CN114752175B - Thermal-oxidative aging-resistant ABS resin composite material and preparation method and application thereof - Google Patents
Thermal-oxidative aging-resistant ABS resin composite material and preparation method and application thereof Download PDFInfo
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000000805 composite resin Substances 0.000 title claims abstract description 87
- 230000032683 aging Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000000049 pigment Substances 0.000 claims abstract description 100
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 53
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 45
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 25
- 239000004611 light stabiliser Substances 0.000 claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 13
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 13
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- 229920000578 graft copolymer Polymers 0.000 claims description 6
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- IUWCPXJTIPQGTE-UHFFFAOYSA-N chromium cobalt Chemical compound [Cr].[Co].[Co].[Co] IUWCPXJTIPQGTE-UHFFFAOYSA-N 0.000 claims 2
- 150000003254 radicals Chemical class 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000013329 compounding Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- -1 chromium cobalt metal complex Chemical class 0.000 description 9
- 230000006698 induction Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- AXTNPHLCOKUMDY-UHFFFAOYSA-N chromium cobalt Chemical compound [Co][Cr][Co] AXTNPHLCOKUMDY-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
-
- 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 discloses a thermo-oxidative aging resistant ABS resin composite material, a preparation method and application thereof. The invention discloses a thermo-oxidative aging resistant ABS resin composite material, which comprises the following components in parts by weight: 100 parts of ABS resin, 0.5-5 parts of antioxidant, 0.5-5 parts of light stabilizer and 1-5 parts of infrared reflection pigment, wherein the infrared reflection pigment is a mixture of metal oxide and metal complex, and the weight ratio of the metal oxide to the metal complex is 1 (1-4). The heat-resistant and oxygen-aging-resistant ABS resin composite material is compounded by adopting the infrared reflection pigment of a specific type and then is matched with the antioxidant for use, so that free macromolecular free radicals in the ABS resin composite material can be effectively reduced, the damage of free radical chain reaction to the ABS resin composite material is further weakened, and the heat-resistant and oxygen-aging-resistant performance of the ABS resin composite material is remarkably improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a thermo-oxidative aging resistant ABS resin composite material, a preparation method and application thereof.
Background
ABS resin has excellent mechanical property, good processing property, chemical reagent resistance, good surface gloss and other properties, and is widely used in the fields of automobiles, household appliances, office equipment, communication and the like. However, the ABS resin is easily affected by temperature, oxygen and mechanical factors in the use process, and is easily changed from a steady state to an excited state after absorbing energy, and a free base generated by excitation is easily reacted with oxygen to generate an oxidized free radical, which can trigger the ABS resin to further react to generate hydroperoxide, and the hydroperoxide can further catalyze the degradation of the ABS resin, so that the performance of the ABS resin is deteriorated.
Aiming at the problem that ABS resin is easy to be degraded under the condition of hot oxygen, the main solution in the prior art is that (1) the structure is optimized when ABS resin is synthesized; (2) adding an additional antioxidant auxiliary during processing. For example, the prior art discloses a preparation method of anti-yellowing and high-whiteness ABS resin, wherein a copolymerization method is adopted to directly copolymerize a phosphate monomer to the surface of ABS particles, so as to construct an in-situ metal ion chelating agent, promote the chelating agent to disperse, prevent the chelating agent from migrating in the processing process, and enhance the thermo-oxidative aging resistance of the ABS resin, but the yellow index is still larger (18.1-18.7), and the thermo-oxidative aging resistance is to be improved.
Disclosure of Invention
The invention aims to overcome the defect and the defect of poor thermal-oxidative aging resistance of the existing ABS resin, and provides the thermal-oxidative aging resistance ABS resin composite material, and by introducing a specific type of infrared reflection pigment compound to be combined with an antioxidant, the generated macromolecular free radicals are captured while the macromolecular free radicals in the composite material are reduced, so that the macromolecular free radicals in the ABS resin composite material can be obviously reduced, the damage of free radical chain reaction to the composite material is further weakened, and the thermal-oxidative aging resistance of the ABS resin composite material is effectively improved.
The invention also aims to provide a preparation method of the thermo-oxidative aging resistant ABS resin composite material.
It is still another object of the present invention to provide the use of the heat and oxygen aging resistant ABS-based resin composite material in plastic articles.
The above object of the present invention is achieved by the following technical scheme:
the heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the following components in parts by weight:
wherein the infrared reflective pigment is a mixture of a metal oxide and a metal complex; the weight ratio of the metal oxide to the metal complex is 1 (1-4).
The thermal oxidative aging of ABS-based resins is generally divided into two stages: (1) absorbing energy transitions to generate free radicals; (2) the free radical chain reaction and the two stages of reactions are endothermic reactions, so that the generation and growth of free radicals can be inhibited by reducing the temperature of a reaction system, and the thermo-oxidative aging resistance of the ABS resin is improved. Aiming at two stages of thermal oxidation aging heat of ABS resin, the invention adds a specific kind of infrared reflection pigment compound into the ABS resin, wherein the compound is composed of metal oxide and metal complex, the metal oxide can efficiently reflect energy in a near infrared region, the temperature of a reaction system is reduced, and the generation of macromolecular free radicals is reduced; the metal complex can efficiently reflect energy in the middle infrared region and the far infrared region, has an electron-withdrawing effect on unsaturated groups such as C=O and carboxyl in macromolecular free radicals, further reduces the number of free macromolecular free radicals in the ABS resin, and weakens the damage of the macromolecular free radicals to the ABS resin structure in a thermo-oxidative aging environment, thereby improving the thermo-oxidative aging resistance of the ABS resin.
In addition, the special type of infrared reflection pigment compound is matched with an antioxidant, the antioxidant can capture macromolecular free radicals, the number of the free macromolecular free radicals in the ABS resin composite material is further reduced, the damage of free radical chain reaction to the ABS resin composite material is weakened, and the thermo-oxidative aging resistance of the ABS resin composite material is further remarkably improved.
The addition amount of the metal complex in the infrared reflection pigment is higher than that of the metal oxide, and the following two reasons are mainly included: (1) the reflection efficiency of the metal complex is smaller than that of the metal oxide, and the addition amount of the metal complex needs to be increased to achieve the optimal reflection efficiency; (2) the metal complex mainly reflects energy in the mid-infrared and far-infrared bands, and a wider band range requires a corresponding increase in the amount of the metal complex added. The addition amount of the metal complex is too small, the reflection efficiency of the composite pigment in the wave bands of the middle infrared region and the far infrared region is reduced, the addition amount of the metal complex is too large, the plasticization and the processability of the material are reduced, and the cost is increased.
The antioxidant, the light stabilizer and the infrared reflection pigment in the heat-resistant and oxygen-aging-resistant ABS resin composite material have the dosage ranges, mainly because when the addition amount of the antioxidant, the light stabilizer and the infrared reflection pigment is small, the improvement on the heat-resistant and oxygen-aging resistance of the ABS resin is limited, and when the addition amount of the antioxidant, the light stabilizer and the infrared reflection pigment is excessive, the other properties of the material are influenced, for example, when the antioxidant is excessive, the antioxidant can also directly act with molecular oxygen to form free radicals to generate advanced oxidation effect to accelerate the aging process, and when the concentration is too high, the negative influence generated by the advanced oxidation effect can offset the stabilizing effect of the antioxidant; when the addition amount of the light stabilizer is too large, a frosting phenomenon can be generated, and the light stabilizer migrates and separates out to the surface of the plastic, so that the application of the material is affected; too much infrared reflective pigment is added, which can lead to the decrease of the melt index of the composite material, and the molding processing is difficult.
Preferably, the thermo-oxidative aging resistant ABS resin composite material comprises the following components in parts by weight:
preferably, the weight ratio of the metal oxide to the metal complex is 1 (1-3).
In a specific embodiment, the metal complex of the present invention may be a mixture of a chromium cobalt metal complex and a nickel titanium metal complex.
Preferably, the weight ratio of the chromium cobalt metal complex to the nickel titanium metal complex is 1 (0.5-2).
The addition amount of the nickel-titanium metal complex is too small, and the reflection of the composite pigment on the wave band of the far infrared region is reduced; excessive addition of the nickel-titanium metal complex results in plasticization of the material and degradation of processability, and increase of cost.
In a specific embodiment, the metal oxide of the present invention may be one or more of bismuth vanadate, tungsten oxide, antimony oxide and zinc oxide.
In a specific embodiment, the chromium cobalt metal complex and nickel titanium metal complex of the present invention may be chromium cobalt blue and nickel titanium yellow, respectively.
In a specific embodiment, the antioxidant of the present invention may be two or more of hindered phenol antioxidants, amine antioxidants and phosphite antioxidants.
Preferably, the antioxidant is a phosphite antioxidant and hindered phenol antioxidant compound, wherein the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1 (0.5-1.5).
The hindered phenol antioxidant is a phenol compound with a space hindered structure, belongs to a chain termination type antioxidant and has the main function of interrupting a chain oxidation reaction; and phosphite antioxidants can be combined with peroxide to form an inactive product, so that the autocatalysis of the phosphite antioxidants is inhibited. In addition, too much hindered phenol antioxidant can be precipitated on the surface of the plastic, and too little hindered phenol antioxidant can cause too weak oxidation resistance.
In a specific embodiment, the ABS-based resin of the present invention may be one or more of acrylonitrile-butadiene-styrene graft copolymer, acrylonitrile-styrene-acrylic acid terpolymer and methyl methacrylate-butadiene-styrene graft copolymer.
In a specific embodiment, the light stabilizer of the present invention may be one or more of a hindered amine light stabilizer, a benzotriazole light stabilizer, a benzophenone light stabilizer and a hindered benzoate light stabilizer.
The invention also provides a preparation method of the thermo-oxidative aging resistant ABS resin composite material, which comprises the following steps:
and uniformly mixing the ABS resin, the antioxidant, the light stabilizer and the infrared reflection pigment, and then adding the mixture into a melt extrusion device for melt extrusion granulation to obtain the thermo-oxidative aging resistant ABS resin composite material.
Wherein the melt extrusion device is a double-screw extruder, the length-diameter ratio of an extrusion screw is 30:1-40:1, the temperature of the extruder is set to be 100-130 ℃ in a T1 zone, 190-205 ℃ in a T2-T5 zone, 205-210 ℃ in a T6-T12 zone, and the rotating speed is 300-450 r/min.
The application of the heat-resistant and oxygen-aging-resistant ABS resin composite material in plastic parts is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a thermal-oxidative aging-resistant ABS resin composite material, which is prepared by compounding a specific infrared reflection pigment and then using the specific infrared reflection pigment with an antioxidant, wherein the compounded infrared reflection pigment can obviously reduce the absorption of the ABS resin composite material to infrared light energy, so that macromolecular free radicals generated by energy absorption transition in the ABS resin composite material are reduced; meanwhile, the antioxidant can capture macromolecular free radicals, so that the quantity of the free macromolecular free radicals in the ABS resin composite material is further reduced, the damage of free radical chain reaction to the ABS resin composite material is further weakened, the thermo-oxidative aging resistance of the ABS resin composite material is remarkably improved, and the yellow index is reduced to 8.75-18.69.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The ABS resin 1 is acrylonitrile-butadiene-styrene graft copolymer, ABS POWHR18, korean Jinhu Co., ltd;
the ABS resin 2 is acrylonitrile-styrene-acrylic acid terpolymer, ASA LI941, guangzhou city image chemical industry Co., ltd;
ABS resin 3 is methyl methacrylate-butadiene-styrene graft copolymer, MBS2081, guangzhou Dai trade Co., ltd;
the antioxidant 1 is phosphite antioxidant, YFK-168, wind and light chemical industry Co., yikou city;
the antioxidant 2 is a hindered phenol antioxidant, YFK-1010, wind and light chemical industry Co., yikou city;
the light stabilizer is hindered amine light stabilizer, UV-3808PP5, available from Shanghai, cyanit surface technology;
the infrared reflective pigment 1 is a metal oxide: a mixture of tungsten oxide and antimony oxide wherein the weight fraction of tungsten is about 35% and the weight fraction of antimony is about 13.5% Black10C909, shepherd company, usa;
the infrared reflective pigments 2 are metal complexes: chromium cobalt blue, JF-A3601, hunan giant hair pigment;
the infrared reflective pigments 3 are metal complexes: nickel titanium yellow, JF-B5302, hunan macrohair pigment.
Examples 1 to 5
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the following components in parts by weight:
ABS resin, antioxidant, light stabilizer and infrared reflection pigment, wherein the antioxidant comprises antioxidant 1 and antioxidant 2 according to the weight ratio of 1:1, wherein the infrared reflection pigment is obtained by compounding an infrared reflection pigment 1 and an infrared reflection pigment 2 according to the weight ratio of 1:1, the specific content of each component is shown in the following table 1.
Table 1 composition (in parts by weight) of heat and oxygen aging resistant ABS resin composite in examples 1 to 5
| Sequence number | 1 | 2 | 3 | 4 | 5 |
| ABS resin 1 | 100 | 100 | 100 | 100 | 100 |
| Antioxidant | 5 | 0.5 | 1 | 3 | 1 |
| Light stabilizers | 5 | 0.5 | 1 | 3 | 3 |
| Infrared reflective pigment | 1 | 5 | 2 | 4 | 3 |
The heat and oxygen aging resistant ABS resin composite materials in the above examples 1 to 5 were prepared by the following preparation method:
uniformly mixing ABS resin, an antioxidant, a light stabilizer and an infrared reflection pigment, and then adding the mixture into a double-screw extruder for melt extrusion and granulation to obtain the thermo-oxidative aging resistant ABS resin composite material;
wherein the length-diameter ratio of the double-screw extruder is 30:1, the extrusion temperature is set to be 100-130 ℃ in a T1 zone, 190-205 ℃ in a T2-T5 zone, 205-210 ℃ in a T6-T12 zone, and the rotating speed is 350r/min.
Example 6
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the example 5 in parts by weight, wherein the infrared reflection pigment comprises an infrared reflection pigment 1 and an infrared reflection pigment 3 in a weight ratio of 1:1, compounding to obtain the compound;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 7
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the example 5 in parts by weight, wherein the infrared reflection pigment comprises an infrared reflection pigment 1 and an infrared reflection pigment 2 in a weight ratio of 1:2, compounding to obtain the compound;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 8
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the example 5 in parts by weight, wherein the infrared reflection pigment comprises an infrared reflection pigment 1 and an infrared reflection pigment 2 in a weight ratio of 1:3, compounding to obtain the compound;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 9
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the example 5 in parts by weight, wherein the infrared reflection pigment comprises an infrared reflection pigment 1 and an infrared reflection pigment 2 in a weight ratio of 1:4, compounding to obtain the compound;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 10
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 5 in parts by weight, wherein the infrared reflection pigment consists of an infrared reflection pigment 1, an infrared reflection pigment 2 and an infrared reflection pigment 3;
wherein the infrared reflective pigment 1: (infrared-reflective pigment 2+infrared-reflective pigment 3) in a weight ratio of 1:2, the weight ratio of the infrared reflection pigment 2 to the infrared reflection pigment 3 is 1:0.5;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 11
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 5 in parts by weight, wherein the infrared reflection pigment consists of an infrared reflection pigment 1, an infrared reflection pigment 2 and an infrared reflection pigment 3;
wherein the infrared reflective pigment 1: (infrared-reflective pigment 2+infrared-reflective pigment 3) in a weight ratio of 1:2, the weight ratio of the infrared reflection pigment 2 to the infrared reflection pigment 3 is 1:1, a step of;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 12
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 5 in parts by weight, wherein the infrared reflection pigment consists of an infrared reflection pigment 1, an infrared reflection pigment 2 and an infrared reflection pigment 3;
wherein the infrared reflective pigment 1: (infrared-reflective pigment 2+infrared-reflective pigment 3) in a weight ratio of 1:2, the weight ratio of the infrared reflection pigment 2 to the infrared reflection pigment 3 is 1:2;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 13
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the same components and contents as in example 5 in parts by weight, wherein the ABS resin is ABS resin 2;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Example 14
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the same components and contents as in example 5 in parts by weight, wherein the ABS resin is ABS resin 3;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 5.
Comparative example 1
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the following components in parts by weight:
100 parts of ABS resin, 0.5 part of antioxidant, 0.5 part of light stabilizer and 7 parts of infrared reflection pigment, wherein the antioxidant comprises antioxidant 1 and antioxidant 2 in a weight ratio of 1:1, wherein the infrared reflection pigment is obtained by compounding an infrared reflection pigment 1 and an infrared reflection pigment 2 according to the weight ratio of 1:1, and compounding to obtain the product.
The preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 2.
Comparative example 2
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the following components in parts by weight:
100 parts of ABS resin, 5 parts of antioxidant, 5 parts of light stabilizer and 0.5 part of infrared reflection pigment, wherein the antioxidant comprises antioxidant 1 and antioxidant 2 in a weight ratio of 1:1, wherein the infrared reflection pigment is obtained by compounding an infrared reflection pigment 1 and an infrared reflection pigment 2 according to the weight ratio of 1:1, and compounding to obtain the product.
The preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 1.
Comparative example 3
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 1 in parts by weight, wherein the infrared reflection pigment comprises an infrared reflection pigment 1 and an infrared reflection pigment 2 in a weight ratio of 1:0.5, compounding to obtain the compound;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 1.
Comparative example 4
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 1 in parts by weight, wherein the infrared reflection pigment comprises an infrared reflection pigment 1 and an infrared reflection pigment 2 in a weight ratio of 1:7, compounding to obtain the compound;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 1.
Comparative example 5
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 1 in parts by weight, wherein the infrared reflection pigment is an infrared reflection pigment 1;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 1.
Comparative example 6
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 1 in parts by weight, wherein the infrared reflection pigment is an infrared reflection pigment 2;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 1.
Comparative example 7
The heat-resistant and oxygen-aging-resistant ABS resin composite material comprises the components and the contents which are basically the same as those of the embodiment 1 in parts by weight, wherein the infrared reflection pigment is an infrared reflection pigment 3;
the preparation method of the thermo-oxidative aging resistant ABS resin composite material is the same as that of example 1.
Result detection
The thermal oxidative aging-resistant ABS resin composite materials in examples 1-14 and comparative examples 1-7 were subjected to performance test, and a gold-colored standard color plate (50 mm. Times.80 mm. Times.2 mm) was injection molded by an injection molding machine, and the thermal oxidative aging test, color difference and yellow index of the ABS material were all tested by using the color plate, and the specific test method was as follows:
(1) Thermal oxidative aging test: see GB/T7141-2008 for specific test methods;
(2) Yellow index test: see HG/T3862-2006 for specific test methods.
The color difference delta E represents the color change of the color plate before and after the thermo-oxidative aging test, and the calculation formula is delta E 2 ＝(△L) 2 +(△a) 2 +(△b) 2 The smaller the color difference delta E data is, the better the thermal oxidative aging performance of the material is shown; and the yellow index Y is consistent with the yellow degree of the sample observed under the irradiation of sunlight, so that the aging degree of the high polymer material can be evaluated by testing the yellow index of the sample.
The experiment is carried out by measuring the yellow index of the ABS resin composite materials with heat resistance and oxygen aging in examples 1-14 and comparative examples 1-7 after the ABS resin composite materials are heated for 360 hours at 90 ℃ to evaluate the stable efficiency of an antioxidant system, wherein the smaller the yellow index Y value is, the smaller the aging degree is, namely, the better the heat resistance and oxygen aging performance of the ABS resin composite materials is; the oxidation induction time and the oxidation induction temperature are two important indexes for representing that the antioxidant combines free radicals in the polymer and inhibits the oxidation of the polymer, and the longer the oxidation induction time is, the higher the oxidation temperature is, the better the thermal-oxidative aging resistance of the ABS resin composite material is.
TABLE 3 Properties of heat-aging-resistant ABS-based resin composite materials in examples 1 to 14 and comparative examples 1 to 7
| Numbering device | Color difference delta E | Yellow index Y | Oxidation induction time/min | Oxidation induction temperature/°c |
| Example 1 | 5.45 | 18.69 | 44.5 | 218 |
| Example 2 | 3.03 | 15.25 | 54.9 | 219 |
| Example 3 | 2.86 | 14.73 | 51.2 | 221 |
| Example 4 | 1.89 | 12.33 | 57.5 | 227 |
| Example 5 | 1.78 | 11.99 | 59.4 | 228 |
| Example 6 | 1.84 | 12.13 | 58.2 | 227 |
| Example 7 | 1.66 | 11.54 | 60.8 | 229 |
| Example 8 | 1.75 | 11.84 | 60.1 | 228 |
| Example 9 | 2.02 | 12.72 | 56.2 | 225 |
| Example 10 | 1.17 | 9.22 | 65.5 | 234 |
| Example 11 | 0.95 | 8.75 | 67.9 | 236 |
| Example 12 | 1.34 | 9.49 | 63.4 | 232 |
| Example 13 | 2.05 | 12.88 | 55.6 | 224 |
| Example 14 | 1.84 | 12.17 | 58.1 | 227 |
| Comparative example 1 | 12.93 | 26.44 | 36.2 | 212 |
| Comparative example 2 | 18.79 | 31.2 | 32 | 210 |
| Comparative example 3 | 6.03 | 20.12 | 43.7 | 217 |
| Comparative example 4 | 6.89 | 21.25 | 42.9 | 216 |
| Comparative example 5 | 7.27 | 22.58 | 42.2 | 215 |
| Comparative example 6 | 7.94 | 23.19 | 41.5 | 215 |
| Comparative example 7 | 8.84 | 24.31 | 39.5 | 214 |
From examples 5 and examples 7 to 9, it is understood that the heat-aging resistance of the ABS resin exhibits a first increase and a second decrease with an increase of the metal complex in the infrared reflective pigment, and when the weight ratio of the metal oxide to the metal complex is 1:2, the heat-aging resistance of the ABS resin composite is optimal;
as is clear from examples 7 and examples 10 to 12, the effect of the infrared reflection pigment obtained by ternary compounding of 1 metal oxide and 2 metal complexes is better than that of the infrared reflection pigment obtained by binary compounding of 1 metal oxide and 1 metal complex; and when the weight ratio of the metal oxide to the metal complex is 1:2, the weight ratio of the chromium cobalt complex to the nickel titanium complex is 1:1, the ABS resin composite material has optimal thermo-oxidative aging resistance;
as can be seen from comparative examples 1 and 2, the ABS resin composite material in comparative example 1 has much larger color difference Δe and yellow index than those in example 2, and the oxidation induction time and oxidation induction temperature are also smaller than those in example 2, which suggests that excessive infrared reflective pigments are not beneficial to improving the thermo-oxidative aging resistance of ABS resin composite material; as is clear from comparative example 2 and example 1, the ABS resin composite material in comparative example 2 has much larger color difference Δe and yellow index than those in example 1, and the oxidation induction time and oxidation induction temperature are smaller than those in example 1, which means that the improvement effect of a small amount of infrared reflective pigment on the thermo-oxidative aging resistance of ABS resin composite material is limited;
as can be seen from comparative example 3 and example 1, when the amount of the metal complex in the infrared reflective pigment is too small, the reflection efficiency of the infrared reflective pigment in the mid-infrared region and the far-infrared region is low, thereby affecting the thermo-oxidative aging performance of the ABS resin composite material; as can be seen from comparative example 4 and example 9, too much metal complex in the infrared reflective pigment is detrimental to the thermo-oxidative aging resistance of the ABS-based resin composite material.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (7)
1. The heat-resistant and oxygen-aging-resistant ABS resin composite material is characterized by comprising the following components in parts by weight:
100 parts of ABS resin;
0.5-5 parts of an antioxidant;
0.5-5 parts of a light stabilizer;
1-5 parts of infrared reflection pigment;
wherein the infrared reflective pigment is a mixture of a metal oxide and a metal complex;
the weight ratio of the metal oxide to the metal complex is 1 (1-4);
the metal complex is a mixture of chromium cobalt blue and nickel titanium yellow, and the weight ratio of the chromium cobalt blue to the nickel titanium yellow is 1 (0.5-2); the metal oxide is at least one of tungsten oxide and antimony oxide.
2. The thermo-oxidative aging resistant ABS resin composite material according to claim 1, comprising the following components in parts by weight:
100 parts of ABS resin;
1-3 parts of an antioxidant;
1-3 parts of a light stabilizer;
2-4 parts of infrared reflection pigment.
3. The heat-aging resistant ABS resin composite material according to claim 1, wherein the weight ratio of the metal oxide to the metal complex is 1 (1-3).
4. The heat-aging resistant ABS resin composite according to claim 1, wherein the antioxidant is two or more of hindered phenol antioxidants, amine antioxidants and phosphite antioxidants.
5. The heat-aging resistant ABS-based resin composite according to claim 1, wherein the ABS-based resin is one or more of acrylonitrile-butadiene-styrene graft copolymer, acrylonitrile-styrene-acrylic acid terpolymer and methyl methacrylate-butadiene-styrene graft copolymer.
6. A method for preparing the thermal oxidative aging-resistant ABS resin composite material according to any one of claims 1 to 5, comprising the steps of:
and uniformly mixing the ABS resin, the antioxidant, the light stabilizer and the infrared reflection pigment, and then adding the mixture into a melt extrusion device for melt extrusion granulation to obtain the thermo-oxidative aging resistant ABS resin composite material.
7. Use of the thermal oxidative aging-resistant ABS resin composite material according to any one of claims 1 to 5 in plastic parts.
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