CN111138797A - ABS composition for improving ultrasonic welding strength and preparation method thereof - Google Patents
ABS composition for improving ultrasonic welding strength and preparation method thereof Download PDFInfo
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- CN111138797A CN111138797A CN201911368094.7A CN201911368094A CN111138797A CN 111138797 A CN111138797 A CN 111138797A CN 201911368094 A CN201911368094 A CN 201911368094A CN 111138797 A CN111138797 A CN 111138797A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
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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 an ABS composition for improving ultrasonic welding strength and a preparation method thereof, wherein the composition comprises the following components in parts by weight: ABS resin: 80-99 parts of a modifier; reversible reactive crosslinking agent: 1-20 parts; antioxidant: 0.1 to 1 portion. The reversible reaction cross-linking agent consists of a copolymer A with a furan functional group on a lateral group and a copolymer B with a maleimide on a lateral group. The preparation method of the ABS composition comprises the following steps: (1) adding ABS resin, a reversible reaction cross-linking agent and an antioxidant into a mixer for premixing; (2) and (2) melting, blending, extruding and granulating the mixture obtained in the step (1) by a double-screw extruder, and granulating to obtain the ABS composition with improved ultrasonic welding strength. Compared with the prior art, the ABS composition provided by the invention can obviously improve the welding strength with PMMA products after the reversible reaction cross-linking agent is added, and can achieve the purpose of improving the welding efficiency.
Description
Technical Field
The invention relates to the field of polymer modified materials, in particular to an ABS composition for improving ultrasonic welding strength and a preparation method thereof.
Background
ABS resin is a general-purpose thermoplastic engineering plastic, which is composed of three monomers of acrylonitrile, butadiene and styrene, so that the ABS resin keeps the luster and the processing fluidity of Polystyrene (PS) and has excellent impact toughness, 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. For applications of rear taillights of automobiles, heat-resistant grade ABS resin is generally used, which is a preferred material for rear taillights due to its good toughness, high heat resistance and excellent processability. Generally, the housing of the rear tail lamp is made of heat-resistant ABS material, and the cover of the tail lamp is made of polymethyl methacrylate (PMMA) material, so that the two are welded and assembled together. The welding processes mainly adopted by the current car lamp include hot plate welding, vibration friction welding, ultrasonic welding, laser welding and the like. Among them, the ultrasonic welding process is widely used for welding automobile tail lamps at present due to its advantages of rapidness, flexibility, stable welding process, no need of welding auxiliary agent or protective gas, no generation of harmful gas, and the like.
The working principle of ultrasonic welding is that ultrasonic waves act on a plastic contact surface, ultrasonic energy is transmitted to a welding area through an upper weldment, and local high temperature is generated due to the fact that the welding area, namely the sound resistance of the interface of two welds is large. Meanwhile, because the heat conductivity of the plastic is poor and the plastic cannot diffuse in time, heat is gathered at the welding interface, so that two plastic contact surfaces needing to be welded are quickly melted, and after a certain pressure is applied, the interface is fused by intermolecular infiltration, permeation and entanglement. At present, most of ABS materials which can be used for ultrasonic welding are black, because carbon black components in black materials have strong heat absorption capacity, and other light-color materials have poor heat absorption capacity, the welding surface melting degree of the materials under the same condition is weak, and the welding strength is insufficient. In general, the strength of the weld surface can be improved by increasing the welding time, increasing the ultrasonic oscillation frequency, or the like. However, this causes a decrease in production efficiency and an increase in cost. For example, in the patent "an ABS modified resin suitable for ultrasonic welding and its preparation method (patent No. CN 107312289A)", it is proposed to improve the welding strength between ABS resin and PMMA by adding PMMA-coated mica powder and a compatibilizer. However, the modified ABS resin needs to be added with a high content of mica powder inorganic filler, so that the processing and forming properties of the material are affected. Therefore, the development of an ABS material for improving the ultrasonic welding strength is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ABS composition for improving ultrasonic welding strength and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an ABS composition for improving ultrasonic welding strength comprises the following components in parts by weight:
ABS resin: 80-99 parts of a modifier;
reversible reactive crosslinking agent: 1-20 parts;
antioxidant: 0.1 to 1 portion.
In the above-mentioned ABS composition, the ABS resin composition,
the molecular weight of the ABS resin is 100000-200000, and the melt index is 5-30 g/10 min.
The reversible reaction cross-linking agent consists of a copolymer A with a furan functional group on a lateral group and a copolymer B with a maleimide on a lateral group. The copolymer A is any one or the combination of more than two of polymethyl methacrylate with a furan functional group on a lateral group, methyl methacrylate-butadiene-styrene copolymer with a furan functional group on a lateral group and ethylene-methyl methacrylate copolymer with a furan functional group on a lateral group. The copolymer B is any one or the combination of more than two of polystyrene with lateral group containing maleimide, styrene-maleic anhydride copolymer with lateral group containing maleimide, styrene-acrylonitrile-maleic anhydride copolymer with lateral group containing maleimide, styrene-acrylonitrile-acrylic acid copolymer with lateral group containing maleimide and methyl methacrylate-butadiene-styrene copolymer with lateral group containing maleimide.
The molar ratio of the side group furan in the copolymer A to the side group maleimide in the copolymer B in the reversible reaction cross-linking agent is 1-6: 1.
The antioxidant is a hindered classified antioxidant or phosphite antioxidant, and comprises any one or a combination of more than two of a commercially available antioxidant 1010, an antioxidant 1076, an antioxidant 1098, an antioxidant 168 and an antioxidant 618.
The invention also relates to a preparation method of the ABS composition for improving the ultrasonic welding strength, which comprises the following steps:
(1) adding ABS resin, a reversible reaction cross-linking agent and an antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixing stirrer to be 100-300 r/min and the mixing time to be 5-20 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 300-600 r/min and the vacuum degree to be-0.06-0.08 MPa, and granulating to obtain the ABS composition for improving the ultrasonic welding strength.
Compared with the prior art, the invention has the following beneficial effects:
the reversible reaction cross-linking agent is added into the ABS composition for improving the ultrasonic welding strength, wherein the reversible reaction cross-linking agent consists of the copolymer A with the side group containing the furan functional group and the copolymer B with the side group containing the maleimide. When the ABS/PMMA composite material is welded with materials such as PMMA, the copolymer A with the furan functional group on the side group has the same or similar structure with PMMA due to a macromolecular chain, has smaller molecular weight compared with ABS resin, can be quickly soaked and diffused into a PMMA matrix, and when the interface temperature of the ABS material and the PMMA material is lower, the copolymer A with the furan functional group on the side group diffused into the PMMA matrix can perform cycloaddition reaction with the copolymer B with the maleimide on the side group in the ABS matrix, so that the interface bonding strength of the ABS material and the PMMA material can be effectively improved, and the effect of improving the welding strength of a finished piece is achieved. In addition, the reversible cross-linking agent contains maleimide monomers, so that the heat resistance of the ABS material can be effectively improved, a heat-resistant agent does not need to be added, and the purpose of widening the ultrasonic welding process window can be achieved. Due to the existence of the reversible cross-linking agent, the filler such as carbon black and the like for enhancing the heat absorption capacity can be reduced or not added on the premise of ensuring the welding strength, and the single color system of the ABS material for ultrasonic welding can be improved, so that the application of the ABS material in the interior and exterior trim of the automobile is widened.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Comparative example 1
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) 99 parts of ABS resin (the melt index is 15g/10min), 10100.1 parts of antioxidant and 1680.1 parts of antioxidant are added into a mixing stirrer for premixing, the rotating speed of the mixing stirrer 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 ABS composition.
Example 1
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) adding 99 parts of ABS resin (the melt index is 15g/10min), 1 part of reversible reaction cross-linking agent, 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, wherein a copolymer A in the reversible reaction cross-linking agent is polymethyl methacrylate with a furan functional group on a side group, a copolymer B is polystyrene with a maleimide side group, the molar ratio of the furan side group in the copolymer A to the maleimide side group in the copolymer B is 1:1, the rotating speed of the mixer 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 ABS composition.
Example 2
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) adding 90 parts of ABS resin (the melt index is 15g/10min), 10 parts of reversible reaction cross-linking agent, 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, wherein the copolymer A in the reversible reaction cross-linking agent is polymethyl methacrylate with a furan functional group on a side group, the copolymer B is polystyrene with a maleimide side group, the molar ratio of the furan side group in the copolymer A to the maleimide side group in the copolymer B is 1:1, the rotating speed of the mixer 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 ABS composition.
Example 3
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) adding 80 parts of ABS resin (the melt index is 5g/10min), 20 parts of reversible reaction cross-linking agent, 10760.5 parts of antioxidant and 6180.5 parts of antioxidant into a mixing stirrer for premixing, wherein the copolymer A in the reversible reaction cross-linking agent is a methyl methacrylate-butadiene-styrene copolymer with a furan functional group on a side group, the copolymer B is a styrene-maleic anhydride copolymer with a maleimide on a side group, the molar ratio of furan on the side group in the copolymer A to 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 600r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the ABS composition.
Example 4
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) adding 85 parts of ABS resin (the melt index is 30g/10min), 15 parts of reversible reaction cross-linking agent, 10980.4 parts of antioxidant and 6180.6 parts of antioxidant into a mixing stirrer for premixing, wherein the copolymer A in the reversible reaction cross-linking agent is an ethylene-methyl methacrylate copolymer with a furan functional group on a side group, the 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 3:1, the rotating speed of the mixer is controlled to be 200r/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 500r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the ABS composition.
Example 5
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) adding 85 parts of ABS resin (the melt index is 8g/10min), 15 parts of reversible cross-linking agent, 10980.2 parts of antioxidant and 1680.4 parts of antioxidant into a mixing stirrer for premixing, wherein the copolymer A in the reversible cross-linking agent is a blend of polymethyl methacrylate containing furan functional groups on lateral groups and ethylene-methyl methacrylate copolymer containing furan functional groups on lateral groups (the mass ratio of the polymethyl methacrylate to the ethylene-methyl methacrylate copolymer is 2:1), the copolymer B is a blend of styrene-acrylonitrile copolymer containing maleimide on lateral groups and styrene-acrylonitrile-maleic anhydride copolymer containing maleimide on lateral groups (the mass ratio of the styrene-acrylonitrile copolymer to the styrene-acrylonitrile-maleic anhydride copolymer is 1:1), the molar ratio of the furan side group in the copolymer A to the maleimide side 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 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 ABS composition.
Example 6
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) adding 90 parts of ABS resin (the melt index is 22g/10min), 10 parts of a reversible reaction crosslinking agent, 10100.2 parts of an antioxidant and 1680.4 parts of an antioxidant into a mixing stirrer for premixing, wherein the copolymer A in the reversible reaction crosslinking agent is a blend of polymethyl methacrylate containing a furan functional group on a side group and a methyl methacrylate-butadiene-styrene copolymer containing a furan functional group on a side group (the mass ratio of the polymethyl methacrylate to the methyl methacrylate-butadiene-styrene copolymer is 1:1), the copolymer B is a blend of a styrene-acrylonitrile-acrylic copolymer containing maleimide on a side group and a methyl methacrylate-butadiene-styrene copolymer containing maleimide on a side group (the mass ratio of the styrene-acrylonitrile-acrylic copolymer to the methyl methacrylate-butadiene-styrene copolymer is 1:1), 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 300r/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 500r/min and the vacuum degree to be-0.07 MPa, and granulating to obtain the ABS composition.
Example 7
An ABS composition for improving ultrasonic welding strength and a preparation method thereof comprise the following steps:
(1) 95 parts of ABS resin (the melt index is 15g/10min), 5 parts of a reversible reaction crosslinking agent, 10100.4 parts of an antioxidant and 6180.4 parts of an antioxidant are added into a mixing stirrer for premixing, wherein the copolymer A in the reversible reaction crosslinking agent is a blend of polymethyl methacrylate with a furan functional group on a side group, a methyl methacrylate-butadiene-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 mass ratio of the polymethyl methacrylate, the methyl methacrylate-butadiene-styrene copolymer and the ethylene-methyl methacrylate copolymer is 1:2:1), and the copolymer B is a styrene-acrylonitrile-acrylic acid copolymer with a maleimide group on a side group, a methyl methacrylate-butadiene-styrene copolymer with a maleimide group on a side group and a polystyrene with a maleimide group on a side group The ethylene blend (the mass ratio of styrene-acrylonitrile-acrylic acid copolymer, methyl methacrylate-butadiene-styrene copolymer and polystyrene is 2:1:1), the molar ratio of the side group furan in the copolymer A to the side group maleimide in the copolymer B is 5:1, the rotating speed of a mixer is controlled to be 300r/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 450r/min and the vacuum degree to be-0.08 MPa, and granulating to obtain the ABS composition.
Comparative and example strips of 80mm by 10mm by 2mm were injection molded, the injection molded strips were interleaved with clear PMMA strips and welded using an ultrasonic instrument. And comparing the interface strength of the welded sample strips by adjusting the welding time. And clamping an ABS sample strip by using one end of a clamp of the universal testing machine, clamping a PMMA sample strip by using one end of the clamp, and representing the welding strength by using the maximum tensile force of a pull-off force experiment.
As can be seen from the above table, the addition of the reversible reaction crosslinking agent can significantly improve the welding strength of the product, and thus the welding time can be reduced and the welding efficiency can be improved on the premise of ensuring the welding strength. The invention proves that the invention is an effective method for preparing the ABS composition for improving the ultrasonic welding strength.
Claims (8)
1. An ABS composition for improving ultrasonic welding strength is characterized in that: the paint comprises the following components in parts by weight:
ABS resin: 80-99 parts of a modifier;
reversible reactive crosslinking agent: 1-20 parts;
antioxidant: 0.1 to 1 portion.
2. The ABS composition for improving ultrasonic welding strength according to claim 1, wherein: the molecular weight of the ABS resin is 100000-200000, and the melt index is 5-30 g/10 min.
3. The ABS composition for improving ultrasonic welding strength according to claim 1, wherein: the reversible reaction cross-linking agent consists of a copolymer A with a furan functional group on a lateral group and a copolymer B with a maleimide on a lateral group.
4. The ABS composition for improving ultrasonic welding strength according to claim 3, wherein: the copolymer A is any one or the combination of more than two of polymethyl methacrylate with a side group containing a furan functional group, methyl methacrylate-butadiene-styrene copolymer with a side group containing a furan functional group and ethylene-methyl methacrylate copolymer with a side group containing a furan functional group.
5. The ABS composition for improving ultrasonic welding strength according to claim 3, wherein: the copolymer B is any one or the combination of more than two of polystyrene with lateral group containing maleimide, styrene-maleic anhydride copolymer with lateral group containing maleimide, styrene-acrylonitrile-maleic anhydride copolymer with lateral group containing maleimide, styrene-acrylonitrile-acrylic acid copolymer with lateral group containing maleimide and methyl methacrylate-butadiene-styrene copolymer with lateral group containing maleimide.
6. The ABS composition for improving ultrasonic welding strength according to claim 3, wherein: the molar ratio of the side group furan in the copolymer A to the side group maleimide in the copolymer B in the reversible reaction cross-linking agent is 1-6: 1.
7. The ABS composition for improving ultrasonic welding strength according to claim 1, wherein: the antioxidant is a hindered classified antioxidant or phosphite antioxidant, and comprises any one or a combination of more than two of a commercially available antioxidant 1010, an antioxidant 1076, an antioxidant 1098, an antioxidant 168 and an antioxidant 618.
8. The method for preparing an ABS composition with improved ultrasonic welding strength according to any of claims 1-7, characterized by comprising the steps of:
(1) adding ABS resin, a reversible reaction cross-linking agent and an antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixing stirrer to be 100-300 r/min and the mixing time to be 5-20 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 300-600 r/min and the vacuum degree to be-0.06-0.08 MPa, and granulating to obtain the ABS composition for improving the ultrasonic welding strength.
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