WO2023077644A1 - Environmentally friendly functional membrane material, preparation method thereof, and use thereof - Google Patents

Environmentally friendly functional membrane material, preparation method thereof, and use thereof Download PDF

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WO2023077644A1
WO2023077644A1 PCT/CN2021/142053 CN2021142053W WO2023077644A1 WO 2023077644 A1 WO2023077644 A1 WO 2023077644A1 CN 2021142053 W CN2021142053 W CN 2021142053W WO 2023077644 A1 WO2023077644 A1 WO 2023077644A1
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parts
environment
friendly functional
antioxidant
water
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PCT/CN2021/142053
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French (fr)
Chinese (zh)
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李芳丽
张万虎
李宪强
孙文奇
张兆洋
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绍兴兆丽新材料科技有限公司
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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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/16—Biodegradable polymers
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • the invention relates to the technical field of membrane materials, in particular to an environment-friendly functional membrane material and its preparation method and application.
  • PSf polysulfone
  • PES polyethersulfone
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • CA cellulose acetate
  • the purpose of the present invention is to provide an environment-friendly functional membrane material and its preparation method and application.
  • the environment-friendly functional membrane material provided by the invention can completely separate the oil-water mixture, has complete biodegradability, and is more environmentally friendly.
  • the invention provides an environment-friendly functional membrane material, which comprises the following raw materials in parts by mass:
  • the following preparation materials are included: 87-90 parts of tapioca starch, 10-13 parts of polyvinyl alcohol resin, 23-25 parts of plasticizing modifier, 6-8 parts of water-based lubricant, and 6-8 parts of nuclear modifier, 6-8 parts of heat stabilizer, 0.5-0.8 parts of antioxidant and 7-10 parts of water.
  • the tapioca starch has a particle size of 1-10 microns.
  • the polyvinyl alcohol resin is PVA22-99H; the particle size of the polyvinyl alcohol resin is 1-10 microns.
  • the plasticizing modifier includes glycerin, 1,2-propylene glycol, 1,4-butanediol, soybean oil polyol and dipropylene glycol; the glycerin, 1,2-propylene glycol, 1,4- The mass ratio of butylene glycol, soybean oil polyol and dipropylene glycol is 4-7:0.5-2:0.5-1.5:1-2:1.
  • the water-based lubricant includes simethicone, polymeric alcohol lubricant, erucamide and methyl methacrylate; the simethicone, polymeric alcohol lubricant, erucamide and methyl methacrylate
  • the mass ratio of the ester is 2-5:2-5:1-2:1-2.
  • the thermal stabilizer includes zinc stearate, calcium ricinoleate and epoxidized soybean oil; the mass ratio of the zinc stearate, calcium ricinoleate and epoxidized soybean oil is 2-4:3- 4: 3-4.
  • the nucleating modifier includes nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent; the mass ratio of nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent is 1.5-4: 1.5 ⁇ 4: 2 ⁇ 7.
  • the present invention provides a method for preparing an environment-friendly functional membrane material described in the above technical solution, comprising the following steps:
  • the pellets are extruded and blown to obtain an environment-friendly functional film material.
  • the present invention provides the application of the environment-friendly functional membrane material described in the above technical solution or the environment-friendly functional membrane material prepared by the preparation method described in the above technical solution in the treatment of oily sewage.
  • the invention provides an environment-friendly functional film material, which comprises the following preparation raw materials in parts by mass: 80-91 parts of tapioca starch, 9-20 parts of polyvinyl alcohol resin, 20-28 parts of plasticizing modifier, water 5-10 parts of base lubricant, 5-10 parts of nucleating modifier, 5-10 parts of heat stabilizer and 0.3-0.8 parts of antioxidant.
  • the preparation raw materials adopted in the present invention are all biodegradable, and the compounded cassava starch and polyvinyl alcohol resin have excellent water permeability and oil barrier properties.
  • the present invention controls the amount of each preparation raw material within the above range, which can improve the oil-water resistance of the membrane material. The separation efficiency of the mixture is improved, while ensuring that the membrane material has high strength.
  • the environmental-friendly functional membrane material provided by the present invention has a biodegradation rate of more than 68% in 180 days; it can be completely dissolved in hot water greater than 90°C; the water vapor transmission rate is >900g/(m 2 ⁇ 24h); It has complete barrier properties to all kinds of oils and fats.
  • the environment-friendly functional film material provided by the present invention has excellent strength, and the tensile strength is >25MPa.
  • Figure 1 is a schematic diagram of the principle of oil-water separation by an environmentally friendly functional membrane material
  • Fig. 2 is an effect diagram of the oil-water separation test of the environment-friendly functional membrane material prepared in Example 1.
  • the invention provides an environment-friendly functional membrane material, which comprises the following raw materials in parts by mass:
  • the raw materials for the preparation of the environment-friendly functional membrane material include 80-91 parts of tapioca starch, preferably 87-90 parts.
  • the particle size of the tapioca starch is preferably 1-10 microns, more preferably 5-6.5 microns.
  • the raw material for the preparation of the environment-friendly functional film material includes 9-20 parts of polyvinyl alcohol (PVA) resin, preferably 10-13 parts.
  • the polyvinyl alcohol resin is preferably PVA22-99H; the PVA22-99H is preferably PVA22-99H sold by Anhui Wanwei High-tech Materials Co., Ltd.
  • the particle size of the polyvinyl alcohol resin is preferably 1-10 microns, more preferably 5-6.5 microns.
  • the raw material for the preparation of the environment-friendly functional film material includes 20-28 parts of plasticizing modifier, preferably 23-25 parts.
  • the plasticizing modifier preferably includes glycerin, 1,2-propanediol, 1,4-butanediol, soybean oil polyol and dipropylene glycol; the glycerin, 1,2-propanediol, 1 ,
  • the mass ratio of 4-butanediol, soybean oil polyol and dipropylene glycol is preferably 4-7:0.5-2:0.5-1.5:1-2:1, more preferably 5-6:1-1.5:1 ⁇ 1.5:1 ⁇ 1.5:1.
  • the present invention adopts the composite plastic modifier, which can significantly improve the tensile strength of the environment-friendly functional film material.
  • the raw material for the preparation of the environment-friendly functional membrane material includes 5-10 parts of water-based lubricant, preferably 6-8 parts.
  • the water-based lubricant preferably includes simethicone oil, polymer alcohol lubricant, erucamide and methyl methacrylate; the simethicone oil, polymer alcohol lubricant, erucamide and formaldehyde
  • the mass ratio of methyl acrylate is preferably 2-5:2-5:1-2:1-2, more preferably 3-4:3-4:1.5-1:1.5-1.
  • the manufacturer and model of the polyalcohol lubricant are Dow Chemical Voranol WD2104.
  • the present invention adopts the composite water-based lubricant, which can effectively improve the melting fluidity of the mixed material under high-temperature environment.
  • the raw material for the preparation of the environment-friendly functional membrane material includes 5-10 parts of nucleating modifier, preferably 6-8 parts.
  • the nucleating modifier preferably includes nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent; the mass ratio of the nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent is preferably 1.5-4: 1.5-4: 2-7, more preferably 2-3: 2-3: 4-5.
  • the particle size of the nano-silica is preferably 1-10 microns, more preferably 3-5 microns; the particle size of the nano-titanium dioxide is preferably 1-10 microns, more preferably 3-5 microns .
  • the sorbitol-based nucleating agent is preferably a sorbitol-based nucleating agent WBQ.
  • the nucleating modifier can accelerate the crystallization rate, increase the crystallization density, and promote the miniaturization of the grain size by changing the crystallization behavior of the resin, so as to shorten the molding cycle, improve the transparency, surface gloss, and tensile strength of the product.
  • the raw material for the preparation of the environment-friendly functional film material includes 5-10 parts of heat stabilizer, preferably 6-8 parts.
  • the heat stabilizer preferably includes zinc stearate, calcium ricinoleate and epoxidized soybean oil; the mass ratio of the zinc stearate, calcium ricinoleate and epoxidized soybean oil is preferably 2- 4:3-4:3-4, more preferably 4:3:3.
  • the present invention adopts the above-mentioned composite heat stabilizer, which can improve the heat processing performance of the mixed material, is more conducive to processing and molding, and ensures the film-forming effect of the material.
  • the raw materials for the preparation of the environment-friendly functional film material include 0.3-0.8 parts of antioxidant, preferably 0.5-0.8 parts.
  • the antioxidant preferably includes antioxidant 1010, antioxidant 246 and antioxidant H10; the mass ratio of the antioxidant 1010, antioxidant 246 and antioxidant H10 is preferably 4- 6:2 to 4:1 to 2, more preferably 5:3:2.
  • the raw materials for the preparation of the environment-friendly functional membrane material include 6-12 parts of water, preferably 7-10 parts.
  • the water is preferably deionized water.
  • the schematic diagram of the principle of oil-water separation by the environment-friendly functional membrane material is shown in Fig. 1 , the environment-friendly functional membrane material can permeate water molecules and completely block oily molecules.
  • the present invention also provides a preparation method of the environment-friendly functional membrane material described in the above technical solution, comprising the following steps:
  • the pellets are extruded and blown to obtain an environment-friendly functional film material.
  • the invention mixes the preparation raw materials and performs plasticizing treatment to obtain the mixed material.
  • the mixing of the preparation raw materials is preferably carried out in a high-speed mixer; the stirring speed of the mixing is preferably 60-80 rpm.
  • the temperature of the plasticizing treatment is preferably 40-60°C, more preferably 50°C; the time of the plasticizing treatment is preferably 60-120min, more preferably 90-100min.
  • the plasticizing treatment of the invention can make the plasticizing modifier fully penetrate into the space between the starch and the PVA molecules, destroy the van der Waals force between the molecules, and improve the melting fluidity of the resin.
  • the obtained material is cooled and left to stand for more than 48 hours to obtain a mixed material.
  • the cooling and standing time is more preferably 48-72 hours.
  • the water content of the mixed material is preferably 16-18wt%.
  • the present invention extrudes the mixed material to obtain pellets.
  • the extrusion granulation is preferably carried out in a twin-screw extruder.
  • the processing temperature of the extrusion granulation is preferably 80-140°C
  • the segmental temperature from the feed port to the discharge port is preferably 80°C, 130°C, 135°C, 140°C, 120°C , 115°C, 110°C.
  • the present invention extrudes the pellets and blows the film to obtain an environment-friendly functional film material.
  • the extrusion film blowing is preferably carried out in a film blowing machine.
  • the processing temperature of the extrusion blown film is preferably 130-200°C
  • the segmental temperature from the feed port to the discharge port is preferably 140°C, 180°C, 200°C, 180°C, 150°C , 130°C.
  • the thickness of the environment-friendly functional film material is preferably 0.08-1.0 mm.
  • the present invention also provides the application of the environment-friendly functional membrane material described in the above technical solution or the environment-friendly functional membrane material prepared by the preparation method described in the above technical solution in the treatment of oily sewage.
  • the oil phase in the oily sewage preferably includes animal oil, vegetable oil, mineral oil or aromatic hydrocarbons.
  • the present invention has no special requirements on the content of the oily phase in the oily sewage, and is especially suitable for difficult-to-separate oily sewage containing a small amount of oily phase.
  • the mass content of the oil phase is preferably 1-95%, more preferably 1-5%.
  • the temperature of the application is preferably room temperature.
  • the invention utilizes the water permeability and oil barrier properties of the environmentally friendly functional membrane material to separate the oil-water mixture in the oily sewage, and the separation efficiency is as high as 100%, and the environmentally friendly functional membrane material can be completely dissolved in 90°C hot water after being discarded Among them, it can achieve biodegradation and be converted into carbon dioxide and water, which is a real environmentally friendly functional membrane material.
  • the environment-friendly functional film material prepared in this example consists of 91 parts of tapioca starch, 9 parts of PVA resin, 23 parts of plasticizing modifier, 6 parts of water-based lubricant, 6 parts of nucleating modifier, Composed of 6 parts of heat stabilizer, 9 parts of deionized water and 0.8 part of antioxidant;
  • the average particle diameter of the tapioca starch is 6.5 microns.
  • the PVA resin is selected from PVA22-99H sold by Anhui Wanwei High-tech Material Co., Ltd., with an average particle size of 6.5 microns.
  • the plasticizing modifier is 40% of glycerin, 20% of 1,2-propylene glycol, 10% of 1,4-butanediol, soybean oil polyol 20% and dipropylene glycol 10% mixture.
  • the water-based lubricant is 30% of simethicone oil, 30% of polyalcohol lubricant, 20% of erucamide and 20% of methyl methacrylate.
  • the nucleating modifier is 30% of nano-silicon dioxide (average particle diameter is 5 microns), 30% of nano-titanium dioxide (average particle diameter is 5 microns) % and sorbitol-type nucleating agent WBQ 40% mixture.
  • the heat stabilizer is a mixture of 40% zinc stearate, 30% calcium ricinoleate and 30% epoxidized soybean oil. Based on the total mass of the antioxidant as 100%, the antioxidant is a mixture of antioxidant 101050%, antioxidant 24630% and antioxidant H1020%.
  • the preparation method of the environment-friendly functional membrane material is:
  • the tapioca starch, PVA resin, plasticizing modifier, water-based lubricant, nucleating modifier, heat stabilizer, deionized water and antioxidant are placed in a high-speed mixer, heated while stirring, and Perform plasticizing treatment at 50°C for 90 minutes, then cool and place for 56 hours, control the moisture content to 18wt%, and obtain the mixed material;
  • the processing temperature is controlled at 80-140°C, and the segmental temperature from the inlet to the outlet is 80°C, 130°C, 135°C °C, 140°C, 120°C, 115°C, 110°C to obtain pellets;
  • the pellets into the film blowing machine, extrude and blow the film to make an environment-friendly functional film material.
  • the thickness of the environmental-friendly functional film material is 0.08 mm.
  • the environment-friendly functional film material prepared in this embodiment consists of 80 parts of tapioca starch, 20 parts of PVA resin, 20 parts of plasticizing modifier, 5 parts of water-based lubricant, 5 parts of nucleating modifier, Composed of 5 parts of heat stabilizer, 7 parts of deionized water and 0.3 part of antioxidant;
  • the average particle diameter of the tapioca starch is 6.5 microns.
  • the PVA resin is selected from PVA22-99H sold by Anhui Wanwei High-tech Material Co., Ltd., with an average particle size of 6.5 microns.
  • the plasticizing modifier is 70% of glycerin, 5% of 1,2-propanediol, 5% of 1,4-butanediol, soybean oil polyol 10% and dipropylene glycol 10% mixture.
  • the water-based lubricant is 20% of simethicone oil, 50% of polyalcohol lubricant, 15% of erucamide and 15% of methyl methacrylate. mixture.
  • the nucleating modifier is 15% of nano-silicon dioxide (average particle diameter is 10 microns), 15% of nano-titanium dioxide (average particle diameter is 10 microns) % and sorbitol-type nucleating agent WBQ 70% mixture.
  • the heat stabilizer is a mixture of 20% zinc stearate, 40% calcium ricinoleate and 40% epoxidized soybean oil. Taking the total mass of the antioxidant as 100%, the antioxidant is a mixture of antioxidant 1010 50%, antioxidant 246 30% and antioxidant H10 20%.
  • the preparation method of the environment-friendly functional membrane material is:
  • the tapioca starch, PVA resin, plasticizing modifier, water-based lubricant, nucleating modifier, heat stabilizer, deionized water and antioxidant are placed in a high-speed mixer, heated while stirring, and Perform plasticizing treatment at 50°C for 90 minutes, then cool and place for 48 hours, control the moisture content to 16wt%, and obtain the mixed material;
  • the processing temperature is controlled at 80-140°C, and the segmental temperature from the inlet to the outlet is 80°C, 130°C, 135°C °C, 140°C, 120°C, 115°C, 110°C to obtain pellets;
  • the pellets into the film blowing machine, extrude and blow the film to make an environment-friendly functional film material.
  • the thickness of the environmental-friendly functional film material is 0.08 mm.
  • the environment-friendly functional film material prepared in this example consists of 87 parts of tapioca starch, 13 parts of PVA resin, 28 parts of plasticizing modifier, 10 parts of water-based lubricant, 10 parts of nucleating modifier, 10 parts of heat stabilizer, 10 parts of deionized water and 0.5 parts of antioxidant;
  • the average particle diameter of the tapioca starch is 6.5 microns.
  • the PVA resin is selected from PVA22-99H sold by Anhui Wanwei High-tech Material Co., Ltd., with an average particle size of 6.5 microns.
  • the plasticizing modifier is 50% of glycerin, 10% of 1,2-propylene glycol, 15% of 1,4-butanediol, soybean oil polyol 15% and dipropylene glycol 10% mixture.
  • the water-based lubricant is 50% of simethicone oil, 30% of polyalcohol lubricant, 10% of erucamide and 10% of methyl methacrylate.
  • the nucleating modifier is 40% of nano-silicon dioxide (average particle diameter is 3 microns), nano-titanium dioxide (average particle diameter is 3 microns) 40% % and sorbitol-type nucleating agent WBQ 20% mixture.
  • the heat stabilizer is a mixture of 20% zinc stearate, 40% calcium ricinoleate and 40% epoxidized soybean oil.
  • the antioxidant is a mixture of antioxidant 1010 50%, antioxidant 246 30% and antioxidant H10 20%.
  • the preparation method of the environment-friendly functional membrane material is:
  • the tapioca starch, PVA resin, plasticizing modifier, water-based lubricant, nucleating modifier, heat stabilizer, deionized water and antioxidant are placed in a high-speed mixer, heated while stirring, and Perform plasticizing treatment at 50°C for 90 minutes, then cool and place for 72 hours, control the moisture content to 18wt%, and obtain the mixed material;
  • the processing temperature is controlled at 80-140°C, and the segmental temperature from the inlet to the outlet is 80°C, 130°C, 135°C °C, 140°C, 120°C, 115°C, 110°C to obtain pellets;
  • the pellets into the film blowing machine, extrude and blow the film to make an environment-friendly functional film material.
  • the thickness of the environmental-friendly functional film material is 0.08 mm.
  • the national standard GB/T 1040.3-2006 is adopted, and the spline width is 15mm.
  • the test result proves that the oil-water mixture can be separated by 100% by adopting the environment-friendly functional membrane material provided by the invention.
  • the environmentally friendly functional membrane material provided by the present invention has complete biodegradability and can be used in the field of oil-water separation. It can use its water permeability and oil barrier properties to separate oil-water mixtures, and the separation efficiency can reach 100%.
  • the process equipment is simple and easy to operate, and this membrane can be completely dissolved in hot water at 90°C after being discarded, and can further achieve biodegradation. It is a real environmentally friendly functional membrane material.

Abstract

Provided are an environmentally friendly functional membrane material, a preparation method therefor, and a use thereof, relating to the technical field of membrane materials. The provided environmentally friendly functional membrane material comprises the following preparation raw materials in parts by mass: 80-91 parts of tapioca starch, 9-20 parts of a polyvinyl alcohol resin, 20-28 parts of a plasticizing modifier, 5-10 parts of a water-based lubricant, 5-10 parts of a nucleating modifier, 5-10 parts of a heat stabilizer, and 0.3 to 0.8 parts of an antioxidant. The provided environmentally friendly functional membrane material can completely separate an oil-water mixture, and is completely biodegradable and more environmentally friendly.

Description

一种环保型功能膜材料及其制备方法和应用A kind of environment-friendly functional membrane material and its preparation method and application
本申请要求于2021年11月04日提交中国专利局、申请号为CN202111299878.6、发明名称为“一种环保型功能膜材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on November 04, 2021, the application number is CN202111299878.6, and the invention title is "An environment-friendly functional film material and its preparation method and application", all of which The contents are incorporated by reference in this application.
技术领域technical field
本发明涉及膜材料技术领域，具体涉及一种环保型功能膜材料及其制备方法和应用。The invention relates to the technical field of membrane materials, in particular to an environment-friendly functional membrane material and its preparation method and application.
背景技术Background technique
由于含油污水的成分复杂，因此实现油水分离较为困难，传统的油水分离方法包括物理方法和化学方法：物理方法如活性炭、有机黏土、沸石等在吸油的同时会吸收水，使分离过程繁琐、效率低；化学方法如氧化、电化学工艺、光催化处理、臭氧处理和破乳等会使用有毒化合物，增加成本的同时也会产生二次污染。过去十几年中，膜技术已成为重要的分离技术，其优点在于无须添加其他化学品即可工作，具有较低的能量需求，过程简单而易于操作。Due to the complex composition of oily sewage, it is difficult to achieve oil-water separation. Traditional oil-water separation methods include physical methods and chemical methods: physical methods such as activated carbon, organoclay, zeolite, etc. will absorb water while absorbing oil, making the separation process cumbersome and inefficient. Low; chemical methods such as oxidation, electrochemical process, photocatalytic treatment, ozone treatment and demulsification will use toxic compounds, which will increase the cost and produce secondary pollution. In the past ten years, membrane technology has become an important separation technology. Its advantages are that it can work without adding other chemicals, has low energy demand, simple process and easy operation.
目前常见的膜材料包括聚砜(PSf)、聚醚砜(PES)、聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)和醋酸纤维素(CA)等，但上述膜材料普遍存在油水分离不彻底、材料废弃后难以降解的缺陷。Common membrane materials currently include polysulfone (PSf), polyethersulfone (PES), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), and cellulose acetate (CA), but the above membrane materials generally suffer from oil-water separation. Defects that are not thorough and difficult to degrade after materials are discarded.
发明内容Contents of the invention
本发明的目的在于提供一种环保型功能膜材料及其制备方法和应用，本发明提供的环保型功能膜材料能够对油水混合物进行彻底分离，且具有完全生物降解性，更加环保。The purpose of the present invention is to provide an environment-friendly functional membrane material and its preparation method and application. The environment-friendly functional membrane material provided by the invention can completely separate the oil-water mixture, has complete biodegradability, and is more environmentally friendly.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种环保型功能膜材料，按质量份数计，包括以下制备原料：The invention provides an environment-friendly functional membrane material, which comprises the following raw materials in parts by mass:
木薯淀粉80～91份、聚乙烯醇树脂9～20份、塑化改性剂20～28份、水基润滑剂5～10份、成核改性剂5～10份、热稳定剂5～10份、抗氧剂 0.3～0.8份和水6～12份。80-91 parts of tapioca starch, 9-20 parts of polyvinyl alcohol resin, 20-28 parts of plasticizing modifier, 5-10 parts of water-based lubricant, 5-10 parts of nucleating modifier, 5-10 parts of heat stabilizer 10 parts, 0.3-0.8 parts of antioxidant and 6-12 parts of water.
优选地，按质量份数计，包括以下制备原料：木薯淀粉87～90份、聚乙烯醇树脂10～13份、塑化改性剂23～25份、水基润滑剂6～8份、成核改性剂6～8份、热稳定剂6～8份、抗氧剂0.5～0.8份和水7～10份。Preferably, in parts by mass, the following preparation materials are included: 87-90 parts of tapioca starch, 10-13 parts of polyvinyl alcohol resin, 23-25 parts of plasticizing modifier, 6-8 parts of water-based lubricant, and 6-8 parts of nuclear modifier, 6-8 parts of heat stabilizer, 0.5-0.8 parts of antioxidant and 7-10 parts of water.
优选地，所述木薯淀粉的粒径为1～10微米。Preferably, the tapioca starch has a particle size of 1-10 microns.
优选地，所述聚乙烯醇树脂为PVA22-99H；所述聚乙烯醇树脂的粒径为1～10微米。Preferably, the polyvinyl alcohol resin is PVA22-99H; the particle size of the polyvinyl alcohol resin is 1-10 microns.
优选地，所述塑化改性剂包括甘油、1,2-丙二醇、1,4-丁二醇、大豆油多元醇和一缩二丙二醇；所述甘油、1,2-丙二醇、1,4-丁二醇、大豆油多元醇和一缩二丙二醇的质量比为4～7：0.5～2：0.5～1.5：1～2：1。Preferably, the plasticizing modifier includes glycerin, 1,2-propylene glycol, 1,4-butanediol, soybean oil polyol and dipropylene glycol; the glycerin, 1,2-propylene glycol, 1,4- The mass ratio of butylene glycol, soybean oil polyol and dipropylene glycol is 4-7:0.5-2:0.5-1.5:1-2:1.
优选地，所述水基润滑剂包括二甲基硅油、聚合醇润滑剂、芥酸酰胺和甲基丙烯酸甲酯；所述二甲基硅油、聚合醇润滑剂、芥酸酰胺和甲基丙烯酸甲酯的质量比为2～5：2～5：1～2：1～2。Preferably, the water-based lubricant includes simethicone, polymeric alcohol lubricant, erucamide and methyl methacrylate; the simethicone, polymeric alcohol lubricant, erucamide and methyl methacrylate The mass ratio of the ester is 2-5:2-5:1-2:1-2.
优选地，所述热稳定剂包括硬脂酸锌、蓖麻油酸钙和环氧大豆油；所述硬脂酸锌、蓖麻油酸钙和环氧大豆油的质量比为2～4：3～4：3～4。Preferably, the thermal stabilizer includes zinc stearate, calcium ricinoleate and epoxidized soybean oil; the mass ratio of the zinc stearate, calcium ricinoleate and epoxidized soybean oil is 2-4:3- 4: 3-4.
优选地，所述成核改性剂包括纳米二氧化硅、纳米二氧化钛和山梨醇类成核剂；所述纳米二氧化硅、纳米二氧化钛和山梨醇类成核剂的质量比为1.5～4：1.5～4：2～7。Preferably, the nucleating modifier includes nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent; the mass ratio of nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent is 1.5-4: 1.5~4: 2~7.
本发明提供了上述技术方案所述环保型功能膜材料的制备方法，包括以下步骤：The present invention provides a method for preparing an environment-friendly functional membrane material described in the above technical solution, comprising the following steps:
将所述制备原料混合，进行增塑处理，得到混合物料；mixing the preparation raw materials and performing plasticizing treatment to obtain a mixed material;
将所述混合物料进行挤出造粒，得到粒料；Extruding and granulating the mixed material to obtain pellets;
将所述粒料进行挤出吹膜，得到环保型功能膜材料。The pellets are extruded and blown to obtain an environment-friendly functional film material.
本发明提供了上述技术方案所述环保型功能膜材料或上述技术方案所述制备方法制备得到的环保型功能膜材料在含油污水处理中的应用。The present invention provides the application of the environment-friendly functional membrane material described in the above technical solution or the environment-friendly functional membrane material prepared by the preparation method described in the above technical solution in the treatment of oily sewage.
本发明提供了一种环保型功能膜材料，按质量份数计，包括以下制备原料：木薯淀粉80～91份、聚乙烯醇树脂9～20份、塑化改性剂20～28份、水基润滑剂5～10份、成核改性剂5～10份、热稳定剂5～10份和抗氧剂0.3～0.8份。本发明采用的制备原料均具有生物分解性，木薯淀粉和聚乙烯醇树脂复合后具有优异的透水性和油脂阻隔性，本发明将各制备原料的 用量控制在上述范围，能够提高膜材料对油水混合物的分离效率，同时保证膜材料具有较高的强度。实施例结果表明，本发明提供的环保型功能膜材料180天生物分解率在68％以上；在大于90℃热水中能够完全溶解；水蒸气透过量>900g/(m 2·24h)，同时对各种油脂有完全阻隔性。另外，本发明提供的环保型功能膜材料具有优异的强度，拉伸强度>25MPa。 The invention provides an environment-friendly functional film material, which comprises the following preparation raw materials in parts by mass: 80-91 parts of tapioca starch, 9-20 parts of polyvinyl alcohol resin, 20-28 parts of plasticizing modifier, water 5-10 parts of base lubricant, 5-10 parts of nucleating modifier, 5-10 parts of heat stabilizer and 0.3-0.8 parts of antioxidant. The preparation raw materials adopted in the present invention are all biodegradable, and the compounded cassava starch and polyvinyl alcohol resin have excellent water permeability and oil barrier properties. The present invention controls the amount of each preparation raw material within the above range, which can improve the oil-water resistance of the membrane material. The separation efficiency of the mixture is improved, while ensuring that the membrane material has high strength. The results of the examples show that the environmental-friendly functional membrane material provided by the present invention has a biodegradation rate of more than 68% in 180 days; it can be completely dissolved in hot water greater than 90°C; the water vapor transmission rate is >900g/(m 2 ·24h); It has complete barrier properties to all kinds of oils and fats. In addition, the environment-friendly functional film material provided by the present invention has excellent strength, and the tensile strength is >25MPa.
说明书附图Instructions attached
图1为环保型功能膜材料进行油水分离的原理示意图；Figure 1 is a schematic diagram of the principle of oil-water separation by an environmentally friendly functional membrane material;
图2为对实施例1制备的环保型功能膜材料进行油水分离测试的效果图。Fig. 2 is an effect diagram of the oil-water separation test of the environment-friendly functional membrane material prepared in Example 1.
具体实施方式Detailed ways
本发明提供了一种环保型功能膜材料，按质量份数计，包括以下制备原料：The invention provides an environment-friendly functional membrane material, which comprises the following raw materials in parts by mass:
木薯淀粉80～91份、聚乙烯醇树脂9～20份、塑化改性剂20～28份、水基润滑剂5～10份、成核改性剂5～10份、热稳定剂5～10份、抗氧剂0.3～0.8份和水6～12份。80-91 parts of tapioca starch, 9-20 parts of polyvinyl alcohol resin, 20-28 parts of plasticizing modifier, 5-10 parts of water-based lubricant, 5-10 parts of nucleating modifier, 5-10 parts of heat stabilizer 10 parts, 0.3-0.8 parts of antioxidant and 6-12 parts of water.
在本发明中，以质量份数计，所述环保型功能膜材料的制备原料包括木薯淀粉80～91份，优选为87～90份。在本发明中，所述木薯淀粉的粒径优选为1～10微米，更优选为5～6.5微米。In the present invention, in terms of parts by mass, the raw materials for the preparation of the environment-friendly functional membrane material include 80-91 parts of tapioca starch, preferably 87-90 parts. In the present invention, the particle size of the tapioca starch is preferably 1-10 microns, more preferably 5-6.5 microns.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括聚乙烯醇(PVA)树脂9～20份，优选为10～13份。在本发明中，所述聚乙烯醇树脂优选为PVA22-99H；所述PVA22-99H优选为安徽皖维高新材料有限公司售卖的PVA22-99H。在本发明中，所述聚乙烯醇树脂的粒径优选为1～10微米，更优选为5～6.5微米。In the present invention, based on the mass fraction of the tapioca starch, the raw material for the preparation of the environment-friendly functional film material includes 9-20 parts of polyvinyl alcohol (PVA) resin, preferably 10-13 parts. In the present invention, the polyvinyl alcohol resin is preferably PVA22-99H; the PVA22-99H is preferably PVA22-99H sold by Anhui Wanwei High-tech Materials Co., Ltd. In the present invention, the particle size of the polyvinyl alcohol resin is preferably 1-10 microns, more preferably 5-6.5 microns.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括塑化改性剂20～28份，优选为23～25份。在本发明中，所述塑化改性剂优选包括甘油、1,2-丙二醇、1,4-丁二醇、大豆油多元醇和一缩二丙二醇；所述甘油、1,2-丙二醇、1,4-丁二醇、大豆油多元醇和一缩二丙二醇的质量比优选为4～7：0.5～2：0.5～1.5：1～2：1，更优 选为5～6：1～1.5：1～1.5：1～1.5：1。本发明采用上述复合型的塑化改性剂，能够显著提高环保型功能膜材料的拉伸强度。In the present invention, based on the mass fraction of the tapioca starch, the raw material for the preparation of the environment-friendly functional film material includes 20-28 parts of plasticizing modifier, preferably 23-25 parts. In the present invention, the plasticizing modifier preferably includes glycerin, 1,2-propanediol, 1,4-butanediol, soybean oil polyol and dipropylene glycol; the glycerin, 1,2-propanediol, 1 , The mass ratio of 4-butanediol, soybean oil polyol and dipropylene glycol is preferably 4-7:0.5-2:0.5-1.5:1-2:1, more preferably 5-6:1-1.5:1 ~1.5:1~1.5:1. The present invention adopts the composite plastic modifier, which can significantly improve the tensile strength of the environment-friendly functional film material.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括水基润滑剂5～10份，优选为6～8份。在本发明中，所述水基润滑剂优选包括二甲基硅油、聚合醇润滑剂、芥酸酰胺和甲基丙烯酸甲酯；所述二甲基硅油、聚合醇润滑剂、芥酸酰胺和甲基丙烯酸甲酯的质量比优选为2～5：2～5：1～2：1～2，更优选为3～4：3～4：1.5～1：1.5～1。在本发明的具体实施例中，所述聚合醇润滑剂的生产厂家和型号为陶氏化学Voranol WD2104。本发明采用上述复合型的水基润滑剂，能够有效提高高温环境下混合物料的熔融流动性。In the present invention, based on the mass fraction of the tapioca starch, the raw material for the preparation of the environment-friendly functional membrane material includes 5-10 parts of water-based lubricant, preferably 6-8 parts. In the present invention, the water-based lubricant preferably includes simethicone oil, polymer alcohol lubricant, erucamide and methyl methacrylate; the simethicone oil, polymer alcohol lubricant, erucamide and formaldehyde The mass ratio of methyl acrylate is preferably 2-5:2-5:1-2:1-2, more preferably 3-4:3-4:1.5-1:1.5-1. In a specific embodiment of the present invention, the manufacturer and model of the polyalcohol lubricant are Dow Chemical Voranol WD2104. The present invention adopts the composite water-based lubricant, which can effectively improve the melting fluidity of the mixed material under high-temperature environment.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括成核改性剂5～10份，优选为6～8份。在本发明中，所述成核改性剂优选包括纳米二氧化硅、纳米二氧化钛和山梨醇类成核剂；所述纳米二氧化硅、纳米二氧化钛和山梨醇类成核剂的质量比优选为1.5～4：1.5～4：2～7，更优选为2～3：2～3：4～5。在本发明中，所述纳米二氧化硅的粒径优选为1～10微米，更优选为3～5微米；所述纳米二氧化钛的粒径优选为1～10微米，更优选为3～5微米。在本发明中，所述山梨醇类成核剂优选为山梨醇型成核剂WBQ。In the present invention, based on the mass fraction of the tapioca starch, the raw material for the preparation of the environment-friendly functional membrane material includes 5-10 parts of nucleating modifier, preferably 6-8 parts. In the present invention, the nucleating modifier preferably includes nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent; the mass ratio of the nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent is preferably 1.5-4: 1.5-4: 2-7, more preferably 2-3: 2-3: 4-5. In the present invention, the particle size of the nano-silica is preferably 1-10 microns, more preferably 3-5 microns; the particle size of the nano-titanium dioxide is preferably 1-10 microns, more preferably 3-5 microns . In the present invention, the sorbitol-based nucleating agent is preferably a sorbitol-based nucleating agent WBQ.
在本发明中，所述成核改性剂能够通过改变树脂的结晶行为，加快结晶速率、增加结晶密度和促使晶粒尺寸微细化，达到缩短成型周期、提高制品透明性、表面光泽、抗拉强度、刚性、热变形温度、抗冲击性、抗蠕变性等的效果。In the present invention, the nucleating modifier can accelerate the crystallization rate, increase the crystallization density, and promote the miniaturization of the grain size by changing the crystallization behavior of the resin, so as to shorten the molding cycle, improve the transparency, surface gloss, and tensile strength of the product. The effects of strength, rigidity, heat distortion temperature, impact resistance, creep resistance, etc.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括热稳定剂5～10份，优选为6～8份。在本发明中，所述热稳定剂优选包括硬脂酸锌、蓖麻油酸钙和环氧大豆油；所述硬脂酸锌、蓖麻油酸钙和环氧大豆油的质量比优选为2～4：3～4：3～4，更优选为4：3：3。本发明采用上述复合型的热稳定剂，能够提高混合物料的热加工性能，更有利于加工成型，保证材料的成膜效果。In the present invention, based on the mass fraction of the tapioca starch, the raw material for the preparation of the environment-friendly functional film material includes 5-10 parts of heat stabilizer, preferably 6-8 parts. In the present invention, the heat stabilizer preferably includes zinc stearate, calcium ricinoleate and epoxidized soybean oil; the mass ratio of the zinc stearate, calcium ricinoleate and epoxidized soybean oil is preferably 2- 4:3-4:3-4, more preferably 4:3:3. The present invention adopts the above-mentioned composite heat stabilizer, which can improve the heat processing performance of the mixed material, is more conducive to processing and molding, and ensures the film-forming effect of the material.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括抗氧剂0.3～0.8，优选为0.5～0.8份。在本发明中，所 述抗氧剂优选包括抗氧剂1010、抗氧剂246和抗氧剂H10；所述抗氧剂1010、抗氧剂246和抗氧剂H10的质量比优选为4～6：2～4：1～2，更优选为5：3：2。In the present invention, based on the mass fraction of the tapioca starch, the raw materials for the preparation of the environment-friendly functional film material include 0.3-0.8 parts of antioxidant, preferably 0.5-0.8 parts. In the present invention, the antioxidant preferably includes antioxidant 1010, antioxidant 246 and antioxidant H10; the mass ratio of the antioxidant 1010, antioxidant 246 and antioxidant H10 is preferably 4- 6:2 to 4:1 to 2, more preferably 5:3:2.
在本发明中，以所述木薯淀粉的质量份数为基准，所述环保型功能膜材料的制备原料包括水6～12份，优选为7～10份。在本发明中，所述水优选为去离子水。In the present invention, based on the mass fraction of the tapioca starch, the raw materials for the preparation of the environment-friendly functional membrane material include 6-12 parts of water, preferably 7-10 parts. In the present invention, the water is preferably deionized water.
在本发明中，所述环保型功能膜材料进行油水分离的原理示意图如图1所示，所述环保型功能膜材料能够使水分子透过，对油性分子进行完全阻隔。In the present invention, the schematic diagram of the principle of oil-water separation by the environment-friendly functional membrane material is shown in Fig. 1 , the environment-friendly functional membrane material can permeate water molecules and completely block oily molecules.
本发明还提供了上述技术方案所述环保型功能膜材料的制备方法，包括以下步骤：The present invention also provides a preparation method of the environment-friendly functional membrane material described in the above technical solution, comprising the following steps:
将所述制备原料混合，进行增塑处理，得到混合物料；mixing the preparation raw materials and performing plasticizing treatment to obtain a mixed material;
将所述混合物料进行挤出造粒，得到粒料；Extruding and granulating the mixed material to obtain pellets;
将所述粒料进行挤出吹膜，得到环保型功能膜材料。The pellets are extruded and blown to obtain an environment-friendly functional film material.
本发明将所述制备原料混合，进行增塑处理，得到混合物料。在本发明中，所述制备原料混合优选在高速混合机中进行；所述混合的搅拌速度优选为60～80转/分钟。在本发明中，所述增塑处理的温度优选为40～60℃，更优选为50℃；所述增塑处理的时间优选为60～120min，更优选为90～100min。本发明进行增塑处理能够使塑化改性剂充分渗透到淀粉和PVA分子间，破坏其分子间范德华力，提高树脂熔融流动性。The invention mixes the preparation raw materials and performs plasticizing treatment to obtain the mixed material. In the present invention, the mixing of the preparation raw materials is preferably carried out in a high-speed mixer; the stirring speed of the mixing is preferably 60-80 rpm. In the present invention, the temperature of the plasticizing treatment is preferably 40-60°C, more preferably 50°C; the time of the plasticizing treatment is preferably 60-120min, more preferably 90-100min. The plasticizing treatment of the invention can make the plasticizing modifier fully penetrate into the space between the starch and the PVA molecules, destroy the van der Waals force between the molecules, and improve the melting fluidity of the resin.
本发明优选在所述增塑处理后，将所得物料进行冷却静置48h以上，得到混合物料。在本发明中，所述冷却静置的时间更优选为48～72h。在本发明中，所述混合物料的含水量优选为16～18wt％。In the present invention, preferably after the plasticizing treatment, the obtained material is cooled and left to stand for more than 48 hours to obtain a mixed material. In the present invention, the cooling and standing time is more preferably 48-72 hours. In the present invention, the water content of the mixed material is preferably 16-18wt%.
得到混合物料后，本发明将所述混合物料进行挤出造粒，得到粒料。在本发明中，所述挤出造粒优选在双螺杆挤出机中进行。在本发明中，所述挤出造粒的加工温度优选为80～140℃，由进料口到出料口的分段温度具体优选为80℃、130℃、135℃、140℃、120℃、115℃、110℃。After the mixed material is obtained, the present invention extrudes the mixed material to obtain pellets. In the present invention, the extrusion granulation is preferably carried out in a twin-screw extruder. In the present invention, the processing temperature of the extrusion granulation is preferably 80-140°C, and the segmental temperature from the feed port to the discharge port is preferably 80°C, 130°C, 135°C, 140°C, 120°C , 115°C, 110°C.
得到粒料后，本发明将所述粒料进行挤出吹膜，得到环保型功能膜材料。在本发明中，所述挤出吹膜优选在吹膜机中进行。在本发明中，所述挤出吹膜的加工温度优选为130～200℃，由进料口到出料口的分段温度具 体优选为140℃、180℃、200℃、180℃、150℃、130℃。在本发明中，所述环保型功能膜材料的厚度优选为0.08～1.0毫米。After the pellets are obtained, the present invention extrudes the pellets and blows the film to obtain an environment-friendly functional film material. In the present invention, the extrusion film blowing is preferably carried out in a film blowing machine. In the present invention, the processing temperature of the extrusion blown film is preferably 130-200°C, and the segmental temperature from the feed port to the discharge port is preferably 140°C, 180°C, 200°C, 180°C, 150°C , 130°C. In the present invention, the thickness of the environment-friendly functional film material is preferably 0.08-1.0 mm.
本发明还提供了上述技术方案所述环保型功能膜材料或上述技术方案所述制备方法制备得到的环保型功能膜材料在含油污水处理中的应用。在本发明中，所述含油污水中的油相优选包括动物油、植物油、矿物油或芳烃。本发明对所述含油污水中油相的含量没有特殊要求，尤其适用于含少量油相的难分离含油污水。在本发明中，所述油相的质量含量优选为1～95％，更优选为1～5％。在本发明中，所述应用的温度优选为室温。The present invention also provides the application of the environment-friendly functional membrane material described in the above technical solution or the environment-friendly functional membrane material prepared by the preparation method described in the above technical solution in the treatment of oily sewage. In the present invention, the oil phase in the oily sewage preferably includes animal oil, vegetable oil, mineral oil or aromatic hydrocarbons. The present invention has no special requirements on the content of the oily phase in the oily sewage, and is especially suitable for difficult-to-separate oily sewage containing a small amount of oily phase. In the present invention, the mass content of the oil phase is preferably 1-95%, more preferably 1-5%. In the present invention, the temperature of the application is preferably room temperature.
本发明利用环保型功能膜材料的透水性和油脂阻隔性对含油污水中的油水混合物进行分离，分离效率高达100％，而且在废弃后所述环保型功能膜材料可完全溶于90℃热水中，实现生物降解，转化为二氧化碳和水，是真正的环保型功能膜材料。The invention utilizes the water permeability and oil barrier properties of the environmentally friendly functional membrane material to separate the oil-water mixture in the oily sewage, and the separation efficiency is as high as 100%, and the environmentally friendly functional membrane material can be completely dissolved in 90°C hot water after being discarded Among them, it can achieve biodegradation and be converted into carbon dioxide and water, which is a real environmentally friendly functional membrane material.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
以质量份数计，本实施例制备的环保型功能膜材料由木薯淀粉91份、PVA树脂9份、塑化改性剂23份、水基润滑剂6份、成核改性剂6份、热稳定剂6份、去离子水9份和抗氧剂0.8份组成；In parts by mass, the environment-friendly functional film material prepared in this example consists of 91 parts of tapioca starch, 9 parts of PVA resin, 23 parts of plasticizing modifier, 6 parts of water-based lubricant, 6 parts of nucleating modifier, Composed of 6 parts of heat stabilizer, 9 parts of deionized water and 0.8 part of antioxidant;
其中，所述木薯淀粉的平均粒径为6.5微米。所述PVA树脂选用安徽皖维高新材料有限公司售卖的PVA22-99H，平均粒径为6.5微米。以所述塑化改性剂的总质量为100％计，所述塑化改性剂为甘油40％、1,2-丙二醇20％、1,4-丁二醇10％、大豆油多元醇20％和一缩二丙二醇10％的混合物。以所述水基润滑剂的总质量为100％计，所述水基润滑剂为二甲基硅油30％、聚合醇润滑剂30％、芥酸酰胺20％和甲基丙烯酸甲酯20％的混合物。以所述成核改性剂的总质量为100％计，所述成核改性剂为纳米二氧化硅(平均粒径为5微米)30％、纳米二氧化钛(平均粒径为5微米)30％和山梨醇型成核剂WBQ 40％的混合物。以所述热稳定剂的总质量为100％计，所述热稳定剂为硬脂酸锌40％、蓖麻油酸钙30％和环氧大豆油 30％的混合物。以所述抗氧剂的总质量为100％计，所述抗氧剂为抗氧剂101050％、抗氧剂24630％和抗氧剂H1020％的混合物。Wherein, the average particle diameter of the tapioca starch is 6.5 microns. The PVA resin is selected from PVA22-99H sold by Anhui Wanwei High-tech Material Co., Ltd., with an average particle size of 6.5 microns. Based on the total mass of the plasticizing modifier as 100%, the plasticizing modifier is 40% of glycerin, 20% of 1,2-propylene glycol, 10% of 1,4-butanediol, soybean oil polyol 20% and dipropylene glycol 10% mixture. Based on the total mass of the water-based lubricant as 100%, the water-based lubricant is 30% of simethicone oil, 30% of polyalcohol lubricant, 20% of erucamide and 20% of methyl methacrylate. mixture. Taking the total mass of the nucleating modifier as 100%, the nucleating modifier is 30% of nano-silicon dioxide (average particle diameter is 5 microns), 30% of nano-titanium dioxide (average particle diameter is 5 microns) % and sorbitol-type nucleating agent WBQ 40% mixture. Taking the total mass of the heat stabilizer as 100%, the heat stabilizer is a mixture of 40% zinc stearate, 30% calcium ricinoleate and 30% epoxidized soybean oil. Based on the total mass of the antioxidant as 100%, the antioxidant is a mixture of antioxidant 101050%, antioxidant 24630% and antioxidant H1020%.
所述环保型功能膜材料的制备方法为：The preparation method of the environment-friendly functional membrane material is:
将所述木薯淀粉、PVA树脂、塑化改性剂、水基润滑剂、成核改性剂、热稳定剂、去离子水和抗氧剂置于高速混合机中，边搅拌边加热，在50℃进行90min增塑处理，然后冷却放置56小时，控制水分含量为18wt％，得到混合物料；The tapioca starch, PVA resin, plasticizing modifier, water-based lubricant, nucleating modifier, heat stabilizer, deionized water and antioxidant are placed in a high-speed mixer, heated while stirring, and Perform plasticizing treatment at 50°C for 90 minutes, then cool and place for 56 hours, control the moisture content to 18wt%, and obtain the mixed material;
将所述混合物料投入双螺杆挤出机中，熔融塑化挤出造粒，加工温度控制在80～140℃，由进料口到出料口的分段温度为80℃、130℃、135℃、140℃、120℃、115℃、110℃，得到粒料；Put the mixed material into a twin-screw extruder, melt, plasticize, extrude and granulate. The processing temperature is controlled at 80-140°C, and the segmental temperature from the inlet to the outlet is 80°C, 130°C, 135°C ℃, 140℃, 120℃, 115℃, 110℃ to obtain pellets;
将所述粒料投入吹膜机中，挤出吹膜，制成环保型功能膜材料，加工温度控制在130～200℃，由进料口到出料口的分段温度为140℃、180℃、200℃、180℃、150℃、130℃；所述环保型功能膜材料的厚度为0.08毫米。Put the pellets into the film blowing machine, extrude and blow the film to make an environment-friendly functional film material. °C, 200 °C, 180 °C, 150 °C, 130 °C; the thickness of the environmental-friendly functional film material is 0.08 mm.
实施例2Example 2
以质量份数计，本实施例制备的环保型功能膜材料由木薯淀粉80份、PVA树脂20份、塑化改性剂20份、水基润滑剂5份、成核改性剂5份、热稳定剂5份、去离子水7份和抗氧剂0.3份组成；In parts by mass, the environment-friendly functional film material prepared in this embodiment consists of 80 parts of tapioca starch, 20 parts of PVA resin, 20 parts of plasticizing modifier, 5 parts of water-based lubricant, 5 parts of nucleating modifier, Composed of 5 parts of heat stabilizer, 7 parts of deionized water and 0.3 part of antioxidant;
其中，所述木薯淀粉的平均粒径为6.5微米。所述PVA树脂选用安徽皖维高新材料有限公司售卖的PVA22-99H，平均粒径为6.5微米。以所述塑化改性剂的总质量为100％计，所述塑化改性剂为甘油70％、1,2-丙二醇5％、1,4-丁二醇5％、大豆油多元醇10％和一缩二丙二醇10％的混合物。以所述水基润滑剂的总质量为100％计，所述水基润滑剂为二甲基硅油20％、聚合醇润滑剂50％、芥酸酰胺15％和甲基丙烯酸甲酯15％的混合物。以所述成核改性剂的总质量为100％计，所述成核改性剂为纳米二氧化硅(平均粒径为10微米)15％、纳米二氧化钛(平均粒径为10微米)15％和山梨醇型成核剂WBQ 70％的混合物。以所述热稳定剂的总质量为100％计，所述热稳定剂为硬脂酸锌20％、蓖麻油酸钙40％和环氧大豆油40％的混合物。以所述抗氧剂的总质量为100％计，所述抗氧剂为抗氧剂1010 50％、抗氧剂246 30％和抗氧剂H10 20％的混合物。Wherein, the average particle diameter of the tapioca starch is 6.5 microns. The PVA resin is selected from PVA22-99H sold by Anhui Wanwei High-tech Material Co., Ltd., with an average particle size of 6.5 microns. Based on the total mass of the plasticizing modifier as 100%, the plasticizing modifier is 70% of glycerin, 5% of 1,2-propanediol, 5% of 1,4-butanediol, soybean oil polyol 10% and dipropylene glycol 10% mixture. Based on the total mass of the water-based lubricant as 100%, the water-based lubricant is 20% of simethicone oil, 50% of polyalcohol lubricant, 15% of erucamide and 15% of methyl methacrylate. mixture. Based on the total mass of the nucleating modifier as 100%, the nucleating modifier is 15% of nano-silicon dioxide (average particle diameter is 10 microns), 15% of nano-titanium dioxide (average particle diameter is 10 microns) % and sorbitol-type nucleating agent WBQ 70% mixture. Based on the total mass of the heat stabilizer being 100%, the heat stabilizer is a mixture of 20% zinc stearate, 40% calcium ricinoleate and 40% epoxidized soybean oil. Taking the total mass of the antioxidant as 100%, the antioxidant is a mixture of antioxidant 1010 50%, antioxidant 246 30% and antioxidant H10 20%.
所述环保型功能膜材料的制备方法为：The preparation method of the environment-friendly functional membrane material is:
将所述木薯淀粉、PVA树脂、塑化改性剂、水基润滑剂、成核改性剂、热稳定剂、去离子水和抗氧剂置于高速混合机中，边搅拌边加热，在50℃进行90min增塑处理，然后冷却放置48小时，控制水分含量为16wt％，得到混合物料；The tapioca starch, PVA resin, plasticizing modifier, water-based lubricant, nucleating modifier, heat stabilizer, deionized water and antioxidant are placed in a high-speed mixer, heated while stirring, and Perform plasticizing treatment at 50°C for 90 minutes, then cool and place for 48 hours, control the moisture content to 16wt%, and obtain the mixed material;
将所述混合物料投入双螺杆挤出机中，熔融塑化挤出造粒，加工温度控制在80～140℃，由进料口到出料口的分段温度为80℃、130℃、135℃、140℃、120℃、115℃、110℃，得到粒料；Put the mixed material into a twin-screw extruder, melt, plasticize, extrude and granulate. The processing temperature is controlled at 80-140°C, and the segmental temperature from the inlet to the outlet is 80°C, 130°C, 135°C ℃, 140℃, 120℃, 115℃, 110℃ to obtain pellets;
将所述粒料投入吹膜机中，挤出吹膜，制成环保型功能膜材料，加工温度控制在130～200℃，由进料口到出料口的分段温度为140℃、180℃、200℃、180℃、150℃、130℃；所述环保型功能膜材料的厚度为0.08毫米。Put the pellets into the film blowing machine, extrude and blow the film to make an environment-friendly functional film material. °C, 200 °C, 180 °C, 150 °C, 130 °C; the thickness of the environmental-friendly functional film material is 0.08 mm.
实施例3Example 3
以质量份数计，本实施例制备的环保型功能膜材料由木薯淀粉87份、PVA树脂13份、塑化改性剂28份、水基润滑剂10份、成核改性剂10份、热稳定剂10份、去离子水10份和抗氧剂0.5份组成；In parts by mass, the environment-friendly functional film material prepared in this example consists of 87 parts of tapioca starch, 13 parts of PVA resin, 28 parts of plasticizing modifier, 10 parts of water-based lubricant, 10 parts of nucleating modifier, 10 parts of heat stabilizer, 10 parts of deionized water and 0.5 parts of antioxidant;
其中，所述木薯淀粉的平均粒径为6.5微米。所述PVA树脂选用安徽皖维高新材料有限公司售卖的PVA22-99H，平均粒径为6.5微米。以所述塑化改性剂的总质量为100％计，所述塑化改性剂为甘油50％、1,2-丙二醇10％、1,4-丁二醇15％、大豆油多元醇15％和一缩二丙二醇10％的混合物。以所述水基润滑剂的总质量为100％计，所述水基润滑剂为二甲基硅油50％、聚合醇润滑剂30％、芥酸酰胺10％和甲基丙烯酸甲酯10％的混合物。以所述成核改性剂的总质量为100％计，所述成核改性剂为纳米二氧化硅(平均粒径为3微米)40％、纳米二氧化钛(平均粒径为3微米)40％和山梨醇型成核剂WBQ 20％的混合物。以所述热稳定剂的总质量为100％计，所述热稳定剂为硬脂酸锌20％、蓖麻油酸钙40％和环氧大豆油40％的混合物。以所述抗氧剂的总质量为100％计，所述抗氧剂为抗氧剂1010 50％、抗氧剂246 30％和抗氧剂H10 20％的混合物。Wherein, the average particle diameter of the tapioca starch is 6.5 microns. The PVA resin is selected from PVA22-99H sold by Anhui Wanwei High-tech Material Co., Ltd., with an average particle size of 6.5 microns. Based on the total mass of the plasticizing modifier as 100%, the plasticizing modifier is 50% of glycerin, 10% of 1,2-propylene glycol, 15% of 1,4-butanediol, soybean oil polyol 15% and dipropylene glycol 10% mixture. Based on the total mass of the water-based lubricant as 100%, the water-based lubricant is 50% of simethicone oil, 30% of polyalcohol lubricant, 10% of erucamide and 10% of methyl methacrylate. mixture. Taking the total mass of the nucleating modifier as 100%, the nucleating modifier is 40% of nano-silicon dioxide (average particle diameter is 3 microns), nano-titanium dioxide (average particle diameter is 3 microns) 40% % and sorbitol-type nucleating agent WBQ 20% mixture. Based on the total mass of the heat stabilizer being 100%, the heat stabilizer is a mixture of 20% zinc stearate, 40% calcium ricinoleate and 40% epoxidized soybean oil. Taking the total mass of the antioxidant as 100%, the antioxidant is a mixture of antioxidant 1010 50%, antioxidant 246 30% and antioxidant H10 20%.
所述环保型功能膜材料的制备方法为：The preparation method of the environment-friendly functional membrane material is:
将所述木薯淀粉、PVA树脂、塑化改性剂、水基润滑剂、成核改性 剂、热稳定剂、去离子水和抗氧剂置于高速混合机中，边搅拌边加热，在50℃进行90min增塑处理，然后冷却放置72小时，控制水分含量为18wt％，得到混合物料；The tapioca starch, PVA resin, plasticizing modifier, water-based lubricant, nucleating modifier, heat stabilizer, deionized water and antioxidant are placed in a high-speed mixer, heated while stirring, and Perform plasticizing treatment at 50°C for 90 minutes, then cool and place for 72 hours, control the moisture content to 18wt%, and obtain the mixed material;
将所述混合物料投入双螺杆挤出机中，熔融塑化挤出造粒，加工温度控制在80～140℃，由进料口到出料口的分段温度为80℃、130℃、135℃、140℃、120℃、115℃、110℃，得到粒料；Put the mixed material into a twin-screw extruder, melt, plasticize, extrude and granulate. The processing temperature is controlled at 80-140°C, and the segmental temperature from the inlet to the outlet is 80°C, 130°C, 135°C ℃, 140℃, 120℃, 115℃, 110℃ to obtain pellets;
将所述粒料投入吹膜机中，挤出吹膜，制成环保型功能膜材料，加工温度控制在130～200℃，由进料口到出料口的分段温度为140℃、180℃、200℃、180℃、150℃、130℃；所述环保型功能膜材料的厚度为0.08毫米。Put the pellets into the film blowing machine, extrude and blow the film to make an environment-friendly functional film material. °C, 200 °C, 180 °C, 150 °C, 130 °C; the thickness of the environmental-friendly functional film material is 0.08 mm.
测试例1test case 1
对实施例制备的环保型功能膜材料进行检测The environment-friendly functional membrane material prepared by the embodiment is detected
1、拉伸强度和拉伸断裂应变测试：1. Tensile strength and tensile breaking strain test:
采用国家标准GB/T 1040.3-2006，样条宽度为15mm。The national standard GB/T 1040.3-2006 is adopted, and the spline width is 15mm.
2、水蒸气透过量测试：2. Water vapor transmission rate test:
采用国家标准GB/T1037-2000，在38℃、90％RH条件下，对实施例制备的环保型功能膜材料进行测试。Using the national standard GB/T1037-2000, under the conditions of 38° C. and 90% RH, the environment-friendly functional membrane materials prepared in the examples were tested.
3、氧气透过量测试：3. Oxygen transmission rate test:
采用国家标准GB/T1038-2000，在23℃、0％RH条件下，对实施例制备的环保型功能膜材料进行测试。Using the national standard GB/T1038-2000, under the conditions of 23° C. and 0% RH, the environment-friendly functional film materials prepared in the examples were tested.
4、生物降解性：4. Biodegradability:
依据ISO14855-1：2012进行实验室堆肥测试生物分解率。According to ISO14855-1:2012, the biodegradation rate of laboratory composting was tested.
5、高温水溶性：5. High temperature water solubility:
在90℃热水中能够完全溶解。It can be completely dissolved in hot water at 90°C.
6、具有优异的油脂阻隔性，对各种油脂有完全阻隔性。6. It has excellent oil barrier properties and has complete barrier properties to various oils.
实施例1～3制备的环保型功能膜材料的试验结果见表1。See Table 1 for the test results of the environment-friendly functional membrane materials prepared in Examples 1-3.
表1 实施例1～3制备的环保型功能膜材料的检测结果Table 1 The detection results of the environment-friendly functional membrane materials prepared in Examples 1-3
Figure PCTCN2021142053-appb-000001
Figure PCTCN2021142053-appb-000001
Figure PCTCN2021142053-appb-000002
Figure PCTCN2021142053-appb-000002
测试例2test case 2
将100g纯净水和100g食用油混合，得到油水混合物；采用实施例1的环保型功能膜材料制成30cm*30cm的袋子；将所述油水混合物装入上述袋子中并称重，记录总重量为239g(袋子+油水混合物)，封口后悬挂于恒温干燥箱中静置；经过48小时后，袋子中的水分完全透出，再次称重，记录总重量为139g。袋中残留油的重量为100g，没有变化，如图2所示。100g of purified water and 100g of edible oil are mixed to obtain an oil-water mixture; the environmental-friendly functional membrane material of Example 1 is used to make a 30cm*30cm bag; the oil-water mixture is packed into the above-mentioned bag and weighed, and the total weight is recorded as 239g (bag+oil-water mixture), after sealing, hang it in a constant temperature drying box and let it stand still; after 48 hours, the moisture in the bag completely penetrated, weighed again, and recorded the total weight as 139g. The weight of the residual oil in the bag was 100g, which did not change, as shown in Figure 2.
试验结果证明，采用本发明提供的环保型功能膜材料能够使油水混合物得到100％的分离。The test result proves that the oil-water mixture can be separated by 100% by adopting the environment-friendly functional membrane material provided by the invention.
由以上实施例可以看出，本发明提供的环保型功能膜材料具有完全生物降解性，可用于油水分离领域，利用其透水性和油脂阻隔性对油水混合物进行分离，分离效率可以达到100％，工艺设备简单易行，而且在废弃后这种膜可完全溶于90℃热水中，进一步的可实现生物降解，是真正的环保型功能膜材料。It can be seen from the above examples that the environmentally friendly functional membrane material provided by the present invention has complete biodegradability and can be used in the field of oil-water separation. It can use its water permeability and oil barrier properties to separate oil-water mixtures, and the separation efficiency can reach 100%. The process equipment is simple and easy to operate, and this membrane can be completely dissolved in hot water at 90°C after being discarded, and can further achieve biodegradation. It is a real environmentally friendly functional membrane material.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术 人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (14)

  1. 一种环保型功能膜材料，其特征在于，按质量份数计，包括以下制备原料：An environment-friendly functional membrane material is characterized in that, in parts by mass, it comprises the following preparation raw materials:
    木薯淀粉80～91份、聚乙烯醇树脂9～20份、塑化改性剂20～28份、水基润滑剂5～10份、成核改性剂5～10份、热稳定剂5～10份、抗氧剂0.3～0.8份和水6～12份。80-91 parts of tapioca starch, 9-20 parts of polyvinyl alcohol resin, 20-28 parts of plasticizing modifier, 5-10 parts of water-based lubricant, 5-10 parts of nucleating modifier, 5-10 parts of heat stabilizer 10 parts, 0.3-0.8 parts of antioxidant and 6-12 parts of water.
  2. 根据权利要求1所述的环保型功能膜材料，其特征在于，包括以下制备原料：木薯淀粉87～90份、聚乙烯醇树脂10～13份、塑化改性剂23～25份、水基润滑剂6～8份、成核改性剂6～8份、热稳定剂6～8份、抗氧剂0.5～0.8份和水7～10份。The environment-friendly functional film material according to claim 1, characterized in that it comprises the following preparation raw materials: 87-90 parts of tapioca starch, 10-13 parts of polyvinyl alcohol resin, 23-25 parts of plasticizing modifier, water-based 6-8 parts of lubricant, 6-8 parts of nucleating modifier, 6-8 parts of heat stabilizer, 0.5-0.8 parts of antioxidant and 7-10 parts of water.
  3. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述木薯淀粉的粒径为1～10微米。The environment-friendly functional membrane material according to claim 1 or 2, characterized in that the tapioca starch has a particle size of 1-10 microns.
  4. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述聚乙烯醇树脂为PVA22-99H；所述聚乙烯醇树脂的粒径为1～10微米。The environment-friendly functional film material according to claim 1 or 2, wherein the polyvinyl alcohol resin is PVA22-99H; the particle size of the polyvinyl alcohol resin is 1-10 microns.
  5. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述塑化改性剂包括甘油、1,2-丙二醇、1,4-丁二醇、大豆油多元醇和一缩二丙二醇；所述甘油、1,2-丙二醇、1,4-丁二醇、大豆油多元醇和一缩二丙二醇的质量比为4～7：0.5～2：0.5～1.5：1～2：1。The environment-friendly functional membrane material according to claim 1 or 2, wherein the plasticizing modifier comprises glycerin, 1,2-propanediol, 1,4-butanediol, soybean oil polyol, and dimethylbenzene Propylene glycol; the mass ratio of glycerin, 1,2-propanediol, 1,4-butanediol, soybean oil polyol and dipropylene glycol is 4-7:0.5-2:0.5-1.5:1-2:1.
  6. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述水基润滑剂包括二甲基硅油、聚合醇润滑剂、芥酸酰胺和甲基丙烯酸甲酯；所述二甲基硅油、聚合醇润滑剂、芥酸酰胺和甲基丙烯酸甲酯的质量比为2～5：2～5：1～2：1～2。The environment-friendly functional film material according to claim 1 or 2, wherein the water-based lubricant comprises simethicone, polyalcohol lubricant, erucamide and methyl methacrylate; the dimethyl The mass ratio of base silicone oil, polyalcohol lubricant, erucamide and methyl methacrylate is 2-5:2-5:1-2:1-2.
  7. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述热稳定剂包括硬脂酸锌、蓖麻油酸钙和环氧大豆油；所述硬脂酸锌、蓖麻油酸钙和环氧大豆油的质量比为2～4：3～4：3～4。The environment-friendly functional film material according to claim 1 and 2, wherein the heat stabilizer includes zinc stearate, calcium ricinoleate and epoxy soybean oil; the zinc stearate, ricinoleic acid The mass ratio of calcium and epoxidized soybean oil is 2-4:3-4:3-4.
  8. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述成核改性剂包括纳米二氧化硅、纳米二氧化钛和山梨醇类成核剂；所述纳米二氧化硅、纳米二氧化钛和山梨醇类成核剂的质量比为1.5～4：1.5～4：2～7。The environment-friendly functional membrane material according to claim 1 or 2, wherein the nucleating modifier comprises nano silicon dioxide, nano titanium dioxide and sorbitol nucleating agent; the nano silicon dioxide, nano The mass ratio of titanium dioxide and sorbitol nucleating agent is 1.5-4:1.5-4:2-7.
  9. 根据权利要求1或2所述的环保型功能膜材料，其特征在于，所述抗氧剂包括抗氧剂1010、抗氧剂246和抗氧剂H10；所述抗氧剂1010、抗氧剂246和抗氧剂H10的质量比为4～6：2～4：1～2。The environment-friendly functional film material according to claim 1 or 2, wherein the antioxidant comprises antioxidant 1010, antioxidant 246 and antioxidant H10; the antioxidant 1010, antioxidant The mass ratio of 246 and antioxidant H10 is 4-6:2-4:1-2.
  10. 权利要求1～9任一项所述环保型功能膜材料的制备方法，包括以下步骤：The preparation method of the environment-friendly functional membrane material according to any one of claims 1 to 9, comprising the following steps:
    将所述制备原料混合，进行增塑处理，得到混合物料；mixing the preparation raw materials and performing plasticizing treatment to obtain a mixed material;
    将所述混合物料进行挤出造粒，得到粒料；Extruding and granulating the mixed material to obtain pellets;
    将所述粒料进行挤出吹膜，得到环保型功能膜材料。The pellets are extruded and blown to obtain an environment-friendly functional film material.
  11. 根据权利要求10所述的制备方法，其特征在于，所述增塑处理的温度为40～60℃，所述增塑处理的时间为60～120min。The preparation method according to claim 10, characterized in that, the temperature of the plasticizing treatment is 40-60° C., and the time of the plasticizing treatment is 60-120 minutes.
  12. 根据权利要求10所述的制备方法，其特征在于，所述挤出造粒的加工温度为80～140℃。The preparation method according to claim 10, characterized in that, the processing temperature of the extrusion granulation is 80-140°C.
  13. 根据权利要求10所述的制备方法，其特征在于，所述挤出吹膜的加工温度为130～200℃。The preparation method according to claim 10, characterized in that, the processing temperature of the extrusion blown film is 130-200°C.
  14. 权利要求1～9任一项所述环保型功能膜材料或权利要求10～13任一项所述制备方法制备得到的环保型功能膜材料在含油污水处理中的应用。The application of the environment-friendly functional membrane material according to any one of claims 1-9 or the environment-friendly functional membrane material prepared by the preparation method according to any one of claims 10-13 in the treatment of oily sewage.
PCT/CN2021/142053 2021-11-04 2021-12-28 Environmentally friendly functional membrane material, preparation method thereof, and use thereof WO2023077644A1 (en)

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CN101240086A (en) * 2008-03-14 2008-08-13 上海悦仕生物材料有限公司 Total-biodegradation plastic film and preparation method thereof
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WO1992016583A1 (en) * 1991-03-19 1992-10-01 Parke, Davis & Company Biodegradable compositions comprising starch derivatives
CN101240086A (en) * 2008-03-14 2008-08-13 上海悦仕生物材料有限公司 Total-biodegradation plastic film and preparation method thereof
CN106519311A (en) * 2016-10-18 2017-03-22 青岛科技大学 Thermoplastic starch-polyvinyl alcohol fogging-resistance film and preparation method thereof
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