CN113214589A - ASA composition for laser welding and preparation method thereof - Google Patents
ASA composition for laser welding and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to an ASA composition for laser welding and a preparation method thereof, wherein the ASA composition comprises the following raw material components in parts by weight: ASA resin: 80-99 parts of a modifier; reversible crosslinking agent: 1-20 parts; indium tin oxide: 0.1-2 parts; antioxidant: 0.1-1 part; lubricant: 0.1-1 part; the preparation method comprises the steps of mixing ASA resin, reversible cross-linking agent, indium tin oxide, antioxidant and lubricant, and then carrying out melt blending extrusion granulation to obtain the ASA modified ABS resin. According to the invention, the polymer containing furan functional groups and maleimide functional groups is used as a cross-linking agent, and the copolymer A with the side group containing furan functional groups has the same or similar macromolecular chain structure as PMMA, so that the interface bonding strength of an ASA material and a PMMA material is effectively improved, and the purpose of improving the welding strength of a workpiece is achieved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to an ASA composition for laser welding and a preparation method thereof.
Background
ASA resin is a general-purpose thermoplastic engineering plastic, which consists of three monomers of acrylonitrile, acrylic ester and styrene, so that the ASA resin keeps the luster and the processing fluidity of Polystyrene (PS) and has excellent weather resistance, and the acrylonitrile increases the rigidity and the strength and has very excellent comprehensive performance. Therefore, the method is widely applied to the fields of automobiles, electronics, office equipment and the like. In the application of automobile rear tail lamps, heat-resistant grade ASA resin is usually adopted, and is a preferred material for a fog lamp cover plate due to good weather resistance, higher heat resistance and excellent processability. Generally, a fog lamp cover plate is made of heat-resistant ASA material, and a fog lamp shade is made of polymethyl methacrylate (PMMA) material, so that the two are welded and assembled together.
At present, the welding processes mainly adopted by the car lamp comprise ultrasonic welding, hot plate welding, vibration friction welding, laser welding and the like. The laser welding process has the advantages that due to the characteristics of good laser directionality, high energy density, small spot diameter, non-contact welding and the like, a precise, firm and sealed welding line can be obtained, plastics are less decomposed, few chips are generated, welding marks and damages cannot be seen on the welding surface, pollution cannot be caused, and the laser welding process becomes a novel welding technology with huge development potential in the field of vehicle lamp welding in recent years.
The so-called laser welding process, i.e. the plastic part to be welded is divided into two parts, one part is a transparent part and the other part is an absorbing part, the laser passes through the transparent part, the energy is absorbed in the absorbing part in a large amount, the contact surface of the two parts is heated to a molten state, and the two parts are welded together under the action of clamping pressure and thermal expansion. Laser welding mainly achieves the purpose of melting materials by absorbing infrared energy through the materials, but the conventional ASA materials have weak infrared absorption effect, so that higher laser energy and longer welding time are needed. This not only reduces the production efficiency, but also easily causes poor welding of the product. For example, when the laser energy is too low, the welding strength of the product is weak, and when the energy is too high, the material is easily degraded and carbonized, so that the welded product cannot meet the application requirements.
CN 110527259A discloses a fiber-reinforced PBT/ASA alloy material with good weldability and a preparation method thereof, and the material comprises the following specific raw materials: 35-65 parts of PBT resin, 10-30 parts of ASA resin, 3-10 parts of heat conducting agent, 2-8 parts of toughening agent and 10-30 parts of surface modified carbon fiber; the surface modified carbon fiber is carbon fiber treated by an acrylate prepolymer. The surface modified carbon fiber replaces the traditional glass fiber reinforcement. On one hand, the modified carbon fiber surface is covered with the acrylate prepolymer, and can form better mutual adhesion with ASA resin in a matrix, thereby promoting the dispersion distribution condition of the ASA resin and improving the welding fastness and the smoothness of the PBT/ASA alloy material; on the other hand, the modified carbon fiber not only can endow the PBT/ASA material with better mechanical property performance, but also can obviously improve the heat conductivity coefficient of the alloy material after being matched with a small amount of heat-conducting auxiliary agent, which is particularly important for avoiding the poor heat welding phenomenon of the PBT/ASA material.
However, reports about single ASA laser welding are still few, and conventionally, a near-infrared absorbent and PMMA are added to make an ASA composition have a strong absorption capacity in a near-infrared region, so that an effect of improving welding is achieved. In addition, it is necessary to introduce a specific heat-resistant agent to improve heat resistance and melt strength. However, the enhancement of the melt strength deteriorates the processability of the material, and the near infrared absorber is carbon black, aniline black or the like, so that the ASA material is mostly black or dark in color. In fact, the principle of plastic product welding is based on the fact that after the polymer material absorbs energy, interfacial polymer molecular chains rapidly infiltrate, diffuse and entangle, thereby achieving effective welding.
Therefore, the key to improving the welding strength is to increase the energy locally at the interface and to improve the interdiffusion and entanglement of the molecular chains of the two polymers at the interface.
Disclosure of Invention
The invention aims to overcome the defects of poor interface connection performance and poor welding in the welding process of ASA materials in the prior art, and provides an ASA composition for laser welding, which is easy to laser welding process, strong in interface bonding force and high in welding strength.
In order to achieve the purpose, the invention adopts the technical scheme that:
a laser-welded ASA composition comprises the following raw material components in parts by weight:
ASA resin: 80-99 parts of a modifier;
reversible crosslinking agent: 1-20 parts;
indium tin oxide: 0.1-2 parts;
antioxidant: 0.1-1 part;
lubricant: 0.1 to 1 portion.
Preferably, the weight part of the reversible cross-linking agent is 5-20 parts, the addition amount of the reversible cross-linking agent has a large influence on the welding strength of the product, and the addition amount is within the range, so that the welding performance is better.
Further preferably, the weight part of the reversible cross-linking agent is 10-20 parts, the content of the reversible cross-linking agent is too low, and the welding strength is not obviously improved; the cost is improved higher due to the over-high content, and meanwhile, the welding strength is not obviously improved any more.
The molecular weight of the ASA resin is 10-20 ten thousand, the melt index is 5-30 g/10min, and the test condition of the melt index is 10KG at 220 ℃. The ASA molecular weight is more than 20 ten thousand, the melt index is lower than 5g/10min, the injection molding is not facilitated, and the injection molding production efficiency and the yield of products are influenced; the ASA molecular weight is less than 10 ten thousand, the melt index is higher than 30g/10min, and the mechanical property of the ASA is low, which can affect the strength of the product.
The reversible crosslinking agent comprises a copolymer A with a furan functional group on a side group and a copolymer B with a maleimide group on a side group. The invention proposes to add a reversible crosslinking agent into ASA, wherein the reversible crosslinking agent consists of a copolymer A with a furan functional group on a side group and a copolymer B with a maleimide on a side group, and the furan functional group and the maleimide can generate a reverse reaction of cycloaddition in a high-temperature extrusion processing process, so that the processing performance of the ASA composition is not influenced. When the copolymer A with the furan functional group on the side group is welded with materials such as PMMA in a laser mode, the copolymer A with the furan functional group on the side group is the same as or similar to PMMA in structure of a macromolecular chain, compared with ASA resin, the copolymer A with the furan functional group on the side group, which is diffused into a PMMA matrix, has a smaller molecular weight, and can be rapidly infiltrated and diffused into the PMMA matrix. In addition, the reversible cross-linking agent contains maleimide monomers, so that the heat resistance of the ASA material can be effectively improved, a heat-resistant agent does not need to be added, and the aim of widening a laser welding process window can be fulfilled.
The copolymer A is any one or a mixture of a plurality of polymethyl methacrylate with a furan functional group on a side group, a methacrylic acid value-acrylate-styrene copolymer with a furan functional group on a side group, and an ethylene-methyl methacrylate copolymer with a furan functional group on a side group.
The copolymer B is any one or a mixture of more of polystyrene with a lateral group containing maleimide, styrene-maleic anhydride copolymer with a lateral group containing maleimide, styrene-acrylonitrile-maleic anhydride copolymer with a lateral group containing maleimide, styrene-acrylonitrile-acrylic acid copolymer with a lateral group containing maleimide and methyl methacrylate-acrylate-styrene copolymer with a lateral group containing maleimide.
The molar ratio of furan functional groups of the copolymer A to maleimide functional groups of the copolymer B in the reversible crosslinking agent is 1-6: 1. the molar ratio is less than 1, the proportion of reversible addition of rings is too small, and the effect of improving the welding performance cannot be achieved; if the molar ratio is more than 6, the processability and appearance of ASA are affected, and the cost is increased too much, but the effect is not improved significantly.
The indium tin oxide is nano indium tin oxide, and the particle size is 50-200 nm. On the basis of the reversible cross-linking agent, the nano indium tin oxide adopted by the invention has stronger absorption to near infrared light, ensures that a matrix material can efficiently absorb laser energy for welding, and meanwhile, the nano indium tin oxide has lighter color than carbon materials such as graphite and the like, is easy to prepare a welding product with a light color system, and widens the application field of the welding product. Due to the existence of the reversible cross-linking agent, the addition amount of the near infrared absorbent nano indium tin oxide can be properly reduced, so that the material cost can be reduced, the processability of the ASA composition material can be improved, and a workpiece with good surface appearance can be obtained. The particle size of indium tin oxide has an influence on the appearance and welding effect of the product.
The antioxidant is a hindered classified antioxidant or phosphite antioxidant, and comprises one or a combination of more than two of an antioxidant 1010, an antioxidant 1076, an antioxidant 1098, an antioxidant 168 and an antioxidant 618;
the lubricant comprises any one or the combination of more than two of silicone oil, silicone master batch, ethylene distearamide and pentaerythritol stearic acid.
The invention also provides a preparation method of the laser-welded ASA composition, which comprises the following steps:
(1) premixing ASA resin, a reversible cross-linking agent, indium tin oxide, an antioxidant and a lubricant, and controlling the rotating speed of a mixer to be 100-300 r/min and the mixing time to be 5-20 min;
(2) and (2) carrying out melt blending on the mixture obtained in the step (1), extruding and granulating, wherein the melt blending temperature is 210-250 ℃, and carrying out granulation to obtain the laser-welded ASA composition.
The melt blending can be carried out by adopting a double-screw extruder, the rotating speed of a screw is 300-600 r/min, and the vacuum degree is-0.06-0.08 Mpa.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, a polymer containing furan functional groups and maleimide functional groups is used as a cross-linking agent, when the copolymer A with the side group containing the furan functional groups is subjected to laser welding with materials such as PMMA (polymethyl methacrylate), the macromolecular chain structure of the copolymer A is the same as or similar to that of PMMA, the copolymer A has smaller molecular weight compared with ASA resin, the copolymer A can be quickly infiltrated and diffused into a PMMA substrate, and the maleimide functional groups and the furan functional groups perform cycloaddition reaction, so that the interface bonding strength of the ASA material and the PMMA material can be effectively improved, and the purpose of improving the welding strength of a workpiece is achieved.
(2) The ASA composition disclosed by the invention contains a maleimide structure, and a heat-resistant agent is not required to be added additionally, so that the aim of widening a laser welding process window can be achieved.
(3) The color of the carbon materials such as the indium tin oxide is lighter than that of the carbon materials such as graphite, so that a light-color welding product is easy to prepare, the application field of the welding product is widened, and the obtained ASA product has good appearance.
Drawings
FIG. 1 is a graph comparing the welding strength of examples and comparative examples at different welding speeds.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention. The raw materials used in the invention are all commercially available.
Example 1
(1) Adding 99 parts of ASA resin (the melt index is 15g/10min), 1 part of reversible reaction cross-linking agent, 1 part of nano indium tin oxide, 10100.1 parts of antioxidant, 1680.1 parts of antioxidant and 0.1 part of lubricant silicone oil into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is polymethyl methacrylate with a side group containing furan functional groups, a copolymer B is polystyrene with a side group containing maleimide, the molar ratio of the side group furan in the copolymer A to the side group maleimide in the copolymer B is 1:1, the rotating speed of the mixing machine is controlled to be 100r/min, and the mixing time is 5 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 300r/min and the vacuum degree to be-0.06 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 2
A preparation method of a laser welding processable ASA composition comprises the following steps:
(1) adding 80 parts of ASA resin (the melt index is 15g/10min), 20 parts of a reversible reaction cross-linking agent, 0.5 part of nano indium tin oxide, 10760.1 parts of an antioxidant, 6180.1 parts of an antioxidant and 0.1 part of lubricant silicone oil into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is an ethylene-methyl methacrylate copolymer with a furan functional group on a side group, a copolymer B is a styrene-acrylonitrile copolymer with a maleimide on a side group, the molar ratio of the furan on the side group in the copolymer A to the maleimide on the side group in the copolymer B is 2:1, the rotating speed of the mixer is controlled to be 100r/min, and the mixing time is 20 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 600r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 3
(1) Adding 85 parts of ASA resin (the melt index is 25g/10min), 15 parts of a reversible reaction cross-linking agent, 0.4 part of nano indium tin oxide, 10980.2 parts of an antioxidant, 6180.3 parts of an antioxidant and 1 part of lubricant silicone oil into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is an ethylene-methyl methacrylate copolymer and polymethyl methacrylate blend (the mass ratio of the ethylene-methyl methacrylate copolymer to the polymethyl methacrylate is 1:1), a copolymer B is a styrene-acrylonitrile-maleic anhydride copolymer with a side group containing maleimide, the molar ratio of the side group furan in the copolymer A to the side group maleimide in the copolymer B is 3:1, the rotating speed of the mixer is controlled to be 250r/min, and the mixing time is 15 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 500r/min and the vacuum degree to be-0.07 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 4
(1) Adding 90 parts of ASA resin (the melt index is 30g/10min), 10 parts of a reversible reaction cross-linking agent, 0.8 part of nano indium tin oxide, 10100.5 parts of an antioxidant, 6180.5 parts of an antioxidant, 0.5 part of lubricant silicone oil and 0.5 part of silicone master batch into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is a methyl methacrylate-acrylate-styrene copolymer with a furan functional group on a side group, a copolymer B is a styrene-maleic anhydride copolymer with a maleimide on a side group, the molar ratio of the furan on the side group in the copolymer A to the maleimide on the side group in the copolymer B is 6:1, the rotating speed of the mixer is controlled to be 300r/min, and the mixing time is 20 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 550r/min and the vacuum degree to be-0.06 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 5
(1) Adding 90 parts of ASA resin (the melt index is 20g/10min), 10 parts of a reversible reaction cross-linking agent, 2 parts of nano indium tin oxide, 10760.5 parts of antioxidant, 1680.5 part of antioxidant, 0.5 part of lubricant ethylene bis stearamide and 0.2 part of pentaerythritol stearic acid into a mixing stirrer for premixing, wherein the copolymer A in the reversible reaction cross-linking agent is a methyl methacrylate-acrylate-styrene copolymer and polymethyl methacrylate blend (the mass ratio of the methyl methacrylate-acrylate-styrene copolymer to the polymethyl methacrylate is 3: 1) of which the side groups contain furan functional groups, and the copolymer B is a blend of a styrene-acrylonitrile-maleic anhydride copolymer and a styrene-acrylonitrile-acrylic acid copolymer (the blend of the styrene-acrylonitrile-maleic anhydride copolymer and the styrene-acrylonitrile-acrylic acid copolymer) of which the side groups contain maleimide The mass ratio is 1:1), the molar ratio of the furan pendant group in the copolymer A to the maleimide pendant group in the copolymer B is 2:1, the rotating speed of a mixer is controlled to be 150r/min, and the mixing time is 20 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 350r/min and the vacuum degree to be-0.06 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 6
(1) Adding 95 parts of ASA resin (the melt index is 5g/10min), 5 parts of a reversible reaction cross-linking agent, 1.2 parts of nano indium tin oxide, 10760.3 parts of an antioxidant, 6180.5 parts of an antioxidant, 0.5 part of lubricant silicone oil and 0.3 part of pentaerythritol stearic acid into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is a methyl methacrylate-acrylate-styrene copolymer and polymethyl methacrylate blend (the mass ratio of the methyl methacrylate-acrylate-styrene copolymer to the polymethyl methacrylate is 2:1) of which the lateral group contains a furan functional group, and a copolymer B is a blend of a methyl methacrylate-acrylate-styrene copolymer, a styrene-acrylonitrile-maleic anhydride copolymer and a styrene-maleic anhydride copolymer (the methyl methacrylate-acrylate-styrene copolymer, the styrene-maleic anhydride copolymer, the copolymer and the styrene-maleic anhydride copolymer of which the lateral group contains maleimide, The mass ratio of the styrene-acrylonitrile-maleic anhydride copolymer to the styrene-maleic anhydride copolymer is 1:1:2), the molar ratio of the furan pendant group in the copolymer A to the maleimide pendant group in the copolymer B is 4:1, the rotating speed of a mixer is controlled to be 250r/min, and the mixing time is 8 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 450r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 7
(1) Adding 90 parts of ASA resin (the melt index is 20g/10min), 10 parts of a reversible reaction cross-linking agent, 1.5 parts of nano indium tin oxide, 10980.2 parts of an antioxidant, 6180.4 parts of an antioxidant, 0.2 part of lubricant silicone oil and 0.4 part of pentaerythritol stearic acid into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is a methyl methacrylate-acrylate-styrene copolymer, an ethylene-methyl methacrylate copolymer and a polymethyl methacrylate blend (the mass ratio of methyl methacrylate-acrylate-styrene copolymer, ethylene-methyl methacrylate copolymer and polymethyl methacrylate is 1:1: 1) of which the lateral groups contain furan functional groups, a copolymer B is a methyl methacrylate-acrylate-styrene copolymer of which the lateral groups contain maleimide, the molar ratio of the furan side group in the copolymer A to the maleimide side group in the copolymer B is 3:1, the rotating speed of a mixer is controlled to be 100r/min, and the mixing time is 10 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 300r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 8
(1) 93 parts of ASA resin (the melt index is 20g/10min), 7 parts of a reversible reaction cross-linking agent, 0.5 part of nano indium tin oxide, 10980.4 parts of an antioxidant, 6180.2 parts of an antioxidant, 0.3 part of lubricant silicone oil and 0.2 part of ethylene distearamide are added into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is a methyl methacrylate-acrylate-styrene copolymer, an ethylene-methyl methacrylate copolymer and a polymethyl methacrylate blend (the mass ratio of methyl methacrylate-acrylate-styrene copolymer, ethylene-methyl methacrylate copolymer and polymethyl methacrylate is 1: 2:1) of which the lateral groups contain furan functional groups, and a copolymer B is a blend of a methyl methacrylate-acrylate-styrene copolymer and a styrene-maleic anhydride copolymer (methyl methacrylate- The mass ratio of the acrylate-styrene copolymer to the styrene-maleic anhydride copolymer is 2:1), the molar ratio of the furan pendant group in the copolymer A to the maleimide pendant group in the copolymer B is 2:1, the rotating speed of a mixer is controlled to be 200r/min, and the mixing time is 5 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 300r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Example 9
(1) Adding 80 parts of ASA resin (the melt index is 15g/10min), 20 parts of reversible reaction cross-linking agent, 0.5 part of nano indium tin oxide (the average particle diameter is 50nm-100nm), 10760.1 parts of antioxidant, 6180.1 parts of antioxidant and 0.1 part of lubricant silicone oil into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is an ethylene-methyl methacrylate copolymer with a furan functional group on a side group, a copolymer B is a styrene-acrylonitrile copolymer with a maleimide on a side group, the molar ratio of the furan on the side group in the copolymer A to the maleimide on the side group in the copolymer B is 2:1, the rotating speed of the mixer is controlled to be 100r/min, and the mixing time is 20 min;
(2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 600r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the laser-welded processable ASA composition
Example 10
(1) Adding 80 parts of ASA resin (the melt index is 15g/10min), 20 parts of reversible reaction cross-linking agent, 0.5 part of nano indium tin oxide (the average particle diameter is 150nm-200nm), 10760.1 parts of antioxidant, 6180.1 parts of antioxidant and 0.1 part of lubricant silicone oil into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is an ethylene-methyl methacrylate copolymer with a furan functional group on a side group, a copolymer B is a styrene-acrylonitrile copolymer with a maleimide on a side group, the molar ratio of the furan on the side group in the copolymer A to the maleimide on the side group in the copolymer B is 2:1, the rotating speed of the mixer is controlled to be 100r/min, and the mixing time is 20 min;
(2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 600r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the laser-welded processable ASA composition
Comparative example 1
(1) Adding 99 parts of ASA resin (the melt index is 15g/10min), 10100.1 parts of antioxidant, 1680.1 parts of antioxidant and 0.1 part of lubricant silicone oil into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 100r/min and the mixing time to be 5 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 300r/min and the vacuum degree to be-0.06 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Comparative example 2
(1) Adding 99 parts of ASA resin (the melt index is 15g/10min), 1 part of nano indium tin oxide, 10100.1 parts of antioxidant, 1680.1 parts of antioxidant and 0.1 part of lubricant silicone oil into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 100r/min, and mixing for 5 min;
(2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, controlling the extrusion temperature to be 210-250 ℃, the screw rotating speed to be 300r/min and the vacuum degree to be-0.06 MPa, and granulating to obtain the laser-welded easy-to-process ASA composition.
Performance testing
The ASA compositions prepared in each of the comparative examples were injection-molded into 80mm by 10mm by 2mm bars, the injection-molded bars were placed alternately with transparent PMMA bars and irradiated with a semiconductor laser (960nm) having a beam diameter of 2 mm. And comparing the appearance of the welded sample strip by adjusting the laser power and the welding rate. The ASA spline was clamped at one end and the PMMA spline was clamped at the other end by a jig of a universal tester, and the weld strength was evaluated by measuring the tensile shear strength, which is the tensile strength/(width of weld seam x length of weld seam), and the test results are shown in table 1 and fig. 1.
TABLE 1 examples and comparative examples ASA compositions with PMMA weld
As can be seen from the above table and fig. 1, the welding strength is significantly improved after the reversible reaction cross-linking agent is added, so that the purpose of widening the processing window of the laser welding process is achieved, and meanwhile, the production efficiency is improved on the premise of ensuring the welding strength.
Claims (10)
1. The laser-welded ASA composition is characterized by comprising the following raw material components in parts by weight:
ASA resin: 80-99 parts of a modifier;
reversible crosslinking agent: 1-20 parts;
indium tin oxide: 0.1-2 parts;
antioxidant: 0.1-1 part;
lubricant: 0.1 to 1 portion.
2. The laser-welded ASA composition of claim 1, wherein the reversible crosslinker is present in an amount of 5 to 20 parts by weight.
3. The laser-welded ASA composition of claim 1, wherein the ASA resin has a molecular weight of 10 to 20 ten thousand and a melt index of 5 to 30g/10 min.
4. The laser-welded ASA composition of claim 1, wherein the reversible crosslinker comprises a copolymer A having pendent furan functional groups and a copolymer B having pendent maleimide functional groups.
5. The laser-welded ASA composition of claim 4 wherein the copolymer A is a mixture of any one or more of poly (methyl methacrylate) with pendant furan functional groups, methacrylic acid value-acrylate-styrene copolymer with pendant furan functional groups, ethylene-methyl methacrylate copolymer with pendant furan functional groups.
6. The laser-welded ASA composition of claim 4 wherein the copolymer B is any one or a mixture of more of a maleimide-containing pendant group polystyrene, a maleimide-containing pendant group styrene-maleic anhydride copolymer, a maleimide-containing pendant group styrene-acrylonitrile-maleic anhydride copolymer, a maleimide-containing pendant group styrene-acrylonitrile-acrylic acid copolymer, and a maleimide-containing pendant group methyl methacrylate-acrylate-styrene copolymer.
7. The laser-welded ASA composition of claim 4, wherein the reversible crosslinker has a molar ratio of furan functional groups of copolymer A to maleimide functional groups of copolymer B of 1 to 6: 1.
8. the laser-welded ASA composition of claim 1, wherein the indium tin oxide is nano indium tin oxide with a particle size of 50-200 nm.
9. The laser-welded ASA composition of claim 1, wherein the antioxidant is a hindered antioxidant or a phosphite antioxidant, comprising any one or a combination of more than two of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, and antioxidant 618;
the lubricant comprises any one or the combination of more than two of silicone oil, silicone master batch, ethylene distearamide and pentaerythritol stearic acid.
10. Process for the preparation of a laser-welded ASA composition according to any one of claims 1 to 9 comprising the steps of:
(1) premixing ASA resin, a reversible cross-linking agent, indium tin oxide, an antioxidant and a lubricant, and controlling the rotating speed of a mixer to be 100-300 r/min and the mixing time to be 5-20 min;
(2) and (2) carrying out melt blending on the mixture obtained in the step (1), extruding and granulating, wherein the melt blending temperature is 210-250 ℃, and carrying out granulation to obtain the laser-welded ASA composition.
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