CN101423664B - Reinforced nylon composition and preparation method thereof - Google Patents
Reinforced nylon composition and preparation method thereof Download PDFInfo
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- CN101423664B CN101423664B CN2007101654722A CN200710165472A CN101423664B CN 101423664 B CN101423664 B CN 101423664B CN 2007101654722 A CN2007101654722 A CN 2007101654722A CN 200710165472 A CN200710165472 A CN 200710165472A CN 101423664 B CN101423664 B CN 101423664B
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Abstract
The invention provides a reinforced nylon composition. The reinforced nylon composition contains nylon and glass fiber, wherein the reinforced nylon composition also contains nano titanium dioxide treated by a coupling agent; and the average grain diameter of the nano titanium dioxide treated by the coupling agent is between 10 and 50 nanometers. In the reinforced nylon composition provided by the invention, the nano titanium dioxide treated by the coupling agent is better compatible with the nylon, so that the reinforced nylon composition has good mechanical performances such as tensile strength, elongation at break, flexural strength and flexural modulus; because the titanium dioxide has the function of shielding ultraviolet rays, the reinforced nylon composition can partially or fully replace a light stabilizer, thereby lowering cost.
Description
Technical field
The present invention relates to a kind of Reinforced Nylon composition, also relate to this Reinforced Nylon preparation of compositions method.
Background technology
Nylon is polyamide resin (PA), and its amide group has polarity, has firm hydrogen bond in its structure, makes that the fusing point of nylon is higher, has excellent mechanical property, good wear resistance and self lubricity and erosion resistance preferably.
But pure nylon has, and heat-drawn wire is lower, water-absorbent is big, impact resistance difference and the unsettled shortcoming of size under poor water resistance, dry state and the low-temperature condition, makes the over-all properties of nylon lower, has limited its wider application.At present, adopt the filling enhancing modified agent to reduce the water-intake rate of nylon usually, the rigidity of nylon is increased, high temperature creep and shrinking percentage reduce, and improve dimensional stability, resistance to impact shock, wear resistance and the flame retardant resistance of nylon.
General Reinforced Nylon mainly is to strengthen its mechanical property by adding glass fibre, as shock resistance, stretching and flexural strength, improves dimensional stability by adding inorganic minerals such as wollastonite, kaolin, glass microballon.Titanium dioxide can further increase the mechanical property of glass fibre reinforced nylon, and has a function of shielding ultraviolet rays, but when the preparation Reinforced Nylon,, can not effectively improve the mechanical property of glass fibre reinforced nylon thus because the consistency of titanium dioxide and glass fibre reinforced nylon is very poor.Therefore, in the prior art, when the preparation Reinforced Nylon, also do not adopt and add the method that titanium dioxide further increases the mechanical property of Reinforced Nylon, the Reinforced Nylon of yet not added titanium dioxide.
Summary of the invention
The object of the present invention is to provide a kind of added titanium dioxide and with the good Reinforced Nylon composition of nylon compatibility, this Reinforced Nylon preparation of compositions method also is provided.
The invention provides a kind of Reinforced Nylon composition, this Reinforced Nylon composition contains nylon and glass fibre, wherein, described Reinforced Nylon composition also contains the nano titanium oxide of coupling agent treatment, and the average particulate diameter of the nano titanium oxide of described coupling agent treatment is the 10-50 nanometer.
The present invention also provides a kind of Reinforced Nylon preparation of compositions method, this method comprises nylon is added fusion in the twin screw extruder, then the glass inlet from described twin screw extruder adds glass fibre, extrude together, wherein, this method comprises that also elder generation is mixed the nano titanium oxide of coupling agent treatment with nylon before extruding, and the average particulate diameter of the nano titanium oxide of described coupling agent treatment is the 10-50 nanometer.
Reinforced Nylon composition provided by the invention, the nano titanium oxide of coupling agent treatment and the consistency of nylon are fine, thereby can make Reinforced Nylon composition of the present invention obtain good mechanical property, all fine as tensile strength, elongation at break, flexural strength and modulus in flexure.And, therefore can partly or entirely replace photostabilizer, thereby can reduce cost because titanium dioxide has the function of shielding ultraviolet rays.
Embodiment
Reinforced Nylon composition provided by the invention contains nylon and glass fibre, and wherein, described Reinforced Nylon composition also contains the nano titanium oxide of coupling agent treatment, and the average particulate diameter of the nano titanium oxide of described coupling agent treatment is the 10-50 nanometer.
According to Reinforced Nylon composition provided by the invention, in the preferred case, based on the nylon of 100 weight parts, the content of described glass fibre is the 20-50 weight part, and the content of the nano titanium oxide of described coupling agent treatment is the 10-20 weight part.
Titanium dioxide is a kind of widely used ultraviolet screener material, when in nylon, adding titanium dioxide, the particle diameter of titanium dioxide is more little, disperse just even more, and titanium dioxide is relevant with its size to ultraviolet receptivity, the particle diameter of titanium dioxide is more little, and it is strong more to the receptivity of ultraviolet, therefore uses the titanium dioxide of average particulate diameter as the 10-50 nanometer in the present invention; On the other hand, because the nano titanium oxide surface energy is very big, be easy to produce coacervate and bad dispersibility, therefore the titanium dioxide through coupling agent treatment can be dispersed in the nylon well, thereby effectively improve the mechanical property of nylon, and have the good ultraviolet function of absorption, can partly or entirely replace photostabilizer.
According to Reinforced Nylon composition provided by the invention, in the preferred case, in the nano titanium oxide of described coupling agent treatment, the weight ratio of coupling agent and titanium dioxide is 1: 20-200.
According to Reinforced Nylon composition provided by the invention, in the preferred case, the preparation method of the nano titanium oxide of described coupling agent treatment comprises, under the state that stirs, tetrabutyl titanate solution is joined in the mixed aqueous solution that contains hydrolysis inhibitor and dispersion agent gradually, add coupling agent solution then and mix, adjusting pH is 5-6, mixing time is 20-60 minute, and is then dry under 300-400 ℃ temperature.
Described coupling agent can well known to a person skilled in the art various coupling agents; for example silane coupling agent and/or titanate coupling agent; the example of coupling agent comprises γ-An Bingjisanyiyangjiguiwan (KH550); γ-(methacryloxy) propyl trimethoxy silicane (KH570); γ-r-chloropropyl trimethoxyl silane (A-143); γ-(2; the 3-glycidoxy) propyl trimethoxy silicane (A-187, KH-560); vinyltriethoxysilane (A151) and vinyltrimethoxy silane (A-171); sec.-propyl three (positive ethylamino-ethylamino) titanic acid ester (KB-44) and sec.-propyl three (dioctyl pyrophosphoryl base) titanic acid ester (KR-38S).
According to preparation method provided by the invention, when the nano titanium oxide of preparation coupling agent treatment,, then be difficult to be uniformly dispersed if directly coupling agent is mixed with nano titanium oxide, therefore can't reach nano titanium oxide and the fine compatible purpose of nylon.Therefore the present inventor draws through research, in the process of preparation nano titanium oxide, add coupling agent, nano titanium oxide and coupling agent uniform mixing can be made, thereby the consistency of the nano titanium oxide and the nylon of coupling agent treatment can be improved effectively.
When the nano titanium oxide of above-mentioned preparation coupling agent treatment, in the preferred case, the weight ratio of the coupling agent in tetrabutyl titanate in the described tetrabutyl titanate solution and the hydrolysis inhibitor in the described mixed aqueous solution and dispersion agent and the described coupling agent solution is 1: 0.001-0.02: 0.001-0.04: 0.002-0.05.Described hydrolysis inhibitor is the various hydrolysis inhibitors that can suppress tetrabutyl titanate hydrolysis, for example hydrochloric acid and/or acetic acid, preferably hydrochloric acid; Described dispersion agent be for can make the homodisperse various dispersion agents of tetrabutyl titanate, preferred Vltra tears.
Above-mentioned titanic acid ester solution is the solution of titanic acid ester in organic solvent, and described organic solvent is for dissolving the various organic solvents of tetrabutyl titanate, for example one or more in ethanol, white oil and the Virahol.Tetrabutyl titanate in the tetrabutyl titanate solution and volume of organic solvent ratio are not particularly limited, and for even sprinkling, the volume ratio of preferred tetrabutyl titanate and solvent is 1: 1-4.
Concentration to hydrolysis inhibitor in the mixed aqueous solution of described hydrolysis inhibitor and dispersion agent and dispersion agent is not particularly limited, in order rationally to suppress hydrolysis, promote to disperse, the concentration of described hydrolysis inhibitor is preferably 0.01-0.1 weight %, and the concentration of described dispersion agent is preferably 0.01-0.1 weight %.
Above-mentioned coupling agent solution is the solution of coupling agent in organic solvent, and described organic solvent is for dissolving the various organic solvents of coupling agent, for example one or more in ethanol, white oil and the Virahol.Coupling agent in the described coupling agent solution and volume of organic solvent ratio are had no particular limits, and for even sprinkling, preferred described coupling agent is 1 with the volume of organic solvent ratio: 5-10.
According to Reinforced Nylon composition provided by the invention, in the preferred case, described glass fibre is an E type alkali-free roving glass fiber.Described nylon is nylon 6 (polycaprolactam) or nylon 66 (polyhexamethylene adipamide).
According to Reinforced Nylon composition provided by the invention, in the preferred case, described Reinforced Nylon composition also contains auxiliary agent, nylon based on 100 weight parts, the content of described auxiliary agent is the 0.04-4 weight part, described auxiliary agent is for well known to a person skilled in the art various auxiliary agents, for example oxidation inhibitor, anti-glass one or more in agent, lubricant and the photostabilizer that leak outside.
Wherein oxidation inhibitor contains primary antioxidant and auxiliary antioxidant; and the weight ratio of primary antioxidant and auxiliary antioxidant is 1: 1-4; described primary antioxidant is hindered phenol antioxygen and/or hindered amine oxidation inhibitor; the example of hindered phenol antioxygen comprises the oxidation inhibitor 1098 and 1010 of Switzerland Ciba company; the main component of oxidation inhibitor 1098 is N; N '-two-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionyl); the main component of antioxidant 1010 is that four [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane; the example of hindered amine oxidation inhibitor comprises pentanoic; compound such as Ursol D and dihydroquinoline and derivative thereof or polymkeric substance; described auxiliary antioxidant is a phosphite antioxidant; the example of industry phosphoric acid ester oxidation inhibitor comprises the oxidation inhibitor 168 of Switzerland Ciba company; its main component is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
The leak outside example of agent of described anti-glass is ethylene bis stearic amide grafts (TAF).
The example of described lubricant comprises at least a in polyethylene wax, paraffin wax, stearic acid wax, metallic soap salt and the silicone.
The example of described photostabilizer comprises hindered amine light stabilizer, as photostabilizer 622, and chemical name: Succinic Acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-pyridine alcohol; Photostabilizer 770, chemical name: two (2,2,6,6-tetramethyl--4-piperidyl) sebate.
Reinforced Nylon preparation of compositions method of the present invention comprises to be extruded with glass fibre fused nylon in twin screw extruder, wherein, this method also comprises, elder generation is mixed the nano titanium oxide of coupling agent treatment with nylon before extruding, and the average particulate diameter of the nano titanium oxide of described coupling agent treatment is the 10-50 nanometer.
According to preparation method provided by the invention, in the preferred case, based on the nylon of 100 weight parts, the consumption of described glass fibre is the 20-50 weight part, and the consumption of the nano titanium oxide of described coupling agent treatment is the 10-20 weight part.
According to preparation method provided by the invention, in the preferred case, this method also comprises, adding auxiliary agent when described nano titanium oxide with coupling agent treatment mixes with nylon mixes, and nylon based on 100 weight parts, the consumption of described auxiliary agent is the 0.04-4 weight part, and described auxiliary agent is leak outside in agent, lubricant and the photostabilizer one or more of oxidation inhibitor, anti-glass.
Adopt specific embodiment that the present invention is described in further detail below.
Embodiment 1
1, the preparation of the nano titanium oxide of coupling agent treatment
The 1.5L tetrabutyl titanate is joined in the 1.5L dehydrated alcohol, make the alcoholic solution that volume ratio is 1: 1 a tetrabutyl titanate;
The dilute solution (concentration is 1.1 weight %) of 250mL dilute hydrochloric acid (concentration is 0.54 weight %) and 300ml Vltra tears (HPMC) is joined in the 2L deionized water, stir, obtain the mixing solutions of hydrochloric acid and HPMC, wherein the concentration of hydrochloric acid is weight 0.1%, and the concentration of HPMC is 0.08 weight %.
The alcoholic solution of the above-mentioned tetrabutyl titanate that obtains is joined gradually in the mixed aqueous solution of above-mentioned dilute hydrochloric acid that obtains and HPMC (weight ratio of tetrabutyl titanate and hydrochloric acid and HPMC is 1: 0.0 1: 0.02), vigorous stirring, slowly add in the coupling agent solution that is made into by 6ml coupling agent (KH570) and 50ml milliliter dehydrated alcohol (weight ratio of tetrabutyl titanate and coupling agent is 1: 0.004) then, acetic acid solution with 2.5ml 0.1 weight % is adjusted to 5-6 with the pH value, stir and mixed 20 minutes, ageing obtained flocks after 8 hours then.Then dried 2 hours down at 400 ℃, obtain the nano-titanium dioxide powder of the coupling agent treatment of white, average particulate diameter is 25 nanometers, and wherein the weight ratio of coupling agent and titanium dioxide is 1: 90.
2, preparation Reinforced Nylon composition
Nylon 6 with 100 weight parts, the nano titanium oxide of 10 weight part coupling agent treatment, 0.008 weight part composite antioxidant (by oxidation inhibitor 1 68 and 1098 by weight 1: 1 composite forming), the agent TAF 1.2 the anti-glass of weight part leaks outside, 0.6 weight part lubricant silicone, join in the high mixer and mixed 3 minutes with high gear, join fusion in the twin screw extruder then, the E type alkali-free roving glass fiber that adds 20 weight parts after the fusion from the glass fibre inlet of twin screw extruder, extrude together, nylon composite is enhanced.
Each section temperature to twin screw extruder from charging opening to the head discharge port is controlled to be respectively: a district 210-220 ℃, two district 215-225 ℃, three district 220-230 ℃, four district 225-235 ℃, five district 230-245 ℃, six district 240-250 ℃.
Engine speed is 150 rev/mins, and the feeding rotating speed is 30 rev/mins.With pelletizing after the Reinforced Nylon composition water cooling of extruding, 90 ℃ of oven dry injection moulding tests after 4 hours down.
Embodiment 2
1, the preparation of the nano titanium oxide of coupling agent treatment
The 1.5L tetrabutyl titanate is joined in the 3L dehydrated alcohol, make the alcoholic solution that volume ratio is 1: 2 a tetrabutyl titanate;
The dilute solution (concentration is 1.35 weight %) of 400mL dilute hydrochloric acid (concentration is 0.35 weight %) and 100ml Vltra tears (HPMC) is joined in the 2L deionized water, stir, obtain the mixing solutions of hydrochloric acid and HPMC, wherein the concentration of hydrochloric acid is weight 0.05%, and the concentration of HPMC is 0.05 weight %.
The alcoholic solution of the above-mentioned tetrabutyl titanate that obtains is joined gradually in the mixed aqueous solution of above-mentioned dilute hydrochloric acid that obtains and HPMC (weight ratio of tetrabutyl titanate and hydrochloric acid and HPMC is 1: 0.0015: 0.0015), vigorous stirring, slowly add in the coupling agent solution that is made into by 3ml coupling agent (KH570) 24ml milliliter dehydrated alcohol (weight ratio of tetrabutyl titanate and coupling agent is 1: 0.002) then, acetic acid solution with 2.5ml 0.1 weight % is adjusted to 5-6 with the pH value, stir and mixed 40 minutes, ageing obtained flocks after 8 hours then.Then dried 3 hours down at 300 ℃, obtain the nano-titanium dioxide powder of the coupling agent treatment of white, average particulate diameter is 50 nanometers, and wherein the weight ratio of coupling agent and titanium dioxide is 1: 180.
2, preparation Reinforced Nylon composition
Nylon 6 with 100 weight parts, the nano titanium oxide of 15 weight part coupling agent treatment, 0.01 weight part composite antioxidant (by oxidation inhibitor 168 and 1098 by weight 1: 1 composite forming), agent TAF and 0.6 weight part lubricant polyethylene wax join in the high mixer and mixed 3 minutes with high gear 1.2 the anti-glass of weight part leaks outside, join fusion in the twin screw extruder then, the E type alkali-free roving glass fiber that adds 30 weight parts after the fusion from the glass fibre inlet of twin screw extruder, extrude together, nylon composite is enhanced.
Each section temperature to twin screw extruder from charging opening to the head discharge port is controlled to be respectively: a district 210-220 ℃, two district 215-225 ℃, three district 220-230 ℃, four district 225-235 ℃, five district 230-245 ℃, six district 240-250 ℃.
Engine speed is 165 rev/mins, and the feeding rotating speed is 30 rev/mins.With pelletizing after the Reinforced Nylon composition water cooling of extruding, 90 ℃ of oven dry injection moulding tests after 4 hours down.
Embodiment 3
1, the preparation of the nano titanium oxide of coupling agent treatment
The 1.5L tetrabutyl titanate is joined in the 6L dehydrated alcohol, make the alcoholic solution that volume ratio is 1: 4 a tetrabutyl titanate;
Dilute solution (concentration is 0.08 weight %) with 2.5L dilute hydrochloric acid (concentration is 0.07 weight %) and 4L Vltra tears (HPMC), stir, obtain the mixing solutions of hydrochloric acid and HPMC, wherein the concentration of hydrochloric acid is weight 0.025%, and the concentration of HPMC is 0.06 weight %.
The alcoholic solution of the above-mentioned tetrabutyl titanate that obtains is joined gradually in the mixed aqueous solution of above-mentioned dilute hydrochloric acid that obtains and HPMC (weight ratio of tetrabutyl titanate and hydrochloric acid and HPMC is 1: 0.02: 0.04), vigorous stirring, slowly add in the coupling agent solution that is made into by 18ml coupling agent (KH570) and 180ml milliliter dehydrated alcohol (weight ratio of tetrabutyl titanate and coupling agent is 1: 0.018) then, acetic acid solution with 2.5ml 0.1 weight % is adjusted to 5-6 with the pH value, stir and mixed 60 minutes, ageing obtained flocks after 8 hours then.Then dried 3 hours down at 300 ℃, obtain the nano-titanium dioxide powder of the coupling agent treatment of white, average particulate diameter is 10 nanometers, and wherein the weight ratio of coupling agent and titanium dioxide is 1: 30.
2, preparation Reinforced Nylon composition
Nylon 66 with 100 weight parts, the nano titanium oxide of 20 weight part coupling agent treatment, 0.01 part composite antioxidant (by oxidation inhibitor 168 and 1098 by weight 1: 1 composite forming), the agent TAF 1.2 the anti-glass of weight part leaks outside, 0.6 joining in the high mixer, weight part lubricant silicone and 0.2 weight part photostabilizer 622 mixed 2 minutes with high gear, join fusion in the twin screw extruder then, the E type alkali-free roving glass fiber that adds 45 weight parts after the fusion from the glass fibre inlet of twin screw extruder, extrude together, nylon composite is enhanced.
Each section temperature to twin screw extruder from charging opening to the head discharge port is controlled to be respectively: a district 235-245 ℃, two district 240-245 ℃, three district 245-255 ℃, four district 250-260 ℃, five district 255-265 ℃, six district 255-265 ℃.
Engine speed is 200 rev/mins, and the feeding rotating speed is 35 rev/mins.With pelletizing after the Reinforced Nylon composition water cooling of extruding, 90 ℃ of oven dry injection moulding tests after 4 hours down.
Comparative Examples 1
Nylon 6 with 100 weight parts, 0.01 weight part composite antioxidant (by oxidation inhibitor 168 and 1098 by weight 1: 1 composite forming), the agent TAF 1.2 the anti-glass of weight part leaks outside, 0.6 joining in the high mixer, weight part lubricant polyethylene wax and 0.4 weight part photostabilizer 622 mixed 3 minutes with high gear, join fusion in the twin screw extruder then, the E type alkali-free roving glass fiber that adds 30 weight parts after the fusion from the glass fibre inlet of twin screw extruder, extrude together, nylon composite is enhanced.
Each section temperature to twin screw extruder from charging opening to the head discharge port is controlled to be respectively: a district 210-220 ℃, two district 215-225 ℃, three district 220-230 ℃, four district 225-235 ℃, five district 230-245 ℃, six district 240-250 ℃.
Engine speed is 165 rev/mins, and the feeding rotating speed is 30 rev/mins.With pelletizing after the Reinforced Nylon composition water cooling of extruding, 90 ℃ of oven dry injection moulding tests after 4 hours down.
Comparative Examples 2
Nylon 6 with 100 weight parts, 0.01 weight part composite antioxidant (by oxidation inhibitor 168 and 1098 by weight 1: 1 composite forming), the agent TAF 1.2 the anti-glass of weight part leaks outside, 0.6 joining in the high mixer, mixed 3 minutes by weight part lubricant polyethylene wax with high gear, join fusion in the twin screw extruder then, add the E type alkali-free roving glass fiber of 30 weight parts after the fusion from the glass fibre inlet of twin screw extruder, extrude together, nylon composite is enhanced.
Each section temperature to twin screw extruder from charging opening to the head discharge port is controlled to be respectively: a district 210-220 ℃, two district 215-225 ℃, three district 220-230 ℃, four district 225-235 ℃, five district 230-245 ℃, six district 240-250 ℃.
Engine speed is 165 rev/mins, and the feeding rotating speed is 30 rev/mins.With pelletizing after the Reinforced Nylon composition water cooling of extruding, 90 ℃ of oven dry injection moulding tests after 4 hours down.
Performance test
1, Mechanics Performance Testing
The testing method of tensile strength and elongation at break is tested according to the method for ASTMD638 regulation, the testing method of notched Izod impact strength is according to the method test of ASTMD256 regulation, and the testing method of flexural strength and modulus in flexure is according to the method test of ASTMD790 regulation.According to the method described above embodiment 1-3 and Comparative Examples 1 resulting material are carried out Mechanics Performance Testing, the results are shown in Table 1 for gained.
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 |
| Tensile strength (MPa) | 105.95 | ?114.89 | ?156.51 | ?105.30 | ?116.25 |
| Elongation at break (%) | 2.53 | ?2.98 | ?3.1 | ?2.83 | ?2.89 |
| Notched Izod impact strength (J/M) | 90.19 | ?118.27 | ?157.86 | ?125.22 | ?129.00 |
| Flexural strength (MPa) | 149.91 | ?169.39 | ?221.31 | ?165.36 | ?170.36 |
| Modulus in flexure (MPa) | 5536.65 | ?5895.16 | ?7626.24 | ?5902.31 | ?5905.1 |
As can be seen from Table 1, the resulting material of embodiment 1-3 still keeps certain mechanical property, and the embodiment 2 that various conditions are suitable compares with Comparative Examples 2 with Comparative Examples 1, various mechanical properties are all suitable, the consistency that the titanium dioxide of coupling agent treatment and nylon are described is fine, and the Reinforced Nylon that obtains has good mechanical property.
2, anti-light aging performance test
Carry out the anti-light aging experiment, use Japanese WEL-6XS-HC type climate box, use German 4.8KW water-cooled xenon lamp as light source, blackboard temperature is 63 ± 3 ℃, relative humidity is 65 ± 5%, and the water spray cycle is 12min/ illumination 60min (continuous illumination), so handles 400 hours.Anti-light aging performance to embodiment 2 and Comparative Examples 1, Comparative Examples 2 gained materials is tested, and the results are shown in Table 2 for gained.
Table 2
| Embodiment 2 | Comparative Examples 1 | Comparative Examples 2 | |||||||
| Pre-irradiation | After the irradiation | Rate of descent | Pre-irradiation | After the irradiation | Rate of descent | Pre-irradiation | After the irradiation | Rate of descent | |
| Tensile strength (MPa) | 114.89 | ?107.86 | ?6.1％ | 105.30 | ?100.28 | ?4.8％ | 116.25 | ?90.36 | ?22.32％ |
| Elongation at break (%) | 2.98 | ?2.65 | ?11％ | 2.83 | ?2.54 | ?10.2％ | 3.01 | ?22.15 | ?2.28 |
| Flexural strength (MPa) | 169.39 | ?154.24 | ?8.9％ | 165.36 | ?153.33 | ?7.3％ | 170.36 | ?125.7 | ?26.5％ |
As can be seen from Table 2, with embodiment 2 resulting materials with the rate of descent of xenon lamp irradiation mechanical property after 400 hours and the quite basic of Comparative Examples 1 and much lower than Comparative Examples 2, illustrate that Reinforced Nylon composition provided by the invention has the performance of anti-light aging, can be used for nylon material by part instead of optical stablizer, thereby can reduce cost, but also has the good mechanical performance.
Claims (15)
1. Reinforced Nylon composition, this Reinforced Nylon composition contains nylon and glass fibre, it is characterized in that, described Reinforced Nylon composition also contains the nano titanium oxide of coupling agent treatment, the average particulate diameter of the nano titanium oxide of described coupling agent treatment is the 10-50 nanometer, and described coupling agent is silane coupling agent and/or titanate coupling agent.
2. Reinforced Nylon composition according to claim 1, wherein, based on the nylon of 100 weight parts, the content of described glass fibre is the 20-50 weight part, the content of the nano titanium oxide of described coupling agent treatment is the 10-20 weight part.
3. Reinforced Nylon composition according to claim 1, wherein, in the nano titanium oxide of described coupling agent treatment, the weight ratio of coupling agent and titanium dioxide is 1: 20-200.
4. Reinforced Nylon composition according to claim 1, wherein, the preparation method of the nano titanium oxide of described coupling agent treatment comprises, under the state that stirs, tetrabutyl titanate solution is joined in the mixed aqueous solution that contains hydrolysis inhibitor and dispersion agent gradually, add coupling agent solution then and mix, adjusting pH is 5-6, mixing time is 20-60 minute, and is then dry under 300-400 ℃ temperature.
5. Reinforced Nylon composition according to claim 4, wherein, the weight ratio of the coupling agent in tetrabutyl titanate in the described tetrabutyl titanate solution and the hydrolysis inhibitor in the described mixed aqueous solution and dispersion agent and the described coupling agent solution is 1: 0.001-0.02: 0.001-0.04: 0.002-0.05, described hydrolysis inhibitor are hydrochloric acid and/or acetic acid; Described dispersion agent is a Vltra tears.
6. according to any described Reinforced Nylon composition among the claim 1-4, wherein, described glass fibre is an E type alkali-free roving glass fiber, and described nylon is nylon 6 or nylon 66.
7. Reinforced Nylon composition according to claim 1; wherein; described coupling agent is one or more in γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxy) propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, γ-(2, the 3-glycidoxy) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane, sec.-propyl three (positive ethylamino-ethylamino) titanic acid ester and sec.-propyl three (the dioctyl pyrophosphoryl base) titanic acid ester.
8. Reinforced Nylon composition according to claim 1 and 2, wherein, described Reinforced Nylon composition also contains auxiliary agent, nylon based on 100 weight parts, the content of described auxiliary agent is the 0.04-4 weight part, and described auxiliary agent is leak outside in agent, lubricant and the photostabilizer one or more of oxidation inhibitor, anti-glass.
9. the described Reinforced Nylon preparation of compositions of claim 1 method, this method comprises to be extruded with glass fibre fused nylon in twin screw extruder, it is characterized in that, this method also comprises, elder generation is mixed the nano titanium oxide of coupling agent treatment with nylon before extruding, the average particulate diameter of the nano titanium oxide of described coupling agent treatment is the 10-50 nanometer, and described coupling agent is silane coupling agent and/or titanate coupling agent.
10. preparation method according to claim 9, wherein, based on the nylon of 100 weight parts, the consumption of described glass fibre is the 20-50 weight part, the consumption of the nano titanium oxide of described coupling agent treatment is the 10-20 weight part.
11. according to claim 9 or 10 described preparation methods, wherein, the preparation method of the nano titanium oxide of described coupling agent treatment comprises, under the state that stirs, tetrabutyl titanate solution is joined in the mixed aqueous solution that contains hydrolysis inhibitor and dispersion agent gradually, add coupling agent solution then and mix, adjusting pH is 5-6, mixing time is 20-60 minute, and is then dry under 300-400 ℃ temperature.
12. preparation method according to claim 11, wherein, the weight ratio of the coupling agent in tetrabutyl titanate in the described tetrabutyl titanate solution and the hydrolysis inhibitor in the described mixed aqueous solution and dispersion agent and the described coupling agent solution is 1: 0.001-0.02: 0.001-0.04: 0.002-0.05.
13. preparation method according to claim 11, wherein, described hydrolysis inhibitor is hydrochloric acid and/or acetic acid; Described dispersion agent is a Vltra tears; Described coupling agent is silane coupling agent and/or titanate coupling agent.
14. according to claim 9 or 10 described preparation methods, wherein, described glass fibre is an E type alkali-free roving glass fiber, described nylon is nylon 6 or nylon 66.
15. according to claim 9 or 10 described preparation methods, wherein, this method also comprises, adding auxiliary agent when described nano titanium oxide with coupling agent treatment mixes with nylon mixes, and nylon based on 100 weight parts, the consumption of described auxiliary agent is the 0.04-4 weight part, and described auxiliary agent is leak outside in agent, lubricant and the photostabilizer one or more of oxidation inhibitor, anti-glass.
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| CN102031022A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for modifying nano titanium dioxide sol by utilizing silane coupling agent |
| CN102911499B (en) * | 2011-08-03 | 2016-02-10 | 上海杰事杰新材料(集团)股份有限公司 | A kind of high stability uvioresistant high temperature resistant nylon and preparation method thereof |
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