CN1702100A - Microporous membrane and its preparing process and use thereof - Google Patents
Microporous membrane and its preparing process and use thereof Download PDFInfo
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- CN1702100A CN1702100A CN 200510018798 CN200510018798A CN1702100A CN 1702100 A CN1702100 A CN 1702100A CN 200510018798 CN200510018798 CN 200510018798 CN 200510018798 A CN200510018798 A CN 200510018798A CN 1702100 A CN1702100 A CN 1702100A
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- 239000012982 microporous membrane Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 18
- 229920002678 cellulose Polymers 0.000 claims abstract description 40
- 239000001913 cellulose Substances 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- 238000005345 coagulation Methods 0.000 claims abstract description 9
- 230000015271 coagulation Effects 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000004907 flux Effects 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 229920005372 Plexiglas® Polymers 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 12
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000007790 scraping Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 6
- 239000004627 regenerated cellulose Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一种微孔膜及其制备方法和用途。该微孔膜由纤维素构成，为多孔网眼结构，平均孔径小于60nm，孔隙率为81～87％。其制法为：在室温下，用经－8℃～－15℃预冷的7～8wt％的氢氧化钠和11～12wt％尿素水溶液溶解纤维素，制成纤维素浓溶液，以流延法在玻璃板上刮膜，在凝固浴中凝固再生后得到微孔膜。本发明的微孔膜具有厚度薄、均相多孔的网眼结构、孔径分布窄、较好的渗透性能以及优良的力学性能和透光率等优点，而且制造方法简单、生产成本低廉。可用于农业、化工、食品、环境领域中的育苗、覆盖、透气性包装及分离材料。
The invention discloses a microporous membrane, a preparation method and application thereof. The microporous membrane is made of cellulose and has a porous mesh structure, the average pore diameter is less than 60nm, and the porosity is 81-87%. The preparation method is as follows: at room temperature, dissolve cellulose with 7-8wt% sodium hydroxide and 11-12wt% urea aqueous solution pre-cooled at -8°C to -15°C to make a concentrated cellulose solution and cast Scrape the film on a glass plate by scraping the film, and obtain a microporous film after coagulation and regeneration in a coagulation bath. The microporous membrane of the present invention has the advantages of thin thickness, homogeneous porous mesh structure, narrow pore size distribution, good permeability, excellent mechanical properties and light transmittance, and the manufacturing method is simple and the production cost is low. It can be used for seedling raising, covering, air-permeable packaging and separation materials in the fields of agriculture, chemical industry, food and environment.
Description
技术领域technical field
本发明涉及一种微孔膜及其制备方法和用途，属于天然高分子领域，也属于化学化工、农业、环境工程、分离工程领域。The invention relates to a microporous membrane, a preparation method and application thereof, and belongs to the field of natural polymers, and also belongs to the fields of chemical engineering, agriculture, environmental engineering, and separation engineering.
背景技术Background technique
植物纤维素是地球最丰富的可再生资源，可望成为21世纪的主要化工原料之一。然而，传统上纤维素加工制膜总是通过化学改性的办法，即将纤维素转变成可溶性的纤维素衍生物，再用溶剂再生得到再生纤维素膜如常见的由粘胶法生产的赛珞玢(Cellphane)或者由铜氨法生产的再生铜氨纤维素膜(Cuprophane)(ZL 02132866.8)。迄今已工业化的粘胶法制备玻璃纸已有100多年历史，由于生产中存在严重环境污染，包括粘胶制备过程中CS2的引入、凝固再生过程中纤维素黄原酸酯遇酸分解释放的H2S和SO2以及废液中Zn2+的排放等问题(J.Macromol.Sci.-Rev.Macromol.Chem.，1980，C18(1)，1)，致使不少发达国家已关闭粘胶法生产玻璃纸的工厂。近年出现了新溶剂，即N-甲基氧化吗啉(NMMO)(J.Polym.Sci.：Polym.Lett.Ed.1979，17，219)，而且1989年布鲁塞尔国际人造丝及合成纤维标准局(BISFA)把由这类方法制造的纤维素纤维的分类定名为“Lyocell”。但由于其价格昂贵、纺丝温度高，工业化生产发展缓慢。此外，已报道纤维素和尿素在高温下反应生成纤维素氨基甲酸酯，然后直接溶解在稀碱中得到纺丝液(Finnish Patent 61003；Finnish Patent 62318；U.S.Patent 4404369)，但是尿素用量高，而且还有副产物，难以大规模产业化。最近，我们采用7～8wt％NaOH/10～12wt％尿素水溶液预冷到-8℃～-12℃，立即加入棉短绒纤维素，在室温搅拌下可快速溶解纤维素(ZL 03128386.1)。该种方法由于快速简单的纤维素溶解步骤以及价廉、无污染的溶剂体系，使其在工业上具有应用前景。Plant cellulose is the most abundant renewable resource on earth and is expected to become one of the main chemical raw materials in the 21st century. However, traditionally, cellulose processing and film production is always through chemical modification, that is, converting cellulose into soluble cellulose derivatives, and then regenerating with solvents to obtain regenerated cellulose films, such as the common celluloid produced by the viscose method. Cellphane or regenerated cuprophane (Cuprophane) produced by the copper ammonia method (ZL 02132866.8). So far, the viscose method that has been industrialized to prepare cellophane has a history of more than 100 years. Due to the serious environmental pollution in the production, including the introduction of CS 2 in the viscose preparation process, and the H released from the decomposition of cellulose xanthate in the process of solidification and regeneration when encountering acid 2 S and SO 2 and the discharge of Zn 2+ in waste liquid (J.Macromol.Sci.-Rev.Macromol.Chem., 1980, C18(1), 1), resulting in many developed countries have closed viscose A factory that produces cellophane. In recent years, a new solvent has emerged, namely N-methylmorpholine oxide (NMMO) (J.Polym.Sci.: Polym.Lett.Ed.1979, 17, 219), and in 1989 Brussels International Rayon and Synthetic Fiber Standards Bureau (BISFA) designates the classification of cellulose fibers produced by this method as "Lyocell". However, due to its high price and high spinning temperature, the development of industrial production is slow. In addition, it has been reported that cellulose and urea react at high temperature to generate cellulose carbamate, which is then directly dissolved in dilute alkali to obtain spinning solution (Finnish Patent 61003; Finnish Patent 62318; USPatent 4404369), but the amount of urea is high, and There are also by-products, which are difficult to industrialize on a large scale. Recently, we use 7-8wt% NaOH/10-12wt% urea aqueous solution to pre-cool to -8°C--12°C, add cotton linters cellulose immediately, and dissolve the cellulose quickly under stirring at room temperature (ZL 03128386.1). This method is promising in industry due to the fast and simple cellulose dissolution step and the cheap and non-polluting solvent system.
发明内容Contents of the invention
本发明的目的是提供一种微孔膜及其制备方法和用途，所得到的微孔膜可作为透气性和渗透性覆盖、包装及分离材料。The object of the present invention is to provide a microporous membrane and its preparation method and application. The obtained microporous membrane can be used as air-permeable and permeable covering, packaging and separation materials.
为实现上述目的，本发明提供的技术方案是：一种微孔膜，该微孔膜由纤维素构成，为多孔网眼结构，平均孔径小于60nm，孔隙率为81～87％。To achieve the above object, the technical solution provided by the present invention is: a microporous membrane, which is made of cellulose and has a porous mesh structure, with an average pore diameter of less than 60nm and a porosity of 81-87%.
上述微孔膜具有直通孔，微孔膜水流通量为25-250mLh-1m-2mmHg-1。The above-mentioned microporous membrane has through holes, and the water flux of the microporous membrane is 25-250 mLh -1 m -2 mmHg -1 .
本发明还提供了上述微孔膜的制备方法，在室温下，用经-8℃～-15℃预冷的7～8wt％的氢氧化钠和11～12wt％尿素水溶液溶解纤维素，制成纤维素浓溶液，以流延法在玻璃板上刮膜，在凝固浴中凝固再生后得到微孔膜；所述凝固浴为5～20wt％Na2SO4的水溶液、3～20wt％(NH4)2SO4的水溶液、H2O、C2H5OH或(CH3)2CO，凝固时间为10～25min，凝固温度为0～55℃。The present invention also provides a preparation method of the above-mentioned microporous membrane, which is prepared by dissolving cellulose with 7-8wt% sodium hydroxide and 11-12wt% urea aqueous solution pre-cooled at -8°C to -15°C at room temperature. Concentrated cellulose solution, scraping the film on a glass plate by casting, coagulating and regenerating in a coagulation bath to obtain a microporous film; 4 ) For aqueous solution of 2 SO 4 , H 2 O, C 2 H 5 OH or (CH 3 ) 2 CO, the coagulation time is 10-25 minutes, and the coagulation temperature is 0-55°C.
将制得的微孔膜可保存在2％甲醛/20％异丙醇中用作纤维素多孔膜，也可固定在有机玻璃板上在空气中晾干制成透气性透明纤维素膜。The prepared microporous membrane can be stored in 2% formaldehyde/20% isopropanol to be used as a cellulose porous membrane, and can also be fixed on a plexiglass plate and dried in the air to make a breathable transparent cellulose membrane.
上述纤维素浓溶液为3-6wt％的纤维素溶液。The above concentrated cellulose solution is a 3-6 wt% cellulose solution.
本发明制得的微孔膜在农业、化工、食品或环境领域中作为育苗、覆盖或透气性包装或分离材料的应用。The microporous membrane prepared by the invention can be used as seedling raising, covering or air-permeable packaging or separation material in the field of agriculture, chemical industry, food or environment.
与已有技术相比，本发明具有显著技术进步。首先本方法是在预冷的氢氧化钠/尿素水溶液直接快速溶解纤维素，然后制备出微孔膜。它与传统的粘胶法和铜氨法以及03128386.1号专利申请的方法相比，通过对凝固剂和凝固条件的选择，使得本发明制得的微孔膜具有厚度薄、均匀的多孔网眼结构、较大的平均孔径、孔径分布窄、较好的渗透性能、较均匀的直通孔以及较高的力学性能和透光率，而且制造方法简单、生产成本低廉。可广泛用于农业、化工、食品、环境领域中的育苗、覆盖、透气性包装及分离材料。Compared with the prior art, the present invention has significant technical progress. Firstly, the method is to directly and rapidly dissolve cellulose in a precooled sodium hydroxide/urea aqueous solution, and then prepare a microporous membrane. Compared with the traditional viscose method, copper ammonia method and the method of No. 03128386.1 patent application, the microporous membrane made by the present invention has a thin, uniform porous mesh structure, Larger average pore size, narrow pore size distribution, better permeability, more uniform straight through holes, higher mechanical properties and light transmittance, and simple manufacturing method and low production cost. It can be widely used in seedling raising, covering, air-permeable packaging and separation materials in the fields of agriculture, chemical industry, food and environment.
附图说明Description of drawings
附图为本发明制得的微孔膜的扫描电镜图；其中图(a)为微孔膜与凝固剂接触的一面的扫描电镜图；图(b)为微孔膜截面的扫描电镜图；图(c)为微孔膜与玻璃板接触的一面的扫描电镜图。Accompanying drawing is the scanning electron microscope picture of the microporous membrane that the present invention makes; Wherein figure (a) is the scanning electron microscope picture of the side that microporous membrane contacts with coagulant; Figure (b) is the scanning electron microscope picture of microporous membrane section; Figure (c) is a scanning electron microscope image of the side of the microporous membrane in contact with the glass plate.
具体实施方式Detailed ways
以下结合具体的实施例对本发明的技术方案作进一步说明：The technical scheme of the present invention is further described below in conjunction with specific embodiment:
实施例1Example 1
取棉短绒纤维素浆(聚合度500)8.4g，加入200g预冷至-10℃的7wt％NaOH/12wt％尿素混合水溶液中，在室温下搅拌5分钟，纤维素完全溶解。用超速离心机在10,000转/分钟，15℃下离心30分钟使之脱气，得到透明的纤维素溶液。用两端系有铜丝(直径0.5mm)的玻管在玻璃板上刮膜后立即放入15℃、15wt％Na2SO4水溶液中凝固、再生15分钟后取出，用水冲洗干净。湿膜保存在2wt％甲醛/20wt％异丙醇水溶液中作为多孔膜用于分离和渗透等。该湿膜直接进行孔径和水流通量的测定。为测定其力学性能将湿膜贴在有机玻璃板上于空气中自然晾干得到再生纤维素膜，它可用作透气性和具有渗透能力的包装和覆盖膜材料。由流速法和小型超滤装置测得其平均孔径(2rf)、孔隙率(Pr)和水流通量(J)。其抗张强度(σb)与断裂伸长率(εb)在拉力试验机上根据国际标准ISO 527-2，1993(E)测定。透光率(Tr)用紫外-可见光谱仪测得(400～800nm)。Take 8.4 g of cotton linter cellulose pulp (500 degree of polymerization), add 200 g of 7wt% NaOH/12wt% urea mixed aqueous solution precooled to -10°C, stir at room temperature for 5 minutes, and the cellulose is completely dissolved. Centrifuge at 10,000 rpm at 15° C. for 30 minutes with an ultracentrifuge to degas it to obtain a transparent cellulose solution. Use a glass tube with copper wires (diameter 0.5 mm) tied at both ends to scrape the film on the glass plate, immediately put it into 15°C, 15wt% Na 2 SO 4 aqueous solution to solidify, regenerate for 15 minutes, take it out, and rinse it with water. Wet membranes were kept in 2 wt% formaldehyde/20 wt% isopropanol aqueous solution as porous membranes for separation and permeation etc. The wet membranes were directly subjected to pore size and water flux measurements. In order to measure its mechanical properties, the wet film is pasted on a plexiglass plate and dried naturally in the air to obtain a regenerated cellulose film, which can be used as a packaging and covering film material with air permeability and permeability. The average pore size (2r f ), porosity (P r ) and water flux (J) were measured by flow velocity method and small ultrafiltration device. Its tensile strength (σ b ) and elongation at break (ε b ) are measured on a tensile testing machine according to the international standard ISO 527-2, 1993 (E). The light transmittance (T r ) was measured with an ultraviolet-visible spectrometer (400-800nm).
实施例2Example 2
取棉短绒纤维素浆(聚合度500)8.4g，加入200g预冷至-12℃的7wt％NaOH/11wt％尿素混合水溶液中，在室温下搅拌5分钟，纤维素完全溶解。用超速离心机在10,000转/分钟，15℃下离心30分钟使之脱气，得到透明的纤维素溶液。用两端系有铜丝(直径0.5mm)的玻管在玻璃板上刮膜后立即放入25℃、5wt％(NH4)2SO4水溶液中凝固、再生10分钟后取出，用水冲洗干净。湿膜保存在2wt％甲醛/20wt％异丙醇水溶液中作为多孔膜用于分离和渗透等。该湿膜直接进行孔径和水流通量的测定。为测定其力学性能将湿膜贴在有机玻璃板上于空气中自然晾干得到再生纤维素膜，它可用作透气性和具有渗透能力的包装和覆盖膜材料。由流速法和小型超滤装置测得其平均孔径(2rf)、孔隙率(Pr)和水流通量(J)。其抗张强度(σb)与断裂伸长率(εb)在拉力试验机上根据国际标准ISO 527-2，1993(E)测定。透光率(Tr)用紫外-可见光谱仪测得(400～800nm)。Take 8.4 g of cotton linter cellulose pulp (polymerization degree 500), add 200 g of 7wt% NaOH/11wt% urea mixed aqueous solution precooled to -12°C, stir at room temperature for 5 minutes, and the cellulose is completely dissolved. Centrifuge at 10,000 rpm at 15° C. for 30 minutes with an ultracentrifuge to degas it to obtain a transparent cellulose solution. Use a glass tube with copper wires (diameter 0.5mm) tied at both ends to scrape the film on the glass plate, immediately put it in 25°C, 5wt% (NH 4 ) 2 SO 4 aqueous solution to solidify, regenerate for 10 minutes, take it out, and rinse it with water . Wet membranes were kept in 2 wt% formaldehyde/20 wt% isopropanol aqueous solution as porous membranes for separation and permeation etc. The wet membranes were directly subjected to pore size and water flux measurements. In order to measure its mechanical properties, the wet film is pasted on a plexiglass plate and dried naturally in the air to obtain a regenerated cellulose film, which can be used as a packaging and covering film material with air permeability and permeability. The average pore size (2r f ), porosity (P r ) and water flux (J) were measured by flow velocity method and small ultrafiltration device. Its tensile strength (σ b ) and elongation at break (ε b ) are measured on a tensile testing machine according to the international standard ISO 527-2, 1993 (E). The light transmittance (T r ) was measured with an ultraviolet-visible spectrometer (400-800nm).
实施例3Example 3
取棉短绒纤维素浆(聚合度500)8.4g，加入200g预冷至-10℃的7wt％NaOH/12wt％尿素混合水溶液中，在室温下搅拌5分钟，纤维素完全溶解。用超速离心机在10,000转/分钟，15℃下离心30分钟使之脱气，得到透明的纤维素溶液。用两端系有铜丝(直径0.5mm)的玻管在玻璃板上刮膜后立即放入25℃、纯水中凝固、再生15分钟后取出，用水冲洗干净。湿膜保存在2wt％甲醛/20wt％异丙醇水溶液中作为多孔膜用于分离和渗透等。该湿膜直接进行孔径和水流通量的测定。为测定其力学性能将湿膜贴在有机玻璃板上于空气中自然晾干得到再生纤维素膜，它可用作透气性和具有渗透能力的包装和覆盖膜材料。由流速法和小型超滤装置测得其平均孔径(2rf)、孔隙率(Pr)和水流通量(J)。其抗张强度(σb)与断裂伸长率(εb)在拉力试验机上根据国际标准ISO 527-2，1993(E)测定。透光率(Tr)用紫外-可见光谱仪测得(400～800nm)。Take 8.4 g of cotton linter cellulose pulp (500 degree of polymerization), add 200 g of 7wt% NaOH/12wt% urea mixed aqueous solution precooled to -10°C, stir at room temperature for 5 minutes, and the cellulose is completely dissolved. Centrifuge at 10,000 rpm at 15° C. for 30 minutes with an ultracentrifuge to degas it to obtain a transparent cellulose solution. Use a glass tube with copper wires (diameter 0.5mm) tied at both ends to scrape the film on the glass plate and immediately put it in pure water at 25°C to solidify, regenerate for 15 minutes, take it out, and rinse it with water. Wet membranes were kept in 2 wt% formaldehyde/20 wt% isopropanol aqueous solution as porous membranes for separation and permeation etc. The wet membranes were directly subjected to pore size and water flux measurements. In order to measure its mechanical properties, the wet film is pasted on a plexiglass plate and dried naturally in the air to obtain a regenerated cellulose film, which can be used as a packaging and covering film material with air permeability and permeability. The average pore size (2r f ), porosity (P r ) and water flux (J) were measured by flow velocity method and small ultrafiltration device. Its tensile strength (σ b ) and elongation at break (ε b ) are measured on a tensile testing machine according to the international standard ISO 527-2, 1993 (E). The light transmittance (T r ) was measured with an ultraviolet-visible spectrometer (400-800nm).
实施例4Example 4
取棉短绒纤维素浆(聚合度500)8.4g，加入200g预冷至-13℃的8wt％NaOH/12wt％尿素混合水溶液中，在室温下搅拌5分钟，纤维素完全溶解。用超速离心机在10,000转/分钟，15℃下离心30分钟使之脱气，得到透明的纤维素溶液。用两端系有铜丝(直径0.5mm)的玻管在玻璃板上刮膜后立即放入55℃、无水乙醇中凝固、再生20分钟后取出，用水冲洗干净。湿膜保存在2wt％甲醛/20wt％异丙醇水溶液中作为多孔膜用于分离和渗透等。该湿膜直接进行孔径和水流通量的测定。为测定其力学性能将湿膜贴在有机玻璃板上于空气中自然晾干得到再生纤维素膜，它可用作透气性和具有渗透能力的包装和覆盖膜材料。由流速法和小型超滤装置测得其平均孔径(2rf)、孔隙率(Pr)和水流通量(J)。其抗张强度(σb)与断裂伸长率(εb)在拉力试验机上根据国际标准ISO 527-2，1993(E)测定。透光率(Tr)用紫外-可见光谱仪测得(400～800nm)。Take 8.4 g of cotton linter cellulose pulp (500 degree of polymerization), add 200 g of 8 wt% NaOH/12 wt % urea mixed aqueous solution precooled to -13°C, stir at room temperature for 5 minutes, and the cellulose is completely dissolved. Centrifuge at 10,000 rpm at 15° C. for 30 minutes with an ultracentrifuge to degas it to obtain a transparent cellulose solution. Use a glass tube with copper wires (diameter 0.5mm) tied at both ends to scrape the film on the glass plate, immediately put it in 55°C, absolute ethanol to solidify, regenerate for 20 minutes, take it out, and rinse it with water. Wet membranes were kept in 2 wt% formaldehyde/20 wt% isopropanol aqueous solution as porous membranes for separation and permeation etc. The wet membranes were directly subjected to pore size and water flux measurements. In order to measure its mechanical properties, the wet film is pasted on a plexiglass plate and dried naturally in the air to obtain a regenerated cellulose film, which can be used as a packaging and covering film material with air permeability and permeability. The average pore size (2r f ), porosity (P r ) and water flux (J) were measured by flow velocity method and small ultrafiltration device. Its tensile strength (σ b ) and elongation at break (ε b ) are measured on a tensile testing machine according to the international standard ISO 527-2, 1993 (E). The light transmittance (T r ) was measured with an ultraviolet-visible spectrometer (400-800nm).
实施例5Example 5
取棉短绒纤维素浆(聚合度500)8.4g，加入200g预冷至-10℃的7wt％NaOH/12wt％尿素混合水溶液中，在室温下搅拌5分钟，纤维素完全溶解。用超速离心机在10,000转/分钟，15℃下离心30分钟使之脱气，得到透明的纤维素溶液。用两端系有铜丝(直径0.5mm)的玻管在玻璃板上刮膜后立即放入15℃、丙酮中凝固、再生25分钟后取出，用水冲洗干净。湿膜保存在2wt％甲醛/20wt％异丙醇水溶液中作为多孔膜用于分离和渗透等。该湿膜直接进行孔径和水流通量的测定。为测定其力学性能将湿膜贴在有机玻璃板上于空气中自然晾干得到再生纤维素膜，它可用作透气性和具有渗透能力的包装和覆盖膜材料。由流速法和小型超滤装置测得其平均孔径(2rf)、孔隙率(Pr)和水流通量(J)。其抗张强度(σb)与断裂伸长率(εb)在拉力试验机上根据国际标准ISO 527-2，1993(E)测定。透光率(Tr)用紫外-可见光谱仪测得(400～800nm)。Take 8.4 g of cotton linter cellulose pulp (500 degree of polymerization), add 200 g of 7wt% NaOH/12wt% urea mixed aqueous solution precooled to -10°C, stir at room temperature for 5 minutes, and the cellulose is completely dissolved. Centrifuge at 10,000 rpm at 15° C. for 30 minutes with an ultracentrifuge to degas it to obtain a transparent cellulose solution. Use a glass tube with copper wires (diameter 0.5mm) tied at both ends to scrape the film on the glass plate and immediately put it in acetone at 15°C to solidify, regenerate for 25 minutes, take it out, and rinse it with water. Wet membranes were kept in 2 wt% formaldehyde/20 wt% isopropanol aqueous solution as porous membranes for separation and permeation etc. The wet membranes were directly subjected to pore size and water flux measurements. In order to measure its mechanical properties, the wet film is pasted on a plexiglass plate and dried naturally in the air to obtain a regenerated cellulose film, which can be used as a packaging and covering film material with air permeability and permeability. The average pore size (2r f ), porosity (P r ) and water flux (J) were measured by flow velocity method and small ultrafiltration device. Its tensile strength (σ b ) and elongation at break (ε b ) are measured on a tensile testing machine according to the international standard ISO 527-2, 1993 (E). The light transmittance (T r ) was measured with an ultraviolet-visible spectrometer (400-800nm).
以上实施例中各微孔膜的性能测定结果汇集于附表1。附图示出了由扫描电镜观测到的微孔膜的表面(a)(与凝固剂接触的一面)、截面(b)和背面(c)(与玻璃板接触的一面)的形貌。由图可知微孔膜表现出均匀的多孔网眼结构。The performance measurement results of each microporous membrane in the above examples are collected in Attached Table 1. Accompanying drawing shows the morphology of the surface (a) (the side in contact with the coagulant), the section (b) and the back (c) (the side in contact with the glass plate) of the microporous membrane observed by the scanning electron microscope. It can be seen from the figure that the microporous membrane exhibits a uniform porous network structure.
附表1微孔膜的性能测定结果
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