CN103102684A - Weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and its preparation method - Google Patents
Weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and its preparation method Download PDFInfo
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Abstract
The invention discloses a weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material, which is prepared from the following components by weight: 400-560 parts of PA66, 100-140 parts of PA6, 300-500 parts of continuous glass fiber, 6-10 parts of an antioxidant, 1-6 parts of a composite anti-hydrolysis agent, 2-5 parts of a composite light stabilizer, 4-8 parts of a lubricant, and 5-15 parts of a carbon black masterbatch. The weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material provided in the invention has excellent weatherability and good hydrolysis resistance, and at the same time has excellent rigidity and impact toughness. An injection molding piece made of the composite material has a good surface appearance. Besides, the material can be directly shaped through injection molding, the production efficiency is high, and the used piece can be recycled after smashing.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material and preparation method thereof.
Background technology
Nylon 66(PA66) contain the amide group of strong polarity in molecular backbone chain, and the hydrogen bond between amide group makes intermolecular bonding force stronger, easily make structure generation crystallization, so material has good mechanical property, as high in intensity, good rigidly, shock resistance etc., advantage, the especially thermotolerance such as material also has oil resistant in addition and chemical drugs moral character, wear resistance, self lubricity and processing fluidity be good and creep resistance are better.The PA66 raw material is easy to get in addition, and cost is low, thereby is widely applied to the fields such as industry, clothes, decoration, engineering plastics.But the impact property of PA66 under dry state and low temperature is relatively poor, and Young's modulus is low, and particularly easily suction and affect the dimensional stability of goods, can not satisfy the requirement of environmental stress resistance and high manufacturing accuracy.
Nylon and glass fibre affinity are very good, fiber reinforcement can reduce the resin water-intake rate, can work under high temperature, high humidity, especially the continuous glass-fiber reinforced polyamide is because its staple length is longer, not only have excellent rigidity and have simultaneously good impelling strength, the fields such as automobile, aviation, military project that are widely used in replace metallic substance.
Although after fiber glass reinforced polyamide, the water-intake rate of material can be reduced to 2% left and right, water-intake rate well below polyamide raw materials, but still the performance of material had a great impact, cause the material extending performance to reduce by 50% left and right, reasons such as photoaging in use procedure under condition out of doors particularly, the material property conservation rate has limited the use field of fiber glass reinforced polyamide material greatly less than initial state 40%.Therefore for mechanical property and the higher structure unit of outdoor service requirements, need the continuous glass-fiber reinforced polyamide matrix material that the development mechanics performance is higher, have better weathering resistance and resistant to hydrolysis.Adopt single nylon hydrolysis-resisting agent, can not guarantee the material property of long-term hygrometric state.
Chinese patent CN102010590A proposes a kind of long glass fibre reinforced nylon material and preparation method thereof, and component is: nylon 29-67wt%, long glass fibres 30-60wt%, compatilizer 2-10wt%, oxidation inhibitor 0.3-1.0wt%.Preparation method: first nylon, compatilizer, oxidation inhibitor are mixed; Mixture is joined in twin screw extruder, processing temperature is at 235-300 ℃ again; Resin melt is clamp-oned in the impregnation mold that is connected with the twin-screw extrusion machine head; Then with long glass fibres by impregnation mold, the dipping temperature of impregnation mold is 260-320 ℃, and long glass fibres is fully flooded by melt, cooling, traction at last, pelletizing namely obtain the Long Glass Fiber Reinforced Pa pellet.This invention only proposes material of roving glass fiber Reinforced Nylon and preparation method thereof, but fails to further investigate on the resistant to hydrolysis performance of long fiber reinforced nylon material and weather resistance.
Chinese patent CN101921474A provides a kind of enhancing high-temperature nylon and preparation method thereof.Strengthening high-temperature nylon is made by the raw material of following weight part ratio: polyphenyl diamide 55%-80%, glass fibre 20%-45%, Brueggemann oxidation inhibitor 0.1%-1.2%.Strengthen high-temperature nylon by polyphenyl diamide being mixed with glass fibre and Brueggemann oxidation inhibitor generate, make and strengthen chemical resistant properties and the easy advantage of processing that high-temperature nylon has not only kept other nylon to have, and under the effect of glass fibre and Brueggemann oxidation inhibitor, improved enhancing high-temperature nylon resistance to elevated temperatures and impact strength, thereby the enhancing high-temperature nylon can be more widely used.This invention adopts the Brueggemann copper salt antioxidant to improve to a certain extent the resistance to hydrolysis of material, but adopt the direct blending and modifying of twin screw extruder, because the shearing action of screw rod causes staple length very little, improve limitedly for the performance of nylon material, especially shock strength is lower.
Summary of the invention
The technical problem to be solved in the present invention is: for shortcoming and the problem of above prior art existence, a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material and preparation method thereof is provided, this material not only has good weather resistance and resistant to hydrolysis performance, and owing to adopting continuous glass-fiber to strengthen, the blend of glass and resin is not carried out in twin screw, also possesses simultaneously excellent rigidity and impelling strength, the Injection moulded part appearance is good, this material can be by the injection moulding straight forming, production efficiency is high, and the product after use can be recycled after crushed.
Technical scheme of the present invention is:
A kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material, it is characterized in that, be prepared from by the component of following parts by weight: PA66:400-560 part, PA6:100-140 part, continuous glass fibre: 300-500 part, oxidation inhibitor: 6-10 part, composite hydrolysis-resisting agent: 1-6 part, the steady agent of composite light: 2-5 part, lubricant: 4-8 part, black masterbatch: 5-15 part.
The melting index of described PA66 resin under 275 ℃ of test temperatures, test load 0.325Kg is 20g-40g/10min.
The melting index of described PA6 resin under 230 ℃ of test temperatures, test load 2.16Kg is 20-40g/10min.
Described continuous glass fibre is selected from alkali free glass fibre, and its diameter is 13-22 μ m, and linear density is 1200-4800g/km.
Described oxidation inhibitor comprises N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (anti-168), and both weight part ratio is 1:2.
Described composite hydrolysis-resisting agent is polycarbodiimide and diisobutyl phosphorodithioic acid copper, and both weight is 1:1;
The steady agent of described composite light is hindered amines light stabilizer: N, N '-two formyls-N, and N '-two (2,2,6,6-tetramethyl--4-piperidines)-hexamethylene-diamine and Octabenzone, both weight part ratio is 1:1;
Described lubricant is selected from the one or more kinds of mixtures in ethylene-acrylic acid copolymerization wax, calcium stearate (CaSt), silicone and tetramethylolmethane stearate.
In described black masterbatch, content of carbon black 50%, and matrix resin is ethylene-vinyl acetate copolymer;
A kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture method comprises the following steps:
(1), PA66, PA6, oxidation inhibitor, composite hydrolysis-resisting agent, the steady agent of composite light, lubricant and black masterbatch were joined in high mixer successively at 40-60 ℃ of batch mixing 3-5 minute.Then mixed uniform mixture is added in the hopper of forcing machine standbyly, the drying temperature of forcing machine hopper is set as 80-90 ℃;
(2), adopt the special-purpose impregnating equipment of continuous fiber reinforced thermoplastic material, by forcing machine, above-mentioned material melting is injected in impregnating equipment, simultaneously continuous glass fibre is joined in impregnating equipment and the molten resin Uniform Dispersion, select the size 2.5-3.5mm of typing mouthful mould, adjust simultaneously the engine speed of forcing machine at 16-22Hz, rate of feeding is at 15.0-17.0Hz, adjust the cutting knife rotating speed of dicing machine, make the weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material pelletizing length for preparing be controlled at 11-13mm;
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, the mixed melting Temperature Setting is: 200-280 ℃;
Described impregnating equipment temperature is 280-320 ℃;
Described PA66, PA6 before mixing under the environment of temperature 90-100 ℃ dry 6-8h.
The present invention is owing to having adopted above technical scheme, namely prepare continuous glass-fiber reinforced polyamide matrix material by adding the steady agent of composite light and hydrolysis-resisting agent, because glass carries out dispersing and mixing with molten resin in impregnating equipment, glass fibre is orientated by same direction in this material, and the length of glass fibre is greater than 3mm, thereby increased substantially rigidity and impelling strength and the weather-proof and resistant to hydrolysis performance of material.Owing to adopting PA6 as the processing auxiliary material, reduced the viscosity of system, improve the processibility of material, and solved the problem of product surface floating fiber, improved the product surface quality.
The present invention compares with prior art, has following advantage and beneficial effect:
1, with prior art first than, the present invention adopts the continuous glass fibre reinforced plastic PA66, by impregnating equipment, continuous glass fibre is carried out Uniform Dispersion, thorough impregnation, improved the interface interaction of glass fibre and PA66, guarantee the useful length of glass fibre, thereby greatly improved the rigidity of this material and the shock resistance of intensity and material.
2, compared with prior art, the present invention adopts compound nylon hydrolysis-resisting agent and the steady agent of complex light, makes the matrix material of system have excellent resistance to hydrolysis and good weathering resistance;
3, with prior art first than, due to the use of PA6, reduced the viscosity of system, use the product appearance surfaces of material injection moulding of the present invention's preparation good, without glass emergence on the surface and floating fine;
4, the present invention is reasonable in design, simple to operate, practical, product is the pellet (grain length: 11-13mm with certain-length, diameter: 2.5-3.5mm), directly injection moulding after drying treatment, production efficiency is high, and product can also be recycled through pulverization process after using, and is free from environmental pollution.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Wherein, the PA66 resin, melting index is 20-40g/10min, test condition is 275 ℃, 0.325Kg; PA6 resin, melting index are 20-40g/10min, and test condition is 230 ℃, 2.16Kg; Continuous glass fibre is the alkali-free continuous glass fibre, and Fibre diameter is 17 μ m, and linear density is 1200-4800g/km; Oxidation inhibitor comprises N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (anti-168), and weight part ratio both is 1:2; Compound hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphorodithioic acid copper of Lay mattress chemistry, and both weight is 1:1; The steady agent of complex light is UV531 and the UV4050 of BASF, and weight part ratio both is 1:1; Lubricant comprises ethylene-acrylic acid copolymerization wax (AC540A), calcium stearate (CaSt), silicone (GM100) and tetramethylolmethane stearate (PETS); The black masterbatch trade mark is MBB2801;
Embodiment 1
(1), a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material, this material pelletizing length 11-13mm, particle diameter 3.5mm, it comprises the component of following weight part ratio: PA6:140 part, PA66:560 part, continuous glass fibre: 300 parts, oxidation inhibitor: 8 parts, composite hydrolysis-resisting agent: 4 parts, and the steady agent of composite light: 4 parts, lubricant: 6 parts, black masterbatch: 10 parts; Wherein, the PA66 resin, melting index is 24g/10min, test condition is 275 ℃, 0.325Kg; PA6 resin, melting index are 20g/10min, and test condition is 230 ℃, 2.16Kg; Continuous glass fibre is the alkali-free continuous glass fibre, and Fibre diameter is 17 μ m, and linear density is 2400g/km; Oxidation inhibitor comprises N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (anti-168), and weight part ratio both is 1:2; Compound hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphorodithioic acid copper of Lay mattress chemistry, and both weight is 1:1; The steady agent of complex light is UV531 and the UV4050 of BASF, and weight part ratio both is 1:1; Lubricant comprises ethylene-acrylic acid copolymerization wax (AC540A) and calcium stearate (CaSt), and weight part ratio both is 1:1; The black masterbatch trade mark is MBB2801;
(2), a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture method, comprise the following steps:
A, the dry preparation: the PA66/PA6 raw material is placed in moisture eliminator, drying temperature: 95 ℃, time of drying: 6h;
B, batch mixing are prepared: join successively 560 parts of PA66,140 parts of PA6,8 parts of oxidation inhibitor, 4 parts of composite hydrolysis-resisting agents, 4 parts of steady agent of composite light, 6 parts of lubricants, 10 parts of black masterbatchs in high mixer, mixture temperature is controlled at 50 ℃, mixing time stopped after 4 minutes, then mixed material is added in the hopper of forcing machine standbyly, the drying temperature of forcing machine hopper is set as 85 ℃;
c, weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture: adopt patent (CN1488674, the open date: the special-purpose impregnating equipment of the continuous fiber reinforced thermoplastic material that proposes 2004.04.14), forcing machine is injected into above-mentioned material melting in impregnating equipment, simultaneously continuous glass fibre is joined in impregnating equipment and the molten resin Uniform Dispersion, by the finalize the design size 3.5mm of mouthful mould of selection, , adjust simultaneously the engine speed of forcing machine at 16-22Hz, rate of feeding is at 15.0-17.0Hz, glass fiber content is controlled at 300 parts, adjust the cutting knife rotating speed of dicing machine, make the weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material pelletizing length for preparing be controlled at 11-13mm,
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, the mixed melting Temperature Setting is: 210 ℃ of first paragraphs, 250 ℃ of second segments, the 3rd section 260 ℃, the 4th section 270 ℃, the 5th section 280 ℃, 265 ℃ of melt temperatures, 280 ℃ of head temperatures;
Described impregnating equipment design temperature is 280 ℃;
D, injection moulding and batten test: weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material obtained above is carried out injection moulding after dry 6h under 100 ℃ of environment in baking oven, the injection moulding batten is the ASTM batten, and injection temperature is as follows:
Blanking section: 260 ℃; Second segment: 280 ℃; The 3rd section: 290 ℃; Nozzle: 270 ℃;
At last the injection moulding batten is put in and carries out status adjustment in moisture eliminator: regulate temperature: 23 ℃; The adjusting time: 16h; Testing standard in performance test is to specifications carried out, and test result sees Table 2.
Weather-proof test:
Testing standard: SAE J1960-2004. is with controlling the acceleration irradiation of water-cooled xenon arc lamp to the automobile external material; Adopt the performance comparison of the aging 1000h of injection moulding batten test front and back, test result sees Table 3;
The hydrolysis test:
95 ℃ of heating in water bath 100h of distilled water are placed in 100 ℃ of oven drying 6h, after status adjustment 16h, and the batten performance before and after the test water-bath, test result sees Table 4;
Embodiment 2
(1), a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material, this material pelletizing length 11-13mm, particle diameter 3.0mm, the component that comprises following weight part ratio: PA6:120 part, PA66:480 part, continuous glass fibre: 400 parts, oxidation inhibitor: 8 parts, composite hydrolysis-resisting agent: 4 parts, the steady agent of composite light: 5 parts, lubricant: 8 parts, black masterbatch: 5 parts; Wherein, the PA66 resin, melting index is 24g/10min, test condition is 275 ℃, 0.325Kg; PA6 resin, melting index are 20g/10min, and test condition is 230 ℃, 2.16Kg; Continuous glass fibre is the alkali-free continuous glass fibre, and Fibre diameter is 17 μ m, and linear density is 1200g/km; Oxidation inhibitor comprises N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (anti-168), and weight part ratio both is 1:2; Compound hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphorodithioic acid copper of Lay mattress chemistry, and both weight is 1:1; The steady agent of complex light is UV531 and the UV4050 of BASF, and weight part ratio both is 1:1; Lubricant comprises ethene-acrylic acid copolymer wax (AC540A) and silicone (GM100), and weight part ratio both is 1:1; Black masterbatch is MBB2801;
(2), a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture method, comprise the following steps:
A, the dry preparation: the PA66/PA6 raw material is placed in moisture eliminator, drying temperature: 95 ℃, time of drying: 6h;
B, batch mixing are prepared: join successively 480 parts of PA66,120 parts of PA6,8 parts of oxidation inhibitor, 4 parts of compound hydrolysis-resisting agents, 5 parts of steady agent of complex light, 8 parts of lubricants, 5 parts of black masterbatchs in high mixer, mixture temperature is controlled at 50 ℃, mixing time stopped after 4 minutes, then mixed material is added in the hopper of forcing machine standbyly, the drying temperature of forcing machine hopper is set as 85 ℃;
c, weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture: adopt patent (CN1488674, the open date: the special-purpose impregnating equipment of the continuous fiber reinforced thermoplastic material that proposes 2004.04.14), forcing machine is injected into above-mentioned material melting in impregnating equipment, simultaneously continuous glass fibre is joined in impregnating equipment and the molten resin Uniform Dispersion, by the finalize the design size 3.0mm of mouthful mould of selection, , adjust simultaneously the engine speed of forcing machine at 16-22Hz, rate of feeding is at 15.0-17.0Hz, glass fiber content is controlled at 400 parts, adjust the cutting knife rotating speed of dicing machine, make the weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material pelletizing length for preparing be controlled at 11-13mm,
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, the mixed melting Temperature Setting is: 210 ℃ of first paragraphs, 250 ℃ of second segments, the 3rd section 260 ℃, the 4th section 270 ℃, the 5th section 280 ℃, 265 ℃ of melt temperatures, 280 ℃ of head temperatures;
Described impregnating equipment temperature is 300 ℃;
D, injection moulding and batten test: weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material obtained above is carried out injection moulding after dry 6h under 100 ℃ of environment in baking oven, the injection moulding batten is the ASTM batten, and injection temperature is as follows:
Blanking section: 260 ℃; Second segment: 280 ℃; The 3rd section: 290 ℃; Nozzle: 270 ℃;
At last the injection moulding batten is put in and carries out status adjustment in moisture eliminator: regulate temperature: 23 ℃; The adjusting time: 16h; Testing standard in performance test is to specifications carried out, and test result sees Table 2.
Weather-proof test:
Testing standard: SAE J1960-2004. is with controlling the acceleration irradiation of water-cooled xenon arc lamp to the automobile external material; Adopt the performance comparison of the aging 1000h of injection moulding batten test front and back, test result sees Table 3;
The hydrolysis test:
95 ℃ of heating in water bath 100h of distilled water are placed in 100 ℃ of oven drying 6h, after status adjustment 16h, and the batten performance before and after the test water-bath, test result sees Table 4;
Embodiment 3
(1), a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material, this material pelletizing length 11-13mm, particle diameter 3.5mm, the component that comprises following weight part ratio: PA6:100 part, PA66:400 part, continuous glass fibre: 500 parts, oxidation inhibitor: 8 parts, composite hydrolysis-resisting agent: 4 parts, the steady agent of composite light: 2 parts, lubricant: 4 parts, black masterbatch: 15 parts; Wherein, the PA66 resin, melting index is 24g/10min, test condition is 275 ℃, 0.325Kg; PA6 resin, melting index are 20g/10min, and test condition is 230 ℃, 2.16Kg; Continuous glass fibre is the alkali-free continuous glass fibre, and Fibre diameter is 17 μ m, and linear density is 4800g/km; Oxidation inhibitor comprises N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (anti-168), and weight part ratio both is 1:2; Compound hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphorodithioic acid copper of Lay mattress chemistry, and both weight is 1:1; The steady agent of complex light is UV531 and the UV4050 of BASF, and weight part ratio both is 1:1; Lubricant comprises silicone (GM100) and tetramethylolmethane stearate (PETS), and weight part ratio both is 1:1; Black masterbatch is MBB2801;
(2), a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture method, comprise the following steps:
A, the dry preparation: the PA66/PA6 raw material is placed in moisture eliminator, drying temperature: 95 ℃, time of drying: 6h;
B, batch mixing are prepared: join successively 400 parts of PA66,100 parts of PA6,8 parts of oxidation inhibitor, 4 parts of composite hydrolysis-resisting agents, 2 parts of steady agent of composite light, 4 parts of lubricants, 15 parts of black masterbatchs in high mixer, mixture temperature is controlled at 50 ℃, mixing time stopped after 4 minutes, then mixed material is added in the hopper of forcing machine standbyly, the drying temperature of forcing machine hopper is set as 85 ℃;
c, weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture: adopt patent (CN1488674, the open date: the special-purpose impregnating equipment of the continuous fiber reinforced thermoplastic material that proposes 2004.04.14), forcing machine is injected into above-mentioned material melting in impregnating equipment, simultaneously continuous glass fibre is joined in impregnating equipment and the molten resin Uniform Dispersion, by the finalize the design size 2.5mm of mouthful mould of selection, , adjust simultaneously the engine speed of forcing machine at 16-22Hz, rate of feeding is at 15.0-17.0Hz, glass fiber content is controlled at 500 parts, adjust the cutting knife rotating speed of dicing machine, make the weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material pelletizing length for preparing be controlled at 11-13mm,
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, the mixed melting Temperature Setting is: 210 ℃ of first paragraphs, 250 ℃ of second segments, the 3rd section 260 ℃, the 4th section 270 ℃, the 5th section 280 ℃, 265 ℃ of melt temperatures, 280 ℃ of head temperatures;
Described impregnating equipment temperature is 320 ℃;
D, injection moulding and batten test: weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material obtained above is carried out injection moulding after dry 6h under 100 ℃ of environment in baking oven, the injection moulding batten is the ASTM batten, and injection temperature is as follows:
Blanking section: 260 ℃; Second segment: 280 ℃; The 3rd section: 290 ℃; Nozzle: 270 ℃;
At last the injection moulding batten is put in and carries out status adjustment in moisture eliminator: regulate temperature: 23 ℃; The adjusting time: 16h; Testing standard in performance test is to specifications carried out, and test result sees Table 2.
Weather-proof test:
Testing standard: SAE J1960-2004. is with controlling the acceleration irradiation of water-cooled xenon arc lamp to the automobile external material; Adopt the performance comparison of the aging 1000h of injection moulding batten test front and back, test result sees Table 3;
The hydrolysis test:
95 ℃ of heating in water bath 100h of distilled water are placed in 100 ℃ of oven drying 6h, after status adjustment 16h, and the batten performance before and after the test water-bath, test result sees Table 4;
Comparative Examples 1
In order to compare with prior art, adopt continuous glass fibre and PA66/PA6 resin to disperse in the direct melting mixing of twin screw extruder in this Comparative Examples, namely in (2), continuous glass fibre directly is added to twin screw extruder from fiber entry, by adjusting screw speed and feeding rotating speed, control content of glass fiber at 300 parts, pull out material strip from twin screw extruder, material strip is crossed water cooling, blower fan dries up the water on material strip surface, then carries out pelletizing; Other components, formula rate and preparation method and embodiment 1 are identical, and its performance test results sees Table 4.
Comparative Examples 2
In order to compare with technical scheme of the present invention, in this Comparative Examples, hydrolysis-resisting agent is selected from the polycarbodiimide (Stabaxol P) of Lay mattress chemistry, add-on is 4 parts, and other components and formula rate, preparation method and embodiment 1 are identical, and its performance test results sees Table 4.
Comparative Examples 3
In order to compare with technical scheme of the present invention, in this Comparative Examples, hydrolysis-resisting agent is selected from the diisobutyl phosphorodithioic acid, and add-on is 4 parts, and other components and formula rate, preparation method and embodiment 1 are identical, and its performance test results sees Table 4.
Comparative Examples 4
In order to compare with technical scheme of the present invention, in this Comparative Examples, the steady agent of light is the UV531 of BASF, and add-on is 4 parts, and other components and formula rate, preparation method and embodiment 1 are identical, and its performance test results sees Table 3.
Comparative Examples 5
In order to compare with technical scheme of the present invention, in this Comparative Examples, the steady agent of light is the UV4050 of BASF, and add-on is 4 parts, and other components and formula rate, preparation method and embodiment 1 are identical, and its performance test results sees Table 3.
Comparative Examples 6
In order to compare with technical scheme of the present invention, in this Comparative Examples, the steady agent of complex light is UV531 and the UV4050 of BASF, and add-on is 2 parts, and other components and formula rate, preparation method and embodiment 1 are identical, and its performance test results sees Table 3.
Comparative Examples 7
In order to compare with technical scheme of the present invention, in this Comparative Examples, hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphorodithioic acid copper of Lay mattress chemistry, both weight is 1:1, add-on is 2 parts, other components and formula rate, preparation method and embodiment 1 are identical, and its performance test results sees Table 4.
Injection moulding and batten test:
Weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material obtained above is carried out injection moulding after dry 6-8h under 80-100 ℃ of environment in baking oven, the injection moulding batten is the ASTM batten, and injection temperature is as follows:
Blanking section: 260 ℃; Second segment: 280 ℃; The 3rd section: 290 ℃; Nozzle: 270 ℃;
At last the injection moulding batten is put in and carries out status adjustment in moisture eliminator: regulate temperature: 23 ℃, the adjusting time: 16h; The batten performance test is carried out according to following standard meter 1, and test result sees Table 2.
Table 1 Mechanics Performance Testing standard
| Test event | Measuring unit | Testing standard | Remarks |
| Tensile strength | MPa | ASTM D638 | ? |
| Flexural strength | MPa | ASTM D790 | ? |
| Modulus in flexure | MPa | ASTM D790 | ? |
| The socle girder notched Izod impact strength | KJ/m 2 | ASTM D256 | 23℃ |
| Glass fiber content | % | ASTM D2584 | ? |
| Density | g/cm3 | ASTM D792 | ? |
| Heat-drawn wire | ℃ | ASTM D648 | 1.82MPa |
Weather-proof test:
Testing standard: SAE J1960-2004. is with controlling the acceleration irradiation of water-cooled xenon arc lamp to the automobile external material; Adopt the performance comparison of the aging 1000h of injection moulding batten test front and back, test result sees Table 3;
The hydrolysis test:
95 ℃ of heating in water bath 100h of distilled water are placed in 100 ℃ of oven drying 6h, after status adjustment 16h, and the batten performance before and after the test water-bath, test result sees Table 4;
Test data contrast in each embodiment of table 2
| ASTM | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Remarks |
| Tensile strength (MPa) | 182 | 229 | 246 | 165 | ? |
| Flexural strength (MPa) | 280 | 305 | 355 | 245 | ? |
| Modulus in flexure (MPa) | 7500 | 12500 | 16000 | 6800 | ? |
| Socle girder notched Izod impact strength (KJ/m 2） | 35 | 43 | 48 | 11 | 23℃ |
| Glass fiber content (%) | 31 | 40 | 51 | 30 | ? |
| Density (g/cm3) | 1.36 | 1.46 | 1.58 | 1.36 | ? |
| Heat-drawn wire (℃) | 220 | 220 | 221 | 190 | 1.82MPa |
The contrast of each embodiment xenon lamp aging of table 3 1000h test data
| ASTM | Embodiment 1 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | Remarks |
| Tensile strength (MPa) | 110 | 82 | 78 | 95 | ? |
| Flexural strength (MPa) | 190 | 132 | 145 | 166 | ? |
| Modulus in flexure (MPa) | 6300 | 3600 | 3800 | 4200 | ? |
| Socle girder notched Izod impact strength (KJ/m 2） | 32 | 26 | 24 | 27 | 23℃ |
| Glass fiber content (%) | 31 | 30 | 31 | 30 | ? |
The contrast of each embodiment heating in water bath of table 4 100h test data
| ASTM | Embodiment 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 7 | Remarks |
| Tensile strength (MPa) | 115 | 79 | 81 | 86 | ? |
| Flexural strength (MPa) | 185 | 130 | 127 | 142 | ? |
| Modulus in flexure (MPa) | 5900 | 3550 | 3801 | 4655 | ? |
| Socle girder notched Izod impact strength (KJ/m 2） | 38 | 24 | 26 | 29 | 23℃ |
| Glass fiber content (%) | 31 | 30 | 31 | 30 | ? |
Find out according to the data in table 2, in embodiment 1,2,3, along with the increase of continuous glass fibre content, the mechanical strength of material presents the trend that increases gradually.Comparative Examples 1 and the test result that embodiment 1 makes material are compared, can find out, the embodiment of the present invention 1 adopts roving glass fiber dipping reinforced polyamide matrix material, because the material property of staple length than the granulation of common double screw rod will exceed a lot, so especially particularly evident aspect notched Izod impact strength on mechanical property.
The xenon lamp aging data can be found out from table 3, and comparative example 1 and Comparative Examples 4,5,6 after reducing the content of the steady agent of light or adopt the steady agent system of single light, all do not reach material property of the present invention.
Test data contrast after the hot water bath heating from table 4, can find out from embodiment 1 and Comparative Examples 2,3,7 test data, after reducing the add-on of hydrolysis-resisting agent or adopting single resistant to hydrolysis system, the obvious step-down of material property illustrates that the compound hydrolysis-resisting agent in the present invention has significant effect aspect the resistant to hydrolysis of polymeric amide.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and in the General Principle of this explanation is applied to other embodiment and needn't pass 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 breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material, it is characterized in that, be prepared from by the component of following parts by weight: PA66:400-560 part, PA6:100-140 part, continuous glass fibre: 300-500 part, oxidation inhibitor: 6-10 part, composite hydrolysis-resisting agent: 1-6 part, the steady agent of composite light: 2-5 part, lubricant: 4-8 part, black masterbatch: 5-15 part.
2. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1, it is characterized in that: the melting index of described PA66 resin under 275 ℃ of test temperatures, test load 0.325Kg is 20g-40g/10min.
3. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1, it is characterized in that: the melting index of described PA6 resin under 230 ℃ of test temperatures, test load 2.16Kg is 20-40g/10min.
4. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1, it is characterized in that: described continuous glass fibre is selected from alkali free glass fibre, and its diameter is 13-22 μ m, and linear density is 1200-4800g/km.
5. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1; it is characterized in that: described oxidation inhibitor comprises N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester, both weight part ratio is 1:2.
6. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1, it is characterized in that: described composite hydrolysis-resisting agent is selected from polycarbodiimide and diisobutyl phosphorodithioic acid copper, and both weight is 1:1.
7. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1, it is characterized in that: the steady agent of described composite light is selected from hindered amines light stabilizer N, N '-two formyls-N, N '-two (2,2,6,6-tetramethyl--4-piperidines)-hexamethylene-diamine and Octabenzone, both weight part ratio is 1:1.
8. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material according to claim 1, it is characterized in that: described lubricant is selected from the one or more kinds of mixtures in ethylene-acrylic acid copolymerization wax, calcium stearate, silicone and tetramethylolmethane stearate.
9. the described weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture method of claim 1-8 any one is characterized in that: comprise the following steps:
(1), PA66, PA6, oxidation inhibitor, composite hydrolysis-resisting agent, the steady agent of composite light, lubricant and black masterbatch were joined in high mixer successively at 40-60 ℃ of batch mixing 3-5 minute; Then mixed uniform mixture is added in the hopper of forcing machine standbyly, the drying temperature of forcing machine hopper is set as 80-90 ℃;
(2), adopt the special-purpose impregnating equipment of continuous fiber reinforced thermoplastic material, by forcing machine, above-mentioned material melting is injected in impregnating equipment, simultaneously continuous glass fibre is joined in impregnating equipment and the molten resin Uniform Dispersion, select the size 2.5-3.5mm of typing mouthful mould, adjust simultaneously the engine speed of forcing machine at 16-22Hz, rate of feeding is at 15.0-17.0Hz, adjust the cutting knife rotating speed of dicing machine, make the weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide matrix material pelletizing length for preparing be controlled at 11-13mm;
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, the mixed melting Temperature Setting is: 200-280 ℃.
10. a kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite manufacture method according to claim 9, it is characterized in that: described impregnating equipment temperature is 280-320 ℃; Described PA66, PA6 before mixing under the environment of temperature 90-100 ℃ dry 6-8h.
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|---|---|---|---|---|
| CN103289335A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Hydrolysis-resistant enhanced PBT |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733959A (en) * | 1994-12-01 | 1998-03-31 | Basf Aktiengesellschaft | Stabilized polyester molding compositions |
| CN101250332A (en) * | 2008-04-08 | 2008-08-27 | 赵卫国 | Reactive golden yellow RNL diazo dyes and preparation method thereof |
| CN101460562A (en) * | 2006-06-06 | 2009-06-17 | 拜尔材料科学有限公司 | Hydrolysis stabilizer for thermoplastic molding composition |
| CN101914289A (en) * | 2010-08-30 | 2010-12-15 | 南京聚隆科技股份有限公司 | Glassfiber-reinforced hydrolysis-resistant low-warpage nylon 66 composite material and preparation method thereof |
| CN102558847A (en) * | 2010-12-29 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Hydrolysis resistant continuous carbon fiber reinforced nylon 6 material and preparation method thereof |
-
2013
- 2013-02-20 CN CN201310053783.5A patent/CN103102684B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733959A (en) * | 1994-12-01 | 1998-03-31 | Basf Aktiengesellschaft | Stabilized polyester molding compositions |
| CN101460562A (en) * | 2006-06-06 | 2009-06-17 | 拜尔材料科学有限公司 | Hydrolysis stabilizer for thermoplastic molding composition |
| CN101250332A (en) * | 2008-04-08 | 2008-08-27 | 赵卫国 | Reactive golden yellow RNL diazo dyes and preparation method thereof |
| CN101914289A (en) * | 2010-08-30 | 2010-12-15 | 南京聚隆科技股份有限公司 | Glassfiber-reinforced hydrolysis-resistant low-warpage nylon 66 composite material and preparation method thereof |
| CN102558847A (en) * | 2010-12-29 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Hydrolysis resistant continuous carbon fiber reinforced nylon 6 material and preparation method thereof |
Cited By (15)
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|---|---|---|---|---|
| CN103289335A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Hydrolysis-resistant enhanced PBT |
| CN104277759A (en) * | 2013-07-10 | 2015-01-14 | 浙江新安化工集团股份有限公司 | Ageing resistant type solar photovoltaic component sealing material and preparation method thereof |
| CN104277759B (en) * | 2013-07-10 | 2016-12-28 | 浙江新安化工集团股份有限公司 | Aging-resisting type solar photovoltaic assembly encapsulant and preparation method thereof |
| CN106317867A (en) * | 2015-06-18 | 2017-01-11 | 合肥杰事杰新材料股份有限公司 | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof |
| CN105419320A (en) * | 2015-11-19 | 2016-03-23 | 东莞市众一新材料科技有限公司 | High glass fiber filled and reinforced nylon composite and preparation method thereof |
| CN106995606A (en) * | 2016-01-26 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | A kind of dissaving polymer modified polyamide composite and preparation method thereof |
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