CN108440817A - A kind of hydrophobic oleophobic polyolefine material and preparation method thereof - Google Patents
A kind of hydrophobic oleophobic polyolefine material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of hydrophobic oleophobic polyolefine materials and preparation method thereof, 1., by thionyl chloride are dissolved in solvent, and catalyst is added, and perfluoro hexyl acetic acid is added dropwise, and stirring vacuum distillation obtains perfluoro hexyl chloroacetic chloride；2., nano silicon dioxide is dissolved in ethanol water, ultrasonic disperse 30min；Amino silicane coupling agent is added dropwise in above-mentioned mixed liquor, heating stirring, obtains amination nanometer titanium dioxide silicon suspension；3., perfluoro hexyl chloroacetic chloride is dissolved in organic solvent, be then gradually added dropwise in amination nanometer titanium dioxide silicon suspension, products therefrom is dried in vacuo by stirring vacuum distillation, and ball milling simultaneously seals and obtains nano silicon dioxide load perfluoro hexyl acetamide；4., vistanex and nano silicon dioxide loaded into perfluoro hexyl acetamide through high mixer after mixing, melting extrusion granulation prepares hydrophobic oleophobic polyolefine material.Present invention reduces surface energies, effectively prevent dirty layer, save energy consumption.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly, to a kind of perfluorinated surfactant improved polyalkene material
Material and preparation method thereof.
Background technology
China is an energy shortage big country and an energy consumption big country.In all energy consumptions, building energy consumption
The 30% of whole society's energy consumption has been accounted for, huge pressure is brought to resource and environment.Heating energy consumption is maximum in building energy consumption
Part, it is annual up to 1.3 hundred million tons of mark coals, account for 11.5% or so of national total energy consumption, energy saving task is arduous, has a high potential.
Low temperature ground radiation heating is a kind of novel heating system, has the advantages that energy conservation and environmental protection and comfortable safety, it is big to meet government
The energy-saving and emission-reduction led and sustainable development idea are striven vigorously to advocate, therefore super-speed development is obtained in China.
The common tubing of low temperature ground radiation heating system has heat-resisting enhancing polyethylene pipe (PE-RT), crosslinked polyethylene pipe
(PE-X) and Polybutylene Pipe (PB) etc. the high standards of building hot water and heating system pressure pipeline, and simultaneous interpretation, can be met
System metal pipe material is compared, and has the clear superiorities such as light, easy to install.But the mineral member such as the calcium due to containing in heating water, magnesium
Element easily occurs to combine to form sediment, in addition ground heating system coil shape complexity, the longer characteristic of pipeline in temperature change,
For floor heating pipe after using several Heating Seasons, inner wall can form dirty layer, cause hot water circuit unsmooth, reduce heat transfer efficiency, cause
Energy loss influences heating effect, and increasing the clean and maintenance cost of user, (according to measuring and calculating, floor heating inside pipe wall dirt layer thickness often increases
The indoor temperature of 1mm, heating decline 6 DEG C), reduce the service life of ground heating system.Realize in terms of with people's energy conservation and environmental protection
Reinforce, the scale formation of ground heating system gradually draws attention, and carries out anti-scaling property research for common plastics tubing, develops low
The antiscale tubing of cost is increasingly becoming the research hotspot in the field.
Fluorine carbon molecules have many advantages, such as extremely low surface energy, superior heat resistance, weatherability, chemical resistance.Therefore,
Some enterprises are moulded using inner wall of the pipe is lining in fluoroplastics or fluoroplastics and the blend of other macromolecule resins using internal layer fluorine
The self-lubricating of material and corrosion resistance improve the performance of pipe-line system, but since that there are costs of material and technical difficulty is double high for it
The problem of, it is mainly used in oil field gasoline feed field at present, it is difficult to be generalized to common industry infusion and common plumbing
System, and fluorine material resistance to low temperature is poor, it is difficult to it is applied in north cold area.
Other than fluorine material, organosilicon has both inorganic matter and Organic Compound energy, it may have good hydrophobic and oil repellent performance,
And high and low temperature resistance, durability in oxidative degradation can be good.If both fluorine material and organosilicon material are organically combined, can be achieved
Have complementary advantages.It is currently used to have fluoro organosilicon polymer and siliceous organo-fluorine polymer, there is not yet being applied to polyene
The relevant report of hydrocarbon pipeline.
Invention content
The object of the present invention is to provide a kind of hydrophobic oleophobic polyolefine materials, can be used for low temperature heating tubing, effectively anti-
Locking system fouling promotes heating system Operating ettectiveness.
It is a further object of the present invention to provide a kind of preparation methods of hydrophobic oleophobic polyolefine material.
Technical solution of the invention is：A kind of hydrophobic oleophobic polyolefine material, raw material by following parts by weight group
Part composition, 100 parts of polyolefin, 1-50 parts of nano silicon dioxide load perfluoro hexyl acetamide, wherein nano silicon dioxide
It loads perfluoro hexyl acetamide and reacts obtained by perfluoro hexyl acetic acid, thionyl chloride, nano silicon dioxide, amino silane, perfluor
The molar ratio of hexylacetic acid and thionyl chloride is 1：The weight ratio of 1.5-2, perfluoro hexyl acetic acid and nano silicon dioxide is 1：
The weight ratio of 0.1-0.5, nano silicon dioxide and amino silane is 1：4-7.
Amino silane has longer C-C chains, can be well compatible with polyolefin, solves perfluoro hexyl acetic acid and polyolefin phase
The problem of capacitive difference, C-C chains and the polyolefin macromolecular chain of amino silane mutually tangle, and slow down perfluoro hexyl acetic acid to matrix table
The speed of face migration, keeps hydrophobic oleophobic performance persistently effective, since amino silane and perfluoro hexyl acetic acid are all liquid, using receiving
The surface smoothness of product can be improved in rice SiO2, and the mechanical performance of polyolefin also can be improved, and easily reunites, and hardly possible dispersion substantially improves
Compatibility and dispersibility ensure modified effect, introduce fluorine atom and silicon atom, substantially reduce the surface of polyolefine material
Can, play the role of hydrophobic oleophobic, prevents floor heating pipe from generating dirty layer, save energy consumption.
The molar ratio of the perfluoro hexyl acetic acid and thionyl chloride is 1：2, perfluoro hexyl acetic acid and nano silicon dioxide
Weight ratio is 1：0.2, the weight ratio of nano silicon dioxide and amino silane is 1：6.Both it can guarantee the hydrophobic oleophobic for improving material
Performance and tensile strength, and can prevent the comprehensive performance of material from declining.
The present invention another technical solution be：A kind of preparation method of hydrophobic oleophobic polyolefine material, including it is following
Step：1., thionyl chloride is dissolved in solvent, catalyst is added, perfluoro hexyl acetic acid is added dropwise, is depressurized after being sufficiently stirred reaction
Distillation removes solvent and excess thionyl chloride, obtains perfluoro hexyl chloroacetic chloride, and reaction temperature is 60-90 DEG C, reaction time 3-
5h；Wherein solvent for use is one kind in dichloromethane, chloroform, acetone, ethyl alcohol, petroleum ether, and dosage is every gram of perfluoro hexyl second
Sour 10-20ml/g；Used catalyst is dimethylformamide (DMF), and dosage is every gram of perfluoro hexyl acetic acid 0.5ml/g；2., will
Nano silicon dioxide is dissolved in ethanol water, the ethyl alcohol in ethanol water：Water=9：1, ultrasonic disperse 30min；By amino silicone
Alkane coupling agent is added dropwise in above-mentioned mixed liquor, heats magnetic agitation, and controls temperature at 55 DEG C -95 DEG C, and it is small that constant temperature stirs 2-3
When, obtain amination nanometer titanium dioxide silicon suspension；Ethanol water 5-15ml/g used in every gram of nano silicon dioxide；3., will
Perfluoro hexyl chloroacetic chloride is dissolved in organic solvent, is then gradually added dropwise to amination nanometer titanium dioxide silicon suspension, is sufficiently stirred anti-
Should after be evaporated under reduced pressure, and products therefrom is dried in vacuo 12 hours at 60 DEG C, last ball milling simultaneously seals and obtains nano-silica
SiClx loads perfluoro hexyl acetamide；Reaction temperature is 60-90 DEG C, reaction time 3-5h；Solvent for use is dichloromethane, chlorine
One kind imitative, in acetone, ethyl alcohol, petroleum ether, dosage are every gram of perfluoro hexyl chloroacetic chloride 10-20ml/g；4., by vistanex
Perfluoro hexyl acetamide is loaded with nano silicon dioxide through high mixer after mixing, and it is poly- that melting extrusion granulation prepares hydrophobic oleophobic
Olefin material, melting temperature are 130-210 DEG C.Preparation method is simple, easy to operate, and the cost of material is low.
It is an advantage of the invention that：The surface energy for substantially reducing polyolefine material plays the effect of hydrophobic oleophobic, effectively prevent
Dirty layer is generated in floor heating pipe, saves energy consumption.
Specific implementation mode
The raw material used in the embodiment of the present invention for：
Polyethylene：Chevron Phillips, 3802, tensile strength 19MPa；
Perfluoro hexyl acetic acid, Haimen De Sihang medicine companies Science and Technology Ltd., purity 99%
Nano silicon dioxide, Guangzhou Ji Bisheng, HL-200, SiO2 >=99.8%
Gamma-aminopropyl-triethoxy-silane, DOW CORNING Z-6011
Embodiment 1：
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 4.7g (39.6mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.23g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 12g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.23g is dissolved in 92ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
21.87g。
4., Si mixes polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 21.87g through high mixer
After even, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Embodiment 2
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.86g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 12g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.86g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
22.59g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 22.59g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 1
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, by thionyl chloride 3.14g (26.4mmol)
It is dissolved in 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 6.43g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 12g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 6.43g is dissolved in 64ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
17.32g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 17.32g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 2
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, by thionyl chloride 9.42g (79.2mmol)
It is dissolved in 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.83g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 12g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.83g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
22.51g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 22.51g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Table 1：Compare influence of the thionyl chloride additive amount to material property
From the test result of table 1 it is found that thionyl chloride is insufficient, then perfluoro hexyl acetic acid cannot be fully converted to perfluoro hexyl
Chloroacetic chloride influences the hydrophobic oleophobic performance of material；The ratio of thionyl chloride and perfluoro hexyl acetic acid is 1：1.5 and 1：When 2, perfluor
Hexylacetic acid is substantially completely converted into perfluoro hexyl chloroacetic chloride；Ratio is more than 1：After 2, no significant change, so there is no need to add chlorine again
Change sulfoxide.
Embodiment 3
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.86g.
2., nano silicon dioxide 1g is dissolved in 15ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 6g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.86g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
13.23g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 13.23g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Embodiment 4
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.82g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 12g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.82g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
22.57g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 22.57g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Embodiment 5
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.87g.
2., nano silicon dioxide 5g is dissolved in 75ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 30g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.87g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
44.64g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 44.64g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 3
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.85g.
2., nano silicon dioxide 0.5g is dissolved in 7.5ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 3g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.85g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide 7.46g.
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 7.46g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 4
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.87g.
2., nano silicon dioxide 6g is dissolved in 90ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 36g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.87g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
49.33g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 49.33g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Table 2：Influence of the nano silicon dioxide additive amount to material property
It can be seen that as the ratio of perfluoro hexyl acetic acid and nano silicon dioxide increases, in the process from 2 test result of table
The dosage of nanosized SiO_2 and amino silane increases therewith, and perfluoro hexyl chloroacetic chloride can be made fully to be reacted with-NH, turned to greatest extent
Become nano silicon dioxide load perfluoro hexyl acetamide, to improve the hydrophobic oleophobic performance and tensile strength of material.Perfluor
The ratio of hexylacetic acid and nano silicon dioxide is too small, and reaction is incomplete, and ratio is excessive, and amino silane is too many, can make material
Comprehensive performance decline.
Embodiment 6
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.84g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 8g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.84g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
18.96g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 18.96g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Embodiment 7
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.85g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 14g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.85g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
24.37g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 24.37g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 5
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.84g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 6g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.84g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
16.44g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 16.44g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 6
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 6.3g (52.8mmol) is molten
In 200ml dichloromethane, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 10g is then added dropwise
(26.4mmol), is sufficiently stirred, and 90 DEG C of reaction 4h, then vacuum distillation removes solvent and excess thionyl chloride, obtain perfluor oneself
Base chloroacetic chloride 9.86g.
2., nano silicon dioxide 2g is dissolved in 30ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 16g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 9.86g is dissolved in 98ml dichloromethane, be then gradually added dropwise to ammonia obtained by step (2)
Base nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C very
Drying 12 hours in empty drying box, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide
26.85g。
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 26.85g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Table 3：Influence of the coupling agent dosage to material property
As in table 3 comparing result can be seen that with amino silicane coupling agent dosage increase, with nanosized SiO_2 surface-
OH reactions are more perfect, can prevent nanosized SiO_2 from reuniting, preferably be scattered in base polyethylene, to play the role of enhancing.
But material comprehensive performance can excessively declined.
Comparative example 7
Pure polyethylene material.
Comparative example 8
Perfluoro hexyl acetic acid 10g is directly granulated with polyethylene 100g melting extrusions, melting temperature is 130 DEG C.
Comparative example 9
By 2g nanosized SiO_2s and polyethylene 100g mixed melting extruding pelletizations, melting temperature is 130 DEG C.
Comparative example 10
Nano silicon dioxide 2g is dissolved in 30ml ethanol waters, is placed in ultrasonic disperse 30min in ultrasonic generator；So
Amino silicane coupling agent 12g is added dropwise in above-mentioned mixed liquor afterwards, 80 DEG C of constant temperature on electromagnetic agitation platform is placed in and stirs 3 hours,
Amination nanometer titanium dioxide silicon suspension is obtained, the nanosized SiO_2 being surface-treated through amino silane is obtained after distillation is dry.
By the nanosized SiO_2 being surface-treated through amino silane and polyethylene 100g mixed melting extruding pelletizations, melting temperature is
130℃。
Comparative example 11
Perfluoro hexyl acetic acid 10g, amino silicane coupling agent 12g are directly granulated with polyethylene 100g melting extrusions, melting
Temperature is 130 DEG C.
Comparative example 12
Perfluoro hexyl acetic acid 10g, nano silicon dioxide 2g are directly granulated with polyethylene 100g melting extrusions, melting temperature
It is 130 DEG C.
Table 4：Compare influence of the preparation process to material property
Embodiment 8
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 3.14g is dissolved in 100ml chlorine
It is imitative, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 5g is then added dropwise, is sufficiently stirred, 90 DEG C of reaction 4h,
Then vacuum distillation removes solvent and excess thionyl chloride, obtains perfluoro hexyl chloroacetic chloride 4.73g.
2., nano silicon dioxide 1g is dissolved in 15ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 6g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 4.73g is dissolved in 50ml chloroforms, be then gradually added dropwise to amination obtained by step (2)
Nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C of vacuum and is done
Drying 12 hours in dry case, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide 10.42g.
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 10.42g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 13
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, perfluoro hexyl acetic acid 5g is dissolved in 100ml
Chloroform, and dimethylformamide (DMF) 5ml is added, thionyl chloride 3.14g is then added dropwise, is sufficiently stirred, 90 DEG C of reactions
4h, then vacuum distillation remove solvent and excess thionyl chloride, obtain perfluoro hexyl chloroacetic chloride 3.26g.
2., nano silicon dioxide 1g is dissolved in 15ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 6g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 3.26g is dissolved in 50ml chloroforms, be then gradually added dropwise to amination obtained by step (2)
Nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C of vacuum and is done
Drying 12 hours in dry case, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide 9.97g.
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 9.97g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 14
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, perfluoro hexyl acetic acid 5g is dissolved in 100ml
Chloroform, and dimethylformamide (DMF) 5ml is added, thionyl chloride 3.14g is then added dropwise, is sufficiently stirred, 90 DEG C of reactions
8h, then vacuum distillation remove solvent and excess thionyl chloride, obtain perfluoro hexyl chloroacetic chloride 4.45g.
2., nano silicon dioxide 1g is dissolved in 15ml ethanol waters, be placed in ultrasonic disperse in ultrasonic generator
30min；Then amino silicane coupling agent 6g is added dropwise in above-mentioned mixed liquor, is placed in 80 DEG C of constant temperature stirrings on electromagnetic agitation platform
3 hours, obtain amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 4.45g is dissolved in 50ml chloroforms, be then gradually added dropwise to amination obtained by step (2)
Nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C of vacuum and is done
Drying 12 hours in dry case, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide 10.21g.
4. polyethylene 100g is uniformly mixed with nano silicon dioxide load perfluoro hexyl acetamide 10.21g through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Comparative example 15
1., in the three-necked flask equipped with stirrer, thermometer and condenser pipe, thionyl chloride 3.14g is dissolved in 100ml chlorine
It is imitative, and dimethylformamide (DMF) 5ml is added, perfluoro hexyl acetic acid 5g is then added dropwise, is sufficiently stirred, 90 DEG C of reaction 4h,
Then vacuum distillation removes solvent and excess thionyl chloride, obtains perfluoro hexyl chloroacetic chloride 4.74g.
2., amino silicane coupling agent 6g is dissolved in 100ml ethanol waters, fully then by nano silicon dioxide after dissolving
1g is added in above-mentioned solution, prior to ultrasonic disperse 30min in ultrasonic generator, then is placed in 80 DEG C of constant temperature on electromagnetic agitation platform and stirs
It mixes 3 hours, obtains amination nanometer titanium dioxide silicon suspension.
3., perfluoro hexyl chloroacetic chloride 4.73g is dissolved in 50ml chloroforms, be then gradually added dropwise to amination obtained by step (2)
Nanometer titanium dioxide silicon suspension, is sufficiently stirred, and is evaporated under reduced pressure after 90 DEG C of reaction 4h, and products therefrom is placed on 60 DEG C of vacuum and is done
Drying 12 hours in dry case, last ball milling and sealing obtain nano silicon dioxide load perfluoro hexyl acetamide 9.93g.
4., polyethylene 100g and nano silicon dioxide load perfluoro hexyl acetamide 9.93g is uniformly mixed through high mixer
Afterwards, melting extrusion, which is granulated, is made hydrophobic oleophobic polythene material.Melting temperature is 130 DEG C.
Table 5：Compare influence of the charging sequence to material property
It is found that the charging sequence of the method for the present invention is reasonable, reaction is very fast for comparing embodiment 8, comparative example 13 and 14.According to
The charging sequence of comparative example then needs the longer reaction time just perfluoro hexyl acetic acid can be made to be completely transformed into perfluoro hexyl acetyl
Chlorine.
Comparing embodiment 8, comparative example 15 are it is found that change the sequence of aminosilane-treated nanosized SiO_2, to material surface
The influence of energy is little, but tensile strength reduces, it may be possible to which after occurring due to amino silane hydrolysis, self-condensation causes to nanometer
Caused by the processing of SiO2 not exclusively.
Use the other kinds of polyolefine material such as polypropylene, polybutene instead, income effect rule is roughly the same, only because of resin
The difference of matrix performance itself, and numerical value difference is caused, therefore no longer repeat one by one herein.
Hydrophobic oleophobic polythene material obtained by the present invention is used as tubing raw material, the polyethylene floor heating pipe of DN20 is squeezed out, takes 3
Root sample tests it by the front and back surface property of water extracting.From the point of view of test result, before and after high-temperature water cycle extracting for a long time,
Tubing changes less the surface contact angle of water and hexadecane, and it is poly- to illustrate that the method for the present invention well introduces fluosilicic atom
Olefin substrate, durability, the water-wash resistance of modified material are all preferable, and overcoming the easy fast transferring of micromolecule additive causes to be modified
The problem of failure.
Above-listed detailed description is illustrating for possible embodiments of the present invention, which is not to limit this hair
Bright the scope of the claims, all equivalence enforcements or change without departing from carried out by the present invention are intended to be limited solely by the scope of the claims of this case.
Claims (3)
1. a kind of hydrophobic oleophobic polyolefine material, it is characterised in that：Its raw material is made of the component of following parts by weight, 100 parts
Polyolefin, 1-50 parts of nano silicon dioxide load perfluoro hexyl acetamide, and wherein nano silicon dioxide loads perfluoro hexyl second
Amide is reacted by perfluoro hexyl acetic acid, thionyl chloride, nano silicon dioxide, amino silane to be made, perfluoro hexyl acetic acid and chlorination
The molar ratio of sulfoxide is 1：The weight ratio of 1.5-2, perfluoro hexyl acetic acid and nano silicon dioxide is 1：0.1-0.5, nano-silica
SiClx and the weight ratio of amino silane are 1：4-7.
2. a kind of hydrophobic oleophobic polyolefine material according to claim 1, it is characterised in that：The perfluoro hexyl acetic acid with
The molar ratio of thionyl chloride is 1：2, the weight ratio of perfluoro hexyl acetic acid and nano silicon dioxide is 1：0.2, nano silicon dioxide
Weight ratio with amino silane is 1：6.
3. a kind of preparation method of hydrophobic oleophobic polyolefine material as described in claim 1, it is characterised in that：Including following step
Suddenly：1., thionyl chloride is dissolved in solvent, catalyst is added, perfluoro hexyl acetic acid is added dropwise, is sufficiently stirred after reaction to depressurize and steam
It evaporates, removes solvent and excess thionyl chloride, obtain perfluoro hexyl chloroacetic chloride, reaction temperature is 60-90 DEG C, reaction time 3-5h；
Wherein solvent for use is one kind in dichloromethane, chloroform, acetone, ethyl alcohol, petroleum ether, and dosage is every gram of perfluoro hexyl acetic acid
10-20ml/g；Used catalyst is dimethylformamide (DMF), and dosage is every gram of perfluoro hexyl acetic acid 0.5ml/g；2., will receive
Rice silica is dissolved in ethanol water, the ethyl alcohol in ethanol water：Water=9：1, ultrasonic disperse 30min；By amino silane
Coupling agent is added dropwise in above-mentioned mixed liquor, heats magnetic agitation, and controls temperature at 55 DEG C -95 DEG C, and it is small that constant temperature stirs 2-3
When, obtain amination nanometer titanium dioxide silicon suspension；Ethanol water 5-15ml/g used in every gram of nano silicon dioxide；3., will
Perfluoro hexyl chloroacetic chloride is dissolved in organic solvent, is then gradually added dropwise to amination nanometer titanium dioxide silicon suspension, is sufficiently stirred anti-
Should after be evaporated under reduced pressure, and products therefrom is dried in vacuo 12 hours at 60 DEG C, last ball milling simultaneously seals and obtains nano-silica
SiClx loads perfluoro hexyl acetamide；Reaction temperature is 60-90 DEG C, reaction time 3-5h；Solvent for use is dichloromethane, chlorine
One kind imitative, in acetone, ethyl alcohol, petroleum ether, dosage are every gram of perfluoro hexyl chloroacetic chloride 10-20ml/g；4., by vistanex
Perfluoro hexyl acetamide is loaded with nano silicon dioxide through high mixer after mixing, and it is poly- that melting extrusion granulation prepares hydrophobic oleophobic
Olefin material, melting temperature are 130-210 DEG C.
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| CN110773127A (en) * | 2019-11-13 | 2020-02-11 | 中国科学院过程工程研究所 | Hydrophobic active carbon material, preparation method and application thereof |
| CN113357446A (en) * | 2021-06-01 | 2021-09-07 | 天津市伟星新型建材有限公司 | Self-cleaning floor heating pipeline and preparation method thereof |
| CN113861563A (en) * | 2021-11-09 | 2021-12-31 | 上海锦湖日丽塑料有限公司 | Anti-fingerprint polyolefin resin composition and preparation method and application thereof |
| CN114262480A (en) * | 2021-12-03 | 2022-04-01 | 广东顺威精密塑料股份有限公司 | Hydrophobic and oleophobic self-cleaning material and preparation method thereof |
| CN114716746A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Hydrophobic and oleophobic polyethylene master batch, preparation method thereof and polyethylene pipeline material |
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