CN109485976A - A kind of super-hydrophobic sheet material of low density polyethylene (LDPE) and preparation method thereof - Google Patents
A kind of super-hydrophobic sheet material of low density polyethylene (LDPE) and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) and preparation method thereof, the sheet material is by including that the raw material of following components and parts by weight content is prepared: 42-60 parts of low density polyethylene (LDPE), 8-12 parts of corncob, 3-5 parts of modified nano zinc oxide, 16-24 parts of White Mineral Oil and 0.4-0.8 parts of oxidized polyethylene wax.Compared with prior art, step of preparation process of the present invention is simple, controllability is good, it is low in cost, it is reproducible, no pollution to the environment, sheet surface obtained intimate 100% has super-hydrophobic effect, the surface of the super-hydrophobic sheet material of low density polyethylene (LDPE) obtained and the contact angle of water are at 153 ° -158 °, water droplet the super-hydrophobic sheet surface of low density polyethylene (LDPE) roll angle less than 8 °, it can be realized by changing the relative amount of pellet each component to the regulation of the super-hydrophobic sheet material roll angle of low density polyethylene (LDPE), be had a good application prospect, be convenient for commercial introduction.
Description
Technical field
The invention belongs to super hydrophobic material preparation technical field, it is related to a kind of super-hydrophobic sheet material of low density polyethylene (LDPE) and its system
Preparation Method.
Background technique
In recent years, by the inspiration of lotus leaf effect, the super hydrophobic surface with water contact angle greater than 150 ° causes extensive pass
Note.On super hydrophobic surface, the drop taken water as a solvent is usually formed glistening spherical droplet, is slightly tilted certain angle
Degree, drop will be tumbled from super hydrophobic surface, and the pollutants such as the dust of material surface are taken away while tumbling, thus be had fabulous
Self-cleaning ability；Since the contact area of drop and super hydrophobic surface is very small, and it cannot steadily rest on super-hydrophobic table
Face, thus will be inhibited to the greatest extent using water as chemical reaction of medium and electrochemical reaction etc. in super hydrophobic surface.
Therefore, super hydrophobic surface has the function of anticorrosion, prevents electric current conduction, is anti-oxidant, preventing sticking for snow from even inhibiting frost etc..
Low density polyethylene (LDPE) (LDPE) is also known as high pressure polyethylene, is a kind of plastic material, it is suitble to thermoplastic molding's processing
Various moulding process, molding processibility is good.Currently, the super-hydrophobicization research about low density polyethylene (LDPE) has been a concern.
However, the contact angle of existing low density polyethylene sheet material and water is between 90 °~110 °, therefore do not have self-cleaning property.Cause
This, seek it is a kind of easy to industrialized production, it is at low cost, and the super-hydrophobic sheet material based on low density polyethylene (LDPE) with self-cleaning property
It is particularly important.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of preparation method is simple,
Controllability is good, and economic cost is low, with excellent self-cleaning property and the controllable super-hydrophobic sheet material of low density polyethylene (LDPE) of roll angle and its
Preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of super-hydrophobic sheet material of low density polyethylene (LDPE), the sheet material by including the raw material preparation of following components and parts by weight content and
At: 42-60 parts of low density polyethylene (LDPE), 8-12 parts of corncob, 3-5 parts of modified nano zinc oxide, 16-24 parts of White Mineral Oil and oxidation
0.4-0.8 parts of polyethylene wax.
The modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): rapeseed oil 20-32 g is added in reactor, and the NaOH first that 8-12 g mass concentration is 6-8% is then added dropwise
Alcoholic solution after dripping off, reacts 1-1.5 h at 75-82 DEG C, is washed after reaction to neutrality, removes water drying, obtain fatty acid
Methyl esters；
Step (II): at 65-72 DEG C to 8-12 g fatty acid methyl ester, 12-15 ml acetic acid and catalyst A highly acid sun from
H is added dropwise in mixture in sub-exchange resin2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.5-2:1, is kept the temperature after dripping off
2-4 h is reacted, is washed after reaction to neutrality, is removed water drying, epoxy-modified rapeseed oil is made；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 10-20 minutes, at 55-70 DEG C, be added catalyst B, continue to surpass
Sound disperses 15-30 minutes, obtains homogeneous solution, then vacuum dried, obtains modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil described in step (I), level-one squeezing.
Ultrasonic power is preferably 100W in step (I).
Catalyst A described in step (II) is butyl titanate, and the additive amount of catalyst A is fatty acid methyl ester matter
The 3-5% of amount, and the strong acidic ion resin is the 732# cation of Sinopharm Chemical Reagent Co., Ltd.'s production
Exchanger resin.
The mass ratio of nano zine oxide described in step (III) and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution
100:20-35: 50-80。
The end hydroxyl silicone oil solution is mixed by end hydroxyl silicone oil and organic solvent 8-15:100 in mass ratio.
The viscosity of the end hydroxyl silicone oil is 16-30mm2/s。
The mass ratio of catalyst B described in step (III) and nano zine oxide is 0.2-0.8:100, the catalysis
Agent B is selected from dibutyl tin dilaurate or tin dilaurate dioctyl tin.
The partial size of the nano zine oxide is 60-120nm.
Vacuum drying condition in step (III) are as follows: dried 5-10 hours in 50-65 DEG C of vacuum oven.
The surface of the super-hydrophobic sheet material of the low density polyethylene (LDPE) and the contact angle of water are at 153 ° -158 °, and water droplet is described
The super-hydrophobic sheet surface of low density polyethylene (LDPE) roll angle less than 8 °.
A kind of preparation method of the super-hydrophobic sheet material of low density polyethylene (LDPE), this method comprise the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 115-120 DEG C of discharging, then is placed in the cold blender cooling of low speed
To room temperature, mixed powder is obtained；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, mold is then preheated into 10- at 132-136 DEG C with vulcanizing press
15 minutes, and pressure maintaining 5-10 minutes at dwell pressure 6-8MPa, after be cooled to room temperature, it is super-hydrophobic to obtain low density polyethylene (LDPE)
Sheet material.
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1700-1900mm, twin-screw plastic granulating
The temperature in the area Ji Ge is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head
160 DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Compared with prior art, the invention has the characteristics that:
1) using epoxy-modified rapeseed oil and organic silicone oil as surface modifier, by point for controlling suitable surface modifier
On the one hand subchain length is effectively combined with nano zine oxide, being formed has hydrophobic uniform surface coating layer, on the other hand
Retain suitable molecular chain length on surface again, promotes to form " the island chain network " being formed by connecting by nano zine oxide, to make
Modified nano zinc oxide and low density polyethylene (LDPE) compound tense, can be uniformly effectively through in low-density polyethylene body, can
The reunion effectivelying prevent between nano granular of zinc oxide is effectively improved the super-hydrophobicity of low density polyethylene sheet material；
2) step of preparation process is simple, and controllability is good, low in cost, reproducible, no pollution to the environment, sheet surface obtained
Intimate 100% has a super-hydrophobic effect, the contact angle of the surface of the super-hydrophobic sheet material of low density polyethylene (LDPE) obtained and water 153 °-
158 °, water droplet the super-hydrophobic sheet surface of low density polyethylene (LDPE) roll angle less than 8 °, can pass through change pellet each group
Point relative amount realize to the regulation of the super-hydrophobic sheet material roll angle of low density polyethylene (LDPE), have a good application prospect, just
In commercial introduction.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1:
The super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE) is prepared by the raw material for including following components and parts by weight content:
48 parts of low density polyethylene (LDPE), 10 parts of corncob, 3 parts of modified nano zinc oxide, 18 parts of White Mineral Oil and oxidized polyethylene wax 0.4
Part.
Wherein, modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): 28 g of rapeseed oil is added in reactor, and the NaOH methanol solution that 8 g mass concentrations are 6%, drop is then added dropwise
After complete, 1 h is reacted at 78 DEG C, is washed after reaction to neutrality, is removed water drying, obtain fatty acid methyl ester；
Step (II): to 10 g fatty acid methyl esters, 12 ml acetic acid and catalyst A in strongly acidic cation exchange tree at 70 DEG C
H is added dropwise in mixture in rouge2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.8:1, drips off rear 2.5 h of insulation reaction,
It is washed after reaction to neutrality, removes water drying, epoxy-modified rapeseed oil is made；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 15 minutes, at 65 DEG C, be added catalyst B, continue ultrasonic disperse
20 minutes, homogeneous solution is obtained, it is then vacuum dried, obtain modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil in step (I), level-one squeezing；And during ultrasonic disperse, ultrasound
Power be preferably 100W.
Catalyst A is butyl titanate in step (II), and the additive amount of catalyst A is fatty acid methyl ester quality
4%, and strong acidic ion resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
The mass ratio 100:30 of nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution in step (III):
65。
End hydroxyl silicone oil solution is to be mixed by end hydroxyl silicone oil and organic solvent 10:100 in mass ratio, and hold hydroxyl
The viscosity of base silicone oil is 25mm2/s。
The mass ratio of catalyst B and nano zine oxide is 0.5:100 in step (III), and catalyst B is selected from tin dilaurate two
Butyl tin.The partial size of nano zine oxide is 80nm.
Vacuum drying condition in step (III) are as follows: dried 8 hours in 55 DEG C of vacuum ovens.
The preparation method of the super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE), comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 118 DEG C of dischargings, then be placed in the cold blender of low speed and be cooled to often
Temperature obtains mixed powder；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, then being preheated mold 10 minutes at 134 DEG C with vulcanizing press,
And pressure maintaining 8 minutes at dwell pressure 7.2MPa, after be cooled to room temperature, obtain the super-hydrophobic sheet material of low density polyethylene (LDPE).
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1800mm, double-screw plastic granulator
The temperature in each area is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head 160
DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Embodiment 2:
The super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE) is prepared by the raw material for including following components and parts by weight content:
52 parts of low density polyethylene (LDPE), 8 parts of corncob, 3.5 parts of modified nano zinc oxide, 20 parts of White Mineral Oil and oxidized polyethylene wax 0.5
Part.
Wherein, modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): 24 g of rapeseed oil is added in reactor, and the NaOH methanol solution that 10g mass concentration is 7%, drop is then added dropwise
After complete, 1.2 h are reacted at 80 DEG C, are washed after reaction to neutrality, are removed water drying, obtain fatty acid methyl ester；
Step (II): to 10 g fatty acid methyl esters, 14 ml acetic acid and catalyst A in strongly acidic cation exchange tree at 68 DEG C
H is added dropwise in mixture in rouge2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.6:1, drips off rear 3 h of insulation reaction, instead
Washing removes water drying, epoxy-modified rapeseed oil is made to neutrality after answering；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 15 minutes, at 60 DEG C, be added catalyst B, continue ultrasonic disperse
20 minutes, homogeneous solution is obtained, it is then vacuum dried, obtain modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil in step (I), level-one squeezing；And during ultrasonic disperse, ultrasound
Power be preferably 100W.
Catalyst A is butyl titanate in step (II), and the additive amount of catalyst A is fatty acid methyl ester quality
4.6%, and strong acidic ion resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
The mass ratio 100:28 of nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution in step (III):
72。
End hydroxyl silicone oil solution is to be mixed by end hydroxyl silicone oil and organic solvent 12:100 in mass ratio, and hold hydroxyl
The viscosity of base silicone oil is 20mm2/s。
The mass ratio of catalyst B and nano zine oxide is 0.4:100 in step (III), and catalyst B is selected from tin dilaurate two
Butyl tin.The partial size of nano zine oxide is 70nm.
Vacuum drying condition in step (III) are as follows: dried 10 hours in 54 DEG C of vacuum ovens.
The preparation method of the super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE), comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 118 DEG C of dischargings, then be placed in the cold blender of low speed and be cooled to often
Temperature obtains mixed powder；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, then being preheated mold 10 minutes at 134 DEG C with vulcanizing press,
And pressure maintaining 8 minutes at dwell pressure 7.2MPa, after be cooled to room temperature, obtain the super-hydrophobic sheet material of low density polyethylene (LDPE).
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1800mm, double-screw plastic granulator
The temperature in each area is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head 160
DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Embodiment 3:
The super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE) is prepared by the raw material for including following components and parts by weight content:
54 parts of low density polyethylene (LDPE), 9 parts of corncob, 4 parts of modified nano zinc oxide, 20.6 parts of White Mineral Oil and oxidized polyethylene wax 0.4
Part.
Wherein, modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): rapeseed oil 28g is added in reactor, and the NaOH methanol solution that 12g mass concentration is 6%, drop is then added dropwise
After complete, 1.5 h are reacted at 75 DEG C, are washed after reaction to neutrality, are removed water drying, obtain fatty acid methyl ester；
Step (II): to 9 g fatty acid methyl esters, 12 ml acetic acid and catalyst A in storng-acid cation exchange resin at 68 DEG C
In mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.6:1, drips off rear 3.5 h of insulation reaction, instead
Washing removes water drying, epoxy-modified rapeseed oil is made to neutrality after answering；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 20 minutes, at 55 DEG C, be added catalyst B, continue ultrasonic disperse
25 minutes, homogeneous solution is obtained, it is then vacuum dried, obtain modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil in step (I), level-one squeezing；And during ultrasonic disperse, ultrasound
Power be preferably 100W.
Catalyst A is butyl titanate in step (II), and the additive amount of catalyst A is fatty acid methyl ester quality
3.6%, and strong acidic ion resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
The mass ratio 100:30 of nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution in step (III):
75。
End hydroxyl silicone oil solution is to be mixed by end hydroxyl silicone oil and organic solvent 9:100 in mass ratio, and hold hydroxyl
The viscosity of base silicone oil is 18mm2/s。
The mass ratio of catalyst B and nano zine oxide is 0.6:100 in step (III), and catalyst B is selected from tin dilaurate two
Tin octylate.The partial size of nano zine oxide is 90nm.
Vacuum drying condition in step (III) are as follows: dried 7 hours in 62 DEG C of vacuum ovens.
The preparation method of the super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE), comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 115 DEG C of dischargings, then be placed in the cold blender of low speed and be cooled to often
Temperature obtains mixed powder；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, then being preheated mold 15 minutes at 132 DEG C with vulcanizing press,
And pressure maintaining 10 minutes at dwell pressure 7.6MPa, after be cooled to room temperature, obtain the super-hydrophobic sheet material of low density polyethylene (LDPE).
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1700mm, double-screw plastic granulator
The temperature in each area is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head 160
DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Embodiment 4:
The super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE) is prepared by the raw material for including following components and parts by weight content:
60 parts of low density polyethylene (LDPE), 12 parts of corncob, 5 parts of modified nano zinc oxide, 24 parts of White Mineral Oil and oxidized polyethylene wax 0.8
Part.
Wherein, modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): rapeseed oil 32g is added in reactor, and the NaOH methanol solution that 11g mass concentration is 8%, drop is then added dropwise
After complete, 1 h is reacted at 82 DEG C, is washed after reaction to neutrality, is removed water drying, obtain fatty acid methyl ester；
Step (II): to 12 g fatty acid methyl esters, 15 ml acetic acid and catalyst A in strongly acidic cation exchange tree at 72 DEG C
H is added dropwise in mixture in rouge2O2Solution, wherein H2O2Molar ratio with acetic acid is 2:1, drips off rear 4 h of insulation reaction, is reacted
After washing to neutrality, remove water drying, epoxy-modified rapeseed oil be made；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 20 minutes, at 70 DEG C, be added catalyst B, continue ultrasonic disperse
15 minutes, homogeneous solution is obtained, it is then vacuum dried, obtain modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil in step (I), level-one squeezing；And during ultrasonic disperse, ultrasound
Power be preferably 100W.
Catalyst A is butyl titanate in step (II), and the additive amount of catalyst A is fatty acid methyl ester quality
5%, and strong acidic ion resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
The mass ratio 100:35 of nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution in step (III):
80。
End hydroxyl silicone oil solution is to be mixed by end hydroxyl silicone oil and organic solvent 15:100 in mass ratio, and hold hydroxyl
The viscosity of base silicone oil is 30mm2/s。
The mass ratio of catalyst B and nano zine oxide is 0.8:100 in step (III), and catalyst B is selected from tin dilaurate two
Tin octylate.The partial size of nano zine oxide is 120nm.
Vacuum drying condition in step (III) are as follows: dried 5 hours in 65 DEG C of vacuum ovens.
The preparation method of the super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE), comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 115 DEG C of dischargings, then be placed in the cold blender of low speed and be cooled to often
Temperature obtains mixed powder；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, then being preheated mold 15 minutes at 132 DEG C with vulcanizing press,
And pressure maintaining 10 minutes at dwell pressure 7.6MPa, after be cooled to room temperature, obtain the super-hydrophobic sheet material of low density polyethylene (LDPE).
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1700mm, double-screw plastic granulator
The temperature in each area is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head 160
DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Embodiment 5:
The super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE) is prepared by the raw material for including following components and parts by weight content:
42 parts of low density polyethylene (LDPE), 8 parts of corncob, 4.5 parts of modified nano zinc oxide, 16 parts of White Mineral Oil and oxidized polyethylene wax 0.5
Part.
Wherein, modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): rapeseed oil 20g is added in reactor, and the NaOH methanol solution that 8g mass concentration is 6% is then added dropwise, drips off
Afterwards, 1.5 h are reacted at 75 DEG C, are washed after reaction to neutrality, are removed water drying, obtain fatty acid methyl ester；
Step (II): to 8 g fatty acid methyl esters, 12 ml acetic acid and catalyst A in storng-acid cation exchange resin at 65 DEG C
In mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.5:1, drips off rear 2 h of insulation reaction, is reacted
After washing to neutrality, remove water drying, epoxy-modified rapeseed oil be made；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 10 minutes, at 55 DEG C, be added catalyst B, continue ultrasonic disperse
20 minutes, homogeneous solution is obtained, it is then vacuum dried, obtain modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil in step (I), level-one squeezing；And during ultrasonic disperse, ultrasound
Power be preferably 100W.
Catalyst A is butyl titanate in step (II), and the additive amount of catalyst A is fatty acid methyl ester quality
3%, and strong acidic ion resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
The mass ratio 100:20 of nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution in step (III):
50。
End hydroxyl silicone oil solution is to be mixed by end hydroxyl silicone oil and organic solvent 8:100 in mass ratio, and hold hydroxyl
The viscosity of base silicone oil is 16mm2/s。
The mass ratio of catalyst B and nano zine oxide is 0.2:100 in step (III), and catalyst B is selected from tin dilaurate two
Tin octylate.The partial size of nano zine oxide is 60nm.
Vacuum drying condition in step (III) are as follows: dried 10 hours in 50 DEG C of vacuum ovens.
The preparation method of the super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE), comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 120 DEG C of dischargings, then be placed in the cold blender of low speed and be cooled to often
Temperature obtains mixed powder；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, then being preheated mold 10 minutes at 132 DEG C with vulcanizing press,
And pressure maintaining 10 minutes at dwell pressure 6MPa, after be cooled to room temperature, obtain the super-hydrophobic sheet material of low density polyethylene (LDPE).
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1900mm, double-screw plastic granulator
The temperature in each area is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head 160
DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Embodiment 6:
The super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE) is prepared by the raw material for including following components and parts by weight content:
46 parts of low density polyethylene (LDPE), 10 parts of corncob, 4 parts of modified nano zinc oxide, 17 parts of White Mineral Oil and oxidized polyethylene wax 0.6
Part.
Wherein, modified nano zinc oxide is the modified nano zine oxide of surface hydrophobicity, mainly following steps is used to prepare
It forms:
Step (I): rapeseed oil 26g is added in reactor, and the NaOH methanol solution that 10g mass concentration is 7.5% is then added dropwise,
After dripping off, 1.4 h are reacted at 78 DEG C, are washed after reaction to neutrality, are removed water drying, obtain fatty acid methyl ester；
Step (II): to 10 g fatty acid methyl esters, 14 ml acetic acid and catalyst A in strongly acidic cation exchange tree at 70 DEG C
H is added dropwise in mixture in rouge2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.8:1, drips off rear 2.5 h of insulation reaction,
It is washed after reaction to neutrality, removes water drying, epoxy-modified rapeseed oil is made；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 15 minutes, at 60 DEG C, be added catalyst B, continue ultrasonic disperse
25 minutes, homogeneous solution is obtained, it is then vacuum dried, obtain modified nano zinc oxide.
The preferred non-transgenic rapeseed oil of rapeseed oil in step (I), level-one squeezing；And during ultrasonic disperse, ultrasound
Power be preferably 100W.
Catalyst A is butyl titanate in step (II), and the additive amount of catalyst A is fatty acid methyl ester quality
4.2%, and strong acidic ion resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
The mass ratio 100:32 of nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution in step (III):
75。
End hydroxyl silicone oil solution is to be mixed by end hydroxyl silicone oil and organic solvent 12:100 in mass ratio, and hold hydroxyl
The viscosity of base silicone oil is 24mm2/s。
The mass ratio of catalyst B and nano zine oxide is 0.4:100 in step (III), and catalyst B is selected from tin dilaurate two
Tin octylate.The partial size of nano zine oxide is 80nm.
Vacuum drying condition in step (III) are as follows: dried 8 hours in 60 DEG C of vacuum ovens.
The preparation method of the super-hydrophobic sheet material of the present embodiment low density polyethylene (LDPE), comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 118 DEG C of dischargings, then be placed in the cold blender of low speed and be cooled to often
Temperature obtains mixed powder；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, then being preheated mold 15 minutes at 136 DEG C with vulcanizing press,
And pressure maintaining 10 minutes at dwell pressure 7MPa, after be cooled to room temperature, obtain the super-hydrophobic sheet material of low density polyethylene (LDPE).
Wherein, in step (2), the spiro rod length of double-screw plastic granulator is 1800mm, double-screw plastic granulator
The temperature in each area is respectively as follows: 155 DEG C of an area, 165 DEG C of 2nd area, 170 DEG C of 3rd area, 175 DEG C of 4th area, 165 DEG C of merging core, head 160
DEG C, 85 DEG C of the thermally conductive oil temperature of screw core.
Comparative example 1:
The super-hydrophobic sheet material of this comparative example low density polyethylene (LDPE) prepares raw material using nano zine oxide to replace modified Nano to aoxidize
Zinc, remaining is the same as embodiment 1.
Comparative example 2:
Certain commercially available super-hydrophobic sheet material of low density polyethylene (LDPE).
The surface of the super-hydrophobic sheet material of the low density polyethylene (LDPE) of embodiment 1-6 and comparative example 1-2 and contact angle, the rolling of water droplet
The test result at angle is as shown in table 1.
1 test result of table
| Project | With the contact angle of water droplet | The roll angle of water droplet |
| Embodiment 1 | 155° | 6° |
| Embodiment 2 | 156° | 5° |
| Embodiment 3 | 154° | 4° |
| Embodiment 4 | 153° | 6° |
| Embodiment 5 | 154° | 7° |
| Embodiment 6 | 158° | 3° |
| Comparative example 1 | 153° | 11° |
| Comparative example 2 | 152° | 15° |
By 1 test result analysis of table it is found that the present invention by using epoxy-modified rapeseed oil and organic silicone oil to nano oxygen
Change zinc progress surface hydrophobicity to be modified, nano zine oxide and low density polyethylene (LDPE) after modified is mutually compound, can be effectively improved low close
The super-hydrophobicity of polyethylene sheets is spent, there is excellent superhydrophobic characteristic, self-cleaning property is excellent, and can be each by changing pellet
The relative amount of component realizes the regulation to the super-hydrophobic sheet material roll angle of low density polyethylene (LDPE), designs more flexible, applicability
It is wider.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of super-hydrophobic sheet material of low density polyethylene (LDPE), which is characterized in that the sheet material is by including following components and parts by weight content
Raw material be prepared: 42-60 parts of low density polyethylene (LDPE), 8-12 parts of corncob, 3-5 parts of modified nano zinc oxide, White Mineral Oil 16-
24 parts and 0.4-0.8 parts of oxidized polyethylene wax.
2. the super-hydrophobic composite sheet of a kind of low density polyethylene (LDPE) according to claim 1, which is characterized in that the modification
Nano zine oxide is the modified nano zine oxide of surface hydrophobicity, is mainly prepared using following steps:
Step (I): rapeseed oil 20-32 g is added in reactor, and the NaOH first that 8-12 g mass concentration is 6-8% is then added dropwise
Alcoholic solution after dripping off, reacts 1-1.5 h at 75-82 DEG C, is washed after reaction to neutrality, removes water drying, obtain fatty acid
Methyl esters；
Step (II): at 65-72 DEG C to 8-12 g fatty acid methyl ester, 12-15 ml acetic acid and catalyst A highly acid sun from
H is added dropwise in mixture in sub-exchange resin2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.5-2:1, is kept the temperature after dripping off
2-4 h is reacted, is washed after reaction to neutrality, is removed water drying, epoxy-modified rapeseed oil is made；
Step (III): nano zine oxide is added in end hydroxyl silicone oil solution, and step (II) is then added while stirring and is made
Epoxy-modified rapeseed oil, after addition, ultrasonic disperse 10-20 minutes, at 55-70 DEG C, be added catalyst B, continue to surpass
Sound disperses 15-30 minutes, obtains homogeneous solution, then vacuum dried, obtains modified nano zinc oxide.
3. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 2, which is characterized in that described in step (II)
Catalyst A be butyl titanate, and the additive amount of catalyst A is the 3-5% of fatty acid methyl ester quality, and described strong
Acidic cationic resin is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
4. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 2, which is characterized in that institute in step (III)
The mass ratio 100:20-35:50-80 of the nano zine oxide and epoxy-modified rapeseed oil, end hydroxyl silicone oil solution stated.
5. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 4, which is characterized in that the terminal hydroxy group silicon
Oil solution is mixed by end hydroxyl silicone oil and organic solvent 8-15:100 in mass ratio.
6. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 5, which is characterized in that the terminal hydroxy group silicon
The viscosity of oil is 16-30mm2/s。
7. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 2, which is characterized in that institute in step (III)
The mass ratio of the catalyst B and nano zine oxide that state are 0.2-0.8:100, and the catalyst B is selected from di lauric dibutyl
Tin or tin dilaurate dioctyl tin.
8. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 2, which is characterized in that described is nano oxidized
The partial size of zinc is 60-120nm.
9. the super-hydrophobic sheet material of a kind of low density polyethylene (LDPE) according to claim 1, which is characterized in that the low-density is poly-
The surface of the super-hydrophobic sheet material of ethylene and the contact angle of water are at 153 ° -158 °, and water droplet is at described low density polyethylene (LDPE) super-hydrophobic
The roll angle on material surface is less than 8 °.
10. the preparation method of the super-hydrophobic sheet material of low density polyethylene (LDPE) as described in any one of claim 1 to 9, which is characterized in that
This method comprises the steps of:
Step (1): by weight by low density polyethylene (LDPE), corncob, modified nano zinc oxide, White Mineral Oil and oxidic polyethylene
High-speed stirred is carried out in wax investment high-speed mixer, mediates and stirs to 115-120 DEG C of discharging, then is placed in the cold blender cooling of low speed
To room temperature, mixed powder is obtained；
Step (2): above-mentioned mixed powder being put into the feeding hopper of double-screw plastic granulator, then is added by the quantitative of feeding hopper
Expect screw rod, mixed powder is quantitatively adding in twin-screw plastic granulating extruder and is granulated, fervent pellet is cooled to lower than 35
DEG C, preprocessing pellet is made；
Step (3): by preprocessing pellet as in mold, mold is then preheated into 10- at 132-136 DEG C with vulcanizing press
15 minutes, and pressure maintaining 5-10 minutes at dwell pressure 6-8MPa, after be cooled to room temperature, it is super-hydrophobic to obtain low density polyethylene (LDPE)
Sheet material.
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