WO2020238270A1 - 一种用于油水分离的改性聚乳酸无纺布及其制备方法与应用 - Google Patents

一种用于油水分离的改性聚乳酸无纺布及其制备方法与应用 Download PDF

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WO2020238270A1
WO2020238270A1 PCT/CN2020/073447 CN2020073447W WO2020238270A1 WO 2020238270 A1 WO2020238270 A1 WO 2020238270A1 CN 2020073447 W CN2020073447 W CN 2020073447W WO 2020238270 A1 WO2020238270 A1 WO 2020238270A1
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woven fabric
polylactic acid
oil
water separation
pdla
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PCT/CN2020/073447
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English (en)
French (fr)
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江伟
朱晨曦
胡晶磊
孙平
李爱民
张全兴
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南京大学
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/08—Thickening liquid suspensions by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28038—Membranes or mats made from fibers or filaments
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the invention relates to oil-water separation technology, in particular to a modified polylactic acid non-woven fabric used for oil-water separation, and a preparation method and application thereof.
  • Polylactic acid is a completely biodegradable polymer material with a wide range of synthetic pathways, and the final degradation products are CO 2 and H 2 O. It has the advantages of good biocompatibility, good application prospects and research value.
  • the predecessors simply used the phase separation method to produce a superhydrophobic polylactic acid film, but the mechanical properties of this film were too poor to be suitable for the oil-water separation industry.
  • polylactic acid can be divided into L-polylactic acid (PLLA) and D-polylactic acid (PDLA).
  • PLLA L-polylactic acid
  • PDLA D-polylactic acid
  • SC stereocomplex
  • PLA-sc has a higher melting temperature, which is nearly 50°C higher than the melting point of the homopolymers of PLLA and PDLA; 2) PLA-sc crystals are triclinic crystals stacked in a 31-helical conformation and belong to the ⁇ crystal form; (3) Compared with the respective homopolymers of PLLA and PDLA, it has excellent impact and mechanical properties.
  • this application provides a modified polylactic acid non-woven fabric for oil-water separation and a preparation method thereof, and its application in the treatment of oily wastewater.
  • the method for preparing a modified polylactic acid non-woven fabric for oil-water separation described in this application includes the following steps:
  • step (2) Take the PLLA non-woven fabric, drop the mixed solution obtained in step (1), so that the non-woven fabric is immersed in the mixed solution;
  • step (2) After step (2), let it stand for 12-36h, and then dry.
  • the molecular weight of the PDLA is 20,000-200,000; the organic solvent is methylene chloride or chloroform; the poor solvent of polylactic acid is at least one of ethanol, n-butanol and butyl acetate .
  • step (1) the concentration of the PDLA solution is 0.1%wt to 5%wt; the volume ratio of the PDLA solution to the poor solvent of polylactic acid is 1:1-5.
  • step (2) the molecular weight of the PLLA is 40,000-200,000.
  • step (3) it is sufficient to stand still in a room temperature environment, and the drying refers to drying in an oven at 20-80°C for 4-24 hours.
  • the modified polylactic acid non-woven fabric for oil-water separation prepared according to the above method is also within the protection scope of this application.
  • the modified polylactic acid non-woven fabric used for oil-water separation has a contact angle with water around 150° and a contact angle with oil around 0°.
  • the oil absorption of the prepared non-woven fabric is increased by more than 40%, and can be recycled more than 10 times.
  • modified polylactic acid non-woven fabric for oil-water separation in the treatment of oily wastewater is also within the protection scope of this application.
  • a dichloromethane solution of PDLA containing a poor solvent is dripped on the PLLA non-woven fabric, thereby forming a slightly soluble surface containing PLLA on the PLLA non-woven fabric.
  • the PDLA contained in the PDLA solution is blended with the above-mentioned PLLA dissolved in the solution, and phase separation occurs during the volatilization of the solvent and the poor solvent, and a stereocomplex of polylactic acid is formed on the surface of the non-woven fabric.
  • the surface of the oil-water separation non-woven fabric prepared by the present invention forms a stereocomplex due to self-assembly, and the stereocomplex is directly connected to the non-woven fabric through a strong chemical bond. Therefore, the prepared oil-water separation non-woven fabric has Good stability and abrasion resistance.
  • PDLA refers to poly-dextro-lactic acid
  • PLLA refers to poly-L-lactic acid
  • the contact angle of the polylactic acid oil-water separation non-woven fabric in the air to water is around 150°; the contact angle to oil is around 0°; it can be used in the field of oil-water separation, and the oil absorption is increased by more than 40%. It can be recycled more than 10 times and has good durability.
  • the present invention proves through experiments that the prepared oil-water separation non-woven fabric has the characteristics of stable wear resistance and efficient separation; and after being used and discarded, it can be degraded in the natural environment without secondary pollution; it can be used for oil-water separation of oily sewage, If it can be used for oil-water separation containing edible oil, gasoline and other oily sewage, it has broad application prospects.
  • Figure 1 is an enlarged scanning electron microscope photo of the prepared oil-water separation non-woven fabric
  • Figure 2 is a photo of the shape of water droplets (3 microliters) on the surface of the prepared oil-water separation non-woven fabric measured in the air;
  • Figure 3 is a photo of the shape of oil droplets (3 microliters) measured in the air on the surface of the prepared oil-water separation non-woven fabric;
  • Fig. 5 is a data chart of water contact angle changes of the oil-water separation non-woven fabric prepared in the embodiment repeatedly used for 10 times.
  • PLLA non-woven fabric was purchased from Jiangxi Guoqiao Industrial Co., Ltd.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • step (3) Place the non-woven fabric in the petri dish of step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a method for preparing modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 0.1%wt with an organic solvent then add 4 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring of equal volume of ethanol, n-butanol, and butyl acetate for 30 minutes.
  • the molecular weight of PDLA is 20000 and the organic solvent is methylene chloride;
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • step (3) Place the non-woven fabric in the petri dish in step (2) at room temperature for 24 hours, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 5% wt using an organic solvent then add 4 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring with equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 20,000, and the organic solvent is methylene chloride;
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a method for preparing modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 0.1%wt with an organic solvent then add 4 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring of equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 200,000, and the organic solvent is chloroform;
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a method for preparing modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 5% wt using an organic solvent then add an equal volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring of equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 200,000, and the organic solvent is chloroform;
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 5% wt using an organic solvent then add 4 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring of equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 200,000, and the organic solvent is chloroform;
  • step (3) Place the non-woven fabric in the petri dish in step (2) at room temperature for 24 hours, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 0.5%wt with an organic solvent then add 1.5 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring of equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 100,000, and the organic solvent is dichloromethane;
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • step (3) Place the non-woven fabric in the petri dish in step (2) at room temperature for 24 hours, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 2%wt with an organic solvent then add 1.5 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 minutes.
  • the poor solvent is prepared by magnetic stirring of equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 100,000, and the organic solvent is dichloromethane;
  • step (3) Place the non-woven fabric in the petri dish in step (2) for 24 hours at room temperature, then place it in an oven and dry it at 40° C. for 6 hours to obtain the oil-water separation non-woven fabric.
  • a preparation method of modified polylactic acid non-woven fabric for oil-water separation the specific steps are:
  • a PDLA solution with a concentration of 0.5% wt using an organic solvent then add 2 times the volume of a poor solvent to the above PDLA solution, and magnetically stir for 30 min.
  • the poor solvent is prepared by magnetic stirring of equal volumes of ethanol, n-butanol, and butyl acetate.
  • the molecular weight of PDLA is 100,000, and the organic solvent is chloroform;
  • step (3) Place the non-woven fabric in the petri dish in step (2) at room temperature for 24 hours, then place it in an oven and dry it at 40°C for 6 hours to obtain the oil-water separation non-woven fabric.
  • the oil-water separation non-woven fabric obtained in the above example was scanned by electron microscope, and the surface morphology was observed at 3000 times. The result is shown in Figure 1. It can be seen that a block structure is formed on the fiber surface, which increases the surface roughness of the non-woven fabric .
  • the oil-water separation non-woven fabric prepared in the above example has a good absorption capacity for oily substances, as shown in Figure 4.
  • Example 1 After the oil-water separation non-woven fabric prepared in Example 1 was repeatedly used for 10 times, as shown in FIG. 5, it still has a strong hydrophobic effect, indicating that the non-woven fabric has good stability.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Nonwoven Fabrics (AREA)
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Abstract

本发明提供了一种用于油水分离的改性聚乳酸无纺布的制备方法，包括以下步骤：(1)将PDLA溶于有机溶剂中，配制成0.1％wt-5％wt的PDLA溶液，加入1-4倍体积的聚乳酸的不良溶剂，搅拌得到混合溶液；(2)将步骤(1)的混合溶液倒入装有PLLA无纺布的容器中；(3)室温下静置一定时间后干燥即可。本申请制备所得改性聚乳酸无纺布上生成了微米级小颗粒，增加了聚乳酸无纺布的表面粗糙度，无纺布在空气中对水的接触角最高为150°，对油的接触角为0°，吸附容量相比未改性聚乳酸无纺布提高了40％以上，重复利用10次仍然具有较好的稳定性。本发明制备方法简单，完全可生物降解，不会引起二次污染，可大范围用于处理含油废水。

Description

一种用于油水分离的改性聚乳酸无纺布及其制备方法与应用 技术领域
本发明涉及油水分离技术，具体为一种用于油水分离的改性聚乳酸无纺布及其制备方法与应用。
背景技术
近年来，随着工业污染日益加重，含油废水的排放也日趋增加。频繁的石油泄漏以及有机溶剂的工业排放，在世界各地造成了严重的环境污染和生态问题。传统的油水分离技术普遍存在效率低、耗时长、成本高等不足之处。为了解决这些问题，新的油水分离方法和材料被不断研究和开发，吸油材料逐渐成长为油水分离的主力军。
近几十年来，前人对油水分离材料的研究愈发重视，传统的油水分离材料，如海绵等孔材料用途广泛。但是材料本身存在着对油的选择性低、吸附量少等缺点，且使用寿命很短。以此为基础，人工合成材料开始作为油水分离材料的主力军被广泛使用，但是此类材料普遍具有化学性质不稳定，重复使用率低的缺点，而且大都不可生物降解，存在着引发二次污染的风险。
聚乳酸(PLA)是一种合成途径广泛，最终降解产物为CO 2和H 2O的可完全生物降解的高分子材料。它具有生物相容性好的优点，具有很好的应用前景和研究价值。前人简单利用相分离的方法，生产出了超疏水的聚乳酸薄膜，但是这种薄膜机械性能太差，不适合用于油水分离行业。还有报道研究了通过在聚乳酸无纺布表面涂覆粘附层后吸附纳米SiO2颗粒，但是这种方法实验操作复杂，所得的油水分离材料由于添加了其他微粒，耐磨性较差。
有报道指出根据其聚合物分子链旋光性的不同，聚乳酸可分为左旋聚乳酸(PLLA)、右旋聚乳酸(PDLA)。当PLLA与PDLA以一定比例共混时，可形成一种立构复合体(SC)。它不同于PLLA和PDLA各自的均聚物，主要体现在以下3个方面：(1)PLA-sc具有较高的熔融温度，比PLLA和PDLA各自均聚物的熔点高出近50℃；(2)PLA-sc晶体是以31螺旋构象堆积的三斜晶体，属于β晶型；(3)相比于PLLA和PDLA各自的均聚物，它具有优异的冲击性能和力学性能。
发明内容
发明目的：针对上述现有技术中存在的技术问题，本申请提供了一种用于油水分离 的改性聚乳酸无纺布及其制备方法，以及其在处理含油废水中的应用。
技术方案：本申请所述的一种用于油水分离的改性聚乳酸无纺布的制备方法，包括如下步骤：
(1)取PDLA溶于有机溶剂中得到PDLA溶液，加入聚乳酸的不良溶剂；
(2)取PLLA无纺布，滴加步骤(1)得到的混合溶液，使无纺布浸在混合溶液中；
(3)步骤(2)操作后，静置12-36h，然后干燥即可。
步骤(1)中，所述PDLA的分子量为20000—200000；所述有机溶剂为二氯甲烷或三氯甲烷；所述聚乳酸的不良溶剂为乙醇、正丁醇和乙酸丁酯中的至少一种。
步骤(1)中，所述PDLA溶液的浓度为0.1％wt-5％wt；所述PDLA溶液与聚乳酸的不良溶剂的体积比为1:1-5。
步骤(2)中，所述PLLA分子量为40000—200000。
步骤(3)中，在室温环境中静置即可，所述干燥是指在20-80℃烘箱中干燥4-24h。
根据上述方法制备所得用于油水分离的改性聚乳酸无纺布也在本申请的保护范围内。所述用于油水分离的改性聚乳酸无纺布对水的接触角在150°附近，对油的接触角在0°附近。并且，所制得的无纺布吸油量提升了40％以上，可以循环使用10次以上。
所述用于油水分离的改性聚乳酸无纺布在处理含油废水中的应用也在本申请的保护范围内。
本发明在PLLA无纺布上滴加含有不良溶剂的PDLA的二氯甲烷溶液，从而在PLLA无纺布上形成含有PLLA的微溶表面。PDLA溶液中含有的PDLA与上述溶在溶液中的PLLA共混，在溶剂、不良溶剂挥发过程中发生相分离并在无纺布表面形成聚乳酸的立构复合物。本发明所制得的油水分离无纺布表面由于自组装形成了立构复合物，并且该立构复合物通过强化学键直接与无纺布相连，因此，所制得的油水分离无纺布具有良好的稳定性和耐磨性。
本申请中PDLA指聚右旋乳酸，PLLA指聚左旋乳酸。
有益效果：本申请聚乳酸油水分离无纺布在空气中对水的接触角在150°附近；对油的接触角在0°附近；可以用于油水分离领域，吸油量提升了40％以上，可以循环使用10次以上，耐用性好。本发明通过实验证明，制备的油水分离无纺布具有稳定耐磨、高效分离的特点；并且使用废弃后，可在自然环境中降解，不会产生二次污染；可用于含油污水的油水分离，如可用于含有食用油、汽油等含油污水的油水分离，应用前景广阔。
附图说明
图1为制备的油水分离无纺布的放大的表面形貌扫描电镜照片；
图2为在空气中测量水滴(3微升)在制备的油水分离无纺布表面的形状照片；
图3为在空气中测量油滴(3微升)在制备的油水分离无纺布表面的形状照片；
图4为实施例制备的油水分离无纺布用于吸收油性物质的效果照片；
图5为实施例制备的油水分离无纺布重复使用10次水接触角变化数据图。
具体实施方式
下面通过具体实施例对本发明进行说明。
PLLA无纺布购自江西国桥实业有限公司。
实施例1
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用配制浓度为0.1％wt的PDLA溶液，随后往上述PDLA溶液中加入等体积的不良溶剂，磁力搅拌30min；其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为20000，有机溶剂为二氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例2
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为0.1％wt的PDLA溶液，随后往上述PDLA溶液中加入4倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌30min配制而成，其中PDLA的分子量为20000，有机溶剂为二氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例3
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为5％wt的PDLA溶液，随后往上述PDLA溶液中加入等体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为20000，有机溶剂为二氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例4
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为5％wt的PDLA溶液，随后往上述PDLA溶液中加入4倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为20000，有机溶剂为二氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例5
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为0.1％wt的PDLA溶液，随后往上述PDLA溶液中加入等体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为200000，有机溶剂为三氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例6
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为0.1％wt的PDLA溶液，随后往上述PDLA溶液中加入4倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙 酸丁酯磁力搅拌配制而成，PDLA的分子量为200000，有机溶剂为三氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例7
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为5％wt的PDLA溶液，随后往上述PDLA溶液中加入等倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为200000，有机溶剂为三氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例8
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为5％wt的PDLA溶液，随后往上述PDLA溶液中加入4倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为200000，有机溶剂为三氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝40000)的培养皿中，其中PLLA的分子量为40000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例9
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为0.5％wt的PDLA溶液，随后往上述PDLA溶液中加入1.5倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为100000，有机溶剂为二氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布 (Mw＝100000)的培养皿中，其中PLLA的分子量为100000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例10
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为1％wt的PDLA溶液，随后往上述PDLA溶液中加入1.5倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为60000，有机溶剂为三氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝60000)的培养皿中，其中PLLA的分子量为60000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例11
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为2％wt的PDLA溶液，随后往上述PDLA溶液中加入1.5倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为100000，有机溶剂为二氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝100000)的培养皿中，其中PLLA的分子量为100000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件下干燥6h，制得油水分离无纺布。
实施例12
一种用于油水分离的改性聚乳酸无纺布的制备方法，具体步骤为：
(1)用有机溶剂配制浓度为0.5％wt的PDLA溶液，随后往上述PDLA溶液中加入2倍体积的不良溶剂，磁力搅拌30min。其中不良溶剂由等体积的乙醇、正丁醇、乙酸丁酯磁力搅拌配制而成，PDLA的分子量为100000，有机溶剂为三氯甲烷；
(2)将15ml步骤(1)所得的混合液滴入装有直径为6cm的圆形PLLA无纺布(Mw＝100000)的培养皿中，其中PLLA的分子量为100000；
(3)常温下将无纺布在步骤(2)中培养皿里静置24h后，置于烘箱中于40℃条件 下干燥6h，制得油水分离无纺布。
实施例13
油水分离改性聚乳酸无纺布的特征及功能鉴定
1、电镜扫描观察
将上述实例得到的油水分离无纺布进行电镜扫描，放大3000倍观察表面形貌，结果如图1所示，可以看出在纤维表面生成了块状结构，增加了无纺布的表面粗糙度。
2、油水分离网膜的吸油性和疏水性研究
在空气中，将3微升水滴滴在实施例1中得到的油水分离无纺布上，利用接触角测量仪测定，结果如图2所示，在空气中对水的接触角为150°。在空气中，将3微升正己烷滴在实施例1中得到的油水分离无纺布上，利用接触角测量仪检测，结果如图3所示，在空气中对油的接触角为0°。
3、油水分离无纺布分离油水混合物
上述实例所制得油水分离无纺布对油性物质有很好的吸收能力，如图4所示。
4、稳定性测定
实施例1制得的油水分离无纺布在重复使用10次之后，如图5所示，仍具有很强的疏水效果，说明该无纺布具有良好的稳定性。

Claims (8)

  1. 一种用于油水分离的改性聚乳酸无纺布的制备方法，其特征在于，包括如下步骤：
    (1)取PDLA溶于有机溶剂中得到PDLA溶液，加入聚乳酸的不良溶剂，搅拌均匀得到混合溶液；
    (2)取PLLA无纺布，滴加步骤(1)得到的混合溶液，使无纺布浸在混合溶液中；
    (3)步骤(2)操作后，静置12-36h，然后干燥即可。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述PDLA的分子量为20000—200000；所述有机溶剂为二氯甲烷或三氯甲烷；所述聚乳酸的不良溶剂为乙醇、正丁醇和乙酸丁酯中的至少一种。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述PDLA溶液的浓度为0.1％wt-5％wt；所述PDLA溶液与聚乳酸的不良溶剂的体积比为1:1-5。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述PLLA分子量为40000—200000。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(3)中，在室温环境中静置即可，所述干燥是指在20-80℃烘箱中干燥4-24h。
  6. 权利要求1-5中任一所述制备方法制备所得用于油水分离的改性聚乳酸无纺布。
  7. 根据权利要求6所述的用于油水分离的改性聚乳酸无纺布，其特征在于，其对水的接触角在150°附近，对油的接触角在0°附近。
  8. 权利要求1-5中任一所述制备方法制备所得用于油水分离的改性聚乳酸无纺布在处理含油废水中的应用。
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