CN113429620B - Hydrophobic polyurethane foam modified by organosilicon compound and preparation method thereof - Google Patents

Hydrophobic polyurethane foam modified by organosilicon compound and preparation method thereof Download PDF

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CN113429620B
CN113429620B CN202110860039.0A CN202110860039A CN113429620B CN 113429620 B CN113429620 B CN 113429620B CN 202110860039 A CN202110860039 A CN 202110860039A CN 113429620 B CN113429620 B CN 113429620B
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polyurethane foam
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organosilicon compound
organic silicon
water
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CN113429620A (en
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任龙芳
汤正
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/204—Keeping clear the surface of open water from oil spills

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Abstract

The invention discloses hydrophobic polyurethane foam modified by an organic silicon compound and a preparation method thereof, belonging to the field of preparation and application of oil-water separation materials.A carbamate group is generated by the reaction of an isocyanate group and a hydroxyl group, an organic silicon chain segment is introduced into a polyurethane main chain, and then the polyurethane foam is prepared by the reaction with water; after chromic acid etching, silane with long carbon chains is grafted on the surface of the polyurethane foam, and the silane with long carbon chains is hydrolyzed to generate silicon hydroxyl which can be dehydrated and condensed with hydroxyl on the surface of the polyurethane foam, so that the hydrophobic polyurethane foam modified by organic silicon is obtained. The invention reasonably introduces the silicon compound into the polyurethane system, thereby improving the oil-water selectivity of the polyurethane foam and improving the hydrophobicity and lipophilicity of the polyurethane foam. The test results of the morphology characterization and the water contact angle also prove that the hydrophobic polyurethane foam prepared by the invention can obviously improve the problem of poor oil-water selectivity of the polyurethane foam in the oil-water separation process.

Description

Hydrophobic polyurethane foam modified by organic silicon compound and preparation method thereof
Technical Field
The invention belongs to the field of preparation and application of oil-water separation materials, and relates to hydrophobic polyurethane foam modified by an organic silicon compound and a preparation method thereof.
Background
With the rapid development of economy and society, environmental problems become more noticeable. Frequent oil spilling events and the discharge of oily wastewater cause great harm to the water environment, so that a plurality of oil-water separation researches are carried forward. In many studies, adsorption is of great interest due to its simple implementation and oil recovery. The traditional oil absorption material has the defects of low oil absorption multiplying power, poor durability and the like, and practical application of the material is limited. Therefore, a stable, durable, high adsorption capacity substrate is needed for oil-water separation.
The polyurethane foam is a type of polyurethane product, has mature process, low material density, excellent elasticity and rich pore structure, and can be used as a stable oil-water separation material for repeated use. However, the polyurethane foam has a certain hydrophilicity, so that the polyurethane foam absorbs water while absorbing oil, resulting in poor oil-water selectivity, and therefore, hydrophobic modification is required.
Disclosure of Invention
The invention aims to overcome the defect of poor oil-water selectivity of oil-water separation base material polyurethane foam in the prior art, and provides hydrophobic polyurethane foam modified by an organic silicon compound and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for preparing hydrophobic polyurethane foam modified by organosilicon compound, comprising the following steps:
step 1) mixing the isocyanate-terminated polyurethane prepolymer with the dried organic silicon compound, and obtaining an organic silicon modified polyurethane prepolymer after mixing reaction;
step 2) mixing and stirring the organic silicon modified polyurethane prepolymer and deionized water to obtain a mixed solution, and foaming and curing the mixed solution to obtain polyurethane foam;
and 3) sequentially washing and drying the polyurethane foam, immersing the polyurethane foam into chromic acid for etching, washing and drying the polyurethane foam sequentially after etching, immersing the polyurethane foam after secondary drying in a long carbon chain organic silicon compound solution for grafting reaction, and drying to obtain the hydrophobic polyurethane foam modified by the organic silicon compound.
Preferably, in step 1), the organosilicon compound is hydroxy-terminated polydimethylsiloxane or aminopropyl-terminated polydimethylsiloxane.
Preferably, in step 1),
when the organosilicon compound is hydroxyl-terminated polydimethylsiloxane, the conditions of the mixing reaction are as follows: the temperature is 70-80 ℃, and the time is 40-60 min;
when the organosilicon compound is aminopropyl terminated polydimethylsiloxane, the conditions of the mixing reaction are as follows: the temperature is 20-35 ℃, and the time is 40-60 min.
Preferably, in the step 1), the weight ratio of the isocyanate-terminated polyurethane prepolymer to the dried organosilicon compound is (4-20): 1;
in the step 2), when the organic silicon modified polyurethane prepolymer is mixed with deionized water, the mass ratio of the deionized water to the isocyanate-terminated polyurethane prepolymer is (1.5-2.5): 1.
preferably, in step 3), the long carbon chain organosilicon compound is hexadecyl trimethoxy silane or octadecyl trichlorosilane.
Preferably, in the step 3), the solvent in the long carbon chain organosilicon compound solution is cyclohexane;
in the long carbon chain organosilicon compound solution, the volume ratio of the long carbon chain organosilicon compound to cyclohexane is (1-5): 100.
preferably, in step 3),
during etching, the feeding ratio of the polyurethane foam to chromic acid is (0.8-1.2) g:30ml;
the concentration of chromic acid is 10-100 g/L, and the etching time is 0.5-3 min.
Preferably, when the organic silicon modified polyurethane prepolymer in the step 1) is prepared, acetone is dropwise added into the mixed solution after the mixing reaction;
the feeding ratio of the acetone to the isocyanate-terminated polyurethane prepolymer is (0.18-0.3) ml:10g.
Preferably, in step 1), the conditions for drying the organosilicon compound are: the temperature is 110-140 ℃, and the time is 2-4 h.
In the step 2), the stirring conditions are as follows: the temperature is 20-35 ℃, and the time is 40-60 s; the foaming and curing conditions are as follows: the temperature is 20-35 ℃, and the time is 5-10 min.
In the step 3), washing before etching is to alternately wash for 2-3 times by using deionized water and ethanol in sequence; the washing after etching is washing by using deionized water;
the drying conditions are as follows: the temperature is 60-80 ℃, and the time is 4-6 h;
the impregnation conditions were: the temperature is 20-35 ℃, and the time is 30-60 min.
The organosilicon compound modified hydrophobic polyurethane foam prepared by the preparation method of the organosilicon compound modified hydrophobic polyurethane foam has a water contact angle ranging from 138 degrees to 148 degrees.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of hydrophobic polyurethane foam modified by an organic silicon compound, which comprises the steps of firstly utilizing hydroxyl-terminated polydimethylsiloxane to react with isocyanate-terminated polyurethane prepolymer, wherein isocyanate groups and hydroxyl groups react to generate carbamate groups, introducing an organic silicon chain segment into a polyurethane main chain, and then reacting with water to prepare polyurethane foam; after chromic acid etching, the chromic acid etching can increase the surface roughness of the polyurethane foam and generate hydroxyl groups, then long-carbon-chain silane is grafted on the surface of the polyurethane foam, and the long-carbon-chain silane is hydrolyzed to generate silicon hydroxyl which can be dehydrated and condensed with the hydroxyl on the surface of the polyurethane foam, so that the organosilicon modified hydrophobic polyurethane foam is obtained. The invention reasonably introduces the silicon compound into the polyurethane system, thereby improving the oil-water selectivity of the polyurethane foam and improving the hydrophobicity and lipophilicity of the polyurethane foam. The appearance characteristics and the test results of water contact angles also prove that the hydrophobic polyurethane foam prepared by the invention can obviously improve the problem of poor oil-water selectivity of the polyurethane foam in the oil-water separation process.
Furthermore, the ratio of the hydroxyl-terminated polydimethylsiloxane to the isocyanate-terminated polyurethane prepolymer is that the isocyanate equivalent in the polyurethane prepolymer is considered first, and the organosilicon modified polyurethane prepolymer is required to have isocyanate groups, so that the reaction with water can be carried out in the foaming process. In the aspect of reaction time, the reaction time is short, the hydroxyl and the isocyanate group are completely reacted, the reaction time is long, the system viscosity is increased, and the subsequent foaming process is influenced.
Further, when the mixture is mixed with deionized water in the step two, the mass ratio of water is too large, and water remains after reaction; when the amount of water is too small, the system rapidly becomes viscous and solidified while stirring, and the cells become uneven and fine.
Furthermore, the concentration and the time of the chromic acid solution are selected, and when the concentration of the chromic acid solution is low, the effect of roughening the surface of the polyurethane foam is difficult to achieve or is not obvious; the chromic acid solution with too high concentration can cause great damage to the skeleton structure of the foam, the mechanical strength can be reduced, and the repeated use of the foam is not facilitated.
Further, the concentration of the long carbon chain organosilicon solution is optimized, when the concentration of the long carbon chain organosilicon solution is low, the effect is not obvious, and when the concentration is too high, the improvement space is limited, and the material is wasted.
Furthermore, the grafting reaction time is optimized, the grafting reaction time is short, the organosilicon chain segment cannot be well grafted on the polyurethane foam, and the organosilicon chain segment is hydrolyzed and condensed when the grafting reaction time is long, so that the preparation effect of the polyurethane foam is seriously influenced.
The invention also discloses organosilicon compound modified hydrophobic polyurethane foam which is prepared based on the method, the range of the water contact angle of the organosilicon compound modified hydrophobic polyurethane foam is 138-148 degrees, compared with the existing unmodified polyurethane foam, the water contact angle is obviously increased, the hydrophobic property is obviously enhanced, on one hand, strong acid etching liquid enables the surface of polyurethane to be coarsened, a micro-nano rough structure is obtained, on the other hand, the introduction of organosilicon compound further reduces the surface energy of the polyurethane foam, and the polyurethane foam is modified by two steps of organosilicon, so that the hydrophobic property is improved.
Drawings
FIG. 1 is a schematic preparation scheme of a hydrophobic polyurethane foam modified with an organosilicon compound;
FIG. 2 shows the IR spectra of polyurethane foams prepared from hydroxyl-terminated polydimethylsiloxane-modified polyurethane prepolymers (the mass of the hydroxyl-terminated polydimethylsiloxane is 0%, 5% or 10% of the mass of the isocyanate-terminated polyurethane prepolymer);
FIG. 3 is the infrared spectra of Si-PUF-10 before and after etching and after immersion in hexadecyltrimethoxysilane;
FIG. 4 is a scanning electron microscope image, (a) is Si-PUF-0 amplified 150 times, (b) is Si-PUF-0 amplified 5000 times, (c) is Si-PUF-10 amplified 150 times, and (d) is Si-PUF-10 amplified 5000 times;
fig. 5 is a graph showing the results of the water contact angle test, (a) is the water contact angle without adding the organic silicon compound, (b) is the water contact angle of the polyurethane foam prepared before etching with the addition of Si-PUF-10, and (c) is the water contact angle of the hydrophobic polyurethane foam modified with the organic silicon compound finally prepared with the addition of Si-PUF-10.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
example 1
A method for preparing hydrophobic polyurethane foam modified by organosilicon compound, the synthetic route is shown in figure 1, comprising the following steps:
the method comprises the following steps: accurately weighing 20.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g (5% of the mass fraction of the isocyanate-terminated polyurethane prepolymer) of hydroxyl-terminated polydimethylsiloxane, and stirring at 75 ℃ for 40min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 40.0g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 40 seconds with the rotation speed of a mechanical stirrer set at 900rpm to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 100g/L CrO 3 Soaking in water solution for 1min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the mixture into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of hexadecyl trimethoxy silane to cyclohexane is 3.
The application method of the invention comprises the following steps: placing the hydrophobic polyurethane foam modified by the organosilicon compound into a beaker mixed with kerosene and water, taking out the hydrophobic polyurethane foam after the hydrophobic polyurethane foam is adsorbed and saturated, respectively weighing the mass of the polyurethane foam before and after adsorption, and calculating the adsorption capacity.
During regeneration, the adsorbed kerosene is extruded out and collected, and then the polyurethane foam is placed in absolute ethyl alcohol for repeated extrusion to replace the residual kerosene. And (3) drying the cleaned polyurethane foam in a 70 ℃ oven for the next oil-water separation experiment.
Example 2
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 20.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 2.0g (10% of the mass fraction of the isocyanate-terminated polyurethane prepolymer) of hydroxyl-terminated polydimethylsiloxane, and stirring at 70 ℃ for 50min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 35.0g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 40 seconds at 900rpm with a mechanical stirrer to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And (4) washing the powder with distilled water and absolute ethyl alcohol for three times respectively, and then drying the powder in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 80g/L CrO 3 Soaking in water solution for 2min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the polyurethane foam into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of hexadecyl trimethoxy silane to cyclohexane is 5.
The application method of the invention comprises the following steps: placing the hydrophobic polyurethane foam modified by the organosilicon compound into a beaker mixed with kerosene and water, taking out after the adsorption is saturated, respectively weighing the mass of the polyurethane foam before and after adsorption, and calculating the adsorption capacity.
During regeneration, the adsorbed kerosene is extruded out and collected, and then the polyurethane foam is placed in absolute ethyl alcohol for repeated extrusion to replace the residual kerosene. And (3) drying the cleaned polyurethane foam in a 70 ℃ oven for the next oil-water separation experiment.
Example 3
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 20.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 3.0g (15% of the mass fraction of the isocyanate-terminated polyurethane prepolymer) of aminopropyl polydimethylsiloxane, stirring at room temperature for 50min, and dropwise adding acetone during the stirring to adjust the viscosity of the system.
Step two: 30.0g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at 850rpm for 40 seconds at room temperature to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 50g/L CrO 3 Soaking in water solution for 3min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. And then placing the polyurethane foam in a cyclohexane solution of octadecyltrichlorosilane (the volume ratio of the octadecyltrichlorosilane to the cyclohexane is 4.
The application method of the invention comprises the following steps: placing the hydrophobic polyurethane foam modified by the organosilicon compound into a beaker mixed with kerosene and water, taking out the hydrophobic polyurethane foam after the hydrophobic polyurethane foam is adsorbed and saturated, respectively weighing the mass of the polyurethane foam before and after adsorption, and calculating the adsorption capacity.
During regeneration, the adsorbed kerosene is extruded out and collected, and then the polyurethane foam is placed in absolute ethyl alcohol for repeated extrusion to replace the residual kerosene. And (3) drying the cleaned polyurethane foam in a 70 ℃ drying oven for the next oil-water separation experiment.
Example 4
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 20.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 4.0g (20% of the mass fraction of the isocyanate-terminated polyurethane prepolymer) of aminopropyl polydimethylsiloxane, stirring at room temperature for 45min, and dropwise adding acetone to adjust the viscosity of the system.
Step two: 45.0g of distilled water was added to the reaction system, and the mixture was rapidly stirred at 900rpm for 45 seconds at room temperature to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 70g/L CrO 3 Soaking in water solution for 3min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. And then placing the polyurethane foam in a cyclohexane solution of octadecyltrichlorosilane (the volume ratio of the octadecyltrichlorosilane to the cyclohexane is 5.
The application method of the invention comprises the following steps: placing the hydrophobic polyurethane foam modified by the organosilicon compound into a beaker mixed with kerosene and water, taking out after the adsorption is saturated, respectively weighing the mass of the polyurethane foam before and after adsorption, and calculating the adsorption capacity.
During regeneration, the adsorbed kerosene is extruded out and collected, and then the polyurethane foam is placed in absolute ethyl alcohol for repeated extrusion to replace the residual kerosene. And (3) drying the cleaned polyurethane foam in a 70 ℃ oven for the next oil-water separation experiment.
Example 5
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 18.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of hydroxyl-terminated polydimethylsiloxane, and stirring at 75 ℃ for 60min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: adding 45.0g of distilled water into the reaction system, and rotating the reaction system at room temperature by arranging a mechanical stirrerThe mixture was stirred rapidly at 900rpm for 58s to give a mixture. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 95g/L CrO 3 Soaking in water for 2.8min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the polyurethane foam into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of the hexadecyl trimethoxy silane to the cyclohexane is 1.
Example 6
A method for preparing hydrophobic polyurethane foam modified by organosilicon compound, the synthetic route is shown in figure 1, comprising the following steps:
the method comprises the following steps: accurately weighing 16.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of hydroxyl-terminated polydimethylsiloxane, and stirring at 75 ℃ for 50min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 25.6g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 57 seconds with a mechanical stirrer set at 900rpm to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 75g/L CrO 3 Soaking in water for 2.5min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the mixture into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of the hexadecyl trimethoxy silane to the cyclohexane is 2A hydrophobic polyurethane foam.
Example 7
A method for preparing hydrophobic polyurethane foam modified by organosilicon compound, the synthetic route is shown in figure 1, comprising the following steps:
the method comprises the following steps: accurately weighing 15.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of hydroxyl-terminated polydimethylsiloxane, and stirring at 75 ℃ for 40min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 36.0g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 45 seconds with the rotation speed of a mechanical stirrer set at 900rpm, to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 90g/L CrO 3 Soaking in water solution for 3min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the mixture into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of the hexadecyl trimethoxy silane to the cyclohexane is 3.5.
Example 8
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 12.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of hydroxyl-terminated polydimethylsiloxane, and stirring at 75 ℃ for 40min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 27.6g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 40 seconds with a mechanical stirrer rotating at 900rpm to obtain a mixed solution. Quickly transferring the mixed solution to an evaporation dishAnd (4) foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 60g/L CrO 3 Soaking in water solution for 2min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. And then placing the mixture into a cyclohexane solution of octadecyl trichlorosilane (the volume ratio of the octadecyl trichlorosilane to the cyclohexane is 2.
Example 9
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 8.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of aminopropyl polydimethylsiloxane, and stirring for 45min at 28 ℃; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 14.4g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 40 seconds with a mechanical stirrer set at 900rpm to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 40g/L CrO 3 Soaking in water solution for 1.8min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. And then placing the polyurethane foam in a cyclohexane solution of octadecyltrichlorosilane (the volume ratio of the octadecyltrichlorosilane to the cyclohexane is 1.
Example 10
A method for preparing hydrophobic polyurethane foam modified by organosilicon compound, the synthetic route is shown in figure 1, comprising the following steps:
the method comprises the following steps: accurately weighing 6.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of aminopropyl polydimethylsiloxane, and stirring for 60min at 30 ℃; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 14.7g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 60 seconds with the rotation speed of a mechanical stirrer set at 900rpm, to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 30g/L CrO 3 Soaking in water solution for 1min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the mixture into a cyclohexane solution of octadecyl trichlorosilane (the volume ratio of the octadecyl trichlorosilane to the cyclohexane is 1.5.
Example 11
A method for preparing hydrophobic polyurethane foam modified by organosilicon compound, the synthetic route is shown in figure 1, comprising the following steps:
the method comprises the following steps: accurately weighing 4.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of aminopropyl-terminated polydimethylsiloxane, and stirring at 35 ℃ for 40min; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 7.6g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 50 seconds with the rotation speed of a mechanical stirrer set at 900rpm, to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 Size, distilled water and nothing respectivelyWashing with water and ethanol for three times, and drying in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 10g/L CrO 3 Soaking in water solution for 0.5min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the polyurethane foam into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of hexadecyl trimethoxy silane to cyclohexane is 4.5.
Example 12
A method for preparing hydrophobic polyurethane foam modified by organosilicon compounds, the synthetic route is shown in figure 1, and the method comprises the following steps:
the method comprises the following steps: accurately weighing 13.0g of isocyanate-terminated polyurethane prepolymer into a three-neck flask, adding 1.0g of aminopropyl polydimethylsiloxane, and stirring for 50min at 25 ℃; then cooled to room temperature. During which acetone was added dropwise to adjust the viscosity of the system.
Step two: 27.3g of distilled water was added to the above reaction system, and the mixture was rapidly stirred at room temperature for 55 seconds with a mechanical stirrer set at 900rpm to obtain a mixed solution. And (3) quickly transferring the mixed solution to an evaporation dish, foaming and curing at room temperature for 10min to obtain the polyurethane foam. Then cutting it into 2X 2cm 3 And the size of the product is washed by distilled water and absolute ethyl alcohol for three times respectively, and then the product is dried in an oven at 70 ℃.
Step three: immersing the dried polyurethane foam in 80g/L CrO 3 Soaking in water solution for 1.5min, taking out, repeatedly squeezing and cleaning with clear water, cleaning, and oven drying at 70 deg.C. Then placing the polyurethane foam into a cyclohexane solution of hexadecyl trimethoxy silane (the volume ratio of the hexadecyl trimethoxy silane to the cyclohexane is 2.5 to 100) for 30min, taking out the polyurethane foam, and placing the polyurethane foam in an oven at 70 ℃ for drying to obtain the hydrophobic polyurethane foam modified by the organic silicon compound.
Comparative example
The procedure was the same as in example 1 except that no organosilicon compound was added.
Comparative ratioThe polyurethane foams prepared in examples 1 and 2 were characterized and the IR spectrum is shown in FIG. 2. From the results, it can be seen that most of the functional groups of the three foams showed the same appearance, but Si-PUF-5 and Si-PUF-10 had a wavelength of 804.3cm -1 The peak intensity of the Si-PUF-10 is higher than that of the Si-PUF-5, and the peak is a stretching vibration peak of an Si-O bond after being checked, which indicates that the polyurethane prepolymer is successfully modified.
The modified hydrophobic polyurethane foam prepared in example 2 was investigated by characterizing the Si-PUF-10 polyurethane foam prepared before etching in step 2), the Si-PUF-10 polyurethane foam after chromic acid etching in step 3), and the polyurethane foam after grafting reaction (impregnated with hexadecyltrimethoxysilane), and the results of the IR spectrum are shown in FIG. 3. As can be seen from FIG. 3, the polyurethane foam after impregnation had a wavelength of 2920 cm and 2862cm -1 Double peak is shown, and is-CH with long carbon chain 2 And (4) a stretching vibration peak shows that the method can successfully modify the polyurethane foam.
The surface morphology of the polyurethane foam prepared in comparative example 2 was studied, that is, SEM characterization of the Si-PUF-0 polyurethane foam without organosilicon compound and the Si-PUF-10 polyurethane foam after etching and grafting reaction was performed, and as shown in fig. 4, it can be seen from the results that, as the original finger-shaped pores on the polyurethane foam surface were changed by etching with strong acid, and many nano-scale small spots appeared on the foam surface under the high power lens, mainly caused by the corrosion of the polyurethane foam surface, the roughness of the modified polyurethane foam surface was improved, a hydrophobic interface was provided, and according to the surface wettability mechanism, the wettability was mainly affected by the microstructure of the solid surface chemical component group, and the rough structure was favorable for water repellency of the material.
Referring to fig. 5, the contact angles of the comparative example, the Si-PUF-10 polyurethane foam before etching in example 2, and the Si-PUF-10 hydrophobic polyurethane foam after grafting reaction in example 2 were measured, and the results are shown in fig. 5, where the water contact angle of (a) is 93 °, (b) is 136 °, (c) is 146.2 °, and it can be seen from the results that the water contact angle of the modified polyurethane foam is significantly increased, which indicates that the hydrophobicity of the polyurethane foam after modification with silicone is significantly enhanced, and the hydrophobicity enhancement is mainly due to two reasons, that is, the strongly acidic etching liquid coarsens the surface of polyurethane, so as to obtain a micro-nano coarse structure, and that the introduction of the organic silicon compound further reduces the surface energy of the polyurethane foam, and the hydrophobicity of the polyurethane foam is improved through two-step silicone modification.
The stability and reproducibility of the hydrophobic polyurethane foam modified with organosilicon compound prepared in example 3 of the present invention were investigated, specifically as follows:
stability: the hydrophobic polyurethane foam modified by the organosilicon compound prepared in the example is divided into three parts, and the three parts are respectively immersed in 0.1M hydrochloric acid, sodium hydroxide and sodium chloride solution for 30min, dried and measured for water contact angle, and compared with the normal state, the result shows that the water contact angle is not reduced basically, which indicates that the hydrophobic polyurethane foam modified by the organosilicon compound prepared by the method of the invention has good stability.
Reproducibility: after the hydrophobic polyurethane foam modified by the organosilicon compound prepared in example 3 is subjected to 8 times of circulating oil-water separation, the oil absorption multiplying power and the water contact angle of the modified polyurethane foam are measured, and the result shows that the oil absorption multiplying power and the water contact angle are not obviously reduced, which indicates that the hydrophobic polyurethane foam modified by the organosilicon compound prepared by the method has good reproducibility, high recycling rate and strong practicability.
In conclusion, the organic silicon compound has the characteristics of low surface tension, hydrophobicity and the like due to the unique structure of the organic silicon compound, and is widely applied to the aspects of water resistance, moisture resistance and the like. According to the invention, the hydrophobic organic silicon chain segment is introduced into the main chain structure and the surface of the polyurethane foam, so that the hydrophobicity of the polyurethane foam can be greatly improved. In addition, the polyurethane foam prepared by the invention has good stability and reproducibility, and the performance of the polyurethane foam is basically kept unchanged after repeated use.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (5)

1. A preparation method of hydrophobic polyurethane foam modified by organosilicon compounds is characterized by comprising the following steps:
step 1) mixing the isocyanate-terminated polyurethane prepolymer with the dried organic silicon compound, and mixing and reacting to obtain an organic silicon modified polyurethane prepolymer;
step 2) mixing and stirring the organic silicon modified polyurethane prepolymer and deionized water to obtain a mixed solution, and foaming and curing the mixed solution to obtain polyurethane foam;
step 3) sequentially washing and drying the polyurethane foam, immersing the polyurethane foam into chromic acid for etching, washing and drying the polyurethane foam sequentially after etching, immersing the polyurethane foam subjected to secondary drying into a long carbon chain organic silicon compound solution for grafting reaction, and drying to obtain organic silicon compound modified hydrophobic polyurethane foam;
when the organic silicon modified polyurethane prepolymer in the step 1) is prepared, acetone is dropwise added into the mixed solution after the mixing reaction;
the feeding ratio of the acetone to the isocyanate-terminated polyurethane prepolymer is (0.18 to 0.3) ml:10g of a mixture;
in the step 1), the organic silicon compound is hydroxyl-terminated polydimethylsiloxane or aminopropyl-terminated polydimethylsiloxane;
in the step 1), the mass ratio of the isocyanate-terminated polyurethane prepolymer to the dried organic silicon compound is (4-20): 1;
in the step 2), when the organic silicon modified polyurethane prepolymer is mixed with deionized water, the mass ratio of the deionized water to the isocyanate-terminated polyurethane prepolymer is (1.5-2.5): 1;
in the step 3), the long-carbon-chain organosilicon compound is hexadecyl trimethoxy silane or octadecyl trichlorosilane;
in the step 3), the step (c),
during etching, the feeding ratio of the polyurethane foam to chromic acid is (0.8 to 1.2) g:30ml;
the concentration of chromic acid is 10-100 g/L, and the etching time is 0.5-3 min.
2. The method of producing the hydrophobic polyurethane foam modified with an organosilicon compound according to claim 1, wherein in step 1),
when the organosilicon compound is hydroxyl-terminated polydimethylsiloxane, the mixing reaction conditions are as follows: the temperature is 70-80 ℃, and the time is 40-60 min;
when the organosilicon compound is aminopropyl terminated polydimethylsiloxane, the conditions of the mixing reaction are as follows: the temperature is 20 to 35 ℃, and the time is 40 to 60min.
3. The method for producing hydrophobic polyurethane foam modified with organosilicon compound according to claim 1, wherein in step 3), the solvent in the solution of long carbon chain organosilicon compound is cyclohexane;
in the long carbon chain organosilicon compound solution, the volume ratio of the long carbon chain organosilicon compound to cyclohexane is (1 to 5): 100.
4. the method for producing hydrophobic polyurethane foam modified with organosilicon compound according to claim 1, wherein in step 1), the conditions for drying organosilicon compound are: the temperature is 110-140 ℃, and the time is 2-4 h;
in the step 2), the stirring conditions are as follows: the temperature is 20 to 35 ℃, and the time is 40 to 60s; the foaming and curing conditions are as follows: the temperature is 20 to 35 ℃, and the time is 5 to 10min;
in the step 3), washing before etching is carried out, wherein the washing is carried out for 2 to 3 times by alternately washing with deionized water and ethanol in sequence; the washing after etching is washing by using deionized water;
the drying conditions are as follows: the temperature is 60 to 80 ℃, and the time is 4 to 6 hours;
the impregnation conditions were: the temperature is 20 to 35 ℃, and the time is 30 to 60min.
5. An organosilicon compound-modified hydrophobic polyurethane foam prepared by the preparation method of the organosilicon compound-modified hydrophobic polyurethane foam according to any one of claims 1 to 4, wherein the range of the water contact angle of the organosilicon compound-modified hydrophobic polyurethane foam is 138-148 °.
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