CN104098885A - Glass-fiber reinforced polyphenylene oxide /polyamide alloy material and preparation method thereof - Google Patents
Glass-fiber reinforced polyphenylene oxide /polyamide alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high-molecular alloy materials, and relates to a glass-fiber reinforced PPO (polyphenylene oxide)/PA (polyamide) alloy material and a preparation method thereof. The alloy material is composed of the following compositions in parts by weight: 20-60 parts of PPO resin, 40-80 parts of PA resin, 0.2-1.0 part of epoxy resin, 5-25 parts of a flexibilizer, 0.1-0.5 part of an anti-oxidant, 0.2-1.0 part of a lubricant, 0.02-1.0 part of a coupling agent and 15-75 parts of glass fiber. By adding a small amount of multifunctional epoxy resin into the PPO/PA alloy material as a compatibilizer, the compatibility and the interface bonding force between PPO resin and PA resin are effectively improved. The addition of the flexibilizer is capable of improving the impact resistance of the alloy material. Additionally, by adding some high-strength high-modulus short glass fiber into PPO/PA alloy, the mechanical properties of the alloy material is substantially improved, and also the dimension stability, the heat stability and the like of the alloy are improved.
Description
Technical field
The invention belongs to high molecule alloy material technical field, relate to a kind of glass fibre and strengthen PPO/PA alloy material and preparation method thereof.
Background technology
Polyamide (PA) is a kind of engineering plastics of excellent performance, it makes it have the advantages such as solvent resistance is good, mechanical strength is high, easy processing because degree of crystallinity is higher, but the shortcomings such as the product size poor stability that it exists, and shock strength is low, thermotolerance is poor, cause because of high-hydroscopicity, are restricted its application in a lot of fields.And PPO has the features such as good physical and mechanical property, electrical property, thermotolerance, flame retardant resistance and chemical stability, simultaneously PPO also has under high temperature the characteristics such as creep resistant is good, molding shrinkage is low, good stability of the dimension, but its heat-drawn wire (HDT) is very high, must use very high processing temperature, melt viscosity is also quite high, machine-shaping difficulty.
In PPO/PA6 alloy, PPO component can provide good thermostability and water tolerance, and PA component can be given the good processing characteristics of alloy and solvent resistance, by increase-volume, PPO/PA alloy can reach the performance requriements of conventional engineering plastics, but for meeting the engineering application of some needs high-tensiles and high-modulus, need in PPO/PA alloy, add the fiber of some high strength and high-modulus, particularly short glass fiber (SGF), add in PPO/PA alloy to improve the mechanical property of alloy material, improve dimensional stability and the thermostability etc. of alloy simultaneously.
Conventionally, the performance of multicomponent polymeric/short glass fiber type matrix material and its phase morphology structure are closely related.Strengthen in PPO/PA matrix material at short glass fiber, not only to consider the phase morphology structure between PPO and PA polymeric matrix, also to consider the deployment conditions of short glass fiber in polymeric matrix, because these phase morphology structures and deployment conditions are the important factors that affects composite property.
In this patent, strengthen in order to solve above short glass fiber the problem occurring in PPO/PA matrix material, in matrix material, add the expanding material of a small amount of polyfunctional epoxy resin as PPO, PA, epoxy resin respectively with PPO in-in OH, PA-NH-reaction, between PPO and PA, play " bridge linking effect ", thereby improve the consistency between PPO and PA.In addition, use coupling agent to process glass fibre, thereby improve the interface binding power between polymeric matrix and glass fibre, thereby improve the mechanical property of matrix material.
Summary of the invention
Object of the present invention is exactly to provide a kind of glass fibre to strengthen PPO/PA alloy material and preparation method thereof in order to overcome the defect that above-mentioned prior art exists.
For achieving the above object, the present invention is by the following technical solutions:
The present invention, by adding a small amount of polyfunctional epoxy resin as expanding material in PPO/PA alloy material, can improve compatilizer and the interfacial adhesion of PPO resin and PA interlaminar resin effectively; Adding of toughner, can improve the impact property of alloy material.In addition, in PPO/PA alloy, add the short glass fiber of some high strength and high-modulus, can greatly improve the mechanical property of alloy material, can also improve dimensional stability and the thermostability etc. of alloy simultaneously.
A kind of glass fibre strengthens PPO/PA alloy material, is made up of the component that comprises following weight part:
20～60 parts of polyphenylene oxide (PPO) resins,
40～80 parts of polyamide (PA) resins,
0.2～1.0 part of epoxy resin,
5～25 parts of toughner,
0.1～0.5 part, oxidation inhibitor,
0.2～1.0 part of lubricant,
0.02～1.0 part of coupling agent,
15～75 parts, glass fibre.
Described PA resin is polymeric amide, is selected from PA6, PA11, PA12, PA46, PA66, PA610, PA612 or PA1010, preferably PA6 or PA66.
Described epoxy resin is selected from triphenol methylmethane triglycidyl ether, four phenolic group ethane four glycidyl ethers, triglycidyl group p-aminophenol, triglycidyl group isocyanuric acid ester, four glycidyl group-4,4 '-diaminodiphenylmethane, four glycidyl group m-xylene diamine, 1, two (the N of 3-, N-2-glycidyl aminomethyl) hexanaphthene or four glycidyl group-4,4 '-diaminodiphenyl oxide, preferably four glycidyl group-4,4 '-diaminodiphenylmethane;
Described toughner is selected from terpolymer EP rubber (EPDM), glycidyl methacrylate graft terpolymer EP rubber (EPDM-g-GMA), maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), high-impact polystyrene (HIPS), MBS (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-ethylene-butylene-styrene block copolymer (SEBS), one or more in maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer (SEBS-g-MAH) or SBS (SBS), preferably SEBS, SEBS-g-MAH or SBS.
Described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), three ［ 2,4-di-tert-butyl-phenyl ］ one or more in phosphorous acid ester (irgasfos 168) or β-(3,5-di-tert-butyl-hydroxy phenyl) positive octadecanol ester of propionic acid (antioxidant 1076).
Described lubricant is selected from whiteruss, TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) or RH-313C(pentaerythritol stearate, the Dongguan City plasthetics company limited that hikes) in one or more.
Described coupling agent is selected from one or more in 3-aminopropyl triethoxysilane (KH550), 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (KH570).
Described glass fibre is alkali-free short glass fiber, and length is 3.0～12.0mm.
Above-mentioned glass fibre strengthens a preparation method for PPO/PA alloy material, comprises the following steps:
(1) by even to 20～60 parts of dry polyphenylene oxide resins, 40～80 parts of polyamide resins and 0.2～1.0 part of epoxy resin, 5～25 parts of toughner, 0.1～0.5 part of oxidation inhibitor and 0.2～1.0 part of mix lubricant;
(2) 0.02～1.0 part of coupling agent is dissolved in dehydrated alcohol, is mixed with coupling agent-ethanolic soln, utilize spray method by spray solution on 15～75 parts of glass fibre, and the glass fibre that is sprayed with coupling agent solution is dry in baking oven;
(3) by compound in step (1) through upstream spout, send into twin screw extruder, simultaneously by 15～75 parts of glass fibre in step (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, obtain glass fiber reinforced polyester phenylate/polyamide alloy material.
After above-mentioned pellet is dry, through injection moulding machine preparation standard batten, survey its physicals.
In described step (1), the drying conditions of polyphenylene oxide resin is: dry 8～10h in 80～100 DEG C of baking ovens;
In described step (1), the drying conditions of polyamide resin is: dry 8～10h in 80～100 DEG C of baking ovens;
The device mixing in described step (1) is high-speed mixer, and mixing time is 3～7min;
In described step (2), the concentration of coupling agent-ethanolic soln is 0.5～2.0wt%, and the glass fibre drying conditions that is sprayed with coupling agent solution is: dry 30～90min in the baking oven of 80～120 DEG C;
In described step (3) twin screw extruder, melt extruding temperature is 270～300 DEG C;
In described step (4), pellet drying conditions is: dry 6～10h in 100～120 DEG C of baking ovens, the temperature of injection moulding machine preparation standard batten is 280～310 DEG C.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) in the present invention, selected reactive compatibilizer polyfunctional epoxy resin, a small amount of polyfunctional epoxy resin just can improve the consistency between PPO and PA, but also has greatly improved the mechanical property of alloy material.
(2) because polystyrene (PS) can well hold mutually with PPO, so select the segmented copolymer that contains PS as toughner, can improve widely the impelling strength of alloy material.
(3) in PPO/PA alloy, add the short glass fiber of some high strength and high-modulus, can greatly improve the mechanical property of alloy material, can also improve dimensional stability and the thermostability etc. of alloy simultaneously.
(4) in the present invention, selected coupling agent to fiberglass surfacing processing, the use of coupling agent can obviously improve matrix is combined with the interface of corpus fibrosum, can improve well the impact property of matrix material.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
In following examples, the tensile property of products obtained therefrom is according to standard A STM-D638 test, and bending property is according to standard A STM-D790 test, and socle girder notch shock performance is tested according to standard A STM-D256.
Embodiment 1
(1) by PPO resin dry 10h, PA66 resin dry 10h in 80 DEG C of baking ovens in 80 DEG C of baking ovens, then get 60 parts of the PPO resins, 40 parts of the PA66 resins that were dried, with 0.2 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 5 parts of toughner SEBS, 0.1 part of antioxidant 1010 and 0.2 part of lubricant whiteruss mix 3min in high-speed mixer, mix;
(2) the coupling agent 3-aminopropyl triethoxysilane (KH550) of 0.02 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 0.5%, utilize spray method that spray solution is upper at 15 parts of short glass fibers (length is 3.0mm), and will be sprayed with glass fibre dry 30min in 120 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 15 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 10h in 100 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 2
(1) by PPO resin dry 9h, PA66 resin dry 9h in 90 DEG C of baking ovens in 90 DEG C of baking ovens, then get 50 parts of the PPO resins, 50 parts of the PA66 resins that were dried, with 0.4 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 5 parts of toughner SEBS-g-MAH, 0.2 part of antioxidant 1076 and 0.4 part of lubricant TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) in high-speed mixer, mix 4min, mix;
(2) the coupling agent 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) of 0.25 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.0%, utilize spray method that spray solution is upper at 30 parts of short glass fibers (length is 5.0mm), and will be sprayed with glass fibre dry 45min in 110 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 30 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 8h in 110 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 3
(1) by PPO resin dry 8h, PA66 resin dry 8h in 100 DEG C of baking ovens in 100 DEG C of baking ovens, then get 40 parts of the PPO resins, 60 parts of the PA66 resins that were dried, with 0.6 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 5 parts of toughner SBS, 0.3 part of irgasfos 168 and 0.6 part of lubricant RH-313C(pentaerythritol stearate, the Dongguan City plasthetics company limited that hikes) in high-speed mixer, mix 5min, mix;
(2) the coupling agent 3-of 0.51 part (iso-butylene acyl-oxygen) propyl trimethoxy silicane (KH570) is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.25%, utilize spray method that spray solution is upper at 45 parts of short glass fibers (length is 7.5mm), and will be sprayed with glass fibre dry 60min in 100 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 45 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 6h in 120 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 4
(1) by PPO resin dry 10h, PA66 resin dry 10h in 80 DEG C of baking ovens in 80 DEG C of baking ovens, then get 30 parts of the PPO resins, 70 parts of the PA66 resins that were dried, with 0.8 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 5 parts of toughner SBS, 0.4 part of irgasfos 168 and 0.8 part of lubricant RH-313C(pentaerythritol stearate, the Dongguan City plasthetics company limited that hikes) in high-speed mixer, mix 6min, mix;
(2) the coupling agent 3-of 0.75 part (iso-butylene acyl-oxygen) propyl trimethoxy silicane (KH570) is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.75%, utilize spray method that spray solution is upper at 60 parts of short glass fibers (length is 10.0mm), and will be sprayed with glass fibre dry 75min in 90 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 60 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 10h in 100 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 5
(1) by PPO resin dry 9h, PA66 resin dry 9h in 90 DEG C of baking ovens in 90 DEG C of baking ovens, then get 20 parts of the PPO resins, 80 parts of the PA66 resins that were dried, with 1.0 parts of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 5 parts of toughner SEBS-g-MAH, 0.5 part of antioxidant 1010 and 1.0 parts of lubricant TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) in high-speed mixer, mix 7min, mix;
(2) the coupling agent 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) of 1.0 parts is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 2.0%, utilize spray method that spray solution is upper at 75 parts of short glass fibers (length is 12.0mm), and will be sprayed with glass fibre dry 90min in 80 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 75 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 8h in 110 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 6
(1) by PPO resin dry 9h, PA66 resin dry 9h in 90 DEG C of baking ovens in 90 DEG C of baking ovens, then get 50 parts of the PPO resins, 50 parts of the PA66 resins that were dried, with 0.4 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 10 parts of toughner SEBS-g-MAH, 0.2 part of antioxidant 1076 and 0.4 part of lubricant TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) in high-speed mixer, mix 4min, mix;
(2) the coupling agent 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) of 0.25 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.0%, utilize spray method that spray solution is upper at 30 parts of short glass fibers (length is 5.0mm), and will be sprayed with glass fibre dry 45min in 110 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 30 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 8h in 110 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 7
(1) by PPO resin dry 9h, PA66 resin dry 9h in 90 DEG C of baking ovens in 90 DEG C of baking ovens, then get 50 parts of the PPO resins, 50 parts of the PA66 resins that were dried, with 0.4 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 15 parts of toughner SEBS-g-MAH, 0.2 part of antioxidant 1076 and 0.4 part of lubricant TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) in high-speed mixer, mix 4min, mix;
(2) the coupling agent 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) of 0.25 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.0%, utilize spray method that spray solution is upper at 30 parts of short glass fibers (length is 5.0mm), and will be sprayed with glass fibre dry 45min in 110 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 30 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 8h in 110 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 8
(1) by PPO resin dry 9h, PA66 resin dry 9h in 90 DEG C of baking ovens in 90 DEG C of baking ovens, then get 50 parts of the PPO resins, 50 parts of the PA66 resins that were dried, with 0.4 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 20 parts of toughner SEBS-g-MAH, 0.2 part of antioxidant 1076 and 0.4 part of lubricant TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) in high-speed mixer, mix 4min, mix;
(2) the coupling agent 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) of 0.25 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.0%, utilize spray method that spray solution is upper at 30 parts of short glass fibers (length is 5.0mm), and will be sprayed with glass fibre dry 45min in 110 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 30 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 8h in 110 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 9
(1) by PPO resin dry 9h, PA66 resin dry 9h in 90 DEG C of baking ovens in 90 DEG C of baking ovens, then get 50 parts of the PPO resins, 50 parts of the PA66 resins that were dried, with 0.4 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 25 parts of toughner SEBS-g-MAH, 0.2 part of antioxidant 1076 and 0.4 part of lubricant TAF(modification ethylene bis-fatty acid amides, photochemistry auxiliary agent company limited of Suzhou Xingtai state) in high-speed mixer, mix 4min, mix;
(2) the coupling agent 3-glycidyl ether oxygen propyl trimethoxy silicane (KH560) of 0.25 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 1.0%, utilize spray method that spray solution is upper at 30 parts of short glass fibers (length is 5.0mm), and will be sprayed with glass fibre dry 45min in 110 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 30 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 285 DEG C, districts, three 295 DEG C, districts, four 300 DEG C, districts, five 300 DEG C, districts, head temperature is 290 DEG C;
By above-mentioned pellet dry 8h in 110 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 290 DEG C of first paragraphs, 300 DEG C, the 3rd section 310 DEG C of second segments, head temperature is 310 DEG C.
Embodiment 10
(1) by PPO resin dry 8h, PA6 resin dry 8h in 100 DEG C of baking ovens in 100 DEG C of baking ovens, then get 30 parts of the PPO resins, 70 parts of the PA6 resins that were dried, with 0.6 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 10 parts of toughner SBS, 0.4 part of irgasfos 168 and 0.8 part of lubricant RH-313C(pentaerythritol stearate, the Dongguan City plasthetics company limited that hikes) in high-speed mixer, mix 6min, mix;
(2) the coupling agent 3-aminopropyl triethoxysilane (KH550) of 0.20 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 0.5%, utilize spray method that spray solution is upper at 50 parts of short glass fibers (length is 4.5mm), and will be sprayed with glass fibre dry 30min in 120 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 15 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 280 DEG C, districts, three 285 DEG C, districts, four 290 DEG C, districts, five 290 DEG C, districts, head temperature is 285 DEG C;
By above-mentioned pellet dry 6h in 120 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 280 DEG C of first paragraphs, 290 DEG C, the 3rd section 300 DEG C of second segments, head temperature is 300 DEG C.
Embodiment 11
(1) (1) is by PPO resin dry 8h, PA6 resin dry 8h in 100 DEG C of baking ovens in 100 DEG C of baking ovens, then get 30 parts of the PPO resins, 70 parts of the PA6 resins that were dried, with 0.8 part of epoxy resin four glycidyl group-4,4 '-diaminodiphenylmethane, 10 parts of toughner SBS, 0.4 part of irgasfos 168 and 0.8 part of lubricant RH-313C(pentaerythritol stearate, the Dongguan City plasthetics company limited that hikes) in high-speed mixer, mix 6min, mix;
(2) the coupling agent 3-aminopropyl triethoxysilane (KH550) of 0.20 part is dissolved in dehydrated alcohol, be mixed with concentration and be coupling agent-ethanolic soln of 0.5%, utilize spray method that spray solution is upper at 50 parts of short glass fibers (length is 4.5mm), and will be sprayed with glass fibre dry 30min in 120 DEG C of baking ovens of coupling agent solution;
(3) by compound in above-mentioned (1) through upstream spout, send into twin screw extruder, simultaneously by 15 parts of glass fibre in above-mentioned (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation, each section of temperature of forcing machine is: 270 DEG C, a district, two 280 DEG C, districts, three 285 DEG C, districts, four 290 DEG C, districts, five 290 DEG C, districts, head temperature is 285 DEG C;
By above-mentioned pellet dry 6h in 120 DEG C of baking ovens, through injection moulding machine preparation standard batten, survey its physicals, refer to table 1, wherein each section of temperature of injection moulding machine is: 280 DEG C of first paragraphs, 290 DEG C, the 3rd section 300 DEG C of second segments, head temperature is 300 DEG C.
Table 1 glass fibre strengthens the performance of PPO/PA alloy material
| Performance index | Tensile strength/MPa | Flexural strength/MPa | Modulus in flexure/MPa | Shock strength/kJm -2 |
| Embodiment 1 | 115 | 159 | 4780 | 81 |
| Embodiment 2 | 148 | 192 | 5336 | 94 |
| Embodiment 3 | 166 | 213 | 5680 | 102 |
| Embodiment 4 | 187 | 226 | 5910 | 107 |
| Embodiment 5 | 193 | 234 | 6120 | 110 |
| Embodiment 6 | 180 | 221 | 5732 | 105 |
| Embodiment 7 | 168 | 206 | 5595 | 114 |
| Embodiment 8 | 159 | 195 | 5410 | 121 |
| Embodiment 9 | 153 | 188 | 5283 | 124 |
| Embodiment 10 | 175 | 217 | 5776 | 104 |
| Embodiment 11 | 181 | 225 | 5895 | 106 |
From table 1, embodiment 1～5 can find out, in PPO/PA66 alloy material, PA and PPO proportioning and epoxy resin, coupling agent, content of glass fiber are different, all can affect the mechanical property of alloy material; From table 1, embodiment 6～9 can find out, along with the increase of toughner content, the shock strength of PPO/PA66 alloy material improves widely, and intensity declines to some extent; From table 1, embodiment 10～11 can find out, along with the increase of epoxy resin content, the mechanical property of PPO/PA6 alloy material increases.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can, easily to these embodiment, make various amendments, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (10)
1. glass fiber reinforced polyester phenylate/polyamide alloy material, is characterized in that: be made up of the component that comprises following weight part:
20～60 parts of polyphenylene oxide resins,
40～80 parts of polyamide resins,
0.2～1.0 part of epoxy resin,
5～25 parts of toughner,
0.1～0.5 part, oxidation inhibitor,
0.2～1.0 part of lubricant,
0.02～1.0 part of coupling agent,
15～75 parts, glass fibre.
2. glass fiber reinforced polyester phenylate/polyamide alloy material according to claim 1, is characterized in that: described PA resin is polymeric amide, is selected from PA6, PA11, PA12, PA46, PA66, PA610, PA612 or PA1010, preferably PA6 or PA66.
3. glass fiber reinforced polyester phenylate/polyamide alloy material according to claim 1, it is characterized in that: described epoxy resin is selected from triphenol methylmethane triglycidyl ether, four phenolic group ethane four glycidyl ethers, triglycidyl group p-aminophenol, triglycidyl group isocyanuric acid ester, four glycidyl group-4, 4 '-diaminodiphenylmethane, four glycidyl group m-xylene diamine, 1, two (the N of 3-, N-2-glycidyl aminomethyl) hexanaphthene or four glycidyl group-4, 4 '-diaminodiphenyl oxide, preferably four glycidyl group-4, 4 '-diaminodiphenylmethane.
4. glass fiber reinforced polyester phenylate/polyamide alloy material according to claim 1, it is characterized in that: described toughner is selected from terpolymer EP rubber, glycidyl methacrylate graft terpolymer EP rubber, maleic anhydride grafted ethene-octene copolymer, high-impact polystyrene, MBS, acrylonitrile-butadiene-styrene copolymer, styrene-ethylene-butylene-styrene block copolymer, one or more in maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer or SBS, optimization styrene-ethene-butylene-styrene segmented copolymer, maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer or SBS.
5. glass fiber reinforced polyester phenylate/polyamide alloy material according to claim 1, it is characterized in that: described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three ［ 2,4-di-tert-butyl-phenyl ］ one or more in phosphorous acid ester or the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
Or described lubricant is selected from one or more in whiteruss, modification ethylene bis-fatty acid amides or pentaerythritol stearate.
6. glass fiber reinforced polyester phenylate/polyamide alloy material according to claim 1, is characterized in that: described coupling agent is selected from 3-aminopropyl triethoxysilane, 3-glycidyl ether oxygen propyl trimethoxy silicane or 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane;
Or described glass fibre is alkali-free short glass fiber, length is 3.0～12.0mm.
7. a preparation method for arbitrary described glass fiber reinforced polyester phenylate/polyamide alloy material in claim 1-6, is characterized in that: comprise the following steps:
(1) by even to 20～60 parts of dry polyphenylene oxide resins, 40～80 parts of polyamide resins and 0.2～1.0 part of epoxy resin, 5～25 parts of toughner, 0.1～0.5 part of oxidation inhibitor and 0.2～1.0 part of mix lubricant;
(2) 0.02～1.0 part of coupling agent is dissolved in dehydrated alcohol, is mixed with coupling agent-ethanolic soln, utilize spray method by spray solution on 15～75 parts of glass fibre, and the glass fibre that is sprayed with coupling agent solution is dry in baking oven;
(3) by compound in step (1) through upstream spout, send into twin screw extruder, simultaneously by 15～75 parts of glass fibre in step (2) through downstream spout, send into that twin screw extruder melt extrudes, granulation; Obtain glass fiber reinforced polyester phenylate/polyamide alloy material.
8. preparation method according to claim 7, is characterized in that: in described step (1), the drying conditions of polyphenylene oxide resin is: dry 8～10h in 80～100 DEG C of baking ovens;
Or in described step (1), the drying conditions of polyamide resin is: dry 8～10h in 80～100 DEG C of baking ovens.
9. preparation method according to claim 7, is characterized in that: the device mixing in described step (1) is high-speed mixer, and mixing time is 3～7min;
Or the concentration of coupling agent-ethanolic soln is 0.5～2.0wt% in described step (2), the glass fibre drying conditions that is sprayed with coupling agent solution is: dry 30～90min in the baking oven of 80～120 DEG C.
10. preparation method according to claim 7, is characterized in that: in described step (3) twin screw extruder, melt extruding temperature is 270～300 DEG C;
In described step (4), pellet drying conditions is: dry 6～10h in 100～120 DEG C of baking ovens, the temperature of injection moulding machine preparation standard batten is 280～310 DEG C.
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| CN105273390A (en) * | 2015-11-30 | 2016-01-27 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Processing method of hydrolysis and alcoholysis resistant PPE (polyphenylene ether)/glass fiber masterbatch |
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