CN114316503A - High-heat-resistance modified ABS material strongly bonded with PUR and preparation method thereof - Google Patents
High-heat-resistance modified ABS material strongly bonded with PUR and preparation method thereof Download PDFInfo
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- CN114316503A CN114316503A CN202111644106.1A CN202111644106A CN114316503A CN 114316503 A CN114316503 A CN 114316503A CN 202111644106 A CN202111644106 A CN 202111644106A CN 114316503 A CN114316503 A CN 114316503A
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Abstract
The invention discloses a high heat-resistant ABS material strongly bonded with PUR and a preparation method thereof, wherein the material formula comprises the following components: 65-80 wt% of ABS resin, 10-25 wt% of heat-resistant agent, 3-10% of toughening agent, 0-10% of reactive compatilizer and 0.4% of antioxidant. Compared with the prior art, the MS-NI heat-resistant agent has high glass transition temperature so as to improve heat resistance, and contains imide groups to increase polarity; the introduced MBS toughening agent endows the material with high elasticity, and also improves the surface dyne value and the initial adhesion; the poor compatibility of the reactive compatilizer is intensively distributed on the surface, the active GMA group can form a chemical bond with hydroxyl and amino in the moisture-cured polyurethane, and the strong adhesion effect ensures that the reactive compatilizer has high and low temperature resistance and damp and heat aging resistance, and can be used for automobile interior and exterior trim parts.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to an adhesion modified ABS material and a preparation method thereof, in particular to a high heat-resistant ABS material for polyurethane adhesion and a preparation method thereof
Background
The ABS material has good toughness, high mechanical strength and excellent processability, so the ABS material is widely applied to the fields of electronic and electric appliances, transportation, light industrial products and the like, particularly in the field of automobiles, and the ABS material simultaneously has high heat resistance and high toughness and is applied to important parts such as door panels, stand columns, auxiliary instrument panels and the like. In order to improve the plastic texture of ABS materials, the aesthetic appearance and decoration are often shown by post-treatment methods such as coating, electroplating and spray painting, wherein in the coating process, polar adhesives such as acrylates, epoxies and polyurethanes are often used to match ABS materials with high polarity in order to achieve excellent bonding strength between the materials and the adhesives.
At present, solvent glues such as epoxy glue and the like are commonly adopted for the lamination of the ABS material, leather and flocked cloth, and the solvent molecules are required to be volatilized by baking after the glue is sprayed, so that the environmental pollution is inevitably caused. The hot melt adhesive has a solid content of one hundred percent, can be roll-coated or sprayed on the surfaces of various materials after being heated and melted, can be quickly bonded after being cooled, does not use any solvent in the production and application processes, is convenient to process and operate, is suitable for continuous production, and is most widely applied. The polyurethane hot melt adhesive can be divided into thermoplastic polyurethane hot melt adhesive and reactive polyurethane hot melt adhesive (PUR), wherein the thermoplastic polyurethane hot melt adhesive is cooled and solidified after being heated and melted, and the reactive polyurethane hot melt adhesive is cooled and reacted with moisture to be crosslinked and solidified after being heated and melted. Although the thermoplastic polyurethane hot melt adhesive can be recycled, the bonding strength is not high, the high temperature resistance is poor, and the hot pressing process needs high hot pressing temperature (higher than 100 ℃); the closed polyurethane hot melt adhesive in the reactive hot melt adhesive is only used for maintenance treatment and other applications because the closed polyurethane hot melt adhesive causes bubbles to form on an adhesive layer due to the decomposition of a sealing agent. With the development of technology and equipment, the hidden danger of moisture isolation of the moisture-curing hot melt adhesive in the preparation, transportation and gluing processes is solved, and the moisture-curing hot melt adhesive has the characteristics of high bonding strength, high and low temperature resistance, humidity and heat resistance and the like.
Chinese patent document CN112662085A discloses an ABS material for bonding thermoplastic polyurethane hot melt adhesive and a preparation method thereof, the contact area of the surface is increased by adding pumice into the ABS, the polyurethane component in the formula can effectively promote the bonding effect, and the ABS material is different from the ABS material applied to moisture-curing type hot melt adhesive in the patent and has limited bonding strength in the test; chinese patent document CN104927337B discloses a high PU foam bonding strength PC/ABS material, which is prepared by adding SMA (styrene-maleic anhydride copolymer) into PC/ABS to enhance the bonding strength between the substrate and PU foam, and the added GMA type reactive compatibilizer reacts with the PC terminal hydroxyl group to inhibit aging degradation, and maleic anhydride or maleic amide derivatives are often introduced into high heat resistant ABS to improve heat resistance.
At present, the hot melt adhesive for the ABS material is thermoplastic polyurethane hot melt adhesive, the two are bonded into intermolecular weak interaction force, such as Van der Waals force and hydrogen bond force, the interaction force is easy to damage in high-temperature and high-humidity environments, the high-strength requirement cannot be met, and the required hot-pressing process temperature is high (more than 100 ℃) to influence the dimensional stability of parts. The epoxy group with reactivity is added into the ABS, so that the epoxy group can perform chemical reaction and crosslinking with the moisture-curing hot melt adhesive, and a chemical bond is formed on the interface layers of the ABS and the hot melt adhesive after curing, the bonding force of the chemical bond is far greater than that of a non-bonding effect (weak interaction), the bonding strength is very firm, the high temperature and medium corrosion can be obviously improved, and the epoxy group plays an important role in resisting stress damage and crack propagation.
Disclosure of Invention
The invention designs a high heat-resistant modified ABS material which is strongly bonded with PUR and a preparation method thereof in order to overcome the defects that the bonding of the ABS material and polyurethane in the prior art cannot resist high temperature, high humidity, high temperature, hot pressing and the like.
The purpose of the invention is realized by the following technical scheme.
A high heat-resistant modified ABS material strongly bonded with PUR comprises the following raw materials in percentage by mass: 65-80 wt% of ABS resin, 10-25 wt% of heat-resistant agent, 3-10% of toughening agent, 0-10% of reactive compatilizer and 0.4% of antioxidant.
Wherein the content of the first and second substances,
the ABS resin is prepared by emulsion method, and Qimei PA-727 and Tianjin staphyl DG-417 can be selected;
the heat-resistant agent is a styrene-N-phenylmaleimide-maleic anhydride copolymer, and Japanese electrochemical MS-NI can be selected;
the toughening agent is MBS (methyl methacrylate-butadiene-styrene) polymer, and Japanese Brillouin Kane Ace M-732 can be selected.
The reactive compatibilizer is an ethylene-acrylate-glycidyl ester (GMA) terpolymer, and can be selected from DuPont Elvaloy PTW or Acoma AX 8900.
The antioxidant is prepared from antioxidant 1010 and antioxidant 619F in a mass ratio of 1: 1 and mixing.
The preparation method of the high heat-resistant modified ABS material strongly bonded with the PUR comprises the following steps: preparing raw materials according to the mass ratio, pouring the raw materials into a stirrer for premixing for 10-15min, then pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃, the screw rotating speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator to obtain the modified ABS material.
The invention has the beneficial effects that:
the invention provides a high heat-resistant modified ABS material strongly bonded with PUR and a preparation method thereof, wherein the styrene-N-phenylmaleimide-maleic anhydride copolymer in the formula can improve the heat resistance of the material to over 107 ℃, and imide and anhydride groups can improve the dyne value and form hydrogen bonds with polyurethane; the MBS toughening agent can effectively promote the compatibility of the heat-resistant agent and the ABS base material, make up for the reduction of the toughness of the material, and the contrast test shows that the dyne value and the bonding strength can be more efficiently improved; finally, the ethylene-acrylate-glycidyl ester (GMA) terpolymer with reaction activity used in the invention is concentrated on the surface of the material due to poor compatibility to cause extinction effect, and in the process of bonding and curing of the moisture-curing reaction type polyurethane, an epoxy group and hydroxyl and carboxyl in the polyurethane are subjected to ring-opening reaction to form an interface chemical bond, so that the peel strength of the composite material is further improved. Because of the advantages of high heat resistance, good toughness, strong adhesion and the like, the composite material can be continuously produced and applied to parts such as automobile door plates, stand columns and the like.
Detailed Description
The present invention is illustrated in detail below by means of specific examples, which are only intended to aid the understanding of the present invention, but are not intended to be limiting in any way. It is to be noted that any changes and modifications made without departing from the concept of the present invention are within the protection scope of the present invention.
The ABS in the following examples and comparative examples selected from Qimeiae 8000 and Tianjin staphyl DG-417; the heat-resistant agent is Japanese electrochemical MS-NI; the toughening agent is MBS polymer which selects Japanese Brillouin Kane Ace M-732. The reaction type compatilizer is DuPont Elvaloy PTW or Akoma AX 8900. Antioxidant is selected from Nuochi 1010 and 619F.
Comparative example 1
Weighing 0.2 part of each of ABS DG-41740 parts, ABS AE 800050 parts, MBS-M73210 parts, antioxidant 1010 and 619F in parts by weight, placing the mixture in a stirrer for premixing for 10-15min, pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃ and the screw rotation speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator.
Comparative example 2
Weighing 0.2 part of each of ABS DG-41740 parts, ABS AE 800050 parts, AX 890010 parts, antioxidant 1010 and 619F in parts by weight, placing the mixture in a stirrer for premixing for 10-15min, pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃ and the screw rotation speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator.
Comparative example 3
Weighing 0.2 part of each of ABS DG-41740 parts, ABS AE 800050 parts, PTW 10 parts, antioxidant 1010 and 619F according to the weight, placing the mixture in a stirrer for premixing for 10-15min, pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃ and the screw rotation speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator.
Comparative example 4
Weighing 0.2 part of each of ABS DG-41740 parts, ABS AE 800050 parts, MS-NI 10 parts, antioxidant 1010 and 619F according to the weight parts, placing the mixture in a stirrer for premixing for 10-15min, pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃ and the screw rotation speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator.
Example 1
Weighing 0.2 part of each of ABS DG-41730 parts, ABS AE 800050 parts, MS-NI 15 parts, MBS-M7325 parts and antioxidants 1010 and 619F in parts by weight, placing the materials in a stirrer for premixing for 10-15min, pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃ and the screw rotation speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator.
Examples 2 to 4
ABS resins of examples 2-4 were prepared according to the procedure of example 1, with the specific formulations shown in Table 1.
Extruding particles in the comparative example and the example, baking the particles at 90 ℃/4h, and injection molding the particles into 80 x 10 x 4mm sample strips, wherein the bending strength and modulus in the performance test result adopt ISO 178 standard; the notch impact strength adopts the ISO 179/1eA standard; the Vicat softening temperature adopts the test method of ISO 306-B50; using an A.shine dyne value pen to draw a pen on the smooth template, if the liquid does not shrink within three seconds, reaching the selected dyne, otherwise, not reaching the selected dyne; the surface tension is measured by an optical contact angle measurement method.
Claims (10)
1. The high heat-resistant modified ABS material strongly bonded with the PUR is characterized by comprising the following raw materials in percentage by mass: 65-80 wt% of ABS resin, 10-25 wt% of heat-resistant agent, 3-10% of toughening agent, 0-10% of reactive compatilizer and 0.4% of antioxidant.
2. The high heat-resistant modified ABS material with strong bonding property with PUR according to claim 1, wherein: the ABS resin is prepared by an emulsion method and is selected from Qimei PA-727 and Tianjin staphyl DG-417.
3. The high heat-resistant modified ABS material with strong bonding property with PUR according to claim 1, wherein: the heat-resistant agent is a styrene-N-phenylmaleimide-maleic anhydride copolymer.
4. The high-heat-resistance modified ABS material with strong bonding property with PUR according to claim 3, wherein: the heat-resistant agent is Japanese electrochemical MS-NI.
5. The high heat-resistant modified ABS material with strong bonding property with PUR according to claim 1, wherein: the toughening agent is MBS (methyl methacrylate-butadiene-styrene) polymer.
6. The high-heat-resistance modified ABS material with strong bonding property with PUR according to claim 5, wherein: the toughening agent is Japanese Brillouin Kane Ace M-732.
7. The high heat-resistant modified ABS material with strong bonding property with PUR according to claim 1, wherein: the reactive compatilizer is ethylene-acrylate-glycidyl ester (GMA) terpolymer.
8. The high-heat-resistance modified ABS material with strong bonding property with PUR according to claim 7, wherein: the reaction type compatilizer is DuPont Elvaloy PTW or Acoma AX 8900.
9. The high heat-resistant modified ABS material with strong bonding property with PUR according to claim 1, wherein: the antioxidant is prepared from antioxidant 1010 and antioxidant 619F in a mass ratio of 1: 1 and mixing.
10. A method for preparing a highly heat-resistant modified ABS material strongly adhered to PUR according to any of claims 1 to 9, characterized in that it comprises the steps of: preparing raw materials according to the mass ratio, pouring the raw materials into a stirrer for premixing for 10-15min, then pouring the mixture into a main feeding port of a double-screw extruder, adjusting the extrusion temperature to be 220-240 ℃, the screw rotating speed to be 450-600rpm, extruding, cooling by a water tank, and granulating by a granulator to obtain the modified ABS material.
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