring for 6 hours, removing liquid by suction filtration, washing the solid particles for three times, and drying in vacuum to obtain the aminosilane activated tantalum diboride; the mass ratio of the tantalum diboride hydroxylation particles, the silane coupling agent KH-550 and the deionized water is 1:0.6:20.
The preparation method of the modified ABS composite plastic particles comprises the following steps:
step 1, mixing ABS resin, organic silicon rubber and a modified additive in a high-speed stirrer, wherein the stirring speed is 1000rpm, the stirring time is 10min, and fully stirring and mixing to obtain a first mixture;
step 2, adding a plasticizer, a lubricant and an antioxidant into the first mixture, fully stirring and mixing again, wherein the stirring speed is 800rpm, and the stirring time is 20min, so as to obtain a second mixture;
and step 3, placing the second mixture into a double-screw extruder, extruding and granulating, wherein the working temperature is 240 ℃, the length-diameter ratio of the screw is 30:1, and the rotating speed is 500rpm, so as to obtain the modified ABS composite plastic particles.
Comparative example 1
An ABS composite plastic particle is different from example 1 in that the modification additive is replaced with tantalum diboride particles having a particle size of 200-300nm, and the other components are the same as in example 1.
The preparation method comprises the following steps of:
84 parts of ABS resin, 26 parts of organic silicon rubber, 17 parts of tantalum diboride particles, 8 parts of plasticizer, 1.9 parts of lubricant and 0.6 part of antioxidant.
Comparative example 2
An ABS composite plastic particle is different from example 1 in that the modified additive is replaced with aminosilane activated tantalum diboride, the tantalum diboride hydroxide particles are prepared in the same manner as in example 1, and the other components are prepared in the same manner as in example 1.
The preparation method comprises the following steps of:
84 parts of ABS resin, 26 parts of organic silicon rubber, 17 parts of aminosilane activated tantalum diboride, 8 parts of plasticizer, 1.9 parts of lubricant and 0.6 part of antioxidant.
Comparative example 3
An ABS composite plastic particle is different from example 1 in that the modifying additive is a mixture of 2-methylbenzenesulfonamide (commercially available) and tantalum diboride particles in a mass ratio of 1:1.62, and other components are the same as in example 1.
The preparation method comprises the following steps of:
84 parts of ABS resin, 26 parts of organic silicon rubber, 17 parts of modifying additive, 8 parts of plasticizer, 1.9 parts of lubricant and 0.6 part of antioxidant.
Experimental detection
The performance of the ABS composite plastic particle materials prepared in the example 1 and the comparative examples 1-3 is tested, and the test comprises the following steps: tensile strength (reference standard ASTM D638), flexural strength (reference standard ASTM D790), impact strength (reference standard ASTM D256, 23 ℃), heat distortion temperature (reference standard ASTM D648,1.8 MPa), oxygen index (reference standard GB/T2406), fire rating (reference standard UL-94,3.0 mm), aging treatment (reference standard GB/T7141, thermal oxidative aging 100 ℃ C., 48 h).
The test results are shown in the following table:
table 1 results of performance measurements of different ABS composite plastic particle materials
As can be seen from Table 1, the ABS plastic particle material prepared in example 1 of the present invention has high flame retardance (oxygen index and fire rating are both at higher levels), high strength (tensile strength, flexural strength, notch impact strength are higher), good high temperature resistance (heat distortion temperature is higher) and excellent aging resistance (retention rate of tensile strength and flexural strength after aging is more than 90%), which indicates that the ABS plastic particle material prepared in example 1 of the present invention has excellent comprehensive performance and is suitable for use as a plastic material with higher requirements.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms should not be understood as necessarily being directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The modified ABS composite plastic particle is characterized by comprising the following components in parts by weight:
72-96 parts of ABS resin, 17-34 parts of organic silicon rubber, 11-22 parts of modified additive, 5-10 parts of plasticizer, 1.3-2.6 parts of lubricant and 0.5-1 part of antioxidant.
2. According to the weightsThe modified ABS composite plastic particle as claimed in claim 1, wherein said ABS resin has a brand of POLYLAC ABS PA-756 and a density of 1.05g/cm 3 The volume flow rate of the melt was 45cm at 200℃and 10kg 3 /10min。
3. The modified ABS composite plastic particle according to claim 1, wherein the silicone rubber is of the brand TPSIV 3451-80A-TF or XIAMETERTM RBB-2881-80.
4. The modified ABS composite plastic particle according to claim 1, wherein the plasticizer is at least one of dioctyl phthalate, diethyl phthalate, and dihexyl phthalate.
5. The modified ABS composite plastic particle according to claim 1, wherein the lubricant is any one of ethylene bis stearamide, pentaerythritol stearate, butyl stearate and polyethylene wax.
6. The modified ABS composite plastic particle according to claim 1, wherein the antioxidant is any one of basf antioxidant 1010, basf antioxidant 168, basf antioxidant 1330, basf antioxidant 1076.
7. The modified ABS composite plastic particle according to claim 1, wherein the preparation method of the modified additive comprises:
(1) Dispersing 3-pyridine sulfonic acid in thionyl chloride, introducing inert gas as shielding gas, dropwise adding a plurality of drops of DMF (N, N-dimethylformamide), fully stirring, condensing and refluxing at 65-75 ℃ for 4-6h, and removing the solvent by rotary evaporation after the reaction is finished to obtain 3-pyridine sulfonyl chloride;
wherein the mass ratio of 3-pyridine sulfonic acid to DMF to thionyl chloride is 1.23-2.46:0.05-0.1:6-10;
(2) Fully dispersing aminosilane activated tantalum diboride in chloroform, wherein the mass ratio of the aminosilane activated tantalum diboride to the chloroform is 1:8-12, so as to form a first solution; dispersing 3-pyridine sulfonyl chloride in chloroform sufficiently to form a second solution, wherein the mass ratio of 3-pyridine sulfonyl chloride to chloroform is 1.37-2.74:8-12;
(3) Adding a small amount of triethylamine into the first solution at room temperature, then adding the second solution dropwise while stirring the reaction solution, continuing stirring for 8-12h after the dripping is completed, and removing the solvent and impurities after the reaction is completed to obtain a modified additive;
wherein the mass ratio of the triethylamine to the first solution to the second solution is 0.02-0.06:1:1.3-1.9.
8. The modified ABS composite plastic particle according to claim 7, wherein the preparation method of the aminosilane activated tantalum diboride comprises:
s1, dispersing tantalum diboride nano particles in hydrogen peroxide, stirring for 30min at room temperature, then dropwise adding concentrated sulfuric acid, continuously stirring for 30min, removing liquid by suction filtration, washing solid particles to be neutral, and drying in vacuum to obtain tantalum diboride hydroxide particles;
wherein, the grain diameter of the tantalum diboride nano-particles is 200-300nm, and the mass concentration of the concentrated sulfuric acid is 98%; the mass ratio of the tantalum diboride nano particles to the concentrated sulfuric acid to the hydrogen peroxide is 1:0.1-0.3:6-10;
s2, dispersing the tantalum diboride hydroxylate particles in deionized water, adding a silane coupling agent KH-550, heating to 70-80 ℃, preserving heat, stirring for 2-6 hours, removing liquid by suction filtration, washing the solid particles for three times, and vacuum drying to obtain the aminosilane activated tantalum diboride;
wherein the mass ratio of the tantalum diboride hydroxylation particles to the silane coupling agent KH-550 to the deionized water is 1:0.2-0.6:10-20.
9. A method for preparing the modified ABS composite plastic particles of claim 1, comprising the steps of:
step 1, mixing ABS resin, organic silicon rubber and a modified additive in a high-speed stirrer, and fully stirring and mixing to obtain a first mixture;
step 2, adding a plasticizer, a lubricant and an antioxidant into the first mixture, and fully stirring and mixing again to obtain a second mixture;
and step 3, placing the second mixture into a double-screw extruder, extruding and granulating to obtain modified ABS composite plastic particles.
10. The method for preparing modified ABS composite plastic particles according to claim 9, wherein the stirring speed in the step 1 is 800-1000rpm, and the stirring time is 5-10min; the stirring speed in the step 2 is 600-800rpm, and the stirring time is 10-20min; the working temperature of the double-screw extruder in the step 3 is 200-240 ℃, the length-diameter ratio of the screw is 20-30:1, and the rotating speed is 300-500rpm.
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