CN102040767A - Uvioresistant polypropylene composition and preparation method thereof - Google Patents
Uvioresistant polypropylene composition and preparation method thereof Download PDFInfo
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Abstract
The invention provides an uvioresistant polypropylene composition, comprising the following components in parts by weight: 100 parts of polypropylene resin, 1-6 parts of surface-modified nanowires, 0.3-1.0 part of photostabilizer and 0.15-1.0 part of antioxidant. In the preparation method, the polypropylene resin, surface-modified nanowires, photostabilizer and antioxidant are added in a high-speed mixer to mix for 4+/-2 minutes; and melting granulation is carried out at 180-240 DEG C by using a double-screw extruder to obtain the uvioresistant polypropylene material. After the uvioresistant polypropylene material is subject to accelerated ageing for 200 hours with an ultraviolet B (UVB) lamp, the tensile strength retention rate of the component resin (sample wafer thickness of 2mm) is more than 95%, e.g. a flexible freight bag has the advantages of better tensile strength, fracture strength and uvioresistant ageing property. Detection is carried out on the basis of an ASTM (American Society for Testing Material) G154 method, and after a sample is aged for 144 and 200 hours, the fracture strength retention rate of the sample can reach above 70%.
Description
One, technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of uvioresistant poly propylene compositions, said composition has a wide range of applications in the polypropylene packaging material field, be specially adapted to the outdoor application scenario higher, as long day area, highlands, area that temperature is high to the anti-ultraviolet ageing performance requriements.
Two, background technology
Polypropylene (PP) in the Plastic Packaging Materials field, has crucial application as one of five big general-purpose plastics.Compare with the Traditional Packing material, with PP is the wrapping material of raw material, have light weight, intensity height, corrosion-resistant, easy recovery, pollution-free, characteristics such as cleaning is easy, good combination property, thereby be widely used in salt, chemical fertilizer, grain, ore in sand form, building materials, tent and other material package.It is poor that yet the shortcoming of PP maximum is a weather resisteant, under sunlight, light or the irradiation of space energetic ray, tertiary carbon atom on the PP macromolecular chain is easy to take off a hydrogen atom that is attached thereto and forms initial active center, photoaging takes place rapidly, phenomenons such as gloss disappears, becomes fragile, fission, variable color occur, physical strength reduces greatly.This has greatly limited PP and has used application and development in the packing articles out of doors.
Tradition is improved the method for PP light stability, mainly be to add organic uv absorbers (UVA) and hindered amine as light stabilizer (HALS), but UVA and HALS are the organic synthesis things lower than acrylic resin molecular weight, be certain limitation all to be arranged to the absorption of UV-light or to catching of free radical, and along with migration and degraded can take place in the prolongation of duration of service, cause the ultraviolet light performance of material can descend ultimate failure gradually.
Improving the PP light stability with inorganic nano material, is a new technology of development in recent years, and relevant patent has CN02218333, CN200510010538, CN200610040163.Compare with conventional art, the inorganic materials of nanoscale has stronger function of shielding ultraviolet radiation, and have nontoxic, stable, good characteristic such as do not move, can overcome the deficiency of above-mentioned organic stabilizer preferably.Studies show that the size of specific surface area is determining nano material to improve the degree of light stability.Usually the method for increasing specific surface area is to reduce particle size as far as possible, but particle is more little, disperses difficultly more, easily is agglomerated into macrobead, can descend on the contrary to the screening ability of UV-light.At present, there is more employing inorganic nanoparticles to improve the report of PP light stability in the patent, though wherein adopt surface-modifying agents such as some silane coupling agents, titanate coupling agent can improve the dispersiveness of nano particle, but it is limited to improve effect, is still waiting further improvement for the raising of PP light stability.
Inorganic nanowires is emerging in recent years a kind of monodimension nanometer material, than the nano particle of zero dimension, because nano wire is being a nanoscale laterally, makes it have excellent function of shielding ultraviolet radiation equally.On the other hand, because nano wire is being a micro-meter scale vertically, reunite than the nano particle of same amount is difficult.In addition, nano wire has outstanding mechanical property, and the adding of nano wire can also improve the mechanical property of body material.It is still rare to adopt nano wire to improve the report of optical stability of PP now in the document.
Three, summary of the invention
The objective of the invention is to: overcome deficiency of the prior art, a kind of uvioresistant polypropene composition and preparation method of excellent combination property is provided.By adopting the novel inorganic nano-material, in conjunction with traditional UV light absorber and hindered amine light stabilizer, the polyacrylic light stability of collaborative improvement, overcome the disadvantage that general inorganic nanoparticles is reunited and disperseed inequality in polypropylene, improved polyacrylic anti-ultraviolet ageing performance to a greater degree.
Technical solution of the present invention is: the uvioresistant polypropene composition comprises following composition (being weight part):
Described acrylic resin is that a kind of, any two kinds or three kinds in homo-polypropylene, block polypropylene or the Atactic Polypropelene mix.
Described surface-modified nano line can be one or more in zinc oxide, zirconium white, aluminum oxide, magnesium oxide, the silicon oxide.
Described photostabilizer can be one or more in one or more and the hindered amines radical scavenger of UV light absorber such as benzophenone, benzotriazole category, acrylonitrile derivative class, triazines.Comprise: Octabenzone, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two-hydroxyl-four-n-octyl group dihydroxy benaophenonel, poly-{ (6-morpholinyl-5-triazine-2,4--two bases) (2,2,6, the 6-tetramethyl-piperidyl) imido grpup hexa-methylene [(2,2,6, the 6-tetramethyl-piperidyl)-imido grpup], Succinic Acid and 4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidines alcohol, poly--{ [6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-], 1,6 hexanediamines, N, N '-two (2,2,6,6-tetramethyl-, 4-pyridyl)-with 2,4-dichloro morpholinyl-1,3, the polymkeric substance of 5-triazine, 1,6 hexanediamine, N, N '-two (1,2,2,6, the 6-pentamethyl-, the 4-pyridyl)-same morpholine-2,4,6-three chloro-1,3, the polymkeric substance of 5-triazine, or the like.
Described antioxidant can be one or more in the oxidation inhibitor such as phenols, phosphorous acid esters, triazines.Comprise: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 1,3,5, three (3, the 5-di-t-butyl, the 4-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) three ketones, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) 1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, four (2, the 4-di-tert-butylphenol)-4,4 '-the xenyl diphosphites or the like.
The preparation method of uvioresistant polypropylene material of the present invention comprises following steps:
(1) with surface-modifying agent nano wire is carried out surface modification earlier, wherein the consumption of surface-modifying agent is the 0.5%-5% of nano wire.The kind of surface-modifying agent is one or more in silane coupling agent, titante coupling agent or the aluminate class coupling agent.
(2) nano wire after acrylic resin, the surface modification, photostabilizer, oxidation inhibitor are joined in the high-speed mixer, mixed about 4 ± 2 minutes, under temperature 180-240 ℃ condition, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Beneficial effect of the present invention is: compared with prior art, by the outdoor packing articles that uvioresistant polypropylene material provided by the invention is produced, its anti-ultraviolet aging performance and mechanical property be improved significantly.On the one hand, goods are subjected to the stable protection of dual light, and not only UV light absorber and hindered amine light stabilizer have stabilization to material, and the zinc oxide inorganic nanowires can shield UV-light, reduce ultraviolet (uv) transmission, and it is aging further to delay goods; On the other hand, because the enhancement of zinc oxide inorganic nanowires makes the intensity of polypropylene material and rigidity increase; In addition, the tint permanence of goods also makes moderate progress.Through the accelerated deterioration of 200 hours UVB lamps, stretching strength retentivity is greater than 95% for this component resin (print thickness 2mm).Such as the Shipping Sack goods, have better intensity and anti-ultraviolet aging performance, the method for stipulating according to ASTM G154 detects, and through the accelerated deterioration of 200 hours UVB lamps, the breaking tenacity conservation rate is greater than 70%.
Four, embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this, and the add-on of each material is all represented with weight part among the embodiment.
Embodiment 1
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 5% of the total consumption of nano wire.It is fully mixed that surface modification is that surface-modifying agent carries out nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Comparative Examples 1
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Comparative Examples 2
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
According to ASTM G154 regulation, through 200 hours UVB lamp accelerated weathering tests, the performance test that resin of 3 kinds of different ingredients (print thickness 2mm) and Shipping Sack are weaved cotton cloth was as follows:
Embodiment 2
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 3% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Comparative Examples 3
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Comparative Examples 4
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
According to ASTM G154 regulation, through 200 hours UVB lamp accelerated weathering tests, the performance test that resin of 3 kinds of different ingredients (print thickness 2mm) and Shipping Sack are weaved cotton cloth was as follows:
Embodiment 3
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 2% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Comparative Examples 5
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Comparative Examples 6
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
According to ASTM G154 regulation, through 200 hours UVB lamp accelerated weathering tests, the performance test that resin of 3 kinds of different ingredients (print thickness 2mm) and Shipping Sack are weaved cotton cloth was as follows:
Embodiment 4
Adopt the surface-modifying agent titanate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 4% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 5
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 3% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 6
Adopt the surface-modifying agent titanate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 5% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 4 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 7
Adopt the surface-modifying agent aluminate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 3% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 8
Adopt the surface-modifying agent titanate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 2% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 9
Adopt the surface-modifying agent titanate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 2% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 10
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 2% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 11
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 1% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 12
Adopt the surface-modifying agent aluminate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 0.5% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 13
Adopt the surface-modifying agent aluminate coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 1% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 14
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 2% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 15
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 1% of the total consumption of nano wire.
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
Embodiment 16
Adopt the surface-modifying agent silane coupling agent, nano wire is carried out surface modification, wherein the consumption of surface-modifying agent is 2% of the total consumption of nano wire (weight).
Above component is joined in the high-speed mixer, mixed 3 minutes, under 180 ℃ of-240 ℃ of conditions of temperature, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
All can replace mutually between the kind of photostabilizer and oxidation inhibitor.
Claims (6)
1. uvioresistant polypropene composition is characterized in that comprising that following components by weight percent forms:
Wherein, described acrylic resin is in homo-polypropylene, block polypropylene or the Atactic Polypropelene a kind of, any two kinds or three kinds.
2. uvioresistant polypropene composition according to claim 1 is characterized in that described photostabilizer is one or more in one or more and the hindered amines radical scavenger of benzophenone, benzotriazole category, acrylonitrile derivative class or triazines UV light absorber; Described antioxidant is one or more in phenols, phosphorous acid esters or the triazines oxidation inhibitor.
3. uvioresistant polypropene composition according to claim 1 is characterized in that with surface-modifying agent nano wire being carried out surface modification earlier, and wherein the consumption of surface-modifying agent is the 0.5%-5% of nano wire.The kind of surface-modifying agent is silane coupling agent, titante coupling agent or aluminate class coupling agent.
4. uvioresistant polypropene composition according to claim 1 is characterized in that photostabilizer is an Octabenzone, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two-hydroxyl-four-n-octyl group dihydroxy benaophenonel, poly-{ (6-morpholinyl-5-triazine-2,4--two bases) (2,2,6, the 6-tetramethyl-piperidyl) imido grpup hexa-methylene [(2,2,6, the 6-tetramethyl-piperidyl)-imido grpup], Succinic Acid and 4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidines alcohol, poly--{ [6-[(1,1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5-triazine-2, [2-(2 for 4-two bases, 2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-], 1,6 hexanediamine, N, N '-two (2,2,6, the 6-tetramethyl-, the 4-pyridyl)-with 2, the polymkeric substance of 4-dichloro morpholinyl-1,3,5-triazines, 1,6 hexanediamines, N, N '-two (1,2,2,6,6-pentamethyl-, 4-pyridyl)-same morpholine-2,4, in the polymkeric substance of 6-three chloro-1,3,5-triazines more than one.
5. uvioresistant polypropene composition according to claim 1 is characterized in that described antioxidant is one or more in the oxidation inhibitor such as phenols, phosphorous acid esters, triazines.
6. the preparation method of uvioresistant polypropylene material is characterized in that comprising following steps:
(1) with surface-modifying agent nano wire is carried out surface modification earlier, wherein the consumption of surface-modifying agent is the 0.5%-5% of nano wire, and the kind of surface-modifying agent is silane coupling agent, titante coupling agent or aluminate class coupling agent;
(2) nano wire after acrylic resin, the surface modification, photostabilizer, oxidation inhibitor are joined in the high-speed mixer, mixed 4 ± 2 minutes, under temperature 180-240 ℃ condition, use the twin screw extruder melt pelletization then, promptly obtain the uvioresistant polypropylene material.
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