CN114316440B - Antistatic polypropylene-based composite material, and preparation method and application thereof - Google Patents
Antistatic polypropylene-based composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an antistatic polypropylene-based composite material and a preparation method and application thereof.A dandelion-shaped zinc oxide modified powder is obtained by carrying out surface hydrophobic modification on dandelion-shaped zinc oxide powder, the surface of the dandelion-shaped zinc oxide modified powder can obtain better interface compatibility and lower agglomeration effect with a polypropylene matrix, and the convex structures of different dandelion-shaped zinc oxide powders can be contacted with each other in the resin matrix, so that the antistatic effect is improved; the native hydrophobic nano silicon dioxide, the glass fiber and the dandelion-shaped zinc oxide powder synergistically improve the mechanical property of the polypropylene-based composite material, and improve the application range and the service life of the polypropylene-based composite material taking the dandelion-shaped zinc oxide powder as the antistatic agent; the surface resistivity of the composite material was 8.5 x 109‑9.5*1011Omega, tensile strength of 70-85Mpa, elongation at break of 20-30%, used as antistatic structural member.
Description
Technical Field
The invention belongs to the field of polymer composite materials, particularly relates to the field of polypropylene-based composite materials, and particularly relates to an antistatic polypropylene-based composite material as well as a preparation method and application thereof.
Background
Polypropylene (PP) is a common plastic engineering material. The polypropylene has good processing performance, excellent corrosion resistance and mechanical property, and is widely applied as a structural part. However, polypropylene has a relatively high surface resistivity (10)16-1018Omega), the surface of the polypropylene-based structural component is easy to accumulate electric charges, thereby being charged with static electricity, being capable of adsorbing particles in the air and influencing the appearance and the reality of the polypropylene-based structural componentPerformance in service.
In the prior art, CN101759921A adds conductive fibers into polypropylene to reduce the surface resistivity of the polypropylene; however, the addition of the conductive fiber has a limited decrease in surface resistivity, and the compatibility of the conductive fiber with the matrix resin is not stable. CN102719020A added a cationic antistatic agent to the composite material to reduce the surface resistivity of the material, but its antistatic effect period was short. CN105646999A discloses a polypropylene composition and a preparation method thereof, the composite material is prepared by 40-80 parts of polypropylene, 0-30 parts of reinforcing agent, 0-15 parts of toughening agent, 0-0.3 part of coupling agent, 0.1-0.5 part of antioxidant, 0.5-10 parts of zinc oxide, 0.5-10 parts of polyvinyl alcohol, 0-5 parts of graft and 0-2 parts of other auxiliary agent according to the parts by weight; the composition can not adsorb dust in the production and use processes, and the antistatic agent is selected from zinc oxide powder with the mesh number of more than 800 meshes and polyvinyl alcohol, so that the surface resistivity of the polypropylene composite material can be reduced. However, the antistatic effect is still difficult to meet the actual requirement, and the mechanical structure performance of the material is greatly limited due to the added granular zinc oxide powder.
Therefore, the development of an antistatic polypropylene-based composite material remains an important research and development content in the field of polypropylene-based composite materials.
Disclosure of Invention
Aiming at the technical problems that the polypropylene-based composite material in the prior art has poor antistatic property and cannot balance the antistatic property and the mechanical property, the invention provides the antistatic polypropylene-based composite material as well as a preparation method and application thereof.
The antistatic polypropylene-based composite material can solve the technical problems of poor antistatic effect and insufficient mechanical property of the polypropylene-based composite material in the prior art. The antistatic polypropylene-based composite material of the invention has a surface resistivity of 8.5 x 109-9.5*1011Omega, the antistatic polypropylene-based composite material has excellent mechanical property, the tensile strength is 70-85Mpa, and the elongation at break is 20-30%. The antistatic polypropylene-based composite material has remarkable antistatic effect and can be enhancedThe structural strength of the structural parts made of the polypropylene-based composite material greatly widens the application range of the antistatic polypropylene-based composite material.
The invention discloses an antistatic polypropylene-based composite material in a first aspect, and the technical scheme is as follows.
An antistatic polypropylene-based composite material comprises the following components in parts by weight:
polypropylene: 40-100 parts;
dandelion-like zinc oxide modified powder: 2-20 parts of a solvent;
glass fiber: 10-25 parts;
hydrophobic silica: 1-5 parts;
antioxidant: 0.1-2 parts;
a compatilizer: 0.1-2 parts;
lubricant: 0.1-2 parts.
As a preferable scheme, the polypropylene is homo-polypropylene or co-polypropylene, and the melt index is 30-1500g/10 min.
Preferably, the dandelion-like zinc oxide modified powder is obtained by performing surface hydrophobic modification on dandelion-like zinc oxide powder. The dandelion-shaped zinc oxide powder has a three-dimensional structure and dendritic protrusions, and can be synthesized by a low-temperature hydrothermal method known in the art, and details are not repeated here.
Preferably, the method for modifying the dandelion-shaped zinc oxide modified powder comprises the following steps; adding the dandelion-shaped zinc oxide powder into a modification container, adding the modification liquid, heating to 50-60 ℃, and stirring for 3-5h for surface modification to obtain modified powder; wherein the weight ratio of the dandelion-shaped zinc oxide powder to the modification liquid is 10: 0.5-2; the modified liquid comprises ethanol, gamma-aminopropyltriethoxysilane, a PEO-PPO-PEO block copolymer, ethylene glycol and a surfactant; ethanol, gamma-aminopropyltriethoxysilane, a PEO-PPO-PEO block copolymer, ethylene glycol and a surfactant in a mass ratio of 10: 0.5-2: 0.1-0.5: 0.1-1: 0.01-0.2;
the invention develops specific modifying liquid aiming at the structure of dandelion-shaped zinc oxide powder, and the modifying method for the powder hydrophobic modification in the prior art is difficult to be used for dandelion-shaped zinc oxide powder with a specific structure. The invention can uniformly graft hydrophobic organic groups in the three-dimensional structure of dandelion-shaped zinc oxide. Wherein, in the modification solution, ethanol is used as a solvent; gamma-aminopropyltriethoxysilane as a hydrophobic modifier; the PEO-PPO-PEO block copolymer has amphipathy, plays a role in bridging connection, can be connected with hydrophilic dandelion-shaped zinc oxide powder and hydrophobic gamma-aminopropyltriethoxysilane, and can also be directly grafted on the surface of the dandelion-shaped zinc oxide powder; the glycol is used as a dispersing aid, so that the flowability of the modified liquid is improved, the surface of the dandelion-shaped zinc oxide is wetted, and the grafting uniformity is improved; the surfactant plays a role in dispersing all components of the modified solution and simultaneously plays a role in preventing the zinc oxide powder from agglomerating during modification. In the invention, the dandelion structure of the dandelion-shaped zinc oxide can be grafted with hydrophobic organic groups, and the modification effect is uniform.
Preferably, the surfactant is one or more of polyoxyethylene stearate, tetrabutylammonium bromide, sodium dodecyl benzene sulfonate and disodium lauryl sulfosuccinate monoester.
The invention uses dandelion-shaped zinc oxide modified powder as antistatic agent of polypropylene composite material. For spherical or granular zinc oxide powder, dandelion form zinc oxide powder has bellied three-dimensional structure, through this application specific modified liquid hydrophobic modification after, because its bellied dandelion structure, dandelion form zinc oxide powder's surface can obtain better interfacial compatibility with the polypropylene base member, and modified dandelion form zinc oxide powder disperses more evenly in the resin base member. Different dandelion form zinc oxide powder protruding structures can contact each other in the resin matrix, have improved antistatic effect. Meanwhile, the protruding structure of the dandelion-shaped zinc oxide powder plays a role in reinforcing fibers, and the mechanical property of the polypropylene-based composite material is also improved. Moreover, the dandelion-shaped zinc oxide powder has lower agglomeration effect compared with spherical or granular zinc oxide powder, can ensure more uniform dispersion in a resin matrix, and has more uniform and excellent antistatic effect.
Preferably, the hydrophobic silica powder may be native hydrophobic nano-silica, for example, native hydrophobic nano-silica synthesized in situ by a combustion method, and the contact angle of the native hydrophobic nano-silica to water in the air is preferably 110 ° to 120 °. Compared with later-stage hydrophobic modified silicon dioxide powder, the method adopts the primary hydrophobic nano silicon dioxide, the organic groups on the surface of the primary hydrophobic nano silicon dioxide are distributed more uniformly, the organic groups on the surface of the silicon dioxide particles are distributed in a molecular scale, and the interface compatibility of the hydrophobic silicon dioxide powder and a resin matrix is better. Compared with later-stage hydrophobically modified silicon dioxide, the primary hydrophobic nano silicon dioxide has molecular-scale organic group distribution and is more firmly combined with a resin matrix. The original hydrophobic nano silicon dioxide, the glass fiber and the dandelion-shaped zinc oxide powder cooperate to improve the mechanical property of the polypropylene-based composite material, and the application range and the service life of the polypropylene-based composite material taking the dandelion-shaped zinc oxide modified powder as the antistatic agent are improved.
Preferably, the glass fiber is a continuous long glass fiber with the filament diameter of 10-17 μm and the filament diameter of 600-2400 tex.
The antioxidant is a known antioxidant in the field, and preferably is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester or tri [ 2, 4-di-tert-butylphenyl ] phosphite.
The compatibilizer is an antioxidant known in the art, preferably maleic anhydride grafted polypropylene.
The lubricant is an antioxidant known in the art, preferably N, N' -ethylene bis stearamide.
The second aspect of the invention discloses a preparation method of an antistatic polypropylene-based composite material, and the technical scheme is as follows.
A preparation method of an antistatic polypropylene-based composite material comprises the following steps:
step 1: uniformly mixing polypropylene, dandelion-shaped zinc oxide modified powder, hydrophobic silicon dioxide, an antioxidant, a compatilizer and a lubricant according to the weight ratio, heating the mixture in a double-screw extruder until the mixture is melted and mixed, and extruding the polypropylene melt into a fiber impregnation tank; wherein the temperature of the polypropylene melt is 200-230 ℃. Wherein the dandelion-shaped zinc oxide modified powder is prepared by the method.
Step 2: preheating glass fiber to the same temperature as the polypropylene melt, feeding the glass fiber into a fiber impregnation tank, fully soaking the glass fiber and the polypropylene melt in the impregnation tank for 1-5 minutes, cooling, and pelletizing to obtain the antistatic polypropylene-based composite material.
Preferably, in the step 2, the length of the granulated particles is 10-12mm, and the diameter is 2.0-4.5 mm.
The antistatic polypropylene-based composite material of the invention has a surface resistivity of 8.5 x 109-9.5*1011Omega, tensile strength of 70-85MPa, and elongation at break of 20-30%.
In a third aspect of the invention, the use of the aforementioned antistatic polypropylene-based composite material as an antistatic structural member is disclosed.
The invention achieves remarkable technical effects.
The dandelion-shaped zinc oxide powder is subjected to surface hydrophobic modification and is used as an antistatic agent; compared with spherical or granular zinc oxide powder, the dandelion-shaped zinc oxide powder has a convex three-dimensional structure, after the hydrophobic modification by the modification liquid, due to the convex dandelion structure, the surface of the dandelion-shaped zinc oxide powder can obtain better interface compatibility with a polypropylene matrix, the dandelion-shaped zinc oxide powder has lower agglomeration effect, and different dandelion-shaped zinc oxide powder convex structures can be in mutual contact in the resin matrix, so that the antistatic effect is improved. Meanwhile, the protruding structure of the dandelion-shaped zinc oxide powder can also improve the mechanical property of the polypropylene-based composite material. The invention develops specific modifying liquid aiming at the raised three-dimensional structure of the dandelion-shaped zinc oxide powder to improve the surface grafting modification effect of the dandelion-shaped zinc oxide powder. The primary hydrophobic nano-silica of the invention is hydrophobically modified in the later stageThe silicon oxide has organic group distribution with molecular scale, and is combined with the resin matrix more firmly. The original hydrophobic nano silicon dioxide, the glass fiber and the dandelion-shaped zinc oxide powder cooperate to improve the mechanical property of the polypropylene-based composite material, and the application range and the service life of the polypropylene-based composite material taking the dandelion-shaped zinc oxide powder as the antistatic agent are improved. The antistatic polypropylene-based composite material has the surface resistivity of 8.5 to 109-9.5*1011Omega, the antistatic polypropylene-based composite material has excellent mechanical property, the tensile strength is 70-85Mpa, and the elongation at break is 20-30%. The antistatic polypropylene-based composite material has a remarkable antistatic effect, can enhance the structural strength of a structural part made of the polypropylene-based composite material, and greatly widens the application range of the antistatic polypropylene-based composite material.
Detailed Description
The following specific examples are provided to further illustrate the technical solutions and effects of the present invention.
Example 1: preparation of Taraxacum-like modified Zinc oxide powder
The dandelion-shaped zinc oxide powder was added to a modification vessel, and the modification solution was added thereto, and the mixture was heated to 55 ℃ and stirred for 3.5 hours to carry out surface modification, thereby obtaining dandelion-shaped zinc oxide modified powder, which was used in the following examples 2 to 4. Wherein the weight ratio of the dandelion-shaped zinc oxide powder to the modification liquid is 10: 1. The modified liquid comprises ethanol, gamma-aminopropyltriethoxysilane, a PEO-PPO-PEO block copolymer, glycol and polyoxyethylene stearate; the proportion is 10: 1: 0.2: 0.5: 0.1.
example 2: preparation of antistatic polypropylene-based composite
Step 1: the preparation method comprises the following steps of preparing 100 parts of polypropylene, 20 parts of dandelion-shaped zinc oxide modified powder, 20 parts of glass fiber, 5 parts of hydrophobic silicon dioxide, 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 1 part of maleic anhydride grafted polypropylene and 1 part of N, N' -ethylene bis stearamide. Uniformly mixing polypropylene, dandelion-shaped zinc oxide modified powder, hydrophobic silicon dioxide, an antioxidant, a compatilizer and a lubricant, heating in a double-screw extruder until the mixture is melted and mixed, and extruding a polypropylene melt into a fiber impregnation tank; wherein the temperature of the polypropylene melt is 220 ℃.
Step 2: preheating glass fiber to 220 ℃, sending the glass fiber into a fiber dipping tank, fully soaking the glass fiber and the polypropylene melt in the dipping tank for 3 minutes, cooling, and pelletizing to obtain the antistatic polypropylene-based composite material, wherein the length of the pelletized particle is 10mm, and the diameter of the pelletized particle is 2.0 mm.
Example 3: preparation of antistatic Polypropylene-based composite Material
Step 1: the material is prepared according to the following mixture ratio of 50 parts of polypropylene, 5 parts of dandelion-shaped zinc oxide modified powder, 20 parts of glass fiber, 2 parts of hydrophobic silicon dioxide, 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 1 part of maleic anhydride grafted polypropylene and 1 part of N, N' -ethylene bis stearamide. Uniformly mixing polypropylene, dandelion-shaped zinc oxide modified powder, hydrophobic silicon dioxide, an antioxidant, a compatilizer and a lubricant, heating in a double-screw extruder until the mixture is melted and mixed, and extruding a polypropylene melt into a fiber impregnation tank; wherein the temperature of the polypropylene melt is 220 ℃.
And 2, step: preheating glass fiber to 220 ℃, then sending the glass fiber into a fiber dipping tank, fully soaking the glass fiber and a polypropylene melt in the dipping tank for 3 minutes, then cooling, and pelletizing, wherein the length of the pelletized particle is 10mm, and the diameter is 2.0mm, so as to obtain the antistatic polypropylene-based composite material.
Example 4: preparation of antistatic Polypropylene-based composite Material
Step 1: the preparation method comprises the following steps of preparing 80 parts of polypropylene, 10 parts of dandelion-shaped zinc oxide modified powder, 20 parts of glass fiber, 3 parts of hydrophobic silicon dioxide, 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 1 part of maleic anhydride grafted polypropylene and 1 part of N, N' -ethylene bis stearamide. Uniformly mixing polypropylene, dandelion-shaped zinc oxide modified powder, hydrophobic silicon dioxide, an antioxidant, a compatilizer and a lubricant, heating in a double-screw extruder until the mixture is melted and mixed, and extruding a polypropylene melt into a fiber impregnation tank; wherein the temperature of the polypropylene melt is 220 ℃.
Step 2: preheating glass fiber to 220 ℃, then sending the glass fiber into a fiber dipping tank, fully soaking the glass fiber and a polypropylene melt in the dipping tank for 3 minutes, then cooling, and pelletizing, wherein the length of the pelletized particle is 10mm, and the diameter is 2.0mm, so as to obtain the antistatic polypropylene-based composite material.
Comparative example: preparation of Polypropylene-based composite Material
Step 1: the preparation method comprises the following steps of preparing 100 parts of polypropylene, 20 parts of zinc oxide powder (without organic hydrophobic modification), 20 parts of glass fiber, 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 1 part of maleic anhydride grafted polypropylene and 1 part of N, N' -ethylene bis stearamide. Uniformly mixing polypropylene, zinc oxide powder, an antioxidant, a compatilizer and a lubricant, heating in a double-screw extruder until the mixture is melted and mixed, and extruding a polypropylene melt into a fiber impregnation tank; wherein the temperature of the polypropylene melt is 220 ℃.
And 2, step: preheating glass fiber to 220 ℃, then sending the glass fiber into a fiber dipping tank, fully soaking the glass fiber and the polypropylene melt in the dipping tank for 3 minutes, then cooling, and pelletizing, wherein the length of the pelletized particles is 10mm, and the diameter of the pelletized particles is 2.0mm, so as to obtain the polypropylene-based composite material.
The polypropylene-based composites obtained in examples 2 to 4 and comparative example were subjected to antistatic and mechanical property tests. Wherein, the surface resistivity is tested according to GB/T1410, and the tensile strength and the elongation at break are tested according to GB/T1040.1. The results are as follows.
| Surface resistivity | Tensile strength | Elongation at break | |
| Example 2 | 8.9*109Ω | 82Mpa | 26% |
| Example 3 | 9.3*1011Ω | 73Mpa | 23% |
| Example 4 | 9.2*1010Ω | 75Mpa | 27% |
| Comparative example | 1.6*1013Ω | 62Mpa | 20% |
It can be seen that the dandelion-shaped zinc oxide modified powder and the native hydrophobic nano-silica adopted in the embodiments 2 to 4 of the application have obvious antistatic effect and mechanical property compared with the unmodified zinc oxide adopted in the comparative example, and the application range of the antistatic polypropylene-based composite material is greatly widened.
Claims (6)
1. The antistatic polypropylene-based composite material is characterized by comprising the following components in parts by weight:
polypropylene: 40-100 parts;
dandelion-shaped zinc oxide modified powder: 2-20 parts of a solvent;
glass fiber: 10-25 parts;
hydrophobic silica: 1-5 parts;
antioxidant: 0.1-2 parts;
a compatilizer: 0.1-2 parts;
lubricant: 0.1-2 parts;
the preparation method of the antistatic polypropylene-based composite material comprises the following steps:
step 1: uniformly mixing polypropylene, dandelion-shaped zinc oxide modified powder, hydrophobic silicon dioxide, an antioxidant, a compatilizer and a lubricant according to the weight ratio, heating the mixture in a double-screw extruder until the mixture is melted and mixed, and extruding the polypropylene melt into a fiber impregnation tank; wherein the temperature of the polypropylene molten mass is 200-230 ℃;
step 2: preheating glass fiber to the same temperature as the polypropylene melt, feeding the glass fiber into a fiber impregnation tank, fully soaking the glass fiber and the polypropylene melt in the fiber impregnation tank for 1-5 minutes, cooling, and granulating to obtain the antistatic polypropylene-based composite material;
wherein the dandelion-shaped zinc oxide modified powder is obtained by performing surface hydrophobic modification on the dandelion-shaped zinc oxide powder;
the surface hydrophobic modification method comprises the following steps: adding the dandelion-shaped zinc oxide powder into a modification container, adding the modification liquid, heating to 50-60 ℃, and stirring for 3-5h for surface modification to obtain modified powder;
wherein the weight ratio of the dandelion-shaped zinc oxide powder to the modifying liquid is 10:0.5 to 2;
the modified liquid comprises ethanol, gamma-aminopropyltriethoxysilane, a PEO-PPO-PEO block copolymer, ethylene glycol and a surfactant; ethanol, gamma-aminopropyltriethoxysilane, a PEO-PPO-PEO block copolymer, ethylene glycol and a surfactant in a mass ratio of 10: 0.5-2: 0.1-0.5: 0.1-1: 0.01-0.2;
the hydrophobic silicon dioxide powder is native hydrophobic nano silicon dioxide, and the contact angle of the hydrophobic silicon dioxide powder to water in the air is 110-120 degrees;
the antistatic polypropylene-based composite material has the surface resistivity of 8.5*109-9.5*1011Omega, tensile strength of 70-85 MPa.
2. The antistatic polypropylene-based composite of claim 1, wherein the polypropylene is a homo-polypropylene or a co-polypropylene.
3. The antistatic polypropylene-based composite according to claim 1 or 2, wherein the glass fiber is a continuous long glass fiber.
4. The antistatic polypropylene-based composite material according to claim 1 or 2, wherein the surfactant is one or more of polyoxyethylene stearate, tetrabutylammonium bromide, sodium dodecylbenzenesulfonate, and disodium laurylsulfosuccinate monoester.
5. The antistatic polypropylene-based composite material according to claim 1 or 2, wherein the length of the pelletized particles in step 2 is 10 to 12mm and the diameter thereof is 2.0 to 4.5 mm.
6. Use of the antistatic polypropylene-based composite material according to any one of claims 1 to 5 as an antistatic structural member.
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| TW557315B (en) * | 1998-03-27 | 2003-10-11 | Azdel Inc | Filled composite material |
| EP1511802B1 (en) * | 2002-06-05 | 2010-09-08 | Showa Denko K.K. | Powder comprising silica-coated zinc oxide, organic polymer composition containing the powder and shaped article thereof |
| CN101565524B (en) * | 2009-04-28 | 2011-04-27 | 华南理工大学 | HDPE-carbon fiber-zinc oxide crystal whisker conductive composite material and preparation method thereof |
| CN102965755B (en) * | 2012-11-26 | 2014-07-30 | 浙江理工大学 | Preparation method of antistatic polypropylene fiber |
| CN103849067A (en) * | 2012-12-07 | 2014-06-11 | 上海杰事杰新材料(集团)股份有限公司 | Enhanced antistatic polypropylene composite material and preparation method thereof |
| CN104774510B (en) * | 2014-12-04 | 2017-05-03 | 上海卫星装备研究所 | Antistatic thermal control coating composition, preparation method and applications thereof |
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| CN107604458B (en) * | 2017-10-31 | 2022-01-07 | 稀美师新材料科技(常州)有限公司 | Preparation method of durable ultraviolet-resistant polypropylene fiber |
| CN113512254B (en) * | 2021-07-16 | 2023-05-23 | 中广核俊尔(浙江)新材料有限公司 | Conductive antibacterial long glass fiber reinforced polypropylene composite material and preparation method and application thereof |
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