CN102218889B - Preparation method of inner wall super-hydrophobic surface of plastic bottle - Google Patents
Preparation method of inner wall super-hydrophobic surface of plastic bottle Download PDFInfo
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- CN102218889B CN102218889B CN 201110050665 CN201110050665A CN102218889B CN 102218889 B CN102218889 B CN 102218889B CN 201110050665 CN201110050665 CN 201110050665 CN 201110050665 A CN201110050665 A CN 201110050665A CN 102218889 B CN102218889 B CN 102218889B
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Abstract
The invention relates to a preparation method of an inner wall super-hydrophobic surface of a plastic bottle, which belongs to the field of plastic forming. The preparation method comprises the following steps of: taking a silane coupling agent as a surface modifier, and dissolving the silane coupling agent in a solvent to form solution, wherein the solvent is one of ethanol, propanol and butanone; pouring hollow glass micro-balloons into the solution, stirring for 1 to 2 hours, putting the stirred hollow glass micro-balloons in a water bath at the temperature of between 80 and 90 DEG C, and reacting for 1 to 2 hours; and cooling a reaction product, filtering, washing, and drying in a blasting drying box at 100 to 110 DEG C for 8 to 9 hours. Based on a multi-layer blow molding process, the multi-layer volume is formed by performing blow molding on an extrusion molding cylindrical multi-layer mold blank, wherein the inner layer of three extruding layers is a super-hydrophobic layer, the middle layer of the three extruding layer is an adhesive layer, and the outer layer of the three extruding layers is a body layer. The prepared plastic bottle inner wall with a super-hydrophobic function can reduce the adhesion residual amount of fluid on the plastic bottle inner wall, thereby improving the utilization ratio of a fluid product in a bottle and obtaining an economical effect.
Description
Technical field
The present invention relates to a kind of preparation method of inner wall super-hydrophobic surface of plastic bottle.
Background technology
Super hydrophobic surface refers to contact angle with water greater than 150 °, and roll angle is less than the surface of 10 °.Super hydrophobic surface more and more receives people's concern due to its excellent automatically cleaning and the good characteristics such as viscous anti-pollution, hydrophobic, that can reduce fluid, is one of focus of present functional material research.In recent years, super hydrophobic surface has caused people's extensive concern owing to having broad application prospects in industrial and agricultural production, national defense construction and daily life.In each field, very high using value is arranged as a kind of functional material.Be used for building, anti-fog and antifrost can be removed manual cleaning from; Be used for textile, oily dirt free is dirty, need not wash; Be used for communication equipment, can guarantee high-quality acknowledge(ment) signal; Be used for the ships design, can relatively improve headway, simultaneously significantly fuel saving consumption; At the biological field face, free of losses liquid is carried and the aspect such as anti-oxidant also has very large application potential.
What the method for preparing at present super hydrophobic surface had phase separation method, template, sol-gel process, pulling method, Electrospinning Method, vapour deposition process self assembly, mechanical processing method, etching method, etch, electrochemical process and an above-mentioned certain methods unites utilization etc.In recent years, the bibliographical information on relevant preparation super-hydrophobic automatic cleaning surface is more and more, but these reports mostly carry out on flat board, and complicated process of preparation, somewhat expensive, make super hydrophobic surface at the inwall of container has certain difficulty at present, rarely report.Adopt multi-layer co-extruded method, the body layer plastics can satisfy various mechanical properties, and functional layer material makes material satisfy ultra-hydrophobicity, and the internal layer that makes plastic bottle is that super-hydrophobic layer is a relatively design of innovation.
It is more expensive again that yet the performance price is not stained with on the existing outstanding surface of polytetrafluoroethylene (PTFE), and we reduce costs by adding glass microballoon in institute, can reduce density by material simultaneously, improve the mechanical properties such as toughness of material.Glass microballoon is a kind of of many uses, a kind of new material that performance is special that development in recent years is got up.Yet great amount of hydroxy group is contained on the hollow glass micropearl surface, be easy to adsorbed water molecule, and hollow glass micropearl belongs to inorganic matter, very large with the organic polymer polarity difference, if directly add in polymer, may cause dispersion inhomogeneous, mutual active force is very little, and grain diameter also can cause the stress concentration point of composite when larger, becomes the weak link of institutional framework in material, so need to carry out surface modification to glass microballoon.Surface modifier refers to can reduce the viscosity of molten synthetic resin in the plastic processing process, improve the decentralization of filler to improve processing characteristics.Surface modifier generally is comprised of two parts: a part is close inorganic group, can with inorganic filler or reinforcing material effect; Another part is close organic group, can with the synthetic resin effect.The effect of surface modifier in composite be it can with some radical reaction on functional material surface, can react with matrix resin again, form a boundary layer between functional material and resin matrix, boundary layer can transmit stress, thereby strengthened bonding strength between functional material and resin, improve the performance of composite, improved interface state.The preparation super hydrophobic surface has two kinds of approach: a kind of is to carry out surface roughening on the hydrophobic material surface with low-surface-energy to process; Another kind is to have modification low-surface-energy material on the surface of certain roughness.The plastic bottle internal layer is the mixture of plastics and polytetrafluoroethylene (PTFE) and hollow glass micropearl, and hollow glass micropearl provides micro-structural, increases the roughness of internal face, and polytetrafluoroethylene (PTFE) provides again low surface energy when increasing roughness.
The coextrusion combination process is to adopt two or several extruders that the resin of various difference in functionalitys is melt extruded respectively, and the runner by separately converges in die head or outside die head, then through inflation, together cooling combined.This technique has not only been simplified production process greatly, and materials are few, can cut down the consumption of raw materials and production cost simultaneously; Adopt the compound package material of this explained hereafter same structure can save 30% production cost than other techniques.By multi-layer co-extruded moulding process, cladding material is body layer, and the layer for main holding capacity makes goods can satisfy the mechanical properties such as strength of materials rigidity, and inner layer material provides micro-structural, makes inwall realize super hydrophobic functional.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of plastic liner super hydrophobic surface.Below minute, two steps are completed:
A: the surface modification of glass microballoon: the quality that takes silane coupler is 0.5～2% of hollow glass micropearl quality, and silane coupler is dissolved in solvent, forms solution, and described solvent is a kind of in ethanol, propyl alcohol, butanone.After being stirred to the solution clarification, solution is poured in the beaker that hollow glass micropearl is housed, stirred 1～2 hour, the hollow glass micropearl of then inciting somebody to action is put into the water-bath of 80～90 ℃, reacts 1～2 hour.Product is put into air dry oven dry 8～9h under 100～110 ℃ simultaneously with polytetrafluorethylepowder powder after cooling, filtration, washing.
B. Coextrusion Blow Moulding process
First the mixture with inner plastic, polytetrafluoroethylene (PTFE) and modification hollow glass micropearl later tentatively mixes, and then by the double screw extruder extruding pelletization, mixture is mixed more even.Then respectively the mixture of outer layer plastic, adhesive, inner plastic and polytetrafluoroethylene (PTFE) and modification hollow glass micropearl later is respectively charged in the hopper of three extruders, extruder is to making base head feed, obtain the molten parison of multilayer, then parison is introduced the mould of splitting, pass into compressed air in closed backward die cavity and make its expansion and be attached to die cavity wall and moulding, obtain multilayer plastic articles by pressurize, cooling, typing, exhaust at last.The preparation super hydrophobic surface has two kinds of approach: a kind of is to carry out surface roughening on the hydrophobic material surface with low-surface-energy to process; Another kind is to have modification low-surface-energy material on the surface of certain roughness.The plastic bottle internal layer is the mixture of plastics and polytetrafluoroethylene (PTFE) and hollow glass micropearl, hollow glass micropearl provides micro-structural, increase the roughness of internal face, polytetrafluoroethylene (PTFE) provides again low surface energy when increasing roughness, thereby makes plastic bottle inner wall can realize super hydrophobic functional.
The particle diameter of hollow glass micropearl is 10～30 μ m, and the particle diameter of polytetrafluoroethylene (PTFE) is 10～30 μ m, and the mass fraction of hollow glass micropearl and polytetrafluoroethylene (PTFE) and be no more than 70%.
C. the measurement of contact angle
Cut next flat surface with scissors from the laminated plastics bottle product, measure the contact angle of goods internal face by the contact angle tester.
Can be according to the purposes of goods and the difference of environmental condition, plastic layer also can be different, can be a kind of in PE (polyethylene), PP (polypropylene), PVC (polyvinyl chloride), PC (Merlon), PET (polyethylene terephthalate) usually.
In order to improve the adhesive strength of each layer, one deck gluing layer is set between basic unit and functional layer, see Fig. 1 for details.In Fig. 1,1 for skin is body layer, and 2 for the intermediate layer is gluing layer, 3 for internal layer be functional layer.
Adhesive can be a kind of in EVA (ethane-acetic acid ethyenyl resin copolymer), EAA (ethylene-acrylic acid copolymer), polyacrylate, maleic anhydride.Described silane coupler is a kind of in KH550, KH560, KH570, KH792.
Advantage of the present invention is: broken through and can only prepare in the plane the limitation of super-drainage structure in the past, novel, technique is simple, and is pollution-free.
Description of drawings
Fig. 1 is the structural representation of patent of the present invention
Fig. 2 is the activation flow chart of the glass microballoon of patent of the present invention
Fig. 3 is the process chart of the goods of patent of the present invention
The specific embodiment
Embodiment 1
The surface modification of A glass microballoon
Adopt KH550 solution as surface modifier, take KH5501g, absolute ethyl alcohol 500ml, be mixed with the ethanol solution that is made into KH550, after being stirred to the solution clarification, solution is poured in the container that the 45g hollow glass micropearl is housed, stirred after 1 hour, then hollow glass micropearl is put into the water-bath of 80 ℃, reacted 1 hour.Product through cooling, filter, put into after washing air dry oven under 100 ℃ dry 8 hours.
B Coextrusion Blow Moulding process
Outer layer plastic is PE, intermediate layer material is EVA, and in inner layer composite material, the mass fraction of PP, polytetrafluoroethylene (PTFE) and hollow glass micropearl is respectively 70%, 15%, 15%, the particle diameter 10 μ m of glass microballoon, the particle diameter of polytetrafluoroethylene (PTFE) is 30 μ m, and adhesive is EVA.First the mixture with 210gPP, 45g polytetrafluoroethylene (PTFE) and 45g modification hollow glass micropearl later tentatively mixes, and then by the double screw extruder extruding pelletization, mixture is mixed more even.Then respectively with the PE of 500g, the EVA of 300g, the mixture of the PP of granulation 210g later and the polytetrafluoroethylene (PTFE) of 45g and 45g modification hollow glass micropearl later is respectively charged in the hopper of three extruders, extruder is to making base head feed, obtain the molten parison of multilayer, pass into compressed air in closed backward die cavity and make its expansion and be attached to die cavity wall and moulding, obtain multilayer plastic articles by pressurize, cooling, typing, exhaust at last.The model SPZADIII-1.5 of three-layer co-extruded blow molding machine.
The test of C contact angle
Cut next flat surface with scissors from the laminated plastics bottle product, measure through the contact angle tester, the contact angle of article inner surface is 151.8 °.
The surface modification of A glass microballoon
Adopt KH560 as surface modifier, take KH5601g, propyl alcohol 600ml, be made into the propanol solution of KH560, after being stirred to the solution clarification, solution is poured in the container that the 60g hollow glass micropearl is housed, stirred 1.5 hours, then hollow glass micropearl is put into the water-bath of 85 ℃, reacted 1.5 hours.Product through cooling, filter, after washing with put into air dry oven under 110 ℃ dry 9 hours.B Coextrusion Blow Moulding process
Outer layer plastic is PP, intermediate layer material is EAA, and in inner layer composite material, the mass fraction of PET, polytetrafluoroethylene (PTFE) and hollow glass micropearl is respectively 60%, 20%, 20%, the particle diameter 20 μ m of glass microballoon, the particle diameter of polytetrafluoroethylene (PTFE) is 20 μ m, and adhesive is EAA.First 180g PET, 60g polytetrafluoroethylene (PTFE) and 60g modification hollow glass is later tentatively mixed, and then by the double screw extruder extruding pelletization, mixture is mixed more even.Then respectively with the PP of 500g, the EAA of 300g, the mixture of the PET of granulation 180g later and the polytetrafluoroethylene (PTFE) of 60g and 60g modification hollow glass micropearl later is respectively charged in the hopper of three extruders, extruder is to making base head feed, obtain the molten parison of multilayer, pass into compressed air in closed backward die cavity and make its expansion and be attached to die cavity wall and moulding, obtain multilayer plastic articles by pressurize, cooling, typing, exhaust at last.
The test of C contact angle
Cut next flat surface with scissors from the laminated plastics bottle product, measure through the contact angle tester, the contact angle of article inner surface is 152.3 °.
Embodiment 3
The surface modification of A glass microballoon
Adopt KH570 as surface modifier, take KH5701g, propyl alcohol 600ml, be made into the butanol solution of KH570, after being stirred to the solution clarification, solution is poured in the container that the 75g hollow glass micropearl is housed, stirred 1.5 hours, then hollow glass micropearl is put into the water-bath of 85 ℃, reacted 1.5 hours.Product through cooling, filter, after washing with put into air dry oven under 105 ℃ dry 8 hours.B Coextrusion Blow Moulding process
Outer layer plastic is PET, intermediate layer material is maleic anhydride, and in inner layer composite material, the mass fraction of PVC, polytetrafluoroethylene (PTFE) and hollow glass micropearl is respectively 60%, 15%, 25%, the particle diameter 20 μ m of glass microballoon, the particle diameter of polytetrafluoroethylene (PTFE) is 30 μ m, and adhesive is maleic anhydride.First 180g PVC, 45g polytetrafluoroethylene (PTFE) and 75g modification hollow glass is later tentatively mixed, and then by the double screw extruder extruding pelletization, mixture is mixed more even.Then respectively with the PET of 500g, the maleic anhydride of 300g, the mixture of the PVC of granulation 180g later and the polytetrafluoroethylene (PTFE) of 45g and 75g modification hollow glass micropearl later is respectively charged in the hopper of three extruders, extruder is to making base head feed, obtain the molten parison of multilayer, pass into compressed air in closed backward die cavity and make its expansion and be attached to die cavity wall and moulding, coextrusion blowing goes out the plastic bottle goods.
The test of C contact angle
Cut next flat surface with scissors from the laminated plastics bottle product, measure through the contact angle tester, the contact angle of article inner surface is 154.6 °.
Embodiment 4
The surface modification of A glass microballoon
Adopt KH792 as surface modifier, take KH7921g, butanone 600ml, be made into the butanol solution of KH792, after being stirred to the solution clarification, solution is poured in the container that the 45g hollow glass micropearl is housed, stirred 1.5 hours, then hollow glass micropearl is put into the water-bath of 90 ℃, reacted 1.5 hours.Product through cooling, filter, after washing with put into air dry oven under 110 ℃ dry 9 hours.B Coextrusion Blow Moulding process
Outer layer plastic is PVC, intermediate layer material is polyacrylate, and in inner layer composite material, the mass fraction of PC, polytetrafluoroethylene (PTFE) and hollow glass micropearl is respectively 60%, 25%, 15%, the particle diameter 30 μ m of glass microballoon, the particle diameter of polytetrafluoroethylene (PTFE) is 30 μ m, and adhesive is polyacrylate.First 180g PC, 75g polytetrafluoroethylene (PTFE) and 45g modification hollow glass is later tentatively mixed, and then by the double screw extruder extruding pelletization, mixture is mixed more even.Then respectively with the PVC of 500g, the polyacrylate of 300g, the mixture of the PC of granulation 180g later and the polytetrafluoroethylene (PTFE) of 75g and 45g modification hollow glass micropearl later is respectively charged in the hopper of three extruders, extruder is to making base head feed, obtain the molten parison of multilayer, pass into compressed air in closed backward die cavity and make its expansion and be attached to die cavity wall and moulding, coextrusion blowing goes out the plastic bottle goods.
The test of C contact angle
Cut next flat surface with scissors from the laminated plastics bottle product, measure through the contact angle tester, the contact angle of article inner surface is 152.7 °.
Claims (3)
1. the preparation method of an inner wall super-hydrophobic surface of plastic bottle, is characterized in that, step is as follows:
A. the surface modification of glass microballoon
Get silane coupler as surface modifier, silane coupler is dissolved in solvent, form solution, described solvent is a kind of in ethanol, propyl alcohol, butanone; Hollow glass micropearl is poured in solution, stirred 1～2 hour, then hollow glass micropearl is put into the water-bath of 80～90 ℃, reacted 1～2 hour; Product is put into air dry oven dry 8～9h under 100～110 ℃ simultaneously with polytetrafluorethylepowder powder after cooling, filtration, washing;
B. Coextrusion Blow Moulding process
The mixture of outer layer plastic, adhesive, inner plastic and polytetrafluoroethylene (PTFE) and modification hollow glass micropearl later is contained in respectively in the barrel of three extruders, extruder is to making base head feed, coextrusion blowing goes out multilayer plastic articles, and internal layer has super-hydrophobic superfine structure;
The particle diameter of described hollow glass micropearl is 10～30 μ m, and the particle diameter of polytetrafluoroethylene (PTFE) is 10～30 μ m, and the mass fraction of hollow glass micropearl and polytetrafluoroethylene (PTFE) and be no more than 70%;
Described silane coupler mass content is 0.5～2% of hollow glass micropearl quality.
2. the preparation method of a kind of inner wall super-hydrophobic surface of plastic bottle according to claim 1, is characterized in that, described silane coupler is a kind of in KH550, KH560, KH570, KH792; Described adhesive is a kind of in EVA, EAA, maleic anhydride, polyacrylate.
3. the preparation method of a kind of inner wall super-hydrophobic surface of plastic bottle according to claim 1, is characterized in that, outer layer plastic used is a kind of in PE, PP, PVC, PC, PET, and inner plastic used is a kind of in PE, PP, PVC, PC, PET.
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| CN102218889B true CN102218889B (en) | 2013-06-19 |
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| CN108372671B (en) * | 2018-02-06 | 2021-03-02 | 日丰企业（佛山）有限公司 | Hydrophobic material, inner-layer hydrophobic pipe and preparation method thereof |
| CN112606364A (en) * | 2021-01-11 | 2021-04-06 | 南通瑞卓模塑有限公司 | Bottle blowing process for hand cream with butt-joint-free bottom |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090339A (en) * | 1997-07-24 | 2000-07-18 | Western Industries, Inc. | Process for manufacture of a blow molded plastic extruded product |
| CN1296044A (en) * | 1999-11-12 | 2001-05-23 | 陈光宇 | Low surface energy repelling type dirt-proof paint and use method thereof |
| CN1872533A (en) * | 2005-06-03 | 2006-12-06 | 中国科学院化学研究所 | Composite membrane of biomimetic water catchment, preparation method and usage |
| CN101717580A (en) * | 2009-12-30 | 2010-06-02 | 四川华通特种工程塑料研究中心有限公司 | High-performance polyphenylene sulfide insulating composite material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130979A (en) * | 1997-10-31 | 1999-05-18 | Toray Ind Inc | Production of surface-treated inorganic fine particle |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090339A (en) * | 1997-07-24 | 2000-07-18 | Western Industries, Inc. | Process for manufacture of a blow molded plastic extruded product |
| CN1296044A (en) * | 1999-11-12 | 2001-05-23 | 陈光宇 | Low surface energy repelling type dirt-proof paint and use method thereof |
| CN1872533A (en) * | 2005-06-03 | 2006-12-06 | 中国科学院化学研究所 | Composite membrane of biomimetic water catchment, preparation method and usage |
| CN101717580A (en) * | 2009-12-30 | 2010-06-02 | 四川华通特种工程塑料研究中心有限公司 | High-performance polyphenylene sulfide insulating composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平11-130979A 1999.05.18 |
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