CN112679917B - Cold-heat-resistant high-strength high-toughness PBT (polybutylene terephthalate) composite material suitable for full-shading lamp and preparation and application thereof - Google Patents
Cold-heat-resistant high-strength high-toughness PBT (polybutylene terephthalate) composite material suitable for full-shading lamp and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a cold-heat-resistant high-strength high-toughness PBT (polybutylene terephthalate) composite material suitable for a full-shading lamp, and a preparation method and application thereof in preparation of the full-shading lamp. The material comprises the following raw materials in parts by weight: 45 to 55 parts of polybutylene terephthalate, 22 to 26 parts of reinforcing material, 5 to 10 parts of compound toughening agent, 8 to 15 parts of flame retardant, 5 to 10 parts of light-shielding filler, 0.5 to 1 part of lubricant, 0.1 to 0.4 part of compound antioxidant and 0.1 to 0.3 part of anti-dripping agent. The preparation method of the material comprises the following steps: and uniformly mixing all the raw materials except the reinforcing material according to a ratio by adopting a double-screw extruder, feeding the raw materials from a main feeding port, feeding the reinforcing material from a side feeding port, and carrying out melt extrusion to obtain the cold-heat-resistant high-strength high-toughness PBT composite material suitable for the full-shading lamp.
Description
Technical Field
The invention relates to the technical field of PBT (polybutylene terephthalate) composite materials, in particular to a cold-heat-resistant high-strength high-toughness PBT composite material suitable for a full shading lamp and preparation and application thereof.
Background
A proper amount of titanium dioxide (such as patent technologies with publication numbers CN101914270A and CN 103819883A) is generally required to be added into a PBT (polybutylene terephthalate) composite material for shading lamps; if customers require full shading light fixture structural members, a high proportion of titanium dioxide needs to be added to the PBT composite material.
Because titanium dioxide is a high-hardness material, glass fibers are broken and crushed in the processing process; the excessively crushed glass fibers weaken the reinforcing effect on the PBT composite material, so that the mechanical property of the PBT composite material is reduced sharply.
In addition, titanium dioxide is an inorganic filler, and the mechanical property of the PBT composite material is further reduced due to excessive addition proportion. The PBT composite material is easy to crack in the process of injection molding of an LED lamp structural part; even if the injection molding process does not crack, the lamp structural part has great cracking hidden trouble when a thermal shock resistance test is carried out due to low mechanical property of the material.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides the cold-heat resistant high-strength high-toughness PBT composite material suitable for the full shading lamp, and solves the technical problem that the existing full shading PBT composite material is difficult to pass a cold-heat shock resistance test due to low mechanical properties because of filling high-proportion titanium dioxide.
The cold-heat-resistant high-strength high-toughness PBT composite material suitable for the full shading lamp comprises the following raw materials in parts by mass:
the reinforcing material is at least one of glass fiber, carbon fiber and basalt fiber;
the compound toughening agent is an ethylene-methyl acrylate copolymer and an ethylene-butyl acrylate-glycidyl methacrylate copolymer with the mass ratio of 1-3;
the shading filler is titanium dioxide.
Tests show that in the PBT composite material system of the invention, due to the reasons of more (5-10 parts by mass) titanium dioxide and the like, the reinforcing material must be in the above-mentioned addition range, the obtained PBT composite material can give consideration to rigidity and toughness, and has better bending strength, bending modulus, tensile strength and impact strength, better cold and heat shock resistance, too little addition, poorer mechanical properties (including bending strength, bending modulus, tensile strength and impact strength) of the obtained PBT composite material, poor cold and heat shock resistance, too much addition, rather reduced impact strength of the obtained PBT composite material, and reduced cold and heat shock resistance.
The invention is also characterized in that a compound of ethylene-methyl acrylate copolymer and ethylene-butyl acrylate-glycidyl methacrylate copolymer in a specific mass ratio (1-3) is used as a compound toughening agent, and the addition amount is only 5-10 parts by mass. Although ethylene-methyl acrylate copolymer and ethylene-butyl acrylate-glycidyl methacrylate copolymer are both tougheners commonly used in PBT composites, a single component is usually used alone. Through a large number of tests, the inventor unexpectedly finds that the ethylene-methyl acrylate copolymer and the ethylene-butyl acrylate-glycidyl methacrylate copolymer are compounded according to the mass ratio of 1-3 and then have an obvious synergistic effect when being applied to the glass fiber reinforced and titanium dioxide light-shielding PBT composite material disclosed by the invention. Compared with the single component of the ethylene-methyl acrylate copolymer or the ethylene-butyl acrylate-glycidyl methacrylate copolymer, the PBT composite material prepared by adopting the compound toughening agent with the specific mass ratio has more excellent comprehensive mechanical property, particularly more excellent impact strength, and obviously improved cold and heat shock resistance.
On the basis of the formula, in order to better solve the technical problem and enable the PBT composite material to be better suitable for a full-shading lamp, the invention further optimizes the types and properties of the components, the addition amounts and the addition proportions of the components and the like, and the PBT composite material comprises the following specific components:
the intrinsic viscosity of the polybutylene terephthalate is preferably 0.8 to 1.0dL/g.
The compound toughening agent is preferably an ethylene-methyl acrylate copolymer and an ethylene-butyl acrylate-glycidyl methacrylate copolymer with the mass ratio of 1.
The flame retardant is preferably a compound flame retardant, and is further preferably compounded by a flame retardant and a synergistic flame retardant, wherein the flame retardant is preferably at least one of brominated polystyrene and brominated epoxy resin, and the synergistic flame retardant is preferably at least one of antimony trioxide and zinc borate.
The lubricant is preferably at least one of silicone master batch, ethylene bisstearamide and pentaerythritol stearate.
The compound antioxidant is preferably compounded by a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is preferably at least one of antioxidant 1010 and antioxidant 1098, and the auxiliary antioxidant is preferably at least one of antioxidant 626 and antioxidant 168.
The anti-dripping agent is preferably polytetrafluoroethylene.
The invention also provides a preferable preparation method of the cold-heat-resistant high-strength high-toughness PBT composite material, which comprises the following steps: and uniformly mixing all the raw materials except the reinforcing material according to a ratio by adopting a double-screw extruder, feeding the raw materials from a main feeding port, feeding the reinforcing material from a side feeding port, and carrying out melt extrusion to obtain the cold-heat-resistant high-strength high-toughness PBT composite material suitable for the full-shading lamp.
Preferably, the temperature of each zone of the screw barrel of the double-screw extruder is kept between 180 and 230 ℃, and the screw rotating speed of the double-screw extruder is 350rpm.
The PBT composite material with the formula is prepared by the optimal preparation method, and the optimal comprehensive mechanical property and cold and heat shock resistance can be realized.
The invention also provides application of the cold-resistant, high-strength and high-toughness PBT composite material in preparation of a full shading lamp.
Compared with the prior art, the invention has the main advantages that: the PBT composite material is a system with a high proportion of titanium dioxide, and the PBT composite material has high strength, high toughness and cold and heat shock resistance by adding specific amounts of components such as reinforcing materials such as glass fibers and specific compound toughening agents and controlling specific mass ratios of ethylene-methyl acrylate copolymer and ethylene-butyl acrylate-glycidyl methacrylate copolymer in the compound toughening agents, and the PBT composite material can pass a cold and heat shock test.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Comparative example 1
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 20 parts of ethylene-methyl acrylate copolymer: 8 parts, titanium dioxide: 8 parts, brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part, antioxidant 1010:0.1 part, antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, performing melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
Comparative example 2
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 23 parts, ethylene-methyl acrylate copolymer: 8 parts, titanium dioxide: 8 parts, brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part, antioxidant 1010:0.1 part, antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, carrying out melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
Comparative example 3
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 23 parts, ethylene-methyl acrylate copolymer: 6 parts of an ethylene-butyl acrylate-glycidyl methacrylate copolymer: 2 parts, titanium dioxide: 8 parts, brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part of antioxidant 1010:0.1 part, antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, performing melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
Example 1
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 23 parts, ethylene-methyl acrylate copolymer: 4 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymer: 4 parts, titanium dioxide: 8 parts, brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part of antioxidant 1010:0.1 part, antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, performing melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
Example 2
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 23 parts of ethylene-methyl acrylate copolymer: 2 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymer: 6 parts of titanium dioxide: 8 parts, brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part, antioxidant 1010:0.1 part, antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, performing melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
Comparative example 4
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 23 parts of an ethylene-butyl acrylate-glycidyl methacrylate copolymer: 8 parts, titanium dioxide: 8 parts of brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part of antioxidant 1010:0.1 part, antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, performing melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
Comparative example 5
(1) Weighing the following components in parts by mass: PBT:48 parts, glass fiber: 30 parts of ethylene-methyl acrylate copolymer: 4 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymer: 4 parts, titanium dioxide: 8 parts, brominated epoxy resin: 9 parts of antimony trioxide: 2 parts of pentaerythritol stearate: 0.3 part, silicone master batch: 0.3 part, antioxidant 1010:0.1 part of antioxidant 168:0.1 part, polytetrafluoroethylene: 0.1 part.
(2) Uniformly mixing raw materials except the glass fiber in a high-speed mixer, feeding the glass fiber from a side feeding port, carrying out melt extrusion through a double-screw extruder at the extrusion temperature of 180-230 ℃ and the screw rotation speed of 350rpm, and then cooling, drying and granulating into granules to obtain the product.
The results of the tests on the mechanical properties, light-shielding properties, flame retardancy and thermal shock resistance of the products of comparative examples 1 to 5 and examples 1 to 2 are shown in table 1 below.
TABLE 1
a Each proportion and the embodiment are natural color materials, the natural color materials are molded into a color plate with the thickness of 2mm, and the color plate is irradiated by a whole lamp light source; and if the irradiance of the color plate with the thickness of 2mm is less than 20LUX, the material is defined as a full-shading material, and the LED lamp structural part formed by corresponding injection molding is a full-shading product.
b The structural parts (5 parts each) of the LED plastic-coated aluminum lamp prepared by injecting the materials of the comparative examples and the examples are placed in a cold and hot impact oven with the set parameters of 30min at minus 30 ℃ and 30min at 120 ℃, and the cracking condition of the comparative examples and the examples is checked after 500 cycles.
As can be seen from the comparison of comparative examples 1 and 2 and the comparison of example 1 and comparative example 5, in the PBT composite material system of the invention, only a sufficient and proper amount of glass fiber is added, so that the PBT composite material has better strength and toughness, the overall mechanical property is excellent, and the PBT composite material has better cold and hot shock resistance.
As can be seen from comparison of comparative examples 2-4 and examples 1 and 2, the PBT composite material has good rigidity, toughness and thermal shock resistance only by simultaneously using the ethylene-methyl acrylate copolymer and the ethylene-butyl acrylate-glycidyl methacrylate copolymer in a proper proportion.
Examples 1 and 2 showed good comprehensive mechanical properties, and 5 plastic-clad aluminum heat dissipation shells made of the two materials also can pass the cold and heat shock test. The PBT composite of example 1 is more competitive in the market in view of the overall mechanical properties and cost.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The cold-heat-resistant high-strength high-toughness PBT composite material suitable for the full shading lamp is characterized by comprising the following raw materials in parts by mass:
the reinforcing material is at least one of glass fiber, carbon fiber and basalt fiber;
the compound toughening agent is an ethylene-methyl acrylate copolymer and an ethylene-butyl acrylate-glycidyl methacrylate copolymer with the mass ratio of 1-3;
the shading filler is titanium dioxide.
2. The cold and hot resistant high strength high toughness PBT composite material of claim 1, wherein said polybutylene terephthalate has an intrinsic viscosity of 0.8-1.0dL/g.
3. The cold-heat resistant high-strength high-toughness PBT composite material according to claim 1, wherein the compound toughening agent is an ethylene-methyl acrylate copolymer and an ethylene-butyl acrylate-glycidyl methacrylate copolymer in a mass ratio of 1.
4. The cold-heat resistant high-strength high-toughness PBT composite material according to claim 1, wherein the flame retardant is a compound flame retardant, and is compounded from a flame retardant and a synergistic flame retardant, wherein the flame retardant is at least one of brominated polystyrene and brominated epoxy resin, and the synergistic flame retardant is at least one of antimony trioxide and zinc borate.
5. The cold-hot resistant high-strength high-toughness PBT composite material according to claim 1, wherein the lubricant is at least one of silicone master batch, ethylene bisstearamide and pentaerythritol stearate.
6. The cold-heat resistant high-strength high-toughness PBT composite material according to claim 1, wherein the compound antioxidant is a compound of a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is at least one of antioxidant 1010 and antioxidant 1098, and the auxiliary antioxidant is at least one of antioxidant 626 and antioxidant 168.
7. The cold-hot resistant high-strength high-toughness PBT composite material according to claim 1, wherein said anti-dripping agent is polytetrafluoroethylene.
8. The preparation method of the cold and hot resistant high-strength high-toughness PBT composite material according to any one of claims 1 to 7, which is characterized by comprising the following steps: and uniformly mixing all the raw materials except the reinforcing material according to a ratio by adopting a double-screw extruder, feeding the raw materials from a main feeding port, feeding the reinforcing material from a side feeding port, and carrying out melt extrusion to obtain the cold-heat-resistant high-strength high-toughness PBT composite material suitable for the full-shading lamp.
9. The method for preparing the polypropylene composition according to claim 8, wherein the temperature of each zone of the screw cylinder of the twin-screw extruder is kept between 180 and 230 ℃, and the screw rotating speed of the twin-screw extruder is 350rpm.
10. Use of the cold and hot resistant high-strength high-toughness PBT composite material according to any one of claims 1 to 7 in the preparation of a full-shading lamp.
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