WO2016037508A1 - 皮革鞣制用磺化杯芳烃鞣剂及其制备方法 - Google Patents

皮革鞣制用磺化杯芳烃鞣剂及其制备方法 Download PDF

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WO2016037508A1
WO2016037508A1 PCT/CN2015/081759 CN2015081759W WO2016037508A1 WO 2016037508 A1 WO2016037508 A1 WO 2016037508A1 CN 2015081759 W CN2015081759 W CN 2015081759W WO 2016037508 A1 WO2016037508 A1 WO 2016037508A1
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calixarene
tanning
resorcinol
acid
agent
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PCT/CN2015/081759
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English (en)
French (fr)
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马建中
周永香
高党鸽
张盼盼
吕斌
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陕西科技大学
马建中
周永香
高党鸽
张盼盼
吕斌
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Application filed by 陕西科技大学, 马建中, 周永香, 高党鸽, 张盼盼, 吕斌 filed Critical 陕西科技大学
Priority to US15/322,219 priority Critical patent/US9970069B2/en
Publication of WO2016037508A1 publication Critical patent/WO2016037508A1/zh

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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
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes

Definitions

  • the present invention relates to an expectorant, and in particular to a sulfonated calixarene tanning agent for leather tanning and a preparation method thereof
  • tanners In order to reduce chromium emissions, tanners have developed many techniques and methods to alleviate chromium pollution. These methods are grouped into two categories, one is to treat waste chromium liquid, to reduce the chromium content of waste liquid; The sputum recycling or increasing the chromium absorption rate and reducing the amount of chromium, these traditional "terminal management" methods are a passive mode, with large pollution investment, high operating costs, difficult governance, and will not bring any business. Economic benefits, it is necessary to solve the problem of chromium pollution from the source. It is a hot spot to develop clean materials for tanning and tin-free tanning agents.
  • Calixarene is a class of cyclic oligomers formed by the reaction of phenol or a derivative thereof with an aldehyde via a methylene group.
  • the calixarene has high chemical stability, good thermal stability, adjustable cavity size and simple synthesis.
  • the derivatization can introduce groups such as sulfonic acid group, amino group, carboxyl group and amide group into calixarene, these groups and collagen fibers.
  • the upper amino group, the carboxyl group and the like are valence-bonded or hydrogen-bonded, and the skin collagen fibers are used for the production of sputum, the chemical resistance of the collagen fibers, the heat and humidity resistance, and the phenolic hydroxyl group at the lower edge of the calixarene have a coordination ability. It can hydrogen bond with amino groups, sulfhydryl groups, and peptide groups in collagen fibers, and it can also be used for the production of collagen fibers.
  • the calixarene synthetic raw material is non-toxic or low-toxic, the synthesis process is simple and easy, and the synthetic product is non-toxic. Therefore, it is feasible to use sulfonated calixarene as a chrome-free tincture for leather tanning.
  • the sulfonated calixarene tanning agent is non-toxic and environmentally friendly.
  • the new chrome-free tincture can reduce the amount of chromium, reduce chromium pollution, and achieve clean production of the tanning process
  • An object of the present invention is to provide a sulfonated calixarene tanning agent for leather tanning and a preparation method thereof, and to obtain a non-toxic environmentally friendly new chrome-free tanning agent.
  • a sulfonated calixarene tanning agent for leather tanning characterized in that:
  • the sulfonating agent is selected from the group consisting of sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid.
  • the resorcinol calixarene is made of the following materials:
  • the inorganic strong acid catalyst is selected from the group consisting of hydrochloric acid having a mass fraction of 37%, nitric acid having a mass fraction of 65%, and sulfuric acid having a mass fraction of 98%;
  • a method for preparing a sulfonated calixarene tanning agent for leather tanning characterized in that:
  • Step 1 Add 5.5g of resorcinol to a four-necked flask, add ethanol solution under stirring at 200r/min, and in an ice water bath at 5 ° C and protect it, two constant pressure dropping funnels 7-1 Slowly add 7-13 mL of inorganic strong acid catalyst, and 4.24-6.4 g of benzaldehyde or 5-7 g of p-hydroxybenzaldehyde.
  • Step 2 After the completion of the dropwise addition, the temperature is raised to 60-80 ° C, the reaction is 6 h;
  • Step 3 After the reaction is finished, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after the filtration is completed, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene;
  • Step 4 Weighing resorcinol calixarene 3.0-5.0g, adding sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 9-25 mL, sulfonation temperature 70-80 ° C, sulfonation 2- 4h, an aqueous solution of a sulfonated calixarene oxime agent was obtained.
  • the mixing ratio of anhydrous ethanol and water in the ethanol solution is (1:5) - (5:1);
  • the inorganic strong acid catalyst is selected from the group consisting of hydrochloric acid having a mass fraction of 37%, nitric acid having a mass fraction of 65%, and sulfuric acid having a mass fraction of 98%.
  • the present invention uses resorcinol and an aldehyde monomer as raw materials to obtain resorcinol calixarene by a one-step synthesis method, and the preparation method is simple and feasible, and the reactants and products are low-toxic or non-toxic, and after sulfonation Good water solubility, the sulfonated cup aromatic barium agent is used in leather tanning, which can improve the moisture and heat stability of the collagen fiber, increase the shrinkage temperature of the skin to 80 ° C, and make the skin collagen fiber into a crucible; Physical and mechanical properties test, its tensile strength and tensile properties are superior to conventional chrome tanning, and the hand feels full, soft, and the thickening rate is obvious. Therefore, this patent considers that sulfonated calixarene can be used in leather tanning instead of chrome powder to reduce the amount of chromium powder and reduce chromium pollution.
  • the present invention relates to a sulfonated calixarene tanning agent for leather tanning, which is prepared from the following components:
  • the sulfonating agent is selected from the group consisting of sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid;
  • the resorcinol calixarene is made of the following materials:
  • the above inorganic strong acid catalyst is selected from the group consisting of hydrochloric acid having a mass fraction of 37%, nitric acid having a mass fraction of 65%, and sulfuric acid having a mass fraction of 98%;
  • a method for preparing a sulfonated calixarene tanning agent for leather tanning is achieved by the following steps:
  • Step 1 Add 5.5 g of resorcinol to a four-necked flask, and add an ethanol solution with stirring at 200 r/min.
  • the inorganic strong acid catalyst is selected from the group consisting of hydrochloric acid having a mass fraction of 37%, nitric acid having a mass fraction of 65%, and sulfuric acid having a mass fraction of 98%.
  • Step 2 After the completion of the dropwise addition, the temperature is raised to 60-80 ° C, and the reaction is carried out for 6 hours.
  • Step 3 After the reaction is finished, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after drying, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weighing resorcinol calixarene 3.0-5.0g, adding sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 9-25 mL, sulfonation temperature 70-80 ° C, sulfonation 2- 4h, an aqueous solution of a sulfonated calixarene oxime agent was obtained.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Step 1 Add 5.5g of resorcinol to the four-necked flask, add the ethanol solution under stirring of 200r/min, and under the ice water bath at 5 ° C, protect the two constant pressure dropping funnels. 7 mL of an inorganic strong acid catalyst and 6.4 g of benzaldehyde were slowly added dropwise dropwise.
  • the inorganic strong acid catalyst is sulfuric acid having a mass fraction of 98%.
  • Step 2 After the completion of the dropwise addition, the temperature was raised to 60 ° C, and the reaction was carried out for 6 hours.
  • Step 3 After the reaction is finished, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after the filtration is completed, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weigh 5.0g of resorcinol calixarene, add sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 9mL, sulfonation temperature 80 ° C, sulfonation 2h, to obtain sulfonated calixarene tanning agent Aqueous solution.
  • Step 1 Add 5.5g of resorcinol to a four-necked flask, add ethanol solution under stirring of 200r/min, and in an ice water bath at 5 ° C and protect it, two constant pressure dropping funnels 8 mL of an inorganic strong acid catalyst and 5.32 g of benzaldehyde were slowly added dropwise dropwise.
  • the inorganic strong acid catalyst is a nitric acid having a mass fraction of 65%.
  • Step 2 After the completion of the dropwise addition, the temperature was raised to 65 ° C, and the reaction was carried out for 6 hours.
  • Step 3 After the reaction is finished, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after drying, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weigh 4.5g of resorcinol calixarene, add sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 12mL, sulfonation temperature 78 ° C, sulfonation for 2.5h, to obtain sulfonated calixarene Aqueous solution.
  • Step 1 Add 5.5g of resorcinol to a four-necked flask, add ethanol solution under stirring of 200r/min, and in an ice water bath at 5 ° C and protect it, two constant pressure dropping funnels 9 mL of an inorganic strong acid catalyst and 4.24 g of benzaldehyde were slowly added dropwise dropwise.
  • the inorganic strong acid catalyst is hydrochloric acid having a mass fraction of 37%.
  • Step 2 After the completion of the dropwise addition, the temperature was raised to 70 ° C, and the reaction was carried out for 6 hours.
  • Step 3 After the reaction is finished, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after the filtration is completed, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weigh 4.0 g of resorcinol calixarene, add sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 15 mL, sulfonation temperature 76 ° C, sulfonation for 3 h, to obtain sulfonated calixarene tanning agent Aqueous solution.
  • Step 1 Add 5.5 g of resorcinol to a four-necked flask, add an ethanol solution under stirring at 200 r/min, and under an ice water bath at 5 ° C, protect the two constant pressure dropping funnels. l Slowly add l lml of inorganic strong acid catalyst, and 7 g of p-hydroxybenzaldehyde.
  • the inorganic strong acid catalyst is sulfuric acid having a mass fraction of 98%.
  • Step 2 After the completion of the dropwise addition, the temperature was raised to 70 ° C, and the reaction was carried out for 6 hours.
  • Step 3 After the reaction is completed, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after the filtration is completed, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weigh 3.5 g of resorcinol calixarene, add sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 18 mL, sulfonation temperature 74 ° C, sulfonation 3.5 h, to obtain sulfonated calixarene Aqueous solution.
  • Step 1 Add 5.5 g of resorcinol to a four-necked flask, add an ethanol solution under stirring at 200 r/min, and under an ice water bath at 5 ° C, protect the two constant pressure dropping funnels. 12 mL of a strong inorganic acid catalyst, 6 g of p-hydroxybenzaldehyde, was slowly added dropwise.
  • the inorganic strong acid catalyst is a nitric acid having a mass fraction of 65%.
  • Step 2 After the completion of the dropwise addition, the temperature is raised to 75 ° C, and the reaction is carried out for 6 hours.
  • Step 3 After the reaction is finished, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after the filtration is completed, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weigh 3.0g of resorcinol calixarene, add sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 21mL, sulfonation temperature 72 ° C, sulfonation 4h, to obtain sulfonated calixarene tanning agent Aqueous solution.
  • Step 1 Add 5.5 g of resorcinol to a four-necked flask, add an ethanol solution under stirring at 200 r/min, and under an ice water bath at 5 ° C, and protect the two constant pressure dropping funnels. 13 mL of an inorganic strong acid catalyst and 5 g of p-hydroxybenzaldehyde were slowly added dropwise dropwise.
  • the inorganic strong acid catalyst is hydrochloric acid having a mass fraction of 37%.
  • Step 2 After the completion of the dropwise addition, the temperature is raised to 80 ° C, and the reaction is carried out for 6 hours.
  • Step 3 After the reaction is completed, cooling, suction filtration, suction filtration, repeated washing with ethanol and distilled water, the solid product gradually changes from dark green to yellow, and after the filtration is completed, the product is dried in a vacuum oven at 80 ° C. , a pale yellow powder, which is the prepared resorcinol calixarene.
  • Step 4 Weigh 3.0g of resorcinol calixarene, add sulfonating agent sulfuric acid, fuming sulfuric acid or chlorosulfonic acid 25mL, sulfonation temperature 70 ° C, sulfonation 4h, to obtain sulfonated calixarene tanning agent Aqueous solution.

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Abstract

一种皮革鞣制用磺化杯芳烃鞣剂及其制备方法。该鞣剂以间苯二酚、醛类单体为原料，通过在间苯二酚中加入乙醇溶液，滴加无机强酸催化剂和醛类衍生物，升温反应后，冷却抽滤，用乙醇和蒸馏水反复洗涤，干燥得间苯二酚杯芳烃；称取间苯二酚杯芳烃，加磺化剂反应，得到磺化杯芳烃鞣剂水溶液。

Description

说明书 发明名称:皮革鞣制用磺化杯芳烃鞣剂及其制备方法 技术领域
[0001] 本发明涉及一种鞣剂， 具体涉及一种皮革鞣制用磺化杯芳烃鞣剂及其制备方法 背景技术
[0002] 为了减少铬排放， 制革工作者已经幵发出许多能缓解铬污染的技术和方法， 这 些方法归纳起来分为两类， 一是处理废铬液， 降低废液铬含量； 二是铬鞣液循 环利用或提高铬吸收率， 减少铬用量， 这些传统的"终端治理"方式， 是一种被动 的模式， 治污投入大， 运行费用高， 治理难度大， 不会给企业带来任何经济效 益， 故应该从源头解决铬污染问题， 研制制革鞣制用无铬鞣剂的清洁化材料是 目前的热点。
[0003] 杯芳烃是一类由苯酚或其衍生物与醛类反应， 通过亚甲基连接而成的环状低聚 物。 杯芳烃化学稳定性高、 热稳定性好、 空腔大小可调、 合成简单， 通过衍生 化可将磺酸基、 氨基、 羧基、 酰胺基等基团引入杯芳烃， 这些基团与皮胶原纤 维上氨基、 羧基等发生电价结合或氢键结合， 对皮胶原纤维起到鞣制作用， 提 高胶原纤维的耐化学试剂作用、 耐湿热稳定性等， 且杯芳烃下缘的酚羟基， 具 有配位能力， 能与胶原纤维中的氨基、 胍基、 肽基发生氢键结合， 同样对皮胶 原纤维起到鞣制作用。 杯芳烃合成原料无毒或低毒， 合成过程简单易行， 合成 产品无毒， 因此将磺化杯芳烃作为皮革鞣制用无铬鞣剂是可行的， 磺化杯芳烃 鞣剂属于无毒环保型新型无铬鞣剂， 可减少铬用量， 降低铬污染， 实现制革鞣 制过程的清洁化生产。
技术问题
[0004] 本发明的目的是提供一种皮革鞣制用磺化杯芳烃鞣剂及其制备方法， 制得一种 无毒环保型新型无铬鞣剂。
问题的解决方案
技术解决方案 [0005] 皮革鞣制用磺化杯芳烃鞣剂， 其特征在于：
[0006] 由以下组分制成：
[0007] 间苯二酚杯芳烃 lg
[0008] 磺化剂 3-5mL;
[0009] 其中：
[0010] 磺化剂选自硫酸、 发烟硫酸、 氯磺酸。
[0011] 所述间苯二酚杯芳烃由以下物质制成：
[0012] 间苯二酚 5.5g
[0013] 苯甲醛 4.24-6.4g 或 对羟基苯甲醛 5-7g
[0014] 无机强酸催化剂 7-13mL
[0015] 反应溶剂 乙醇溶液。
[0016] 所述无机强酸催化剂选自质量分数为 37%的盐酸、 质量分数为 65%的硝酸、 质 量分数为 98%的硫酸；
[0017] 乙醇溶液中， 无水乙醇和水的体积混合比为 （1:5) - (5:1) 。
[0018] 皮革鞣制用磺化杯芳烃鞣剂的制备方法， 其特征在于：
[0019] 由以下步骤实现：
[0020] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 7-13mL的 无机强酸催化剂， 以及 4.24-6.4g苯甲醛或 5-7g对羟基苯甲醛；
[0021] 步骤二： 待滴加完成后， 升温至 60-80°C， 反应 6h;
[0022] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃；
[0023] 步骤四： 称取间苯二酚杯芳烃 3.0-5.0g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 9-25 mL， 磺化温度 70-80°C， 磺化 2-4h， 得到磺化杯芳烃鞣剂水溶液。
[0024] 步骤一中， 乙醇溶液中无水乙醇和水的混合比为 （1:5) - (5:1) ；
[0025] 无机强酸催化剂选自质量分数为 37%的盐酸、 质量分数为 65%的硝酸、 质量分 数为 98%的硫酸。 发明的有益效果
有益效果
[0026] 本发明以间苯二酚、 醛类单体为原料， 通过一步合成法得到间苯二酚杯芳烃， 制备方法简单可行， 反应物及产物低毒或无毒， 且经磺化后水溶性良好， 该磺 化杯芳烃鞣剂用于皮革鞣制中， 可提高胶原纤维耐湿热稳定性， 将生皮收缩温 度提高至 80°C， 对皮胶原纤维起到鞣制作用； 通过鞣制后皮坯物理机械性能测试 ， 其抗张强度和拉伸性能均优于常规铬鞣， 且手感丰满、 柔软， 增厚率明显。 因此本专利认为可将磺化杯芳烃替代铬粉鞣制用于皮革鞣制中， 减少铬粉用量 ， 降低铬污染。
本发明的实施方式
[0027] 下面结合具体实施方式对本发明进行详细的说明。
[0028] 本发明涉及的皮革鞣制用磺化杯芳烃鞣剂， 由以下组分制成：
[0029] 间苯二酚杯芳烃 lg (涉及间苯二酚杯 [4]、 杯 [6]、 杯 [8]芳烃）
[0030] 磺化剂 3-5mL。
[0031] 其中：
[0032] 磺化剂选自硫酸、 发烟硫酸、 氯磺酸；
[0033] 间苯二酚杯芳烃由以下物质制成：
[0034] 间苯二酚 5.5g
[0035] 苯甲醛 4.24-6.4g 或 对羟基苯甲醛 5-7g
[0036] 无机强酸催化剂 7-13mL
[0037] 反应溶剂 乙醇溶液。
[0038] 上述无机强酸催化剂选自质量分数为 37%的盐酸、 质量分数为 65%的硝酸、 质 量分数为 98%的硫酸；
[0039] 乙醇溶液中， 无水乙醇和水的体积混合比为 （1:5) - (5: 1) 。
[0040] 皮革鞣制用磺化杯芳烃鞣剂的制备方法， 由以下步骤实现：
[0041] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液
， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 7-13mL的 无机强酸催化剂， 以及 4.24-6.4g苯甲醛或 5-7g对羟基苯甲醛。
[0042] 上述乙醇溶液中无水乙醇和水的混合比为 （1:5) - (5:1) ；
[0043] 无机强酸催化剂选自质量分数为 37%的盐酸、 质量分数为 65%的硝酸、 质量分 数为 98%的硫酸。
[0044] 步骤二： 待滴加完成后， 升温至 60-80°C， 反应 6h。
[0045] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。
[0046] 步骤四： 称取间苯二酚杯芳烃 3.0-5.0g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 9-25 mL， 磺化温度 70-80°C， 磺化 2-4h， 得到磺化杯芳烃鞣剂水溶液。
[0047] 实施例 1 :
[0048] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 7mL的无 机强酸催化剂， 以及 6.4g苯甲醛。
[0049] 上述乙醇溶液中无水乙醇和水的混合比为 1:5;
[0050] 无机强酸催化剂为质量分数为 98%的硫酸。
[0051] 步骤二： 待滴加完成后， 升温至 60°C， 反应 6h。
[0052] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。
[0053] 步骤四： 称取间苯二酚杯芳烃 5.0g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 9mL， 磺化温度 80°C， 磺化 2h， 得到磺化杯芳烃鞣剂水溶液。
[0054] 实施例 2:
[0055] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 8mL的无 机强酸催化剂， 以及 5.32g苯甲醛。
[0056] 上述乙醇溶液中无水乙醇和水的混合比为 1:1 ;
[0057] 无机强酸催化剂为质量分数为 65%的硝酸。 [0058] 步骤二： 待滴加完成后， 升温至 65°C， 反应 6h。
[0059] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。
[0060] 步骤四： 称取间苯二酚杯芳烃 4.5g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 12mL， 磺化温度 78°C， 磺化 2.5h， 得到磺化杯芳烃鞣剂水溶液。
[0061] 实施例 3:
[0062] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 9mL的无 机强酸催化剂， 以及 4.24g苯甲醛。
[0063] 上述乙醇溶液中无水乙醇和水的混合比为 2:1 ;
[0064] 无机强酸催化剂为质量分数为 37%的盐酸。
[0065] 步骤二： 待滴加完成后， 升温至 70°C， 反应 6h。
[0066] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。
[0067] 步骤四： 称取间苯二酚杯芳烃 4.0g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 15mL， 磺化温度 76°C， 磺化 3h， 得到磺化杯芳烃鞣剂水溶液。
[0068] 实施例 4:
[0069] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 l lml 无机强酸催化剂， 以及 7g对羟基苯甲醛。
[0070] 上述乙醇溶液中无水乙醇和水的混合比为 3:1 ;
[0071] 无机强酸催化剂为质量分数为 98%的硫酸。
[0072] 步骤二： 待滴加完成后， 升温至 70°C， 反应 6h。
[0073] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。 [0074] 步骤四： 称取间苯二酚杯芳烃 3.5g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 18mL， 磺化温度 74°C， 磺化 3.5h， 得到磺化杯芳烃鞣剂水溶液。
[0075] 实施例 5:
[0076] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 12mL的 无机强酸催化剂， 6g对羟基苯甲醛。
[0077] 上述乙醇溶液中无水乙醇和水的混合比为 4:1 ;
[0078] 无机强酸催化剂为质量分数为 65%的硝酸。
[0079] 步骤二： 待滴加完成后， 升温至 75°C， 反应 6h。
[0080] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。
[0081] 步骤四： 称取间苯二酚杯芳烃 3.0g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 21mL， 磺化温度 72°C， 磺化 4h， 得到磺化杯芳烃鞣剂水溶液。
[0082] 实施例 6:
[0083] 步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入乙醇溶液 ， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐滴缓慢滴加 13mL的 无机强酸催化剂， 以及 5g对羟基苯甲醛。
[0084] 上述乙醇溶液中无水乙醇和水的混合比为 5:1 ;
[0085] 无机强酸催化剂为质量分数为 37%的盐酸。
[0086] 步骤二： 待滴加完成后， 升温至 80°C， 反应 6h。
[0087] 步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤， 固体产 物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空烘箱里干燥， 得淡黄 色粉末， 即为制备的间苯二酚杯芳烃。
[0088] 步骤四： 称取间苯二酚杯芳烃 3.0g， 加磺化剂硫酸、 发烟硫酸或氯磺酸 25mL， 磺化温度 70°C， 磺化 4h， 得到磺化杯芳烃鞣剂水溶液。
[0089] 本发明的内容不限于实施例所列举， 本领域普通技术人员通过阅读本发明说明 书而对本发明技术方案采取的任何等效的变换， 均为本发明的权利要求所涵盖 。

Claims

权利要求书
[权利要求 1] 皮革鞣制用磺化杯芳烃鞣剂， 其特征在于：
由以下组分制成：
间苯二酚杯芳烃 lg
磺化剂 3-5mL;
其中：
磺化剂选自硫酸、 发烟硫酸、 氯磺酸。
[权利要求 2] 根据权利要求 1所述的皮革鞣制用磺化杯芳烃鞣剂， 其特征在于： 所述间苯二酚杯芳烃由以下物质制成：
间苯二酚 5.5g
苯甲醛 4.24-6.4g 或 对羟基苯甲醛 5-7g
无机强酸催化剂 7-13mL
反应溶剂 乙醇溶液。
[权利要求 3] 根据权利要求 2所述的皮革鞣制用磺化杯芳烃鞣剂， 其特征在于： 所述无机强酸催化剂选自质量分数为 37%的盐酸、 质量分数为 65%的 硝酸、 质量分数为 98%的硫酸；
乙醇溶液中， 无水乙醇和水的体积混合比为 （1:5) - (5:1) 。
[权利要求 4] 皮革鞣制用磺化杯芳烃鞣剂的制备方法， 其特征在于：
由以下步骤实现：
步骤一： 在四口烧瓶中加入 5.5g间苯二酚， 在 200r/min的搅拌下加入 乙醇溶液， 并在 5°C的冰水浴和 护下， 两个恒压滴液漏斗同吋逐 滴缓慢滴加 7-13mL的无机强酸催化剂， 以及 4.24-6.4g苯甲醛或 5-7g对 羟基苯甲醛；
步骤二： 待滴加完成后， 升温至 60-80°C， 反应 6h;
步骤三： 反应结束后， 冷却， 抽滤， 抽滤吋用乙醇和蒸馏水反复洗涤
， 固体产物由墨绿色逐渐变为黄色， 抽滤完成后将产物在 80°C的真空 烘箱里干燥， 得淡黄色粉末， 即为制备的间苯二酚杯芳烃； 步骤四： 称取间苯二酚杯芳烃 3.0-5.0g， 加磺化剂硫酸、 发烟硫酸或 氯磺酸 9-25mL， 磺化温度 70-80°C， 磺化 2-4h， 得到磺化杯芳烃鞣剂 水溶液。
[权利要求 5] 根据权利要求 4所述的皮革鞣制用磺化杯芳烃鞣剂的制备方法， 其特 征在于：
步骤一中， 乙醇溶液中无水乙醇和水的混合比为 （1:5) - (5:1) ； 无机强酸催化剂选自质量分数为 37%的盐酸、 质量分数为 65%的硝酸 、 质量分数为 98%的硫酸。
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