WO2020258792A1 - Method for preparing composite antioxidant for better improving yellowing of polymer caused by processing and long-term aging - Google Patents

Method for preparing composite antioxidant for better improving yellowing of polymer caused by processing and long-term aging Download PDF

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WO2020258792A1
WO2020258792A1 PCT/CN2019/128319 CN2019128319W WO2020258792A1 WO 2020258792 A1 WO2020258792 A1 WO 2020258792A1 CN 2019128319 W CN2019128319 W CN 2019128319W WO 2020258792 A1 WO2020258792 A1 WO 2020258792A1
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antioxidant
composite
composite antioxidant
main
powder
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PCT/CN2019/128319
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French (fr)
Chinese (zh)
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郭骄阳
赵崇鑫
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江苏极易新材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic 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
    • C08K5/04—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to a method for preparing a composite antioxidant that can better improve polymer processing and long-term aging and yellowing, and belongs to the technical field of antioxidant composites.
  • Polymers such as polypropylene resins, polyethylene resins, EVA, polycarbonate resins, etc., during the synthesis process caused structural defects, residual metal ions and other problems, or damage to the molecular structure during thermal processing, and long-term storage During the process of aging, some chromophores will be produced. These chromophores will cause the color of the polymer. Most of the polymer's many chromophores are yellow and mixed with red or green chromophores.
  • Antioxidant is a functional additive that protects polymer processing and long-term aging, and can delay the chromophore formed by polymer aging, so as to avoid polymer yellowing. However, antioxidants cannot structurally damage the formed chromophore to change the color.
  • pigments can be used to complement the color. If the antioxidant and pigment are separated Adding to the polymer for compounding can color and complement the color of the polymer, but the uneven distribution of the pigment in the polymer makes the color correction effect poor. Therefore, there is an urgent need for a method that can compound antioxidants and pigments to better improve polymer processing and long-term aging yellowing.
  • the present invention provides a method for preparing a composite antioxidant that can better improve polymer processing and long-term aging and yellowing.
  • the dispersant function and ultrasonic technology are combined to improve the primary and secondary antioxidants.
  • the uniformity of the compound and the pigment is simple.
  • the present invention adopts the following technical solution: a method for preparing a composite antioxidant that can better improve polymer processing and long-term aging and yellowing.
  • the composite antioxidant adopts a primary antioxidant, an auxiliary antioxidant, Dispersants, organic pigments, and inorganic pigments are prepared as main raw materials.
  • the specific preparation methods are as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, and the organic pigment powder in the above step (1) is added to the above step (1) after the ultrasonic time is 2 to 3 minutes Inorganic pigment powder, continue ultrasonic treatment, uniform dispersion, ultrasonic time is 3 to 4 minutes, to obtain composite antioxidant emulsion;
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • the primary antioxidant is a phenolic antioxidant or an amine antioxidant.
  • the phenolic antioxidant includes antioxidant 1010, antioxidant 1076, and antioxidant 1098.
  • Amine antioxidants include antioxidants.
  • the dispersant It is calcium stearate or zinc stearate;
  • the organic pigment is phthalocyanine blue, transparent violet B, vat brilliant violet RR, transparent green 5B, or a mixture of two or more in any ratio; the inorganic pigment is ultramarine blue .
  • the primary antioxidant is 1010 antioxidant; the auxiliary antioxidant is 168 antioxidant; the dispersant is calcium stearate or zinc stearate; and the organic pigment is phthalocyanine blue and transparent violet A mixture of B; the inorganic pigment is ultramarine blue.
  • the total mass of the main antioxidant and the auxiliary antioxidant in the raw materials accounts for 75% to 90% of the total mass of the main raw material composed of the main antioxidant, auxiliary antioxidant, dispersant, organic pigment, and inorganic pigment ,
  • the mass ratio of the main antioxidant and the auxiliary antioxidant is 1:4 to 1:0.5.
  • the mass of the dispersant in the raw materials accounts for 8% to 20% of the total mass of the main raw materials composed of the main antioxidant, auxiliary antioxidant, dispersant, organic pigment, and inorganic pigment, and the rest are organic pigment powder and inorganic Pigment powder.
  • the mass ratio of the organic pigment powder and the inorganic pigment powder in the raw material is 17:1-30:1.
  • the ultrasonic power is 1000-1200W
  • the frequency is 20KHz
  • the temperature is 190-200°C.
  • the primary antioxidant is a phenolic antioxidant or an amine antioxidant
  • the invention uses the melt of the main and auxiliary antioxidants to compound with the pigment, combines the function of the dispersant with ultrasonic technology, so that the pigment powder is more uniformly dispersed in the melt of the antioxidant, and effectively prevents the sedimentation and agglomeration of the pigment powder.
  • the invention adds a dispersant to the melt of the main and auxiliary antioxidants to effectively reduce the viscosity of the melt of the antioxidant, improve the mobility of the pigment particles, and ensure that the composite antioxidant has a higher effect on the color and color of the polymer.
  • the amount of color while improving the stability of the composite antioxidant, enhances the coloring power of the composite antioxidant, and has high color saturation.
  • organic pigments are used as the main complementary dyes, which have a better complementary effect on the color of polymers; at the same time, inorganic pigments are used as auxiliary complementary dyes, and the inorganic pigments use ultramarine blue.
  • the synergistic effect of ultramarine and organic dyes On the other hand, the inorganic pigment ultramarine contains sodium polysulfide and has a special crystal lattice inside, which has the effect of eliminating yellow shade, greatly improving the complementary effect of coloring the polymer color.
  • it can be used for the main and auxiliary antioxidants and complementary dyes. Screening, the obtained compound combination synergistic effect makes the composite antioxidant have the best thermal and oxygen stability during processing, and achieve the best effect on improving the aging and yellowing of polypropylene resin.
  • the composite technology of the present invention has no solvent use, avoids solvent waste, reduces production costs, and is environmentally friendly; the composite technology adopts ultrasonic technology, which effectively shortens production time, improves production efficiency, saves energy consumption, and improves economic benefits.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant pellets.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • All steps (1), (2), (3), (5) in this screening example are exactly the same as all steps (1), (2), (3), (5) in screening example 1, The difference is that (4) of this screening example will ultrasonically treat the composite antioxidant mixture II in the above step (3) under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C.
  • Add 3.60g of phthalocyanine blue powder in the above step (1) add 0.15g of ultramarine blue powder in the above step (1) after the ultrasonic time is 2 ⁇ 3min, continue the ultrasonic treatment, the dispersion is uniform, the ultrasonic time is 3 ⁇ 4min, get Compound antioxidant emulsion.
  • the ultrasonic technology is used to treat the pigments to be evenly dispersed in the main and antioxidant 168 melts, and the obtained composite antioxidant has the best effect on improving the aging and yellowing of polypropylene resin.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 2.88g phthalocyanine blue powder, ultrasonic time is 2 ⁇ 3min, add 0.12g ultramarine blue powder in the above step (1), continue ultrasonic treatment, dispersion uniformly, ultrasonic time is 3 ⁇ 4min, to obtain composite antioxidant emulsion;
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • step (3) of this screening example 6g of calcium stearate is weighed, and in step (4), 1.44g is respectively weighed Phthalocyanine blue powder, 0.06g ultramarine blue powder.
  • step (2) of this screening example 20 g of antioxidant 1010 and 40 g of antioxidant 168 are weighed, step (3) Weigh 6 g of calcium stearate in step (4), weigh 8.64 g of phthalocyanine blue powder and 0.36 g of ultramarine blue powder in step (4).
  • step (2) of this screening example 20 g of antioxidant 1010 and 40 g of antioxidant 168 are weighed, step (3) Weigh 11.25 g of calcium stearate in step (4), respectively weigh 3.65 g of phthalocyanine blue powder and 0.15 g of ultramarine blue powder.
  • step (2) of this screening example 18.75g of antioxidant 1010 and 37.5g of antioxidant 168 are weighed, and step ( 3) Weigh 15 g of calcium stearate, and respectively weigh 3.60 g of phthalocyanine blue powder and 0.15 g of ultramarine blue powder in step (4).
  • step (2) of this screening example 18.75g antioxidant 1010 and 37.5g antioxidant 168 are weighed, and step ( In 3), weigh 16.5 g of calcium stearate.
  • step (4) weigh 2.16 g of phthalocyanine blue powder and 0.09 g of ultramarine blue powder.
  • the total mass of antioxidant 1010 and antioxidant 168 accounted for the total mass of primary antioxidant and auxiliary antioxidant in step (2) above accounted for the total mass of primary antioxidant 1010 and antioxidant 168 , Calcium stearate, Phthalocyanine blue, Ultramarine blue constitute 75 to 90% of the total mass of the main raw materials, calcium stearate accounts for the main antioxidant 1010, antioxidant 168, calcium stearate, phthalocyanine blue, ultramarine blue
  • the total mass of the main raw material is 8-20%, the pigment dispersion is uniform and stable, and the obtained composite antioxidant has better aging and yellowing effect on polypropylene resin and better color uniformity. At the same time, improved polypropylene resin particles are observed. The colors have high saturation.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 3.
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant pellets.
  • All steps in this screening example are the same as all steps in screening example 9, except that in step (2) of this screening example, 12 g of antioxidant 1010 and 48 g of antioxidant 168 are weighed and mixed.
  • All steps in this screening example are the same as all steps in screening example 9, except that in step (2) of this screening example, 20 g of antioxidant 1010 and 40 g of antioxidant 168 are weighed and mixed.
  • step (2) of this screening example 40 g of antioxidant 1010 and 20 g of antioxidant 168 are weighed and mixed.
  • All steps in this screening example are the same as all steps in screening example 9, except that 41.38 g of antioxidant 1010 and 18.62 g of antioxidant 168 are weighed and mixed in step (2) of this screening example.
  • the obtained composite antioxidant has a better effect on improving the aging and yellowing of polypropylene resin.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 3.53g phthalocyanine blue powder, sonication time is 2 ⁇ 3min, add 0.22g ultramarine blue powder in the above step (1), continue sonication, the dispersion is uniform, the sonication time is 3 ⁇ 4min, to obtain composite antioxidant emulsion;
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • All steps in this screening example are the same as all steps in screening example 14, except that in step (4) of this screening example, 0.19 g of phthalocyanine blue powder and 3.56 g of ultramarine blue powder are respectively weighed.
  • All steps in this screening example are the same as all steps in screening example 14, except that in step (4) of this screening example, 3.56 g of phthalocyanine blue powder and 0.19 g of ultramarine blue powder are respectively weighed.
  • All steps in this screening example are the same as all steps in screening example 14, except that in step (4) of this screening example, 3.60 g of phthalocyanine blue powder and 0.15 g of ultramarine blue powder are respectively weighed.
  • All steps in this screening example are the same as all steps in screening example 13, except that in step (4) of this screening example, 3.63 g of phthalocyanine blue powder and 0.12 g of ultramarine blue powder are respectively weighed.
  • the obtained composite antioxidant has a better effect on the aging and yellowing of polypropylene resin, but organic pigment powder and inorganic pigment
  • the mass ratio of the powder is 0-16:1
  • the color of the polypropylene polymer is different. Therefore, when the mass ratio of the organic pigment powder and the inorganic pigment powder is 17:1-30:1, the composite antioxidant is to the polypropylene resin The aging yellowing effect and color uniformity are better.
  • antioxidant 626 40g antioxidant 626, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
  • antioxidant 626 40g antioxidant 626, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
  • select antioxidant DLTDP As the main antioxidant, select antioxidant DLTDP, 40g antioxidant DLTDP, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue;
  • antioxidant DSTDP as main antioxidant, 40g antioxidant DSTDP and 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, 0.15g ultramarine blue for compounding;
  • the main antioxidant is selected as antioxidant antioxidant 412S, 40g antioxidant antioxidant 412S, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue.
  • antioxidant 1076 as the main antioxidant and antioxidant 618 as the auxiliary antioxidant, 20g antioxidant 1076 and 40g antioxidant 618, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue.
  • antioxidant 1098 for main antioxidant antioxidant 626 for auxiliary antioxidant
  • 20g antioxidant 1098 and 40g antioxidant 626 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue.
  • antioxidant 5057 as the main antioxidant and DSTDP as the auxiliary antioxidant, 20g antioxidant 5057 and 40g antioxidant DSTDP, 11.25g calcium stearate, 3.60g phthalocyanine blue, 0.15g ultramarine blue Compound
  • antioxidant 405 as the main antioxidant and DLTDP as the auxiliary antioxidant, 20g antioxidant 405 and 40g antioxidant DLTDP, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue. Compound.
  • Organic pigments are made of transparent violet B, 3.60g transparent violet B, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine blue;
  • Organic pigments are made of Vat Violet RR, 3.60g Vat Violet RR, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine;
  • Organic pigments are made of transparent green 5B, 3.60g transparent green 5B, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine blue;
  • Organic pigments are made of Phthalocyanine Blue, Transparent Violet B, 3g Phthalocyanine Blue and 0.6g Transparent Violet B, 20g Antioxidant 1010, 40g Antioxidant 168, 11.25g Calcium Stearate, 0.15g Ultramarine;
  • Organic pigments are made of phthalocyanine blue, transparent green 5B, 3g phthalocyanine blue and 0.6g transparent green 5B, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine blue.
  • the compound antioxidant prepared by antioxidant 1010, antioxidant 168, calcium stearate, phthalocyanine blue, and ultramarine blue has an effect on polypropylene resin aging. Yellow has a better improvement effect, and a composite antioxidant made of phthalocyan blue and transparent violet B compounded organic pigments and antioxidant 1010, antioxidant 168, calcium stearate, and ultramarine blue is used for polypropylene resin Aging yellowing has a better improvement effect.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 3.75g phthalocyanine blue powder, ultrasonic time is 2 ⁇ 3min, and the dispersion is uniform, and a composite antioxidant emulsion is obtained;
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 1.9g phthalocyanine blue powder, 1.85g transparent violet B, ultrasonic time is 2 ⁇ 3min, and the dispersion is uniform to obtain a composite antioxidant emulsion;
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 3.
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and then added to the above step (1) 1.8g phthalocyanine blue powder, 1.8g transparent violet B powder, ultrasonic time is 2 ⁇ 3min, add 0.15g ultramarine blue powder in the above step (1), continue ultrasonic treatment, the dispersion is even, the ultrasonic time is 3 ⁇ 4min, the composite Antioxidant emulsion;
  • the composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant pellets.
  • a preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing is as follows:
  • the composite antioxidant mixture I in the above step (2) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000 ⁇ 1200W, the frequency is 20KHz, and the temperature is 190 ⁇ 200°C, and it is added to the above step (1) 3.6 g of phthalocyanine blue powder, sonication time of 2 to 3 minutes, add 0.15 g of ultramarine blue powder in the above step (1), continue ultrasonic treatment, uniform dispersion, ultrasonic time of 3 to 4 minutes, to obtain a composite antioxidant emulsion;
  • the composite antioxidant emulsion in the above step (3) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  • Example 1 the composite antioxidants prepared in Example 1, Example 2, Example 3, Example 4, and Example 5 were used to compound the improved polypropylene resin particles obtained by compounding polypropylene resin.
  • Comparative Example 1 The improved polypropylene resin particles obtained in Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5 were tested for their yellowness index by HunterLab LabScan XE colorimeter-yellow index meter, and the results are shown in Table 9 below:
  • organic pigments have a complementary effect on the yellowing of polypropylene resin.
  • the synergistic effect of organic pigments and inorganic pigments improves the yellowing of polymers.
  • the added dispersant calcium stearate makes The pigment is uniformly dispersed and stable, and the aging and yellowing of the polymer is further improved.
  • the composite antioxidant obtained in the present invention has better aging and yellowing effect on polypropylene resin and better color uniformity, and the color of polypropylene resin particles has higher saturation.

Abstract

Disclosed is a method for preparing a composite antioxidant for better improving the yellowing of a polymer caused by processing and long-term aging. The composite antioxidant is prepared by using a main antioxidant, an auxiliary antioxidant, a dispersant, an organic pigment, and an inorganic pigment as main raw materials, wherein, first, the main antioxidant and the auxiliary antioxidant are mixed and melted to form a molten liquid, then, the dispersant is added and mixed until uniform, then same is ultrasonically treated under an ultrasonic wave, an organic pigment powder and an inorganic pigment powder are added and dispersed uniformly, and finally, extrusion granulation is performed via a twin screw extruder to obtain composite antioxidant particles. By compositing the molten liquid of the main and auxiliary antioxidants with the pigments, and combining the function of the dispersant and the ultrasonic technology, the pigment powders are more uniformly dispersed into the molten liquid of the antioxidants, such that the pigment content in a single composite antioxidant particle is uniform; furthermore, by compounding the composite antioxidant with a polymer, the color complementary effect of the pigment on the coloring of the polymer is improved, and yellowing of the polymer caused by processing and long-term aging is effectively improved.

Description

一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法Preparation method of composite antioxidant capable of better improving polymer processing and long-term aging and yellowing 技术领域Technical field
本发明涉及一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，属于抗氧剂复合技术领域。The invention relates to a method for preparing a composite antioxidant that can better improve polymer processing and long-term aging and yellowing, and belongs to the technical field of antioxidant composites.
背景技术Background technique
聚合物，如聚丙烯树脂、聚乙烯树脂、EVA、聚碳酸酯树脂等，在合成时由于工艺造成结构缺陷、金属离子的残留等问题，或者在热加工时对分子结构的破坏，以及长期存放过程中发生老化都会产生一些生色团，这些生色团会造成聚合物颜色着色，在聚合物众多的生色团中大部分是显黄色的同时也会参杂着红或者绿生色团。抗氧化剂是保护聚合物加工及长期老化的功能性助剂，能够延缓聚合物老化而形成的生色团，从而避免聚合物的黄变。但是抗氧剂并不能对已经形成的生色团进行结构上的破坏而改变颜色，针对原料中生色团造成聚合物颜色着色的问题，可以采用颜料进行补色，如果将抗氧剂、颜料分别加入聚合物中进行复混，能够对聚合物颜色着色补色，但是颜料在聚合物中的分布不均匀使得补色效果较差。因此，急需一种能够将抗氧剂与颜料复合、更好地改善聚合物加工及长期老化黄变的方法。Polymers, such as polypropylene resins, polyethylene resins, EVA, polycarbonate resins, etc., during the synthesis process caused structural defects, residual metal ions and other problems, or damage to the molecular structure during thermal processing, and long-term storage During the process of aging, some chromophores will be produced. These chromophores will cause the color of the polymer. Most of the polymer's many chromophores are yellow and mixed with red or green chromophores. Antioxidant is a functional additive that protects polymer processing and long-term aging, and can delay the chromophore formed by polymer aging, so as to avoid polymer yellowing. However, antioxidants cannot structurally damage the formed chromophore to change the color. For the problem of polymer coloration caused by the chromophore in the raw material, pigments can be used to complement the color. If the antioxidant and pigment are separated Adding to the polymer for compounding can color and complement the color of the polymer, but the uneven distribution of the pigment in the polymer makes the color correction effect poor. Therefore, there is an urgent need for a method that can compound antioxidants and pigments to better improve polymer processing and long-term aging yellowing.
发明内容Summary of the invention
针对上述现有技术存在的问题，本发明提供一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，将分散剂功能和超声波技术结合，能够提高主、辅抗氧剂与颜料的复混均匀度，工艺简单。In view of the above-mentioned problems in the prior art, the present invention provides a method for preparing a composite antioxidant that can better improve polymer processing and long-term aging and yellowing. The dispersant function and ultrasonic technology are combined to improve the primary and secondary antioxidants. The uniformity of the compound and the pigment is simple.
为了实现上述目的，本发明采用如下技术方案：一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，该复合抗氧剂采用主抗氧剂、辅助抗氧剂、分散剂、有机颜料、无机颜料为主原料制备，具体制备方法如下：In order to achieve the above objective, the present invention adopts the following technical solution: a method for preparing a composite antioxidant that can better improve polymer processing and long-term aging and yellowing. The composite antioxidant adopts a primary antioxidant, an auxiliary antioxidant, Dispersants, organic pigments, and inorganic pigments are prepared as main raw materials. The specific preparation methods are as follows:
(1)先将有机颜料、无机颜料分别研磨，并用800～900目滤网过滤，得 到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigments and inorganic pigments separately, and filter them with a 800-900 mesh filter to obtain organic pigment powders and inorganic pigment powders for use;
(2)将主抗氧剂、辅助抗氧剂混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Mix the main antioxidant and auxiliary antioxidant, heat and stir, gradually increase the temperature to 250°C, then keep it for 30-60 minutes, then lower the temperature to 230°C, stir for 40-50 minutes, and stir at 1000-1500r /min, to obtain the composite antioxidant mixture I;
(3)接着向上述步骤(2)中的复合抗氧剂混合液Ⅰ中加入分散剂，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Then add the dispersant to the composite antioxidant mixture I in the above step (2), stir at 230℃ for 30-40min, mix evenly, reduce the temperature to 200℃, stir for 40-50min to obtain the composite Antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，加入上述步骤(1)中的有机颜料粉末，超声时间为2～3min后加入上述步骤(1)中的无机颜料粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, and the organic pigment powder in the above step (1) is added to the above step (1) after the ultrasonic time is 2 to 3 minutes Inorganic pigment powder, continue ultrasonic treatment, uniform dispersion, ultrasonic time is 3 to 4 minutes, to obtain composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
优选地，所述主抗氧剂为酚类抗氧剂或胺类抗氧剂，酚类抗氧剂包括抗氧剂1010、抗氧剂1076、抗氧剂1098，胺类抗氧剂包括抗氧剂5057、抗氧剂405；辅助抗氧化剂为亚磷酸酯类抗氧剂或硫酯类抗氧剂；辅助抗氧化剂为亚磷酸酯类抗氧剂或硫酯类抗氧剂，亚磷酸酯类抗氧剂抗氧剂168、抗氧剂626、抗氧剂618、抗氧剂9228，硫酯类抗氧剂包括抗氧剂DLTDP、抗氧剂DSTDP、抗氧剂412S；所述分散剂为硬脂酸钙或硬脂酸锌；所述有机颜料为酞青蓝、透明紫B、还原艳紫RR、透明绿5B的一种或两种以上的任意比例混合；所述无机颜料为群青。Preferably, the primary antioxidant is a phenolic antioxidant or an amine antioxidant. The phenolic antioxidant includes antioxidant 1010, antioxidant 1076, and antioxidant 1098. Amine antioxidants include antioxidants. Oxidizer 5057, antioxidant 405; auxiliary antioxidant is phosphite antioxidant or thioester antioxidant; auxiliary antioxidant is phosphite antioxidant or thioester antioxidant, phosphite Antioxidant Antioxidant 168, Antioxidant 626, Antioxidant 618, Antioxidant 9228, Thioester Antioxidant includes Antioxidant DLTDP, Antioxidant DSTDP, Antioxidant 412S; The dispersant It is calcium stearate or zinc stearate; the organic pigment is phthalocyanine blue, transparent violet B, vat brilliant violet RR, transparent green 5B, or a mixture of two or more in any ratio; the inorganic pigment is ultramarine blue .
优选地，所述主抗氧剂为1010抗氧剂；辅助抗氧化剂为168抗氧剂；所述分散剂为硬脂酸钙或硬脂酸锌；所述有机颜料为酞青蓝和透明紫B的混合物；所述无机颜料为群青。Preferably, the primary antioxidant is 1010 antioxidant; the auxiliary antioxidant is 168 antioxidant; the dispersant is calcium stearate or zinc stearate; and the organic pigment is phthalocyanine blue and transparent violet A mixture of B; the inorganic pigment is ultramarine blue.
优选地，所述原料中主抗氧剂和辅助抗氧剂的总质量占主抗氧剂、辅助抗氧剂、分散剂、有机颜料、无机颜料组成的主原料总质量的75％～90％，所述 主抗氧剂、辅助抗氧剂的质量比为1:4～1:0.5。Preferably, the total mass of the main antioxidant and the auxiliary antioxidant in the raw materials accounts for 75% to 90% of the total mass of the main raw material composed of the main antioxidant, auxiliary antioxidant, dispersant, organic pigment, and inorganic pigment , The mass ratio of the main antioxidant and the auxiliary antioxidant is 1:4 to 1:0.5.
优选地，所述原料中分散剂的质量占主抗氧剂、辅助抗氧剂、分散剂、有机颜料、无机颜料组成的主原料总质量的8％～20％，其余为有机颜料粉末和无机颜料粉末。Preferably, the mass of the dispersant in the raw materials accounts for 8% to 20% of the total mass of the main raw materials composed of the main antioxidant, auxiliary antioxidant, dispersant, organic pigment, and inorganic pigment, and the rest are organic pigment powder and inorganic Pigment powder.
优选地，所述原料中有机颜料粉末、无机颜料粉末的质量比为17:1～30:1。Preferably, the mass ratio of the organic pigment powder and the inorganic pigment powder in the raw material is 17:1-30:1.
优选地，上述步骤(4)中的超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃。Preferably, in the ultrasonic treatment in the above step (4), the ultrasonic power is 1000-1200W, the frequency is 20KHz, and the temperature is 190-200°C.
优选地，所述主抗氧剂为酚类抗氧剂或胺类抗氧剂，Preferably, the primary antioxidant is a phenolic antioxidant or an amine antioxidant,
本发明的有益效果：The beneficial effects of the present invention:
本发明通过主、辅助抗氧剂的熔液与颜料进行复合，将分散剂功能和超声波技术结合，使颜料粉末在抗氧剂的熔液分散更加均匀，有效地防止颜料粉末的沉降和凝聚，使单个复合抗氧剂颗粒中的颜料含量均匀，将该复合抗氧剂与聚合物中复混，提高了颜料对聚合物颜色着色的补色效果，有效地改善了聚合物加工及长期老化变黄。The invention uses the melt of the main and auxiliary antioxidants to compound with the pigment, combines the function of the dispersant with ultrasonic technology, so that the pigment powder is more uniformly dispersed in the melt of the antioxidant, and effectively prevents the sedimentation and agglomeration of the pigment powder. Make the pigment content in a single composite antioxidant particle uniform, compound the composite antioxidant with the polymer, improve the color complementary effect of the pigment on the color of the polymer, and effectively improve the polymer processing and long-term aging yellowing .
本发明在主、辅助抗氧剂的熔液中加入分散剂，有效降低抗氧剂的熔液的粘度，提高颜料粒子的运动性，确保复合抗氧剂对聚合物颜色着色补色的较高得色量，同时提高复合抗氧剂的稳定性，增强了复合抗氧剂的着色力，颜色饱和度高。The invention adds a dispersant to the melt of the main and auxiliary antioxidants to effectively reduce the viscosity of the melt of the antioxidant, improve the mobility of the pigment particles, and ensure that the composite antioxidant has a higher effect on the color and color of the polymer. The amount of color, while improving the stability of the composite antioxidant, enhances the coloring power of the composite antioxidant, and has high color saturation.
本发明的复合抗氧剂中以有机颜料作为主补色染料，其对聚合物颜色着色的补色效果较佳；同时，无机颜料作为辅助补色染料，无机颜料采用群青，一方面群青与有机染料协同效果，另一方面无机颜料群青因含有多硫化钠，内部有特殊结晶格子，具有消除黄色色光的效能，大大提高了对聚合物颜色着色的补色效果，同时通过对主、辅助抗氧剂和补色染料的筛选，得到的复配组合协同作用使得复合抗氧剂在加工过程中具有最佳的热氧稳定性，并对聚丙烯树脂的老化变黄达到最佳改善效果。In the composite antioxidant of the present invention, organic pigments are used as the main complementary dyes, which have a better complementary effect on the color of polymers; at the same time, inorganic pigments are used as auxiliary complementary dyes, and the inorganic pigments use ultramarine blue. On the one hand, the synergistic effect of ultramarine and organic dyes On the other hand, the inorganic pigment ultramarine contains sodium polysulfide and has a special crystal lattice inside, which has the effect of eliminating yellow shade, greatly improving the complementary effect of coloring the polymer color. At the same time, it can be used for the main and auxiliary antioxidants and complementary dyes. Screening, the obtained compound combination synergistic effect makes the composite antioxidant have the best thermal and oxygen stability during processing, and achieve the best effect on improving the aging and yellowing of polypropylene resin.
本发明的复合技术中无溶剂使用，避免溶剂的浪费，降低生产成本，绿色 环保；该复合技术采用超声波技术，有效地缩短了生产时间，提高了生产效率，节约能耗，提高经济效益。The composite technology of the present invention has no solvent use, avoids solvent waste, reduces production costs, and is environmentally friendly; the composite technology adopts ultrasonic technology, which effectively shortens production time, improves production efficiency, saves energy consumption, and improves economic benefits.
具体实施方式Detailed ways
下面用具体实施例说明本发明，但并不是对发明的限制。The following specific examples illustrate the present invention, but they do not limit the invention.
空白例Blank example
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(1) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture liquid I;
(2)称取20g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(2) Weigh 20g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40～ 50min, get the composite antioxidant mixture II;
(3)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(3) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant pellets.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数为-1.2。After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved Polypropylene resin particles have a yellow index of -1.2 detected by HunterLab LabScan XE colorimeter-yellow index meter.
一、颜料与主、辅助抗氧剂复混工艺的筛选实施例：1. Screening examples of the compounding process of pigments and main and auxiliary antioxidants:
筛选实施例1Screening Example 1
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将酞青蓝、群青为分别研磨，并用800～900目滤网过滤，得到酞青蓝粉末、群青粉末，备用；(1) Grind phthalocyanine blue and ultramarine blue separately, and filter with 800-900 mesh filter to obtain phthalocyanine blue powder and ultramarine blue powder for use;
(2)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture liquid I;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ，温度保持200℃，加入上述步骤(1)中的3.60g酞青蓝粉末，搅拌60～90min后加入上述步骤(1)中的0.15g群青粉末，继续搅拌，分散均匀，搅拌90～100min，得到复合抗氧剂乳液；(4) Put the composite antioxidant mixture II in the above step (3) at a temperature of 200°C, add 3.60g of the phthalocyanine blue powder in the above step (1), stir for 60 to 90 minutes and then add the above step (1) 0.15g ultramarine powder in the medium, continue to stir, disperse evenly, and stir for 90-100min to obtain a composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
筛选实施例2Screening Example 2
本筛选实施例中的所有步骤(1)、(2)、(3)、(5)与筛选实施例1中的所有步骤(1)、(2)、(3)、(5)完全相同，不同在于，本筛选实施例的(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的3.60g酞青蓝粉末，超声时间为2～3min后加入上述步骤(1)中的0.15g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液。All steps (1), (2), (3), (5) in this screening example are exactly the same as all steps (1), (2), (3), (5) in screening example 1, The difference is that (4) of this screening example will ultrasonically treat the composite antioxidant mixture II in the above step (3) under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃. Add 3.60g of phthalocyanine blue powder in the above step (1), add 0.15g of ultramarine blue powder in the above step (1) after the ultrasonic time is 2~3min, continue the ultrasonic treatment, the dispersion is uniform, the ultrasonic time is 3~4min, get Compound antioxidant emulsion.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表1所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 1 below:
 To 黄色指数Yellow index
空白例Blank example -1.2-1.2
筛选实施例1Screening Example 1 -5.4-5.4
筛选实施例2Screening Example 2 -7.3-7.3
经上表1所述，采用超声波技术处理颜料在主、抗氧剂168熔液中分散均匀，得到的复合抗氧剂对聚丙烯树脂的老化变黄改善效果最佳。As described in Table 1 above, the ultrasonic technology is used to treat the pigments to be evenly dispersed in the main and antioxidant 168 melts, and the obtained composite antioxidant has the best effect on improving the aging and yellowing of polypropylene resin.
二、主抗氧剂和辅助抗氧剂的总质量、分散剂质量占主原料总质量的比例筛选实施例：2. The total mass of the main antioxidant and auxiliary antioxidant, and the ratio of the mass of the dispersant to the total mass of the main raw materials Screening examples:
筛选实施例3Screening Example 3
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将酞青蓝、群青为分别研磨，并用800～900目滤网过滤，得到酞青蓝粉末、群青粉末，备用；(1) Grind phthalocyanine blue and ultramarine blue separately, and filter with 800-900 mesh filter to obtain phthalocyanine blue powder and ultramarine blue powder for use;
(2)称取22.5g抗氧剂1010、45g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 22.5g antioxidant 1010, 45g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir 40-50min, stirring speed It is 1000～1500r/min to get the composite antioxidant mixture I;
(3)称取4.5g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 4.5g of calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40 minutes, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的2.88g酞青蓝粉末，超声时间为2～3min后加入上述步骤(1)中的0.12g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 2.88g phthalocyanine blue powder, ultrasonic time is 2~3min, add 0.12g ultramarine blue powder in the above step (1), continue ultrasonic treatment, dispersion uniformly, ultrasonic time is 3~4min, to obtain composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
筛选实施例4Screening Example 4
本筛选实施例中的所有步骤与筛选实施例3中的所有步骤相同，不同在于，本筛选实施例的步骤(3)中称取6g硬脂酸钙，步骤(4)中分别称取1.44g酞青蓝粉末、0.06g群青粉末。All steps in this screening example are the same as all steps in screening example 3. The difference is that in step (3) of this screening example, 6g of calcium stearate is weighed, and in step (4), 1.44g is respectively weighed Phthalocyanine blue powder, 0.06g ultramarine blue powder.
筛选实施例5Screening Example 5
本筛选实施例中的所有步骤与筛选实施例3中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取20g抗氧剂1010、40g抗氧剂168，步骤(3)中称取6g硬脂酸钙，步骤(4)中分别称取8.64g酞青蓝粉末、0.36g群青粉末。All steps in this screening example are the same as all steps in screening example 3. The difference is that in step (2) of this screening example, 20 g of antioxidant 1010 and 40 g of antioxidant 168 are weighed, step (3) Weigh 6 g of calcium stearate in step (4), weigh 8.64 g of phthalocyanine blue powder and 0.36 g of ultramarine blue powder in step (4).
筛选实施例6Screening Example 6
本筛选实施例中的所有步骤与筛选实施例3中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取20g抗氧剂1010、40g抗氧剂168，步骤(3)中称取11.25g硬脂酸钙，步骤(4)中分别称取3.65g酞青蓝粉末、0.15g群青粉末。All steps in this screening example are the same as all steps in screening example 3. The difference is that in step (2) of this screening example, 20 g of antioxidant 1010 and 40 g of antioxidant 168 are weighed, step (3) Weigh 11.25 g of calcium stearate in step (4), respectively weigh 3.65 g of phthalocyanine blue powder and 0.15 g of ultramarine blue powder.
筛选实施例7Screening Example 7
本筛选实施例中的所有步骤与筛选实施例8中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取18.75g抗氧剂1010、37.5g抗氧剂168，步骤(3)中称取15g硬脂酸钙，步骤(4)中分别称取3.60g酞青蓝粉末、0.15g群青粉末。All steps in this screening example are the same as all steps in screening example 8. The difference is that in step (2) of this screening example, 18.75g of antioxidant 1010 and 37.5g of antioxidant 168 are weighed, and step ( 3) Weigh 15 g of calcium stearate, and respectively weigh 3.60 g of phthalocyanine blue powder and 0.15 g of ultramarine blue powder in step (4).
筛选实施例8Screening Example 8
本筛选实施例中的所有步骤与筛选实施例3中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取18.75g抗氧剂1010、37.5g抗氧剂168，步骤(3)中称取16.5g硬脂酸钙，步骤(4)中分别称取2.16g酞青蓝粉末、0.09g群青粉末。All steps in this screening example are the same as all steps in screening example 3. The difference is that in step (2) of this screening example, 18.75g antioxidant 1010 and 37.5g antioxidant 168 are weighed, and step ( In 3), weigh 16.5 g of calcium stearate. In step (4), weigh 2.16 g of phthalocyanine blue powder and 0.09 g of ultramarine blue powder.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表2所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 2 below:
 To 黄色指数Yellow index
空白例Blank example -1.2-1.2
筛选实施例3Screening Example 3 -5.8-5.8
筛选实施例4Screening Example 4 6.86.8
筛选实施例5Screening Example 5 -7.2-7.2
筛选实施例6Screening Example 6 -7.3-7.3
筛选实施例7Screening Example 7 -7.3-7.3
筛选实施例8Screening Example 8 -4.7-4.7
经上表2所述，抗氧剂1010和抗氧剂168的总质量占上述步骤(2)中的主抗氧剂和辅助抗氧剂的总质量占主抗氧剂1010、抗氧剂168、硬脂酸钙、酞青蓝、群青组成的主原料总质量的75～90％，硬脂酸钙质量占主抗氧剂1010、抗氧剂168、硬脂酸钙、酞青蓝、群青组成的主原料总质量的8～20％时，颜料分散均匀且稳定，得到的复合抗氧剂对聚丙烯树脂的老化变黄效果和颜色均匀度更佳，同时观察到改善的聚丙烯树脂颗粒的颜色具有较高的饱和度。As described in Table 2 above, the total mass of antioxidant 1010 and antioxidant 168 accounted for the total mass of primary antioxidant and auxiliary antioxidant in step (2) above accounted for the total mass of primary antioxidant 1010 and antioxidant 168 , Calcium stearate, Phthalocyanine blue, Ultramarine blue constitute 75 to 90% of the total mass of the main raw materials, calcium stearate accounts for the main antioxidant 1010, antioxidant 168, calcium stearate, phthalocyanine blue, ultramarine blue When the total mass of the main raw material is 8-20%, the pigment dispersion is uniform and stable, and the obtained composite antioxidant has better aging and yellowing effect on polypropylene resin and better color uniformity. At the same time, improved polypropylene resin particles are observed. The colors have high saturation.
三、主抗氧剂、辅助抗氧剂的质量比筛选实施例：3. Screening examples of the mass ratio of main antioxidant and auxiliary antioxidant:
筛选实施例9Screening Example 9
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将酞青蓝、群青为分别研磨，并用800～900目滤网过滤，得到酞青蓝粉末、群青粉末，备用；(1) Grind phthalocyanine blue and ultramarine blue separately, and filter with 800-900 mesh filter to obtain phthalocyanine blue powder and ultramarine blue powder for use;
(2)称取10.91g抗氧剂1010、49.09g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 10.91g antioxidant 1010, 49.09g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, stir The speed is 1000～1500r/min, and the composite antioxidant mixture liquid I is obtained;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的3.60g酞青蓝粉末，超声时间为2～3min后加入上述步骤(1)中的0.15g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 3. 60g of phthalocyanine blue powder, sonication time of 2 to 3 minutes, add 0.15g of ultramarine blue powder in the above step (1), continue ultrasonic treatment, uniform dispersion, ultrasonic time of 3 to 4 minutes, to obtain a composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出 造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant pellets.
筛选实施例10Screening Example 10
本筛选实施例中的所有步骤与筛选实施例9中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取12g抗氧剂1010、48g抗氧剂168混合。All steps in this screening example are the same as all steps in screening example 9, except that in step (2) of this screening example, 12 g of antioxidant 1010 and 48 g of antioxidant 168 are weighed and mixed.
筛选实施例11Screening Example 11
本筛选实施例中的所有步骤与筛选实施例9的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取20g抗氧剂1010、40g抗氧剂168混合。All steps in this screening example are the same as all steps in screening example 9, except that in step (2) of this screening example, 20 g of antioxidant 1010 and 40 g of antioxidant 168 are weighed and mixed.
筛选实施例12Screening Example 12
本筛选实施例中的所有步骤与筛选实施例9中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取40g抗氧剂1010、20g抗氧剂168混合。All steps in this screening example are the same as all steps in screening example 9. The difference is that in step (2) of this screening example, 40 g of antioxidant 1010 and 20 g of antioxidant 168 are weighed and mixed.
筛选实施例13Screening Example 13
本筛选实施例中的所有步骤与筛选实施例9中的所有步骤相同，不同在于，本筛选实施例的步骤(2)中称取41.38g抗氧剂1010、18.62g抗氧剂168混合。All steps in this screening example are the same as all steps in screening example 9, except that 41.38 g of antioxidant 1010 and 18.62 g of antioxidant 168 are weighed and mixed in step (2) of this screening example.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表3所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 3 below:
 To 黄色指数Yellow index
空白例Blank example -1.2-1.2
筛选实施例9Screening Example 9 -5.6-5.6
筛选实施例10Screening Example 10 -7.2-7.2
筛选实施例11Screening Example 11 -7.3-7.3
筛选实施例12Screening Example 12 -7.2-7.2
筛选实施例13Screening Example 13 -5.8-5.8
经上表3所述，所述抗氧剂1010、辅抗氧剂的质量比为1:4～1:0.5时，得到的复合抗氧剂对聚丙烯树脂的老化变黄改善效果更佳。As described in Table 3 above, when the mass ratio of the antioxidant 1010 to the auxiliary antioxidant is 1:4 to 1:0.5, the obtained composite antioxidant has a better effect on improving the aging and yellowing of polypropylene resin.
四、有机颜料与无机颜料的质量比筛选实施例：4. Screening examples of the mass ratio of organic pigments and inorganic pigments:
筛选实施例14Screening Example 14
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具 体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将酞青蓝、群青为分别研磨，并用800～900目滤网过滤，得到酞青蓝粉末、群青粉末，备用；(1) Grind phthalocyanine blue and ultramarine blue separately, and filter with 800-900 mesh filter to obtain phthalocyanine blue powder and ultramarine blue powder for use;
(2)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture I;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的3.53g酞青蓝粉末，超声时间为2～3min后加入上述步骤(1)中的0.22g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 3.53g phthalocyanine blue powder, sonication time is 2~3min, add 0.22g ultramarine blue powder in the above step (1), continue sonication, the dispersion is uniform, the sonication time is 3~4min, to obtain composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
筛选实施例15Screening Example 15
本筛选实施例中的所有步骤与筛选实施例14中的所有步骤相同，不同在于，本筛选实施例的步骤(4)中分别称取0.19g酞青蓝粉末、3.56g群青粉末。All steps in this screening example are the same as all steps in screening example 14, except that in step (4) of this screening example, 0.19 g of phthalocyanine blue powder and 3.56 g of ultramarine blue powder are respectively weighed.
筛选实施例16Screening Example 16
本筛选实施例中的所有步骤与筛选实施例14中的所有步骤相同，不同在于，本筛选实施例的步骤(4)中分别称取3.56g酞青蓝粉末、0.19g群青粉末。All steps in this screening example are the same as all steps in screening example 14, except that in step (4) of this screening example, 3.56 g of phthalocyanine blue powder and 0.19 g of ultramarine blue powder are respectively weighed.
筛选实施例17Screening Example 17
本筛选实施例中的所有步骤与筛选实施例14中的所有步骤相同，不同在于，本筛选实施例的步骤(4)中分别称取3.60g酞青蓝粉末、0.15g群青粉末。All steps in this screening example are the same as all steps in screening example 14, except that in step (4) of this screening example, 3.60 g of phthalocyanine blue powder and 0.15 g of ultramarine blue powder are respectively weighed.
筛选实施例18Screening Example 18
本筛选实施例中的所有步骤与筛选实施例13中的所有步骤相同，不同在于，本筛选实施例的步骤(4)中分别称取3.63g酞青蓝粉末、0.12g群青粉末。All steps in this screening example are the same as all steps in screening example 13, except that in step (4) of this screening example, 3.63 g of phthalocyanine blue powder and 0.12 g of ultramarine blue powder are respectively weighed.
筛选实施例19Screening Example 19
本筛选实施例中的所有步骤与筛选实施例13中的所有步骤相同，不同在于，本筛选实施例的步骤(4)中分别称取3.75g酞青蓝粉末。All steps in this screening example are the same as all steps in screening example 13, except that in step (4) of this screening example, 3.75 g of phthalocyanine blue powder is weighed out.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表4所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 4 below:
 To 黄色指数Yellow index
空白例Blank example -1.2-1.2
筛选实施例14Screening Example 14 -7.2-7.2
筛选实施例15Screening Example 15 -7.1-7.1
筛选实施例16Screening Example 16 -7.2-7.2
筛选实施例17Screening Example 17 -7.3-7.3
筛选实施例18Screening Example 18 -6.1-6.1
筛选实施例19Screening Example 19 -6.1-6.1
经上表4所述，有机颜料粉末、无机颜料粉末的质量比为0～30:1时，得到的复合抗氧剂对聚丙烯树脂的老化变黄效果较好，但是有机颜料粉末、无机颜料粉末的质量比为0～16:1时，使得聚丙烯聚合物的颜色有差异，因此有机颜料粉末、无机颜料粉末的质量比为17:1～30:1时复合抗氧剂对聚丙烯树脂的老化变黄效果和颜色均匀度均较佳。As mentioned in Table 4 above, when the mass ratio of organic pigment powder and inorganic pigment powder is 0-30:1, the obtained composite antioxidant has a better effect on the aging and yellowing of polypropylene resin, but organic pigment powder and inorganic pigment When the mass ratio of the powder is 0-16:1, the color of the polypropylene polymer is different. Therefore, when the mass ratio of the organic pigment powder and the inorganic pigment powder is 17:1-30:1, the composite antioxidant is to the polypropylene resin The aging yellowing effect and color uniformity are better.
五、主抗氧剂、辅助抗氧剂、颜料的组分筛选实施例：5. Examples of component screening of main antioxidant, auxiliary antioxidant and pigment:
筛选实施例21Screening Example 21
本筛选实施例中的所有步骤与筛选实施例2中的所有步骤相同，不同在于，选用不同的主抗氧剂与抗氧剂168、硬脂酸钙、酞青蓝、群青进行复配：All steps in this screening example are the same as all steps in screening example 2, except that different primary antioxidants and antioxidants 168, calcium stearate, phthalocyanine blue, and ultramarine blue are selected for compounding:
21.1主抗氧剂选用抗氧剂1076，20g抗氧剂1076与40g抗氧剂168、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；21.1 Select antioxidant 1076, 20g antioxidant 1076, 40g antioxidant 168, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
21.2主抗氧剂选用抗氧剂1098，20g抗氧剂1098与40g抗氧剂168、11.25g 硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；21.2 Select antioxidant 1098, 20g antioxidant 1098 and 40g antioxidant 168, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
21.3主抗氧剂选用抗氧剂5057，20g抗氧剂5057与40g抗氧剂168、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；21.3 Select antioxidant 5057, 20g antioxidant 5057, 40g antioxidant 168, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
21.4主抗氧剂选用抗氧剂405，20g抗氧剂405与40g抗氧剂168、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配。21.4 The main antioxidant selected antioxidant 405, 20g antioxidant 405 and 40g antioxidant 168, 11.25g calcium stearate, 3.60g phthalocyanine blue, 0.15g ultramarine blue.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表5所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 5 below:
Figure PCTCN2019128319-appb-000001
Figure PCTCN2019128319-appb-000001
筛选实施例22Screening Example 22
本筛选实施例中的所有步骤与筛选实施例2中的所有步骤相同，不同在于，选用不同的辅助抗氧剂与主抗氧剂1010、硬脂酸钙、酞青蓝、群青进行复配：All steps in this screening example are the same as all steps in screening example 2, except that different auxiliary antioxidants and main antioxidant 1010, calcium stearate, phthalocyanine blue, and ultramarine blue are selected for compounding:
22.1主抗氧剂选用抗氧剂626，40g抗氧剂626与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；22.1 Select antioxidant 626, 40g antioxidant 626, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
22.2主抗氧剂选用抗氧剂618，40g抗氧剂618与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；22.2 Select antioxidant 618, 40g antioxidant 618, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
22.3主抗氧剂选用抗氧剂626，40g抗氧剂626与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；22.3 Select antioxidant 626, 40g antioxidant 626, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
22.4主抗氧剂选用抗氧剂9228，40g抗氧剂9228与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；22.4 Select antioxidant 9228, 40g antioxidant 9228 and 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue as the main antioxidant;
22.5主抗氧剂选用抗氧剂DLTDP，40g抗氧剂DLTDP与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；22.5 As the main antioxidant, select antioxidant DLTDP, 40g antioxidant DLTDP, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue;
22.6主抗氧剂选用抗氧剂DSTDP，40g抗氧剂抗氧剂DSTDP与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；22.6 Select antioxidant DSTDP as main antioxidant, 40g antioxidant DSTDP and 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, 0.15g ultramarine blue for compounding;
22.7主抗氧剂选用抗氧剂抗氧剂412S，40g抗氧剂抗氧剂412S与20g抗氧剂1010、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配。22.7 The main antioxidant is selected as antioxidant antioxidant 412S, 40g antioxidant antioxidant 412S, 20g antioxidant 1010, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表6所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 6 below:
Figure PCTCN2019128319-appb-000002
Figure PCTCN2019128319-appb-000002
筛选实施例23Screening Example 23
本筛选实施例中的所有步骤与筛选实施例2中的所有步骤相同，不同在于，选用不同的辅助抗氧剂、主抗氧剂与硬脂酸钙、酞青蓝、群青进行复配：All steps in this screening example are the same as those in screening example 2, except that different auxiliary antioxidants, primary antioxidants, calcium stearate, phthalocyanine blue, and ultramarine blue are selected for compounding:
23.1主抗氧剂选用抗氧剂1076、辅助抗氧剂选用抗氧剂618，20g抗氧剂1076与40g抗氧剂618、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；23.1 Select antioxidant 1076 as the main antioxidant and antioxidant 618 as the auxiliary antioxidant, 20g antioxidant 1076 and 40g antioxidant 618, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue. Compound
23.2主抗氧剂选用抗氧剂1098、辅助抗氧剂选用抗氧剂626，20g抗氧剂1098与40g抗氧剂626、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；23.2 Select antioxidant 1098 for main antioxidant, antioxidant 626 for auxiliary antioxidant, 20g antioxidant 1098 and 40g antioxidant 626, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue. Compound
21.3主抗氧剂选用抗氧剂5057、辅助抗氧剂选用抗氧剂DSTDP，20g抗氧剂5057与40g抗氧剂DSTDP、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进行复配；21.3 Use antioxidant 5057 as the main antioxidant and DSTDP as the auxiliary antioxidant, 20g antioxidant 5057 and 40g antioxidant DSTDP, 11.25g calcium stearate, 3.60g phthalocyanine blue, 0.15g ultramarine blue Compound
21.4主抗氧剂选用抗氧剂405、辅助抗氧剂选用抗氧剂DLTDP，20g抗氧剂405与40g抗氧剂DLTDP、11.25g硬脂酸钙、3.60g酞青蓝、0.15g群青进 行复配。21.4 Use antioxidant 405 as the main antioxidant and DLTDP as the auxiliary antioxidant, 20g antioxidant 405 and 40g antioxidant DLTDP, 11.25g calcium stearate, 3.60g phthalocyanine blue, and 0.15g ultramarine blue. Compound.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表7所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 7 below:
Figure PCTCN2019128319-appb-000003
Figure PCTCN2019128319-appb-000003
筛选实施例24Screening Example 24
本筛选实施例中的所有步骤与筛选实施例2中的所有步骤相同，不同在于，选用不同的有机颜料与抗氧剂1010与抗氧剂168、硬脂酸钙群青进行复配：All steps in this screening example are the same as all steps in screening example 2, except that different organic pigments and antioxidant 1010, antioxidant 168, and calcium stearate ultramarine are used for compounding:
24.1有机颜料选用透明紫B，3.60g透明紫B与20g抗氧剂1010、40g抗氧剂168、11.25g硬脂酸钙、0.15g群青进行复配；24.1 Organic pigments are made of transparent violet B, 3.60g transparent violet B, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine blue;
24.2有机颜料选用还原艳紫RR，3.60g还原艳紫RR与20g抗氧剂1010、40g抗氧剂168、11.25g硬脂酸钙、0.15g群青进行复配；24.2 Organic pigments are made of Vat Violet RR, 3.60g Vat Violet RR, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine;
24.3有机颜料选用透明绿5B，3.60g透明绿5B与20g抗氧剂1010、40g抗氧剂168、11.25g硬脂酸钙、0.15g群青进行复配；24.3 Organic pigments are made of transparent green 5B, 3.60g transparent green 5B, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine blue;
24.4有机颜料选用酞青蓝、透明紫B，3g酞青蓝和0.6g透明紫B与20g抗氧剂1010、40g抗氧剂168、11.25g硬脂酸钙、0.15g群青进行复配；24.4 Organic pigments are made of Phthalocyanine Blue, Transparent Violet B, 3g Phthalocyanine Blue and 0.6g Transparent Violet B, 20g Antioxidant 1010, 40g Antioxidant 168, 11.25g Calcium Stearate, 0.15g Ultramarine;
24.5有机颜料选用酞青蓝、透明绿5B，3g酞青蓝和0.6g透明绿5B与20g抗氧剂1010、40g抗氧剂168、11.25g硬脂酸钙、0.15g群青进行复配。24.5 Organic pigments are made of phthalocyanine blue, transparent green 5B, 3g phthalocyanine blue and 0.6g transparent green 5B, 20g antioxidant 1010, 40g antioxidant 168, 11.25g calcium stearate, and 0.15g ultramarine blue.
经上述实验，取各筛选实施例制备的复合抗氧剂颗粒2g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表8所示：After the above experiment, take 2g of the composite antioxidant particles prepared in each screening example, add them to 1000ml of polypropylene resin emulsion, mix them uniformly, and extrude and granulate the machine at 180～210℃ to obtain improved The yellow index of polypropylene resin particles was tested by HunterLab LabScan XE colorimeter-yellow index meter. The results are shown in Table 8 below:
Figure PCTCN2019128319-appb-000004
Figure PCTCN2019128319-appb-000004
经上表5、表6、表7、表8所述，抗氧剂1010与抗氧剂168、硬脂酸钙、酞青蓝、群青复配制得的复合抗氧剂对聚丙烯树脂老化变黄具有较佳的改善效果，且选用酞青蓝和透明紫B复混有机颜料与抗氧剂1010与抗氧剂168、硬脂酸钙、群青复配制得的复合抗氧剂对聚丙烯树脂老化变黄具有更好的改善效果。As described in Table 5, Table 6, Table 7, and Table 8, the compound antioxidant prepared by antioxidant 1010, antioxidant 168, calcium stearate, phthalocyanine blue, and ultramarine blue has an effect on polypropylene resin aging. Yellow has a better improvement effect, and a composite antioxidant made of phthalocyan blue and transparent violet B compounded organic pigments and antioxidant 1010, antioxidant 168, calcium stearate, and ultramarine blue is used for polypropylene resin Aging yellowing has a better improvement effect.
实施例1Example 1
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将有机颜料为酞青蓝为分别研磨，并用800～900目滤网过滤，得到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigment as phthalocyanine blue separately, and filter with 800-900 mesh filter to obtain organic pigment powder and inorganic pigment powder for use;
(2)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture liquid I;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的3.75g酞青蓝粉末，超声时间为2～3min，分散均匀，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 3.75g phthalocyanine blue powder, ultrasonic time is 2~3min, and the dispersion is uniform, and a composite antioxidant emulsion is obtained;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
实施例2Example 2
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将有机颜料为酞青蓝、透明紫B为分别研磨，并用800～900目滤网过滤，得到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigments as Phthalocyanine Blue and Transparent Violet B respectively, and filter them with a 800-900 mesh filter to obtain organic pigment powder and inorganic pigment powder for use;
(2)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture liquid I;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的1.9g酞青蓝粉末、1.85g透明紫B，超声时间为2～3min，分散均匀，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 1.9g phthalocyanine blue powder, 1.85g transparent violet B, ultrasonic time is 2~3min, and the dispersion is uniform to obtain a composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
实施例3Example 3
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将有机颜料为酞青蓝、群青为分别研磨，并用800～900目滤网过滤，得到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigments as phthalocyanine blue and ultramarine blue separately, and filter them with a 800-900 mesh filter to obtain organic pigment powder and inorganic pigment powder for use;
(2)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture liquid I;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ 中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g of calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40 minutes, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的3.60g酞青蓝粉末，超声时间为2～3min后加入上述步骤(1)中的0.15g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 3. 60g of phthalocyanine blue powder, sonication time of 2 to 3 minutes, add 0.15g of ultramarine blue powder in the above step (1), continue ultrasonic treatment, uniform dispersion, ultrasonic time of 3 to 4 minutes, to obtain a composite antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
实施例4Example 4
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将有机颜料为酞青蓝、透明紫B、群青为分别研磨，并用800～900目滤网过滤，得到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigments as Phthalocyanine Blue, Transparent Violet B, and Ultramarine Blue separately, and filter them with a 800-900 mesh filter to obtain organic pigment powder and inorganic pigment powder for use;
(2)将称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010 and 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, stirring speed It is 1000～1500r/min to get the composite antioxidant mixture I;
(3)称取11.25g硬脂酸钙，加入上述步骤(2)中的复合抗氧剂混合液Ⅰ中，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Weigh 11.25g calcium stearate, add it to the composite antioxidant mixture I in step (2) above, stir at 230℃ for 30-40min, mix well, lower the temperature to 200℃, and stir for 40 ~50min to obtain the composite antioxidant mixture II;
(4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的1.8g酞青蓝粉末、1.8g透明紫B粉末，超声时间为2～3min后加入上述步骤(1)中的0.15g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and then added to the above step (1) 1.8g phthalocyanine blue powder, 1.8g transparent violet B powder, ultrasonic time is 2~3min, add 0.15g ultramarine blue powder in the above step (1), continue ultrasonic treatment, the dispersion is even, the ultrasonic time is 3~4min, the composite Antioxidant emulsion;
(5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出 造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant pellets.
实施例5Example 5
一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，具体方法如下：A preparation method of a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing. The specific method is as follows:
(1)先将有机颜料为酞青蓝、群青为分别研磨，并用800～900目滤网过滤，得到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigments as phthalocyanine blue and ultramarine blue respectively, and filter them with a 800-900 mesh filter to obtain organic pigment powder and inorganic pigment powder for use;
(2)称取20g抗氧剂1010、40g抗氧剂168混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Weigh 20g antioxidant 1010, 40g antioxidant 168 and mix, heat and stir, gradually increase the temperature to 250℃, then keep it for 30-60min, then lower the temperature to 230℃, stir for 40-50min, the stirring speed is 1000～1500r/min, get the composite antioxidant mixture liquid I;
(3)将上述步骤(2)中的复合抗氧剂混合液Ⅰ在超声波下超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃，加入上述步骤(1)中的3.6g酞青蓝粉末，超声时间为2～3min后加入上述步骤(1)中的0.15g群青粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(3) The composite antioxidant mixture I in the above step (2) is ultrasonically treated under ultrasonic waves, the ultrasonic power is 1000～1200W, the frequency is 20KHz, and the temperature is 190～200℃, and it is added to the above step (1) 3.6 g of phthalocyanine blue powder, sonication time of 2 to 3 minutes, add 0.15 g of ultramarine blue powder in the above step (1), continue ultrasonic treatment, uniform dispersion, ultrasonic time of 3 to 4 minutes, to obtain a composite antioxidant emulsion;
(4)上述步骤(3)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(4) The composite antioxidant emulsion in the above step (3) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
经上述实验，取各实施例1-4制备的复合抗氧剂颗粒2g、实施例5制备的的复合抗氧剂颗粒1.71g，分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒。After the above experiment, take 2g of the composite antioxidant particles prepared in each of Examples 1-4 and 1.71g of the composite antioxidant particles prepared in Example 5, respectively add them to 1000ml of polypropylene resin emulsion, and mix them evenly. It can be extruded and pelletized by injection molding machine at ~210℃ to obtain improved polypropylene resin particles.
对比例1Comparative example 1
具体方法如下：The specific method is as follows:
(1)先分别称取0.53g抗氧剂1010、1.07g抗氧剂168、0.3g硬脂酸钙、0.1g酞青蓝粉末。(1) Weigh 0.53 g of antioxidant 1010, 1.07 g of antioxidant 168, 0.3 g of calcium stearate, and 0.1 g of phthalocyanine powder.
(2)先将上述称取的抗氧剂1010、抗氧剂168、硬脂酸钙分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，再加入上述称取的酞青蓝粉末，混合均匀。(2) First add the weighed antioxidant 1010, antioxidant 168, and calcium stearate to 1000ml of polypropylene resin emulsion, mix well, then add the phthalocyanine blue powder weighed above, and mix well .
(3)在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒。(3) Injection molding and extrusion granulation at 180-210°C to obtain improved polypropylene resin particles.
对比例2Comparative example 2
具体方法如下：The specific method is as follows:
(1)先分别称取0.53g抗氧剂1010、1.07g抗氧剂168、0.3g硬脂酸钙、0.05g酞青蓝粉末、0.05透明紫B粉末。(1) Firstly, weigh 0.53g antioxidant 1010, 1.07g antioxidant 168, 0.3g calcium stearate, 0.05g phthalocyanine blue powder, and 0.05 transparent violet B powder.
(2)先将上述称取的抗氧剂1010、抗氧剂168、硬脂酸钙分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，再加入上述称取的酞青蓝粉末、透明紫B粉末，混合均匀。(2) First add the weighed antioxidant 1010, antioxidant 168, and calcium stearate to 1000 ml of polypropylene resin emulsion, mix well, and then add the weighed phthalocyanine blue powder and transparent violet B powder, mix well.
(3)在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒。(3) Injection molding and extrusion granulation at 180-210°C to obtain improved polypropylene resin particles.
对比例3Comparative example 3
具体方法如下：The specific method is as follows:
(1)先分别称取0.53g抗氧剂1010、1.07g抗氧剂168、0.3g硬脂酸钙、0.096g酞青蓝粉末、0.004g群青粉末。(1) Firstly, weigh 0.53 g of antioxidant 1010, 1.07 g of antioxidant 168, 0.3 g of calcium stearate, 0.096 g of phthalocyanine blue powder, and 0.004 g of ultramarine blue powder.
(2)先将上述称取的抗氧剂1010、抗氧剂168、硬脂酸钙分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，再加入上述称取的酞青蓝粉末，混合均匀，再加入上述称取的群青粉末，混合均匀。(2) First add the weighed antioxidant 1010, antioxidant 168, and calcium stearate to 1000ml of polypropylene resin emulsion, mix well, then add the phthalocyanine blue powder weighed above, and mix well , Then add the weighed ultramarine powder and mix well.
(3)在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒。(3) Injection molding and extrusion granulation at 180-210°C to obtain improved polypropylene resin particles.
对比例4Comparative example 4
具体方法如下：The specific method is as follows:
(1)先分别称取0.53g抗氧剂1010、1.07g抗氧剂168、0.48g硬脂酸钙、0.048g酞青蓝粉末、0.048g透明紫B粉末、0.004g群青粉末。(1) Weigh 0.53g antioxidant 1010, 1.07g antioxidant 168, 0.48g calcium stearate, 0.048g phthalocyanine blue powder, 0.048g transparent violet B powder, and 0.004g ultramarine blue powder.
(2)先将上述称取的抗氧剂1010、抗氧剂168、硬脂酸钙分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，再加入上述称取的酞青蓝粉末、透明紫B粉末，混合均匀，再加入上述称取的群青粉末，混合均匀。(2) First add the weighed antioxidant 1010, antioxidant 168, and calcium stearate to 1000 ml of polypropylene resin emulsion, mix well, and then add the weighed phthalocyanine blue powder and transparent violet B powder, mix well, then add the ultramarine blue powder weighed above and mix well.
(3)在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒。(3) Injection molding and extrusion granulation at 180-210°C to obtain improved polypropylene resin particles.
对比例5Comparative example 5
具体方法如下：The specific method is as follows:
(1)先分别称取0.53g抗氧剂1010、1.07g抗氧剂168、0.096g酞青蓝粉末、0.004群青粉末。(1) Weigh 0.53 g of antioxidant 1010, 1.07 g of antioxidant 168, 0.096 g of phthalocyanine blue powder, and 0.004 ultramarine blue powder.
(2)先将上述称取的抗氧剂1010、抗氧剂168分别添加到1000ml的聚丙烯树脂乳液中，混合均匀，再加入上述称取的酞青蓝粉末，混合均匀，再加入上述称取的群青粉末，混合均匀。(2) First add the weighed antioxidant 1010 and antioxidant 168 to a 1000ml polypropylene resin emulsion, mix well, then add the weighed phthalocyanine blue powder, mix well, and then add the weighing Take the ultramarine powder and mix well.
(3)在180～210℃下注塑成型出机挤出造粒，得到改善的聚丙烯树脂颗粒。(3) Injection molding and extrusion granulation at 180-210°C to obtain improved polypropylene resin particles.
经上述实验，将用实施例1、实施例2、实施例3、实施例4、实施例5制得的复合抗氧剂来复混聚丙烯树脂得到的改善的聚丙烯树脂颗粒，对比例1、对比例2、对比例3、对比例4、对比例5得到的改善的聚丙烯树脂颗粒，经HunterLab LabScan XE色度仪-黄色指数仪检测其黄色指数，结果如下表9所示：After the above experiment, the composite antioxidants prepared in Example 1, Example 2, Example 3, Example 4, and Example 5 were used to compound the improved polypropylene resin particles obtained by compounding polypropylene resin. Comparative Example 1 The improved polypropylene resin particles obtained in Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5 were tested for their yellowness index by HunterLab LabScan XE colorimeter-yellow index meter, and the results are shown in Table 9 below:
 To 黄色指数Yellow index
空白例Blank example -1.2-1.2
实施例1Example 1 -6.1-6.1
实施例2Example 2 -7.2-7.2
实施例3Example 3 -7.3-7.3
实施例4Example 4 -8.2-8.2
实施例5Example 5 -2.8-2.8
对比例1Comparative example 1 -3.3-3.3
对比例2Comparative example 2 -2.9-2.9
对比例3Comparative example 3 -3.3-3.3
对比例4Comparative example 4 -3.8-3.8
对比例5Comparative example 5 -0.8-0.8
经上表9所述，有机颜料对对聚丙烯树脂的变黄有补色效果，有机颜料与无机颜料协同作用提高了对聚合物的变黄的补色效果较好，添加分散剂硬脂酸钙使颜料分散均匀且稳定，聚合物的老化变黄进一步得到改善，本发明得到的复合抗氧剂对聚丙烯树脂的老化变黄效果和颜色均匀度更佳，聚丙烯树脂颗粒的颜色具有较高的饱和度。As described in Table 9 above, organic pigments have a complementary effect on the yellowing of polypropylene resin. The synergistic effect of organic pigments and inorganic pigments improves the yellowing of polymers. The added dispersant calcium stearate makes The pigment is uniformly dispersed and stable, and the aging and yellowing of the polymer is further improved. The composite antioxidant obtained in the present invention has better aging and yellowing effect on polypropylene resin and better color uniformity, and the color of polypropylene resin particles has higher saturation.
最后应说明的是，以上实施例仅用以说明而非限制本发明的技术方案，尽管参照上述实施例对本发明进行了详细说明，本领域技术人员应当理解，依然 可以对本发明进行修改或者等同替换，而不脱离本发明的精神和范围的任何修改或局部替换，其均应涵盖在本发明的权利要求范围中。Finally, it should be noted that the above embodiments are only used to illustrate rather than limit the technical solutions of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the present invention can still be modified or equivalently replaced. Any modification or partial replacement without departing from the spirit and scope of the present invention shall be covered by the scope of the claims of the present invention.

Claims (7)

  1. 一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，该复合抗氧剂采用主抗氧剂、辅助抗氧剂、分散剂、有机颜料、无机颜料为主原料制备，具体制备方法如下：A method for preparing a composite antioxidant capable of better improving polymer processing and long-term aging and yellowing, characterized in that the composite antioxidant adopts a main antioxidant, an auxiliary antioxidant, a dispersant, an organic pigment, and an inorganic pigment The main raw material is prepared, and the specific preparation method is as follows:
    (1)先将有机颜料、无机颜料分别研磨，并用800～900目滤网过滤，得到有机颜料粉末、无机颜料粉末，备用；(1) Grind the organic pigments and inorganic pigments separately, and filter them with a 800-900 mesh filter to obtain organic pigment powders and inorganic pigment powders for use;
    (2)将主抗氧剂、辅助抗氧剂混合，加热搅拌，逐渐升高温度至250℃，然后保持30～60min，再降低温度至230℃，搅拌40～50min，搅拌速度为1000～1500r/min，得到复合抗氧剂混合液Ⅰ；(2) Mix the main antioxidant and auxiliary antioxidant, heat and stir, gradually increase the temperature to 250°C, then keep it for 30-60 minutes, then lower the temperature to 230°C, stir for 40-50 minutes, and stir at 1000-1500r /min, to obtain the composite antioxidant mixture I;
    (3)接着向上述步骤(2)中的复合抗氧剂混合液Ⅰ中加入分散剂，在温度230℃下搅拌30～40min，混合均匀，降低温度至200℃，搅拌40～50min，得到复合抗氧剂混合液Ⅱ；(3) Then add the dispersant to the composite antioxidant mixture I in the above step (2), stir at 230℃ for 30-40min, mix evenly, reduce the temperature to 200℃, stir for 40-50min to obtain the composite Antioxidant mixture II;
    (4)将上述步骤(3)中的复合抗氧剂混合液Ⅱ在超声波下超声波处理，加入上述步骤(1)中的有机颜料粉末，超声时间为2～3min后加入上述步骤(1)中的无机颜料粉末，继续超声处理，分散均匀，超声时间为3～4min，得到复合抗氧剂乳液；(4) The composite antioxidant mixture II in the above step (3) is ultrasonically treated under ultrasonic waves, and the organic pigment powder in the above step (1) is added to the above step (1) after the ultrasonic time is 2 to 3 minutes Inorganic pigment powder, continue ultrasonic treatment, uniform dispersion, ultrasonic time is 3 to 4 minutes, to obtain composite antioxidant emulsion;
    (5)上述步骤(4)中的复合抗氧剂乳液经双螺杆挤出机挤出造粒，挤出造粒温度为180～200℃，得到复合抗氧剂颗粒。(5) The composite antioxidant emulsion in the above step (4) is extruded and pelletized by a twin-screw extruder, and the extrusion pelletizing temperature is 180-200°C to obtain composite antioxidant particles.
  2. 根据权利要求1所述的一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，所述主抗氧剂为酚类抗氧剂或胺类抗氧剂；辅助抗氧化剂为亚磷酸酯类抗氧剂或硫酯类抗氧剂；所述分散剂为硬脂酸钙或硬脂酸锌；所述有机颜料为酞青蓝、透明紫B、还原艳紫RR、透明绿5B的一种或两种以上的任意比例混合；所述无机颜料为群青。The method for preparing a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing according to claim 1, wherein the primary antioxidant is a phenolic antioxidant or an amine antioxidant The auxiliary antioxidant is a phosphite antioxidant or a thioester antioxidant; the dispersant is calcium stearate or zinc stearate; the organic pigment is phthalocyanine blue, transparent violet B, reduction One or two or more of brilliant purple RR and transparent green 5B are mixed in any ratio; the inorganic pigment is ultramarine blue.
  3. 根据权利要求2所述的一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，所述主抗氧剂为1010抗氧剂；辅助抗氧化剂为168抗氧剂；所述分散剂为硬脂酸钙或硬脂酸锌；所述有机颜料为酞 青蓝和透明紫B的混合物；所述无机颜料为群青。The method for preparing a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing according to claim 2, wherein the primary antioxidant is 1010 antioxidant; the auxiliary antioxidant is 168 Antioxidant; the dispersant is calcium stearate or zinc stearate; the organic pigment is a mixture of phthalocyanine blue and transparent violet B; the inorganic pigment is ultramarine blue.
  4. 根据权利要求3所述的一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，所述原料中主抗氧剂和辅助抗氧剂的总质量占主抗氧剂、辅助抗氧剂、分散剂、有机颜料、无机颜料组成的主原料总质量的75％～90％，所述主抗氧剂、辅助抗氧剂的质量比为1:4～1:0.5。The method for preparing a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing according to claim 3, wherein the total mass of the main antioxidant and auxiliary antioxidant in the raw material accounts for The main antioxidant, auxiliary antioxidant, dispersant, organic pigment, inorganic pigment is composed of 75% to 90% of the total mass of the main raw materials, and the mass ratio of the main antioxidant to auxiliary antioxidant is 1:4 to 1:0.5.
  5. 根据权利要求4所述的一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，所述原料中分散剂的质量占主抗氧剂、辅助抗氧剂、分散剂、有机颜料、无机颜料组成的主原料总质量的8％～20％，其余为有机颜料粉末和无机颜料粉末。The method for preparing a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing according to claim 4, characterized in that the quality of the dispersant in the raw material accounts for the main antioxidant and auxiliary antioxidant. Agent, dispersant, organic pigment and inorganic pigment are composed of 8%-20% of the total mass of the main raw materials, and the rest are organic pigment powder and inorganic pigment powder.
  6. 根据权利要求5所述的一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，所述原料中有机颜料粉末、无机颜料粉末的质量比为17:1～30:1。The method for preparing a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing according to claim 5, wherein the mass ratio of organic pigment powder and inorganic pigment powder in the raw material is 17: 1～30:1.
  7. 根据权利要求6所述的一种具有更好改善聚合物加工及长期老化变黄的复合抗氧剂制备方法，其特征在于，上述步骤(4)中的超声波处理，超声波功率为1000～1200W，频率为20KHz，温度为190～200℃。A method for preparing a composite antioxidant with better improvement in polymer processing and long-term aging and yellowing according to claim 6, characterized in that the ultrasonic treatment in the step (4), the ultrasonic power is 1000-1200W, The frequency is 20KHz and the temperature is 190～200℃.
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