CN114231000A - Environment-friendly flame-retardant weather-resistant ABS/PC composite material and preparation method thereof - Google Patents
Environment-friendly flame-retardant weather-resistant ABS/PC composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly flame-retardant weather-resistant ABS/PC composite material which is characterized by comprising the following components in parts by weight: 55-65 parts of PC resin, 20-35 parts of ABS resin, 5-8 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 8-12 parts of functional copolymer, 3-6 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.6-1.0 part of click reaction initiator, 0.2-1.0 part of antioxidant, 0.1-0.6 part of lubricant and 0.2-0.4 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals. The invention also discloses a preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material. The environment-friendly flame-retardant weather-resistant ABS/PC composite material disclosed by the invention is excellent in mechanical property, remarkable in flame-retardant weather-resistant effect, safe and environment-friendly in use and preparation processes, good in performance stability and long in service life.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an environment-friendly flame-retardant weather-resistant ABS/PC composite material and a preparation method thereof.
Background
The ABS/PC alloy is a mixture of acrylonitrile-butadiene-styrene copolymer and polycarbonate, and the material has good formability, excellent low-temperature impact resistance, higher thermal deformation temperature and light stability, and can be widely applied to the manufacturing industries of automobiles, electronics, office equipment and the like. With the further expansion of the application range, the market demand of ABS/PC alloy materials is larger and larger, and people have higher and higher requirements on the performance of the ABS/PC alloy materials.
The traditional ABS/PC alloy has poor toughness and mechanical property, poor environmental protection property, flame retardance and weather resistance due to the compatibility problem among polymers, is easy to break under the attack of ultraviolet rays, and is easy to cause great reduction of mechanical strength, yellowing and cracking phenomena after long-term use, especially after long-term exposure to the outdoors. In order to improve the performance, the prior art usually adds a large amount of functional additives to the base material, however, the addition of a large amount of functional additives causes poor processing fluidity and insufficient toughness, and the functional additives are easy to bleed out from the base material due to compatibility problems during long-term use, resulting in poor performance stability.
For example, chinese invention patent CN101173090B discloses a PC/ABS alloy, which mainly comprises the following components, expressed in parts by weight: 54-76 parts of Polycarbonate (PC), 7-14 parts of acrylonitrile-butadiene-styrene copolymer (ABS), 2-5 parts of compatilizer, 3-8 parts of flexibilizer, 10-18 parts of phosphate flame retardant, 1-2 parts of magnesium hydroxide, 0.2-0.5 part of polytetrafluoroethylene and 0.1-0.3 part of antioxidant. According to the halogen-free flame-retardant PC/ABS alloy provided by the invention, the phosphate flame retardant is adopted to carry out flame-retardant modification on the PC/ABS alloy, so that the flame-retardant property of the PC/ABS alloy is improved, and the processing fluidity of the PC/ABS is also greatly improved. However, the problem of low mechanical property still exists, and the addition of the phosphate flame retardant inevitably reduces the toughness of the material; the addition of magnesium hydroxide-based inorganic particles may also cause an extravasation phenomenon during long-term use due to compatibility problems.
Therefore, the problem to be solved by researchers in the industry at present is how to provide an environment-friendly flame-retardant weather-resistant ABS/PC composite material with excellent mechanical property, obvious flame-retardant weather-resistant effect, safe and environment-friendly use and preparation processes, good performance stability and long service life.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the environment-friendly flame-retardant weather-resistant ABS/PC composite material which has excellent mechanical property, obvious flame-retardant weather-resistant effect, safe and environment-friendly use and preparation processes, good performance stability and long service life.
The technical scheme adopted by the invention for solving the technical problem is as follows: the environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 55-65 parts of PC resin, 20-35 parts of ABS resin, 5-8 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 8-12 parts of functional copolymer, 3-6 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.6-1.0 part of click reaction initiator, 0.2-1.0 part of antioxidant, 0.1-0.6 part of lubricant and 0.2-0.4 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
Preferably, the lubricant is at least one of pentaerythritol stearate and N, N' -ethylene bis stearamide.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076 and antioxidant 3114.
Preferably, the click reaction initiator is at least one of tert-butyl peroxide and tert-amyl peroxide.
Preferably, the preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 70-80 ℃ in an inert gas atmosphere, then precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally removing the ethanol by rotary evaporation to obtain the functional copolymer.
Preferably, the mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the initiator to the high-boiling point solvent is 1 (2-3): 0.3-0.7): 1-2): 0.05-0.08: 25-35.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the source of the hyperbranched polycarbonate with terminal hydroxyl groups is not particularly required, and in one embodiment of the present invention, the hyperbranched polycarbonate with terminal hydroxyl groups is prepared by the method of the synthesis example 3 in the Chinese patent CN 102421822A.
Preferably, the PC resin is S-2000F of Mitsubishi engineering plastics; the ABS resin is AT-08 of Japan A & L company;
the invention also aims to provide a preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material, which is characterized by comprising the following steps: the components are uniformly mixed according to the weight part content, and then added into a double-screw extruder for melt extrusion molding, so as to obtain the environment-friendly flame-retardant weather-resistant ABS/PC composite material.
Preferably, the temperature of the twin-screw extruder is: the first zone is 190-.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material provided by the invention adopts conventional equipment and a production line, does not need special equipment, has the advantages of simple process, convenience in operation, safe and environment-friendly preparation process and high preparation efficiency and yield, and is suitable for large-scale production and application.
(2) According to the environment-friendly flame-retardant weather-resistant ABS/PC composite material provided by the invention, through the mutual cooperation and combined action of the components, the finally prepared product not only combines the advantages of PC resin and ABS resin, but also obtains better mechanical properties and more remarkable flame-retardant weather-resistant effect, and in addition, the prepared product is safe and environment-friendly in use, good in performance stability and long in service life.
(3) The hyperbranched polycarbonate with terminal hydroxyl groups has a similar structure with PC resin, and has good compatibility, the terminal hydroxyl groups can react with carboxyl groups on a functional copolymer under the catalysis of titanium tetra-n-butoxide, and the bicyclo [2.2.1] hept-2-ene structure on the functional copolymer and partially unsaturated olefinic bonds on the molecular structure of the ABS resin can both have click reaction with sulfydryl groups on pentaerythritol tetra (3-mercaptopropionate), so that the compatibility among the components is enhanced, an organic unified whole is formed, an interpenetrating network structure is constructed, the physical properties of the composite material can be effectively improved, and the defects of poor mechanical properties and durability caused by the compatibility problem of the PC resin and the ABS resin are overcome. Meanwhile, through click reaction, the amount of unsaturated bonds on the molecular chain of the ABS resin can be reduced to a certain extent, and the weather resistance and the oxidation resistance of the ABS resin are improved; the introduction of the hyperbranched polycarbonate structure can compensate the compatibility and toughness among all the components of the material and improve the shock resistance of the material.
(4) The functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxo isoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals. Through copolymerization, a trifluoromethyl quinoline structure, benzotriazole structure and oxo-isoindoline structure are simultaneously introduced into a polymer molecular chain and are mutually matched under the multiple actions of an electronic effect, a steric effect and a conjugated effect, so that the flame retardance and the weather resistance of the prepared material are obviously improved; the addition of a flame retardant and a weather resisting agent is not required, and the defects of processing fluidity and performance stability reduction caused by the addition of the additives are effectively avoided.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention; the hyperbranched polycarbonate with terminal hydroxyl groups in the examples is hyperbranched polycarbonate core A.3 with terminal hydroxyl groups, which is prepared by the method of synthesizing hyperbranched polycarbonate core A.3 with terminal hydroxyl groups in example 3 in Chinese invention patent CN 102421822A; the PC resin is S-2000F of Mitsubishi engineering plastics; the ABS resin is AT-08 available from Japan A & L.
Example 1
The environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 55 parts of PC resin, 20 parts of ABS resin, 5 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 8 parts of functional copolymer, 3 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester, 0.6 part of click reaction initiator, 0.2 part of antioxidant, 0.1 part of lubricant and 0.2 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
The lubricant is pentaerythritol stearate; the antioxidant is an antioxidant 1010; the click reaction initiator is tert-butyl peroxide.
The preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 3 hours at 70 ℃ in an inert gas atmosphere, then precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally performing rotary evaporation to remove the ethanol to obtain the functional copolymer.
The mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the initiator to the high-boiling point solvent is 1:2:0.3:1:0.05: 25; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following steps of: uniformly mixing the components in parts by weight, adding the mixture into a double-screw extruder, and carrying out melt extrusion molding to obtain an environment-friendly flame-retardant weather-resistant ABS/PC composite material; temperature of the twin-screw extruder: 190 ℃ in the first zone, 205 ℃ in the second zone, 215 ℃ in the third zone, 225 ℃ in the fourth zone, 225 ℃ in the fifth zone, 215 ℃ in the sixth zone and 190r/min of twin-screw rotation speed.
Example 2
The environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 58 parts of PC resin, 25 parts of ABS resin, 6 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 9 parts of functional copolymer, 4 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester, 0.7 part of click reaction initiator, 0.4 part of antioxidant, 0.3 part of lubricant and 0.25 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
The lubricant is N, N' -ethylene bis stearamide; the antioxidant is an antioxidant 1076; the click reaction initiator is tert-amyl peroxide.
The preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 3.5 hours at 73 ℃ in an inert gas atmosphere, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally removing the ethanol by rotary evaporation to obtain the functional copolymer.
The mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the initiator to the high-boiling point solvent is 1:2.2:0.4:1.2:0.06: 28; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following steps of: uniformly mixing the components in parts by weight, adding the mixture into a double-screw extruder, and carrying out melt extrusion molding to obtain an environment-friendly flame-retardant weather-resistant ABS/PC composite material; temperature of the twin-screw extruder: 195 deg.C in the first zone, 208 deg.C in the second zone, 219 deg.C in the third zone, 230 deg.C in the fourth zone, 227 deg.C in the fifth zone, 218 deg.C in the sixth zone, and a twin-screw rotation speed of 210 r/min.
Example 3
The environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 60 parts of PC resin, 29 parts of ABS resin, 6.5 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 10 parts of functional copolymer, 4.5 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.8 part of click reaction initiator, 0.7 part of antioxidant, 0.4 part of lubricant and 0.3 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
The lubricant is pentaerythritol stearate; the antioxidant is an antioxidant 3114; the click reaction initiator is tert-butyl peroxide.
The preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 4 hours at 75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally performing rotary evaporation to remove the ethanol to obtain the functional copolymer.
The mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the initiator to the high-boiling point solvent is 1:2.5:0.5:1.5:0.065: 30; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following steps of: uniformly mixing the components in parts by weight, adding the mixture into a double-screw extruder, and carrying out melt extrusion molding to obtain an environment-friendly flame-retardant weather-resistant ABS/PC composite material; temperature of the twin-screw extruder: the first zone is 200 ℃, the second zone is 210 ℃, the third zone is 220 ℃, the fourth zone is 235 ℃, the fifth zone is 228 ℃, the sixth zone is 220 ℃, and the rotating speed of the double screw is 220 r/min.
Example 4
The environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 63 parts of PC resin, 33 parts of ABS resin, 7.5 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 11 parts of functional copolymer, 5.5 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.9 part of click reaction initiator, 0.9 part of antioxidant, 0.5 part of lubricant and 0.35 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
The lubricant is a mixture formed by mixing pentaerythritol stearate and N, N' -ethylene bis stearamide according to the mass ratio of 3: 5; the antioxidant is a mixture formed by mixing an antioxidant 1010, an antioxidant 1076 and an antioxidant 3114 according to the mass ratio of 1:2: 3; the click reaction initiator is a mixture formed by mixing tert-butyl peroxide and tert-amyl peroxide according to the mass ratio of 2: 1.
The preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 4.5 hours at 78 ℃ in an inert gas atmosphere, then precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally removing the ethanol by rotary evaporation to obtain the functional copolymer.
The mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the initiator to the high-boiling point solvent is 1:2.8:0.6:1.8:0.07: 33; the initiator is a mixture formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 7; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:1:3: 2; the inert gas is argon.
The preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following steps of: uniformly mixing the components in parts by weight, adding the mixture into a double-screw extruder, and carrying out melt extrusion molding to obtain an environment-friendly flame-retardant weather-resistant ABS/PC composite material; temperature of the twin-screw extruder: 203 ℃ in the first zone, 213 ℃ in the second zone, 223 ℃ in the third zone, 242 ℃ in the fourth zone, 229 ℃ in the fifth zone, 223 ℃ in the sixth zone and 240r/min of double screw rotation speed.
Example 5
The environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 65 parts of PC resin, 35 parts of ABS resin, 8 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 12 parts of functional copolymer, 6 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester, 1.0 part of click reaction initiator, 1.0 part of antioxidant, 0.6 part of lubricant and 0.4 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
The lubricant is N, N' -ethylene bis stearamide; the antioxidant is an antioxidant 1076; the click reaction initiator is tert-amyl peroxide.
The preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 5 hours at 80 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally performing rotary evaporation to remove the ethanol to obtain the functional copolymer.
The mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate to the initiator to the high-boiling point solvent is 1:3:0.7:2:0.08: 35; the initiator is azobisisoheptonitrile; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is nitrogen.
The preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following steps of: uniformly mixing the components in parts by weight, adding the mixture into a double-screw extruder, and carrying out melt extrusion molding to obtain an environment-friendly flame-retardant weather-resistant ABS/PC composite material; temperature of the twin-screw extruder: the first zone is 205 ℃, the second zone is 215 ℃, the third zone is 225 ℃, the fourth zone is 245 ℃, the fifth zone is 230 ℃, the sixth zone is 225 ℃ and the rotating speed of the double screw is 250 r/min.
Comparative example 1
The formula and the preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material are basically the same as those of the embodiment 1, except that the hyperbranched polycarbonate with terminal hydroxyl groups is replaced by PC resin.
Comparative example 2
An environment-friendly flame-retardant weather-resistant ABS/PC composite material has the same formula and preparation method as those of example 1, except that 4-vinyl-2, 8-bis (trifluoromethyl) quinoline is not added.
The environmental-friendly flame-retardant weather-resistant ABS/PC composite material samples described in examples 1-5 and comparative examples 1-2 are subjected to performance tests, the test results are shown in Table 1, and the test methods are as follows:
(1) tensile strength: the test was carried out according to ISO 527 standard.
(2) Notched izod impact strength: the test was carried out according to ISO 180 standard.
(3) Flame retardant rating: the test was carried out according to the UL94 standard.
(4) Weather resistance: the weather resistance test is measured by the retention rate of tensile strength after the samples are respectively placed in an environment with 85 ℃ multiplied by 85% RH for 2000 hours, and the larger the value is, the better the weather resistance is.
TABLE 1
As can be seen from Table 1, the environment-friendly flame-retardant weather-resistant ABS/PC composite material disclosed by the embodiment of the invention has excellent mechanical properties, weather resistance and flame retardance, which are the result of the synergistic effect of the components.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The environment-friendly flame-retardant weather-resistant ABS/PC composite material is characterized by comprising the following components in parts by weight: 55-65 parts of PC resin, 20-35 parts of ABS resin, 5-8 parts of hyperbranched polycarbonate with terminal hydroxyl groups, 8-12 parts of functional copolymer, 3-6 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.6-1.0 part of click reaction initiator, 0.2-1.0 part of antioxidant, 0.1-0.6 part of lubricant and 0.2-0.4 part of titanium tetra-n-butoxide; the functional copolymer is prepared by polymerizing 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline and 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate according to free radicals.
2. The environment-friendly flame-retardant weather-resistant ABS/PC composite material as claimed in claim 1, wherein the lubricant is at least one of pentaerythritol stearate and N, N' -ethylene bis stearamide.
3. The environment-friendly flame-retardant weather-resistant ABS/PC composite material as claimed in claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1076 and antioxidant 3114.
4. The environment-friendly flame-retardant weather-resistant ABS/PC composite material according to claim 1, wherein the click reaction initiator is at least one of t-butyl peroxide and t-amyl peroxide.
5. The environment-friendly flame-retardant weather-resistant ABS/PC composite material as claimed in claim 1, wherein the preparation method of the functional copolymer comprises the following steps: adding 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, 5-vinyl bicyclo [2.2.1] hept-2-ene, 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 70-80 ℃ in an inert gas atmosphere, then precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally removing the ethanol by rotary evaporation to obtain the functional copolymer.
6. The environment-friendly flame-retardant weather-resistant ABS/PC composite material as claimed in claim 5, wherein the mass ratio of the 2-allyl-1, 3-dioxoisoindoline-5-carboxylic acid, the 5-vinyl bicyclo [2.2.1] hept-2-ene, the 4-vinyl-2, 8-bis (trifluoromethyl) quinoline, the 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, the initiator and the high boiling point solvent is 1 (2-3): 0.3-0.7): 1 (1-2): 0.05-0.08): 25-35.
7. The environment-friendly flame-retardant weather-resistant ABS/PC composite material as claimed in claim 5, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
8. The environment-friendly flame-retardant weather-resistant ABS/PC composite material according to claim 1, wherein the PC resin is S-2000F of Mitsubishi engineering plastics; the ABS resin is AT-08 available from Japan A & L.
9. The preparation method of the environment-friendly, flame-retardant and weather-resistant ABS/PC composite material according to any one of claims 1-8, characterized by comprising the following steps: the components are uniformly mixed according to the weight part content, and then added into a double-screw extruder for melt extrusion molding, so as to obtain the environment-friendly flame-retardant weather-resistant ABS/PC composite material.
10. The preparation method of the environment-friendly flame-retardant weather-resistant ABS/PC composite material as claimed in claim 9, wherein the temperature of the twin-screw extruder is as follows: the first zone is 190-.
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