CN108239344B - Zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material and preparation method thereof - Google Patents
Zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108239344B CN108239344B CN201711453657.3A CN201711453657A CN108239344B CN 108239344 B CN108239344 B CN 108239344B CN 201711453657 A CN201711453657 A CN 201711453657A CN 108239344 B CN108239344 B CN 108239344B
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- composite material
- oxide porous
- flame retardant
- polypropylene composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an uvioresistant halogen-free flame-retardant polypropylene composite material with a synergistic effect of zinc oxide porous nanotubes and a preparation method thereof. The polypropylene composite material is prepared from the following raw materials in parts by mass: polypropylene, P-N compound flame retardant, zinc oxide porous nanotube, hyperbranched polymer, light stabilizer, antioxidant and lubricant. Also discloses a preparation method of the anti-ultraviolet halogen-free flame-retardant polypropylene composite material. The invention adopts the zinc oxide porous nano tube with surface treatment to assist the hyperbranched polymer to disperse, improves the compatibility and the dispersity of the zinc oxide porous nano tube in the polypropylene matrix, and further exerts better ultraviolet resistance and better flame retardant synergistic effect. The zinc oxide nano tube with porous size is more outstanding in carbon forming efficiency and anti-dripping effect, the prepared polypropylene composite material also overcomes the defect that the traditional anti-dripping agent polytetrafluoroethylene obviously reduces the material flowability, and great convenience is brought to the processing of thin-wall multi-cavity products.
Description
Technical Field
The invention relates to an ultraviolet-resistant halogen-free flame-retardant polypropylene composite material with a synergistic effect of zinc oxide porous nanotubes and a preparation method thereof.
Background
The polypropylene is used as a plastic variety with light weight, no toxicity, acid and alkali resistance and relatively low price, and is widely applied to the fields of building, traffic, agriculture and industry. However, polypropylene has an oxygen index of only 17.4%, and is a flammable material.
The halogen-free intumescent flame retardant (P-N system) compounded by taking ammonium polyphosphate (APP) as a main raw material is a research hotspot of the academic community and is widely accepted by the industry because the halogen-free intumescent flame retardant conforms to the development trend of halogen-free environmental protection. However, the flame retardant has certain hygroscopicity, and the main body materials APP belong to inorganic materials, so that the compatibility between the flame retardant and the polypropylene matrix with extremely strong non-polarity is poor. If better mechanical property and better flame retardant effect are required to be obtained, the surface treatment is generally required before the flame retardant is used.
The polypropylene material has poor aging resistance, particularly ultraviolet light aging resistance due to the structural factor of the polypropylene material. Although the industrial application usually adopts direct addition of organic ultraviolet absorbers and hindered amine light stabilizers, the effect can be very good, but the ultraviolet resistance of the material is lost due to the fact that the molecular weight is small and the material is easy to migrate along with the prolonging of the service time.
The nano zinc oxide is a good synergist and activator, and has been accepted by academia and industry for playing a very remarkable synergistic effect when being used for a P-N system. However, most of the nano zinc oxide used in the field of flame retardant polypropylene is of a common nano structure. With the continuous exploration of nanotechnology, it is found that nanotubes and wires with special structures show higher activity and better synergistic effect due to larger surface area, and even have the efficacy of ultraviolet shielding. CN102040767A discloses a polypropylene composition added with zinc oxide nanowires, which shows very good ultraviolet resistance synergistic effect due to the special nanostructure. However, the nanowires are obtained under the condition of higher concentration of zinc oxide (as disclosed in the publication CN102206850A), and have the disadvantages of small specific surface area and low catalytic activity per unit mass relative to the zinc oxide nanotubes. CN101455960A obtains a zinc oxide nanotube with a porous (through hole) structure, and the activity of the zinc oxide nanotube is greatly enhanced. Unfortunately, there are few reports on zinc oxide nanotubes, especially nanotubes with porous structures, for polypropylene applications.
Disclosure of Invention
The invention aims to provide an anti-ultraviolet halogen-free flame-retardant polypropylene composite material with a synergistic effect of zinc oxide porous nanotubes and a preparation method thereof, so that the defect that the traditional organic ultraviolet absorbent and hindered amine light stabilizer are easy to migrate and separate out is overcome.
The technical scheme adopted by the invention is as follows:
the zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material is composed of the following raw materials in parts by mass:
the polypropylene is at least one of homo-polypropylene and co-polypropylene; the melt index of the polypropylene at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
The P-N compound flame retardant is treated by a surface treating agent.
The zinc oxide porous nanotube has an outer diameter of 17-400 nm, an inner diameter of 3-300 nm, a length of 400-4 μm, a pore diameter of 50-150 nm, and a porosity of 40-75%.
The zinc oxide porous nano tube is used after being treated by the surface treating agent.
The hyperbranched polymer is multi-stage branched polyester.
The light stabilizer is at least one of benzophenone, benzotriazole, salicylate, triazine, acrylonitrile derivative and hindered amine light stabilizer.
The antioxidant is at least one of hindered phenol, phosphite ester, hindered amine, thioester, and inorganic phosphate antioxidant.
The lubricant is at least one of stearic acid, stearate, paraffin, polyethylene wax, ethylene bis-stearic acid amide and pentaerythritol bis-stearate.
The surface treating agent for treating the P-N compound flame retardant or the zinc oxide porous nanotube is at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid and phosphate.
The preparation method of the zinc oxide porous nanotube synergistic uvioresistant halogen-free flame-retardant polypropylene composite material comprises the following steps:
1) weighing the raw materials according to the composition;
2) mixing polypropylene, a zinc oxide porous nanotube, a hyperbranched polymer, a light stabilizer, an antioxidant and a lubricant, adding the obtained mixture into a main feeding port of a double-screw extruder, adding a P-N compound flame retardant from a side feeding port of the double-screw extruder, extruding and granulating to obtain the zinc oxide porous nanotube synergistic uvioresistant halogen-free flame retardant polypropylene composite material.
In the preparation method, the technological parameters of the double-screw extruder are as follows: length-diameter ratio (36-44): 1; the processing temperature is 160-185 ℃; the rotating speed of the host is 200 r/min-400 r/min; the vacuum degree is more than or equal to 0.06 MPa.
The invention has the beneficial effects that:
the invention adopts the zinc oxide porous nanotube with surface treatment to assist the hyperbranched polymer to disperse, improves the compatibility and the dispersibility of the zinc oxide porous nanotube in the polypropylene matrix, and further exerts better ultraviolet resistance and better flame retardant synergistic effect. Compared with common nanotubes, nanowires and traditional active nano zinc oxide, the porous zinc oxide nanotubes have more outstanding carbon forming efficiency and anti-dripping effect, the prepared polypropylene composite material also overcomes the defect that the flowability of the material is obviously reduced by the traditional anti-dripping agent polytetrafluoroethylene, and brings great convenience for processing thin-wall multi-cavity products.
Detailed Description
The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material is composed of the following raw materials in parts by mass:
preferably, the polypropylene is at least one of homo-polypropylene and co-polypropylene; the melt index of the polypropylene at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
Preferably, the P-N compound flame retardant is treated by a surface treatment agent and is a conventional common P-N compound flame retardant.
Preferably, the zinc oxide porous nanotube has an outer diameter of 17nm to 400nm, an inner diameter of 3nm to 300nm, a tube length of 400nm to 4 μm, a pore diameter of 50nm to 150nm, and a porosity of 40% to 75%.
Preferably, the zinc oxide porous nanotube is used after being treated by the surface treatment agent.
Preferably, the hyperbranched polymer is a multi-stage branched polyester.
Preferably, the light stabilizer is at least one of benzophenones, benzotriazoles, salicylates, triazines, acrylonitrile derivatives and hindered amine light stabilizers.
Preferably, the antioxidant is at least one of hindered phenol, phosphite ester, hindered amine, thioester and inorganic phosphate antioxidants; more preferably, the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant.
Preferably, the lubricant is at least one of stearic acid, stearate, paraffin, polyethylene wax, ethylene bis-stearamide, pentaerythritol bis-stearate.
Preferably, the surface treating agent for treating the P-N compound flame retardant or the zinc oxide porous nanotube is at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and phosphate; further preferably, the surface treatment agent is phosphate; still more preferably, the surface treatment agent is a trialkyl phosphite.
The preparation method of the zinc oxide porous nanotube synergistic uvioresistant halogen-free flame-retardant polypropylene composite material comprises the following steps:
1) weighing the raw materials according to the composition;
2) mixing polypropylene, a zinc oxide porous nanotube, a hyperbranched polymer, a light stabilizer, an antioxidant and a lubricant, adding the obtained mixture into a main feeding port of a double-screw extruder, adding a P-N compound flame retardant from a side feeding port of the double-screw extruder, extruding and granulating to obtain the zinc oxide porous nanotube synergistic uvioresistant halogen-free flame retardant polypropylene composite material.
Preferably, in the preparation method, the technological parameters of the double-screw extruder are as follows: length-diameter ratio (36-44): 1; the processing temperature is 160-185 ℃; the rotating speed of the host is 200 r/min-400 r/min; the vacuum degree is more than or equal to 0.06 MPa.
Further preferably, in the preparation method, the length-diameter ratio of the twin-screw extruder is 40:1, and the side feeding port of the twin-screw extruder is positioned at the 6 th section.
Further preferably, in the preparation method, the vacuum degree of the double-screw extruder is more than or equal to 0.08 MPa.
The present invention will be described in further detail with reference to specific examples.
The raw materials used are specified below:
the high-flowability, high-rigidity co-polypropylene used was BX3920 produced by SK and having MI of 100g/10min (230 ℃, 2.16 kg). The P-N compound flame retardant, the zinc oxide porous nano-tube, the zinc oxide nano-wire and the active nano-zinc oxide (the effective content is more than or equal to 99.7 percent) are subjected to surface treatment by trialkyl phosphite ester before use. The antioxidant is prepared by compounding 1010 and 168 according to the proportion of 1: 2. Other raw materials used in the following examples are those conventionally commercially available, unless otherwise specified.
The test method is illustrated below:
the ultraviolet lamp irradiation condition is that 3 ultraviolet lamp tubes of 10 watts are placed in an oven at the temperature of 65 +/-5 ℃ and at the height of 8cm above the sample to directly irradiate for 4000 hours, and the sample surface has no chalking and cracking phenomena.
The product processability refers to that when the sample material is injected into thin-wall parts (64 starter shells are produced in each mould), the phenomena of glue shortage or mould sticking and the like cannot occur. Wherein, good means that the product can be continuously produced; the middle is that when the product is injected, a release agent needs to be sprayed every 1 day; the difference represents the phenomenon that the product can be stuck; the extreme difference represents the lack of glue during injection molding.
The flame resistance test was carried out by conducting the UL 94 test directly on the product (starter, thickness 0.75 mm).
Other test methods are conventional or performed according to relevant standard requirements unless otherwise specified.
Example (b):
table 1 shows the detailed amounts of the components of examples 1-3. Weighing raw materials except the P-N compound flame retardant according to the composition listed in Table 1, adding polypropylene resin into a stirring pot, dropwise adding white oil (used for adsorbing auxiliaries such as zinc oxide porous nanotubes and hyperbranched polymers) accounting for 1 per mill of the mass of the polypropylene resin while stirring, then adding the zinc oxide porous nanotubes, the hyperbranched polymers, a light stabilizer, an antioxidant and a lubricant, fully mixing, adding the mixture into a double-screw extruder with a processing temperature of 160-185 ℃ from a main feeding port, a main machine rotating speed of 200-400rpm and a length-diameter ratio of 40:1 (10 sections in total) for granulation, adding the P-N compound flame retardant from a side feeding port (located in the 6 th section), wherein the vacuum degree is more than or equal to 0.08MPa, and finally obtaining particles, namely the halogen-free flame retardant polypropylene composite material with ultraviolet resistance and drip-proof functions.
Comparative example 1:
comparative example 1 is different from example 3 in that zinc oxide nanotubes were used in the formulation and the amount of the flame retardant was 26%.
Comparative example 2:
the comparative example 2 is different from the example 3 in that zinc oxide nanotubes are used in the formulation, the addition amount thereof is increased to 0.9%, and the amount of the flame retardant is 26%.
Comparative example 3:
comparative example 3 is different from example 3 in that zinc oxide nanowires were used in the formulation, the amount of addition was increased to 1.0%, and the amount of flame retardant was 26%.
Comparative example 4:
comparative example 4 is different from example 3 in that zinc oxide nanowires were used in the formulation, the amount of addition was increased to 1.2%, and the amount of flame retardant was 26%.
Comparative example 5:
the main difference between comparative example 5 and example 3 is that active nano zinc oxide is used in the formulation, and the addition amount is 1.2%, and the amount of the flame retardant is increased to 28%.
Comparative example 6:
the main difference between comparative example 6 and example 3 is that the zinc oxide porous nanotubes were replaced with 0.5% active nano zinc oxide + 0.8% anti-dripping agent while increasing the amount of flame retardant to 28%.
Comparative example 7:
the main difference between comparative example 7 and example 3 is that the zinc oxide porous nanotube is replaced by 0.5% active nano zinc oxide + 0.8% anti-dripping agent, the addition amount of light stabilizer is increased to 0.3%, and the amount of flame retardant is increased to 28%.
Comparative example 8:
comparative example 8 differs from example 3 in that no hyperbranched polymer is used and the amount of flame retardant is 26%.
The compositions of comparative examples 1 to 8 are also shown in Table 1.
TABLE 1 raw material composition of examples and comparative examples
The test results of the polypropylene materials of examples 1 to 3 and comparative examples 1 to 8 are shown in Table 2.
TABLE 2 test results of polypropylene materials of examples and comparative examples
As can be seen from the test results of table 2: the zinc oxide with a special structure shows a better ultraviolet resistance synergistic effect (examples 1-3 and comparative examples 1-4), and the flame retardant synergistic effect of the zinc oxide porous nanotube, the zinc oxide nanotube and the zinc oxide nanowire is reduced in sequence. On the premise of obtaining the same effect, the addition amount of the zinc oxide porous nanotube is only 0.5%, and the addition amounts of the zinc oxide porous nanotube and the zinc oxide porous nanotube are respectively 1.8 times and 2.4 times of the zinc oxide porous nanotube (example 2, comparative example 2 and comparative example 4). Under the test proportion (comparative examples 5-7), the common active nano zinc oxide has no anti-dripping effect and no synergistic anti-ultraviolet capability. If the anti-dripping and anti-ultraviolet effects are achieved, an anti-dripping agent and a light stabilizer are required to be additionally added (comparative examples 6-7), but the processability of the obtained composite material is seriously deteriorated, and the actual production requirements cannot be met. The hyperbranched polymer (examples 2-3 and comparative example 8) is added, so that the dispersing effect of the flame retardant and the zinc oxide porous nanotube can be improved, and meanwhile, the fluidity of the material can be obviously improved. Therefore, the zinc oxide porous nanotube can play triple effects of flame retardant synergy, drip prevention and ultraviolet resistance, and the obtained polypropylene halogen-free flame retardant material has excellent processing convenience.
In conclusion, the zinc oxide porous nanotube subjected to surface treatment is adopted to assist the hyperbranched polymer to disperse, so that the compatibility and the dispersibility of the zinc oxide porous nanotube in a polypropylene matrix are improved, and further, the better ultraviolet resistance and the better flame retardant synergistic effect are exerted. The invention also finds that the zinc oxide nanotube with porous size is more outstanding in carbon forming efficiency and anti-dripping effect compared with the common nanotube, the nano wire and the traditional active nano zinc oxide, and the prepared composite material also overcomes the defect that the traditional anti-dripping agent polytetrafluoroethylene obviously reduces the material fluidity, and brings great convenience for processing thin-wall multi-cavity products.
Claims (9)
1. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material is characterized in that: the composite material is prepared from the following raw materials in parts by mass:
the zinc oxide porous nanotube has an outer diameter of 17-400 nm, an inner diameter of 3-300 nm, a length of 400-4 μm, a pore diameter of 50-150 nm, and a porosity of 40-75%.
2. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame retardant polypropylene composite material according to claim 1, characterized in that: the polypropylene is at least one of homo-polypropylene and co-polypropylene; the melt index of the polypropylene at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
3. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame retardant polypropylene composite material according to claim 1, characterized in that: the P-N compound flame retardant is treated by a surface treating agent.
4. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame retardant polypropylene composite material according to claim 1, characterized in that: the zinc oxide porous nano tube is used after being treated by the surface treating agent.
5. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame retardant polypropylene composite material according to claim 1, characterized in that: the hyperbranched polymer is multi-stage branched polyester.
6. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame retardant polypropylene composite material according to claim 1, characterized in that: the light stabilizer is at least one of benzophenone, benzotriazole, salicylate, triazine, acrylonitrile derivative and hindered amine light stabilizer; the antioxidant is at least one of hindered phenol, phosphite ester, hindered amine, thioester and inorganic phosphate antioxidant; the lubricant is at least one of stearic acid, stearate, paraffin, polyethylene wax, ethylene bis-stearic acid amide and pentaerythritol bis-stearate.
7. The zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame retardant polypropylene composite material according to claim 3 or 4, wherein: the surface treating agent is at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid and phosphate.
8. A preparation method of a zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material is characterized by comprising the following steps: the method comprises the following steps:
1) weighing raw materials according to the composition of any one of claims 1 to 6;
2) mixing polypropylene, a zinc oxide porous nanotube, a hyperbranched polymer, a light stabilizer, an antioxidant and a lubricant, adding the obtained mixture into a main feeding port of a double-screw extruder, adding a P-N compound flame retardant from a side feeding port of the double-screw extruder, extruding and granulating to obtain the zinc oxide porous nanotube synergistic uvioresistant halogen-free flame retardant polypropylene composite material.
9. The preparation method of the zinc oxide porous nanotube synergistic uvioresistant halogen-free flame retardant polypropylene composite material according to claim 8, characterized in that: the technological parameters of the double-screw extruder are as follows: length-diameter ratio (36-44): 1; the processing temperature is 160-185 ℃; the rotating speed of the host is 200 r/min-400 r/min; the vacuum degree is more than or equal to 0.06 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711453657.3A CN108239344B (en) | 2017-12-28 | 2017-12-28 | Zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711453657.3A CN108239344B (en) | 2017-12-28 | 2017-12-28 | Zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108239344A CN108239344A (en) | 2018-07-03 |
| CN108239344B true CN108239344B (en) | 2020-07-07 |
Family
ID=62700594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711453657.3A Active CN108239344B (en) | 2017-12-28 | 2017-12-28 | Zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108239344B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101455960B (en) * | 2007-12-14 | 2010-11-17 | 中国科学院合肥物质科学研究院 | Porous zinc bloom nanometer tube with high photocatalysis activity and preparation method thereof |
| CN102040767B (en) * | 2009-10-14 | 2012-07-25 | 中国石油化工股份有限公司 | Uvioresistant polypropylene composition and preparation method thereof |
| CN103333406B (en) * | 2013-06-05 | 2016-01-06 | 华南理工大学 | A kind of modified expanded flame-proof polypropelene composition and preparation method thereof |
| CN103992562A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Halogen-free flame-retardant antibacterial anti-aging polypropylene composite material and preparation method thereof |
| CN105061854A (en) * | 2015-08-03 | 2015-11-18 | 上海科悦高分子材料有限公司 | Halogen-free flame retardation polyolefin material and use thereof |
-
2017
- 2017-12-28 CN CN201711453657.3A patent/CN108239344B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108239344A (en) | 2018-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6386114B2 (en) | Method for producing conductive resin composition | |
| EP2748244B1 (en) | Metal carboxylate additives for thermoplastics | |
| CN103910996A (en) | Antibacterial masterbatch, nano antibacterial super-tough plastic added with antibacterial masterbatch and preparation and application of plastic | |
| CN1143656A (en) | Polyolefin compositions resistant to high energy radiation, and articles produced therefrom | |
| CN105936728B (en) | A kind of ultra-dispersed flame retarding function master batch manufacture method | |
| CN109370043B (en) | Low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA and preparation method thereof | |
| CN103739944A (en) | Low-odour glass-fiber-enhanced polypropylene composite material and preparation method thereof | |
| CN102181093A (en) | Anti-scratching polypropylene composite material and preparation method thereof | |
| CN107759898B (en) | High-shading-degree polypropylene composite material and preparation method thereof | |
| CN103627056B (en) | The polyolefin blend of UV stable | |
| CN103627168A (en) | Special halogen-free flame-retardant master batch for nylon and preparation method thereof | |
| CN106633412A (en) | High-elongation-at-break polypropylene composition and preparation method thereof | |
| EP3224310B1 (en) | Process for extruding polypropylene | |
| CN108467544B (en) | High-strength, high-rigidity and transparent modified polypropylene composite material and preparation method thereof | |
| CN113527858A (en) | High-strength high-toughness antibacterial mildew-proof flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN110872418A (en) | Polypropylene composition and preparation method thereof | |
| CN109337330B (en) | Halogen-free flame-retardant high-shading PC composite material and preparation method thereof | |
| CN107974025B (en) | Non-filling low-shrinkage polypropylene composite material and preparation method thereof | |
| CN108239344B (en) | Zinc oxide porous nanotube synergistic anti-ultraviolet halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN108250565B (en) | High-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for coil framework and preparation method thereof | |
| CN110423461B (en) | Low-water-absorption flame-retardant glass fiber reinforced PA6 composite material and preparation method thereof | |
| CN108117697B (en) | Ultraviolet-resistant anti-dripping halogen-free flame-retardant polypropylene composite material based on zinc oxide nanowire synergism and preparation method thereof | |
| KR102262187B1 (en) | Composition for biodegradability and antibacterial loess masterbatch, plastic product using the same, and manufacturing method thereof | |
| CN109467806A (en) | A kind of preparation method of compound micro-foaming material | |
| EP2857194B1 (en) | Multiwall sheets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |