技术领域technical field
本发明涉及一种纤维素基吸水吸油薄膜，属于天然高分子材料领域。The invention relates to a cellulose-based water-absorbing and oil-absorbing film, which belongs to the field of natural polymer materials.
背景技术Background technique
纤维素是地球上数量最多的天然高聚物，源于树木、植物秸秆、棉花和其它农副产品，其成本低，属于可再生资源。纤维素通过物理和化学改性后的衍生化产品已经被大量应用于化工、医药、环保、建筑材料、石油化学等领域，因此纤维素作为一种环境友好的可再生资源，使世界各国都十分重视对其的研究与开发。传统的纤维接枝共聚反应都是在非均相体系中进行的，如果这些反应在均相体系中进行，就能有效地控制纤维素衍生物的取代度，有规律地将取代基团引入到纤维素主链上，比非均相条件更好地控制所得产品的物理化学性质，有利于提高反应速度和产品性质的均一性，提高其应用范围。因此，采用均相法进行接枝聚合反应，具有更加重要的社会效益。Cellulose is the most abundant natural polymer on the earth. It is derived from trees, plant straw, cotton and other agricultural by-products. It is a low-cost renewable resource. The derivative products of cellulose through physical and chemical modification have been widely used in chemical industry, medicine, environmental protection, building materials, petrochemical and other fields. Therefore, as an environmentally friendly renewable resource, cellulose is very popular all over the world. Pay attention to its research and development. Traditional fiber graft copolymerization reactions are carried out in a heterogeneous system. If these reactions are carried out in a homogeneous system, the degree of substitution of cellulose derivatives can be effectively controlled, and substituent groups can be regularly introduced into the On the cellulose main chain, the physical and chemical properties of the obtained product can be better controlled than heterogeneous conditions, which is conducive to improving the reaction speed and the uniformity of product properties, and improving its application range. Therefore, the use of homogeneous method for graft polymerization has more important social benefits.
两亲性接枝共聚物(简称AGP)是目前功能高分子材料研究领域的热点之一。两亲性是指亲水性和亲油性，是将热力学上不相容的两种链通过化学键连接在一起，从而实现了两亲性物质在分子水平的组装。两亲性聚合物从结构上可分为接枝共聚物和嵌段共聚物。然而双吸性共聚物不同于两亲性共聚物，它不仅是亲水、亲油，更重要的是它能吸水又能吸油。若将该聚合物放入油/水的介质中，其亲油和亲水部分将分别在油/水两相介质中伸展、溶胀和吸收，并悬浮在油与水相连的界面处。Amphiphilic graft copolymer (AGP for short) is one of the hotspots in the research field of functional polymer materials. Amphiphilicity refers to hydrophilicity and lipophilicity. It is to link two thermodynamically incompatible chains together through chemical bonds, thereby realizing the assembly of amphiphilic substances at the molecular level. Amphiphilic polymers can be divided into graft copolymers and block copolymers structurally. However, the double-absorbing copolymer is different from the amphiphilic copolymer. It is not only hydrophilic and lipophilic, but more importantly, it can absorb water and oil. If the polymer is placed in an oil/water medium, its lipophilic and hydrophilic parts will respectively stretch, swell and absorb in the oil/water two-phase medium, and be suspended at the interface where the oil and water are connected.
传统的以树脂为基体的单一吸水吸油材料，原料完全来自于石化产品，这类合成产品在自然界要经过500年才能完全降解，对环境造成极大危害。利用自然界中最广泛存在的纤维素，制取具有广阔应用前景的纤维素基吸水吸油材料，以之作为治理工业及日常生活中的废液处理剂来治理环境，不仅会使吸水吸油产品的综合生产成本大幅度降低，而且由于纤维素细小的内部结构，会使吸水吸油材料的吸液性能得到明显改善。同时，由于纤维素材料本身优异的可降解性，还可消除废弃合成吸液剂对环境的污染，维护生态平衡。因此，研究环境友好的可再生的纤维素基吸水吸油材料，不仅可降低对环境的破坏，能源的浪费，还可以使吸水吸油材料生产成本大幅度降低，这对扩大其应用领域也具有重要的意义。The traditional resin-based single water-absorbing and oil-absorbing materials are entirely derived from petrochemical products. This type of synthetic product will take 500 years to completely degrade in nature, causing great harm to the environment. Utilize the most widely existing cellulose in nature to prepare cellulose-based water-absorbing and oil-absorbing materials with broad application prospects, and use them as waste liquid treatment agents in industrial and daily life to treat the environment, which will not only make the water-absorbing and oil-absorbing products comprehensive The production cost is greatly reduced, and the liquid-absorbing performance of the water-absorbing and oil-absorbing material is obviously improved due to the fine internal structure of the cellulose. At the same time, due to the excellent degradability of the cellulose material itself, it can also eliminate the environmental pollution caused by waste synthetic absorbents and maintain the ecological balance. Therefore, research on environmentally friendly and renewable cellulose-based water and oil-absorbing materials can not only reduce environmental damage and energy waste, but also greatly reduce the production cost of water and oil-absorbing materials, which is also important for expanding its application fields. significance.
张明杰等人在化工新型材料，35(1)，59～60，2007中报道了淀粉接枝丙烯酰胺和甲基丙烯酸甲酯制备吸水吸油树脂的方法。该法制得的淀粉基吸水吸油树脂的吸水倍率为8-12g/g，吸油倍率为4-7g/g。其采用非均相聚合，使产物吸水吸油倍率不高，缺乏社会和经济效益。Zhang Mingjie et al reported a method for preparing water-absorbing and oil-absorbing resins by grafting starch with acrylamide and methyl methacrylate in New Chemical Materials, 35(1), 59-60, 2007. The starch-based water-absorbing and oil-absorbing resin prepared by the method has a water absorption rate of 8-12 g/g, and an oil absorption rate of 4-7 g/g. It adopts heterogeneous phase polymerization, so that the water and oil absorption rate of the product is not high, and it lacks social and economic benefits.
曹爱丽等人在精细化工，21(1)，90～94，2004中报道了一种用分散法制备吸水吸油树脂的方法。采用聚乙烯吡咯烷酮为分散剂，苯乙烯和甲基丙烯酸为共聚单体，偶氮二异丁腈为引发剂，二乙烯苯为交联剂，合成出吸水倍率为4.2g/g、吸油倍率为7.2g/g，具有双吸功能的聚物。同样，其吸水吸油效果不够理想，产品环保性较低，缺乏经济实用性。因此，需要寻找一种更为环境友好且经济实用的吸水吸油材料的制备方法。Cao Aili et al reported a method for preparing water-absorbing and oil-absorbing resins by dispersion method in Fine Chemical Industry, 21(1), 90-94, 2004. Using polyvinylpyrrolidone as the dispersant, styrene and methacrylic acid as the comonomer, azobisisobutyronitrile as the initiator, and divinylbenzene as the crosslinking agent, the water absorption rate is 4.2g/g and the oil absorption rate is 4.2g/g. 7.2g/g, polymer with double suction function. Equally, its water-absorbing and oil-absorbing effect is not ideal enough, and product environmental protection is lower, lacks economical practicability. Therefore, it is necessary to find a more environmentally friendly and economical and practical method for preparing water and oil-absorbing materials.
发明内容Contents of the invention
本发明的目的在于提供一种纤维素基吸水吸油薄膜的制备方法，包括如下步骤：The object of the present invention is to provide a kind of preparation method of cellulose-based water-absorbing oil-absorbing film, comprising the steps:
①将木质纤维素与质量浓度为75％的乙二胺水溶液按质量比为1∶15～20混合，在40℃下搅拌4h，过滤，洗涤至中性，压榨，得木质纤维素I；其中，所述的木质纤维素的聚合度为400～1500；① Mix lignocellulose and ethylenediamine aqueous solution with a mass concentration of 75% in a mass ratio of 1:15-20, stir at 40°C for 4 hours, filter, wash until neutral, and press to obtain lignocellulose I; , the degree of polymerization of the lignocellulose is 400-1500;
②将步骤①得到的木质纤维素I与碱性物质水溶液按质量比为100∶3～6混合，在-10～-20℃下，冷冻1～5h后，室温搅拌，得均匀、透明的混合液I；其中，所述的碱性物质为氢氧化钠与尿素或硫脲的混合物；②Mix the lignocellulose I obtained in step ① with the aqueous solution of alkaline substances in a mass ratio of 100:3~6, freeze at -10~-20°C for 1~5 hours, and stir at room temperature to obtain a uniform and transparent mixture Liquid I; Wherein, described alkaline substance is the mixture of sodium hydroxide and urea or thiourea;
③惰性气体保护下，向混合液I中加入引发剂，在30～60℃下搅拌0.5～1h；其中，所述的引发剂与木质纤维素的质量比为0.01～0.06∶1；③Under the protection of an inert gas, add an initiator to the mixed liquid I, and stir at 30-60° C. for 0.5-1 h; wherein, the mass ratio of the initiator to lignocellulose is 0.01-0.06:1;
④加入木质纤维素质量的1～4倍的单体，在40～70℃下，搅拌1～6h，加入N，N-亚甲基双丙烯酰胺，继续搅拌1～3h，得混合液II；其中，所述的单体为丙烯酰胺和甲基丙烯酸丁酯，所述的N，N-亚甲基双丙烯酰胺与木质纤维素的质量比为0.005～0.04∶1；④ Add monomers 1 to 4 times the weight of lignocellulose, stir for 1 to 6 hours at 40 to 70 ° C, add N, N-methylenebisacrylamide, and continue stirring for 1 to 3 hours to obtain the mixed solution II; Wherein, the monomers are acrylamide and butyl methacrylate, and the mass ratio of N,N-methylenebisacrylamide to lignocellulose is 0.005-0.04:1;
⑤将混合液II离心，刮膜，后置于10wt％的H2SO4和12wt％的Na2SO4混合水溶液中凝固30min，水洗、乙醇洗，晾干，得到纤维素基吸水吸油薄膜。⑤ Centrifuge the mixed solution II, scrape the film, put it in a mixed aqueous solution of 10wt%H2SO4 and 12wt%Na2SO4 for30min , wash with water andethanol , and dry to obtain a cellulose-based water-absorbing and oil-absorbing film.
上述制备方法中，为了优化技术方案，木质纤维素预处理为块状。碱性物质水溶液中氢氧化钠的加入量优选为碱性物质水溶液质量的5～10％，尿素或硫脲的加入量优选为碱性物质水溶液质量的4～12％。In the above preparation method, in order to optimize the technical solution, the lignocellulose is pretreated into block. The added amount of sodium hydroxide in the alkaline substance aqueous solution is preferably 5-10% of the mass of the alkaline substance aqueous solution, and the addition of urea or thiourea is preferably 4-12% of the mass of the alkaline substance aqueous solution.
上述制备方法中，引发剂优选为过硫酸钾，过硫酸铵或过氧化苯甲酰；最优选的是过硫酸钾。In the above preparation method, the initiator is preferably potassium persulfate, ammonium persulfate or benzoyl peroxide; the most preferred is potassium persulfate.
上述制备方法中，为了使接枝效果较好，单体中丙烯酰胺与甲基丙烯酸丁酯优选的质量比为0.25～4∶1。In the above preparation method, in order to make the grafting effect better, the preferred mass ratio of acrylamide to butyl methacrylate in the monomer is 0.25-4:1.
上述反应中，为了进一步的优化，离心优选为在转速为4000～8000r/min，时间为15～30min下进行。In the above reaction, for further optimization, the centrifugation is preferably carried out at a rotational speed of 4000-8000 r/min and a time of 15-30 min.
本发明的另一目的在于提供上述任一所述方法制备得到的纤维素基吸水吸油薄膜。Another object of the present invention is to provide a cellulose-based water-absorbing and oil-absorbing film prepared by any one of the methods described above.
因此，本发明具有以下优点：Therefore, the present invention has the following advantages:
1、本发明实现了纤维素与丙烯酰胺和甲基丙烯酸丁酯的均相接枝共聚，有效避免了非均相聚合微观相分离，接枝效果不理想，组分分布不均匀的问题。1. The invention realizes the homogeneous graft copolymerization of cellulose, acrylamide and butyl methacrylate, which effectively avoids the problems of heterogeneous polymerization microscopic phase separation, unsatisfactory grafting effect and uneven distribution of components.
2、本发明中由于基体材料纤维素本身具有优良的可降解性，可消除废弃合成材料对环境的污染，维护生态平衡，从而满足了一般吸水吸油材料不能同时解决吸水吸油性和生物降解问题的需求。2. In the present invention, since the base material cellulose itself has excellent degradability, it can eliminate the pollution of waste synthetic materials to the environment and maintain ecological balance, thereby satisfying the problem that general water-absorbing and oil-absorbing materials cannot simultaneously solve the problems of water-absorbing, oil-absorbing and biodegradation. need.
3、本发明的原料来源广泛，聚合单体易得且价廉，反应工艺简单，综合生产成本大幅度降低。3. The raw material source of the present invention is wide, the polymerization monomer is easy to obtain and cheap, the reaction process is simple, and the comprehensive production cost is greatly reduced.
4、本发明所采用的溶剂体系比现有的铜氨溶液、离子液体更环保，成本更低，更有利于实现工业化生产，具有重要的社会和经济效益。4. Compared with the existing cuproammonia solution and ionic liquid, the solvent system adopted in the present invention is more environmentally friendly, has lower cost, is more conducive to realizing industrial production, and has important social and economic benefits.
5、本发明所制得的产物为功能薄膜，使用轻巧方便，使应用领域更加广泛。5. The product prepared by the present invention is a functional film, which is light and convenient to use, making the application field more extensive.
具体实施方式Detailed ways
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。The following non-limiting examples can enable those skilled in the art to understand the present invention more fully, but do not limit the present invention in any way.
本发明中通过测定吸水倍率和吸油倍率来考察纤维素基吸水吸油薄膜的性能，吸水倍率和吸油倍率的数值越大其薄膜的性能越好。In the present invention, the performance of the cellulose-based water-absorbing and oil-absorbing film is investigated by measuring the water-absorbing ratio and the oil-absorbing ratio. The larger the values of the water-absorbing ratio and the oil-absorbing ratio, the better the film performance.
1、吸水倍率测定：1. Determination of water absorption ratio:
吸水倍率(Q1，g/g)：准确称取一定量的功能薄膜(m1，g)置于一定量的去离子水中，在室温下，静置24h充分吸液后，经200目的铜网过滤，称重(m2，g)，计算产物吸水倍率；Water absorption rate (Q1 , g/g): Accurately weigh a certain amount of functional film (m1 , g) and place it in a certain amount of deionized water. After standing for 24 hours at room temperature to fully absorb the liquid, pass through 200-mesh copper Net filtration, weighing (m2 , g), and calculating the water absorption ratio of the product;
计算式为：Q1＝(m2-m1)/m1The calculation formula is: Q1 =(m2 -m1 )/m1
2、吸油倍率测定：2. Determination of oil absorption ratio:
吸油倍率(Q2，g/g)：准确称取一定量的聚合产物(m3，g)置于一定量的大豆油中，在室温下，静置24h充分吸液后，经200目的铜网过滤，称重(m4，g)，计算产物吸水倍率。Oil absorption rate (Q2 , g/g): Accurately weigh a certain amount of polymer product (m3 , g) and place it in a certain amount of soybean oil. After standing for 24 hours at room temperature to fully absorb the liquid, pass through 200-mesh copper Filter through a mesh, weigh (m4 , g), and calculate the water absorption capacity of the product.
计算式为：Q2＝(m4-m3)/m3The calculation formula is: Q2 =(m4 -m3 )/m3
实施例1Example 1
①将聚合度为548的纤维素5.0g粉碎成块状，置于250ml的三口烧瓶中，在40℃下，加入100g质量分数为75％的乙二胺溶液，搅拌反应4h，抽滤，蒸馏水洗涤至中性，压榨待用；①Crush 5.0g of cellulose with a degree of polymerization of 548 into blocks, put it in a 250ml three-neck flask, add 100g of ethylenediamine solution with a mass fraction of 75% at 40°C, stir for 4 hours, filter with suction, distilled water Wash until neutral, press for use;
②加入100g含有5wt％的氢氧化钠和8wt％的尿素的碱性物质水溶液，在-12℃下，冷冻5h，室温搅拌，得到均匀、透明的混合液I；②Add 100g of an aqueous solution of alkaline substances containing 5wt% sodium hydroxide and 8wt% urea, freeze for 5 hours at -12°C, and stir at room temperature to obtain a uniform and transparent mixed solution I;
③加入0.24g的过硫酸钾，搅拌反应0.5h；③Add 0.24g of potassium persulfate and stir for 0.5h;
④加入2.5g的丙烯酰胺和2.5g的甲基丙烯酸丁酯，搅拌下升温至70℃，恒温反应2h，加入0.08g N，N-亚甲基双丙烯酰胺，继续搅拌反应1h，得混合液II；④Add 2.5g of acrylamide and 2.5g of butyl methacrylate, raise the temperature to 70°C under stirring, react at constant temperature for 2h, add 0.08g of N,N-methylenebisacrylamide, continue stirring for 1h to obtain a mixed solution II;
⑤将混合液II在离心机上以5000r/min的转速下脱泡20min后，在玻璃板上流延刮膜，而后将膜置于质量分数为10wt％H2SO4和12wt％Na2SO4的混合水溶液中凝固30min，经水洗，乙醇洗，晾干，得到纤维素基吸水吸油薄膜。⑤ After degassing the mixed solution II on a centrifuge at a speed of 5000r/min for 20min, cast the scraped film on a glass plate, and then place the film in an environment with a mass fraction of 10wt% H2 SO4 and 12wt% Na2 SO4 Solidify in the mixed aqueous solution for 30 minutes, wash with water and ethanol, and dry to obtain a cellulose-based water-absorbing and oil-absorbing film.
纤维素基吸水吸油薄膜的吸水吸油测试结果：Water and oil absorption test results of cellulose-based water and oil absorption film:
测试样品 吸液倍率(Q，g/g)Test sample Suction ratio (Q, g/g)
水 23.51Water 23.51
大豆油 11.55。Soybean Oil 11.55.
实施例2Example 2
①将聚合度为655的纤维素4.0g粉碎成块状，置于250ml的三口烧瓶中，在40℃下，加入80g质量分数为75％的乙二胺溶液搅拌反应4h，抽滤，水洗涤至中性，压榨待用；①Crush 4.0g of cellulose with a degree of polymerization of 655 into blocks, put it in a 250ml three-neck flask, add 80g of ethylenediamine solution with a mass fraction of 75% at 40°C, stir for 4 hours, filter with suction, and wash with water to neutral, pressed for use;
②加入100g含有7wt％氢氧化钠和12wt％的尿素的碱性物质水溶液中，在-12℃下，冷冻5小时，室温搅拌，得到均匀、透明的混合液I；② Add 100 g of alkaline substance aqueous solution containing 7wt% sodium hydroxide and 12wt% urea, freeze at -12°C for 5 hours, and stir at room temperature to obtain a uniform and transparent mixed solution I;
③加入0.18g的过硫酸钾，搅拌反应0.5h；③Add 0.18g of potassium persulfate and stir for 0.5h;
④加入2.5g的丙烯酰胺和1.5g的甲基丙烯酸丁酯，搅拌下升温至60℃，恒温反应2h，加入0.06g N，N-亚甲基双丙烯酰胺，继续搅拌反应1h，得混合液II；④Add 2.5g of acrylamide and 1.5g of butyl methacrylate, raise the temperature to 60°C under stirring, react at constant temperature for 2h, add 0.06g of N,N-methylenebisacrylamide, continue stirring for 1h to obtain a mixed solution II;
⑤将混合液II在离心机上以5000r/min的转速下脱泡15min后，在玻璃板上流延刮膜，而后将膜置于质量分数为10wt％H2SO4和12wt％Na2SO4的混合水溶液中凝固30min，经水洗，乙醇洗，晾干，得到纤维素基吸水吸油薄膜。⑤ After degassing the mixed solution II on a centrifuge at a speed of 5000r/min for 15 minutes, cast the scraped film on a glass plate, and then place the film in a solution with a mass fraction of 10wt% H2 SO4 and 12wt% Na2 SO4 Solidify in the mixed aqueous solution for 30 minutes, wash with water and ethanol, and dry to obtain a cellulose-based water-absorbing and oil-absorbing film.
纤维素基吸水吸油薄膜的吸水吸油测试结果：Water and oil absorption test results of cellulose-based water and oil absorption film:
测试样品 吸液倍率(Q，g/g)Test sample Suction ratio (Q, g/g)
水 21.83Water 21.83
大豆油 10.21。Soybean oil 10.21.
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| CN104987466A (en)* | 2015-07-06 | 2015-10-21 | 安徽成方新材料科技有限公司 | Polymer absorbent with enhanced polydimethylsiloxane modified cellulose and preparation method thereof |
| CN105131187A (en)* | 2015-10-09 | 2015-12-09 | 厦门大学 | Modified regenerated cellulose membrane and preparation method and application thereof |
| CN111304949A (en)* | 2020-03-02 | 2020-06-19 | 赛尔睿思复合新材料科技(苏州)有限公司 | Water-absorbing and oil-absorbing paper-like material and preparation method thereof |
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| CN101565488A (en)* | 2009-06-01 | 2009-10-28 | 新疆大学 | Preparation method of cellulose-based oil-absorption material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565488A (en)* | 2009-06-01 | 2009-10-28 | 新疆大学 | Preparation method of cellulose-based oil-absorption material |
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| CN104987466A (en)* | 2015-07-06 | 2015-10-21 | 安徽成方新材料科技有限公司 | Polymer absorbent with enhanced polydimethylsiloxane modified cellulose and preparation method thereof |
| CN105131187A (en)* | 2015-10-09 | 2015-12-09 | 厦门大学 | Modified regenerated cellulose membrane and preparation method and application thereof |
| CN111304949A (en)* | 2020-03-02 | 2020-06-19 | 赛尔睿思复合新材料科技(苏州)有限公司 | Water-absorbing and oil-absorbing paper-like material and preparation method thereof |
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| CN102604134B (en) | 2013-12-04 |
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