WO2022166201A1 - 一种浅色多羧基氧化多糖鞣剂及其制备方法和应用 - Google Patents
一种浅色多羧基氧化多糖鞣剂及其制备方法和应用 Download PDFInfo
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- tanning agent
- polysaccharide
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
Definitions
- the invention relates to the technical field of leather and fur tanning agents, in particular to a light-colored polycarboxylated polysaccharide tanning agent and a preparation method and application thereof.
- Polysaccharide is a macromolecular compound formed by connecting more than ten monosaccharides through glycosidic bonds. It has the advantages of wide source, reproducibility, safety and non-toxicity, and low cost. It is an ideal raw material for preparing ecological tanning agents. Under the strong oxidation of oxidants such as hydrogen peroxide, the hydroxyl groups in the sugar unit structure will be oxidized to carboxyl groups, and the glycosidic bond will be broken. Therefore, the deep oxidative degradation products of polysaccharides can be paired with non-chromium metal salts for leather or fur tanning.
- the reason for the color problem of the above oxidized polysaccharides is that polysaccharides will be degraded under strong oxidation to produce monosaccharide compounds such as glucose. Such monosaccharide compounds will be dehydrated and transformed into furfural compounds under heat or weak acid conditions. Further self-polymerization or polymerization with oxidized polysaccharides forms colored substances.
- the present invention provides a light-colored polycarboxylated polysaccharide tanning agent and a preparation method and application thereof. Chromium salts do not adversely affect the colour of tanned leather or fur when used in combination.
- the first technical scheme adopted in the present invention is:
- a light-colored polycarboxylated polysaccharide tanning agent the raw material of the light-colored polycarboxylated oxidized polysaccharide tanning agent comprises: polysaccharide, organic solvent, catalyst and hydrogen peroxide, wherein, based on the weight of polysaccharide, the weight of the organic solvent It accounts for 1-15 wt%, the weight of the catalyst accounts for 0.05-2 wt ⁇ , and the weight of the hydrogen peroxide accounts for 30-80 wt%.
- the organic solvent is any one or more of tetrahydrofuran, ethyl acetate and methyl isobutyl ketone.
- polysaccharide is any one of starch, dextrin, cellulose, sodium carboxymethyl cellulose and sodium carboxymethyl starch.
- the catalyst is any one or more of copper sulfate, ferrous sulfate and iron sulfate.
- the light-colored polycarboxylated polysaccharide tanning agent also comprises a neutral salt that accounts for 0-30 wt% of the polysaccharide weight, and the neutral salt is in sodium chloride, potassium chloride, sodium sulfate and potassium nitrate. any one or more.
- the carboxyl group content of the light-colored polycarboxylated polysaccharide tanning agent is 5.2-13.1 mmol/g
- the weight-average relative molecular mass is 350-6000 g/mol
- the chromaticity is 1-50.
- the second technical scheme adopted by the present invention is:
- a method for preparing a light-colored polycarboxylated polysaccharide tanning agent comprising:
- the third technical scheme adopted by the present invention is:
- the leather or fur tanning comprises the following steps:
- the pickled bare skin obtained by the conventional process is placed in a rotating drum, and the pickling solution of 80-200 wt %, 4-21 wt % of non-chromium metal salt and 1-4 wt % of the pickled bare skin is added.
- % of oxidized polysaccharide tanning agent wherein the amount of oxidized polysaccharide tanning agent is based on the effective content of the tanning agent, after 2-6 h, the pH is adjusted to 3.8-4.5 with magnesium oxide or baking soda, and the temperature is adjusted to 40 ° C , after turning for 2 h, the tanned leather is obtained; or
- the pickling fur obtained by conventional technology is placed in the drum or the trough, adding the pickling liquid that is 400-600 wt% in terms of the pickling fur weight, and the volume of adding water is 13-32 g/L.
- Non-chromium metal salts and 2-6 g/L of the oxidized polysaccharide tanning agent wherein the amount of the oxidized polysaccharide tanning agent is based on the effective content of the tanning agent.
- non-chromium metal salt is any one or more of aluminum sulfate, zirconium sulfate and titanium sulfate.
- the principle that the present invention can prepare the light-colored oxidized polysaccharide tanning agent is that, adding an organic solvent similar in structure or polarity to furfural substances in the aqueous phase to form a biphasic solution system, so that the small-molecule furfural substances produced in the reaction process can be rapidly It is dissolved in the organic phase, while the oxidized polysaccharide is dissolved in the water phase, which can block the polymerization of small molecular furfural substances and oxidized polysaccharides to form macromolecular colored substances in time.
- the water phase and the organic phase are separated, and the organic phase containing the small-molecule furfural substances and their polymers is discarded, so that the decolorization effect can be achieved, and the light-colored oxidized polysaccharide tanning agent can be prepared.
- the light-colored oxidized polysaccharide tanning agent of the present invention is prepared in a two-phase solution system, and is characterized in that the catalytic oxidation system composed of a catalyst and hydrogen peroxide can carry out deep oxidative degradation of polysaccharides, so that the oxidized polysaccharide tanning agent has sufficient carboxyl groups and non-hydrogen peroxides.
- the chromium metal salts are coordinated and have a sufficiently low molecular weight to ensure uniform penetration of the tanning agent into the hide. More importantly, the organic solvent can efficiently extract the colored substances produced during the oxidation reaction, so that the color of the oxidized polysaccharide tanning agent is light, and will not adversely affect the color of tanned leather or fur.
- the present invention has the following beneficial effects:
- the light-colored oxidized polysaccharide tanning agent provided by the invention significantly reduces the chroma of the oxidized product.
- the preparation method of the light-colored oxidized polysaccharide tanning agent provided by the present invention adopts a two-phase solution system, which is different from the existing oxidation polysaccharide tanning agent preparation technology. In contrast, it can efficiently extract and remove the colored substances produced in the oxidation process, and block its polymerization reaction with the oxidized polysaccharide in time, thereby achieving the effect of significantly reducing the color of the oxidized product.
- the catalytic oxidation system composed of the catalyst and hydrogen peroxide used in the present invention can ensure that the oxidized polysaccharide has sufficient carboxyl group content (5.2-13.1 mmol/g), and has excellent coordination ability with non-chromium metal salts, so that the oxidized polysaccharide tanning agent can be used in It has excellent application effect in leather or fur tanning.
- a certain mass ( m ) of oxidized polysaccharide tanning agent was weighed to prepare an aqueous solution, and placed on a cation exchange column (loaded with Amberlite IR120 hydrogen-type strong acid cation exchange resin, diameter 35 mm, length 370 mm) , with ultrapure water as the mobile phase, and eluted at a constant rate (1.7 mL/min) at room temperature.
- An oxidized polysaccharide tanning agent solution with a mass concentration of 50 mg/mL was prepared with distilled water, filtered through a 0.25 ⁇ m microporous membrane, and used for gel permeation chromatography analysis.
- the chromatographic conditions were: injection volume of 100 ⁇ L, mobile phase NaNO 3 solution (0.1 mol/L), TSK-gel GMPWXL chromatographic column (7.8 mm ⁇ 300 mm), and flow rate of 0.6 mL/min.
- the pickling bare skin obtained by conventional technology is placed in a rotating drum, and the pickling solution that is 140 wt% by weight of the pickling naked skin, 13 wt% aluminum sulfate and 3 wt% oxidized starch tanning agent are added, wherein The amount of the oxidized starch tanning agent is calculated based on the effective content of the tanning agent.
- the pH is adjusted to 3.8-4.5 with magnesium oxide or baking soda, and the temperature is adjusted to 40 °C. After 2 hours of conversion, the tanned leather is obtained.
- the carboxyl content and the weight-average relative molecular mass of the oxidized starch tanning agent provided in Example 1 of the present invention are relatively close to the tanning agent obtained by the method provided by Comparative Example 1, but the chromaticity is far lower than the Comparative Example. 1 the tanning agent. This shows that the organic solvent can effectively remove the colored substances in the solution without affecting the degree of oxidation of the polysaccharide, and significantly reduce the color of the tanning agent.
- the carboxyl group content of the oxidized starch tanning agent provided by the present invention is significantly higher than that of the tanning agents described in Comparative Examples 2 and 3, while the weight-average relative molecular mass is significantly lower than the tanning agents described in Comparative Examples 2 and 3, thus It can effectively coordinate with non-chromium metal salts and penetrate evenly into the hide for tanning. It can be seen that the catalytic oxidation system composed of catalyst and hydrogen peroxide can effectively improve the degree of oxidative degradation of starch and ensure that the tanning agent is suitable for the coordination tanning of leather.
- the organic solvent, catalyst and hydrogen peroxide used in the present invention are all indispensable for preparing the light-colored polycarboxylated polysaccharide tanning agent.
- the carboxyl group content of the oxidized dextrin tanning agent was 5.7 mmol/g; the weight-average relative molecular mass was 1495 g/mol; and the chromaticity was 45.
- the pickled bare skin obtained by conventional technology is placed in a rotating drum, and the pickling solution that is 200 wt% by weight of the pickled naked skin, 21 wt% of zirconium sulfate and 4 wt% of oxidative dextrin tanning agent are added, The amount of oxidized dextrin tanning agent is calculated based on the effective content of the tanning agent.
- the pH is adjusted to 3.8-4.5 with magnesium oxide or baking soda, and the temperature is adjusted to 40 ° C.
- the tanning is obtained. leather.
- the carboxyl group content of the oxidized cellulose tanning agent was 11.8 mmol/g; the weight-average relative molecular mass was 1115 g/mol; and the chromaticity was 10.
- the pickled bare skin obtained by conventional technology is placed in a rotating drum, and the pickling solution that is 200 wt% by weight of the pickled naked skin, 13 wt% of zirconium sulfate and 3 wt% of oxidized cellulose tanning agent are added, The amount of oxidized cellulose tanning agent is calculated based on the effective content of the tanning agent.
- the pH is adjusted to 3.8-4.5 with magnesium oxide or baking soda, and the temperature is adjusted to 40 ° C.
- the tanning is obtained. leather.
- the carboxyl group content of the oxidized carboxymethyl cellulose sodium tanning agent is 5.2 mmol/g; the weight-average relative molecular mass is 6000 g/mol; and the chromaticity is 50.
- the pickling fur obtained by conventional technology is placed in a rotating drum or a groove, adding the pickling solution that is 600 wt% in terms of the pickling fur weight, 13 g/L of zirconium sulfate and 2 g/L in the volume of water added.
- g/L of oxidized carboxymethyl cellulose sodium tanning agent wherein the amount of oxidized carboxymethyl cellulose sodium tanning agent is based on the effective content of the tanning agent, and after rotating or paddling for 8 hours, it is alkalized with magnesium oxide to pH To 3.0, use magnesium oxide or baking soda to alkalinize to pH 3.6-4.2, adjust the temperature to 40°C, and turn or paddle for 2 hours to obtain tanned fur.
- the carboxyl group content of the oxidized sodium carboxymethyl starch tanning agent is 13.1 mmol/g; the weight-average relative molecular mass is 350 g/mol; and the chromaticity is 1.
- the pickling fur obtained by conventional technology is placed in a rotating drum or a groove, adding the pickling solution that is 400 wt% in terms of the pickling fur weight, and the titanium sulfate and 400 wt % in the volume of adding water.
- g/L of oxidized carboxymethyl starch sodium tanning agent wherein the amount of oxidized carboxymethyl starch sodium tanning agent is based on the effective content of the tanning agent, and after rotating or paddling for 4 h, alkali is leached with magnesium oxide to pH 3.0 , using magnesium oxide or baking soda to alkalinize to pH 3.6-4.2, adjusting the temperature to 40°C, and turning or paddling for 2 h to obtain tanned fur.
- the carboxyl group content of the oxidized starch tanning agent was 8.6 mmol/g; the weight-average relative molecular mass was 2319 g/mol; and the chromaticity was 10.
- the pickling fur obtained by conventional technology is placed in a rotating drum or a groove, adding the pickling solution that is 500 wt% in terms of the pickling fur weight, and the zirconium sulfate and 6 g/L of oxidized starch tanning agent, wherein the amount of oxidized starch tanning agent is based on the effective content of the tanning agent.
- the pH is adjusted to 3.6-4.2 with magnesium oxide or baking soda, and the temperature is adjusted.
- the tanned fur was obtained.
- the carboxyl group content of the oxidized dextrin tanning agent was 12.9 mmol/g; the weight-average relative molecular mass was 1326 g/mol; and the chromaticity was 15.
- the pickled bare skin obtained by the conventional process is placed in a rotating drum, and the pickling solution, which is 80 wt% by weight of the pickled naked skin, 4 wt% of titanium sulfate and 1 wt% of an oxidized dextrin tanning agent, is added,
- the amount of oxidized dextrin tanning agent is calculated based on the effective substance content of the tanning agent.
- the pH is adjusted to 3.8-4.5 with magnesium oxide or baking soda, and the temperature is adjusted to 40 ° C.
- the tanning is obtained. leather.
- the carboxyl group content of the oxidized cellulose tanning agent was 8.5 mmol/g; the weight-average relative molecular mass was 867 g/mol; and the chromaticity was 20.
- the pickling fur obtained by conventional technology is placed in a drum or a groove, adding the pickling solution that is 500 wt% in terms of the pickling fur weight, and the aluminum sulfate and 6 g/L of oxidized cellulose tanning agent, wherein the dosage of oxidized cellulose tanning agent is based on the effective content of the tanning agent, after turning or paddling for 2 hours, the pH is adjusted to 3.6-4.2 with magnesium oxide or baking soda, The temperature was adjusted to 40°C, and the tanned fur was obtained after turning or paddling for 2 h.
- the carboxyl group content of the oxidized sodium carboxymethyl starch tanning agent is 6.3 mmol/g; the weight-average relative molecular mass is 3647 g/mol; and the chromaticity is 40.
- the pickled bare skin obtained by the conventional process is placed in a rotating drum, and the pickling solution of 140 wt%, 21 wt% of titanium sulfate and 4 wt% of oxidized sodium carboxymethyl starch is added in the weight of the pickled bare skin.
- Tanning agent wherein the amount of oxidized carboxymethyl starch sodium tanning agent is based on the effective content of the tanning agent. After turning for 2 h, use magnesium oxide or baking soda to alkalize to pH 3.8-4.5, adjust the temperature to 40 ° C, turn After 2 h, tanned leather was obtained.
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Abstract
本发明属于皮革、毛皮鞣剂的技术领域，公开了一种浅色多羧基氧化多糖鞣剂及其制备方法和应用。本发明提供的浅色氧化多糖鞣剂的制备方法，采用了双相溶液体系，与现有的氧化多糖鞣剂制备技术相比，能高效萃取脱除氧化过程中产生的有色物质，及时阻断其与氧化多糖的聚合反应，从而达到显著降低氧化产物色度的效果。同时，本发明使用的催化剂和过氧化氢组成的催化氧化体系可以确保氧化多糖具有足够的羧基含量，与非铬金属盐具有优良的配位能力，使得氧化多糖鞣剂在皮革或毛皮鞣制中具有优良的应用效果。
Description
本发明涉及皮革、毛皮鞣剂的技术领域，特别涉及一种浅色多羧基氧化多糖鞣剂及其制备方法和应用。
背景技术
多糖是由十个以上单糖通过糖苷键连接而形成的大分子化合物，具有来源广泛、可再生、安全无毒、成本低廉等优点，是制备生态鞣剂的理想原料。多糖在双氧水等氧化剂的强氧化作用下，糖单元结构中的羟基会被氧化为羧基，并且糖苷键会发生断裂。因此，多糖的深度氧化降解产物可以与非铬金属盐搭配，用于皮革或毛皮鞣制。
文献（余跃, 王亚楠, 丁伟, 等. 催化剂对双氧水氧化淀粉-锆配合物结构及鞣制性能的影响. 精细化工, 2018, 35(11): 1928-1934; Yu, Y., Wang, Y. N., Ding, W.,
et al. Preparation of highly-oxidized starch using hydrogen peroxide and its
application as a novel ligand for zirconium tanning of leather. Carbohydrate
Polymer, 2017, 174, 823-829.）报道了一种高温（70-98℃）和高双氧水用量（60 wt%）催化氧化淀粉制备深度氧化淀粉的方法。该方法存在的问题是产物颜色较深，用于鞣制会影响皮革或毛皮的色泽和感观，限制了其在无铬皮革制造中的应用。中国专利CN107119154B
“宽分布的多官能团多糖基配体金属配合物鞣剂的制备方法”公开了一种高温（120-160℃）、高压（0.2-0.6 MPa）和高双氧水用量（40-100 wt%）催化氧化制备氧化多糖的方法，其存在的问题是高温高压条件更容易促成有色物质的生成。文献（王学川，李飞虎，强涛涛, 等. 深度氧化淀粉的制备及在制革鞣制中的应用. 皮革科学与工程，2013，23(2)：5-8.）和中国专利CN102747173B“一种铝–氧化淀粉络合物鞣剂的制备方法”报道了一种加热条件下浓硝酸和偏钒酸铵催化氧化淀粉制备深度氧化淀粉的方法，得到的深度氧化淀粉同样富含有色物质，颜色较深。上述氧化多糖产生颜色问题的原因是，多糖在强氧化作用下会被降解产生葡萄糖等单糖化合物，这类单糖化合物在受热或弱酸条件下会脱水转变为糠醛类化合物，该糠醛类化合物会进一步自聚或与氧化多糖聚合形成有色物质。
发明内容
为解决背景技术中的问题，本发明提供了一种浅色多羧基氧化多糖鞣剂及其制备方法和应用，通过本发明方法制备得到的浅色多羧基氧化多糖鞣剂颜色浅淡，与非铬金属盐配合使用后，不会对鞣制皮革或毛皮的颜色带来不利影响。
为达到上述目的，本发明采用的第一个技术方案为：
一种浅色多羧基氧化多糖鞣剂，该浅色多羧基氧化多糖鞣剂的原料包含：多糖、有机溶剂、催化剂和过氧化氢，其中，以多糖重量为基准计，所述有机溶剂的重量占1-15 wt%，所述催化剂的重量占0.05-2 wt‰，所述过氧化氢的重量占30-80 wt%。
进一步地，所述有机溶剂为四氢呋喃、乙酸乙酯和甲基异丁基酮中任一种或多种。
进一步地，所述多糖为淀粉、糊精、纤维素、羧甲基纤维素钠和羧甲基淀粉钠中任一种。
进一步地，所述催化剂为硫酸铜、硫酸亚铁和硫酸铁中任一种或多种。
进一步地，所述浅色多羧基氧化多糖鞣剂还包含占所述多糖重量0-30 wt%的中性盐，所述中性盐为氯化钠、氯化钾、硫酸钠和硝酸钾中任一种或多种。
进一步地，所述浅色多羧基氧化多糖鞣剂的羧基含量为5.2-13.1 mmol/g，重均相对分子质量为350-6000 g/mol，色度为1-50。
本发明采用的第二个技术方案为：
一种制备浅色多羧基氧化多糖鞣剂的方法，该方法包含：
配制浓度为20-60%的多糖水溶液；
向上述多糖水溶液中加入催化剂、有机溶剂和过氧化氢，在温度50-90℃下氧化反应0.5-4
h，得到氧化多糖溶液；以及
向上述氧化多糖溶液中加入中性盐，搅匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，即得所述浅色多羧基氧化多糖鞣剂。
本发明采用的第三个技术方案为：
一种第一个技术方案的浅色多羧基氧化多糖鞣剂或采用第二个技术方案得到的浅色多羧基氧化多糖鞣剂在皮革或毛皮鞣制中的应用。
进一步地，所述皮革或毛皮鞣制包含以下步骤：
将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为80-200 wt%的浸酸液，4-21 wt%的非铬金属盐和1-4 wt%的氧化多糖鞣剂，其中氧化多糖鞣剂用量以该鞣剂的有效物含量计，转2-6 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革；或
将按常规工艺得到的浸酸毛皮置于转鼓或划槽中，加入以浸酸毛皮重量计为400-600 wt%的浸酸液，以加入水的体积计为13-32 g/L的非铬金属盐和2-6
g/L的氧化多糖鞣剂，其中氧化多糖鞣剂用量以该鞣剂的有效物含量计，转动或划动2-8 h后，用氧化镁或小苏打提碱至pH为3.6-4.2，调温至40℃，转动或划动2 h后，得到鞣制毛皮。
进一步地，所述非铬金属盐为硫酸铝、硫酸锆和硫酸钛中任一种或多种。
本发明能够制备浅色氧化多糖鞣剂的原理在于，在水相中加入与糠醛类物质结构或极性相近的有机溶剂形成双相溶液体系，使得反应过程中产生的小分子糠醛类物质能够迅速溶解在有机相中，而氧化多糖则溶解在水相中，及时阻断小分子糠醛类物质与氧化多糖聚合形成大分子有色物质。随后，将水相和有机相进行分离，舍弃含小分子糠醛类物质及其聚合物的有机相，即可达到脱色效果，制得浅色氧化多糖鞣剂。
本发明的浅色氧化多糖鞣剂在双相溶液体系中制备得到，其特点是催化剂和过氧化氢组成的催化氧化体系可以对多糖进行深度氧化降解，使得氧化多糖鞣剂有足够的羧基与非铬金属盐配位，并且有足够低的分子量确保鞣剂能均匀渗透入皮中。更为关键的是，有机溶剂可以高效萃取氧化反应过程中产生的有色物质，使得氧化多糖鞣剂的颜色浅淡，不会对鞣制皮革或毛皮的颜色带来不利影响。
本发明与现有技术相比，具有以下有益效果：
本发明提供的浅色氧化多糖鞣剂显著降低了氧化产物的色度，本发明提供的浅色氧化多糖鞣剂的制备方法，采用了双相溶液体系，与现有的氧化多糖鞣剂制备技术相比，能高效萃取脱除氧化过程中产生的有色物质，及时阻断其与氧化多糖的聚合反应，从而达到显著降低氧化产物色度的效果。
本发明使用的催化剂和过氧化氢组成的催化氧化体系可以确保氧化多糖具有足够的羧基含量（5.2-13.1 mmol/g），与非铬金属盐具有优良的配位能力，使得氧化多糖鞣剂在皮革或毛皮鞣制中具有优良的应用效果。
具体实施方式
下面通过实例对本发明进行具体描述，有必要在此指出的是本实施例只用于对本发明进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。
以下实施例和对比例中，氧化多糖鞣剂的羧基含量测定方法：
根据氧化多糖鞣剂的固含量，称取一定质量（
m）的氧化多糖鞣剂配成水溶液，于阳离子交换柱（装载Amberlite IR120氢型强酸性阳离子交换树脂，直径35 mm，长度370
mm）上，以超纯水作为流动相，常温下恒速洗脱（1.7 mL/min）。收集洗脱液250 mL，于电位滴定仪上用NaOH标液（浓度
C
NaOH
）滴定溶液至pH为 8.3，记录样品消耗NaOH标液的体积（
V
S-NaOH
）。另称取相同质量的多糖配成水溶液进行空白滴定，记录空白消耗NaOH标液的体积（
V
B-NaOH
）。羧基含量计算公式如下：
以下实施例和对比例中，氧化多糖鞣剂的重均相对分子质量测定方法：
用蒸馏水配制质量浓度50 mg/mL的氧化多糖鞣剂溶液，经0.25 μm微孔滤膜过滤后用于凝胶渗透色谱分析。色谱条件为：进样量100 μL，流动相NaNO
3溶液（0.1 mol/L），TSK-gel GMPWXL色谱柱（7.8
mm × 300 mm），流速0.6
mL/min。
以下实施例和对比例中，氧化多糖鞣剂的色度测定方法：
用蒸馏水将氧化多糖鞣剂溶液稀释25倍，用蒸馏水做空白校正，采用色度仪依据铂钴比色法测定氧化多糖鞣剂的色度值。
实施例1
浅色多羧基氧化淀粉鞣剂的制备：
按重量份计，将40份淀粉、100份水、0.04份硫酸亚铁和3.2份四氢呋喃置于反应器中，滴加20份过氧化氢，在温度70℃下氧化反应4 h，得到氧化淀粉溶液；向上述溶液中加入6份氯化钠，搅拌均匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化淀粉鞣剂。
在此步骤中，测定了氧化淀粉鞣剂的羧基含量、重均相对分子质量和色度，结果如表1所示。
浅色多羧基氧化淀粉鞣剂在皮革鞣制中的应用：
将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为140 wt%的浸酸液，13 wt%的硫酸铝和3 wt%的氧化淀粉鞣剂，其中氧化淀粉鞣剂用量以该鞣剂的有效物含量计，转4 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革。
对比例1
按重量份计，将40份淀粉、100份水和0.04份硫酸亚铁置于反应器中，滴加20份过氧化氢，在温度70℃下氧化反应4 h，得到深色多羧基氧化淀粉鞣剂。
该氧化淀粉鞣剂的检测指标和应用方法同实施例1，检测结果如表1所示。
对比例2
按重量份计，将40份淀粉、100份水和3.2份四氢呋喃置于反应器中，滴加20份过氧化氢，在温度70℃下氧化反应4 h，得到浅色少羧基氧化淀粉鞣剂。
该氧化淀粉鞣剂的检测指标和应用方法同实施例1，检测结果如表1所示。
对比例3
按重量份计，将40份淀粉、100份水、0.04份硫酸亚铁和3.2份四氢呋喃置于反应器中，在温度70℃下氧化反应4 h，得到浅色少羧基氧化淀粉鞣剂。
该氧化淀粉鞣剂的检测指标和应用方法同实施例1，检测结果如表1所示。
表1氧化淀粉鞣剂的羧基含量、重均相对分子质量和色度的对比表
由表1可看出，本发明实施例1提供的氧化淀粉鞣剂的羧基含量和重均相对分子质量与对比例1提供的方法制得的鞣剂较为接近，但是色度远低于对比例1所述鞣剂。由此说明，有机溶剂在不影响多糖氧化程度的同时，能够有效的脱除溶液中的有色物质，显著降低鞣剂的色度。此外，本发明提供的氧化淀粉鞣剂的羧基含量显著高于对比例2和对比例3所述鞣剂，而重均相对分子质量显著低于对比例2和对比例3所述鞣剂，因而其能够与非铬金属盐有效配位，并均匀地渗透入皮中发挥鞣制作用。由此可见，催化剂和过氧化氢组成的催化氧化体系能够有效地提高淀粉的氧化降解程度，确保鞣剂适合用于皮革的配位鞣制。综上所述，本发明所使用的有机溶剂、催化剂和过氧化氢对于制备浅色多羧基氧化多糖鞣剂均不可或缺。
实施例2
浅色多羧基氧化糊精鞣剂的制备：
按重量份计，将20份糊精、100份水、0.02份硫酸铁和1.6份乙酸乙酯置于反应器中，滴加16份过氧化氢，在温度70℃下氧化反应0.5 h，得到氧化糊精溶液；将氧化糊精溶液搅拌均匀后静置30
min，待水相和有机相充分分离后，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化糊精鞣剂。
本实施例中氧化糊精鞣剂的羧基含量为5.7 mmol/g；重均相对分子质量为1495 g/mol；色度为45。
浅色多羧基氧化糊精鞣剂在皮革鞣制中的应用：
将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为200 wt%的浸酸液，21 wt%的硫酸锆和4 wt%的氧化糊精鞣剂，其中氧化糊精鞣剂用量以该鞣剂的有效物含量计，转6 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革。
实施例3
浅色多羧基氧化纤维素鞣剂的制备：
按重量份计，将60份纤维素、100份水、0.06份硫酸铜和4.8份四氢呋喃置于反应器中，滴加18份过氧化氢，在温度70℃下氧化反应2 h，得到氧化纤维素溶液；向上述溶液中加入18份氯化钾，搅拌均匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化纤维素鞣剂。
本实施例中氧化纤维素鞣剂的羧基含量为11.8 mmol/g；重均相对分子质量为1115 g/mol；色度为10。
浅色多羧基氧化纤维素鞣剂在皮革鞣制中的应用：
将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为200 wt%的浸酸液，13 wt%的硫酸锆和3 wt%的氧化纤维素鞣剂，其中氧化纤维素鞣剂用量以该鞣剂的有效物含量计，转6 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革。
实施例4
浅色多羧基氧化羧甲基纤维素钠鞣剂的制备：
按重量份计，将20份羧甲基纤维素钠、100份水、0.001份硫酸铜和0.2份甲基异丁基酮置于反应器中，滴加6份过氧化氢，在温度90℃下氧化反应2 h，得到氧化羧甲基纤维素钠溶液；向上述溶液中加入6份硫酸钠，搅拌均匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化羧甲基纤维素钠鞣剂。
本实施例中氧化羧甲基纤维素钠鞣剂的羧基含量为5.2 mmol/g；重均相对分子质量为6000 g/mol；色度为50。
浅色多羧基氧化羧甲基纤维素钠鞣剂在毛皮鞣制中的应用：
将按常规工艺得到的浸酸毛皮置于转鼓或划槽中，加入以浸酸毛皮重量计为600 wt%的浸酸液，以加入水的体积计为13 g/L的硫酸锆和2 g/L的氧化羧甲基纤维素钠鞣剂，其中氧化羧甲基纤维素钠鞣剂用量以该鞣剂的有效物含量计，转动或划动8 h后，用氧化镁提碱至pH为3.0，用氧化镁或小苏打提碱至pH为3.6-4.2，调温至40℃，转动或划动2 h后，得到鞣制毛皮。
实施例5
浅色多羧基氧化羧甲基淀粉钠鞣剂的应用：
按重量份计，将60份羧甲基淀粉钠、100份水、0.003份硫酸亚铁和0.6份甲基异丁基酮置于反应器中，滴加30份过氧化氢，在温度90℃下氧化反应4 h，得到氧化羧甲基淀粉钠溶液；向上述溶液中加入9份硝酸钾，搅拌均匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化羧甲基淀粉钠鞣剂。
本实施例中氧化羧甲基淀粉钠鞣剂的羧基含量为13.1 mmol/g；重均相对分子质量为350 g/mol；色度为1。
浅色多羧基氧化羧甲基淀粉钠鞣剂在毛皮鞣制中的应用：
将按常规工艺得到的浸酸毛皮置于转鼓或划槽中，加入以浸酸毛皮重量计为400 wt%的浸酸液，以加入水的体积计为18 g/L的硫酸钛和4 g/L的氧化羧甲基淀粉钠鞣剂，其中氧化羧甲基淀粉钠鞣剂用量以该鞣剂的有效物含量计，转动或划动4 h后，用氧化镁提碱至pH为3.0，用氧化镁或小苏打提碱至pH为3.6-4.2，调温至40℃，转动或划动2 h后，得到鞣制毛皮。
实施例6
浅色多羧基氧化淀粉鞣剂的制备：
按重量份计，将40份淀粉、100份水、0.002份硫酸铁和0.4份甲基异丁基酮置于反应器中，滴加32份过氧化氢，在温度90℃下氧化反应0.5 h，得到氧化淀粉溶液；将氧化淀粉溶液搅拌均匀后静置30
min，待水相和有机相充分分离后，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化淀粉鞣剂。
本实施例中氧化淀粉鞣剂的羧基含量为8.6 mmol/g；重均相对分子质量为2319 g/mol；色度为10。
浅色多羧基氧化淀粉鞣剂在毛皮鞣制中的应用：
将按常规工艺得到的浸酸毛皮置于转鼓或划槽中，加入以浸酸毛皮重量计为500 wt%的浸酸液，以加入水的体积计为32 g/L的硫酸锆和6 g/L的氧化淀粉鞣剂，其中氧化淀粉鞣剂用量以该鞣剂的有效物含量计，转动或划动4 h后，用氧化镁或小苏打提碱至pH为3.6-4.2，调温至40℃，转动或划动2 h后，得到鞣制毛皮。
实施例7
浅色多羧基氧化糊精鞣剂的制备：
按重量份计，将60份糊精、100份水、0.12份硫酸铁和9份乙酸乙酯置于反应器中，滴加48份过氧化氢，在温度50℃下氧化反应0.5 h，得到氧化糊精溶液；将氧化糊精溶液搅拌均匀后静置30
min，待水相和有机相充分分离后，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化糊精鞣剂。
本实施例中氧化糊精鞣剂的羧基含量为12.9 mmol/g；重均相对分子质量为1326 g/mol；色度为15。
浅色多羧基氧化糊精鞣剂在皮革鞣制中的应用：
将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为80 wt%的浸酸液，4 wt%的硫酸钛和1 wt%的氧化糊精鞣剂，其中氧化糊精鞣剂用量以该鞣剂的有效物含量计，转2 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革。
实施例8
浅色多羧基氧化纤维素鞣剂的制备：
按重量份计，将40份纤维素、100份水、0.08份硫酸铜和6份乙酸乙酯置于反应器中，滴加12份过氧化氢，在温度50℃下氧化反应2 h，得到氧化纤维素溶液；向上述溶液中加入12份氯化钠，搅拌均匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化纤维素鞣剂。
本实施例中氧化纤维素鞣剂的羧基含量为8.5 mmol/g；重均相对分子质量为867 g/mol；色度为20。
浅色多羧基氧化纤维素鞣剂在毛皮鞣制中的应用：
将按常规工艺得到的浸酸毛皮置于转鼓或划槽中，加入以浸酸毛皮重量计为500 wt%的浸酸液，以加入水的体积计为32 g/L的硫酸铝和6 g/L的氧化纤维素鞣剂，其中氧化纤维素鞣剂用量以该鞣剂的有效物含量计，转动或划动2 h后，用氧化镁或小苏打提碱至pH为3.6-4.2，调温至40℃，转动或划动2 h后，得到鞣制毛皮。
实施例9
浅色多羧基氧化羧甲基淀粉钠鞣剂的制备：
按重量份计，将20份羧甲基淀粉钠、100份水、0.04份硫酸亚铁和3份乙酸乙酯置于反应器中，滴加10份过氧化氢，在温度50℃下氧化反应4 h，得到氧化羧甲基淀粉钠溶液；向上述溶液中加入3份氯化钾，搅拌均匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，最终得到水相，即浅色多羧基氧化羧甲基淀粉钠鞣剂。
本实施例中氧化羧甲基淀粉钠鞣剂的羧基含量为6.3 mmol/g；重均相对分子质量为3647 g/mol；色度为40。
浅色多羧基氧化羧甲基淀粉钠鞣剂在皮革鞣制中的应用：
将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为140 wt%的浸酸液，21 wt%的硫酸钛和4 wt%的氧化羧甲基淀粉钠鞣剂，其中氧化羧甲基淀粉钠鞣剂用量以该鞣剂的有效物含量计，转2 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，但本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
- 一种浅色多羧基氧化多糖鞣剂，其特征在于，该浅色多羧基氧化多糖鞣剂的原料包含：多糖、有机溶剂、催化剂和过氧化氢，其中，以多糖重量为基准计，所述有机溶剂的重量占1-15 wt%，所述催化剂的重量占0.05-2 wt‰，所述过氧化氢的重量占30-80 wt%。
- 如权利要求1所述的浅色多羧基氧化多糖鞣剂，其特征在于，所述有机溶剂为四氢呋喃、乙酸乙酯和甲基异丁基酮中任一种或多种。
- 如权利要求1所述的浅色多羧基氧化多糖鞣剂，其特征在于，所述多糖为淀粉、糊精、纤维素、羧甲基纤维素钠和羧甲基淀粉钠中任一种。
- 如权利要求1所述的浅色多羧基氧化多糖鞣剂，其特征在于，所述催化剂为硫酸铜、硫酸亚铁和硫酸铁中任一种或多种。
- 如权利要求1-4任一所述的浅色多羧基氧化多糖鞣剂，其特征在于，所述浅色多羧基氧化多糖鞣剂还包含占所述多糖重量0-30 wt%的中性盐，所述中性盐为氯化钠、氯化钾、硫酸钠和硝酸钾中任一种或多种。
- 如权利要求1所述的浅色多羧基氧化多糖鞣剂，其特征在于，所述浅色多羧基氧化多糖鞣剂的羧基含量为5.2-13.1 mmol/g，重均相对分子质量为350-6000 g/mol，色度为1-50。
- 一种制备如权利要求1-6任一所述的浅色多羧基氧化多糖鞣剂的方法，其特征在于，该方法包含：配制浓度为20-60%的多糖水溶液；向上述多糖水溶液中加入催化剂、有机溶剂和过氧化氢，在温度50-90℃下氧化反应0.5-4 h，得到氧化多糖溶液；以及向上述氧化多糖溶液中加入中性盐，搅匀后静置30 min，将水相和有机相充分分离，舍弃含有色物质的有机相，即得所述浅色多羧基氧化多糖鞣剂。
- 一种如权利要求1-6任一所述的浅色多羧基氧化多糖鞣剂或采用如权利要求7所述的方法制备得到的浅色多羧基氧化多糖鞣剂在皮革或毛皮鞣制中的应用。
- 如权利要求8所述的应用，其特征在于，所述皮革或毛皮鞣制包含以下步骤：将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸酸裸皮重量计为80-200 wt%的浸酸液，4-21 wt%的非铬金属盐和1-4 wt%的氧化多糖鞣剂，其中氧化多糖鞣剂用量以该鞣剂的有效物含量计，转2-6 h后，用氧化镁或小苏打提碱至pH为3.8-4.5，调温至40℃，转2 h后，得到鞣制皮革；或将按常规工艺得到的浸酸毛皮置于转鼓或划槽中，加入以浸酸毛皮重量计为400-600 wt%的浸酸液，以加入水的体积计为13-32 g/L的非铬金属盐和2-6 g/L的氧化多糖鞣剂，其中氧化多糖鞣剂用量以该鞣剂的有效物含量计，转动或划动2-8 h后，用氧化镁或小苏打提碱至pH为3.6-4.2，调温至40℃，转动或划动2 h后，得到鞣制毛皮。
- 如权利要求9所述的应用，其特征在于，所述非铬金属盐为硫酸铝、硫酸锆和硫酸钛中任一种或多种。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117004781A (zh) * | 2023-08-01 | 2023-11-07 | 广州诺普化工科技有限公司 | 一种无铬鞣剂及其制备方法和应用 |
| CN118086599A (zh) * | 2024-04-03 | 2024-05-28 | 陕西科技大学 | 基于氧化k型卡拉胶的无铬鞣剂的制备方法 |
| CN118389754A (zh) * | 2024-05-29 | 2024-07-26 | 陕西科技大学 | 一种具有自蒙囿作用的水滑石纳米无铬鞣剂及其制备方法和应用 |
| CN119193939A (zh) * | 2024-09-30 | 2024-12-27 | 陕西科技大学 | 一种氧化淀粉/锆卤钙钛矿纳米复合鞣剂及其制备方法和应用 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11834724B2 (en) | 2021-02-08 | 2023-12-05 | Sichuan University | Light-colored polycarboxylated polysaccharide tanning agent, and preparation method and use thereof |
| CN112831617B (zh) * | 2021-02-08 | 2021-11-09 | 四川大学 | 一种浅色多羧基氧化多糖鞣剂及其制备方法和应用 |
| CN113999943B (zh) * | 2021-11-15 | 2022-07-29 | 陕西科技大学 | 一种多糖基水滑石纳米复合鞣剂及其制备方法和应用 |
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| CN106478884A (zh) * | 2016-09-30 | 2017-03-08 | 陕西科技大学 | 一种淀粉改性丙烯酸羟乙酯与铝配合物鞣剂的制备方法 |
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| CN107119154B (zh) * | 2017-07-06 | 2019-04-26 | 四川大学 | 宽分布的多官能团多糖基配体金属配合物鞣剂的制备方法 |
| CN111088409B (zh) * | 2019-11-27 | 2022-03-04 | 安徽银河皮革有限公司 | 生态皮革制造用多醛基大分子有机鞣剂及其制备方法 |
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- 2021-02-08 CN CN202110178497.6A patent/CN112831617B/zh active Active
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| CN101575652A (zh) * | 2009-05-08 | 2009-11-11 | 枣庄超越玉米淀粉有限公司 | 一种淀粉鞣剂及其生产方法 |
| EP2607500A1 (en) * | 2011-12-23 | 2013-06-26 | Hermes Sellier | Leather manufacturing process using a soluble oxidized starch-derived polysaccharide and compositions containing it |
| CN106478884A (zh) * | 2016-09-30 | 2017-03-08 | 陕西科技大学 | 一种淀粉改性丙烯酸羟乙酯与铝配合物鞣剂的制备方法 |
| CN110218822A (zh) * | 2019-06-17 | 2019-09-10 | 四川大学 | 一种糖基醛鞣剂及其制备方法 |
| CN112831617A (zh) * | 2021-02-08 | 2021-05-25 | 四川大学 | 一种浅色多羧基氧化多糖鞣剂及其制备方法和应用 |
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| CN117004781A (zh) * | 2023-08-01 | 2023-11-07 | 广州诺普化工科技有限公司 | 一种无铬鞣剂及其制备方法和应用 |
| CN118086599A (zh) * | 2024-04-03 | 2024-05-28 | 陕西科技大学 | 基于氧化k型卡拉胶的无铬鞣剂的制备方法 |
| CN118389754A (zh) * | 2024-05-29 | 2024-07-26 | 陕西科技大学 | 一种具有自蒙囿作用的水滑石纳米无铬鞣剂及其制备方法和应用 |
| CN119193939A (zh) * | 2024-09-30 | 2024-12-27 | 陕西科技大学 | 一种氧化淀粉/锆卤钙钛矿纳米复合鞣剂及其制备方法和应用 |
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| CN112831617A (zh) | 2021-05-25 |
| CN112831617B (zh) | 2021-11-09 |
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