CN111410832B - Composition with high anti-aging paint adhesion performance and preparation method thereof - Google Patents
Composition with high anti-aging paint adhesion performance and preparation method thereof Download PDFInfo
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- CN111410832B CN111410832B CN202010259289.4A CN202010259289A CN111410832B CN 111410832 B CN111410832 B CN 111410832B CN 202010259289 A CN202010259289 A CN 202010259289A CN 111410832 B CN111410832 B CN 111410832B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a composition with high anti-aging paint adhesion performance and a preparation method thereof, wherein the composition is prepared from 46-76% of polycarbonate, 15-25% of polyethylene terephthalate, 5-15% of acrylonitrile-styrene-acrylate graft copolymer, 2-6% of styrene maleic anhydride copolymer, 1-5% of modified titanium dioxide and 1-3% of other auxiliary agents, wherein the acrylonitrile-styrene-acrylate graft copolymer is prepared by emulsion polymerization of acrylonitrile, styrene, methyl acrylate and isooctyl acrylate in a specific proportion, the acrylonitrile-styrene-acrylate graft copolymer is blended and modified with the polyethylene terephthalate and the polycarbonate with specific viscosity numbers, and the styrene maleic anhydride copolymer and the modified titanium dioxide are added simultaneously to obtain the composition with good anti-aging performance, particularly good moisture and heat aging resistance and high temperature aging resistance, and high paint adhesion.
Description
Technical Field
The invention belongs to the field of high molecular polymers, and particularly relates to a composition with high anti-aging paint adhesion performance and a preparation method thereof.
Background
Polycarbonate (abbreviated as PC in english) is a high molecular polymer containing carbonate groups in its molecular chain, and is classified into various types such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester groups. Among them, aliphatic and aliphatic-aromatic polycarbonates have limited their use as engineering plastics due to their low mechanical properties.
In order to improve the mechanical property of PC, the PC is usually blended with resin such as PET and the like for modification. However, the PC and PET alloys have poor humidity and heat resistance, and after being placed for a period of time under high temperature and high humidity conditions, the mechanical properties, especially the impact strength, are greatly attenuated, and the PC/PET alloys have poor weather resistance, so that the PC/PET alloys cannot be applied to the fields with high weather resistance requirements such as automobile exterior parts and the like. Meanwhile, in some application fields, the paint spraying is needed to be carried out on the outer surface of the composition, and the paint surface adhesion of the PC/PET is not high.
Disclosure of Invention
The invention aims to provide a composition with high anti-aging paint adhesion performance, good anti-aging performance, particularly good resistance to wet heat aging and high temperature aging, and high paint adhesion.
The invention also provides a preparation method of the composition with high anti-aging paint adhesion performance.
A composition with high anti-aging paint adhesion performance comprises the following components:
a polycarbonate;
polyethylene terephthalate;
acrylonitrile-styrene-acrylate graft copolymers;
styrene maleic anhydride copolymers;
modifying titanium dioxide;
and (3) other auxiliary agents.
Preferably, the composition with high anti-aging paint adhesion performance comprises the following components:
48-74% by weight of polycarbonate;
15-25% by weight of polyethylene terephthalate;
5-15% by weight of an acrylonitrile-styrene-acrylate graft copolymer;
2-6% by weight of a styrene maleic anhydride copolymer;
2-5% by weight of modified titanium dioxide;
1 to 2 weight percent of other auxiliary agents.
More preferably, the composition with high anti-aging paint adhesion performance comprises the following components:
62% by weight of polycarbonate;
18% by weight of polyethylene terephthalate;
11% by weight of an acrylonitrile-styrene-acrylate graft copolymer;
5% by weight of a styrene maleic anhydride copolymer;
3 percent of modified titanium dioxide;
1 percent of other auxiliary agents.
Wherein the polycarbonate has a melt index of (10-22) g/10min, a test method ASTM D1238, and test conditions of 300 ℃ and a load of 1.2 kg.
Wherein the intrinsic viscosity number of the polyethylene terephthalate is 0.80-0.88dl/g, and the test method is GB/T1632.
The acrylonitrile-styrene-acrylate graft copolymer is prepared from acrylonitrile, styrene, methyl acrylate and isooctyl acrylate by an emulsion polymerization method, wherein the weight ratio of the acrylonitrile to the styrene to the methyl acrylate to the isooctyl acrylate is (22-25): (20-23): (32-35): (30-33).
Wherein the styrene maleic anhydride copolymer is prepared by the following method:
weighing styrene and maleic anhydride, wherein the weight ratio of the styrene to the maleic anhydride is (70-80): (20-30), dissolving maleic anhydride in styrene, putting into a reaction kettle, reacting at 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preferably, wherein the styrene maleic anhydride copolymer is prepared by the following method:
weighing styrene and maleic anhydride, wherein the weight ratio of the styrene to the maleic anhydride is 75:25, dissolving maleic anhydride in styrene, putting the mixture into a reaction kettle, reacting the mixture at the temperature of between 120 and 130 ℃ for 12 hours at normal temperature, and extruding the mixture by a double-screw extruder for granulation.
Preferably, the preparation method of the acrylonitrile-styrene-acrylate graft copolymer comprises the following steps:
1) Adding 30-35 parts by weight of ionized water, 0.02-0.03 part by weight of catalyst, 0.06-0.08 part by weight of emulsifier, 0.1-0.015 part by weight of cross-linking agent, 0.06-0.08 part by weight of initiator and 32-35 parts by weight of methyl acrylate into a reactor, heating to 66-68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100-120 parts by weight of deionized water, 0.04-0.05 part by weight of catalyst, 0.1-0.2 part by weight of emulsifier, 0.01-0.02 part by weight of cross-linking agent, 0.03 part by weight of initiator and 30-33 parts by weight of isooctyl acrylate, heating to 65-68 ℃, and reacting for 4-4.5 hours under the protection of nitrogen to obtain latex;
2) Adding 8-10 parts by weight of acrylonitrile and 5-6 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14-15 parts by weight of acrylonitrile, 15-18 parts by weight of styrene, 0.04-0.05 part by weight of emulsifier and 10-15 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Wherein, the emulsifier is one or more of alkyl sulfate, alkyl sulfonate or alkyl benzene sulfonate; preferably sodium lauryl sulfate;
the initiator is one or more of persulfate, organic peroxide, azo compounds and thiosulfate; preferably potassium persulfate;
the cross-linking agent is one of organic peroxide cross-linking agents; preferably diisopropylbenzene hydroperoxide.
The catalyst is selected from one of sodium chloride, potassium chloride or sodium sulfate.
The modified titanium dioxide is prepared by the following method:
taking 1 part by weight of rutile type TiO 2 Adding into 50 weight parts of distilled water, dispersing, stirring, maintaining the temperature at 65-70 ℃, simultaneously dropwise adding 32-35 weight parts of 5wt% barium hydroxide aqueous solution and 20-25 weight parts of 8wt% sodium bicarbonate aqueous solution, aging at 65-70 ℃ for 3 hours after dropwise addingFiltering, drying and crushing to obtain the modified titanium dioxide.
Preferably, the dropping rate of the aqueous barium hydroxide solution is 5 parts by weight/10 min, and the adding rate of the aqueous sodium bicarbonate solution is 8 parts by weight/10 min.
Preferably, the modified titanium dioxide is prepared by the following method:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging at 65-70 ℃ for 3 hours after the dropwise adding is finished, pouring the reaction solution into a Buchner funnel for suction filtration, drying a filter cake in an oven at 80 ℃ for 12 hours after the suction filtration is finished, and finally, carrying out pulverization treatment on the dried powder cake by using a high-speed pulverizer and a pneumatic pulverizer successively to obtain the modified titanium dioxide.
Wherein the other auxiliary agents are antioxidants and/or light stabilizers.
Preferably, the antioxidant is selected from one or more of zinc oxide, pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] or tris (2,4-di-tert-butylphenol) phosphite.
Preferably, the light stabilizer is a hindered amine light stabilizer or benzoate ultraviolet light absorber, preferably 2,2,6,6-tetramethyl-4-piperidine stearate.
The preparation method of the composition with high anti-aging paint adhesion performance comprises the following steps:
weighing 48-74 wt% of polycarbonate, 15-25 wt% of polyethylene terephthalate, 5-15 wt% of acrylonitrile-styrene-acrylate graft copolymer, 2-5 wt% of styrene maleic anhydride copolymer, 1-5 wt% of modified titanium dioxide and 1-2 wt% of other additives, adding into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, granulating and drying to obtain the composition.
Preferably, in the above preparation method, the melting temperature is 220-250 ℃, and the length-diameter ratio of the twin-screw extruder is 40.
Compared with the prior art, the invention is prepared from 48-74 wt% of polycarbonate, 15-25 wt% of polyethylene terephthalate, 5-15 wt% of acrylonitrile-styrene-acrylate graft copolymer, 2-5 wt% of styrene maleic anhydride copolymer, 1-5 wt% of modified titanium dioxide and 1-2 wt% of other auxiliary agents, wherein the acrylonitrile-styrene-acrylate graft copolymer is prepared from (22-25) by weight: (20-23): (32-35): (30-33) the acrylonitrile, the styrene, the methyl acrylate and the isooctyl acrylate are prepared by emulsion polymerization, the acrylonitrile-styrene-acrylate graft copolymer is blended and modified with polyethylene glycol terephthalate and polycarbonate with specific intrinsic viscosity, and the styrene maleic anhydride copolymer and the modified titanium dioxide are added, so that the composition with good ageing resistance, particularly good wet and heat aging resistance and high temperature aging resistance, and high paint adhesion is obtained, and the composition is suitable for being widely applied to materials with high requirements on ageing resistance and paint adhesion.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the technical field better understand the scheme of the present invention.
Examples and comparative example raw material descriptions:
polycarbonate (C): PC resins, available from LG chemistry under the designations 1300-10 and 1300-22, having melt indices of 10g/10min and 22g/10min, respectively (test method ASTM D1238, test conditions 300 ℃, load of 1.2 kg);
polyethylene terephthalate: PET resin purchased from China petrochemical chemical fiber Limited, under the designations BG80 and BG85, with intrinsic viscosity of 0.80dl/g and 0.88dl/g, respectively, and tested by GB/T1632.
Titanium dioxide:
the antioxidant is tris (2,4-di-tert-butylphenol) phosphite ester which is commercially available;
the emulsifier is sodium dodecyl sulfate, and is sold in the market;
the initiator is potassium persulfate which is commercially available;
the crosslinking agent is dicumyl peroxide, and is commercially available.
The catalyst is sodium sulfate and is commercially available.
The remaining material sources are commercially available.
Example 1 and comparative examples 6 to 7
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load is 1.2 kg;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632 1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 8 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 75 parts by weight of styrene and 25 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preparing modified titanium dioxide:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after dropwise adding, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Example 2
Preparing materials:
polycarbonate (C): the melt index is 22g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load of 1.2 kilograms is carried;
polyethylene terephthalate: the intrinsic viscosity is 0.88dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 35 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 30 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 10 parts by weight of acrylonitrile and 6 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 15 parts by weight of acrylonitrile, 15 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 80 parts by weight of styrene and 20 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preparing modified titanium dioxide:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersion, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after dropwise adding is finished, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Example 3
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load is 1.2 kg;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 8 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 70 parts by weight of styrene and 30 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preparing modified titanium dioxide:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after dropwise adding, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Comparative example 1
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load of 1.2 kilograms is carried;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 8 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparing modified titanium dioxide:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after dropwise adding, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Comparative example 2
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load of 1.2 kilograms is carried;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, raising the temperature to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, raising the temperature to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 8 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 75 parts by weight of styrene and 25 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer and antioxidant according to the weight parts shown in table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Comparative example 3
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load is 1.2 kg;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 5 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 8 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 75 parts by weight of styrene and 25 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preparing modified titanium dioxide:
1 part by weight of rutile type TiO 2 Adding into 50 weight parts of distilled water, dispersing, stirring, maintaining the temperature at 65-70 deg.C, and adding dropwise 32 weight parts of 5wt% barium hydroxide aqueous solution and 20 weight parts of 8wt% sodium bicarbonate aqueous solution at a dropping speed of 5 weight partsAnd (3) 10min, wherein the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after the dropwise adding is finished, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Comparative example 4
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load is 1.2 kg;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 15 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 25 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 75 parts by weight of styrene and 25 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preparing modified titanium dioxide:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after dropwise adding, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Comparative example 5
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load of 1.2 kilograms is carried;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of methyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 8 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 70 parts by weight of styrene and 25 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Preparing modified titanium dioxide:
taking 1 part by weight of rutile type TiO 2 Adding the mixture into 50 parts by weight of distilled water for dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, wherein the dropwise adding speed of the barium hydroxide aqueous solution is 5 parts by weight/10 min, the adding speed of the sodium bicarbonate aqueous solution is 8 parts by weight/10 min, aging for 3 hours at 65-70 ℃ after dropwise adding, filtering, drying and crushing to obtain the modified titanium dioxide.
Weighing polycarbonate, polyethylene terephthalate, acrylonitrile-styrene-acrylate graft copolymer, styrene maleic anhydride copolymer, modified titanium dioxide and antioxidant according to the weight parts shown in Table 1, adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, and performing granulation and drying to obtain the composition.
Comparative example 8
Preparing materials:
polycarbonate (C): the melt index is 10g/10min, the detection method is ASTM D1238, the test conditions are 300 ℃, and the load of 1.2 kilograms is carried;
polyethylene terephthalate: the intrinsic viscosity is 0.80dl/g, and the test method is GB/T1632;
preparation of acrylonitrile-styrene-acrylate graft copolymer:
1) Adding 30 parts by weight of ionized water, 0.02 part by weight of catalyst, 0.08 part by weight of emulsifier, 0.1 part by weight of cross-linking agent, 0.08 part by weight of initiator and 32 parts by weight of methyl acrylate into a reactor, heating to 68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100 parts by weight of deionized water, 0.04 part by weight of catalyst, 0.1 part by weight of emulsifier, 0.01 part by weight of cross-linking agent, 0.03 part by weight of initiator and 33 parts by weight of isooctyl acrylate, heating to 65 ℃, and reacting for 4 hours under the protection of nitrogen to obtain latex;
2) Adding 8 parts by weight of acrylonitrile and 5 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14 parts by weight of acrylonitrile, 18 parts by weight of styrene, 0.04 part by weight of emulsifier and 10 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain the acrylonitrile-styrene-acrylate graft copolymer.
Preparation of styrene maleic anhydride copolymer: weighing 75 parts by weight of styrene and 25 parts by weight of maleic anhydride, dissolving the maleic anhydride in the styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating by a double-screw extruder.
Weighing 62 parts by weight of polycarbonate, 18 parts by weight of polyethylene terephthalate, 11 parts by weight of acrylonitrile-styrene-acrylate graft copolymer, 5 parts by weight of styrene maleic anhydride copolymer, 3 parts by weight of titanium dioxide and 1 part by weight of antioxidant, adding into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion at the melting temperature of 220-250 ℃ and the length-diameter ratio of the double-screw extruder of 40, granulating and drying to obtain the composition.
TABLE 1 raw material formulation tables (parts by weight) of examples and comparative examples
The compositions prepared in the examples and comparative examples were subjected to the following performance tests, and the test results are shown in table 2:
paint adhesion: an acrylic paint, available from Guangzhou Enbi paint GmbH, was sprayed onto a 50mm 100mm square plate of the composition injection molded using a hand paint spray gun, and the paint brand was R-255. The coated panels were baked in an oven at 80 ℃ for 0.5 hour. After 24 hours of room temperature standing, an electronic extensometer is used for carrying out a stripping test, the stripping width is 10mm, the stripping length is 50mm, the stripping speed is 1mm/sec, and the coating adhesion is recorded in units: n/mm.
Resistance to wet heat aging: the composition is placed in a constant temperature and humidity cabinet with the temperature of 85 ℃ and the humidity of 85 percent for 500 hours, and the notched impact strength N of a cantilever beam is respectively tested at normal temperature 0 And N 1 The standard is according to ISO 180.
Heat aging resistance: the composition is placed in a heat aging box at 100 ℃ for 1000 hours and then the notched Izod impact strength M of the cantilever beam is respectively tested at normal temperature 0 And M 1 The standard is according to ISO 180.
Color difference change value Δ E: according to SAE J2527 xenon lamp aging test standard, after xenon lamp irradiation for 500 hours, the color difference change value delta E before and after weather resistance of the test material shows that the smaller delta E is, the better the weather resistance is.
TABLE 2 tables for testing the properties of compositions prepared in examples and comparative examples
The data show that compared with the compositions prepared in comparative examples 1 to 8, the compositions prepared in examples 1 to 3 of the present invention have good aging resistance, especially resistance to wet-heat aging and high-temperature aging, and the paint adhesion is significantly improved, so that the composition is suitable for being widely applied to materials with high requirements on aging resistance and paint adhesion.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The composition with high anti-aging paint adhesion performance is characterized by comprising the following components:
48-74% by weight of polycarbonate;
15-25% by weight of polyethylene terephthalate;
5-15% by weight of an acrylonitrile-styrene-acrylate graft copolymer;
2-6% by weight of a styrene maleic anhydride copolymer;
2-5% by weight of modified titanium dioxide;
1-2% by weight of other auxiliary agents;
the preparation method of the acrylonitrile-styrene-acrylate graft copolymer comprises the following steps:
1) Adding 30-35 parts by weight of ionized water, 0.02-0.03 part by weight of catalyst, 0.06-0.08 part by weight of emulsifier, 0.1-0.015 part by weight of cross-linking agent, 0.06-0.08 part by weight of initiator and 32-35 parts by weight of methyl acrylate into a reactor, heating to 66-68 ℃, reacting for 4 hours under the protection of nitrogen, then adding 100-120 parts by weight of deionized water, 0.04-0.05 part by weight of catalyst, 0.1-0.2 part by weight of emulsifier, 0.01-0.02 part by weight of cross-linking agent, 0.03 part by weight of initiator and 30-33 parts by weight of isooctyl acrylate, heating to 65-68 ℃, and reacting for 4-4.5 hours under the protection of nitrogen to obtain latex;
2) Adding 8-10 parts by weight of acrylonitrile and 5-6 parts by weight of styrene into the latex obtained in the step 1), and reacting for 30min at the temperature of 60 ℃ to obtain primary polymerization emulsion;
3) Mixing 14-15 parts by weight of acrylonitrile, 15-18 parts by weight of styrene, 0.04-0.05 part by weight of emulsifier and 10-15 parts by weight of deionized water, and fully stirring and emulsifying to obtain stable emulsion;
4) Dropwise adding the emulsion obtained in the step 3) into the primary polymerization emulsion obtained in the step 2) containing an initiator, controlling the reaction temperature at 65-80 ℃ for reacting for 2 hours, then heating to 83 ℃ for continuing to react for 1 hour to obtain ASA emulsion, cooling, and then coagulating, dehydrating and drying to obtain an acrylonitrile-styrene-acrylate graft copolymer;
the styrene maleic anhydride copolymer is prepared by the following method:
weighing styrene and maleic anhydride, wherein the weight ratio of the styrene to the maleic anhydride is (70-80): (20-30), dissolving maleic anhydride in styrene, putting the styrene into a reaction kettle, reacting at the temperature of 120-130 ℃ for 12 hours at normal temperature, and extruding and granulating the mixture by a double-screw extruder;
the modified titanium dioxide is prepared by the following method:
taking 1 part by weight of rutile type TiO 2 Adding into 50 weight parts of distilled waterAnd dispersing, keeping stirring, keeping the temperature at 65-70 ℃, simultaneously dropwise adding 32 parts by weight of 5wt% barium hydroxide aqueous solution and 20 parts by weight of 8wt% sodium bicarbonate aqueous solution, aging for 3 hours at 65-70 ℃ after dropwise adding, filtering, drying and crushing to obtain the modified titanium dioxide.
2. The composition having high adhesion to anti-aging paints according to claim 1, wherein:
the polycarbonate has a melt index of (10-22) g/10min, a test method ASTM D1238, test conditions 300 ℃ and a load of 1.2 kg.
3. The composition with high anti-aging paint adhesion performance as claimed in claim 1 or 2, wherein:
the intrinsic viscosity of the polyethylene terephthalate is 0.80-0.88dl/g, and the test method is GB/T1632.
4. The composition with high anti-aging paint adhesion performance as claimed in claim 1 or 2, wherein:
the other auxiliary agents are antioxidants and/or light stabilizers.
5. A method for preparing a composition with high anti-aging paint adhesion performance according to any one of claims 1 to 4, which is characterized by comprising the following steps:
weighing 48-74 wt% of polycarbonate, 15-25 wt% of polyethylene terephthalate, 5-15 wt% of acrylonitrile-styrene-acrylate graft copolymer, 2-6 wt% of styrene maleic anhydride copolymer, 2-5 wt% of modified titanium dioxide and 1-2 wt% of other auxiliary agents, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, granulating and drying to obtain the composition.
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