CN112266492A - Preparation method of hydrophobic film with low water absorption - Google Patents
Preparation method of hydrophobic film with low water absorption Download PDFInfo
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- CN112266492A CN112266492A CN202011315561.2A CN202011315561A CN112266492A CN 112266492 A CN112266492 A CN 112266492A CN 202011315561 A CN202011315561 A CN 202011315561A CN 112266492 A CN112266492 A CN 112266492A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 31
- 229920002261 Corn starch Polymers 0.000 claims abstract description 30
- 239000008120 corn starch Substances 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 235000019710 soybean protein Nutrition 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000011324 bead Substances 0.000 claims abstract description 11
- IMYZYCNQZDBZBQ-SJORKVTESA-N (9S,10R)-epoxyoctadecanoic acid Chemical compound CCCCCCCC[C@H]1O[C@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-SJORKVTESA-N 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000004005 microsphere Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007970 homogeneous dispersion Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229940071440 soy protein isolate Drugs 0.000 abstract description 2
- 229940001941 soy protein Drugs 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004033 plastic Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
Classifications
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K5/15—Heterocyclic compounds having oxygen in the ring
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
The invention discloses a preparation method of a hydrophobic film with low water absorption, which comprises the steps of drying corn starch, placing the corn starch in an oil bath, adding a silane coupling agent and stearic acid under stirring, and activating to obtain hydrophobic corn starch; dissolving soy protein isolate and urea in deionized water, adjusting the pH value with a sodium hydroxide solution, stirring for pretreatment, adding epoxy oleic acid and emulsified epoxy resin, and reacting at constant temperature to obtain a composite modified soy protein emulsion; mixing the obtained hydrophobized corn starch and the composite modified soybean protein emulsion, adding a reduced graphene oxide solution, modified hollow glass beads and surface-treated nano tin antimony oxide, fully and uniformly stirring, casting into a polytetrafluoroethylene mold, and drying in a drying oven to form a film.
Description
Technical Field
The invention belongs to the field of degradable plastic products, and particularly relates to a preparation method of a hydrophobic film with low water absorption.
Background
The plastic product has the advantages of strong stability, light weight, low production cost and the like, thereby being deeply favored by people. In recent decades, the plastic industry has been rapidly developed, and the use of a large number of plastic products, especially disposable plastic products, brings great convenience to human life. However, due to the chemical stability of the general-purpose plastic, the general-purpose plastic can exist in the environment stably for a long time after being abandoned, so that a large amount of plastic waste is accumulated in the environment, and serious harm is brought to the environment, such as white pollution, agricultural white cancer and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a hydrophobic film with low water absorption against the existing problems, and the coating prepared according to the method has excellent hydrophobic property and low water absorption.
The invention is realized by the following technical scheme:
the preparation method of the hydrophobic film with low water absorption is characterized by comprising the following steps of:
(1) preparing the dry method hydrophobic modified corn starch:
drying 20-30 parts of corn starch at 110-120 ℃ for 1-2h, placing the corn starch in an oil bath at 100-105 ℃, adding 0.6-0.9 part of silane coupling agent A-151 and 0.6-0.9 part of stearic acid under stirring, and activating for 10-20min to obtain the hydrophobized corn starch;
performing hydrophobic modification treatment on corn starch by adopting a dry method technology, coating a layer of hydrophobic substance on the surface of starch granules by stirring and activating the corn starch by adopting a silane coupling agent and stearic acid, and preparing the corn starch with strong hydrophobicity, so that the corn starch is converted from a hydrophilic surface to a strong hydrophobic surface;
(2) preparing the compound modified soybean protein:
dissolving 20-30 parts of soybean protein isolate and 10-15 parts of urea in 250-280 parts of deionized water, adjusting the pH value to 10 by using a sodium hydroxide solution, stirring and pretreating at 65-70 ℃ for 30-60min, adding 5-7.5 parts of epoxy oleic acid and 5-7.5 parts of emulsified epoxy resin, and reacting at constant temperature for 1-2h to obtain a composite modified soybean protein emulsion;
epoxy oleic acid-epoxy resin is used as a compound modified compound, urea and sodium hydroxide solution are used for pretreating soybean protein molecules, and epoxy groups react with amino groups in the soybean protein molecules, so that the prepared compound modified soybean protein emulsion has good water resistance and high dry and wet shear strength;
(3) preparation of hydrophobic film with low water absorption:
mixing the hydrophobized corn starch obtained in the step (1) with the composite modified soybean protein emulsion obtained in the step (2), adding 2-3 parts of reduced graphene oxide solution, 1-2 parts of modified hollow glass microspheres and 1-2 parts of surface-treated nano tin antimony oxide, fully and uniformly stirring, casting into a polytetrafluoroethylene mold, and drying in a drying oven at 45-50 ℃ for 20-24 hours to form a film;
epoxy oleic acid-epoxy resin composite modified soybean protein emulsion and hydrophobized corn starch are used as raw materials, and a reduced graphene oxide solution, modified hollow glass beads and surface-treated nano tin antimony oxide are added, and a hydrophobic film with low water absorption rate is prepared by casting a film on a polytetrafluoroethylene plate;
further, the concentration of the sodium hydroxide solution in the step (2) is 0.01-0.02 mol/L; adding a 2% sodium dodecyl sulfate solution into 5-7.5 parts of epoxy resin at a ratio of 1:6, and stirring for reacting for 1-2h to obtain the emulsified epoxy resin.
Further, the preparation of the functional graphene in the step (3): preparing 2-3 parts of graphene oxide into a graphene oxide solution with the concentration of 0.8mg/mL, adding 20-30 parts of vitamin C into the graphene oxide solution, adjusting the pH to 9-10 by using ammonia water, and stirring the mixture in an oil bath at the temperature of 95-97 ℃ for 1-2 hours to obtain a reduced graphene oxide solution.
Further, the preparation of the modified hollow glass beads in the step (3): fully mixing 1-2 parts of hollow glass microspheres and 2-4 parts of oleic acid, adding 30-40 parts of acetone, adjusting the pH to 8 by using sodium hydroxide, carrying out ultrasonic dispersion for 30-40min, carrying out high-speed homogeneous dispersion for 25-35min, heating to 120-125 ℃, and drying to obtain the modified hollow glass microspheres.
Further, the surface treatment method of the nano tin antimony oxide in the step (3) comprises the following steps: adding 1 to 2 parts of nano tin antimony oxide (1: 10) into a sodium hydroxide solution with the mass fraction of 3 to 5 percent, stirring at the temperature of between 90 and 95 ℃ for 30 to 60 minutes, cooling, carrying out suction filtration and drying, dispersing into a mixed solution of 0.1 to 0.2 part of silane coupling agent KH550 and 10 to 20 parts of ethanol, adding 0.01 to 0.02 part of catalyst, refluxing at the temperature of between 80 and 85 ℃ for 30 to 60 minutes, cooling, carrying out suction filtration and drying, and obtaining the nano tin antimony oxide with the surface treated.
Compared with the prior art, the invention has the following advantages:
(1) the corn starch is subjected to hydrophobic modification treatment by adopting a dry method technology, the corn starch is stirred and activated by adopting a silane coupling agent and stearic acid, a layer of hydrophobic substance is coated on the surface of starch granules, the corn starch with strong hydrophobicity is prepared, and the corn starch is converted from a hydrophilic surface to a strong hydrophobic surface.
(2) Epoxy oleic acid-epoxy resin is used as a compound modified compound, urea and sodium hydroxide solution are used for pretreating soybean protein molecules, and epoxy groups react with amino groups in the soybean protein molecules, so that the prepared compound modified soybean protein emulsion has good water resistance and high dry and wet shear strength.
(3) Epoxy oleic acid-epoxy resin composite modified soybean protein emulsion and hydrophobized corn starch are used as raw materials, and a reduced graphene oxide solution, modified hollow glass beads and surface-treated nano tin antimony oxide are added, and a hydrophobic film with low water absorption rate is prepared by casting a film on a polytetrafluoroethylene plate; the water absorption of the film is reduced probably because the epoxy oleic acid, the epoxy resin and the soybean protein react to consume hydrophilic groups in molecules on one hand, and the introduction of long carbon chains can also play a role in water resistance on the other hand; after the soybean protein is modified by epoxy oleic acid and epoxy resin, the proportion of hydrophobic groups in the membrane material is increased, and the contact angle of the modified membrane is increased, probably because the excessive epoxy oleic acid is subjected to ring-opening reaction and exists in the membrane in a micromolecule form, and the hydrophobic groups are easily gathered on the surface of the membrane, so that the hydrophobicity is quickly increased.
(4) The reduced graphene oxide solution is prepared by taking graphene oxide as a reinforcing phase and vitamin C as a green reducing agent and doped into the composite film, and the introduction of the graphene can not only obviously improve the tensile strength and the water and oxygen resistance of the composite film, but also endow the composite film with electric conductivity; the nano tin antimony oxide and the hollow glass beads are used as composite fillers, so that the heat insulation performance is good.
Detailed Description
Example 1
The preparation method of the hydrophobic film with low water absorption is characterized by comprising the following steps of:
(1) preparing the dry method hydrophobic modified corn starch:
drying 20 parts of corn starch at 110 ℃ for 2 hours, putting the corn starch in an oil bath at 100 ℃, adding 0.6 part of silane coupling agent A-151 and 0.6 part of stearic acid under stirring, and activating for 10min to obtain hydrophobized corn starch;
(2) preparing the compound modified soybean protein:
dissolving 20 parts of soybean protein isolate and 10 parts of urea in 250 parts of deionized water, adjusting the pH value to 10 by using a sodium hydroxide solution, stirring and pretreating at 65 ℃ for 60min, adding 5 parts of epoxy oleic acid and 5 parts of emulsified epoxy resin, and reacting at constant temperature for 1h to obtain a composite modified soybean protein emulsion;
wherein the concentration of the sodium hydroxide solution is 0.01 mol/L; adding a 2% sodium dodecyl sulfate solution into 5 parts of epoxy resin at a ratio of 1:6, and stirring for reacting for 1 hour to obtain emulsified epoxy resin;
(3) preparation of hydrophobic film with low water absorption:
mixing the hydrophobized corn starch obtained in the step (1) and the composite modified soybean protein emulsion obtained in the step (2), adding 2 parts of reduced graphene oxide solution, 1 part of modified hollow glass bead and 1 part of nano tin antimony oxide for surface treatment, fully and uniformly stirring, casting into a polytetrafluoroethylene mold, and drying in a drying oven at 45 ℃ for 24 hours to form a film.
Wherein, the preparation of the functional graphene comprises the following steps: preparing 2 parts of graphene oxide into a graphene oxide solution with the concentration of 0.8mg/mL, adding 20 parts of vitamin C into the graphene oxide solution, adjusting the pH to 9 by using ammonia water, and stirring the mixture in an oil bath at 95 ℃ for 2 hours to obtain a reduced graphene oxide solution;
preparing modified hollow glass beads: fully mixing 1 part of hollow glass microsphere and 2 parts of oleic acid, adding 30 parts of acetone, adjusting the pH to 8 by using sodium hydroxide, ultrasonically dispersing for 30min, then, carrying out high-speed homogeneous dispersion for 25min, heating to 120 ℃, and drying to obtain a modified hollow glass microsphere;
the surface treatment method of the nano tin antimony oxide comprises the following steps: adding 1:10 parts of nano tin antimony oxide into a sodium hydroxide solution with the mass fraction of 3%, stirring at 90 ℃ for 60min, cooling, carrying out suction filtration and drying, dispersing into a mixed solution of 0.1 part of silane coupling agent KH550 and 10 parts of ethanol, adding 0.01 part of catalyst, refluxing at 80 ℃ for 60min, cooling, carrying out suction filtration and drying, and thus obtaining the surface-treated nano tin antimony oxide.
Example 2
The preparation method of the hydrophobic film with low water absorption is characterized by comprising the following steps of:
(1) preparing the dry method hydrophobic modified corn starch:
drying 30 parts of corn starch at 120 ℃ for 2 hours, putting the corn starch in an oil bath at 105 ℃, adding 0.9 part of silane coupling agent A-151 and 0.9 part of stearic acid under stirring, and activating for 20min to obtain hydrophobized corn starch;
(2) preparing the compound modified soybean protein:
dissolving 30 parts of soybean protein isolate and 15 parts of urea in 280 parts of deionized water, adjusting the pH value to 10 by using a sodium hydroxide solution, stirring and pretreating at 70 ℃ for 30min, adding 7.5 parts of epoxy oleic acid and 7.5 parts of emulsified epoxy resin, and reacting at constant temperature for 2h to obtain a composite modified soybean protein emulsion;
wherein the concentration of the sodium hydroxide solution is 0.02 mol/L; adding a 2% sodium dodecyl sulfate solution into 7.5 parts of epoxy resin at a ratio of 1:6, and stirring for reacting for 2 hours to obtain emulsified epoxy resin;
(3) preparation of hydrophobic film with low water absorption:
mixing the hydrophobized corn starch obtained in the step (1) and the composite modified soybean protein emulsion obtained in the step (2), adding 3 parts of reduced graphene oxide solution, 2 parts of modified hollow glass beads and 2 parts of nano tin antimony oxide for surface treatment, fully and uniformly stirring, casting into a polytetrafluoroethylene mold, and drying in a drying oven at 50 ℃ for 20 hours to form a film.
Wherein, the preparation of the functional graphene comprises the following steps: preparing 3 parts of graphene oxide into a graphene oxide solution with the concentration of 0.8mg/mL, adding 30 parts of vitamin C into the graphene oxide solution, adjusting the pH to 10 by using ammonia water, and stirring the mixture in an oil bath at the temperature of 97 ℃ for 1 hour to obtain a reduced graphene oxide solution;
preparing modified hollow glass beads: fully mixing 2 parts of hollow glass microspheres and 4 parts of oleic acid, adding 40 parts of acetone, adjusting the pH to 8 by using sodium hydroxide, ultrasonically dispersing for 40min, then, carrying out high-speed homogeneous dispersion for 35min, heating to 125 ℃, and drying to obtain modified hollow glass microspheres;
the surface treatment method of the nano tin antimony oxide comprises the following steps: adding 2 parts of nano tin antimony oxide (1: 10) into a sodium hydroxide solution with the mass fraction of 5%, stirring at 95 ℃ for 60min, cooling, carrying out suction filtration and drying, dispersing into a mixed solution of 0.2 part of silane coupling agent KH550 and 20 parts of ethanol, adding 0.02 part of catalyst, refluxing at 85 ℃ for 30min, cooling, carrying out suction filtration and drying, and thus obtaining the surface-treated nano tin antimony oxide.
Comparative example 1
This comparative example 1 was compared with example 1 in that no silane coupling agent and stearic acid were added in step (1) except that the process steps were the same.
Comparative example 2
In this comparative example 2, compared with example 2, the soybean protein isolate was compositely modified in step (2) without adding epoxy oleic acid and emulsified epoxy resin, except that the other steps of the method were the same.
Control group pure soybean protein film
In order to compare the performance of the films prepared by the invention, the performance of the coating films prepared by the methods of the above examples 1 and 2, the comparative examples 1 and 2 and the pure soybean protein films corresponding to the control groups are tested according to the industry standard: and the modified membrane material is subjected to heat insulation performance test by using a heat insulation box, and specific comparison data are shown in the following table 1:
TABLE 1
| Item | Contact angle (hydrophobicity) | Water absorption rate |
| Example 1 | 91° | 10% |
| Example 2 | 92° | 9% |
| Comparative example 1 | 85° | 10% |
| Comparative example 2 | 93° | 17% |
| Control group | 41° | 28% |
The modified film prepared by the method of the embodiment has excellent hydrophobic property and low water absorption, and the oxygen transmission coefficient of the composite film is 0.9 multiplied by 10-15cm3·cm/( cm2s.Pa); the tensile strength is 81MPa, the laminated structure of the section of the composite film is clear at the moment, and the section structure is uniform; the heat insulation temperature difference of the modified film is 13 ℃, and the heat insulation efficiency reaches 96%.
The absence of the silane coupling agent and stearic acid in comparative example 1 resulted in a decrease in the contact angle of the film, but was still superior to the hydrophobic properties of the control; the complex modification of the soy protein isolate with no epoxy oleic acid and emulsified epoxy resin in comparative example 2 resulted in a greater water absorption of the film, but still lower than that of the control.
Claims (5)
1. The preparation method of the hydrophobic film with low water absorption is characterized by comprising the following steps of:
(1) preparing the dry method hydrophobic modified corn starch:
drying 20-30 parts of corn starch at 110-120 ℃ for 1-2h, placing the corn starch in an oil bath at 100-105 ℃, adding 0.6-0.9 part of silane coupling agent A-151 and 0.6-0.9 part of stearic acid under stirring, and activating for 10-20min to obtain the hydrophobized corn starch;
(2) preparing the compound modified soybean protein:
dissolving 20-30 parts of soybean protein isolate and 10-15 parts of urea in 250-280 parts of deionized water, adjusting the pH value to 10 by using a sodium hydroxide solution, stirring and pretreating at 65-70 ℃ for 30-60min, adding 5-7.5 parts of epoxy oleic acid and 5-7.5 parts of emulsified epoxy resin, and reacting at constant temperature for 1-2h to obtain a composite modified soybean protein emulsion;
(3) preparation of hydrophobic film with low water absorption:
mixing the hydrophobized corn starch obtained in the step (1) and the composite modified soybean protein emulsion obtained in the step (2), adding 2-3 parts of reduced graphene oxide solution, 1-2 parts of modified hollow glass beads and 1-2 parts of surface-treated nano tin antimony oxide, fully and uniformly stirring, casting into a polytetrafluoroethylene mold, and drying in a drying oven at 45-50 ℃ for 20-24 hours to form a film.
2. The method for preparing a hydrophobic film with low water absorption rate of claim 1, wherein the concentration of the sodium hydroxide solution in the step (2) is 0.01-0.02 mol/L; adding a 2% sodium dodecyl sulfate solution into 5-7.5 parts of epoxy resin at a ratio of 1:6, and stirring for reacting for 1-2h to obtain the emulsified epoxy resin.
3. The method for preparing the hydrophobic film with low water absorption rate of claim 1, wherein the preparation of the functional graphene in the step (3):
preparing 2-3 parts of graphene oxide into a graphene oxide solution with the concentration of 0.8mg/mL, adding 20-30 parts of vitamin C into the graphene oxide solution, adjusting the pH to 9-10 by using ammonia water, and stirring the mixture in an oil bath at the temperature of 95-97 ℃ for 1-2 hours to obtain a reduced graphene oxide solution.
4. The method for preparing a hydrophobic film with low water absorption rate of claim 1, wherein the preparation of the modified hollow glass beads in the step (3):
fully mixing 1-2 parts of hollow glass microspheres and 2-4 parts of oleic acid, adding 30-40 parts of acetone, adjusting the pH to 8 by using sodium hydroxide, carrying out ultrasonic dispersion for 30-40min, carrying out high-speed homogeneous dispersion for 25-35min, heating to 120-125 ℃, and drying to obtain the modified hollow glass microspheres.
5. The method for preparing the hydrophobic film with low water absorption rate of claim 1, wherein the surface treatment method of the nano tin antimony oxide in the step (3) comprises the following steps:
adding 1 to 2 parts of nano tin antimony oxide (1: 10) into a sodium hydroxide solution with the mass fraction of 3 to 5 percent, stirring at the temperature of between 90 and 95 ℃ for 30 to 60 minutes, cooling, carrying out suction filtration and drying, dispersing into a mixed solution of 0.1 to 0.2 part of silane coupling agent KH550 and 10 to 20 parts of ethanol, adding 0.01 to 0.02 part of catalyst, refluxing at the temperature of between 80 and 85 ℃ for 30 to 60 minutes, cooling, carrying out suction filtration and drying, and obtaining the nano tin antimony oxide with the surface treated.
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