CN108716118A - A kind of preparation process of tea polyphenols modification viscose rayon - Google Patents
A kind of preparation process of tea polyphenols modification viscose rayon Download PDFInfo
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- CN108716118A CN108716118A CN201810553400.3A CN201810553400A CN108716118A CN 108716118 A CN108716118 A CN 108716118A CN 201810553400 A CN201810553400 A CN 201810553400A CN 108716118 A CN108716118 A CN 108716118A
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- 229920000297 Rayon Polymers 0.000 title claims abstract 55
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract 33
- 235000013824 polyphenols Nutrition 0.000 title claims abstract 33
- 241001122767 Theaceae Species 0.000 title claims abstract 32
- 238000002360 preparation method Methods 0.000 title claims abstract 6
- 230000004048 modification Effects 0.000 title abstract 2
- 238000012986 modification Methods 0.000 title abstract 2
- 239000000835 fiber Substances 0.000 claims abstract 55
- 108010059892 Cellulase Proteins 0.000 claims abstract 15
- 229940106157 cellulase Drugs 0.000 claims abstract 15
- 239000004094 surface-active agent Substances 0.000 claims abstract 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 12
- 239000002699 waste material Substances 0.000 claims 10
- 239000007864 aqueous solution Substances 0.000 claims 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 238000001179 sorption measurement Methods 0.000 claims 3
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims 2
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 claims 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 2
- 239000008213 purified water Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 108090000790 Enzymes Proteins 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 230000003471 anti-radiation Effects 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
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- 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
- D06M13/238—Tannins, e.g. gallotannic acids
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- 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
- D06M13/11—Compounds containing epoxy groups or precursors thereof
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Abstract
一种茶多酚修饰粘胶纤维的制备工艺，属于粘胶纤维修饰技术领域。本发明以市售茶多酚和粘胶纤维为原料，通过制备表面活性剂预处理粘胶纤维，制备纤维素酶水解粘胶纤维，制备吸附茶多酚粘胶纤维，制备接枝茶多酚粘胶纤维的步骤，就制备出茶多酚接枝率为8～10％的粘胶纤维。本发明在制备接枝茶多酚粘胶纤维之前，对其进行了纤维素酶水解，使得粘胶纤维发生一定程度的降解，其上的活性羟基得以充分暴露，便于提高茶多酚的接枝率；本发明方法采用具有双环氧官能团的双缩水甘油醚作为反应交联剂，使得粘胶纤维与茶多酚通过化学共价键稳定连接，茶多酚接枝率高，稳定性增强，从而显著提高了产品的抗氧化、抗辐射、抗菌、螯合金属离子等功能。The invention discloses a preparation process of tea polyphenol modified viscose fiber, which belongs to the technical field of viscose fiber modification. The present invention uses commercially available tea polyphenols and viscose fibers as raw materials, pretreats viscose fibers by preparing surfactants, prepares cellulase hydrolyzed viscose fibers, prepares viscose fibers for absorbing tea polyphenols, and prepares grafted tea polyphenols In the step of viscose fiber, viscose fiber with tea polyphenol grafting rate of 8-10% is prepared. Before preparing the grafted tea polyphenol viscose fiber, the present invention performs cellulase hydrolysis on it, so that the viscose fiber is degraded to a certain extent, and the active hydroxyl groups on it can be fully exposed, which is convenient for improving the grafting of tea polyphenols. rate; the inventive method adopts the bisglycidyl ether with two epoxy functional groups as a reactive crosslinking agent, so that the viscose fiber and tea polyphenols are stably connected by chemical covalent bonds, the grafting rate of tea polyphenols is high, and the stability is enhanced. Thereby significantly improving the anti-oxidation, anti-radiation, antibacterial, chelated metal ion and other functions of the product.
Description
一、技术领域1. Technical field
本发明属于粘胶纤维修饰技术领域，具体涉及一种茶多酚修饰粘胶纤维的制备工艺。The invention belongs to the technical field of viscose fiber modification, and in particular relates to a preparation process of tea polyphenol modified viscose fiber.
二、背景技术2. Background technology
粘胶纤维属于再生纤维素，是由D-葡萄糖以β-1，4糖苷键连接成的高分子聚合物。由于纤维素分子中存在大量亲水羟基，致使粘胶纤维制品具有良好的吸湿、透气性和亲肤性能，加之柔软而保暖，成为纺织工业的重要原料。但是，粘胶纤维也存在弹性差、易皱、洗后易走型和缩水、保型性较差等缺陷；有实验证明，附于纤维上的某些微生物可利用纤维素羟基吸附的水分繁殖生长，分泌降解β-1，4糖苷键的酶，降解纤维素成可利用的葡萄糖，这不但破坏纤维的结构和强度，还进一步导致织物生霉斑进而污染肌肤；除此之外，具有亲肤性能的该纤维却难以阻止自由基对机体的氧化作用，并且缺少抗辐射官能团，也不具备吸附金属离子的位点，这些缺陷使其不能满足现代织物的差异化、功能化和舒适性的需求，进而限制其应用领域的进一步拓展。为了充分开发粘胶纤维潜在的功能，对粘胶纤维进行各种改性研究、提高粘胶纤维的附加值和性能已成为人们研究的一大方向。Viscose fiber belongs to regenerated cellulose, which is a polymer composed of D-glucose linked by β-1,4 glycosidic bonds. Due to the presence of a large number of hydrophilic hydroxyl groups in cellulose molecules, viscose fiber products have good moisture absorption, air permeability and skin-friendly properties, plus they are soft and warm, and have become important raw materials for the textile industry. However, viscose fiber also has defects such as poor elasticity, easy to wrinkle, easy to take shape and shrink after washing, and poor shape retention; experiments have proved that some microorganisms attached to the fiber can use the water absorbed by the cellulose hydroxyl group to reproduce. Growth, secretion of enzymes that degrade β-1, 4 glycosidic bonds, and degrade cellulose into available glucose, which not only destroys the structure and strength of fibers, but also further causes mildew spots on fabrics and pollutes skin; in addition, it has affinity The fiber with skin properties is difficult to prevent free radicals from oxidizing the body, and lacks anti-radiation functional groups, and does not have sites for adsorbing metal ions. These defects make it unable to meet the requirements of differentiation, functionality and comfort of modern fabrics. demand, thereby limiting the further expansion of its application field. In order to fully develop the potential functions of viscose fiber, it has become a major direction of people's research to carry out various modification research on viscose fiber and improve the added value and performance of viscose fiber.
茶多酚是茶叶中多酚类物质的总称。它们的基本结构为2-连(或邻)苯酚基苯并吡喃的衍生物，按其化学结构可分为四类：儿茶素类、黄酮及黄酮醇类、花白素及花青素类、酚酸及缩酚酸类。其中儿茶素类为其主要物质，约为茶叶中多酚类总量的70％～80％。茶多酚分子中的母核为2-苯基色原酮，该母核及连接的苯基上含有多个酚羟基，2-苯基色原酮环上的电子云均匀分布且连接的苯基跨越20余原子的离域电子云，因而使酚羟基具备抗氧化、抗菌和螯合重金属离子的能力，使2-苯基色原酮环及连接的苯基具备抗辐射、抗紫外线性能等。Tea polyphenols is the general term for polyphenols in tea. Their basic structures are derivatives of 2-connected (or o) phenolic benzopyrans, which can be divided into four categories according to their chemical structures: catechins, flavonoids and flavonols, anthocyanins and anthocyanins , phenolic acids and phenolic acids. Among them, catechins are the main substances, which are about 70% to 80% of the total amount of polyphenols in tea. The mother nucleus in the tea polyphenol molecule is 2-phenylchromone, which contains multiple phenolic hydroxyl groups on the mother nucleus and the connected phenyl group, and the electron cloud on the 2-phenylchromone ring is uniformly distributed and the connected phenyl The delocalized electron cloud of more than 20 atoms makes the phenolic hydroxyl group have the ability of anti-oxidation, antibacterial and chelating heavy metal ions, and makes the 2-phenylchromone ring and the connected phenyl group have anti-radiation and anti-ultraviolet properties.
现有制备出茶多酚与粘胶纤维相结合的功能性纤维材料及其衍生物的技术，例如申请号为201610347050.6的专利，公开了一种茶多酚纤维素纤维水刺无纺布及其生产工艺，该茶多酚纤维素纤维水刺无纺布由天丝、粘胶纤维和莫代尔等纤维素纤维为主纤维，加上95％以上纯度的茶多酚纳米级萃取提取物和吸湿导汗抗菌剂，并在生产制作水刺无纺布时加入纤维网内制成高效吸湿、导汗抗菌、抗过敏及消炎的产品。该专利虽然提出了茶多酚纤维素纤维的概念，但并不是真正意义上的茶多酚改性纤维，纤维和茶多酚之间仅仅是物理混合，并不涉及化学反应，因此该产品在使用过程中，茶多酚易脱落，使得产品的抗菌、抗氧化等功能稳定性不高，应用在其他方面得到的效果也甚微。The existing technology of preparing functional fiber materials and derivatives of tea polyphenols and viscose fibers, such as the patent application number 201610347050.6, discloses a tea polyphenol cellulose fiber spunlace non-woven fabric and its Production process, the tea polyphenol cellulose fiber spunlace non-woven fabric is mainly composed of cellulose fibers such as tencel, viscose fiber and modal, plus tea polyphenol nano-scale extracts with a purity of more than 95% and moisture-absorbing materials. Sweat and antibacterial agent, and added to the fiber net during the production of spunlace non-woven fabrics to make products with high moisture absorption, sweat-conducting antibacterial, anti-allergic and anti-inflammatory products. Although the patent proposes the concept of tea polyphenol cellulose fiber, it is not a tea polyphenol modified fiber in the true sense. The fiber and tea polyphenol are only physically mixed and do not involve chemical reactions. During use, tea polyphenols are easy to fall off, which makes the antibacterial, anti-oxidation and other functions of the product less stable, and the effect obtained in other aspects is also very small.
又例如申请号为201611163439.1的专利，公开了一种茶多酚纤维素纤维及其制备方法，利用硅烷偶联剂作为交联剂，将茶多酚接枝在纤维素上。该方法的缺点是：①制备茶多酚预处理液所需的时间为8～10小时，维持交联反应所需的时间为30～36小时，反应时间冗长，用于工业生产所取得的经济效益较低；②所用交联剂为硅烷偶联剂，然而硅烷偶联剂较为适合连接无机材料表面的硅羟基与有机材料表面的活性基团，纤维素为高分子多糖，用硅烷偶联剂进行交联收效不明显。③此外，该专利中所用的硅烷偶联剂为3-缩水甘油醚氧基丙基三乙氧基硅烷，市售价格高，使得成本增加，同样不利于工业的大规模使用和生产。Another example is the patent application number 201611163439.1, which discloses a tea polyphenol cellulose fiber and its preparation method, using a silane coupling agent as a crosslinking agent to graft tea polyphenols on the cellulose. The disadvantages of this method are: 1. The time required for preparing the tea polyphenol pretreatment solution is 8-10 hours, and the time required for maintaining the cross-linking reaction is 30-36 hours. The benefit is low; ②The crosslinking agent used is a silane coupling agent, but the silane coupling agent is more suitable for connecting the silicon hydroxyl groups on the surface of inorganic materials and the active groups on the surface of organic materials. Cellulose is a high molecular polysaccharide, and silane coupling agent The effect of cross-linking is not obvious. ③In addition, the silane coupling agent used in this patent is 3-glycidyloxypropyltriethoxysilane, which has a high market price and increases the cost, which is also unfavorable for large-scale industrial use and production.
三、发明内容3. Contents of the invention
本发明的目的是针对现有茶多酚修饰粘胶纤维工艺的不足之处，提供一种茶多酚修饰粘胶纤维的制备工艺。该工艺不仅使茶多酚与粘胶纤维以共价键连接且接枝率显著提高、接枝粘胶纤维的抗菌及染色性能增强，还保持了粘胶纤维原有的主要力学性能。而且，该工艺还具有操作简单、成本低、便于推广应用等特点，制备出的接枝茶多酚粘胶纤维有抗菌、抗氧化、抗紫外辐射等作用，可应用于纺织、服装、装饰等领域。The object of the present invention is to provide a preparation process of tea polyphenol modified viscose fiber aiming at the shortcomings of the existing tea polyphenol modified viscose fiber technology. This process not only makes the tea polyphenols and viscose fibers covalently bonded and the grafting rate is significantly improved, the antibacterial and dyeing properties of the grafted viscose fibers are enhanced, but also the original main mechanical properties of the viscose fibers are maintained. Moreover, the process also has the characteristics of simple operation, low cost, and easy popularization and application. The prepared grafted tea polyphenol viscose fiber has antibacterial, anti-oxidation, and anti-ultraviolet radiation effects, and can be used in textiles, clothing, decoration, etc. field.
本发明的主要原理是：纤维素酶(β-1，4-葡聚糖-4-葡聚糖水解酶)是降解纤维素生成葡萄糖的一组酶的总称，在分解纤维素时起生物催化作用，可以将纤维素分解成寡糖或单糖；粘胶纤维属于再生纤维素，是由D-葡萄糖以β-1，4糖苷键连接成的高分子聚合物，控制纤维素酶处理粘胶纤维的反应条件，可以使其发生一定程度的降解，从而使粘胶纤维暴露出更多的末端羟基活性基团，以便与茶多酚进行接枝；双缩水甘油醚交联剂是一种双环氧官能团的羟基交联剂，具有良好的润湿能力，还可以提高交联物的柔韧性；经纤维素酶处理后的粘胶纤维和茶多酚均有丰富的游离羟基，在适宜条件下可以与双缩水甘油醚发生交联。The main principle of the present invention is: cellulase (beta-1,4-glucan-4-glucan hydrolase) is the general name of a group of enzymes that degrade cellulose to generate glucose, and play a role in biocatalysis when decomposing cellulose It can decompose cellulose into oligosaccharides or monosaccharides; viscose fiber belongs to regenerated cellulose, which is a high molecular polymer composed of D-glucose connected by β-1,4 glycosidic bonds, and controls cellulase to process viscose The reaction conditions of the fiber can degrade it to a certain extent, so that the viscose fiber can expose more terminal hydroxyl groups for grafting with tea polyphenols; bisglycidyl ether crosslinking agent is a bisglycidyl ether Hydroxyl crosslinking agent with epoxy functional group has good wetting ability and can also improve the flexibility of crosslinked products; viscose fiber and tea polyphenols after cellulase treatment are rich in free hydroxyl groups. It can be cross-linked with bisglycidyl ether.
本发明的目的是这样实现的：一种茶多酚修饰粘胶纤维的制备工艺，以市售茶多酚和粘胶纤维为原料，通过制备表面活性剂预处理粘胶纤维，制备纤维素酶水解粘胶纤维，制备吸附茶多酚粘胶纤维，制备接枝茶多酚粘胶纤维的步骤，就制备出茶多酚接枝率为8～10％的粘胶纤维。其具体的工艺步骤如下：The object of the present invention is achieved in this way: a preparation process of tea polyphenol modified viscose fiber, using commercially available tea polyphenols and viscose fiber as raw materials, pretreating viscose fiber by preparing surfactant, to prepare cellulase The steps of hydrolyzing the viscose fiber, preparing the absorbing tea polyphenol viscose fiber, and preparing the grafted tea polyphenol viscose fiber are to prepare the viscose fiber with a tea polyphenol grafting rate of 8-10%. Its concrete process steps are as follows:
(1)制备表面活性剂预处理粘胶纤维(1) Prepare surfactant pretreatment viscose fiber
首先配制出表面活性剂十二烷基苯磺酸钠质量分数为0.5～2％的预处理液，再按照粘胶纤维质量与该预处理液体积之比为1∶18～22kg/L的比例，将粘胶纤维分散于加有该预处理液的反应釜中，升温至90～100℃，搅拌预处理0.5～1.5h。预处理完成后放液，分别收集预处理后的粘胶纤维和预处理粘胶纤维后的废液。收集的预处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积比为1∶8～12kg/L的比例加入纯净水清洗2～4次。清洗完成后于30～40℃下烘干，即制备出表面活性剂预处理粘胶纤维，用于下步制备纤维素酶水解粘胶纤维；对收集的预处理粘胶纤维后的废液，泵送至生化处理站进行处理，达标后排放。First prepare surfactant sodium dodecylbenzene sulfonate mass fraction and be 0.5～2% pretreatment liquid, then according to the ratio of viscose fiber quality and this pretreatment liquid volume ratio be 1: 18～22kg/L , disperse the viscose fibers in the reaction kettle added with the pretreatment solution, raise the temperature to 90-100° C., and stir for 0.5-1.5 hours for pretreatment. After the pretreatment is completed, the liquid is drained, and the pretreated viscose fiber and the waste liquid after the pretreated viscose fiber are collected respectively. The collected pretreated viscose fibers are washed with pure water for 2 to 4 times according to the ratio of viscose fiber mass to pure water volume ratio of 1:8-12kg/L. After cleaning, dry at 30-40°C to prepare surfactant pretreated viscose fiber, which is used to prepare cellulase hydrolyzed viscose fiber in the next step; for the collected waste liquid after pretreated viscose fiber, It is pumped to the biochemical treatment station for treatment, and discharged after reaching the standard.
(2)制备纤维素酶水解粘胶纤维(2) Preparation of cellulase hydrolyzed viscose fiber
第(1)步完成后，按照表面活性剂预处理粘胶纤维质量与纯净水体积之比为1∶18～22kg/L的比例，将表面活性剂预处理粘胶纤维分散于纯净水中，升温至40～50℃，再加入质量占表面活性剂预处理粘胶纤维1～3％的纤维素酶，调节pH至5.0～6.0后反应2～4h。反应结束后放液，分别收集纤维素酶处理后的粘胶纤维和酶解废液。收集的纤维素酶处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶8～12kg/L的比例加入纯净水清洗2～4次。分别收集清洗后的纤维素酶水解粘胶纤维和清洗纤维素酶水解粘胶纤维后的废液，对收集的清洗纤维素酶水解粘胶纤维后的废液，与收集的酶解废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的纤维素酶水解粘胶纤维，于30～40℃下烘干，即制备出纤维素酶水解粘胶纤维，用于下步制备茶多酚吸附粘胶纤维。After the first (1) step is completed, according to the ratio of surfactant pretreated viscose fiber quality and pure water volume to the ratio of 1: 18～22kg/L, surfactant pretreated viscose fiber is dispersed in pure water, and the temperature rises to 40-50° C., then add cellulase whose mass accounts for 1-3% of the surfactant-pretreated viscose fiber, adjust the pH to 5.0-6.0, and then react for 2-4 hours. After the reaction is finished, the liquid is discharged, and the viscose fiber and the enzymolysis waste liquid after the cellulase treatment are collected respectively. The collected viscose fibers treated with cellulase are washed with pure water for 2 to 4 times according to the ratio of viscose fiber mass to pure water volume of 1:8-12kg/L. Collect the cleaned cellulase hydrolyzed viscose fiber and the waste liquid after cleaning the cellulase hydrolyzed viscose fiber respectively, and carry out the waste liquid after the collected cleaned cellulase hydrolyzed viscose fiber with the collected enzymatic waste liquid Combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. The collected cleaned cellulase-hydrolyzed viscose fibers are dried at 30-40° C. to prepare cellulase-hydrolyzed viscose fibers, which are used in the next step to prepare tea polyphenol-adsorbed viscose fibers.
(3)制备吸附茶多酚粘胶纤维(3) Preparation of Adsorption Tea Polyphenol Viscose Fiber
第(2)步完成后，先用纯净水配制出茶多酚质量百分浓度为0.6～1.2％的水溶液，再按照纤维素酶水解粘胶纤维的质量与茶多酚质量百分浓度为0.6～1.2％的水溶液的体积之比为1∶18～22kg/L的比例，将纤维素酶水解粘胶纤维分散于该茶多酚水溶液中，接着用稀氢氧化钠调节体系pH至9～11，控制温度为80～90℃，吸附1～3h。待吸附完成后放液，分别收集吸附茶多酚后的该粘胶纤维和脱附部分茶多酚后的该溶液，对收集的吸附茶多酚后的该粘胶纤维，即为吸附茶多酚粘胶纤维，用于下步制备接枝茶多酚粘胶纤维；对于收集的脱附部分茶多酚后的该溶液，含未吸附的茶多酚，补加茶多酚和纯净水后可用于制备下批次吸附茶多酚粘胶纤维。After step (2) is completed, first prepare an aqueous solution with a tea polyphenol mass percentage concentration of 0.6 to 1.2% with pure water, and then according to the quality of the cellulase hydrolyzed viscose fiber and the tea polyphenol mass percentage concentration of 0.6 The volume ratio of ~1.2% aqueous solution is 1:18~22kg/L, disperse the viscose fiber hydrolyzed by cellulase in the tea polyphenol aqueous solution, and then adjust the pH of the system to 9~11 with dilute sodium hydroxide , control the temperature at 80-90°C, and adsorb for 1-3 hours. After the adsorption is completed, the liquid is drained, and the viscose fiber after absorbing tea polyphenols and the solution after desorbing part of tea polyphenols are collected respectively. Phenol viscose fiber is used to prepare grafted tea polyphenol viscose fiber in the next step; for the collected desorbed part of the tea polyphenols, the solution contains unadsorbed tea polyphenols, after adding tea polyphenols and purified water It can be used to prepare the next batch of viscose fibers for absorbing tea polyphenols.
(4)制备接枝茶多酚粘胶纤维(4) Preparation of grafted tea polyphenol viscose fiber
第(3)步完成后，按照第(3)步加入的纤维素酶水解粘胶纤维的质量与纯净水的体积之比为1∶14～18kg/L的比例，先向装有吸附茶多酚粘胶纤维的反应釜中加入纯净水，再向其中加入乙二醇双缩水甘油醚或丁二醇双缩水甘油醚或己二醇双缩水甘油醚，加入的乙二醇双缩水甘油醚或丁二醇双缩水甘油醚或己二醇双缩水甘油醚的体积为第(3)步加入茶多酚水溶液体积的0.6～1.2％，在温度为80～90℃的条件下反应2～4h。反应完成后放液，分别收集交联剂处理后的粘胶纤维和反应废液。收集的交联剂处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶8～12kg/L的比例加入纯净水清洗2～4次。分别收集清洗后的接枝茶多酚粘胶纤维和清洗接枝茶多酚粘胶纤维后的废液，对收集的清洗接枝茶多酚粘胶纤维后的废液，与收集的反应废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的接枝茶多酚粘胶纤维，将其移入隧道式烘干机中，在温度为30～40℃、传动速度为0.1～0.5r/min的条件下，处理0.5～1h，即制备出接枝茶多酚粘胶纤维，其中茶多酚接枝率为8～10％。After the (3) step is completed, the ratio of the quality of the cellulase hydrolyzed viscose fiber added in the (3) step to the volume of pure water is 1: 14～18kg/L, and the adsorption tea poly Add pure water to the reaction kettle of phenol viscose fiber, then add ethylene glycol bisglycidyl ether or butanediol bisglycidyl ether or hexanediol bisglycidyl ether to it, the added ethylene glycol bisglycidyl ether or The volume of butanediol diglycidyl ether or hexanediol diglycidyl ether is 0.6-1.2% of the volume of the tea polyphenol aqueous solution added in step (3), and the reaction is carried out at a temperature of 80-90° C. for 2-4 hours. After the reaction is completed, the liquid is released, and the viscose fiber and the reaction waste liquid after the cross-linking agent treatment are collected respectively. The collected viscose fibers treated with the crosslinking agent are washed with pure water for 2 to 4 times according to the ratio of viscose fiber mass to pure water volume of 1:8-12kg/L. Collect the grafted tea polyphenol viscose fiber after cleaning and the waste liquid after cleaning the grafted tea polyphenol viscose fiber respectively, the waste liquid after the cleaning grafted tea polyphenol viscose fiber collected, and the reaction waste collected The liquid is combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. Move the collected and cleaned grafted tea polyphenol viscose fibers into a tunnel dryer, and process them for 0.5-1h at a temperature of 30-40°C and a transmission speed of 0.1-0.5r/min. , that is, the grafted tea polyphenol viscose fiber is prepared, wherein the tea polyphenol grafting rate is 8-10%.
本发明采用上述技术方案后，主要有以下效果：After the present invention adopts above-mentioned technical scheme, mainly have following effect:
1、本发明方法以市售茶多酚和粘胶纤维为原料，生产成本低廉，所用生产设备均为工业化设备，生产条件易实施，操作方便，适合规模化生产。1. The method of the present invention uses commercially available tea polyphenols and viscose fiber as raw materials, and the production cost is low. The production equipment used is all industrialized equipment. The production conditions are easy to implement, easy to operate, and suitable for large-scale production.
2、本发明方法采用具有双环氧官能团的双缩水甘油醚作为反应交联剂，使得粘胶纤维与茶多酚通过化学共价键稳定连接，茶多酚接枝率高，稳定性增强，从而显著提高了产品的抗氧化、抗辐射、抗菌、螯合金属离子等功能。2. The method of the present invention adopts the bisglycidyl ether with two epoxy functional groups as a reactive crosslinking agent, so that the viscose fiber and tea polyphenols are stably connected by chemical covalent bonds, the grafting rate of tea polyphenols is high, and the stability is enhanced. Thereby significantly improving the anti-oxidation, anti-radiation, antibacterial, chelated metal ion and other functions of the product.
3、本发明在制备接枝茶多酚粘胶纤维之前，先对粘胶纤维进行了表面活性剂预处理，使得粘胶纤维的表面基团得以活化；随后又对其进行了纤维素酶水解，使得粘胶纤维发生一定程度的降解，其上的活性羟基得以充分暴露，便于提高茶多酚的接枝率。3. Before preparing the grafted tea polyphenol viscose fiber, the present invention pre-treats the viscose fiber with a surfactant, so that the surface groups of the viscose fiber are activated; then it is hydrolyzed by cellulase , so that the viscose fiber is degraded to a certain extent, the active hydroxyl groups on it can be fully exposed, and it is convenient to increase the grafting rate of tea polyphenols.
4、本发明是典型的绿色生产工艺，便于推广应用，制备得到的接枝茶多酚粘胶纤维产品可广泛应用于纺织、服装、装饰等领域。4. The present invention is a typical green production process, which is convenient for popularization and application. The prepared grafted tea polyphenol viscose fiber product can be widely used in the fields of textile, clothing, decoration and the like.
四、具体实施方式4. Specific implementation
下面结合具体实施方式，进一步说明本发明。The present invention will be further described below in combination with specific embodiments.
实施例1Example 1
一种茶多酚修饰粘胶纤维的制备工艺，其具体的工艺步骤如下：A kind of preparation technology of tea polyphenol modified viscose fiber, its concrete processing steps are as follows:
(1)制备表面活性剂预处理粘胶纤维(1) Prepare surfactant pretreatment viscose fiber
首先配制出表面活性剂十二烷基苯磺酸钠质量分数为0.5％的预处理液，再按照粘胶纤维质量与该预处理液体积之比为1∶18kg/L的比例，将粘胶纤维分散于加有该预处理液的反应釜中，升温至90℃，搅拌预处理0.5h。预处理完成后放液，分别收集预处理后的粘胶纤维和预处理粘胶纤维后的废液。收集的预处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积比为1∶8kg/L的比例加入纯净水清洗2次。清洗完成后于30℃下烘干，即制备出表面活性剂预处理粘胶纤维，用于下步制备纤维素酶水解粘胶纤维；对收集的预处理粘胶纤维后的废液，泵送至生化处理站进行处理，达标后排放。First prepare surfactant sodium dodecylbenzene sulfonate massfraction and be the pretreatment liquid of 0.5%, then according to the ratio of viscose fiber quality and this pretreatment liquid volume ratio be 1: 18kg/L, viscose The fibers are dispersed in the reaction kettle added with the pretreatment solution, the temperature is raised to 90°C, and the pretreatment is carried out with stirring for 0.5h. After the pretreatment is completed, the liquid is drained, and the pretreated viscose fiber and the waste liquid after the pretreated viscose fiber are collected respectively. The collected pretreated viscose fibers were washed twice with pure water according to the ratio of viscose fiber mass to pure water volume ratio of 1:8kg/L. After cleaning, dry at 30°C to prepare surfactant pretreated viscose fiber, which is used to prepare cellulase hydrolyzed viscose fiber in the next step; the collected waste liquid after pretreated viscose fiber is pumped To the biochemical treatment station for treatment, discharge after reaching the standard.
(2)制备纤维素酶水解粘胶纤维(2) Preparation of cellulase hydrolyzed viscose fiber
第(1)步完成后，按照表面活性剂预处理粘胶纤维质量与纯净水体积之比为1∶18kg/L的比例，将表面活性剂预处理粘胶纤维分散于纯净水中，升温至40℃，再加入质量占表面活性剂预处理粘胶纤维1％的纤维素酶，调节pH至5.0后反应2h。反应结束后放液，分别收集纤维素酶处理后的粘胶纤维和酶解废液。收集的纤维素酶处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶8kg/L的比例加入纯净水清洗2次。分别收集清洗后的纤维素酶水解粘胶纤维和清洗纤维素酶水解粘胶纤维后的废液，对收集的清洗纤维素酶水解粘胶纤维后的废液，与收集的酶解废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的纤维素酶水解粘胶纤维，于30℃下烘干，即制备出纤维素酶水解粘胶纤维，用于下步制备茶多酚吸附粘胶纤维。After the (1) step was completed, according to the ratio of the surfactant pretreated viscose fiber quality and the pure water volume to the ratio of 1: 18kg/L, the surfactant pretreated viscose fiber was dispersed in pure water, and the temperature was raised to 40 °C, add cellulase whose mass accounted for 1% of the viscose fiber pretreated with surfactant, adjust the pH to 5.0, and then react for 2 hours. After the reaction is finished, the liquid is drained, and the viscose fiber and enzymolysis waste liquid after cellulase treatment are collected respectively. The collected viscose fibers treated with cellulase were washed twice with purified water according to the ratio of viscose fiber mass to pure water volume ratio of 1:8 kg/L. Collect the cleaned cellulase hydrolyzed viscose fiber and the waste liquid after cleaning the cellulase hydrolyzed viscose fiber respectively, and carry out the waste liquid after the collected cleaned cellulase hydrolyzed viscose fiber with the collected enzymatic waste liquid Combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. The collected cleaned cellulase-hydrolyzed viscose fibers are dried at 30° C. to prepare cellulase-hydrolyzed viscose fibers, which are used in the next step to prepare tea polyphenol-adsorbed viscose fibers.
(3)制备吸附茶多酚粘胶纤维(3) Preparation of Adsorption Tea Polyphenol Viscose Fiber
第(2)步完成后，先用纯净水配制出茶多酚质量百分浓度为0.6％的水溶液，再按照纤维素酶水解粘胶纤维的质量与茶多酚质量百分浓度为0.6％的水溶液的体积之比为1∶18kg/L的比例，将纤维素酶水解粘胶纤维分散于该茶多酚水溶液中，接着用稀氢氧化钠调节体系pH至9，控制温度为80℃，吸附1h。待吸附完成后放液，分别收集吸附茶多酚后的该粘胶纤维和脱附部分茶多酚后的该溶液，对收集的吸附茶多酚后的该粘胶纤维，即为吸附茶多酚粘胶纤维，用于下步制备接枝茶多酚粘胶纤维；对于收集的脱附部分茶多酚后的该溶液，含未吸附的茶多酚，补加茶多酚和纯净水后可用于制备下批次吸附茶多酚粘胶纤维。After the (2) step was completed, it was 0.6% aqueous solution to prepare the tea polyphenols mass percentage concentration with pure water, and then according to the quality of the cellulase hydrolyzed viscose fiber and the tea polyphenols mass percentage concentration was 0.6% The volume ratio of the aqueous solution is 1:18kg/L, the viscose fiber hydrolyzed by cellulase is dispersed in the tea polyphenol aqueous solution, and then the pH of the system is adjusted to 9 with dilute sodium hydroxide, and the temperature is controlled at 80°C. 1h. After the adsorption is completed, the liquid is drained, and the viscose fiber after absorbing tea polyphenols and the solution after desorbing part of tea polyphenols are collected respectively. Phenol viscose fiber is used to prepare grafted tea polyphenol viscose fiber in the next step; for the collected desorbed part of the tea polyphenols, the solution contains unadsorbed tea polyphenols, after adding tea polyphenols and purified water It can be used to prepare the next batch of viscose fibers for absorbing tea polyphenols.
(4)制备接枝茶多酚粘胶纤维(4) Preparation of grafted tea polyphenol viscose fiber
第(3)步完成后，按照第(3)步加入的纤维素酶水解粘胶纤维的质量与纯净水的体积之比为1∶14kg/L的比例，先向装有吸附茶多酚粘胶纤维的反应釜中加入纯净水，再向其中加入乙二醇双缩水甘油醚，加入的乙二醇双缩水甘油醚的体积为第(3)步加入茶多酚水溶液体积的0.6％，在温度为80℃的条件下反应2h。反应完成后放液，分别收集交联剂处理后的粘胶纤维和反应废液。收集的交联剂处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶8kg/L的比例加入纯净水清洗2次。分别收集清洗后的接枝茶多酚粘胶纤维和清洗接枝茶多酚粘胶纤维后的废液，对收集的清洗接枝茶多酚粘胶纤维后的废液，与收集的反应废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的接枝茶多酚粘胶纤维，将其移入隧道式烘干机中，在温度为30℃、传动速度为0.1r/min的条件下，处理0.5h，即制备出接枝茶多酚粘胶纤维，其中茶多酚接枝率为8～10％。After the step (3) was completed, the ratio of the mass of the cellulase hydrolyzed viscose fiber added in the step (3) to the volume of purified water was 1: 14kg/L, and the viscose fiber with adsorption tea polyphenols was charged first. Add pure water in the reactor of rubber fiber, then add ethylene glycol bisglycidyl ether wherein, the volume of the ethylene glycol bisglycidyl ether that adds is (3) step adds 0.6% of tea polyphenol aqueous solution volume, in The reaction was carried out for 2 hours at a temperature of 80°C. After the reaction is completed, the liquid is released, and the viscose fiber and the reaction waste liquid after the cross-linking agent treatment are collected respectively. The collected viscose fibers treated with the cross-linking agent were washed twice with purified water according to the ratio of viscose fiber mass to pure water volume ratio of 1:8 kg/L. Collect the grafted tea polyphenol viscose fiber after cleaning and the waste liquid after cleaning the grafted tea polyphenol viscose fiber respectively, the waste liquid after the cleaning grafted tea polyphenol viscose fiber collected, and the reaction waste collected The liquid is combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. The collected and cleaned grafted tea polyphenol viscose fiber was moved into a tunnel dryer, and treated for 0.5h at a temperature of 30°C and a transmission speed of 0.1r/min, and the grafted tea polyphenol viscose fiber was prepared. Branch tea polyphenol viscose fiber, wherein the grafting rate of tea polyphenol is 8-10%.
实施例2Example 2
一种茶多酚修饰粘胶纤维的制备工艺，其具体的工艺步骤如下：A kind of preparation technology of tea polyphenol modified viscose fiber, its concrete processing steps are as follows:
(1)制备表面活性剂预处理粘胶纤维(1) Prepare surfactant pretreatment viscose fiber
首先配制出表面活性剂十二烷基苯磺酸钠质量分数为1％的预处理液，再按照粘胶纤维质量与该预处理液体积之比为1∶20kg/L的比例，将粘胶纤维分散于加有该预处理液的反应釜中，升温至95℃，搅拌预处理1h。预处理完成后放液，分别收集预处理后的粘胶纤维和预处理粘胶纤维后的废液。收集的预处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积比为1∶10kg/L的比例加入纯净水清洗3次。清洗完成后于35℃下烘干，即制备出表面活性剂预处理粘胶纤维，用于下步制备纤维素酶水解粘胶纤维；对收集的预处理粘胶纤维后的废液，泵送至生化处理站进行处理，达标后排放。First prepare surfactant sodium dodecylbenzene sulfonate massfraction and be the pretreatment liquid of 1%, then according to the ratio of viscose fiber quality and this pretreatment liquid volume ratio be 1: 20kg/L, viscose The fibers are dispersed in the reaction kettle added with the pretreatment solution, the temperature is raised to 95°C, and the pretreatment is carried out with stirring for 1 hour. After the pretreatment is completed, the liquid is drained, and the pretreated viscose fiber and the waste liquid after the pretreated viscose fiber are collected respectively. The collected pretreated viscose fibers were washed with pure water for 3 times according to the ratio of viscose fiber mass to pure water volume ratio of 1:10kg/L. After cleaning, dry at 35°C to prepare surfactant pretreated viscose fiber, which is used to prepare cellulase hydrolyzed viscose fiber in the next step; the collected waste liquid after pretreated viscose fiber is pumped To the biochemical treatment station for treatment, discharge after reaching the standard.
(2)制备纤维素酶水解粘胶纤维(2) Preparation of cellulase hydrolyzed viscose fiber
第(1)步完成后，按照表面活性剂预处理粘胶纤维质量与纯净水体积之比为1∶20kg/L的比例，将表面活性剂预处理粘胶纤维分散于纯净水中，升温至45℃，再加入质量占表面活性剂预处理粘胶纤维2％的纤维素酶，调节pH至5.5后反应3h。反应结束后放液，分别收集纤维素酶处理后的粘胶纤维和酶解废液。收集的纤维素酶处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶10kg/L的比例加入纯净水清洗3次。分别收集清洗后的纤维素酶水解粘胶纤维和清洗纤维素酶水解粘胶纤维后的废液，对收集的清洗纤维素酶水解粘胶纤维后的废液，与收集的酶解废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的纤维素酶水解粘胶纤维，于35℃下烘干，即制备出纤维素酶水解粘胶纤维，用于下步制备茶多酚吸附粘胶纤维。After the (1) step was completed, according to the ratio of the surfactant pretreated viscose fiber quality and the pure water volume to the ratio of 1: 20kg/L, the surfactant pretreated viscose fiber was dispersed in pure water, and the temperature was raised to 45 ℃, then add cellulase whose mass accounts for 2% of the viscose fiber pretreated with surfactant, adjust the pH to 5.5, and then react for 3 hours. After the reaction is finished, the liquid is discharged, and the viscose fiber and the enzymolysis waste liquid after the cellulase treatment are collected respectively. The collected viscose fibers treated with cellulase were washed with pure water for 3 times according to the ratio of viscose fiber mass to pure water volume ratio of 1:10kg/L. Collect the cleaned cellulase hydrolyzed viscose fiber and the waste liquid after cleaning the cellulase hydrolyzed viscose fiber respectively, and carry out the waste liquid after the collected cleaned cellulase hydrolyzed viscose fiber with the collected enzymatic waste liquid Combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. The collected cleaned cellulase-hydrolyzed viscose fibers are dried at 35° C. to prepare cellulase-hydrolyzed viscose fibers, which are used in the next step to prepare tea polyphenol-adsorbed viscose fibers.
(3)制备吸附茶多酚粘胶纤维(3) Preparation of Adsorption Tea Polyphenol Viscose Fiber
第(2)步完成后，先用纯净水配制出茶多酚质量百分浓度为0.9％的水溶液，再按照纤维素酶水解粘胶纤维的质量与茶多酚质量百分浓度为0.9％的水溶液的体积之比为1∶20kg/L的比例，将纤维素酶水解粘胶纤维分散于该茶多酚水溶液中，接着用稀氢氧化钠调节体系pH至10，控制温度为85℃，吸附2h。待吸附完成后放液，分别收集吸附茶多酚后的该粘胶纤维和脱附部分茶多酚后的该溶液，对收集的吸附茶多酚后的该粘胶纤维，即为吸附茶多酚粘胶纤维，用于下步制备接枝茶多酚粘胶纤维；对于收集的脱附部分茶多酚后的该溶液，含未吸附的茶多酚，补加茶多酚和纯净水后可用于制备下批次吸附茶多酚粘胶纤维。After the (2) step was completed, it was 0.9% aqueous solution to prepare the tea polyphenols mass percentage concentration with pure water, and then according to the quality of the cellulase hydrolyzed viscose fiber and the tea polyphenols mass percentage concentration was 0.9% The volume ratio of the aqueous solution is 1:20kg/L, the viscose fiber hydrolyzed by cellulase is dispersed in the tea polyphenol aqueous solution, and then the pH of the system is adjusted to 10 with dilute sodium hydroxide, and the temperature is controlled at 85°C. 2h. After the adsorption is completed, the liquid is drained, and the viscose fiber after absorbing tea polyphenols and the solution after desorbing part of tea polyphenols are collected respectively. Phenol viscose fiber is used to prepare grafted tea polyphenol viscose fiber in the next step; for the collected desorbed part of the tea polyphenols, the solution contains unadsorbed tea polyphenols, after adding tea polyphenols and purified water It can be used to prepare the next batch of viscose fibers for absorbing tea polyphenols.
(4)制备接枝茶多酚粘胶纤维(4) Preparation of grafted tea polyphenol viscose fiber
第(3)步完成后，按照第(3)步加入的纤维素酶水解粘胶纤维的质量与纯净水的体积之比为1∶16kg/L的比例，先向装有吸附茶多酚粘胶纤维的反应釜中加入纯净水，再向其中加入丁二醇双缩水甘油醚，加入的丁二醇双缩水甘油醚的体积为第(3)步加入茶多酚水溶液体积的0.9％，在温度为85℃的条件下反应3h。反应完成后放液，分别收集交联剂处理后的粘胶纤维和反应废液。收集的交联剂处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶10kg/L的比例加入纯净水清洗3次。分别收集清洗后的接枝茶多酚粘胶纤维和清洗接枝茶多酚粘胶纤维后的废液，对收集的清洗接枝茶多酚粘胶纤维后的废液，与收集的反应废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的接枝茶多酚粘胶纤维，将其移入隧道式烘干机中，在温度为35℃、传动速度为0.3r/min的条件下，处理1h，即制备出接枝茶多酚粘胶纤维，其中茶多酚接枝率为8～10％。After the (3) step is completed, according to the ratio of the quality of the cellulase hydrolyzed viscose fiber added in the (3) step to the volume of pure water is 1: 16kg/L, the viscose fiber that absorbs tea polyphenols is installed first. Add pure water in the reactor of glue fiber, then add butanediol bisglycidyl ether wherein, the volume of the butanediol bisglycidyl ether that adds is (3) step adds 0.9% of tea polyphenol aqueous solution volume, in The reaction was carried out at a temperature of 85° C. for 3 hours. After the reaction is completed, the liquid is released, and the viscose fiber and the reaction waste liquid after the cross-linking agent treatment are collected respectively. The collected viscose fibers treated with the crosslinking agent were washed with pure water for 3 times according to the ratio of viscose fiber mass to pure water volume of 1:10kg/L. Collect the grafted tea polyphenol viscose fiber after cleaning and the waste liquid after cleaning the grafted tea polyphenol viscose fiber respectively, the waste liquid after the cleaning grafted tea polyphenol viscose fiber collected, and the reaction waste collected The liquid is combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. Move the collected and cleaned grafted tea polyphenol viscose fibers into a tunnel dryer, and treat them for 1 hour at a temperature of 35°C and a transmission speed of 0.3r/min to prepare grafted fibers. Tea polyphenol viscose fiber, wherein the grafting rate of tea polyphenol is 8-10%.
实施例3Example 3
一种茶多酚修饰粘胶纤维的制备工艺，其具体的工艺步骤如下：A kind of preparation technology of tea polyphenol modified viscose fiber, its concrete processing steps are as follows:
(1)制备表面活性剂预处理粘胶纤维(1) Prepare surfactant pretreatment viscose fiber
首先配制出表面活性剂十二烷基苯磺酸钠质量分数为2％的预处理液，再按照粘胶纤维质量与该预处理液体积之比为1∶22kg/L的比例，将粘胶纤维分散于加有该预处理液的反应釜中，升温至100℃，搅拌预处理1.5h。预处理完成后放液，分别收集预处理后的粘胶纤维和预处理粘胶纤维后的废液。收集的预处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积比为1∶12kg/L的比例加入纯净水清洗4次。清洗完成后于40℃下烘干，即制备出表面活性剂预处理粘胶纤维，用于下步制备纤维素酶水解粘胶纤维；对收集的预处理粘胶纤维后的废液，泵送至生化处理站进行处理，达标后排放。First prepare surfactant sodium dodecylbenzene sulfonate massfraction and be the pretreatment liquid of 2%, then according to the ratio of viscose fiber quality and this pretreatment liquid volume ratio be 1: 22kg/L, viscose glue The fibers are dispersed in the reaction kettle added with the pretreatment solution, the temperature is raised to 100°C, and the pretreatment is carried out with stirring for 1.5 hours. After the pretreatment is completed, the liquid is drained, and the pretreated viscose fiber and the waste liquid after the pretreated viscose fiber are collected respectively. The collected pretreated viscose fibers were washed with pure water for 4 times according to the ratio of viscose fiber mass to pure water volume ratio of 1:12kg/L. After cleaning, dry at 40°C to prepare surfactant pretreated viscose fiber, which is used to prepare cellulase hydrolyzed viscose fiber in the next step; the collected waste liquid after pretreated viscose fiber is pumped To the biochemical treatment station for treatment, discharge after reaching the standard.
(2)制备纤维素酶水解粘胶纤维(2) Preparation of cellulase hydrolyzed viscose fiber
第(1)步完成后，按照表面活性剂预处理粘胶纤维质量与纯净水体积之比为1∶22kg/L的比例，将表面活性剂预处理粘胶纤维分散于纯净水中，升温至50℃，再加入质量占表面活性剂预处理粘胶纤维3％的纤维素酶，调节pH至6.0后反应4h。反应结束后放液，分别收集纤维素酶处理后的粘胶纤维和酶解废液。收集的纤维素酶处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶12kg/L的比例加入纯净水清洗4次。分别收集清洗后的纤维素酶水解粘胶纤维和清洗纤维素酶水解粘胶纤维后的废液，对收集的清洗纤维素酶水解粘胶纤维后的废液，与收集的酶解废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的纤维素酶水解粘胶纤维，于40℃下烘干，即制备出纤维素酶水解粘胶纤维，用于下步制备茶多酚吸附粘胶纤维。After the (1) step was completed, according to the ratio of the surfactant pretreated viscose fiber quality and the pure water volume ratio of 1: 22kg/L, the surfactant pretreated viscose fiber was dispersed in pure water, and the temperature was raised to 50 ℃, and then add cellulase whose mass accounts for 3% of the viscose fiber pretreated with surfactant, adjust the pH to 6.0, and then react for 4 hours. After the reaction is finished, the liquid is discharged, and the viscose fiber and the enzymolysis waste liquid after the cellulase treatment are collected respectively. The collected viscose fibers treated with cellulase were washed with pure water for 4 times according to the ratio of viscose fiber mass to pure water volume ratio of 1:12kg/L. Collect the cleaned cellulase hydrolyzed viscose fiber and the waste liquid after cleaning the cellulase hydrolyzed viscose fiber respectively, and carry out the waste liquid after the collected cleaned cellulase hydrolyzed viscose fiber with the collected enzymatic waste liquid Combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. The collected cleaned cellulase-hydrolyzed viscose fibers were dried at 40° C. to prepare cellulase-hydrolyzed viscose fibers, which were used in the next step to prepare tea polyphenol-adsorbed viscose fibers.
(3)制备吸附茶多酚粘胶纤维(3) Preparation of Adsorption Tea Polyphenol Viscose Fiber
第(2)步完成后，先用纯净水配制出茶多酚质量百分浓度为1.2％的水溶液，再按照纤维素酶水解粘胶纤维的质量与茶多酚质量百分浓度为1.2％的水溶液的体积之比为1∶22kg/L的比例，将纤维素酶水解粘胶纤维分散于该茶多酚水溶液中，接着用稀氢氧化钠调节体系pH至11，控制温度为90℃，吸附3h。待吸附完成后放液，分别收集吸附茶多酚后的该粘胶纤维和脱附部分茶多酚后的该溶液，对收集的吸附茶多酚后的该粘胶纤维，即为吸附茶多酚粘胶纤维，用于下步制备接枝茶多酚粘胶纤维；对于收集的脱附部分茶多酚后的该溶液，含未吸附的茶多酚，补加茶多酚和纯净水后可用于制备下批次吸附茶多酚粘胶纤维。After the (2) step was completed, first prepare an aqueous solution with a tea polyphenol mass percentage concentration of 1.2% with pure water, and then according to the quality of the cellulase hydrolyzed viscose fiber and the tea polyphenol mass percentage concentration of 1.2%. The volume ratio of the aqueous solution is 1:22kg/L, the viscose fiber hydrolyzed by cellulase is dispersed in the tea polyphenol aqueous solution, and then the pH of the system is adjusted to 11 with dilute sodium hydroxide, and the temperature is controlled at 90°C. 3h. After the adsorption is completed, the liquid is drained, and the viscose fiber after absorbing tea polyphenols and the solution after desorbing part of tea polyphenols are collected respectively. Phenol viscose fiber is used to prepare grafted tea polyphenol viscose fiber in the next step; for the collected desorbed part of the tea polyphenols, the solution contains unadsorbed tea polyphenols, after adding tea polyphenols and purified water It can be used to prepare the next batch of viscose fibers for absorbing tea polyphenols.
(4)制备接枝茶多酚粘胶纤维(4) Preparation of grafted tea polyphenol viscose fiber
第(3)步完成后，按照第(3)步加入的纤维素酶水解粘胶纤维的质量与纯净水的体积之比为1∶18kg/L的比例，先向装有吸附茶多酚粘胶纤维的反应釜中加入纯净水，再向其中加入己二醇双缩水甘油醚，加入的己二醇双缩水甘油醚的体积为第(3)步加入茶多酚水溶液体积的1.2％，在温度为90℃的条件下反应4h。反应完成后放液，分别收集交联剂处理后的粘胶纤维和反应废液。收集的交联剂处理后的粘胶纤维，按照粘胶纤维质量与纯净水体积之比为1∶12kg/L的比例加入纯净水清洗4次。分别收集清洗后的接枝茶多酚粘胶纤维和清洗接枝茶多酚粘胶纤维后的废液，对收集的清洗接枝茶多酚粘胶纤维后的废液，与收集的反应废液进行合并，泵送至生化处理站进行处理，达标后排放。对收集的清洗后的接枝茶多酚粘胶纤维，将其移入隧道式烘干机中，在温度为40℃、传动速度为0.5r/min的条件下，处理0.5h，即制备出接枝茶多酚粘胶纤维，其中茶多酚接枝率为8～10％。After the (3) step was completed, the ratio of the quality of the cellulase hydrolyzed viscose fiber added in the (3) step to the volume of purified water was 1: 18kg/L, and the viscose fiber with adsorption tea polyphenols Add pure water in the reactor of glue fiber, then add hexanediol diglycidyl ether wherein, the volume of the hexanediol diglycidyl ether that adds is (3) step adds 1.2% of tea polyphenol aqueous solution volume, in The reaction was carried out for 4 hours at a temperature of 90°C. After the reaction is completed, the liquid is released, and the viscose fiber and the reaction waste liquid after the cross-linking agent treatment are collected respectively. The collected viscose fibers treated with the crosslinking agent were washed with pure water for 4 times according to the ratio of viscose fiber mass to pure water volume ratio of 1:12kg/L. Collect the grafted tea polyphenol viscose fiber after cleaning and the waste liquid after cleaning the grafted tea polyphenol viscose fiber respectively, the waste liquid after the cleaning grafted tea polyphenol viscose fiber collected, and the reaction waste collected The liquid is combined, pumped to the biochemical treatment station for treatment, and discharged after reaching the standard. The collected and cleaned grafted tea polyphenol viscose fiber was moved into a tunnel dryer, and treated for 0.5h at a temperature of 40°C and a transmission speed of 0.5r/min. Branch tea polyphenol viscose fiber, wherein the grafting rate of tea polyphenol is 8-10%.
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| 任蓉 等: "新型含茶抗菌纤维的加工技术研究", 《广东茶业》 * |
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| CN110331584A (en) * | 2019-08-21 | 2019-10-15 | 太原理工大学 | Protein/cellulose fibre preparation method based on cellulase activation processing |
| CN110331584B (en) * | 2019-08-21 | 2021-12-28 | 太原理工大学 | Protein/cellulose fiber preparation method based on cellulase activation treatment |
| CN111809263A (en) * | 2020-07-16 | 2020-10-23 | 宜宾惠美纤维新材料股份有限公司 | Antibacterial and deodorant tea cellulose fiber and preparation method thereof |
| CN111995800A (en) * | 2020-09-03 | 2020-11-27 | 蔡营龙 | Preparation method of cellulose-based antibacterial food packaging film |
| CN112515154A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
| CN112515110A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
| CN112515110B (en) * | 2020-12-08 | 2023-01-10 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
| CN112515154B (en) * | 2020-12-08 | 2023-01-10 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
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