CN110218347A - A kind of preparation method of hydrophobic polymer membrane material - Google Patents

A kind of preparation method of hydrophobic polymer membrane material Download PDF

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CN110218347A
CN110218347A CN201910507954.4A CN201910507954A CN110218347A CN 110218347 A CN110218347 A CN 110218347A CN 201910507954 A CN201910507954 A CN 201910507954A CN 110218347 A CN110218347 A CN 110218347A
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micro
nano
particles
preparation
membrane material
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CN110218347B (en
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陆冲
祁若轩
陈昊
唐涛
屠沁玮
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29D7/00—Producing flat articles, e.g. films or sheets
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Abstract

The present invention provides a kind of preparation methods of hydrophobic polymer membrane material, include following components: 100 parts by weight of polymer；Micro-and nano-particles 0.5-25 parts by weight；Other auxiliary agent 0.5-30 parts by weight；Preparation step: by polymer, micro-and nano-particles and other auxiliary agent melting mixings, film base is made through extrusion, calendering or curtain coating, then stretched；After drawn, the surface of film forms micro-nano protrusion and hole rough surface structure, obtains hydrophobic membrane materials, and 120 ° of water contact angle >, roll angle < 15 °.

Description

A kind of preparation method of hydrophobic polymer membrane material
Technical field
The present invention relates to hydrophobic material fields, and in particular to a kind of hydrophobic polymer membrane material.
Background technique
The hydrophobicity of the surface of solids refers to its surface and the mutually exclusive physical property of water, when drop is contacted with the surface of solids When reaching solid, liquid, gas three-phase equilibrium, the angle between solid and droplet interfaces contact line claims contact angle；Solid surface energy is lower, Its water contact angle is bigger.For water droplet in 90 ° of contact angle > of the surface of solids, which has hydrophobicity, super hydrophobic material Water contact angle >=150 °.
Such as energy 31-33mN/m in the surface PE in polymer, smooth HDPE film surface water contact angle is weak between 90-100 ° Hydrophobic material.In nature with lotus leaf, taro leaves etc. for representative plant leaf blade have ultra-hydrophobicity, lotus leaf surface The wax on micron-nanometer composite construction and surface is that it has super-hydrophobic basic reason.Although the surface of material can be lower, Hydrophobicity is stronger, even if being fluorocarbon resin, the surface of smooth solid that the close ordered arrangement of C, F obtains, and the contact with water Angle maximum is also no more than 120 °.Therefore, the main method of super hydrophobic surface technology of preparing has two kinds: (1) constructing micro-nano coarse Structure；(2) modification of surfaces is carried out with the substance of low-surface-energy (if contained F, containing Si).
Super hydrophobic surface is typically characterised by: when water droplet falls in super hydrophobic surface, the spherical droplet of formation is slightly inclining When the angle of an oblique very little, droplet will be quickly rolled off from super hydrophobic surface, and the dust on surface is taken away while tumbling, display Excellent self-cleaning performance out, this self-cleaning performance are known as " lotus leaf effect ".Super hydrophobic surface also has fabulous waterproof, prevents Dirty performance, and material surface can be kept dry, clean for a long time, it is conducive to extend the service life of material.Therefore, because super-hydrophobic The unique surface characteristic of material makes it can be widely applied to waterproof, automatically cleaning, fluid drag-reduction, antibacterial, the anti-accumulated snow of exterior aerial River, takes turns antifouling, the anti-corrosion of barnacle, anti-adherency, the anti-clogging of petroleum pipeline, microfluid injection, the waterproof of clothes and antifouling etc. Field.
Currently, the common method for preparing super hydrophobic material has template, phase separation method, etching method, chemical vapour deposition technique Deng, these methods or preparation process using largely to environment volatile organic solvent harmful with human body or at high cost, work Skill is complicated or bad adaptability, can not large-scale production or equipment it is expensive the disadvantages of, limit its application.
Template: using natural super-hydrophobic plant surface, being made corresponding template, or using porous microsphere stratum granulosum as template, Or micro-nano template is made using other physico-chemical process, template microscopic appearance is copied into substrate surface, there is substrate The rough surface of micro nano structure obtains super hydrophobic surface.
Phase separation method: stable mixture (such as temperature) when external condition changes becomes unstable, and then separates At two-phase, rough surface micro nano structure is formed during the separation process, obtains super hydrophobic surface, and this method can pass through polymerization Object/solvent-nonsolvent is mutually isolated, can also be isolated by organic phase/inorganic phase.
Etching method: surface portion substance is removed by lithographic method, constructs the microcosmic surface of micro nano structure.There is chemical quarter Erosion and plasma etching etc..
Chemical vapour deposition technique: chemical vapour deposition technique is a kind of using gas phase reaction, method of the product deposition in ground. This method is to carry out gas phase reaction using compound vapor as raw material, re-unites the material for generating various forms.In practical application mistake Cheng Zhong can prepare the material of the different shapes such as film, whisker, crystal grain, particle and superfine powder according to the difference of reaction condition.
In addition to the above methods, can also by method of electrostatic spinning, self-assembly method, sol-gel method, in-situ synthesis etc. its Other party method prepares super hydrophobic material surface.
Chinese patent CN1050014411B, using summer violet petal as primary template, by dimethyl silicone polymer, dibutyl Tin dilaurate tin and ethyl orthosilicate mixing are poured its surface, solidification, and sur-face peeling obtains the 1st opposite mixture mould of structure Plate；Epoxide-resin glue and diethylenetriamine are mixed again, are poured into the 1st template, is solidified, sur-face peeling obtains the 2nd mould Plate；LDPE solution is prepared again, and LDPE solution is cast in the 2nd template, obtains porous super hydrophobic ldpe film.It is clear that should Not only process flow is long for method, complex process, and LDPE solution is configured using a large amount of organic solvents, and it is thin that casting prepares LDPE Film, is related to organic solvent cost recovery height, and film dimensions are not suitable for large-scale production by great number of issues such as template size restrictions.
Chinese patent CN105346146B discloses a kind of super-hydrophobic sheet material/container of the high density polyethylene (HDPE) that roll angle is controllable And preparation method thereof, this method prepares HDPE sheet material first with press and mold, then in a mold by identical two HDPE sheet materials It laminates, two HDPE pieces is removed with hawkbill after being cooled to room temperature, super-hydrophobic HDPE sheet material are obtained, although this method is simply easy System, and solvent-free use, but the size limitation for being limited by mold and vulcanizing press can not prepare continuous film or sheet material, and two Piece is easy to damage sheet material when removing, and deteriorates mechanical property, limits the application field of this method.
Chinese patent CN103341437B discloses a kind of preparation method of functional super-hydrophobic polypropylene coating, this method It is to be dissolved in the polymer such as polypropylene in toluene organic solvent at 120-140 DEG C, adds such as silica functional particle, It is coated on substrate by coating method, super-hydrophobic polypropylene coating is formed, although super-hydrophobic coat made from this method Stable structure, adhesive force are good, but using harmful organic solvents such as a large amount of toluene, are restricted by environmental protection, are not suitable for promoting and applying.
Therefore, super hydrophobic material preparation process requires process flow short as far as possible, and technical process and quality of item simply may be used Control, it is at low cost and few as far as possible with or without the use of influence environment organic solvent etc..
Summary of the invention
The present invention provides the membrane material of a kind of preparation of hydrophobic polymer membrane material and its preparation, the thickness of the film exists Between 1 μm of -5mm, it solves the deficiencies in the prior art, provides a kind of no hazardous solvent, environmentally protective, simple process preparation Technology, and it is suitble to scale continuous production.
The technical program is to provide a kind of preparation method of hydrophobic polymer membrane material, includes following components:
Preparation step: polymer, micro-and nano-particles and other auxiliary agent melting mixings are made through extrusion, calendering or curtain coating Film base, then stretched；After drawn, the surface of film forms micro-nano protrusion and hole rough surface structure, obtains hydrophobicity Membrane material, 120 ° of water contact angle >, roll angle < 15 °.
The present invention provides the design of general technical: using the micro-and nano-particles of polymer and a certain amount of organic/inorganic, For the process industrial art performance and mechanical performance for guaranteeing material, suitable other auxiliary agents are also added.Polymer, micro-nano are weighed according to the ratio Rice corpuscles and other auxiliary agents, using the progress such as mixing machine, kneader just mix, the mixture through just mixing, using open mill, The high temperature such as mixer, extruder plasticizing equipment is plasticized, and the mixture of plasticizing transforms into film base, film base through calender extrolling again Under proper temperature and stretching ratio, simple tension or biaxial tension are carried out using simple tension mechanism or biaxial tension mechanism, The surface of film after drawn forms micro-nano protrusion and hole coarse structure, obtains hydrophobic membrane materials.Extrusion can also be used The mixture film extrusion base just mixed is directly obtained hydrophobic membrane materials after Mo Pi drawn mechanism is stretched by machine.Also Blow molding can be directly extruded, using effective control of blow-up ratio and draw ratio, obtains hydrophobic film material.
In technical solution of the present invention, the hydrophobicity or hydrophily of polymer itself do not influence the surface micronano protrusion of film with The formation of void structure, in the present invention using a kind of in PP, PE, PVC, PET, PA, PS, PVDF, PVDC, PLA, PVA, EVOH or It is a variety of.
Micro nano structure is constructed as polymer surfaces using the micro-and nano-particles of organic/inorganic in technical solution of the present invention Basic raw material.The micro-and nano-particles are organic micro-/ nano particle or/and inorganic micro-and nano-particles.The micro-nano grain of rice Son be polytetrafluoroethylene (PTFE), dimethyl silicone polymer, ACR, calcium carbonate, aluminium hydroxide, magnesium hydroxide, silica, titanium dioxide, Zinc oxide, magnesia, magnesium carbonate, barium sulfate, kaolin, clay or the one or more stuff and other stuff of montmorillonite, particle size range At 1 nanometer -100 microns.
In the micro-and nano-particles, the particle that 1-999 nanometers of partial size accounts for the 0-100% of micro-and nano-particles gross mass, and partial size 1-100 microns of particle accounts for the 0-100% of micro-and nano-particles gross mass.
In micro-and nano-particles described above, the particle that 10-999 nanometers of partial size accounts for the 0- of micro-and nano-particles gross mass 100%, the particle that 1-50 microns of partial size accounts for the 0-100% of micro-and nano-particles gross mass.
In micro-and nano-particles described above, the particle that 20-999 nanometers of partial size accounts for the 0- of micro-and nano-particles gross mass 100%, the particle that 1-20 microns of average grain diameter accounts for the 0-100% of micro-and nano-particles gross mass.
In micro-and nano-particles described above, the particle that 20-999 nanometers of partial size accounts for the 0-70% of micro-and nano-particles total amount, The particle that 1-20 microns of partial size accounts for the 30-100% of micro-and nano-particles gross mass.
In micro-and nano-particles described above, the particle that 20-999 nanometers of partial size accounts for the 10- of micro-and nano-particles gross mass 30%, 1-20 microns of particle accounts for the 70-90% of micro-and nano-particles gross mass.
Organic micro-nano particle accounts for the 0-100% of micro-and nano-particles gross mass, and inorganic micro-nano in the micro-and nano-particles Rice corpuscles accounts for the 0-100% of micro-and nano-particles gross mass.It is preferred that organic micro-nano particle accounts for the 10- of micro-and nano-particles total amount 70%, inorganic micro-nano particle accounts for the 30-90% of micro-and nano-particles total amount.More preferable organic micro-nano particle accounts for micro-nano The 20-50% of particle total amount, inorganic micro-nano particle account for the 50-80% of micro-and nano-particles total amount.
In the identical situation of addition particle total amount, the composite-grain diameter and compound organic/inorganic grain that configure by a certain percentage Son can be more advantageous to the water contact angle for improving polymer surfaces.
The micro-and nano-particles for adding certain content are the piths of technical solution of the present invention, but more importantly promote to add The micro-and nano-particles added can construct micro nano structure in polymer surfaces, effective by implementing to film base in technical solution of the present invention Control stretches, to reach expected purpose.
It is the key that prepare super hydrophobic material that the surface of solids, which constructs micro-nano coarse structure,.It is presented on polymer solids surface When flat and smooth, water contact angle is generally all little, extremely low polytetrafluoroethylene (PTFE), the water contact angle of smooth surface such as surface energy About at 115 ° or so, the water contact angle of smooth paraffin surface is about at 105 ° or so, and the water of polyethylene, polypropylene smooth surface connects Feeler is lower, and 100 ° of <, be weak hydrophobic material.However the plant leaf blades such as lotus leaf, the insects such as water skipper have ultra-hydrophobicity enough, grind Study carefully discovery, micron and nanometer composite structure is that have super-hydrophobic basic reason.Therefore, it is constructed in polymer surfaces micro-nano coarse Structure is extremely important.
At a certain temperature, the elongational flow of polymer and the elongational flow of particle are different, and polymer is being suitble to Stretching at temperature and external force can produce elastic deformation and plastic deformation, and with the particle of mixed with polymers at this in above scheme It is stretched under part and is difficult to deform, therefore when stretching implementation, the polymer of deformation and indeformable particle generate displacement, make polymer The particle on surface is exposed, and forms a certain amount of hole on its periphery, and the micro-nano coarse knot of polymer surfaces is constructed with this Structure achievees the purpose that hydrophobic or super-hydrophobic.Therefore, stretch has great key effect in the present invention.
Preparation step in technical solution of the present invention is the mixing that will include polymer, micro-and nano-particles and other auxiliary agents Object, is squeezed out or rolls or be cast film base is made, and film base is stretched under proper condition, obtains hydrophobic membrane materials, the film The surface texture of material has micro-nano protrusion and void structure.Stretching can be simple tension, be also possible to biaxial tension；It is double It can be to stretching and gradually stretch, be also possible to vertically and horizontally while stretching, gradually stretching can be cross directional stretch behind first longitudinal direction, first Longitudinal stretching after transverse direction.2-10 times of stretching ratio, preferred 3-8 times of simple tension, preferred 3-7 times of biaxial tension.Draft temperature root It is determined according to type of polymer and other factors, if polyethylene draft temperature is at 40-90 DEG C, PET draft temperature is at 80-120 DEG C, PP Draft temperature is at 80-160 DEG C.
When obtaining the method for super hydrophobic surface using extrusion-blown modling, can be reached by regulation blow-up ratio with draw ratio Expected purpose.
In order to guarantee smooth mechanical performance, the presentation quality etc. implemented with membrane material of Polymer moulding, the present invention Technical solution in also added other auxiliary agents, other auxiliary agents are heat stabilizer, antioxidant, plasticizer, filler, profit One of lubrication prescription, modifying agent, colorant are a variety of.For the quality requirement of different polymer or different product, it is added Its auxiliary agent is necessary, and when such as preparing super-hydrophobic PVC film, need to add stabilizer, plasticizer and lubricant；Prepare super-hydrophobic PLA When film, antioxidant etc. need to be added, these auxiliary agents are all conven-tional adjuvants.
Compared with the prior art, the advantages of the present invention are as follows:
1, the present invention is using conventional polyalcohol contour machining equipment, can serialization, large-scale production, production procedure is short, Technical process is simply controllable with quality of item, reproducible, at low cost.
2, the present invention is adaptable, and multiple polymers can be suitble to prepare super-hydrophobicity membrane material.
3, it the particularly important is in technical solution of the present invention without using any solvent, there is huge environment-friendly advantage, belong to green Colour circle protects production, and industrialization prospect is good, it is contemplated that economic benefit is obvious.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, does not therefore limit the present invention to the embodiment Among range.The techniques implemented on the basis of the foregoing are all within the scope of the present invention.For being familiar with this field For personnel, other modifications may be easily implemented, therefore, without departing substantially from general general defined by claim and equivalency range Under thought, the present invention is not limited to specific details.
Embodiment 1-13 and comparative example 1-3
Table 1: the proportion of hydrophobic polymer membrane material is prepared
The sheet material of embodiment and comparative example is subjected to performance measurement, measurement result is as shown in table 2.
Table 2: water contact angle and water roll angle test result:
Embodiment and comparative example Water contact angle/° Water roll angle/°
Embodiment 1 155 5
Embodiment 2 148 6
Embodiment 3 132 12
Embodiment 4 152 7
Embodiment 5 137 11
Embodiment 6 128 13
Embodiment 7 141 6
Embodiment 8 131 8
Embodiment 9 122 12
Embodiment 10 153 7
Embodiment 11 138 6
Embodiment 12 142 8
Embodiment 13 158 3
Comparative example 1 118 21
Comparative example 2 109 27
Comparative example 3 122 17
Therefrom it can be seen that, the accounting of the partial sizes of the micro-and nano-particles of each embodiment and comparative example and organic/inorganic particle, Influence the hydrophobicity of its material.120 ° of the material surface water contact angle > of embodiment preparation, 15 ° of roll angle <, category hydrophobicity Material, wherein embodiment 13,3 ° of roll angle, belong to super-hydrophobic material by 158 ° of water contact angle.The sheet material of each embodiment reaches hydrophobic Or the requirement of super hydrophobic material, there is practicability, and there is huge environment-friendly advantage, industrialization prospect is good.
The accounting of comparative example 1-3 micro-and nano-particles is affected with hydrophobicity of the organic/inorganic particle accounting to material, nothing Its water contact angle of machine particle accounting is high, micro particles accounting is high material is big, and roll angle is small.

Claims (9)

1. a kind of preparation method of hydrophobic polymer membrane material, it is characterised in that:
(1) include following components:
100 parts by weight of polymer；
Micro-and nano-particles 0.5-25 parts by weight；
Other auxiliary agent 0.5-30 parts by weight；
(2) by polymer, micro-and nano-particles and other auxiliary agent melting mixings, film preparation step: is made through extrusion, calendering or curtain coating Base, then stretched；After drawn, the surface of film forms micro-nano protrusion and hole rough surface structure, obtains hydrophobic film Material, 120 ° of water contact angle, roll angle < 15 °.
2. a kind of preparation method of hydrophobic polymer membrane material according to claim 1, which is characterized in that described is poly- It is one or more in PP, PE, PVC, PET, PA, PS, PVDF, PVDC, PLA, PVA, EVOH for closing object.
3. a kind of preparation method of hydrophobic polymer membrane material according to claim 2, which is characterized in that described is poly- Closing object is a kind of a variety of in PE, PP, PVDF, and 10 ° of 150 ° of the water contact angle > of hydrophobic membrane materials, roll angle <.
4. a kind of preparation method of hydrophobic polymer membrane material according to claim 1, which is characterized in that described is micro- Nanoparticle is organic micro-and nano-particles or/and inorganic micro-and nano-particles；Organic micro-and nano-particles include polytetrafluoroethylene (PTFE), poly- two One of methylsiloxane, ACR or a variety of, inorganic micro-and nano-particles include calcium carbonate, aluminium hydroxide, magnesium hydroxide, dioxy SiClx, titanium dioxide, zinc oxide, magnesia, magnesium carbonate, barium sulfate, kaolin, clay or montmorillonite are one or more；Partial size At 1 nanometer -100 microns.
5. a kind of preparation method of hydrophobic polymer membrane material according to claim 1, which is characterized in that the drawing Stretch is one of simple tension, biaxial tension；The biaxial tension includes lateral gradually biaxial tension behind first longitudinal direction, elder generation Longitudinal gradually biaxial tension, simultaneously bi-directionally one of stretching after transverse direction；Stretching ratio is 2-10 times.
6. a kind of preparation method of hydrophobic polymer membrane material according to claim 5, which is characterized in that the list It is 3-8 times to stretching ratio, the biaxial tension multiplying power is 3-7 times.
7. a kind of preparation method of hydrophobic polymer membrane material according to claim 4, which is characterized in that described is micro- In nanoparticle, the particle that 1-999 nanometers of partial size accounts for the 0-100% of micro-and nano-particles gross mass, and 1-100 microns of partial size of grain Son accounts for the 0-100% of micro-and nano-particles gross mass.
8. a kind of preparation method of hydrophobic polymer membrane material according to claim 4, which is characterized in that described is micro- Organic micro-nano particle accounts for the 0-100% of micro-and nano-particles gross mass in nanoparticle, and inorganic micro-and nano-particles account for micro-nano The 0-100% of rice corpuscles gross mass.
9. hydrophobic polymerizable prepared by a kind of preparation method of hydrophobic polymer membrane material according to claims 1 to 8 Object membrane material.
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CN112457592A (en) * 2020-11-30 2021-03-09 上海普利特复合材料股份有限公司 Long-acting stain-resistant, sticky-resistant and illumination-resistant polypropylene composite material for vehicles and preparation method thereof
CN113801360B (en) * 2021-11-18 2022-03-04 赛宁(苏州)生物科技有限公司 Surface treatment method for realizing low-adsorption plastic liquid-transfer suction head
CN113801360A (en) * 2021-11-18 2021-12-17 赛宁(苏州)生物科技有限公司 Surface treatment method for realizing low-adsorption plastic liquid-transfer suction head
CN114437647A (en) * 2021-12-15 2022-05-06 清华大学 Flexible wear-resistant super-hydrophobic material and preparation method and application thereof
CN115109335A (en) * 2022-05-19 2022-09-27 江西联塑科技实业有限公司 Anti-scaling material and lotus leaf bionic tube prepared from same

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