CN113604038A - Ultrahigh-flow high-impact PPO/PA66 alloy material and preparation method thereof - Google Patents
Ultrahigh-flow high-impact PPO/PA66 alloy material and preparation method thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention discloses a PPO/PA66 alloy material with ultrahigh flow and high impact resistance and a preparation method thereof, and relates to the technical field of polymer composite material processing. The invention discloses an ultrahigh-flow high-impact PPO/PA66 alloy material which is prepared from the following raw materials in parts by weight: 30-65 parts of polyphenyl ether resin, 40-68 parts of nylon 6640, 5-18 parts of toughening agent SEBS, 0.1-1.2 parts of composite antioxidant, 0.2-3 parts of lubricant, 0.1-1.5 parts of hyperbranched polymer and 7-22 parts of compatilizer. The PPO/PA66 alloy material with ultrahigh fluidity and high impact resistance provided by the invention solves the problems of stress cracking and difficulty in processing and forming, has good comprehensive mechanical properties and physical properties, can be widely applied to oversized injection-molded products in the fields of automobiles, electronics, medical treatment, mechanical industry, chemical industry and the like, and has wide application prospects.
Description
Technical Field
The invention belongs to the technical field of polymer composite material processing, and particularly relates to a PPO/PA66 alloy material with ultrahigh flow and high impact resistance and a preparation method thereof.
Background
The PPO resin is one of five general engineering plastics in the world, is nontoxic, transparent, small in relative density, excellent in mechanical strength, heat resistance, water resistance and steam resistance, good in dimensional stability, outstanding in electrical insulation and good in wear resistance. However, PPO has poor melt flowability, stress cracking tendency and difficult processing and forming, so that the single application of PPO is greatly limited.
The polyamide PA66 is an engineering plastic with excellent performance, has good comprehensive performance due to high crystallinity, comprises mechanical property, heat resistance, abrasion resistance, chemical solvent resistance and self-lubricating property, has low friction coefficient, certain flame retardance and easy processing, is suitable for filling, reinforcing and modifying glass fibers and other fillers, improves the performance and expands the application range. However, the dimensional stability of the product is poor due to its high water absorption.
With the rapid development of modern industry, steel is replaced by plastic, which becomes the development direction of industrial materials, and PPO/PA66 alloy is a crystalline and noncrystalline incompatible alloy, the performance of the alloy is greatly improved after molding processing, the advantages of the two are complementary, the advantages of the two are combined, the advantages of good high temperature resistance and stable size of PPO are maintained, the wear resistance and organic solvent resistance of PA66 are improved, and a series of alloy varieties prepared by adopting a compatibility technology and a blending technology have excellent comprehensive performance. The PPO/PA66 alloy material has high thermal deformation temperature, good dimensional stability and high precision, still has high toughness, chemical organic solvent resistance and good processability at low temperature, is widely applied to the fields of automobile industry, photovoltaic industry, new energy and electronic and electrical appliances, and can be used for producing electronic and electrical products, household electrical appliances and keyboards, compact discs, facsimile communication and other precision parts. The PPO/PA66 alloy material has high rigidity, small creep, impact resistance, wear resistance and organic solvent resistance, is particularly suitable for the exterior material of automobile bodies, can withstand the spraying and baking temperature of more than 150 ℃ and the corrosion of xylene and toluene which are solvents in spray paint, and has no change of the external dimension and no stress cracking and the like. The prior PPO/PA66 alloy has low general fluidity and has a plurality of inconveniences for manufacturing oversized products, and the critical problem is solved by the ultrahigh fluidity of the invention.
In order to obtain better alloying between PPO and PA66 and obtain a co-mixed alloy with good properties of ultrahigh fluidity and high impact resistance, the compatibility between PPO and PA66 must be improved. The invention prepares the compatilizer which can meet the requirements of the two materials by starting from the compatilizer according to the characteristics of the two materials, and obtains the ultrahigh-performance alloy material with excellent performance by utilizing the interaction of the auxiliary antioxidant and the hyperbranched polymer, which is the key innovation point of the invention.
Disclosure of Invention
Aiming at the problem that the prior art cannot meet the market demand for environment-friendly PPO/PA66 alloy materials with ultrahigh fluidity and high impact resistance, and particularly the demand for oversized injection molding products, the invention mainly aims to provide an environment-friendly PPO/PA66 alloy material with ultrahigh fluidity and high impact resistance.
In order to realize the purpose of the invention, the invention provides an ultrahigh-flow high-impact PPO/PA66 alloy material which is prepared from the following raw materials in parts by weight: 30-65 parts of polyphenyl ether resin, 40-68 parts of nylon 6640, 5-18 parts of toughening agent SEBS, 0.1-1.2 parts of composite antioxidant, 0.2-3 parts of lubricant, 0.1-1.5 parts of hyperbranched polymer and 7-22 parts of compatilizer.
Further, the intrinsic viscosity of the polyphenylene ether resin is 0.3-0.6 dl/g.
Further, the polyphenylene ether resin is any one or more of LXN040, LXN045, and LXN 050.
Further, the relative viscosity of the nylon 66 is 2.4-3.0.
Further, the composite antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
Further, the lubricant is any one of pentaerythritol stearate, calcium stearate, zinc stearate, stearic acid, ethylene bis stearamide or organic silicone.
Further, the density of the hyperbranched polymer is 1.0-1.1 g/cm3The melting range is 160-180 ℃.
Further, the compatilizer is prepared by extruding PPO/PS and maleic anhydride under the action of an initiator.
The invention also provides a preparation method of the ultrahigh-flow high-impact PPO/PA66 alloy material, which comprises the following steps: weighing the raw materials according to the weight part ratio, putting the weighed raw materials into a high-speed stirrer, stirring for 2-5 min by the high-speed stirrer, completely mixing uniformly, blending and extruding by a double-screw extruder, setting the temperature of the double-screw extruder to be 230-260 ℃ and the screw rotating speed to be 35-55 Hz, cooling, and granulating to obtain the PP0/PA66 alloy material.
The invention achieves the following beneficial effects:
1. the invention takes PP0 and PA66 as matrix materials, and the PPO/PA66 alloy material with ultrahigh fluidity and high impact is prepared by blending the matrix materials with a compatilizer under the interaction of a hyperbranched polymer and an auxiliary antioxidant, thus completely overcoming the defects of the prior art, such as the high fluidity guaranteed by the prior product and the insufficient impact strength, or the low fluidity after the impact strength is improved. The invention overcomes the problem of mutual restriction of fluidity and impact resistance, and not only ensures ultrahigh fluidity, but also ensures high impact resistance.
2. The invention has the advantages of high temperature resistance, outstanding electrical insulation, small water absorption and excellent water resistance, solves the problems of stress cracking and difficult processing and forming, has good comprehensive mechanical property and physical property, is a complete green and environment-friendly alloy material, can be widely applied to oversized injection molding products in the fields of automobiles, electronic and electric appliances, medical treatment, mechanical industry, chemical industry and the like, and has wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an ultrahigh-flow high-impact PPO/PA66 alloy material which is prepared from the following raw materials in parts by weight: 30-65 parts of polyphenyl ether resin, 40-68 parts of nylon 6640, 5-18 parts of toughening agent SEBS, 0.1-1.2 parts of composite antioxidant, 0.2-3 parts of lubricant, 0.1-1.5 parts of hyperbranched polymer and 7-22 parts of compatilizer.
The toughening agent SEBS used in the invention is hydrogenated styrene-butadiene block copolymer resin elastomer, the SEBS has excellent aging resistance, plasticity and high elasticity, can be processed and used without vulcanization, can be reused as leftover materials, is widely used for producing high-grade elastomers and plastic modification, and has good weather resistance, heat resistance, compression deformation resistance and excellent mechanical properties. The toughening agent SEBS is added, so that the toughening agent SEBS can be better blended with PPO and PA66, and can be matched with hyperbranched polymer, antioxidant and the like for use, and the fluidity and the impact resistance of the invention are obviously improved.
In the present invention, the density of the hyperbranched polymer is preferably 1.0 to 1.1g/cm3The melting range is 160-180 ℃. The hyperbranched polymer is a resin polymer, is a highly branched three-dimensional macromolecule, has multiple branching points, is not easy to tangle molecular chains, has no viscosity change along with the increase of molecular weight, has rich terminal functional groups, is easy to modify and modify, is beneficial to synthesizing various functional materials, resists high temperature, and has good thermal stability and good demoulding performance. Hyperbranched polymers being added toAccording to the invention, the flow property of the PPO/PA66 alloy material is obviously improved, the melt index is improved in multiples, the glossiness of the product surface is improved, the processing temperature is effectively reduced, the energy is saved, and the consumption is reduced. The addition of a proper amount of hyperbranched polymer can greatly improve the impact resistance of the PPO/PA66 alloy material.
In the present invention, the polyphenylene ether resin preferably has an intrinsic viscosity of 0.3 to 0.6 dl/g. In the present invention, it is preferable that the polyphenylene ether resin is selected from any one or more of LXN040, LXN045, LXN050 which are south china star synthetic materials ltd.
In the invention, the relative viscosity of the nylon 66 is preferably 2.4-3.0, and the PA66 provided by a Shabo base is selected.
In the present invention, preferably, the composite antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098), and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite 168 (antioxidant 168).
In the present invention, the lubricant is preferably any one of pentaerythritol stearate, calcium stearate, zinc stearate, stearic acid, ethylene bis stearamide, or organic silicone.
In the present invention, it is preferable that the compatibilizer is prepared by extruding PPO/PS and maleic anhydride under the action of an initiator. The compatilizer is self-made, and the preparation method comprises the following steps: according to the mass fraction, 80 parts of PPO, 16 parts of PS, 3 parts of maleic anhydride MAH, 0.7 part of catalyst benzoin and 0.3 part of initiator BIPB are placed into a high-speed stirrer, are stirred by the high-speed stirrer for 2-5 min and then are mixed and extruded by a double-screw extruder, the temperature of the double-screw extruder is set to be 230-260 ℃, the rotating speed of a screw is set to be 35-55 Hz, and the mixture is cooled and granulated to prepare the compatilizer for later use.
The self-made compatilizer is added into the alloy polymer by utilizing the characteristics of good thermal stability and fluidity, easy molding and processing, particularly easy injection molding, small molding shrinkage, good dimensional stability of a molded product and good compatibility with PPO when PS is melted, so that the alloy product can be better fused and blended when being compatible, and the polymer can obtain the most ideal performance.
The invention also provides a preparation method of the ultrahigh-flow high-impact PPO/PA66 alloy material, which comprises the following steps: weighing raw materials according to the weight part ratio, putting the weighed raw materials into a high-speed stirrer, stirring by the high-speed stirrer for 2-5 min, completely mixing uniformly, blending and extruding by a double-screw extruder, setting the temperature of the double-screw extruder to be 230-260 ℃ and the rotating speed of a screw to be 35-55 Hz, cooling, and granulating to obtain the PP0/PA66 alloy material.
The ultrahigh-flow high-impact PPO/PA66 alloy material and the preparation method thereof are described in detail with reference to specific examples.
The hyperbranched polymer used in the embodiments of the invention is selected from CYD-701 of westerchen origin.
Comparative example 1
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04540 parts, PA 6653 parts, a toughening agent SEBS 6 part, a compatilizer 0 part, an antioxidant 10980.3 part, an antioxidant 1680.2 part, a lubricant silicone 0.5 part and a hyperbranched polymer 0 part into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein the processing temperature of the double-screw extruder is 230-. The specific temperatures of the sections set up in the twin-screw extruder are shown in Table 1.
Comparative example 2
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04535 parts, PA 6650 parts, toughening agent SEBS 6 parts, compatilizer 8 parts, antioxidant 10980.3 parts, antioxidant 1680.2 parts, lubricant silicone 0.5 parts and hyperbranched polymer 0 part into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein the processing temperature of the double-screw extruder is 230-. The specific temperatures of the sections set up in the twin-screw extruder are shown in Table 1.
Example 1
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04530 parts, PA 6655 parts, toughening agent SEBS 6.5 parts, compatilizer 10 parts, antioxidant 10980.3 parts, antioxidant 1680.2 parts, lubricant silicone 0.3 part and hyperbranched polymer 0.2 part into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein, the specific temperature of each section set by the double-screw extruder is shown in the table 1.
Example 2
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04535 parts, PA 6668 parts, toughening agent SEBS 5 parts, compatilizer 10 parts, antioxidant 10980.2 parts, antioxidant 1680.1 parts, lubricant silicone 0.8 parts and hyperbranched polymer 0.3 parts in parts by mass into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein, the specific temperature of each section set by the double-screw extruder is shown in the table 1.
Example 3
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04565 parts, PA 6630 part, toughening agent SEBS 5 parts, compatilizer 10 parts, antioxidant 10980.2 parts, antioxidant 1680.1 parts, lubricant silicone 0.8 part and hyperbranched polymer 0.3 part into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein, the specific temperature of each section set by the double-screw extruder is shown in the table 1.
Example 4
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04538 parts, PA 6655 parts, toughening agent SEBS 6 parts, compatilizer 8 parts, antioxidant 10980.2 parts, antioxidant 1680.2 parts, lubricant silicone 0.5 parts and hyperbranched polymer 0.9 parts in parts by mass into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein, the specific temperature of each section set by the double-screw extruder is shown in the table 1.
Example 5
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04540 parts, PA 6650 parts, toughening agent SEBS 10 parts, compatilizer 11 parts, antioxidant 10980.2 parts, antioxidant 1680.1 parts, lubricant silicone 0.2 parts and hyperbranched polymer 0.6 parts in parts by mass into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein, the specific temperature of each section set by the double-screw extruder is shown in the table 1.
Example 6
The preparation method of the PPO/PA66 alloy material comprises the following steps: putting PPO LXN 04532 parts, PA 6653 parts, toughening agent SEBS 10 parts, compatilizer 12 parts, antioxidant 10980.3 parts, antioxidant 1680.5 part, lubricant silicone 0.5 part and hyperbranched polymer 0.5 part into a high-speed mixer, mixing for 2-5 minutes, and discharging; and (3) blending and granulating by using a double-screw extruder to prepare the PPO/PA66 alloy material. Wherein, the specific temperature of each section set by the double-screw extruder is shown in the table 1.
Table 1 shows the temperatures of the zones of the twin-screw extruder and the rotational speeds of the main machine during the preparation of the raw material formulations of comparative example 1 and examples 1 to 6 in the following Table 1.
TABLE 1 temperature settings for each zone of the twin-screw extruder and the rotational speed of the main machine
The granular PP0/PA66 alloy material prepared by the twin-screw extruder in the embodiment 1-7 is subjected to injection molding in an injection molding machine at the temperature of 250-280 ℃ to prepare tensile, bending, impact and flame retardant sample strips, and the sample strips are subjected to performance test according to the ASTM national standard, wherein the performance test results are shown in Table 2.
The melt index is measured according to ISO 1133 standard, at 280 ℃ and 5 Kg;
tensile strength is tested according to ASTM D638 standard;
flexural strength was tested according to ASTM D790 standard;
notched impact strength was tested according to ASTM D256 standard;
heat distortion temperature was tested according to ASTM D648 standard;
the test sample specimen is placed in an environment of a normal temperature of 23 + -2 deg.C and a relative humidity of 50 + -10% for 48 hours before the test.
TABLE 2 results of Performance test of examples 1 to 7
The experimental results of comparative examples 1-2 and examples 1-6 show that after the self-made compatilizer and the hyperbranched polymer are added, the melt index of the invention can be obviously improved, namely the popularity of the invention is improved, other physical indexes are changed along with the change of the specific gravity of the hyperbranched polymer, but the impact on the notch impact is the largest, and the notch impact strength is obviously increased, suddenly reduced and then increased along with the increase of the specific gravity of the hyperbranched polymer. Therefore, the PPO/PA66 alloy material has ultrahigh fluidity and high impact resistance.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. The ultrahigh-flow high-impact PPO/PA66 alloy material is characterized by being composed of the following raw materials in parts by weight:
30-65 parts of polyphenyl ether resin;
nylon 6640-68 parts;
5-18 parts of a toughening agent SEBS;
0.1-1.2 parts of a composite antioxidant;
0.2-3 parts of a lubricant;
0.1-1.5 parts of hyperbranched polymer;
7-22 parts of a compatilizer.
2. The ultrahigh-flow high-impact PPO/PA66 alloy material as claimed in claim 1, wherein the intrinsic viscosity of the polyphenylene ether resin is 0.3-0.6 dl/g.
3. The ultrahigh-flow high-impact PPO/PA66 alloy material according to claim 2, wherein the polyphenylene ether resin is any one of a copolymer resin of poly (2, 6-dimethylphenyl) ether and 2,3, 6-trimethylphenol, and a copolymer resin of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol.
4. The ultrahigh-flow high-impact PPO/PA66 alloy material as claimed in claim 1, wherein the relative viscosity of nylon 66 is 2.4-3.0.
5. The ultrahigh-flow high-impact PPO/PA66 alloy material according to claim 1, wherein the composite antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and the secondary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
6. The ultrahigh-flow high-impact PPO/PA66 alloy material according to claim 1, wherein the lubricant is any one of pentaerythritol stearate, calcium stearate, zinc stearate, stearic acid, ethylene bis stearamide, or organic silicone.
7. The ultra-high flow high impact PPO/PA66 alloy material as claimed in claim 1, wherein the alloy material is characterized in thatThe density of the hyperbranched polymer is 1.0-1.1 g/cm3The melting range is 160-180 ℃.
8. The ultrahigh-flow high-impact PPO/PA66 alloy material according to claim 1, wherein the compatibilizer is prepared by extruding PPO/PS and maleic anhydride under the action of an initiator.
9. The preparation method of the ultrahigh-flow high-impact PPO/PA66 alloy material as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
weighing the raw materials according to the weight part ratio, putting the weighed raw materials into a high-speed stirrer, stirring for 2-5 min by the high-speed stirrer, completely mixing uniformly, blending and extruding by a double-screw extruder, setting the temperature of the double-screw extruder to be 230-260 ℃ and the screw rotating speed to be 35-55 Hz, cooling, and granulating to obtain the PP0/PA66 alloy material.
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| CN114231015A (en) * | 2021-12-16 | 2022-03-25 | 湖南恒屹新材料有限公司 | PPE alloy material with arc resistance, tracking resistance and high flame retardance |
| CN115491017A (en) * | 2022-09-15 | 2022-12-20 | 上海普利特复合材料股份有限公司 | High-thermal-conductivity high-flow PPO/PS composite material and preparation method thereof |
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| CN108299823A (en) * | 2017-12-27 | 2018-07-20 | 上海普利特复合材料股份有限公司 | A kind of PPO/PA alloy materials and preparation method thereof suitable for being thinning |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108299823A (en) * | 2017-12-27 | 2018-07-20 | 上海普利特复合材料股份有限公司 | A kind of PPO/PA alloy materials and preparation method thereof suitable for being thinning |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231015A (en) * | 2021-12-16 | 2022-03-25 | 湖南恒屹新材料有限公司 | PPE alloy material with arc resistance, tracking resistance and high flame retardance |
| CN115491017A (en) * | 2022-09-15 | 2022-12-20 | 上海普利特复合材料股份有限公司 | High-thermal-conductivity high-flow PPO/PS composite material and preparation method thereof |
| CN115491017B (en) * | 2022-09-15 | 2024-01-09 | 上海普利特复合材料股份有限公司 | High-heat-conductivity high-flow PPO/PS composite material and preparation method thereof |
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